JP6966769B2 - Chemical Initiators, Adhesive Compositions, Dental Cement and Dental Adhesives - Google Patents

Description

The present invention relates to chemical polymerization initiators, adhesive compositions, dental cements and dental adhesives.

Chemical polymerization initiators that exhibit polymerization activity in the presence of acid and water are used, for example, in dental adhesive compositions that require excellent adhesion to dentin. Various such chemical polymerization initiators have been proposed.

For example, Patent Document 1 proposes a chemical polymerization initiator composed of an arylborate compound, an acidic compound and an organic peroxide and substantially free of an amine compound as a catalyst component, and Patent Document 2 proposes an aryl. Chemical polymerization initiators containing borate compounds, acidic compounds, inorganic peroxides and divalent copper compounds have been proposed.

JP-A-2002-187907. Japanese Unexamined Patent Publication No. 2011-121869

As exemplified in Patent Documents 1 and 2, a peroxide is often used as an oxidizing agent in the chemical polymerization initiator because high polymerization activity can be easily obtained. Peroxides function as strong oxidants and are advantageous for improving polymerization activity, but on the other hand, they are usually extremely unstable and are particularly easily decomposed by heat. Therefore, in the case of a chemical polymerization initiator using a peroxide, even if the peroxide is stored separately from other components in the chemical polymerization initiator that easily reacts with the peroxide, the storage stability is improved. It tends to be disadvantageous.

The present invention has been made in view of the above circumstances, and a chemical polymerization initiator having high polymerization activity in the presence of acid and water and having excellent storage stability, and an adhesive composition using the same. It is an object of the present invention to provide dental cement and dental adhesive.

The above object is achieved by the following invention. That is,
The chemical polymerization initiator of the present invention contains (a) an organic sulfinate, (b) an arylborate compound, and (c) a fourth-period transition metal compound, and does not contain a peroxide, and (c). The fourth period transition metal compound is at least one compound selected from the group consisting of a + IV-valent vanadium compound, a + V-valent vanadium compound, a + II-valent copper compound, and a + III-valent iron compound (a). The blending ratio X of (a) organic sulfinate to the total amount T of () organic sulfinate, (b) arylborate compound, and (c) fourth cycle transition metal compound is 15% by mass to 45% by mass. The compounding ratio Y of the (b) arylborate compound to the total amount T is 55% by mass to 85% by mass, and the compounding ratio Z of the (c) fourth cycle transition metal compound to the total amount T is 0.05% by mass. It is characterized by being % to 20% by mass.

In one embodiment of the chemical polymerization initiator of the present invention, it is preferable that (a) the organic sulfinate contains at least one selected from the group consisting of benzenesulfinate and toluenesulfinate. ..

In another embodiment of the chemical polymerization initiator of the present invention, it is preferable that the (b) arylborate compound contains a compound represented by the following general formula (1).

[In the general formula (1), R ¹ , R ² and R ³ are independently alkyl groups, aryl groups, aralkyl groups or alkenyl groups; R ⁴ and R ⁵ are independent hydrogen groups, respectively. It is an atom, a halogen atom, an alkyl group, or a phenyl group; L ⁺ is a metal cation, a quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a phosphonium ion. ]

In another embodiment of the chemical polymerization initiator of the present invention, (c) any vanadium compound in which the fourth period transition metal compound is selected from the group consisting of an IV-valent vanadium compound and a V-valent vanadium compound. It is preferable to include.

In another embodiment of the chemical polymerization initiator of the present invention, (c) the fourth cycle transition metal compound is vanadium oxide (V), sodium vanadate (V), vanadium oxytrichloride (V), vanadium tetroxide. (IV), vanadium oxide acetylacetonate (IV), vanadil oxalate (IV), vanadil sulfate (IV), oxobis (1-phenyl-1,3-butandionate) vanadium (IV), and bis (maltlate). ) It is preferable to contain at least one vanadium compound selected from the group consisting of oxovanadium (IV).

Another embodiment of the chemical polymerization initiator of the present invention comprises a first agent and a second agent packaged together, wherein the first agent is (a) an organic sulfinate and (b) an arylborate compound. , And (c) of the three components consisting of the fourth cycle transition metal compound, only (a) organic sulfinate and (b) arylborate compound are contained, and the second agent contains of the three components. , (C) It is preferable that only the fourth period transition metal compound is contained.

The adhesive composition of the present invention is characterized by containing the chemical polymerization initiator of the present invention and (d) an acidic group-containing polymerizable monomer.

One embodiment of the adhesive composition of the present invention preferably further contains (e) an acidic group-free polymerizable monomer.

The dental cement of the present invention is characterized by containing the chemical polymerization initiator of the present invention, (d) an acidic group-containing polymerizable monomer, and (f) a filler.

The dental adhesive of the present invention is characterized by containing the chemical polymerization initiator of the present invention, (d) an acidic group-containing polymerizable monomer, and (g) a solvent.

According to the present invention, a chemical polymerization initiator having high polymerization activity in the presence of acid and water and having excellent storage stability, and an adhesive composition, dental cement and dental adhesive using the same. Can be provided.

The chemical polymerization initiator of the present embodiment is characterized by containing (a) an organic sulfinate, (b) an arylborate compound, and (c) a fourth cycle transition metal compound, and containing no peroxide. And.

Since the chemical polymerization initiator of the present embodiment does not contain a peroxide, the chemical polymerization initiator of the present embodiment and the composition using the same are excellent in storage stability. Further, by using (a) an organic sulfinate, (b) an arylborate compound, and (c) a fourth period transition metal compound in combination, high polymerization activity can be obtained in the presence of acid and water. .. In principle, the peroxide is a component that is not contained in the chemical polymerization initiator, but it is permissible that a trace amount of the peroxide is contained in the form of impurities or the like that are inevitably mixed.

Next, (a) an organic sulfinate, (b) an arylborate compound, (c) a fourth period transition metal compound used in the chemical polymerization initiator of the present embodiment, and other substances that can be further added as needed. The components of are described in detail below.

(A) Organic Sulfinate As the organic sulfinate, any known organic sulfinate can be used. Specific examples include benzenesulfinic acid, toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 2,6-diisopropylbenzenesulfinic acid, 2,4. , 6-Triisopropylbenzenesulfinic acid, chlorbenzenesulfinic acid or salts such as naphthalinsulfinic acid can be mentioned. Here, examples of the salt components constituting these organic sulfinates include alkali metal salts such as lithium salt, sodium salt, potassium salt, rubidium salt and cesium salt; and magnesium salt, calcium salt and strontium salt. Alkaline earth metal salts ;, iron salts ;, copper salts ;, zinc salts ;, ammonium salts, tetramethylammonium salts, methyldiethanolammonium salts; or ammonium salts such as triethanolammonium salts and tetraethylammonium salts. Can be done.

Among these sulfinates, benzenesulfinate and toluenesulfinate are preferable because of their high reactivity and high solubility in polymerizable monomers.

Further, as the organic sulfinate, only one kind may be used, or two or more kinds may be used in combination.

(B) Aryl Borate Compound The aryl borate compound is not particularly limited as long as it is a compound having at least one boron-aryl bond in the molecule, and a known compound can be used. However, as the aryl borate compound, it is preferable to use the compound represented by the following general formula (1).

Here, in the general formula (1), R ¹ , R ² and R ³ are independently alkyl groups, aryl groups, aralkyl groups or alkenyl groups; R ⁴ and R ⁵ are independent of each other. , Hydrogen atom, halogen atom, alkyl group, or phenyl group; L ⁺ is a metal cation, a quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a phosphonium ion.

In the general formula (1), groups R ¹ to R ³ is an alkyl group, an aryl group, an aralkyl group or an alkenyl group, these groups may have a substituent.

Among these groups, the alkyl group may be either a linear alkyl group or a branched alkyl group, and is not particularly limited, but an alkyl group having 3 to 30 carbon atoms is preferable, and carbon is more preferable. A linear alkyl group having a number of 4 to 20, for example, an n-butyl group, an n-octyl group, an n-dodecyl group, an n-hexadecyl group and the like. The substituent that the alkyl group may have includes a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a hydroxyl group, a nitro group, a cyano group, a phenyl group, a nitrophenyl group, a chlorophenyl group and the like. Examples thereof include an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group, and an acyl group having 2 to 5 carbon atoms such as an acetyl group. Further, the number and position of the substituents are not particularly limited.

The aryl group is also not particularly limited and may have a substituent, but preferably a single ring or a carbon number of 6 to 14 in which two or three rings are condensed (provided that the carbon is the carbon). From the number, it is an aryl group (excluding the carbon atom constituting the substituent). Examples of the substituent that the aryl group may have include the group exemplified as the substituent of the above alkyl group and the alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a butyl group. .. Specific examples of such an aryl group include a phenyl group, a 1- or 2-naphthyl group, a 1-, 2- or 9-anthrill group, a 1-, 2-, 3-, 4- or 9-phenanthryl group, and the like. p-fluorophenyl group, p-chlorophenyl group, (3,5-bistrifluoromethyl) phenyl group, 3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-) Propyl) Phenyl group, p-nitrophenyl group, m-nitrophenyl group, p-butylphenyl group, m-butylphenyl group, p-butyloxyphenyl group, m-butyloxyphenyl group, p-octyloxyphenyl group, Examples thereof include m-octyloxyphenyl group.

The aralkyl group is not particularly limited and may further have a substituent, but generally, it has 7 to 20 carbon atoms (however, the substituent constitutes a substituent from the carbon number). (Excluding carbon), for example, a benzyl group, a phenethyl group, a tolyl group can be exemplified. Moreover, as a substituent, the substituent exemplified by the above-mentioned aryl group can be mentioned.

The alkenyl group is also not particularly limited and may have a substituent, and is an alkenyl group having 4 to 20 carbon atoms (however, the carbon number thereof excludes the carbon constituting the substituent), for example. A 3-hexenyl group, a 7-octynyl group and the like are suitable. Further, as the substituent, those exemplified as the substituent of the alkyl group can be mentioned.

Further, in the above general formula (1), R ⁴ and R ⁵ are hydrogen atoms, halogen atoms, alkyl groups, or phenyl groups, respectively.

In such R ⁴ and R ⁵ , the alkyl group is not particularly limited, and may be linear or branched, and may further have a substituent, but preferably has 1 to 1 carbon atoms. 10 (however, the carbon number constituting the substituent is excluded from the carbon number). Furthermore, as the substituent include those exemplified as the substituents for the alkyl group represented by the group R ¹ to R ^3. Specific examples of such an alkyl group include a methyl group, an ethyl group, an n- or i-propyl group, an n-, i- or t-butyl group, a chloromethyl group, a trifluoromethyl group, a methoxymethyl group, and 1 , 1,1,3,3,3-hexafluoro-2-methoxy-2-propyl group and the like are exemplified.

Also it may have a phenyl group substituent in R ⁴ and R ^5, as the substituent include those exemplified as the substituent of the aryl group of the radicals R ¹ to R ^3.

Further, in the above general formula (1), L ⁺ is a metal cation, a quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a quaternary phosphonium ion.

The above-mentioned metal cations are preferably alkali metal cations such as sodium ion, lithium ion and potassium ion, alkaline earth metal cations such as magnesium ion and the like, and the quaternary ammonium ion is tetrabutylammonium ion. Examples thereof include tetramethylammonium ion and tetraethylammonium ion. The quaternary pyridinium ion is typically methyl quinolinium ion, ethyl quinolinium ion, butyl quinolium ion or the like, and the quaternary phosphonium ion is tetrabutyl phosphonium ion or methyl tri. A phenylphosphonium ion and the like can be exemplified.

Preferable examples of the arylborate compound represented by the general formula (1) are those having one aryl group in one molecule, those having two aryl groups in one molecule, and three in one molecule. Those having an aryl group and those having 4 aryl groups in one molecule can be mentioned.

Specific examples of the arylborate compound having one aryl group in one molecule include trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, and trialkyl (3,5). -Bistrifluoromethyl) phenylboron, trialkyl [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy2-propyl) phenyl] boron, trialkyl (p-butylphenyl) ) Boron, trialkyl (m-butylphenyl) boron, trialkyl (p-butyloxyphenyl) boron, trialkyl (m-butyloxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron and trialkyl (m) A salt of −octyloxyphenyl) boron (alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.) can be mentioned. The salts include sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt and methylquinolinium salt. , Ethyl quinolinium salt, butyl quinolinium salt and the like.

Examples of the borate compound having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, and dialkyldi (3,5-bistrifluoromethyl) phenylboron. Dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyloxyphenyl) boron and dialkyldi ( Examples thereof include salts of m-octyloxyphenyl) boron (alkyl groups are n-butyl group, n-octyl group, n-dodecyl group, etc.). The salts include sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethyl. There are quinolinium salt, butyl quinolinium salt and the like.

Borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluorophenyl) boron, and monoalkyltris (3,5). -Bistryfluoromethyl) phenylboron, monoalkyltris [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy2-propyl) phenyl] boron, monoalkyltris (p- Butylphenyl) boron, monoalkyltris (m-butylphenyl) boron, monoalkyltris (p-butyloxyphenyl) boron, monoalkyltris (m-butyloxyphenyl) boron, monoalkyltris (p-octyloxyphenyl) Examples thereof include salts of boron and monoalkyltris (m-octyloxyphenyl) boron (alkyl groups are n-butyl group, n-octyl group, n-dodecyl group, etc.). The salts include sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt and ethyl. Examples thereof include quinolinium salt and butyl quinolinium salt.

Examples of the borate compound having four aryl groups in one molecule include tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenylboron, and the like. Tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy2-propyl) phenyl] boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) Boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyloxyphenyl) boron and tetrakis (m-octyloxyphenyl) boron (alkyl group is n-butyl group, Salts of n-octyl group, n-dodecyl group, etc.) can be mentioned. The salts include sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt and ethyl. Examples thereof include quinolinium salt and butyl quinolinium salt.

As the arylborate compound, it is preferable to use an arylborate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability, and further, from the viewpoint of easy handling and availability, 4 Arylbolate compounds having an aryl group are most preferred. Only one kind of the above-mentioned aryl borate compound may be used, or two or more kinds may be mixed and used.

(C) Fourth Period Transition Metal Compound The fourth period transition metal compound is a metal compound of groups 3 to 12 of the fourth period of the periodic table, and specifically, scandium (Sc), titanium (Ti), and vanadium (c). It is a metal compound of V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn).

The transition metal element in the fourth period transition metal compound may have a plurality of valences, but any valence that can exist stably is sufficient, for example, Sc (III), Ti (IV), V. (III-V), Cr (II, III, VI), Mn (II-VII), Fe (II, III), Co (II, III), Ni (II), Cu (I, II), Zn ( II) is applicable.

Specific examples of such compounds include scandium iodide (III) as a +III-valent vanadium compound, titanium chloride (IV), titanium (IV) tetraisopropoxide and the like as +VI-valent titanium compounds. Examples of the + IV vanadium compound include divanadium tetraoxide (IV), vanadium acetylacetonate (IV) oxide, vanadium oxalate (IV), vanadil sulfate (IV), and oxobis (1-phenyl-1). , 3-Butandionate) vanadium (IV), bis (maltrat) oxovanadium (IV) and the like, and examples of the + V-valent vanadium compound include vanadium oxide (V) and sodium vanadate (V). Examples thereof include vanadium oxytrichloride (V).

Further, as a + II-valent chromium compound, chromium (II) chloride and the like can be mentioned, as a + III-valent chromium compound, chromium (III) chloride and the like can be mentioned, and as a + VI-valent chromium compound, chromium acid and a chromate salt can be mentioned. Etc., and examples of the + II-valent manganese compound include manganese acetate (II) and manganese naphthenate (II), and examples of the + II-valent iron compound include iron acetate (II) and iron chloride (II). Examples of the +III-valent iron compound include iron acetate (III) and iron chloride (III), and examples of the +II-valent cobalt compound include cobalt acetate (II) and cobalt naphthenate (II). Nickel chloride (II) and the like can be mentioned as the + II valent nickel compound, and copper (I) chloride, copper (I) and the like can be mentioned as the + I valent copper compound, and the + II valence can be mentioned. Examples of the copper compound of the above include copper chloride (II) and copper acetate (II), and examples of the +II-valent zinc compound include zinc chloride (II) and zinc acetate (II).

Among these, metal compounds of V (IV, V), Mn (II), Fe (II, III), and Co (II) are preferable, and since higher polymerization activity can be obtained, + IV and / or + V valence can be obtained. Vanadium compounds are preferred.

In the chemical polymerization initiator of the present embodiment, in addition to the three components shown in (a) to (c) described above, other components (excluding peroxides) may be further combined and used as necessary. good.

The blending ratio of each component constituting the chemical polymerization initiator is not particularly limited. However, the blending ratio of (a) organic sulfinate to the total amount T of (a) organic sulfinate, (b) arylborate compound, and (c) fourth cycle transition metal compound X [a / (a + b + c)). ] Is 15% by mass to 45% by mass, and (b) the compounding ratio Y [b / (a + b + c)] of the arylborate compound with respect to the total amount T is 55% by mass to 85% by mass, and (b) with respect to the total amount T. c) The compounding ratio Z [c / (a + b + c)] of the fourth cycle transition metal compound is preferably 0.05% by mass to 20% by mass, and (a) organic sulfate and (b) aryl borate. The compounding ratio X of (a) organic sulfinate to the total amount T of the compound and (c) the fourth cycle transition metal compound is 20% by mass to 40% by mass, and (b) aryl borate with respect to the total amount T. It is more preferable that the compounding ratio Y of the compound is 60% by mass to 80% by mass, and the compounding ratio Z of the (c) fourth cycle transition metal compound with respect to the total amount T is 0.1% by mass to 15% by mass. Here, the blending ratios X, Y, and Z are appropriately selected within the above-mentioned range on the premise that X + Y + Z = 100% by mass is satisfied.

Further higher polymerization activity can be obtained by setting the blending ratio X of the organic sulfinic acid to 15% by mass or more. In this case, for example, if the chemical polymerization initiator of the present embodiment is added to the adhesive composition and used, excellent adhesiveness can be easily obtained. On the other hand, when the compounding ratio X of the organic sulfinic acid is too large, the compounding amount of the arylborate compound and / or the fourth period transition metal compound is significantly limited, so that it becomes difficult to achieve compatibility with other properties other than the polymerization activity. Cheap. However, by setting the blending ratio X of the organic sulfinic acid to 45% by mass or less, it becomes extremely easy to avoid the above problem. The blending ratio X of the organic sulfinic acid is more preferably in the range of 20% by mass to 40% by mass, and particularly preferably in the range of 25% by mass to 30% by mass.

Further, by setting the blending ratio Y of the aryl borate compound to 55% by mass or more, the storage stability of the chemical polymerization initiator of the present embodiment and the composition using the same can be further improved. On the other hand, when the blending ratio Y of the aryl borate compound is too large, the blending amount of other components constituting the chemical polymerization initiator is limited, so that it tends to be difficult to achieve compatibility with other properties other than storage stability. However, by setting the mixing ratio Y of the aryl borate compound to 85% by mass or less, it becomes extremely easy to avoid the above problem. The mixing ratio Y of the aryl borate compound is more preferably in the range of 60% by mass to 80% by mass, and particularly preferably in the range of 65% by mass to 75% by mass.

Further, by setting the blending ratio Z of the fourth period transition metal compound to 0.05% by mass or more, even higher polymerization activity can be obtained. In this case, for example, if the chemical polymerization initiator of the present embodiment is added to the adhesive composition and used, excellent adhesiveness can be easily obtained. On the other hand, if the blending ratio of the fourth period transition metal compound is too large, the cured product of the composition using the chemical polymerization initiator of the present embodiment is likely to be colored. In addition, when the cured product is used in applications where the presence or absence of coloring or the degree of coloring is a problem (for example, dental applications) such as applications where aesthetics are required, coloring is an undesired phenomenon. However, by setting the blending ratio of the fourth period transition metal compound to 20% by mass or less, it becomes extremely easy to avoid such a problem. The blending ratio Z of the fourth period transition metal compound is more preferably in the range of 0.1% by mass to 15% by mass, and particularly preferably in the range of 0.1% by mass to 5% by mass.

Further, the chemical polymerization initiator of the present embodiment may be stored in a state in which all the components constituting the chemical polymerization initiator are mixed or in contact with each other in one container (for example, a syringe, a bag, a bottle, etc.). However, each component constituting the chemical polymerization initiator may be stored in a state of being packaged in a first agent and a second agent. Here, the form of the sachet is not particularly limited as long as the composition constituting the first agent and the composition constituting the second agent do not come into contact with each other and mix with each other during storage, but usually, a syringe or the like. The first agent and the second agent are separately stored in various containers such as bags and bottles. When the chemical polymerization initiator of the present embodiment has a first agent and a second agent packaged together, the first agent is used when the chemical polymerization initiator of the present embodiment (and a composition containing the same) is used. The agent and the second agent are mixed.

Whether each component constituting the chemical polymerization initiator is blended in the first agent or the second agent can be appropriately selected. However, among the three components consisting of (a) organic sulfinate, (b) arylborate compound, and (c) fourth cycle transition metal compound, the first agent contains (a) organic sulfinate and , (B) Only the arylborate compound is contained, and it is preferable that the second agent contains only (c) the fourth cycle transition metal compound among the three components shown in (a) to (c) above. When such a package form is adopted, the storage stability can be further improved. In the packaged form, the first agent does not contain the component shown in (c) among the three components shown in (a) to (c) above, but the component shown in (c) is contained. It is permissible that it is inevitably contained in a very small amount in the form of impurities or the like. Similarly, the second agent does not contain, in principle, the components shown in (a) and (b) among the five components shown in (a) to (c) above, but in (a) and (b). It is permissible that the indicated components are inevitably contained in trace amounts in the form of impurities or the like.

When other components other than those shown in (a) to (c) are further used as the chemical polymerization initiator, the other components may be added to either or both of the first agent and the second agent. can. Further, in the composition using the chemical polymerization initiator of the present embodiment (for example, an adhesive composition), each component other than the chemical polymerization initiator in the composition is either the first agent or the second agent. It can be blended in one or both.

The mixing ratio of the first agent and the second agent (first agent / second agent) at the time of use can be appropriately selected as long as the polymerization activity and operability are not significantly impaired, but the handling and product packaging From a practical point of view such as ease of use, the mixing ratio (first agent / second agent) is preferably in the range of 1/5 to 5/1 in terms of volume ratio, and is in the range of 1/3 to 3/1. The inside is more preferable, or the mass ratio is preferably in the range of 1/5 to 5/1, and more preferably in the range of 1/3 to 3/1. In addition, the user of the chemical polymerization initiator of the present embodiment and the composition using the same is usually determined by the developer, manufacturer or seller of the chemical polymerization initiator of the present embodiment and the composition using the same. The first agent and the second agent are mixed according to the mixing ratio (hereinafter referred to as "designated mixing ratio"). The actual mixing ratio at the time of use is allowed to deviate from the specified mixing ratio as long as the polymerization activity and operability are not significantly impaired. For example, when the specified mixing ratio is used as a reference (100%). The actual mixing ratio at the time of use may be in the range of 33% to 300%, preferably in the range of 50% to 200%.

When the chemical polymerization initiator of the present embodiment and the composition using the same are packaged in the first agent and the second agent, the blending amount or blending ratio of the chemical polymerization initiator in the specification of the present application. The description of means a value determined on the assumption that it is mixed at a specified mixing ratio.

The designated mixing ratio can be displayed on the mixing ratio information display medium. Examples of the mixing ratio information display medium include i) a product package consisting of a paper box and the like, ii) a paper medium and / or a product instruction manual provided as electronic data, and iii) first and second agents, respectively. Containers to be stored in a sealed state (bottles, syringes, packaging bags, etc.), iv) Product catalogs provided as paper media and / or electronic data, v) Sent to product users by e-mail or mail separately from the product. You can use the correspondence etc. Further, the designated mixing ratio may be provided to the product user in a manner that can be recognized by the product user by means other than those shown in i) to v) above.

In the chemical polymerization initiator of the present embodiment, in addition to the three components shown in (a) to (c) described above, other components (excluding peroxides) may be further combined and used as necessary. good. Examples of other components include amine compounds, barbituric acid derivatives, organic reducing compounds such as thiourea compounds, and the like.

The chemical polymerization initiator of the present embodiment is usually used by blending it with a composition used for various purposes. In this case, the components other than the chemical polymerization initiator (non-chemical polymerization initiator component) in the composition are appropriately selected according to the use of the composition. However, the non-chemical polymerization initiator component is selected from the components excluding the peroxide. The conditions for using the chemical polymerization initiator of the present embodiment are not particularly limited, but it is particularly preferable to use the chemical polymerization initiator in the presence of acid and water because it can exhibit high polymerization activity. In this case, either or both selected from the acid component and water may be contained in the composition containing the chemical polymerization initiator of the present embodiment, or both the acid component and water may be contained in the composition. It does not have to be contained in the product. However, if the composition does not contain one or both of the acid component and water, the components not contained in the composition (acid component and /) in the reaction system in which the chemical polymerization is carried out. Or water) needs to be present. In the reaction system, when a component (acid component and / or water) not contained in the composition is present in a portion other than the composition, for example, in the vicinity of the surface of the solid to which the composition is applied. The presence of components (acid component and / or water) that are not contained in the composition may be mentioned. Further, the acid component may be present in the reaction system in the form of an acid anhydride or the like, and water may be present in the reaction system in the form of a hydrate or a hydroxyl group.

As the composition containing the chemical polymerization initiator of the present embodiment, an adhesive composition is preferable. In addition, the adhesive composition of the present embodiment is preferably used as a dental adhesive composition (particularly, dental cement and dental adhesive). The details of these compositions will be described below.

The adhesive composition of the present embodiment is not particularly limited as long as it contains the chemical polymerization initiator of the present embodiment, but the chemical polymerization initiator of the present embodiment and (d) an acidic group-containing polymerizable monomer are used. And, it is particularly preferable that it contains. Further, even if the adhesive composition of the present embodiment appropriately contains (e) an acidic group-free polymerizable monomer, (f) a filler, (g) a solvent and the like, if necessary. good. In the following description, when any one or both of (d) an acidic group-containing polymerizable monomer and (e) an acidic group-free polymerizable monomer is indicated, simply "polymerizable simple substance" is used. It is called "polymer". In addition, the blending amount of each component to be blended in the adhesive composition of the present embodiment can be appropriately selected depending on the use of the adhesive composition.

When the adhesive composition of the present embodiment is used as a dental cement, the dental cement is filled with the chemical polymerization initiator of the present embodiment, (d) an acidic group-containing polymerizable monomer, and (f). When the adhesive composition of the present embodiment is used as a dental adhesive, the dental adhesive contains the chemical polymerization initiator of the present embodiment and (d) an acidic group. It is preferable that the contained polymerizable monomer and (g) the solvent are contained. In addition, these dental cements and dental adhesives may further contain other components such as (e) acidic group-free polymerizable monomers.

In the dental cement of the present embodiment, the blending amount of the polymerizable monomer with respect to 100 parts by mass of the dental cement is 10 mass from the viewpoint of ensuring the mechanical strength of the cured product and ensuring the permeability to the dentin. Parts to 50 parts by mass are preferable, and 20 parts to 40 parts by mass are preferable. Further, the polymerizable monomer used in the dental cement may be composed of only the acidic group-containing polymerizable monomer, but the acidic group-containing polymerizable monomer and the acidic group-free polymerizable simpler are used. It is preferably composed of a monomer. In this case, the blending amount of the acidic group-containing polymerizable monomer with respect to 100 parts by mass of the polymerizable monomer is preferably 5 parts by mass or more, and 7 parts by mass or more, from the viewpoint of further strengthening the adhesiveness to the dentin. Is preferable. The blending amount of the acidic group-containing polymerizable monomer with respect to 100 parts by mass of the polymerizable monomer is preferably 50 parts by mass or less from the viewpoint of further improving the adhesive durability to the prosthesis made of dentin and various materials. More preferably, it is 30 parts by mass or less.

The amount of the chemical polymerization initiator used in the dental cement is preferably 0.1 part by mass to 25 parts by mass, and 0.3 part by mass to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Is preferable. This makes it easier to secure the curability of the dental cement and to secure the adhesive strength and the mechanical strength of the hardened body.

In the dental adhesive of the present embodiment, the blending amount of the polymerizable monomer with respect to 100 parts by mass of the dental adhesive is 10 mass from the viewpoint of ensuring the mechanical strength of the cured product and the permeability to the dentin. Parts to 95 parts by mass are preferable, and 20 parts to 80 parts by mass are preferable. Further, the polymerizable monomer used in the dental adhesive may be composed of only the acidic group-containing polymerizable monomer, but the acidic group-containing polymerizable monomer and the acidic group-free polymerizable monomer are used. It is preferably composed of a monomer. In this case, the blending amount of the acidic group-containing polymerizable monomer with respect to 100 parts by mass of the polymerizable monomer is preferably 5 parts by mass or more, and 7 parts by mass or more, from the viewpoint of further strengthening the adhesiveness to the dentin. Is preferable. The blending amount of the acidic group-containing polymerizable monomer with respect to 100 parts by mass of the polymerizable monomer is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, from the viewpoint of further improving the adhesive durability to the dentin. ..

The amount of the chemical polymerization initiator used in the dental adhesive is preferably 0.1 part by mass to 15 parts by mass, and 0.3 part by mass to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer. The unit is preferable. This makes it easier to secure the curability of the dental adhesive and to secure the adhesive strength and the mechanical strength of the cured product.

The amount of the solvent used in the dental adhesive is not particularly limited. However, when water and / or a water-soluble organic solvent is used as the solvent and the polymerizable monomer contains an acidic group-containing polymerizable monomer, the amount of the solvent is 100. It is preferably 10 parts by mass to 500 parts by mass, and preferably 50 parts by mass to 200 parts by mass with respect to parts by mass. As a result, when the dental adhesive is applied to the surface of the tooth, the surface of the tooth can be sufficiently decalcified, and it becomes easier to obtain appropriate viscosity and dryness.

The dental cement and the dental adhesive of the present embodiment contain (d) an acidic group-containing polymerizable monomer, which is an acid component, as an essential component. In addition, dental cement and dental adhesive are applied to at least the surface of the dentin during its use. Moisture caused by saliva may adhere to the surface of this dentin, and the dentin contains an inorganic substance such as hydroxyapatite containing a hydroxyl group as a main component and a small amount as other components. Further contains water and organic matter. Therefore, when a dental cement and a dental adhesive are used, the polymerization reaction is always carried out in the presence of an acid component and water.

(D) Acidic group-containing polymerizable monomer The acidic group-containing polymerizable monomer that can be used in various compositions containing the chemical polymerization initiator of the present embodiment includes at least one acidic group and at least one. Any known polymerizable monomer having one radically polymerizable unsaturated group can be used. From the viewpoint of polymerizable property, a (meth) acrylic acid ester-based acidic group-containing polymerizable monomer is preferably used. Further, the (meth) acrylic acid ester-based acidic group-containing polymerizable monomer is also suitable when used in combination with a dental adhesive composition from the viewpoint of safety to the living body. Only one type of the acidic group-containing polymerizable monomer may be used, or two or more types may be used in combination.

Here, the acidic group means that an aqueous solution or an aqueous suspension of a radically polymerizable monomer having this group exhibits acidity, and is typically a carboxyl group (-COOH) or a sulfo group (-SO _3). Examples thereof include those having a hydroxyl group such as H), a phosphinic group {= P (= O) OH}, and a phosphono group {-P (= O) (OH) _2}. In addition to such a hydroxyl group-containing acidic group, an acid anhydride group having a structure in which two hydroxyl group-containing acidic groups are dehydrated and condensed, an acid halide group in which the hydroxyl group of the hydroxyl group-containing acidic group is substituted with halogen, etc. Can be mentioned. Further, the radically polymerizable unsaturated group is not particularly limited and may be a known one. Examples thereof include (meth) acryloyl groups such as (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, (meth) acryloylthio group, vinyl group, allyl group, styryl group and the like. ..

Examples of the acidic group-containing polymerizable monomer include those exemplified in the following (i) to (v).
(I) Radical polymerizable monomer having one carboxyl group in the molecule (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloyl aspartic acid, N- (meth) acryloyl-5 -Aminosalicylic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, and acid anhydrides or acid halides of the above radically polymerizable monomer.

(Ii) Radical polymerizable monomer having a plurality of carboxyl groups or acid anhydride groups thereof in the molecule 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane-1 , 1-dicarboxylic acid, 12- (meth) acryloyloxide decane-1,1-dicarboxylic acid, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid and acid anhydrides of the radically polymerizable monomer or Acid halides, etc.

(Iii) A radically polymerizable monomer having a phosphinicooxy group or a phosphonooxy group in the molecule (sometimes referred to as a radically polymerizable acidic phosphate ester).
2- (meth) acryloyloxyethyl dihydrogenphosphate, bis (2- (meth) acryloyloxyethyl) hydrogenphosphate, 2- (meth) acryloyloxyethylphenylhydrogenphosphate, 10- (meth) acryloyl Oxydecyldihydrogenphosphate, 6- (meth) acryloyloxyhexyl dihydrogenphosphate, 2- (meth) acryloyloxyethyl 2-bromoethylhydrogenphosphate, 2- (meth) acrylamide ethyl dihydrogenphos Fate, bis (6- (meth) acryloyloxyhexyl) hydrogenphosphate, bis (10- (meth) acryloyloxydecyl) hydrogenphosphate, bis {2- (meth) acryloyloxy- (1-hydroxymethyl) Ethyl} hydrogen phosphate and the like, and acid anhydrides and acid halides of the radically polymerizable acidic phosphoric acid ester.

(Iv) A radically polymerizable monomer having a phosphono group in a molecule such as vinylphosphonic acid and p-vinylbenzenephosphonic acid.
(V) A radically polymerizable monomer having a sulfo group in a molecule such as 2- (meth) acrylamide-2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid, vinylsulfonic acid and the like.

Further, in addition to the acidic group-containing polymerizable monomers shown in (i) to (v) described above, JP-A-54-11149, JP-A-58-140046, and JP-A-59-15468. Japanese Patent Laid-Open No. 58-173175, Japanese Patent Laid-Open No. 61-293951, JP-A-7-179401, JP-A-8-208760, JP-A-8-319209, JP-A-10-236912 The radical polymerizable monomer containing an acidic group described as a component in the dental adhesive composition disclosed in Japanese Patent Application Laid-Open No. 10-245525 is also used as the acidic group-containing polymerizable monomer. Can be suitably used.

(E) Acidic group-free polymerizable monomer The acidic group-free polymerizable monomer that can be used in various compositions containing the chemical polymerization initiator of the present embodiment has at least one radical polymerizable property. Any known polymerizable monomer having an unsaturated group (excluding those further containing an acidic group in the molecule) can be used. From the viewpoint of polymerizable property, a (meth) acrylic acid ester-based acidic group-free polymerizable monomer is preferably used. Further, the (meth) acrylic acid ester-based acidic group-free polymerizable monomer is also suitable when used in combination with a dental adhesive composition from the viewpoint of safety to the living body. Only one kind of acidic group-free polymerizable monomer may be used, or two or more kinds may be used in combination. Examples of the acidic group-containing polymerizable monomer include those exemplified below.

<Monofunctional radically polymerizable monomer>
Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2,3-dihydroxybutyl methacrylate, 2,4-dihydroxybutyl methacrylate , 2-Hydroxymethyl-3-hydroxypropylmethacrylate, 2,3,4-trihydroxybutylmethacrylate, 2,2-bis (hydroxymethyl) -3-hydroxypropylmethacrylate, 2,3,4,5-tetrahydroxypentyl Methacrylates, diethylene glycol monomethacrylates, triethyleneglycolmonomethacrylates, tetraethyleneglycolmonomethacrylates, pentaethyleneglycolmonomethacrylates, N, N-dimethylaminoethylmethacrylates and other methacrylates, and acrylates corresponding to these methacrylates.

<Bifunctional radically polymerizable monomer>
(I) Aromatic compound-based bifunctional radically polymerizable monomer;
2,2-Bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2-bis (4-methacryloyloxyphenyl) propane, 2, , 2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane), 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2, 2-Bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2- (4-methacryloyloxydiethoxyphenyl) -2- (4-methacryloyloxydi) Ethoxyphenyl) propane, 2- (4-methacryloyloxydiethoxyphenyl) -2- (4-methacryloyloxyditriethoxyphenyl) propane, 2- (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytri) Ethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane, and acrylates corresponding to these methacrylates;

Addition of a diisocyanate compound having an aromatic group such as diisocyanate methylbenzene or 4,4'-diphenylmethane diisocyanate and a methacrylate having a hydroxyl group, a methacrylate having an amino group, or an acrylate corresponding to these methacrylates. Jiaduct etc. obtained from.

The above-mentioned hydroxyl group-containing methacrylates include 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, diethylene glycol monomethacrylate, and triethylene glycol monomethacrylate. There are methacrylates, tetraethylene glycol monomethacrylates, pentaethylene glycol monomethacrylates and the like. Examples of amino group-containing methacrylates include 2-aminoethyl methacrylate, 3-aminopropyl methacrylate, 2-aminopropyl methacrylate, 4-aminobutyl methacrylate, 5-aminopentyl methacrylate, 3-aminopentyl methacrylate and the like.

(Ii) Aliphatic compound-based bifunctional radically polymerizable monomer;
Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1 , 6-Hexanediol dimethacrylate, and acrylates corresponding to these methacrylates;

Diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), and methacrylates having a hydroxyl group, methacrylates having an amino group, or methacrylates thereof. Jiaduct etc. obtained by addition with acrylate corresponding to the class. The hydroxyl group-containing methacrylates and the amino group-containing methacrylates are as exemplified above.

<Trifunctional radically polymerizable monomer>
Methacrylates such as trimethylolpropane trimethacrylate, trimethylolethanetrimethacrylate, pentaerythritol trimethacrylate, and trimethylolmethanetrimethacrylate, and acrylates corresponding to these methacrylates.

<Four-functional radically polymerizable monomer>
Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, and diaduct obtained from the addition of a diisocyanate compound and glycidol dimethacrylate.

The above-mentioned diisocyanate compounds include diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 4,4-diphenylmethane diisocyanate, and tolylen-2,4. − Examples include diisocyanate.

It should be noted that, as in the case where the composition containing the chemical polymerization initiator of the present embodiment is used as a dental adhesive composition or the like, the cured product of the composition is required to have excellent mechanical strength. be. In this case, as the acidic group-free polymerizable monomer, it is preferable to use a two, three or tetrafunctional radically polymerizable monomer having a plurality of radically polymerizable groups.

(F) Filler As the filler that can be used in various compositions containing the chemical polymerization initiator of the present embodiment, an organic filler and an inorganic filler can be used. Examples of the organic filler include polymethyl methacrylate, ethyl polymethacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, and ethylene-vinyl acetate copolymer. Examples thereof include a styrene-butadiene copolymer, an acrylonitrile-styrene copolymer, an acrylonitrile-styrene-butadiene copolymer and the like, and these can be used alone or as a mixture of two or more kinds. Examples of the inorganic filler include quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, strontium glass, fluoroaluminosilicate glass and the like. These are also used alone or in admixture of two or more.

The filler may be appropriately selected depending on the intended use, but for example, from the viewpoint of the mechanical strength of the cured product, it is preferable to use an inorganic filler. Further, when an inorganic filler is added to the dental adhesive composition, it is more preferable to use fluoroaluminosilicate glass among the inorganic fillers for the purpose of imparting sustained release of fluorine. The fluoroaluminosilicate glass is not particularly limited as long as it is a filler of acid fluoride glass of aluminum and silicon, and those generally used as an acid-reactive filler and an ion-eluting filler in dental cement and the like are used. Can be used. The preferred composition of the fluoroaluminosilicate glass is 10 to 33% by mass of silicon; 4 to 30% by mass of aluminum; 5 to 36% by mass of alkaline earth metal; 0 to 10% by mass of alkali metal; 0 phosphorus by mass. .2 to 16% by mass; 2 to 40% by mass of fluorine; the remaining amount is oxygen. As the alkaline earth metal, calcium, magnesium, strontium, and barium are preferable. Further, as the alkali metal, sodium, lithium and potassium are preferable, and sodium is particularly preferable. Further, if necessary, a part of the above aluminum replaced with titanium, yttrium, zirconium, hafnium, tantalum, lanthanum or the like can also be used.

Such fluoroaluminosilicate glass is, for example, a method of mixing a metal compound such as silica, alumina, fluorite, cryolite, aluminum fluoride, sintering at 1100 to 1300 ° C., and then pulverizing, a sol-gel method, or the like. Can be manufactured by. The inorganic filler can also be used by surface-treating it by a known method using a surface-treating agent such as a silane coupling agent. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinylethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-chloropropyltri. Preferably used are methoxysilane, hexamethyldisilazane and the like. When fluoroaluminosilicate glass is used as the inorganic filler, the fluoraluminosilicate glass may be coated with a polymer compound or the like for the purpose of improving the kneadability with other components.

The shape of the filler is not particularly limited, and may have an amorphous particle shape as obtained by ordinary pulverization, or may be spherical particles. The average particle size of the filler is not particularly limited, but is preferably about 0.01 μm to 100 μm, more preferably about 0.1 μm to 50 μm.

(G) Solvent As the solvent that can be used in various compositions containing the chemical polymerization initiator of the present embodiment, water and an organic solvent can be used. Only one type of solvent may be used, or two or more types may be used in combination. As the organic solvent, a water-soluble organic solvent is preferable. The term "water-soluble" as used herein means that the solubility in water at 20 ° C. is 20 g / 100 ml or more. Examples of the water-soluble organic solvent include methanol, ethanol, propanol, isopropyl alcohol, acetone, methyl ethyl ketone and the like. When a water-soluble organic solvent is blended in the dental adhesive composition, ethanol, propanol, isopropyl alcohol or acetone is preferable as the water-soluble organic solvent in consideration of harm to the living body.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples.

1. 1. Abbreviations of Substances The abbreviations of the substances used in the chemical polymerization initiators of each Example and Comparative Examples and the compositions containing them will be described below.

<Organic sulfinate>
PTSNa ・ ・ ・ Sodium paratoluenesulfinate PTSLi ・ ・ ・ Lithium paratoluenesulfinate BSNa ・ ・ ・ Sodium benzenesulfinate

<Aryl borate compound>
PhBNa: Sodium salt of tetraphenylboron PhBTEOA: Triethanolammonium salt of tetraphenylboron

<4th period transition metal compound>
V ₂ O ₄ ... divanadium tetrachloride (IV)
VOAA ・ ・ ・ Vanadium oxide acetylacetonate (V)
BMOV ・ ・ ・ Bis (maltrat) oxovanadium (IV)
CuAA ... Copper acetylacetonate (II)
FeCl ₃ ... Iron (III) chloride

<Peroxide>
CHP ... Cumene Hydroperoxide BPO ... Benzoyl Peroxide BPOL ... t-Butyl Peroxylaurate

<Acid group-containing polymerizable monomer>
MDP ・ ・ ・ 10-Methyloxydecyldihydrogen phosphate

<Polymeric monomer containing no acidic group>
BisGMA ・ ・ ・ Bisphenol A diglycidyl methacrylate 3G ・ ・ ・ Triethylene glycol dimethacrylate

2. 2. Preparation of Adhesive Composition As a composition containing a chemical polymerization initiator, a two-component adhesive composition composed of a first agent and a second agent, or a one-component adhesive composition was prepared.

2.1 Preparation of two-component adhesive composition A two-component adhesive composition consisting of the first agent and the second agent was prepared by the following procedure. First, 100 parts by mass of a polymerizable monomer having the composition shown below was added to the first agent and the second agent.
<Polymerizable monomer composition contained in the first agent>
-BisGMA: 60 parts by mass-3G: 40 parts by mass <Polymerizable monomer composition contained in the second agent>
・ MDP: 40 parts by mass ・ BisGMA: 36 parts by mass ・ 3G: 24 parts by mass

Further, each component constituting the chemical polymerization initiator is blended with 100 parts by mass of the polymerizable monomer contained in the first agent in the composition shown in Table 1, and the polymerizable monomer contained in the second agent is blended. Each component constituting the chemical polymerization initiator was blended with respect to 100 parts by mass with the composition shown in Table 2.

When various evaluations are performed using the adhesive composition composed of the first agent and the second agent, the mixing ratio of the first agent and the second agent is the total of the polymerizable monomers contained in the first agent. The mass was mixed so that the total mass of the polymerizable monomers contained in the second agent was 1: 1. Therefore, the "ratio of each component in the chemical polymerization initiator" shown in Table 3 shows the value calculated on the premise of the above mixing ratio.

2.2 Preparation of one-component adhesive composition A one-component adhesive composition consisting of only the first agent was prepared by the following procedure. First, 200 parts by mass of a polymerizable monomer having the composition shown below was blended.
<Polymerizable monomer composition contained in the first agent>
・ MDP: 40 parts by mass ・ BisGMA: 96 parts by mass ・ 3G: 64 parts by mass

In addition, each component constituting the chemical polymerization initiator was blended with 200 parts by mass of the polymerizable monomer contained in the first agent in the composition shown in Table 1.

3. 3. Various evaluations (1) Adhesive strength The cow anterior teeth removed within 24 hours after slaughter were polished with water-resistant polishing paper P600 under water injection, and the enamel plane was carved out so that it was parallel and flat to the lip surface. The adherend and the adherend obtained by carving out the dentin plane were prepared.

Next, a double-sided tape having a hole with a diameter of 3 mm was attached to the polished surface of each of these two types of adherends. Subsequently, the adhesive compositions of Examples and Comparative Examples shown in Tables 1 and 2 are applied to the adhesive surface of the polished surface exposed from the holes of the double-sided tape, and dried by air blowing for 5 seconds. rice field. Here, with respect to the two-component adhesive composition composed of the first agent and the second agent, the first agent and the second agent were mixed on a mixing dish and applied to the adhesive surface.

The adhesive composition to be applied to the adhesive surface includes a sample immediately after preparing the adhesive composition (sample immediately after preparation) and a constant temperature of 50 ° C. after preparing the adhesive composition and sealing it in a container. Two types of samples (samples after 1 week at 50 ° C.) after being stored in the tank for 1 week were used.

A paraffin wax with a thickness of 0.5 mm provided with a hole with a diameter of 8 mm is attached to an adhesive surface coated with an adhesive composition so that the hole of the paraffin wax and the hole of the double-sided tape are concentric circles. Was produced. This simulated cavity is filled with a dental composite resin (Esterite Σ Quick, manufactured by Tokuyama Dental Co., Ltd.), lightly pressed with a polyester film, and then lighted using a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). Photocuring was performed by irradiation for 10 seconds. Then, a pre-polished round bar made of SUS304 (diameter 8 mm, height 18 mm) was bonded with resin cement (Bistite II, manufactured by Tokuyama Dental Co., Ltd.). Finally, a sample for measuring the adhesive strength was obtained by immersing in water at 37 ° C. for 24 hours.

The tensile adhesive strength of these samples was measured using an autograph manufactured by Shimadzu Corporation (crosshead speed 2 mm / min). For each Example and Comparative Example, the measured values of the four samples were averaged and used as the measurement result. In addition, the measurement was carried out within about 1 day by pulling up the sample for adhesive strength measurement from the water.

Table 4 shows the evaluation results of the adhesive strength to enamel and dentin when the sample immediately after preparation was used, and the adhesive strength to enamel and dentin when the sample was used after 1 week at 50 ° C.

(2) Surface hardness A polyacetal mold having a circular hole with a diameter of 5 mm and a thickness of 1 mm is filled with the adhesive compositions of each Example and Comparative Example, and placed in a constant temperature bath under 37 ° C. wet conditions for 15 minutes. It was left to cure. As for the two-component adhesive composition, the first agent and the second agent were mixed and immediately charged into a mold and cured. A measurement sample was obtained by immersing the obtained cured product in water at 37 ° C. for 24 hours. Next, using a microhardness meter (MHT-1, manufactured by Matsuzawa Seiki), the diagonal length (d) of the recess formed under the load condition of 100 gf 30 seconds was measured, and the surface hardness was determined. The hardness was determined using the following formula (1). The results are shown in Table 4.
Equation (1) Hv = 1854.37 × 100 g / d ²

(3) Colorability
The adhesive compositions of the respective examples and comparative examples were placed in a polyacetal mold having a circular hole having a diameter of 5 mm and a thickness of 1 mm, and allowed to stand in a constant temperature bath under 37 ° C. wet conditions for 15 minutes to cure. .. As for the two-component adhesive composition, the first agent and the second agent were mixed and immediately charged into a mold and cured. Next, the obtained cured product was removed from the mold, and measurement was performed with a fair background using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd., "TC-1800MKII") to obtain L, a, and b values in the Lab color space. rice field. Using the obtained values, ΔE was calculated according to the following equation (2), and the colorability was determined. As the reference adhesive composition, the adhesive composition of each Example and Comparative Example to be determined was obtained by curing the polymerizable monomer without using the component (c).
・ Equation (2) ΔE = ((L _{1 −} L ₂ ) ² + (a _{1 −} a ₂ ) ² + (b ₁ − b ₂ ) ² ) ^1/2
The parameters shown on the right side of the equation (2) are as follows.
L ₁ : L value of the reference adhesive composition L ₂ : L value of the adhesive composition _{to be determined a 1} : a value of the reference adhesive composition a ₂ : The adhesive composition to be determined _{a value b 1} : B value of the reference adhesive composition b ₂ : b value of the adhesive composition to be determined

The criteria for determining "colorability" shown in Table 4 are as follows.
A: ΔE is 2 or less B: ΔE is more than 2 and 7 or less C: ΔE is more than 7 and 10 or less D: ΔE is more than 10

Claims (10)

It contains (a) an organic sulfinate, (b) an arylborate compound, and (c) a fourth period transition metal compound, and does not contain a peroxide.
(C) The fourth period transition metal compound is at least one compound selected from the group consisting of a + IV-valent vanadium compound, a + V-valent vanadium compound, a +II-valent copper compound, and a +III-valent iron compound. ,
The blending ratio X of (a) organic sulfinate to the total amount T of (a) organic sulfinate, (b) arylborate compound, and (c) fourth cycle transition metal compound is 15% by mass to 45% by mass. And
The blending ratio Y of the (b) aryl borate compound with respect to the total amount T is 55% by mass to 85% by mass.
A chemical polymerization initiator characterized in that (c) the blending ratio Z of the fourth period transition metal compound with respect to the total amount T is 0.05% by mass to 20% by mass. (A) The chemical polymerization initiator according to claim 1, wherein the organic sulfinate contains at least one selected from the group consisting of benzenesulfinate and toluenesulfinate. (B) The chemical polymerization initiator according to claim 1 or 2, wherein the aryl borate compound contains a compound represented by the following general formula (1).

[In the general formula (1), R ¹ , R ² and R ³ are independently alkyl groups, aryl groups, aralkyl groups or alkenyl groups; R ⁴ and R ⁵ are independent, respectively. It is a hydrogen atom, a halogen atom, an alkyl group, or a phenyl group; L ⁺ is a metal cation, a quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a phosphonium ion. ] (C) Any of claims 1 to 3, wherein the fourth period transition metal compound contains any vanadium compound selected from the group consisting of an IV-valent vanadium compound and a V-valent vanadium compound. The chemical polymerization initiator according to one. (C) The fourth cycle transition metal compound is vanadium oxide (V), sodium vanadate (V), vanadium oxytrichloride (V), divanadium tetroxide (IV), vanadium oxide acetylacetonate (IV), Shu. Selected from the group consisting of vanadium acid (IV), vanadil sulfate (IV), oxobis (1-phenyl-1,3-butandionate) vanadium (IV), and bis (maltrat) oxovanadium (IV). The chemical polymerization initiator according to any one of claims 1 to 4, which comprises any one or more vanadium compounds. It has the first and second agents packaged together,
Of the three components consisting of (a) an organic sulfinate, (b) an arylborate compound, and (c) a fourth cycle transition metal compound, the first agent includes (a) an organic sulfinate and (a) an organic sulfinate. (B) Contains only arylborate compounds,
The chemical polymerization initiator according to any one of claims 1 to 5 , wherein the second agent contains only (c) a fourth period transition metal compound among the three components. An adhesive composition comprising the chemical polymerization initiator according to any one of claims 1 to 6 and (d) an acidic group-containing polymerizable monomer. (E) The adhesive composition according to claim 7 , further comprising an acidic group-free polymerizable monomer. A dental cement comprising the chemical polymerization initiator according to any one of claims 1 to 6 , (d) an acidic group-containing polymerizable monomer, and (f) a filler. A dental adhesive comprising the chemical polymerization initiator according to any one of claims 1 to 6 , (d) an acidic group-containing polymerizable monomer, and (g) a solvent.