CN101636420A - Polymerizable monomer, polymerizable composition and dental material - Google Patents

Abstract

It is intended to provide a polymerizable composition which exerts an excellent adhesiveness to a tooth tissue (in particular, the dentinal matrix) when employed as a dental material, and a polymerizable monomer which is a component of the same. Namely, a polymerizable monomer (A) which is a compound having two or more polymerizable groups and shows a retention time of from 7 minutes to 30 minutes in high-performance liquid chromatography (HPLC) measurement conducted under the following conditions (column: being 3.9 mm in inner diameter and 300 mm in height and packed with a C18 packing agent having been ground to give an average grain size of 10 [mu]m and having a pore size of 125 AA, eluent: a solvent mixture of methanol/water (3/7), flow rate: 1.0 mL/min, measurement temperature: 50 DEG C, sample injection: 10 [mu]L, dead volume from the sample inlet to the detection point: 87 [mu]L); and a composition containing the same.

Description

Polymerizable monomer, Polymerizable composition and dental material

Technical field

【0001】

The present invention relates to be mainly used in hydrophilic polymer monomer dental material, that have a plurality of polymerizable groups, in addition, relate to the composition that contains this polymerizable monomer polymerizability.The invention still further relates to the dental materials such as dental bed material, adhesives, cement and compound resin that use said composition.

Background technology

【0002】

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.

【0003】

For example, international disclosing in the WO2004/047773 brochure, 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 monomer of 1～2 hydroxyl, simple function (methyl) acrylate 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, by the above-mentioned multifunctional polymerization monomer of a small amount of interpolation in composition, adhesiveproperties, cured body rerum natura, almost not influence of operable time to composition 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.

【0004】

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.

【0005】

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 the self-criticism that simplifies to whole 1 step of single component types of integrated above-mentioned decalcifications, above-mentioned penetrant action and above-mentioned solidification.In arbitrary use-pattern, all requirement can be applied to the composition of dental adhesives excellent in adhesion, therefore, requires to become the polymerizable monomer said composition composition, the excellent cementability of performance.

Summary of the invention

【0006】

The objective of the invention is to, provide when using the dental material, performance excellent with the Polymerizable composition of cementability dentine (particularly dentine) and the polymerizable monomer that becomes its composition.The present invention also aims to, the dental material excellent in adhesion with dentine (particularly dentine) is provided.

【0007】

The present invention is polymerizable monomer (A), and it is the compound with the polymerizable group more than 2,

The C18 weighting agent that this polymerizable monomer (A) uses median size to be broken for 10 μ m, have a pore size of 125 dusts is filled the post of the internal diameter 3.9mm * length 300mm that obtains, elutriant be mixed solvent, the flow of methanol=3/7 be 1.0mL/ minute, measure temperature be 50 ℃, sample injection rate be 10 μ L and except post the dead volume from the sample inlet to detection site be under the condition of 87 μ L during with high performance liquid chromatography (HPLC) mensuration, retention time is 7 minutes～30 minutes.

【0008】

Polymerizable monomer of the present invention (A) preferably has the hydroxyl more than 2, more preferably has the hydroxyl more than 3.

【0009】

The group of the preferred following formula of the polymerizable group of polymerizable monomer (A) (1), following formula (2) or following formula (3) expression.

【0010】

[Chemical formula 1]

【0011】

[Chemical formula 2]

【0012】

[chemical formula 3]

【0013】

(in the formula, R ¹, R ²And R ³Represent the aliphatic alkyl of hydrogen atom or carbonatoms 1～10 respectively, * represents associative key.)

【0014】

R ¹, R ²And R ³Be preferably hydrogen atom or methyl.

【0015】

The compound of polymerizable monomer (A) preferred formula (4) expression,

【0016】

[chemical formula 4]

【0017】

(in the formula, G is hydroxyl or polymerizable group, and n is the integer more than 3, and at least 3 is hydroxyl among the G, and among the G at least 2 be polymerizable group.)。

【0018】

Another aspect of the present invention is to contain above-mentioned polymerizable monomer (A) to form composition.

【0019】

Composition of the present invention, as the polymerizable monomer composition, preferably also contain and be selected from least a kind of polymerizable monomer and form with 1 polymerizable functional groups group and the polymerizable monomer (B) of 1 above hydroxyl, polymerizable monomer (C) and bridging property polymerizable monomer (D) with acidic-group.In addition, preferably containing solvent (E) forms.In addition, preferably containing polymerization starter (F) forms.In addition, preferably containing polymerization promotor (G) forms.In addition, preferably containing filler (H) forms.

【0020】

Composition of the present invention is preferably as dental composition.

【0021】

Another aspect of the present invention is the bed material, adhesives, compound resin and the cement that use above-mentioned dental composition to obtain.

【0022】

Polymerizable monomer of the present invention (A) is owing to be the hydrophilic compounds with a plurality of polymerizable groups, therefore in the purposes that requires solidified nature and to require this polymkeric substance be useful in the hydrophilic purposes.Contain polymerizable monomer of the present invention (A) composition with headed by the dental use, useful in various uses.Particularly, use the excellent in adhesion of the dental material such as dental bed material, adhesives, cement and compound resin of said composition and dentine (particularly dentine).

Embodiment

【0023】

At first, describe for polymerizable monomer of the present invention (A).

【0024】

Polymerizable monomer (A)

Polymerizable monomer (A) has 2 above polymerizable groups.To contain polymerizable monomer (A) when composition is used for dental use, the polymeric composition curing by this polymerizable group can be used as dental materials such as bed material, adhesives, compound resin, cement and plays a role.In addition, the polymerizable group number is more than 2, so polymerizable monomer (A) has bridging property.Thereby, contain the solidified nature of composition of polymerizable monomer (A) and the physical strength height of cured article.The polymerizable group number is too much, has to be difficult to guarantee suitable hydrophilic situation, and is therefore preferred below 6.

【0025】

About polymerizable monomer (A), polymerizable group is meant the group that contains functional group that can radical polymerization, for example enumerates, and contains the group of vinyl.Particularly, consider,, among them, consider, most preferably the group of formula (1) expression from the easy viewpoint that imports to polymerizable monomer (A) as the group of the preferred following formula of polymerizable group (1), formula (2) or formula (3) expression from the viewpoint of polymerisation reactivity.

【0026】

[chemical formula 5]

【0027】

[chemical formula 6]

【0028】

[chemical formula 7]

【0029】

At this, R ¹, R ²And R ³Be respectively the aliphatic alkyl of hydrogen atom or carbonatoms 1～10, * represents 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.

【0030】

The alkyl of carbonatoms 1～10 can be straight chain shape, chain and ring-type any one, 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. as an example.

【0031】

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

【0032】

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

【0033】

When in dental purposes etc., using polymerizable monomer (A), carry out radical polymerization.Thereby, consider R from the viewpoint of Raolical polymerizable ¹, R ²And R ³Preferred hydrogen atom of difference or methyl.In addition, when being used for dental composition, because polymerizable groups such as hydrolysis have the worry 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 ²And R ³Be more preferably methyl.

【0034】

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

【0035】

Polymerizable monomer (A) has following feature, the C18 weighting agent that use median size to be broken for 10 μ m, to have a pore size of 125 dusts is filled the post of the internal diameter 3.9mm * length 300mm that obtains, elutriant be mixed solvent, the flow of methanol=3/7 be 1.0mL/ minute, measure temperature be 50 ℃, sample injection rate be 10 μ L and except post the dead volume from the sample inlet to detection site be under the condition of 87 μ L during with high performance liquid chromatography (HPLC) mensuration, retention time is 7 minutes～30 minutes.

【0036】

The dental material that uses dental composition is with dentine when bonding, and dental material is owing to decalcification and bonding with the Dentinal collagen layer that exposes.Thereby in order to obtain strong bonding strength, dental material is important to the intensity of the impregnability of collagen layer and collagen layer and the integrated layer that obtains of dental material (below, be called resin impregnation layer).Thereby the hydrophilicity of the polymerizable monomer that contains in the dental material is important.The inventor finds, utilizes the retention time of the HPLC mensuration specified conditions under, can stipulate to give the hydrophilicity of polymerizable monomer of cementability of the excellence of dental material and dentine, thereby finish the present invention.

【0037】

As the post that median size is broken for 10 μ m, C18 weighting agent with pore size of 125 dusts is filled the internal diameter 3.9mm * length 300mm obtain, for example, can use the system μ Bondapak of Waters (ゥ オ one タ one ズ) society (マ イ Network ロ ボ Application ダ パ Star Network; Registered trademark) C ₁₈Analyze with post (C18 weighting agent (breaking type), median size 10 μ m, pore size 125 dusts, column dimension 3.9 * 300mm).

【0038】

As the dead volume from the sample inlet to detection site except post is the condition of 87 μ L, the central controller of HPLC can use the system CBM-20A of Shimadzu Seisakusho Ltd., automatic sampler can use the system SIL-20A of Shimadzu Seisakusho Ltd., and detector can use the system SPD-M20A of Shimadzu Seisakusho Ltd..

【0039】

Detection is the ultraviolet ray that can use wavelength 254nm, bandwidth 4nm.

【0040】

When carrying out HPLC mensuration under above-mentioned condition determination, the retention time of polymerizable monomer of the present invention (A) is 7 minutes～30 minutes.Be moistening environment in the oral cavity, temperature changes owing to the temperature difference of ingesta, causes the suction or the hydrolysis of cured article.It is too high that retention time is shorter than 7 minutes the wetting ability of polymerizable monomer, causes suction, the hydrolysis of cured article, and the physical strength of layer of adhesive material has the possibility of reduction.In addition, a little remaining uncured polymerizable monomer has the possibility from the dental material stripping.On the other hand, retention time is longer than that 30 minutes the hydrophilicity of polymerizable monomer is too low, and Dentinal collagen layer can not fully soak into, and is difficult to give high cementability with dentine to composition.As retention time, preferred more than 10 minutes.In addition, preferred below 25 minutes.

【0041】

When selecting to carry out under the above-mentioned condition determination HPLC to survey periodic retention time being 7 minutes～30 minutes polymerizable monomer, can consider that the kind of polymerizable monomer bulk of molecule and hydrophilic radical and quantity selects.When the kind of hydrophilic radical was identical with quantity, the size of molecule was big, and then above-mentioned retention time has elongated tendency.On the other hand, during the kind of hydrophilic radical and molecule measure-alike, the quantity of hydrophilic radical is many, and then above-mentioned retention time has the tendency that shortens.In addition, during the quantity of hydrophilic radical and molecule measure-alike, the wetting ability of hydrophilic radical is strong more, and above-mentioned retention time has the tendency that shortens.In addition, than the side chain of molecular chain, hydrophilic radical is positioned at steric hindrances such as end little positions, and above-mentioned retention time has the tendency that shortens.It as above-mentioned retention time 7 minutes～30 minutes polymerizable monomer, for example can enumerate, the compounds (tetrahydroxybutane dimethacrylate, Xylitol dimethacrylate, Sorbitol Powder dimethacrylate, mannitol dimethacrylate etc.) of following formula (5)～(8) expression etc., their retention time is shown in embodiment.In addition, illustrated in the comparative example described later multiple polymerizable monomer with and retention time.Based on above-mentioned tendency, if the retention time of putting down in writing in these embodiment and the comparative example is a benchmark, can select above-mentioned retention time effectively is 7 minutes～30 minutes polymerizable monomer.

【0042】

[chemical formula 8]

【0043】

[chemical formula 9]

【0044】

[Chemical formula 1 0]

【0045】

[Chemical formula 1 1]

【0046】

Polymerizable monomer (A) preferably has the hydroxyl more than 2.Owing to have 2 above hydroxyls, can give high wetting ability to polymerizable monomer (A), make the impregnability of Dentinal collagen layer good.Thus, can give dental composition good cementability to dentine (particularly dentine).The quantity of hydroxyl is considered from the viewpoint of higher cementability, more preferably more than 3.In addition, too many, then have to be difficult to guarantee suitable hydrophilic situation, therefore preferred below 6.

【0047】

Molecular structure for beyond the polymerizable group that constitutes polymerizable monomer (A) is not particularly limited, preferably hydrophilic radicals such as bonding polymerizable group and hydroxyl on hydrocarbon chain.

【0048】

The compound of the preferred following formula of polymerizable monomer (A) (4) expression.

【0049】

[Chemical formula 1 2]

【0050】

At this, G is hydroxyl or polymerizable group, and n is the integer more than 3, and at least 3 is hydroxyl among the G, and among the G at least 2 be polymerizable group.

【0051】

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

【0052】

Consider that from solidified nature and with the cementability of dentine and the viewpoint that obtains the easiness of raw material the integer of n preferred 3～10 is more preferably 3～8 integer, most preferably is 3 or 4.

【0053】

When paying attention to the cementability with dentine, the compound of the preferred following formula of polymerizable monomer (A) (9) expression.

【0054】

[Chemical formula 1 3]

【0055】

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

【0056】

From solidified nature and with the cementability of dentine, and the viewpoint that obtains the easiness of raw material considers, m is preferred 2～5, 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 3～10, and more preferably 3～8, and then preferred 4～6, most preferably 4.

【0057】

The compound of formula (9) expression has the hydroxyl more than 3, and wherein 2 is primary hydroxyl.This primary hydroxyl is very favourable owing to interacting with dentine (particularly dentine), so when the compound compositions that contains formula (9) expression is applied to dental use, the extra high composition of cementability of formation and dentine (particularly dentine).In addition, as polymerizable group, owing to have 2 bases with following formula (1) expression, so solidified nature is also good.

【0058】

And then, in the compound of formula (9) expression, consider the compound of preferred formula (8) and formula (10) expression from solidified nature and with the viewpoint of the cementability of dentine.

【0059】

[Chemical formula 1 4]

【0060】

[Chemical formula 1 5]

【0061】

On the other hand, when paying attention to solidified nature, the compound of the preferred following formula of polymerizable monomer (A) (11) expression.

【0062】

[Chemical formula 1 6]

【0063】

At this R ¹With above-mentioned synonym, p represents the integer more than 3.

【0064】

The compound of formula (11) expression has the polymerizable group that formula (1) is represented at two ends of the non-conjugated carbochain that the continuous bonding of the carbon more than 4 obtains, and considers that from the spatial essential factor it is high especially that polymerization becomes.Thereby, when the compound compositions that contains formula (11) expression is applied to dental use, form the extra high composition of solidified nature.In addition, good owing to the hydroxyl that has more than 3 to the impregnability of Dentinal collagen layer, also good with the cementability of dentine.

【0065】

When generating resolvent owing to the effect of hydrolysis etc. in the oral cavity, because resolvent is safe compounds such as Xylitol, Sorbitol Powder or mannitol, p preferred 3 or 4.Be the compound of 3 or 4 integer as p, for example can enumerate Xylitol two (methyl) acrylate, Sorbitol Powder two (methyl) acrylate.

【0066】

Polymerizable monomer (A) can obtain by the known method manufacturing.Particularly for example, carboxylic acid with polymerizable group (for example, the carboxylic acid of hydrogen bonding atom on the associative key of the group of formula (1) expression) or derivatives thereof and chain polyol compounds (sugar alcohol compound) such as Xylitol, Sorbitol Powder or mannitol carry out esterification according to conventional methods, by refining the getting final product of separation means of chromatography etc.In order to improve yield, carry out esterification after above-mentioned carboxylic acid with polymerizable group can being transformed to the derivative of carboxylic acid halides etc.

【0067】

Particularly polymerizable monomer (A) is the compound of formula (9) expression; when wherein being the compound of formula (8) or formula (10) expression; the compound that the primary hydroxyl of chain polyol compounds such as use mannitol is protected in advance is 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 (1) expression) or derivatives thereof implemented carries out the operation (a) of esterification and the operation (b) of the protecting group deprotection of the primary hydroxyl of the ester cpds that obtains made.As above-mentioned derivative with carboxylic acid of polymerizable group, be not particularly limited, preferably use 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 manufacture method that comprises this operation can obtain polymerizable monomer with high yield, is preferred on industrial production.

【0068】

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, and 6-two-O-benzylidene-D-mannitol (1,3:4; 6-Di-O-benzylidene-D-mannitol) etc., can obtain as commercially available product.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.

【0069】

Protect the operation of the primary hydroxyl of above-mentioned alkylol cpd to implement by the reaction that imports known protecting group.

【0070】

As the protecting group of the primary hydroxyl of above-mentioned alkylol cpd, can select preferentially to import to the group of primary hydroxyl.In addition, protecting group is difficult to cause deprotection reaction when esterification, during this external this deprotection reaction, can select ester bond to be difficult to disconnect.From the viewpoint, preferably using ether as protecting group is that protecting group, silyl ether are that protecting group and acetal are protecting group.As ether is protecting group, more preferably uses 1-ethoxyethyl group ether and trityl group ether.As silyl ether is that protecting group is more preferably used triisopropyl silyl ether, t-butyldimethylsilyl ether and t-butyldiphenylsilyl ether.These protecting groups all can preferentially import to primary hydroxyl, and, because can be, therefore have and need not disconnect the advantage that ester bond just can deprotection at deprotection under the solutions of weak acidity.On the other hand, as acetal be that protecting group is more preferably used isopropylidene, encircled inferior heptyl, benzylidene and to the methoxyl group benzylidene.When using acetal to be protecting group, 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 is that protecting group, silyl ether are that protecting group and acetal are in the protecting group and then preferably to use acetal be protecting group.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.

【0071】

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 protecting group; 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; add up to more than 3 for hydroxyl and the unreacted hydroxyl that makes protection in addition; selective reaction condition (particularly, the compound that is protected in advance of the primary hydroxyl of above-mentioned alkylol cpd and have the usage quantity of the carboxylic acid or derivatives thereof of polymerizable group) is important.

【0072】

The operation of the protecting group of the primary hydroxyl of the ester cpds that deprotection obtains gets final product according to known method according to the kind of protecting group.At this moment, the reaction conditions (particularly, the kind of temperature condition and catalyzer) of selecting to be difficult to disconnect ester bond is important.As above-mentioned, the ether that preferably uses as the protecting group of primary hydroxyl is that protecting group, silyl ether are protecting group and acetal when being protecting group, all can not disconnect ester bond and just can carry out deprotection at deprotection under the solutions of weak acidity.In addition, by using TBAF fluorochemicalss such as (tetrabutyl ammonium fluorides), silyl ether is that protecting group 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.

【0073】

Polymerizable monomer (A) has a plurality of polymerizable groups and possess hydrophilic property, so the crosslinking reaction excellence, 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 composition, in the various uses headed by the dental use, become the composition of excellent solidified nature of performance and cementability.Aggregate into monomer (A) and may be used singly or in combination of two or more kinds, consider, the compound that can also represent with above-mentioned formula (9) and above-mentioned formula (11) from the viewpoint of taking into account with cementability dentine and solidified nature balance composition.

【0074】

Then describe for composition of the present invention.Composition of the present invention is the composition that contains polymerizable monomer (A).For polymerizable monomer (A) composition in addition, suitably select to get final product according to the purposes of composition, composition in the composition that contains known bridging property polymerizable monomer, can be the formation that this known polymerizable monomer is replaced into polymerizable monomer (A) for example.

【0075】

The composition except polymerizable monomer (A) that contains as composition of the present invention, for example can enumerate, have the polymerizable monomer (B) of 1 polymerizable group and the hydroxyl more than 1, polymerizable monomer (C), bridging property polymerizable monomer composition such as (D) polymerizable monomer and solvent (E), polymerization starter (F), polymerization promotor (G), filler (H) etc. with acidic-group.

【0076】

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

【0077】

As the use level of polymerizable monomer (A), according to the purposes of composition suitably decision get final product, common, in total amount 100 mass parts of polymerizable monomer composition, preferably contain polymerizable monomer (A) 1～99 mass parts.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 composition 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 mass parts, and then more than preferred 5 mass parts during less than 1 mass parts.On the other hand, when the use level of polymerizable monomer (A) surpasses 99 mass parts, the possibility that decalcification is insufficient, can not obtain sufficient adhesion strength is arranged, more preferably below 98 mass parts, and then below preferred 95 mass parts.

【0078】

In the following description, use the term of " simple function ", " difunctionality " and " trifunctional ", " simple function ", " difunctionality " and " trifunctional " represent to have in 1 molecule 1,2 and 3 polymerizable groups respectively.This polymerizable group preferably can carry out free-radical polymerized group with the polymerizable group of polymerizable monomer (A).

【0079】

Polymerizable monomer (B) with 1 polymerizable group and the hydroxyl more than 1

The composition that contains polymerizable monomer of the present invention (A) preferably contains polymerizable monomer (B) and forms, and described polymerizable monomer (B) has 1 polymerizable group and the hydroxyl more than 1.When above-mentioned composition contained polymerizable monomer (B), when particularly using as dental composition, bonding strength was good.Polymerizable monomer (B) can carry out radical polymerization owing to have polymerizable group, can carry out copolymerization with other monomers simultaneously.Polymerizable monomer (B) as having 1 polymerizable group and the hydroxyl more than 1 is not particularly limited, and the polymerizable group of polymerizable monomer (B) preferably can carry out free-radical polymerized group with the polymerizable group of polymerizable monomer (A).Be easy to viewpoint from radical polymerization and consider, preferred (methyl) acryl of polymerizable group, or (methyl) acrylamido.Polymerizable monomer (B) preferably uses as the composition of dental composition, because the moistening environment of acid in the oral cavity can break away from by polymerizable groups such as hydrolysis.The polymerizable group that consider to break away from when giving birth to the pungency of body, this polymerizable group preferable methyl acryl or methacryloyl amido.

【0080】

In addition, polymerizable monomer (B) has the hydroxyl more than 1, therefore wetting ability is good, and owing to be simple function polymer monomer with 1 polymerizable group, when the composition that contains polymerizable monomer (A) and polymerizable monomer (B) uses as dental composition, also have the more excellent effect of the impregnability of Dentinal collagen layer.

【0081】

Polymerizable monomer (B) can use separately or appropriate combination is used more than 2 kinds.As polymerizable monomer (B), for example can enumerate, 2-hydroxyethyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, 4-hydroxybutyl (methyl) acrylate, 6-hydroxyl hexyl (methyl) acrylate, 10-hydroxyl decyl (methyl) acrylate, propylene glycol list (methyl) acrylate, glycerine list (methyl) acrylate, tetrahydroxybutane list (methyl) acrylate, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide, N, N-(dihydroxy ethyl) (methyl) acrylamide etc., among them, consider from the viewpoint that the impregnability of Dentinal collagen layer is improved, preferred 2-hydroxyethyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, glycerine list (methyl) acrylate, tetrahydroxybutane list (methyl) acrylate, preferred especially 2-hydroxyethyl methacrylic ester.

【0082】

The use level of above-mentioned polymerizable monomer (B) is not particularly limited, and in total amount 100 mass parts of polymerizable monomer composition, preferably contains polymerizable monomer (B) 1～90 mass parts and forms.The use level of using polymerizable monomer (B) is at the composition of this scope during as dental composition, and is good to soaking into of Dentinal collagen layer, bonding strength is good simultaneously, and is therefore preferred.The use level of polymerizable monomer (B) is during less than 1 mass parts, have can not obtain the contribution that Dentinal collagen layer is soaked into that brings by polymerizable monomer (B) may, the possibility that has bonding strength to reduce simultaneously.The use level of polymerizable monomer (B) is more preferably more than 3 mass parts, and then more than preferred 5 mass parts, more than preferred especially 7 mass parts.On the other hand, when the use level of polymerizable monomer (B) surpasses 90 mass parts, the possibility of the physical strength reduction that can not obtain sufficient solidified nature, cured article is arranged.Therefore, the possibility that has bonding strength to reduce.The use level of polymerizable monomer (B) is more preferably below 80 mass parts, and then below preferred 75 mass parts, below preferred especially 70 mass parts.

【0083】

Polymerizable monomer (C) with acidic-group

Composition of the present invention preferably contains the polymerizable monomer (C) with acidic-group and forms.When use contains the composition of the polymerizable monomer (C) with acidic-group, 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 by combination, can obtain being fit to the composition of self etching bed material, one-pack type adhesives etc.

【0084】

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); be not particularly limited, can enumerate intramolecularly have 1 carboxyl or its anhydride group the simple function polymerizable monomer, have the simple function polymerizable monomer of a plurality of carboxyls or its anhydride group at intramolecularly, have the simple function 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.

【0085】

Example as the simple function polymerizable monomer that has 1 carboxyl or its anhydride group at intramolecularly; can enumerate (methyl) vinylformic acid; N-(methyl) acryl glycine; 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, the 6-tricarboxylic ester; O-(methyl) acryl tyrosine; N-(methyl) acryl tyrosine; N-(methyl) acryl phenylalanine; 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 the compound that the carboxylic acid baseization of these compounds is obtained.

【0086】

Example as the simple function polymerizable monomer that has a plurality of carboxyls or its anhydride group at intramolecularly; can enumerate 11-(methyl) acryl oxygen base undecane-1; the 1-dicarboxylic acid; 10-(methyl) acryl oxygen base decane-1; the 1-dicarboxylic acid; 12-(methyl) acryl oxygen base dodecane-1; the 1-dicarboxylic acid; 6-(methyl) acryl oxygen base hexane-1; the 1-dicarboxylic acid; 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; the 6-tricarboxylic acid anhydride; 6-(methyl) acryl oxygen base ethyl naphthalene-2; 3; the 6-tricarboxylic acid anhydride; 4-(methyl) acryl oxygen base ethyl carbonyl propionyl-1; the 8-naphthalic anhydride; 4-(methyl) acryl oxygen base ethyl naphthalene-1; the 8-tricarboxylic acid anhydride; 9-(methyl) acryl oxygen base nonane-1; the 1-dicarboxylic acid; 13-(methyl) acryl oxygen base tridecane-1; the 1-dicarboxylic acid; 11-(methyl) acrylamide undecane-1,1-dicarboxylic acid etc.

【0087】

As the example of the simple function 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) acrylamide ethyl dihydrogen phosphoric acid ester etc.

【0088】

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

【0089】

Use level with polymerizable monomer (C) of acidic-group is not particularly limited, and usually, in total amount 100 mass parts of polymerizable monomer composition, preferably contains polymerizable monomer (C) 1～90 mass parts with acidic-group and forms.The use level of polymerizable monomer (C) with acidic-group has the possibility that can not obtain the acid etching effect, more preferably more than 2 mass parts, and then more than preferred 5 mass parts during less than 1 mass parts.On the other hand, when the use level with polymerizable monomer (C) of acidic-group surpasses 90 mass parts, the possibility that can not obtain sufficient solidified nature, cause adhesiveproperties to reduce is arranged, more preferably below 80 mass parts, and then below preferred 70 mass parts.

【0090】

Bridging property polymerizable monomer (D)

Composition of the present invention preferably contains bridging property polymerizable monomer (D) and forms.When the composition that will contain bridging property polymerizable monomer (D) uses as dental composition, has the advantage of bonding strength and then raising etc.

【0091】

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

【0092】

Example as the difunctionality polymerizable monomer of aromatics system; can enumerate 2; two ((methyl) acryl oxygen base phenyl) propane of 2-; 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 of 2-; 2; two (4-(methyl) the acryl oxygen Quito ethoxyl phenenyl) propane of 2-; 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 of 2-; 2; two (4-(methyl) the acryl oxygen base five ethoxyl phenenyls) propane of 2-; 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 of 2-; 2; two (4-(methyl) the acryl oxygen base isopropyl phenyl) propane of 2-; 1, two (2-(methyl) acryl oxygen base ethyl) pyromellitic esters of 4-etc.

【0093】

Example as the difunctionality polymerizable monomer of fatty compounds system; can enumerate ethylene glycol bisthioglycolate (methyl) acrylate; glycol ether two (methyl) acrylate; triglycol two (methyl) acrylate; propylene glycol two (methyl) acrylate; butyleneglycol two (methyl) acrylate; neopentyl glycol two (methyl) acrylate; polyoxyethylene glycol two (methyl) acrylate; 1; 3-butyleneglycol two (methyl) acrylate; 1; 5-pentanediol two (methyl) acrylate; 1; 6-hexylene glycol two (methyl) acrylate; 1; 10-decanediol two (methyl) acrylate; 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.

【0094】

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

【0095】

The use level of bridging property polymerizable monomer (D) is not particularly limited, and usually, in total amount 100 mass parts of polymerizable monomer composition, bridging property polymerizable monomer (D) preferably contains 1～90 mass parts.The use level of bridging property polymerizable monomer (D) has the possibility that can not obtain sufficient adhesion strength, more preferably more than 2 mass parts, and then more than preferred 5 mass parts during less than 1 mass parts.On the other hand, when the use level of bridging property polymerizable monomer (D) surpassed 90 mass parts, composition was insufficient to soaking into of Dentinal collagen layer, and the possibility that can not obtain high bonding strength is arranged, more preferably below 80 mass parts, and then below preferred 70 mass parts.

【0096】

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

【0097】

Solvent (E)

Composition of the present invention preferably contains solvent (E) according to its concrete embodiment.As solvent, can enumerate water (I), organic solvent (J) and their mixed solvent etc.

【0098】

As organic solvent (J), can enumerate methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-methyl-2-propyl alcohol, acetone, methyl ethyl ketone, tetrahydrofuran (THF), ether, Di Iso Propyl Ether, hexane, toluene, chloroform, acetate ethyl ester, acetate butyl ester etc.Among them, consider to the security of giving birth to body and based on volatile remove easiness the two the time, organic solvent (J) preferably water solubleness organic solvent, concrete preferred ethanol, 2-propyl alcohol, 2-methyl-2-propyl alcohol, acetone and the tetrahydrofuran (THF) of using.

【0099】

When composition of the present invention contains water (I), when showing excellent bonding strength, show excellent adhesion durability.Water (I) does not preferably contain and brings dysgenic impurity, preferred distilled water or ion exchanged water.

【0100】

According to the difference of embodiment, the situation that does not need to cooperate above-mentioned solvent (E) is arranged also.State in the use in the embodiment of solvent, with respect to total amount 100 mass parts of polymerizable monomer composition, composition preferably contains solvent (E) 1～4000 mass parts and forms.When solvent was the mixed solvent of water (I) or water (I) and organic solvent (J), the use level of water (I) was with respect to total amount 100 mass parts of polymerizable monomer composition, preferred 6～2000 mass parts.The content of water (I) is during less than 6 mass parts, and what have that monomer is insufficient to the impregnability of collagen layer, bonding strength reduces may.On the other hand, when the content of water (I) surpasses 2000 mass parts, there are monomer polymerization reduction, bonding strength to reduce the possibility of adhesion durability reduction simultaneously.The content of water (I) is more preferably more than 7 mass parts, and then more than preferred 10 mass parts.In addition, the content of water (I) is more preferably below 1500 mass parts.The preferred use level of above-mentioned solvent (E) has a great difference according to the difference of the embodiment that uses, and illustrates in the lump with the embodiment of composition of the present invention described later, will show preferably use level of the corresponding above-mentioned organic solvent of each embodiment (E).

【0101】

Polymerization starter (F)

The polymerization starter that uses among the present invention (F) 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 alone or appropriate combination more than 2 kinds is used.

【0102】

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.

【0103】

Among (two) acylphosphine oxide class as above-mentioned Photoepolymerizationinitiater initiater use; as the acylphosphine oxide class; can enumerate 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, 2; 6-dimethoxy benzoyl diphenyl phosphine oxide, 2; 6-dichloro-benzoyl base diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl 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.

【0104】

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

【0105】

Concrete example as 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 of 3-thiazolidine-2-yl); (2; 2-dicyano-1-methylacetylenyl) phosphonic acid ester sodium salt; ethanoyl methyl-phosphorous acid lactazone sodium salt; ethanoyl methylphosphonate-O-benzyl oxime sodium salt; the 1-[(N-ethoxy imino) ethyl] the 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] the methyl-phosphorous acid ester sodium salt; ethanoyl methylphosphonate semicarbazone sodium salt; (1-cyano group-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 ゥ system) (1; the 1-dimethoxy-ethyl)-methylphosphonate; 1-butyl-4-butyl amino methyl amino-3; 5-dipropyl-1; 2; 4-triazole (1; the 1-dimethoxy-ethyl)-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.

【0106】

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.

【0107】

As the thioxanthene ketone of above-mentioned Photoepolymerizationinitiater initiater use or the quaternary ammonium salt of thioxanthene ketone, for example can use thioxanthone, 2-chlorine thioxanthene-9-one, 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)-and 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.

【0108】

In the quaternary ammonium salt of these thioxanthene ketones or thioxanthene ketone, particularly preferred thioxanthene ketone is a 2-chlorine thioxanthene-9-one, and the quaternary ammonium salt of particularly preferred thioxanthene ketone is 2-hydroxyl-3-(3,4-dimethyl-9H-thioxanthene-2-base oxygen base)-N, N, N-trimethylammonium-1-propane ammonium chloride.

【0109】

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.

【0110】

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.

【0111】

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; the 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-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 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 compound of putting down in writing in the Te Kaiping 10-245525 communique.

【0112】

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).

【0113】

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.

【0114】

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.

【0115】

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.

【0116】

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, in the light solidified excellence of visible light and near ultraviolet region,, also obtain showing the composition of sufficient light solidified even use arbitrary light source of halogen lamp, photodiode (LED), xenon lamp.

【0117】

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 particularly 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.

【0118】

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.

【0119】

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.

【0120】

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, 2,4 dichlorobenzoyl peroxide and lauroyl peroxide etc.

【0121】

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

【0122】

Peroxy ketal as above-mentioned chemical polymerisation initiator use, 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.

【0123】

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.

【0124】

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.

【0125】

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

【0126】

The use level of the polymerization starter that uses among the present invention (F) is not particularly limited, and considers that from the viewpoints such as solidified nature of the composition that obtains with respect to total amount 100 mass parts of polymerizable monomer composition, polymerization starter (F) preferably contains 0.001～30 mass parts.The use level of polymerization starter (F) is during less than 0.001 mass parts, and polymerization is insufficient to be carried out, and the possibility of the reduction that causes bonding force is arranged, more preferably more than 0.05 mass parts, and then more than preferred 0.1 mass parts.On the other hand, when the use level of polymerization starter (F) surpasses 30 mass parts, when the polymerization of polymerization starter self hangs down, the possibility that can not obtain sufficient adhesion strength is arranged, and then have cause from composition separate out may, therefore more preferably below 20 mass parts, and then below preferred 15 mass parts, most preferably below 10 mass parts.

【0127】

Polymerization promotor (G)

Composition of the present invention preferably contains polymerization promotor (G).As the polymerization promotor that uses among the present invention (G), can enumerate amine,-sulfinic acid and salt thereof, boron compound, barbituric acid derivatives, triaizine compounds, copper compound, tin compound, vanadium compound, halogen compounds, aldehydes, mercaptan compound, sulphite, hydrosulphite, thiourea compound etc.

【0128】

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 diethanolamine, N-lauryl diethanolamine, 2-(dimethylamino) ethyl-methyl acrylate, N methyldiethanol amine dimethacrylate, N-ethyldiethanolamine dimethacrylate, trolamine monomethacrylates, trolamine dimethacrylate, trolamine trimethacrylate, trolamine, Trimethylamine, triethylamine, tributylamine etc. etc.Among them, consider that from the solidified nature of composition and the viewpoint of storage stability the preferred aliphat tertiary amine wherein more preferably uses N methyldiethanol amine and trolamine.

【0129】

In addition; as aromatic amine; for example; can enumerate N; two (the 2-hydroxyethyls)-3 of N-; the 5-xylidine; N; N-two (2-hydroxyethyl)-para-totuidine; N; two (the 2-hydroxyethyls)-3 of N-; the 4-xylidine; N; two (2-the hydroxyethyl)-4-ethylaniline 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-; the 5-di-tert-butyl aniline; N, accelerine; N, N-dimethyl-para-totuidine; N; N-dimethyl-meta-aminotoluene; N; N-diethyl-para-totuidine; N, N-dimethyl-3,5-xylidine; N; N-dimethyl-3; the 4-xylidine; N, N-dimethyl-4-ethylaniline; N, N-dimethyl-4-isopropyl aniline; N; N-dimethyl-4-tertiary butyl aniline; N; N-dimethyl-3, the 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 benzophenone; 4-dimethylaminobenzoic acid butyl ester etc.Among them, consider from the viewpoint of the solidified nature that can give the composition excellence, 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 benzophenone.

【0130】

-sulfinic acid and salt thereof as polymerization promotor (G) use, for example, can enumerate 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, the 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.

【0131】

As the boron compound that polymerization promotor (G) uses, preferred aryl groups boron compound.The object lesson of the preferred aryl boron compound that uses, as the boron compound 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] 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, (alkyl is selected from normal-butyl to boron for trialkyl (to octyl group oxygen base phenyl) boron and trialkyl (an octyl group oxygen base phenyl), n-octyl and dodecyl etc. at least a kind) sodium salt, lithium salts, sylvite, magnesium salts, 4-butyl ammonium, tetramethyl ammonium, the tetraethyl-ammonium salt, picoline salt, ethylpyridine salt, butyl-pyridinium salt, toluquinoline salt, the ethyl quinolinium, butyl quinolinium etc.

【0132】

In addition, as the boron compound 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] 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, (alkyl is selected from normal-butyl to boron for dialkyl group two (to octyl group oxygen base phenyl) boron and dialkyl group two (an octyl group oxygen base phenyl), n-octyl and dodecyl etc. at least a kind) sodium salt, lithium salts, sylvite, magnesium salts, 4-butyl ammonium, tetramethyl ammonium, the tetraethyl-ammonium salt, picoline salt, ethylpyridine salt, butyl-pyridinium salt, toluquinoline salt, the ethyl quinolinium, butyl quinolinium etc.

【0133】

And then, as the boron compound that has 3 aryl in 1 molecule, can enumerate the 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] 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, (alkyl is selected from normal-butyl to boron for monoalkyl three (to octyl group oxygen base phenyl) boron and monoalkyl three (an octyl group oxygen base phenyl), n-octyl or dodecyl etc. a kind) sodium salt, lithium salts, sylvite, magnesium salts, 4-butyl ammonium, tetramethyl ammonium, the tetraethyl-ammonium salt, picoline salt, ethylpyridine salt, butyl-pyridinium salt, toluquinoline salt, the ethyl quinolinium, butyl quinolinium etc.

【0134】

And then as the boron compound 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] 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, the sodium salt of (an octyl group oxygen base phenyl) triphenyl-boron and (to octyl group oxygen base phenyl) triphenyl-boron, lithium salts, sylvite, magnesium salts, 4-butyl ammonium, tetramethyl ammonium, the tetraethyl-ammonium salt, picoline salt, ethylpyridine salt, butyl-pyridinium salt, toluquinoline salt, the ethyl quinolinium, butyl quinolinium etc.

【0135】

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

【0136】

Barbituric acid derivatives as polymerization promotor (G) use, can enumerate barbituric acid, 1, the 3-dimethyl barbituric acid, 1,3-phenylbenzene barbituric acid, 1, the 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, the 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, the 5-methylbarbituric acid, 5-propyl group barbituric acid, 1, the 5-diethyl barbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutyl-barbituric acid, 1,3-diethyl-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 alkaline-earth metal class), salt as these veronal acids, 5-soneryl acid sodium is for example arranged, 1,3,5-trimethylammonium barbituric acid sodium and 1-cyclohexyl-5-ethyl barbituric acid sodium etc.

【0137】

As particularly preferred 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.

【0138】

Triaizine compounds as polymerization promotor (G) use, for example have 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-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(3,4, 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, 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, N-diallyl amino } oxyethyl group]-4, two (the trichloromethyl)-s-triazines of 6-etc.

【0139】

Among the above-mentioned illustrative triaizine compounds, consider from the polymerization activity aspect, preferred especially 2,4,6-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.

【0140】

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

【0141】

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, two-n-octyl tin, two lauric acid di-n-butyl tin etc.Particularly preferred tin compound is two lauric acid, two-n-octyl tin and two lauric acid di-n-butyl tin.

【0142】

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; for example, the spy that 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.

【0143】

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.

【0144】

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.

【0145】

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.

【0146】

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

【0147】

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

【0148】

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.

【0149】

The use level of the polymerization promotor that uses among the present invention (G) is not particularly limited, consider from the viewpoint of the solidified nature of the composition that obtains etc., with respect to total amount 100 mass parts of polymerizable monomer composition, preferably contain polymerization promotor (G) 0.001～30 mass parts and form.The use level of polymerization promotor (G) is during less than 0.001 mass parts, have cause polymerization insufficiently to be carried out, possibility that bonding force reduces, more preferably more than 0.05 mass parts, and then more than preferred 0.1 mass parts.On the other hand, when the use level of polymerization promotor (G) surpasses 30 mass parts, when the polymerization of polymerization starter self hangs down, the possibility that can not obtain sufficient adhesion strength is arranged, and then have cause from composition separate out may, therefore more preferably below 20 mass parts, and then below preferred 10 mass parts.

【0150】

Filler (H)

In the composition 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, methyl methacrylate-ethyl methacrylate copolymers, cross-linking type polymethylmethacrylate, cross-linking type polyethyl methacrylate, polymeric amide, polyvinyl chloride, polystyrene, 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 particularly limited, and can suitably select the particle diameter of filler and uses.The viewpoint of the operability of the composition 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.

【0151】

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 particularly 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 composition that obtains and physical strength etc.

【0152】

As the shape of mineral filler, can enumerate amorphous filler and ball filler.Consider from the viewpoint of the physical strength that improves composition, preferably use ball filler as above-mentioned mineral filler.And then, when using above-mentioned ball filler, when composition of the present invention is used as the dental compound resin, the advantage of the compound resin that obtains the surface lubrication excellence is arranged.At this, ball filler is meant, takes the photo of filler with scanning electron microscope (below, abbreviate SEM as), the particle of observing in this unit visual field is for circular, and removing average uniformity coefficient that the particle diameter with the vertical direction of this maximum diameter obtains with maximum diameter is filler more than 0.6.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 composition 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.

【0153】

In order to adjust the flowability of composition, 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.

【0154】

The organic and inorganic compounded mix that uses among the present invention is to add monomeric compound in above-mentioned mineral filler in advance, carries out polymerization after making the thickener shape, obtains by 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 particularly 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 composition that obtains and physical strength etc.

【0155】

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

【0156】

In addition, in the composition 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.

【0157】

Composition of the present invention preferably uses as dental composition.This dental composition can be used for bed material, adhesives, cement (resin-bonded agent, glass ionomer (グ ラ ス ア イ オ ノ マ one) cement, resin enhancement type glass ionomer cement), compound resin, little recessed crackle filling material, the dental plate dental material with resin etc., wherein, preferably use as bed material, adhesives, cement or compound resin.At this moment, can be used as composition with composition is divided into two parts two and becomes somatotypes and use.

【0158】

About dental material, 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, having the monomer component that dentin surface is impregnated into the penetrant action of Dentinal collagen layer with acidic component dissolved decalcification, monomer component and 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.

【0159】

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) soaks into Dentinal collagen layer easily owing to wetting ability height (particularly, when having the hydroxyl more than 3).Therefore, the composition 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.

【0160】

Use the bed material of composition of the present invention preferably to contain polymerizable monomer (A), have the polymerizable monomer (C) of acidic-group and the composition of solvent (E).In addition, the also preferred embodiment that contains polymerization promotor (G) that uses.Above-mentioned (A) and use level (C) are in total amount 100 mass parts of polymerizable monomer composition, preferably contain (A) 10～99 mass parts and (C) 1～90 mass parts, more preferably contain (A) 10～95 mass parts and (C) 5～90 mass parts, and then preferably contain (A) 20～90 mass parts and (C) 10～80 mass parts.

【0161】

In addition, when paying attention to primer composition, and then preferably contain polymerizable monomer (B) with 1 polymerizable group and the hydroxyl more than 1 to the impregnability of dentine (particularly dentine).Primer composition contains (A), (B) and (C) time, use level as each composition, in total amount 100 mass parts of polymerizable monomer composition, preferably contain (A) 1～95 mass parts, (B) 1～90 mass parts and (C) 1～90 mass parts, more preferably contain (A) 10～85 mass parts, (B) 5～80 mass parts and (C) 10～85 mass parts, and then preferably contain (A) 15～75 heavy mass parts, (B) 10～70 mass parts and (C) 5～70 mass parts.

【0162】

When particularly improving the cured article intensity of the bed material that uses composition of the present invention, and then can cooperate bridging property polymerizable monomer (D).As above-mentioned (D); consideration is during to the impregnability of dentine (particularly dentine); the difunctionality polymerizable monomer of preferred aliphat series of compounds; more preferably ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, triglycol two (methyl) acrylate and 1; two (the 3-methacryloyl oxygen base-2-hydroxyl propoxy-) ethane of 2-; and then preferred triglycol two (methyl) acrylate and 1, two (the 3-methacryloyl oxygen base-2-hydroxyl propoxy-) ethane of 2-.The use level of above-mentioned (D) is preferred 0～30 mass parts in total amount 100 mass parts of polymerizable monomer composition, more preferably 1～25 mass parts, and then preferred 3～20 mass parts.

【0163】

In addition,, preferably contain above-mentioned polymerization starter (F) 0.001～30 mass parts, more preferably contain 0.05～20 mass parts, and then preferably contain 0.1～10 mass parts with respect to total amount 100 mass parts of polymerizable monomer composition.Use in the bed material of composition of the present invention, and also be preferred embodiment with above-mentioned polymerization starter (F) and above-mentioned polymerization promotor (G), as polymerization promotor (G), preferred amine.At this moment, total amount 100 mass parts with respect to the polymerizable monomer composition, preferably contain (F) 0.001～20 mass parts and (G) 0.001～30 mass parts, more preferably contain (F) 0.05～15 mass parts and (G) 0.05～20 mass parts, and then preferably contain (F) 0.1～10 mass parts and (G) 0.1～10 mass parts.

【0164】

Use in the bed material of composition of the present invention, for Dentinal collagen layer is soaked into, polymerizable monomer (A) has suitable wetting ability.In addition, solvent (E) preferably makes the form of the mixed solvent of water (I) and organic solvent (J).The content of water in the above-mentioned mixed solvent (I) is not particularly limited, more than the preferred 10 quality %, more preferably more than the 20 quality %, and then more than the preferred 30 quality %.In addition, according to the difference of embodiment, the situation that needn't cooperate above-mentioned organic solvent (J) is arranged also.The use level of above-mentioned solvent (E) is with respect to total amount 100 mass parts of polymerizable monomer composition, preferred 1～2000 mass parts, preferred 5～1000 mass parts, and then preferred 10～500 mass parts.In addition, when above-mentioned solvent (E) uses with the form of the mixed solvent of water (I) and organic solvent (J), above-mentioned (I) and use level (J) are with respect to total amount 100 mass parts of polymerizable monomer composition, preferably (I) 6～2000 mass parts and (J) 0～2000 mass parts, more preferably (I) 8～1000 mass parts and (J) 2～1000 mass parts, and then preferably (I) 10～500 mass parts and (J) 5～500 mass parts.

【0165】

Composition of the present invention preferably uses as adhesives.As the adhesives in above-mentioned " bonding system of 2 steps ", the composition that preferably contains above-mentioned polymerizable monomer (A), polymerization starter (F) and filler (H), such composition and then more preferably contain polymerizable monomer (B) and/or bridging property polymerizable monomer (D) with 1 polymerizable group and the hydroxyl more than 1.In addition, the also preferred embodiment that contains polymerization promotor (G) that uses.Use level as each composition, in total amount 100 mass parts of polymerizable monomer composition, preferably contain (A) 1～80 mass parts, (B) 0～80 mass parts and (D) 0～80 mass parts, more preferably contain (A) 3～80 mass parts, (B) 3～80 mass parts and (D) 3～80 mass parts.As above-mentioned (A) that use among the present invention, have the compound of 2 above polymerizable groups by 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, particularly consider, and then preferably contain the difunctionality polymerizable monomer of aromatics system from the viewpoint that obtains high-intensity cured article.As above-mentioned (D), the embodiment of difunctionality polymerizable monomer preferred and that with the difunctionality polymerizable monomer and the aromatics of fatty family be.

【0166】

In addition, total amount 100 mass parts with respect to the polymerizable monomer composition preferably contain (F) 0.001～20 mass parts, more preferably contain 0.05～15 mass parts, and then preferably contain 0.1～10 mass parts.Also preferred and with the embodiment of above-mentioned polymerization starter (F) and above-mentioned polymerization promotor (G), as polymerization promotor (G), preferred amine.At this moment, total amount 100 mass parts with respect to the polymerizable monomer composition, preferably contain (F) 0.001～20 mass parts and (G) 0.001～30 mass parts, more preferably contain (F) 0.05～15 mass parts and (G) 0.05～20 mass parts, and then preferably contain (F) 0.1～10 mass parts and (G) 0.1～10 mass parts.In addition, as the use level of filler (H), total amount 100 mass parts with respect to the polymerizable monomer composition preferably contain (H) 1～30 mass parts, more preferably contain 2～20 mass parts, and then preferably contain 3～15 mass parts.

【0167】

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 and the two-pack that is divided into A liquid and B liquid mixed before use and use 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 composition of the present invention is gone on foot the adhesives use of bonding system as above-mentioned one-pack type 1, above-mentioned composition preferably contains polymerizable monomer (A), has the composition of the polymerizable monomer (C) of acidic-group, polymerization starter (F), filler (H) and solvent (E), such composition and then more preferably contain bridging property polymerizable monomer (D).Use level as each composition, in total amount 100 mass parts of polymerizable monomer composition, preferably contain (A) 1～80 mass parts, (C) 1～80 mass parts and (D) 0～80 mass parts, more preferably contain (A) 3～70 mass parts, (C) 2～60 mass parts and (D) 3～70 mass parts, and then preferably contain (A) 5～70 mass parts, (C) 3～40 mass parts and (D) 5～70 mass parts.In the bonding system of 1 step of one-pack type, " soaking into " and " curing " carries out simultaneously, as above-mentioned (A), when Dentinal collagen layer is soaked into, has suitable wetting ability, and uses the meaning of the polymerizable monomer that contains 2 above polymerizable groups big.

【0168】

In the bonding system of 1 step of above-mentioned one-pack type, when paying attention to the impregnability to dentine (particularly dentine), and then preferably contain polymerizable monomer (B) with 1 polymerizable group and the hydroxyl more than 1.Bonding system of 1 step of above-mentioned one-pack type contains (A), (B), (C) and (D) time, use level as each composition, in total amount 100 mass parts of polymerizable monomer composition, preferably contain (A) 1～80 mass parts, (B) 1～90 mass parts, (C) 1～90 mass parts and (D) 5～90 mass parts, more preferably contain (A) 5～70 mass parts, (B) 5～75 mass parts, (C) 3～75 mass parts and (D) 10～80 mass parts, and then preferably contain (A) 10～60 mass parts, (B) 10～60 mass parts, (C) 5～60 mass parts and (D) 15～75 mass parts.

【0169】

In addition, total amount 100 mass parts with respect to the polymerizable monomer composition preferably contain (F) 0.001～20 mass parts, more preferably contain 0.05～15 mass parts, and then preferably contain 0.1～10 mass parts.Also preferred and with the embodiment of above-mentioned polymerization starter (F) and above-mentioned polymerization promotor (G), as polymerization promotor (G), preferred amine.At this moment, total amount 100 mass parts with respect to the polymerizable monomer composition, preferably contain (F) 0.001～20 mass parts and (G) 0.001～30 mass parts, more preferably contain (F) 0.05～15 mass parts and (G) 0.05～20 mass parts, and then preferably contain (F) 0.1～10 mass parts and (G) 0.1～10 mass parts.In addition, as the use level of filler (H), total amount 100 mass parts with respect to the polymerizable monomer composition preferably contain (H) 1～30 mass parts, more preferably contain 2～20 mass parts, and then preferably contain 3～20 mass parts.

【0170】

In addition, the use level of solvent (E) is with respect to preferred 1～1000 mass parts of total amount 100 mass parts of polymerizable monomer composition, preferred 5～1000 mass parts, and then preferred 7～500 mass parts.Bonding system of one-pack type 1 step needs decalcification, soaks into, the whole technologies of solidified were carried out with 1 step of single component.Therefore, consider,, preferably contain water (I) as above-mentioned solvent (E) from the viewpoint of paying attention to impregnability.On the other hand, consider that from the viewpoint of paying attention to solidified nature above-mentioned bonding system preference contains the bridging property polymerizable monomer (D) of appropriate amount, the solvability of above-mentioned from improving (D), the viewpoint that obtains uniform solution are considered, as above-mentioned solvent (E), preferably contain organic solvent (J).And, the embodiment that above-mentioned solvent (E) more preferably uses with the form of the mixed solvent of water (I) and organic solvent (J).In this embodiment, above-mentioned (I) and use level (J) are with respect to total amount 100 mass parts of polymerizable monomer composition, preferably (I) 1～1000 mass parts and (J) 2～1000 mass parts, more preferably (I) 2～1000 mass parts and (J) 4～1000 mass parts, and then preferably (I) 5～500 mass parts and (J) 6～500 mass parts.

【0171】

Composition of the present invention preferably uses as compound resin.When composition of the present invention was used as compound resin, above-mentioned composition preferably contained the composition of polymerizable monomer (A), bridging property polymerizable monomer (D), polymerization starter (F) and filler (H).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 by photopolymerization usually.Therefore, as above-mentioned (F), preferably use Photoepolymerizationinitiater initiater.In addition, as described above, fill the solidified compound resin and in the oral cavity, be subjected to biting pressure, therefore require excellent physical strength.Therefore, above-mentioned composition preferably contains filler (H) 50～2000 mass parts with respect to total amount 100 mass parts of polymerizable monomer composition, more preferably contains 100～1500 mass parts.The content of filler (H) is during less than 50 mass parts, the physical strength of cured article have inadequate may.On the other hand, when the content of filler (H) surpassed 1500 mass parts, filler in the total amount of polymerizable monomer composition (H) was difficult to homogeneous and disperses, and the possibility that becomes the inadequate composition of physical strength and operability aspect is arranged.

【0172】

Use level as each composition, in total amount 100 mass parts of polymerizable monomer composition, preferably contain (A) 10～80 mass parts and (D) 20～90 mass parts, more preferably contain (A) 10～70 mass parts and (D) 30～90 mass parts, and then preferably contain (A) 10～60 mass parts and (D) 40～90 mass parts.In addition, total amount 100 mass parts with respect to the polymerizable monomer composition preferably contain (F) 0.001～20 mass parts, more preferably contain 0.05～10 mass parts, and then preferably contain 0.05～5 mass parts.Also preferred and with the embodiment of above-mentioned polymerization starter (F) and above-mentioned polymerization promotor (G), as polymerization promotor (G), preferred amine.At this moment, total amount 100 mass parts with respect to the polymerizable monomer composition, preferably contain (F) 0.001～20 mass parts and (G) 0.001～30 mass parts, more preferably contain (F) 0.05～10 mass parts and (G) 0.05～20 mass parts, and then preferably contain (F) 0.05～5 mass parts and (G) 0.1～10 mass parts.

【0173】

In addition, polymerizable monomer of the present invention (A) is with the solidified nature of excellence with to the impregnability of dentine, so particularly preferred as using from the cementability compound resin in the compound resin.As when the cementability compound resin uses, above-mentioned composition preferably contains polymerizable monomer (A), has the polymerizable monomer (C) of acidic-group, bridging property polymerizable monomer (D), polymerization starter (F) and filler (H) with composition of the present invention.Use level as each composition, in total amount 100 mass parts of polymerizable monomer composition, preferably contain (A) 1～80 mass parts, (C) 1～80 mass parts and (D) 1～97 mass parts, more preferably contain (A) 3～70 mass parts, (C) 2～60 mass parts and (D) 5～93 mass parts, and then preferably contain (A) 5～70 mass parts, (C) 2～40 mass parts and (D) 10～90 mass parts.In addition, when paying attention to the impregnability to dentine (particularly dentine), and then preferably contain polymerizable monomer (B) with 1 polymerizable group and the hydroxyl more than 1.Above-mentionedly contain (A), (B), (C) and (D) time from the cementability compound resin, use level as each composition, in total amount 100 mass parts of polymerizable monomer composition, preferably contain (A) 1～80 mass parts, (B) 1～80 mass parts, (C) 1～80 mass parts and (D) 1～97 mass parts, more preferably contain (A) 3～70 mass parts, (B) 2～70 mass parts, (C) 2～60 mass parts and (D) 5～93 mass parts, and then preferably contain (A) 5～70 mass parts, (B) 3～50 mass parts, (C) 2～40 mass parts and (D) 10～90 mass parts.About the use level of polymerization starter (F) and filler (H), can adopt and the above-mentioned common identical use level of compound resin.In addition, same with above-mentioned common compound resin, also preferred and with the embodiment of above-mentioned polymerization starter (F) and above-mentioned polymerization promotor (G), above-mentioned (F) and use level (G) such as above-mentioned.In addition, when particularly paying attention to the impregnability to dentine, can cooperate solvent (E), above-mentioned solvent (E) and then preferably contain water (I).The use level of above-mentioned solvent (E) is with respect to total amount 100 mass parts of polymerizable monomer composition, preferred 0～15 mass parts, more preferably 1～10 mass parts.

【0174】

In addition, composition 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 composition of the present invention is used as the resin-bonded agent, above-mentioned composition preferably contains polymerizable monomer (A), bridging property polymerizable monomer (D), polymerization starter (F), polymerization promotor (G), filler (H) and as the composition of the water (I) of solvent (E), such composition and then can contain the polymerizable monomer (C) with acidic-group.Grafting material when cement for dental applications is for example preferably inlayed the metal of (イ Application Le one) or hat (Network ラ ゥ Application) or pottery system 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 by 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 by 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, be not particularly limited as the filler (H) that uses.

【0175】

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 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.

【0176】

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 by 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, preferably especially use above-mentioned A thickener to contain (A), (C), (F) and (H), above-mentioned B thickener contains (A), (G) and embodiment (H).

【0177】

When composition of the present invention is used as cement for dental applications, use level as each composition is not particularly limited, in total amount 100 mass parts of polymerizable monomer composition, preferably contain (A) 1～90 mass parts, (B) 1～90 mass parts, (C) 1～90 mass parts and (D) 1～90 mass parts, more preferably contain (A) 2～90 mass parts, (B) 2～80 mass parts, (C) 2～80 mass parts and (D) 2～80 mass parts.In addition, use level as above-mentioned (F) and above-mentioned (G), when considering to obtain suitable set time, total amount 100 mass parts with respect to the polymerizable monomer composition, preferably contain (F) 0.001～20 mass parts, (G) 0.001～30 mass parts, more preferably contain (F) 0.05～15 mass parts, (G) 0.05～20 mass parts.

【0178】

And then total amount 100 mass parts with respect to the polymerizable monomer composition preferably contain (H) 30～2000 mass parts, more preferably contain (H) 50～1500 mass parts.(H) content is during less than 30 mass parts, the physical strength of cured article have inadequate may.On the other hand, when content (H) surpasses 2000 mass 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.

【0179】

In addition, composition 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 by mineral filler that the fluorine silicon aluminum silicate glass is such and the such polyolefin acid (acid of Port リ ア Le ケ Application) of polyacrylic acid to react and solidify and obtain.And, think to interact the performance binding function by the calcium in the hydroxyapatite of above-mentioned polyacrylic acid and formation dentine.Composition of the present invention is as glass ionomer cement, when especially preferably using as resin enhancement type glass ionomer cement, above-mentioned composition preferably contains (A), (E), (F), (G), (H) and the composition of polyolefin acid, be more preferably and contain (A), (D), (E), (F), (G), (H) and the composition of polyolefin acid, contain (A), (B), (E), (F), (G), (H) and the composition of polyolefin acid or contain (A), (B), (D), (E), (F), (G), (H) and the composition of polyolefin acid, such composition and then also can contain (C).

【0180】

The polymerizable monomer (B) with 1 polymerizable group and the hydroxyl more than 1 as using is not particularly limited.As described later, consider that from the viewpoint that can carry out the acid-alkali reaction smoothly solvent (E) preferably contains water (I).Therefore, as above-mentioned (B), using and the high monomer of water (I) affinity, from the homogeneity that keeps composition, the viewpoint consideration that obtains stable performance, is preferred.As such and the high monomer of affinity water (I), preferred 2-hydroxyethyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, glycerine list (methyl) acrylate, tetrahydroxybutane list (methyl) acrylate, preferred especially 2-hydroxyethyl methacrylic ester.

【0181】

Bridging property polymerizable monomer (D) as using is not particularly limited, and as above-mentioned, as above-mentioned (D), the high monomer of affinity of use and water (I) from the homogeneity that keeps composition, the viewpoint consideration that obtains stable performance, is preferred.Consider from the angle of the physical strength that has such and affinity water (I) and cured article concurrently; as above-mentioned (D); the difunctionality polymerizable monomer of preferred aliphat series of compounds; more preferably triglycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1; two (the 3-methacryloyl oxygen base-2-hydroxyl propoxy-) ethane and 2 of 2-; 2, two (the 2-formamyl oxygen base ethyl) dimethacrylates of 4-trimethylammonium hexylidene (common name " UDMA ").

【0182】

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 the homopolymer of vinylformic acid, methacrylic 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 ゥ ト ラ コ Application etc. or the monomeric multipolymer of these unsaturated carboxylic acids and copolymerization.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 monomer of ethylenic, for example can enumerate vinylbenzene, acrylamide, vinyl cyanide, methyl methacrylate, 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 composition, 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 composition to mediate, operability reduce.Thereby the weight average molecular weight of preferred polyolefin acid is 5,000～40,000.

【0183】

As the filler (H) that uses, the viewpoint of the solidified nature from the acid-alkali reaction and the fluorine slow-releasing of composition 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.

【0184】

In addition, the solvent of use (E) is not particularly limited, and considers from the viewpoint that can carry out the acid-alkali reaction smoothly, preferably contains water (I).As solvent (E), when making the mixed solvent of water (I) and organic solvent (J), more than the preferred 50 quality % of the content of the water in the above-mentioned mixed solvent (I), more preferably more than the 70 quality %, and then more than the preferred 90 quality %.In the embodiment of the carrying out of special attention acid-alkali reaction, solvent (E) especially preferably only contains water (I) basically.

【0185】

Composition of the present invention as glass ionomer cement, when especially preferably using as resin enhancement type glass ionomer cement, is not particularly limited as the use level of each composition.Composition contains (A) and (B) time, in total amount 100 mass parts of polymerizable monomer composition, preferably contain (A) 1～90 mass parts, (B) 1～90 mass parts and (C) 0～50 mass parts, more preferably contain (A) 2～90 mass parts, (B) 5～90 mass parts and (C) 0～30 mass parts.Composition contains (A) and (D) time, in total amount 100 mass parts of polymerizable monomer composition, preferably contain (A) 1～90 mass parts, (D) 1～90 mass parts and (C) 0～50 mass parts, more preferably contain (A) 2～90 mass parts, (D) 5～90 mass parts and (C) 0～30 mass parts.And, composition contains (A), (B) and (D) time, in total amount 100 mass parts of polymerizable monomer composition, preferably contain (A) 1～90 mass parts, (B) 1～90 mass parts, (D) 1～90 mass parts and (C) 0～50 mass parts, more preferably contain (A) 2～90 mass parts, (B) 5～90 mass parts, (D) 5～90 mass parts and (C) 0～30 mass parts.

【0186】

In addition, use level as above-mentioned (F) and above-mentioned (G), when considering to obtain suitable set time, total amount 100 mass parts with respect to the polymerizable monomer composition, preferably contain (F) 0.001～30 mass parts, (G) 0.001～30 mass parts, more preferably contain (F) 0.05～20 mass parts, (G) 0.05～20 mass parts.And then total amount 100 mass parts with respect to the polymerizable monomer composition preferably contain (H) 30～2000 mass parts, more preferably contain (H) 50～1500 mass parts.(H) content is during less than 30 mass parts, the physical strength of cured article have inadequate may.On the other hand, when content (H) surpassed 2000 mass parts, the flowability of composition 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.

【0187】

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

【0188】

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

【0189】

As above-mentioned, in the glass ionomer cement, the carrying out that reacts by acid-alkali causes curing, therefore considers that from the viewpoint of storage stability the filler (H) and the polyolefin acid of alkalescence are packaged in respectively in the independent container, mixes before the preferred use and uses.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, preferred above-mentioned A thickener contained (A), (E), (F), (H) and polyolefin acid, and above-mentioned B thickener contains (B) and embodiment (H).In addition, the above-mentioned A thickener of preferred too use contains (A), (E), (F), (H) and polyolefin acid, and above-mentioned B thickener contains (D) and embodiment (H).In addition, the above-mentioned A thickener of also preferred use contains (D), (F), (H) and polyolefin acid, and above-mentioned B thickener contains (A), (E), (G) and embodiment (H).At this moment, when particularly paying attention to cementability, in the above-mentioned A thickener and then preferably contain (C), consider, in the above-mentioned B thickener and then also preferably contain (B) from same viewpoint.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.

【0190】

These dental materials can prepare according to conventional methods and use, can be bonding with high bonding strength and dentine.

【0191】

Below, enumerate embodiment and describe the present invention in detail, but the present invention is not limited to these embodiment.

【0192】

(HPLC of polymerizable monomer measures)

(1) sample preparation methods

The about 20mg of weighing monomer in the sample phial is with methyl alcohol (with the pure pharmaceutical worker's industry of light society system, high performance liquid chromatography is used) 1g dilution.After the vibrating example phial makes the monomer component dissolving, use disposable syringe (TERUMO society system, テ Le モ シ リ Application ジ＜trade(brand)name〉tuberculin 1mL) and HPLC disposable filtering unit (Japanese Port one Le society system, エ キ Network ロ デ イ ス Network＜trade(brand)name〉13CR, 0.45 μ mPTFE) filter diluting soln, make the HPLC working sample.

(2) HPLC measures

It is that the HPLC central controller uses the system CBM-20A of Shimadzu Seisakusho Ltd. that the HPLC of the polymerizable monomer that uses in embodiment and the comparative example measures, automatic sampler uses the system SIL-20A of Shimadzu Seisakusho Ltd., detector uses the system SPD-M20A of Shimadzu Seisakusho Ltd., the post baking oven uses the system CTO-20A of Shimadzu Seisakusho Ltd., the liquor charging unit uses LC-20AT, and post uses system μ Bondapak (registered trademark) C of Waters (ゥ オ one タ one ズ) society ₁₈The analysis post (C18 weighting agent (breaking type), median size 10 μ m, pore size 125 dusts, column dimension 3.9 * 300mm) carries out.When using them, except post, the dead volume from the sample inlet to detection site is 87 μ L.Elutriant uses the mixed solvent of methanol=3/7, and flow is 1.0mL/ minute, and measuring temperature is 50 ℃, and the sample injection rate is 10 μ L.Surveying periodic pressure is 5MPa～10MPa (50kgf/cm ²～100kgf/cm ²).Measurement result is shown in table 1.

【0193】

[table 1]

The HPLC measurement result

	Retention time (minute)
		??HEMA	??6.02
??SDMA	??*13.64
		??MDMA	??*12.68
??EDMA	??*18.23
		??XDMA	??*21.27
??ErMA	??34.12
		??GDMA	??41.52
??#801	??＞45

* the scope of claim

【0194】

Embodiment 1 contains the application (one-pack type adhesives) of Polymerizable composition in bonding system of 1 step of polymerizable monomer (A)

(1) preparation of one-pack type adhesives

The one-pack type adhesives of the Polymerizable composition that contains polymerizable monomer (A) is used in preparation.Its composition is shown in table 2.

【0195】

[table 2]

【0196】

EDMA: tetrahydroxybutane dimethacrylate (1, two (the methacryloyl oxygen bases)-2 of 4-, 3-butyleneglycol)

XDMA: Xylitol dimethacrylate (1, two (the methacryloyl oxygen bases)-2,3 of 5-, 4-pentane triol)

SDMA: Sorbitol Powder dimethacrylate (1, two (the methacryloyl oxygen bases)-2,3,4 of 6-, 5-hexane tetrol)

MDMA: mannitol dimethacrylate (3,4-two-O-methacryloyl-D-mannitol)

#801:1, two (the 3-methacryloyl oxygen base-2-hydroxyl propoxy-) ethane of 2-

GDMA: glycerine dimethacrylate (the not polymerizable monomer of using for the comparative example of polymerizable monomer (A))

ErMA: dimethyl pentaerythritol acrylate

HEMA:2-hydroxyethyl methacrylic ester

MDP:10-methacryloyl oxygen base decyl dihydrogen phosphoric acid ester

Bis-GMA: dihydroxyphenyl propane diglycidyl methacrylic ester

TMDPO: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 "

【0197】

MDMA is a new compound, and is synthetic by following method.

Reference example MDMA's is synthetic

(i) 1,2:5,6-two-O-isopropylidene-3,4-two-O-methacryloyl-D-N.F,USP MANNITOL synthetic

After in the split type flask of the 2L that cooling tube has been installed, adding anhydrous pyridine 700mL, 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)

【0198】

(ii) MDMA's (3,4-two-O-methacryloyl-D-N.F,USP MANNITOL) is synthetic

In the 2L round-bottomed flask, add acetate 540mL and water 180mL.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 Zhi Bei solution 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.By 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)

【0199】

(2) with the Dentinal bonding evaluation method of baurodont

The labial surface of ox lower jaw labial teeth is ground with #80 silicon carbide paper (paper society system is ground by Japan) under flowing water, obtain the sample that Dentinal tabular surface exposes.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.

【0200】

Use pen that the one-pack type adhesives of above-mentioned preparation is coated in the above-mentioned circular hole, place after 20 seconds, by 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.

【0201】

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 society system, trade(brand)name " Network リ ア Off イ Le AP-X " (registered trademark)).Then, mounting slide glass on this mould release film by pushing, makes the coated face of above-mentioned compound resin level and smooth.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 by above-mentioned mould release film.

【0202】

Fill the surface of the cured article of using compound resin for the dentistry that obtains, 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, be impregnated in the distilled water.The preparation adhesive test amounts to 10 for test agent, is statically placed in the thermostatted that remains on 37 ℃ 24 hours impregnated in whole samples in the distilled water.At 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.

【0203】

(3) bonding evaluation test (evaluation of bonding strength and adhesion durability)

Above-mentioned adhesive test is measured with universal testing machine (society of Shimadzu Seisakusho Ltd. system) for the stretching bonding strength of test agent, is 2mm/ minute with the pinblock speed setting, with mean value as the stretching bonding strength.

【0204】

＜embodiment 1-1 〉

As the hydrophilic monomer that cooperates in the above-mentioned one-pack type adhesives, use the EDMA be equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0205】

＜embodiment 1-2 〉

As the hydrophilic monomer that cooperates in the above-mentioned one-pack type adhesives, use the XDMA be equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0206】

＜embodiment 1-3 〉

As the hydrophilic monomer that cooperates in the above-mentioned one-pack type adhesives, use the SDMA be equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0207】

＜embodiment 1-4 〉

As the hydrophilic monomer that cooperates in the above-mentioned one-pack type adhesives, use the MDMA be equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0208】

＜embodiment 1-5 〉

In embodiment 1-1, the polymerization starter of use changes to the such of table 2 record, except using polymerization promotor, carries out evaluation test equally with embodiment 1-1.

【0209】

＜embodiment 1-6 〉

As the hydrophilic monomer that cooperates in the above-mentioned one-pack type adhesives, except cooperation is equivalent to the EDMA30 mass parts of polymerizable monomer (A), mismatch beyond the HEMA that is equivalent to polymerizable monomer (B), carry out evaluation test equally with embodiment 1-1.

【0210】

＜comparative example 1-1 〉

As the hydrophilic monomer that cooperates in the above-mentioned one-pack type adhesives, use the #801 (retention time is long) be not equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0211】

＜comparative example 1-2 〉

As the hydrophilic monomer that cooperates in the above-mentioned one-pack type adhesives, use the GDMA (retention time is long) be not equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0212】

＜comparative example 1-3 〉

As the hydrophilic monomer that cooperates in the above-mentioned one-pack type adhesives, use the ErMA (retention time is long) be not equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0213】

＜comparative example 1-4 〉

As the hydrophilic monomer that cooperates in the above-mentioned one-pack type adhesives, mismatch the EDMA that is equivalent to polymerizable monomer (A), cooperate HEMA (retention time is short) 30 mass parts be equivalent to polymerizable monomer (B), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0214】

Table 2 is shown in as a result.As shown in Table 2, use the one-pack type adhesives that contains the Polymerizable composition of polymerizable monomer (A) of the present invention, have excellent initial cementability and adhesion durability for dentine.

【0215】

Embodiment 2

Contain the application (two-component-type adhesives) of Polymerizable composition in bonding system of 2 steps of polymerizable monomer (A)

(1) uses the preparation of the bed material of the Polymerizable composition contain polymerizable monomer (A)

The Polymerizable composition that use contains polymerizable monomer (A) prepares bed material.Its composition is shown in table 3.

【0216】

[table 3]

【0217】

(2) with the Dentinal bonding evaluation method of baurodont

The labial surface of ox lower jaw labial teeth is ground with #80 silicon carbide paper (paper society system is ground by Japan) under flowing water, obtain the sample that Dentinal tabular surface exposes.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.

【0218】

Use pen that the bed material of above-mentioned preparation is coated in the above-mentioned circular hole, place after 20 seconds, by 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 4.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.

【0219】

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, mounting slide glass on this mould release film by pushing, makes the coated face of above-mentioned compound resin level and smooth.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 by above-mentioned mould release film.

【0220】

Fill the surface of the cured article of using compound resin for the dentistry that obtains, 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, be impregnated in the distilled water.The preparation adhesive test amounts to 10 for test agent, is statically placed in the thermostatted that remains on 37 ℃ 24 hours impregnated in whole samples in the distilled water.At 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.

【0221】

[table 4]

The composition of adhesives

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

【0222】

NPG: neopentylglycol dimethacrylate

Mineral filler 2: Japanese ア エ ロ ジ Le society's system " Ar380 "

(other abbreviations and above-mentioned same meaning)

【0223】

(3) bonding evaluation test (evaluation of bonding strength and adhesion durability)

Above-mentioned adhesive test is measured with universal testing machine (society of Shimadzu Seisakusho Ltd. system) for the stretching bonding strength of test agent, is 2mm/ minute with the pinblock speed setting, with mean value as the stretching bonding strength.

【0224】

＜embodiment 2-1 〉

As the hydrophilic monomer that cooperates in the above-mentioned bed material, use the EDMA be equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0225】

＜embodiment 2-2 〉

As the hydrophilic monomer that cooperates in the above-mentioned bed material, use the XDMA be equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0226】

＜embodiment 2-3 〉

As the hydrophilic monomer that cooperates in the above-mentioned bed material, use the SDMA be equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0227】

＜embodiment 2-4 〉

As the hydrophilic monomer that cooperates in the above-mentioned bed material, use the MDMA be equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0228】

＜embodiment 2-5 〉

In embodiment 2-1, the polymerization starter of use changes to the such of table 3 record, except using polymerization promotor, carries out evaluation test equally with embodiment 2-1.

【0229】

＜embodiment 2-6 〉

As the hydrophilic monomer that cooperates in the above-mentioned bed material, except cooperation is equivalent to the EDMA70 mass parts of polymerizable monomer (A), mismatch beyond the HEMA that is equivalent to polymerizable monomer (B), carry out evaluation test equally with embodiment 2-1.

【0230】

＜comparative example 2-1 〉

As the hydrophilic monomer that cooperates in the above-mentioned bed material, use the #801 (retention time is long) be not equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0231】

＜comparative example 2-2 〉

As the hydrophilic monomer that cooperates in the above-mentioned bed material, use the GDMA (retention time is long) be not equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0232】

＜comparative example 2-3 〉

As the hydrophilic monomer that cooperates in the above-mentioned bed material, use the ErMA (retention time is long) be not equivalent to polymerizable monomer (A), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0233】

＜comparative example 2-4 〉

As the hydrophilic monomer that cooperates in the above-mentioned bed material, mismatch the EDMA that is equivalent to polymerizable monomer (A), cooperate HEMA (retention time is short) 70 mass parts be equivalent to polymerizable monomer (B), carry out above-mentioned and the Dentinal bonding evaluation test of baurodont.

【0234】

Table 3 is shown in as a result.As shown in Table 3, use the bed material that contains the Polymerizable composition of polymerizable monomer (A) of the present invention, have excellent initial cementability and adhesion durability for dentine.

【0235】

Embodiment 3

Contain the application of Polymerizable composition in the dental compound resin of polymerizable monomer (A)

(1) uses the preparation of the dental compound resin of the Polymerizable composition contain polymerizable monomer (A)

The dental compound resin of the thickener shape of the Polymerizable composition that contains polymerizable monomer (A) is used in preparation.Dental compound resin preparation is filled with compound resin and from 2 systems of cementability compound resin.Its composition is shown in table 5 (fill and use compound resin) and table 6 (from the cementability compound resin).

【0236】

[table 5]

【0237】

PDE: to (N, N-dimethylamino) phenylformic acid ethyl ester

Mineral filler 3: silane treatment barium glass powder

Barium glass (エ ス テ Star Network society system, goods number " Raysorb E-3000 ") is pulverized with ball mill, obtained the barium glass powder.Using laser diffraction formula particle size distribution device (Shimadzu Seisakusho Ltd.'s system, pattern " SALD-2100 ") to measure the median size of the barium glass powder that obtains, is 2.4 μ m.For these barium glass powder 100 weight parts, by ordinary method, carry out surface treatment with the 3-methacryloyl oxygen base propyl trimethoxy silicane of 3 weight parts, obtain silane treatment barium glass powder.

Mineral filler 4: silane treatment colloidal silica powder

In distilled water 100 weight parts, add 0.3 weight part acetate and 3 weight part 3-methacryloyl oxygen base propyl trimethoxy silicanes and stirring; and then add colloidal silica powder (Japanese ア エ ロ ジ Le society system, goods number " ア エ ロ ジ Le OX50 ") 50 weight parts and stirred 1 hour.Except that after anhydrating, carry out 5 hours heat treated by lyophilize, obtain silane treatment colloidal silica powder at 80 ℃.

(unit of the use level of each composition is a mass parts, other abbreviations and above-mentioned same meaning)

【0238】

[table 6]

【0239】

(2) with the Dentinal bonding evaluation method of baurodont

(the filling compound resin (embodiment 3-1～3-4, comparative example 3-1～3-6))

Is level and smooth with the labial teeth of ox with the moistening grinding of #1000 silicon carbide paper (paper society system is ground by Japan), enamel surface or dentin surface are exposed after, the water on surface blown with the dental air gun fly.In enamel surface that exposes or dentin surface, stickup has sealing tapes diameter 3mm circular hole, the about 150 μ m of thickness, on circular hole, use pen coating dental adhesives (Network ラ レ メ デ イ カ Le society system, trade(brand)name " Network リ ア Off イ Le ト ラ イ エ ス ボ Application De "), place after 20 seconds, use the dental air gun that this dental adhesives composition dries is mobile to not having.Then, use dental light illuminator (モ リ タ society system, trade(brand)name " JETLITE3000 ") to carry out 10 seconds rayed.Then, the above-mentioned filling composite resin composition that makes of mounting on this dental adhesives, after lining mould release film (polyester), mounting slide glass and pushing on this mould release film used dental light illuminator " JETLITE3000 " rayed 20 seconds, solidified.Then, for this curing face, use dental resin cement (Network ラ レ メ デ イ カ Le society system, trade(brand)name " パ Na PVC ア 21 "), one square end face (circular cross section) of the stainless steel system cylindrical rod of bonding diameter 7mm, length 2.5cm left standstill 30 minutes, made test film.Adhesive test all prepares 5 for test agent.

【0240】

(from cementability compound resin (embodiment 3-5～3-8, comparative example 3-7～3-10)

Is level and smooth with the labial teeth of ox with the moistening grinding of #1000 silicon carbide paper (paper society system is ground by Japan), enamel surface or dentin surface are exposed after, the water on surface blown with the dental air gun fly.In enamel surface that exposes or dentin surface, stickup has sealing tapes diameter 3mm circular hole, the about 150 μ m of thickness.On circular hole mounting above-mentioned make from the cementability composite resin composition, lining mould release film (Network ラ レ society system, trade(brand)name " エ バ one Le ") after, mounting slide glass and pushing on this mould release film, use dental light illuminator (モ リ タ society system, trade(brand)name " JETLITE3000 ") rayed is 20 seconds, solidifies.Then, for this curing face, use dental resin cement (Network ラ レ メ デ イ カ Le society system, trade(brand)name " パ Na PVC ア 21 "), one square end face (circular cross section) of the stainless steel system cylindrical rod of diameter 5mm, length 1.5cm left standstill 30 minutes, made test film.Adhesive test all prepares 5 for test agent.

【0241】

(3) bonding evaluation test

Above-mentioned adhesive test utilizes universal testing machine (society of Shimadzu Seisakusho Ltd. system) to measure for the stretching bonding strength of test agent, is 2mm/ minute with the pinblock speed setting wherein, with mean value as the stretching bonding strength.

【0242】

(4) mensuration of flexural strength

At the metal die of stainless steel (after filling composite resin composition among the size 2mm * 2mm * 25mm), use the slide glass crimping up and down, respectively shine 2 minute light with light illuminator (モ リ タ system, ア Le Off ア one ラ イ ト II) from the two sides with the dental skilled worker, make its curing.For each embodiment and comparative example, prepare 5 cured articles, after cured article took out from metal die, keeping was 24 hours in 37 ℃ distilled water.Use the Instron universal testing machine, span: 20mm measures flexural strength under the condition of pinblock speed: 1mm/min, calculates the mean value of the measured value of each test film, as flexural strength.

【0243】

Above-mentioned evaluation result is shown in table 5 and 6.These tables are arranged as can be known, use the dental compound resin that contains the Polymerizable composition of polymerizable monomer (A) of the present invention to have excellent cementability, have good flexural strength for dentine.

【0244】

Embodiment 4

The Polymerizable composition that contains polymerizable monomer (A) is in the application of dental in the cementability cement

(1) uses of the preparation of the dental of the Polymerizable composition that contains polymerizable monomer (A) from the cementability cement

Each composition of table 7 is mixed at normal temperatures preparation A thickener and B thickener.Then, they are mixed with the dental composition cement composition, measure and the Dentinal bonding strength of baurodont.

【0245】

[table 7]

【0246】

THP:1,1,3,3-tetramethyl butyl hydroperoxide

CHP: cumene hydroperoxide

BPO: benzoyl peroxide

BHT: butylated hydroxytoluene (4-methyl-2,6-di-tert-butylphenol)

D-2.6E:2, two (the 4-methacryloyl oxygen Quito ethoxyl phenenyl) propane of 2-

PTU:1-(2-pyridyl)-2-thiocarbamide

DEPT:N, N-di-alcohol-para-totuidine

TPBSS:2,4,6-triisopropyl benzene sulfinic acid sodium

(unit of the use level of each composition is a mass parts, other abbreviations and above-mentioned same meaning)

【0247】

(2) with the Dentinal bonding evaluation method of baurodont

The labial surface of ox lower jaw labial teeth is ground with #80 silicon carbide paper (paper Co., Ltd. system is ground by Japan) under flowing water, obtain the sample that Dentinal tabular surface exposes.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.

【0248】

The A thickener of above-mentioned preparation and B thickener is mixing and obtain cement composition with mass ratio 1: 1, said composition is contained in stainless steel system cylindrical rod (diameter 7mm, length 2.5cm) a square end face (circular cross section), so that the consistent mode in center of the center of above-mentioned circular hole and above-mentioned stainless steel system cylindrical rod, be positioned in the end face of the above-mentioned cement composition of splendid attire on the above-mentioned circular hole and push, for facing, stainless steel system cylindrical rod is vertically set up.

【0249】

After setting up, will remove with equipment, this sample after 30 minutes room temperatures leave standstill, be impregnated in the distilled water from the remaining cement composition that overflows on every side of stainless steel cylindrical rod.Adhesive test amounts to 10 of preparations for test agent, will impregnated in the distilled water all samples, rests in the thermostatted that remains on 37 ℃ 24 hours.For among 10 samples 5, 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.

【0250】

(3) bonding evaluation test (evaluation of bonding strength and adhesion durability)

Above-mentioned 5 adhesive tests are measured with universal testing machine (Shimadzu Scisakusho Ltd's system) for the stretching bonding strength of test agents, are 2mm/ minute with the pinblock speed setting wherein, with mean value as the stretching bonding strength.

【0251】

Table 7 is shown in as a result.As shown in Table 7, use the dental that contains the Polymerizable composition of polymerizable monomer (A) of the present invention to have excellent initial cementability and adhesion durability for dentine from the cementability cement.

【0252】

Embodiment 5 contains the application of Polymerizable composition in dental resin enhancement type glass ionomer cement of polymerizable monomer (A)

(1) uses the preparation of the dental resin enhancement type glass ionomer cement of the Polymerizable composition contain polymerizable monomer (A)

【0253】

(embodiment 5-1, comparative example 5-1～5-2)

Each composition of table 8 is mixed with liquor at normal temperatures.In addition, in the mixed solvent of toluene 80 mass parts, methyl alcohol 20 mass parts, add DEPT2.5 mass parts and BSS1.5 mass parts, stir after 10 minutes, add fluorine silicon aluminum hydrochlorate powder (SCHOTT society system, goods number " G018-117 ", below, be called FAS glass) 500 mass parts, stirred 10 minutes.Decompression is slipped and is desolvated, and after the drying, uses mesh screen (#150) to sieve, the preparation pulvis.Then, these liquid materials and pulvis are mixed with dental resin enhancement type glass ionomer cement with weight ratio at 1: 3, similarly to Example 4, measure and the Dentinal bonding strength of baurodont.The results are shown in table 8.

【0254】

[table 8]

The composition and the cohesiveness evaluation result of powder liquid type resin enhancement type glass ionomer cement

(unit of the use level of each composition is a mass parts, other abbreviations and above-mentioned same meaning)

【0255】

(embodiment 5-2～5-6, comparative example 5-3)

Each composition of table 9 is mixed at normal temperatures preparation A (thickener) and B (thickener).Then, they are mixed, preparation dental resin enhancement type glass ionomer cement similarly to Example 4, is measured and the Dentinal bonding strength of baurodont.The results are shown in table 9.

【0256】

[table 9]

【0257】

By table 8 and 9 as can be known, use the dental resin enhancement type glass ionomer cement that contains the Polymerizable composition of polymerizable monomer (A) of the present invention, have excellent initial cementability and adhesion durability for dentine.

Industrial applicability

【0258】

Polymerizable monomer of the present invention (A) has a plurality of polymerizable groups, and has hydrophily, therefore requires in the hydrophilic purposes useful in the purposes that requires curing property and this polymer. Contain the polymerizable composition, polymerizable composition of this polymerizable monomer with headed by the dental use, can in various uses, use. Particularly, said composition is suitable for the dental material of bed material, adhesives, cement and compound resin etc.

Claims (17)

1. polymerizable monomer (A), it is the compound with 2 above polymerizable groups,

The C18 weighting agent that this polymerizable monomer (A) uses median size to be broken for 10 μ m, have a pore size of 125 dusts is filled the post of the internal diameter 3.9mm * length 300mm that obtains, elutriant be mixed solvent, the flow of methanol=3/7 be 1.0mL/ minute, measure temperature be 50 ℃, sample injection rate be 10 μ L and except post the dead volume from the sample inlet to detection site be under the condition of 87 μ L during with high performance liquid chromatography (HPLC) mensuration, retention time is 7 minutes～30 minutes.

2. polymerizable monomer according to claim 1 (A), it has the hydroxyl more than 2.

3. polymerizable monomer according to claim 1 (A), it has the hydroxyl more than 3

4. according to any described hydrophilic monomer of claim 1～3 (A), above-mentioned polymerizable group is the group of following formula (1), following formula (2) or following formula (3) expression,

[Chemical formula 1]

[Chemical formula 2]

[chemical formula 3]

In the formula, R ¹, R ², and R ³Represent the aliphatic alkyl of hydrogen atom or carbonatoms 1～10 respectively, * represents associative key.

5. polymerizable monomer according to claim 4 (A), R ¹, R ²And R ³Be hydrogen atom or methyl.

6. according to any described polymerizable monomer of claim 1～5 (A), above-mentioned polymerizable monomer (A) is the compound of formula (4) expression,

[chemical formula 4]

In the formula, G is hydroxyl or polymerizable group, and n is the integer more than 3, and at least 3 is hydroxyl among the G, and among the G at least 2 be polymerizable group.

7. composition, it contains any described polymerizable monomer of with good grounds claim 1～6 (A) and forms.

8. composition according to claim 7, as the polymerizable monomer composition, also contain and be selected from least a kind polymerizable monomer and form with 1 polymerizable functional groups group and the polymerizable monomer (B) of the hydroxyl more than 1, polymerizable monomer (C) and bridging property polymerizable monomer (D) with acidic-group.

9. according to claim 7 or 8 described compositions, contain solvent (E) and form.

10. according to any described composition of claim 7～9, contain polymerization starter (F) and form.

11., contain polymerization promotor (G) and form according to any described composition of claim 7～10.

12., contain filler (H) and form according to any described composition of claim 7～11.

13. according to any described composition of claim 7～12, it is a dental.

14. bed material, it uses composition according to claim 13.

15. adhesives, it uses composition according to claim 13.

16. compound resin, it uses composition according to claim 13

17. cement, it uses composition according to claim 13.