JP7148068B2 - Chemical polymerization initiator, adhesive composition, adhesive composition kit, dental material, dental material kit, and method for storing adhesive composition - Google Patents

Description

The present invention relates to a chemical polymerization initiator, an adhesive composition, an adhesive composition kit, a dental material, a dental material kit and a method of storing an adhesive composition.

(Meth)acrylate-based materials are used in a wide range of fields such as paints, printing materials, adhesives and dental materials. For example, in the dental field, it is applied to various materials such as bonding materials, resin cements, resin-reinforced glass ionomers, and composite resins. These materials are usually cured by radical polymerization. The generation of radicals is carried out by one or more suitable initiators selected from photoinitiators, thermal initiators and chemical (redox) initiators.

Among these polymerization initiators, chemical polymerization initiators are particularly useful when they cannot be stimulated by light or heat. Chemical initiators are usually stored in two or more separate portions because they contain a combination of a reducing agent and an oxidizing agent that can react immediately upon contact. The stored form is a combination of paste/paste, liquid/liquid, and powder/liquid. After these are mixed, the reducing agent and the oxidizing agent react to generate radicals.

Chemical polymerization initiators that have been known for a long time include initiators that combine benzoyl peroxide and a tertiary aromatic amine compound. However, benzoyl peroxide has poor storage stability due to its low thermal stability, and tertiary aromatic amine compounds are deactivated in the presence of acid, failing to obtain sufficient polymerization activity.

In the field of dentistry, there are many materials that require acid for reasons such as imparting adhesive properties. Therefore, there has been a demand for a chemical polymerization initiator that exhibits high polymerization activity in the presence of an acid. Chemical polymerization initiators that exhibit high polymerization activity in the presence of acids include hydroperoxides, ketone peroxides, peroxyesters, diacyl peroxides, and other organic peroxides with high thermal stability. and a reducing agent consisting of an amine, a sulfinic acid compound, a thiourea compound, an oxime compound, a transition metal compound, etc. and may be collectively referred to as polymerization accelerators.) is known (see Patent Documents 1 and 2).

Among these, a chemical polymerization initiator that combines a hydroperoxide and a thiourea compound has high storage stability and exhibits high activity in the presence of an acid, so it is particularly suitable for use as a chemical polymerization initiator for dental use. Various characteristics can be imparted by selecting a specific compound as the thiourea compound or by combining with a polymerization accelerator other than the thiourea compound such as a copper compound.

For example, US Pat. A two-component initiator system is disclosed having an accelerator for curing a polymerizable material having a copper compound that is soluble in the material. Patent Document 3 discloses a dental composition containing a radically polymerizable monomer having no acidic group functional group (hereinafter sometimes referred to as "non-acidic monomer") and the two-component initiator system, It is said to have high storage stability in the absence of an acid component, a short inhibition time (polymerization begins immediately upon mixing with the binary initiator), and that the addition of acid improves activity.

Further, Patent Document 4 describes a hydroperoxide compound (a2) and a substituted pyridylthiourea compound (a3) represented by a specific structural formula, and optionally a vanadium compound (a6) and/or a copper compound (a7). A chemical polymerization agent containing is disclosed, and a curable composition containing a radically polymerizable monomer having no acidic group (non-acidic monomer) and the chemical polymerization initiator has appropriate curability, Moreover, it has excellent long-term storage stability, and further has excellent adhesiveness when used in combination with a primer containing an acidic group-containing radically polymerizable monomer (hereinafter sometimes referred to as "acidic monomer"). It is said to indicate

Furthermore, in Patent Document 5, a dental curable composition that can ensure a sufficient operation time for dental treatment and has excellent adhesiveness includes (A) a polymerizable monomer containing an acidic group-containing polymerizable monomer ( acidic monomer), (B) a thiourea derivative, (D) a hydroperoxide-based organic peroxide, and (D) a water-soluble copper compound. Further, it is said that (G) the aryl borate compound can be further blended to promote curing and improve adhesive strength.

JP 2017-088637 A International publication WO2017/098724 pamphlet JP-A-2007-56020 JP 2014-227370 A JP 2014-152106 A JP 2011-121869 A

The polymerization initiators described in these Patent Documents 3 to 5 are used as a curable composition by being blended with a polymerizable monomer component or the like. It must be divided into 1 or more pieces (packaged) and stored. Therefore, when dividing the polymerization initiator, the polymerizable monomer components and the like used in the curable composition are also divided. Then, the curable composition (adhesive composition) is a mixture of two or more compositions ( hereinafter sometimes referred to as "partial compositions"), and are generally stored (packaged) for each of these partial compositions. In addition, just before use, two or more partial compositions that have been packaged and stored are mixed to prepare a curable composition containing all chemical polymerization initiator components. As a result, the chemical polymerization initiator functions simultaneously with mixing, so that the curable composition is polymerized and cured.

At this time, the acid component that plays an important role in adhesion may be (1) blended in the partial composition, or (2) not blended in the partial composition, and In some cases, it is blended in a composition other than the curable composition composed of the combination (hereinafter sometimes referred to as "curing auxiliary composition"). In addition, (2) in the latter case, the auxiliary curing composition and the curable composition are used in this order, or in the reverse order, so that the interface between the auxiliary curing composition and the curable composition It is believed that a composition is formed in which both are partially mixed in the vicinity. Here, when the curable composition is a dental curable composition, examples of the auxiliary curing composition include pretreatment agents such as primers.

Storage stability is an important factor in chemical polymerization initiators, and in the above-described mode of use, it is important that the partial composition in a packaged state has high storage stability. The storage stability in Patent Documents 3 and 4 also means the storage stability of such divided partial compositions. In these patent documents, (2) the storage stability of the latter example, that is, the portion (not including the acid component such as the acidic monomer) in which the (divided) component of the chemical polymerization initiator is blended with the non-acidic monomer The composition is said to have high storage stability.

On the other hand, in the dental curable composition containing an acidic monomer and a chemical polymerization initiator disclosed in Patent Document 5, the acidic group of the acidic monomer has high reactivity. For this reason, when the curable composition is divided into two or more partial compositions for packaging, there are restrictions on the combination of each component to be blended in each partial composition. For example, a partial composition containing a combination of an acidic monomer and a hydroperoxide-based organic peroxide undergoes gelation when stored for a long period of time, so such a combination of components is not preferred.

For this reason, Patent Document 5 discloses that the curable composition includes (A) a polymerizable monomer containing at least an acidic group-containing polymerizable monomer (acidic monomer) among the polymerizable monomers. , (B) a thiourea derivative, and (C) a hydroperoxide-based organic peroxide, and (D) a water-soluble copper compound. and partial composition (II). Further, Patent Document 5 discloses that when the curable composition further contains (E) an arylborate compound, the (E) arylborate compound is blended in the partial composition (II).

The curable composition disclosed in Patent Document 5, particularly the curable composition containing (E) an aryl borate compound, can secure an operation time suitable for dental applications, and has excellent adhesiveness and curability. there is Therefore, this curable composition is useful as a dental material such as a dental resin cement or a dental adhesive. However, regarding the storage stability of this curable composition, Patent Document 5 does not show any study results. Therefore, the present inventors investigated the storage stability of this curable composition. As a result, the present inventors have confirmed that partial composition (II) undergoes gelation when stored at relatively high temperatures for a long period of time.

In view of this situation, the present inventors have proposed an adhesive composition comprising an acidic monomer, a non-acidic monomer, and a chemical polymerization initiator, as disclosed in Patent Document 5, wherein each component has a different composition For an adhesive composition that is divided into two (packaged in two) and stored (stored) as a product, and that exhibits adhesiveness by mixing these compositions at the time of use and curing as the curable composition, An investigation was made to develop an adhesive composition capable of achieving both high polymerization activity and curability and high storage stability. As an adhesive composition having such an effect, a polymerizable monomer containing an acidic monomer contains "a thiourea compound, a peroxyester, a divalent copper compound and an arylborate compound, and substantially contains a hydroperoxide. We have succeeded in finding an adhesive composition containing a "chemical polymerization initiator that does not contain a chemical polymerization initiator" (hereinafter simply referred to as a "peroxyester-based chemical polymerization initiator"), and have already proposed it (Patent application 2017 -249143 and Japanese Patent Application No. 2018-073435).

The adhesive composition is composed of two compositions (hereinafter referred to as "partial initiator composition") in which the components constituting the peroxyester-based chemical polymerization initiator are kept in a state in which they cannot come into contact with each other chemically. When preparing the partial composition by dividing into (a) the thiourea compound and (d) the aryl borate compound as main components, the organic peroxide is substantially containing, as main components, the first partial composition that does not contain, the (b) peroxyester, the (c) divalent copper compound, and the (e) acidic group-containing polymerizable monomer, and a second partial composition substantially free of hydroperoxide are divided into a kit and mixed at the time of use, the storage stability of any of the partial compositions is enhanced. It is an excellent one that has the effect of being able to

However, as a result of further studies on the adhesive composition by the present inventors, it was found that although the adhesive composition exhibits high adhesive performance when used in the absence of water, ivory, which contains a large amount of water, is suitable for use as a dental cement. It has been found that the adhesive strength tends to be insufficient when applied to quality.

Accordingly, the present invention provides an adhesive composition obtained by blending a peroxyester-based chemical polymerization initiator with a polymerizable monomer containing an acidic monomer, while maintaining the polymerization activity in the absence of water. To improve the polymerization activity in the presence of water without impairing the excellent characteristics, specifically, (i) to be used for chemical polymerization in a system in which an acid component is present, and to be chemically polymerized in the state before use. High storage stability and high polymerization activity in the presence of water as well as in the absence of water in a chemical polymerization initiator in which each component constituting the initiator is separately blended in a partial initiator composition. (ii) an adhesive composition, an adhesive composition kit, a dental material and a dental material kit using the chemical polymerization initiator, and (iii) the adhesive composition An object of the present invention is to provide a storage method.

The above objects are achieved by the present invention described below. i.e.
The chemical polymerization initiator of the present invention includes (a) a thiourea compound, (b) a peroxyester, (c) an inorganic peroxide, (d) a divalent copper compound and (e) an arylborate compound , It is characterized in that the (a) thiourea compound is substantially free of hydroperoxide and is a compound represented by the following general formula (1) .

[In formula (1), R ¹ , R ² and R ³ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted a substituted heterocyclic group, a substituted or unsubstituted acyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkenyl group, and R ² is any one selected from R ¹ and R ³ It may combine with the group to form a ring. ]
In another embodiment of the chemical polymerization initiator of the present invention, (b) the peroxyester is preferably a peroxyester having a 10-hour half-life temperature of 80° C. or higher.

In another embodiment of the chemical polymerization initiator of the present invention, (c) the inorganic peroxide is preferably peroxodisulfate.

Another embodiment of the chemical polymerization initiator of the present invention is that (d) the divalent copper compound comprises a divalent copper atom and a ligand that coordinates to the divalent copper atom, wherein the ligand is selected from the group consisting of a halogen atom, an oxygen atom-containing atomic group, and a nitrogen atom-containing atomic group, and when the ligand is an oxygen atom-containing atomic group, the oxygen atom-containing atomic group is Coordinates to the divalent copper atom through an oxygen atom, and when the ligand is a group containing a nitrogen atom, the group containing a nitrogen atom coordinates to the divalent copper atom through a nitrogen atom. It is preferable that

The adhesive composition of the present invention comprises the chemical polymerization initiator of the present invention, (f) an acidic group-containing polymerizable monomer, and is substantially free of hydroperoxide .

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

The adhesive composition kit of the present invention comprises a combination of a first partial composition and a second partial composition that cannot physically contact the first partial composition. The entire combination of the partial composition and the second partial composition constitutes the adhesive composition of the present invention, and the first partial composition comprises the six components in the adhesive composition of the present invention : Among (a) to (f) , the second portion containing (a) the thiourea compound and (e) the aryl borate compound as main components and substantially free of organic peroxides The composition comprises, among the six components, the (b) peroxyester, the (c) inorganic peroxide, the (d) divalent copper compound, and the (f) acidic group-containing polymerizable It is characterized by containing a monomer as a main component and substantially free of hydroperoxide.

In one embodiment of the adhesive composition kit of the present invention, at least one composition selected from the first partial composition and the second partial composition contains (g) an acidic group-free polymerizable monomer It is preferable to further include

In another embodiment of the adhesive composition kit of the present invention, at least one composition selected from the first partial composition and the second partial composition preferably further contains (h) a filler. .

In another embodiment of the adhesive composition kit of the present invention, the first partial composition comprises (a) a thiourea compound, (e) an arylborate compound, and (g) an acidic group-free polymerizable monomer. and (h) a filler, the second part composition comprising (b) a peroxyester, (c) an inorganic peroxide, (d) a divalent copper compound, and (f) ) consisting only of an acidic group-containing polymerizable monomer, (g) an acidic group-free polymerizable monomer, and (h) a filler, (a) the thiourea compound consisting only of acetylthiourea, ( b) the peroxyester consists solely of t-butyl peroxy-3,5,5-trimethylhexanoate, (c) the inorganic peroxide consists solely of sodium peroxodisulfate, and (d) the divalent It is preferred that the copper compound consists exclusively of copper (II) acetate monohydrate and ( e ) the arylborate compound consists exclusively of the sodium salt of tetraphenylboron.

In another embodiment of the adhesive composition kit of the present invention, the first partial composition comprises (a) a thiourea compound, (e) an arylborate compound, and (g) an acidic group-free polymerizable monomer. and (h) a filler, the second part composition comprising (b) a peroxyester, (c) an inorganic peroxide, (d) a divalent copper compound, and (f) ) an acidic group-containing polymerizable monomer, (g) an acidic group-free polymerizable monomer, and (h) a filler, and (a) the thiourea compound consists only of benzoylthiourea, (b) the peroxy ester consists only of t-butyl peroxy-3,5,5-trimethylhexanoate, (c) the inorganic peroxide consists only of sodium peroxodisulfate, and (d) divalent It is preferred that the copper compound of consists exclusively of copper (II) acetate monohydrate and ( e ) the arylborate compound consists exclusively of the sodium salt of tetraphenylboron.

The dental material of the present invention is characterized by containing the adhesive composition of the present invention.

The dental material kit of the present invention is characterized by including the adhesive composition kit of the present invention.

The method for storing the adhesive composition of the present invention comprises storing the adhesive composition of the present invention in a state of being divided into a first partial composition and a second partial composition, and The composition comprises (a) a thiourea compound, (b) a peroxyester, (c) an inorganic peroxide, (d) a divalent copper compound, (e) an arylborate compound, and (f) Of the six components consisting of an acidic group-containing polymerizable monomer, containing (a) a thiourea compound and ( e ) an aryl borate compound as main components and substantially free of organic peroxides, The second part composition comprises, among the six components, (b) a peroxyester, (c) an inorganic peroxide, (d) a divalent copper compound, and (e) an acidic group-containing polymerizable unit. It is characterized in that it contains a polymer as a main component and does not substantially contain hydroperoxide.

According to the present invention, (i) it is used for chemical polymerization in a system in which an acid component is present, and each component constituting the chemical polymerization initiator is in a state in which it is not possible to chemically contact each other before use. A chemical polymerization initiator that is divided and blended into two or more partial initiator compositions maintained at a constant temperature, and has high storage stability and high polymerization activity regardless of the presence or absence or amount of water. A polymerization initiator, (ii) an adhesive composition, an adhesive composition kit, a dental material and a dental material kit using the chemical polymerization initiator, and (iii) a method for storing the adhesive composition are provided. can do.

I. Chemical polymerization initiator The chemical polymerization initiator of the present embodiment includes (a) thiourea compound, (b) peroxy ester, (c) inorganic peroxide , (d) divalent copper compound and (e) aryl borate It is characterized by containing a compound.

The chemical polymerization initiator of this embodiment is used for chemical polymerization in a system in which an acid component exists. In the state before the chemical polymerization initiator is used, each component constituting the chemical polymerization initiator is composed of a combination of two or more partial initiator compositions that are kept in a state in which they cannot chemically contact each other. be done. Also, at least one partial initiator composition selected from two or more partial initiator compositions is present in a mixed state with the acid component.

In the specification of the present application, the term “chemically inaccessible state” means (1) when one composition and another composition are in a “physically inaccessible state”, or (2) Even if one composition and another composition are in a state of physical contact, unidirectional or bidirectional molecular diffusion does not occur between one composition and another composition. means if A specific example of the latter (2) includes a state in which one composition and another composition are in contact with each other in a completely solidified state in the temperature environment when the chemical polymerization initiator is stored. .

In the present specification, the term “physically inaccessible state” means a state in which one composition and another composition are separated by an inhibitor that inhibits molecular diffusion between the two. do. As the inhibiting member, solid members such as resins, glass, metals, and ceramics, which are suitably used as materials for containers and bags, are generally used. A liquid or gas may be used as long as diffusion can be inhibited. A typical example of the "physically inaccessible state" is, for example, a state in which one type of composition is stored in a hermetically sealed container shielded from outside air and outside light.

In order to obtain a chemical polymerization initiator with high storage stability and high polymerization activity, the present inventors investigated a typical chemical blended in a curable composition containing an acid component disclosed in Patent Document 5. A polymerization initiator (a chemical polymerization initiator consisting of a combination of hydroperoxide, thiourea compound, copper compound and arylborate compound) was investigated. As a result, the present inventors found that (i) among a wide variety of organic peroxides, peroxyesters (when an acid component and an organic peroxide are allowed to coexist, gelation sometimes occurs, and storage Contrary to the empirical rule that it is difficult to increase stability,) it can coexist stably with an acidic monomer specifically, and (ii) in the chemical polymerization initiator disclosed in Patent Document 5, instead of hydroperoxide (iii) a peroxyester and a divalent copper compound; High curability and / or adhesiveness is obtained in the adhesive composition (curable composition) using a chemical polymerization initiator containing and (iv) a part of the peroxy ester is an inorganic peroxide It has been found that high curability and/or adhesion can be obtained even in the presence of water when the is replaced with

In addition, the present inventors found that in the chemical polymerization initiator of the present embodiment obtained by improving the chemical polymerization initiator described in Patent Document 5, the chemical polymerization initiator is used as two partial initiator compositions. It has been found that the storage stability of each partial initiator composition is enhanced when the combination of components constituting each partial initiator composition is specified. Here, in the chemical polymerization initiator of the present embodiment, the combination of partial initiator compositions that provide high storage stability is not particularly limited. However, when the chemical polymerization initiator of the present embodiment is composed of two or more partial initiator compositions, among the plurality of types of partial initiator compositions, the partial initiator composition containing at least a peroxyester (however, , limited to the partial initiator composition mixed with the acid component) is substantially free of hydroperoxide.

From a practical point of view, the chemical polymerization initiator of this embodiment is preferably composed of a combination of two partial initiator compositions. In this case, as a combination of two partial initiator compositions that can improve storage stability, a combination of a first partial initiator composition and a second partial initiator composition having the compositions shown below is particularly preferred. preferred.

<First partial initiator composition>
1. Components contained as main components (a) thiourea compound (e) aryl borate compound 2. Ingredients that are not substantially contained ・Organic peroxide <Second partial initiator composition>
1. Components contained as main components (b) Peroxyester (c) Inorganic peroxide (d) Divalent copper compound 2. Substantially not contained Hydroperoxide <Partial initiator composition mixed with acid component>
- A second partial initiator composition.

Here, when preparing an adhesive composition or an adhesive composition kit using the chemical polymerization initiator of the present embodiment, the first partial composition containing the first partial initiator composition and the second Constructed in combination with a second partial composition comprising a partial initiator composition.

In the specification of the present application, the term “main component” means that, when the total amount of a specific component contained in the entire combination of the two compositions is 100% by mass, It means that 98% by mass or more of the specific component is blended. For example, when one of the two compositions contains 98% by mass of a specific component, the specific component is the main component of the one composition. In this case, the other of the two compositions contains the remaining amount (2% by weight) of the specified ingredient. The specific component contained as a main component in one composition may be 98% by mass or more, preferably 99% by mass or more, more preferably 99.5% by mass or more, and even more preferably 99.9% by mass or more. , 100% by weight is most preferred.

Further, when the chemical polymerization initiator of the present embodiment is composed of a combination of two partial initiator compositions, furthermore, an adhesive composition and an adhesive composition kit using the chemical polymerization initiator of the present embodiment is composed of a combination of two part compositions, the terms "substantially free of organic peroxides" and "substantially free of peroxyesters" are used herein as described below. means

That is, in the first partial initiator composition and the first partial composition containing the same, "substantially free of organic peroxide" means that (a) the thiourea compound (i.e., the reducing agent) is (1) When no organic peroxide (oxidizing agent) is contained in the contained partial initiator composition (and the partial composition containing the partial initiator composition) (the content of the organic peroxide is 0 mass %), or (2) (1) When a trace amount of organic peroxide is contained within a range where no obvious significant difference in storage stability is observed when compared with the case where the organic peroxide is not contained , means Here, in the case shown in the above (2), the content of the organic peroxide is more than 0 and 1/100 or less in molar ratio with respect to the content of the thiourea compound (a) contained in the partial initiator composition. is preferably more than 0 and more preferably 1/500 or less.

In addition, in the second partial initiator composition and the second partial composition containing the same, "substantially free of hydroperoxide" means (b) a partial initiator composition containing at least a peroxy ester In the product (and the partial composition containing the partial initiator composition and the acid component), (1) no hydroperoxide is contained (hydroperoxide content is 0% by mass), or (2) (1) When a trace amount of hydroperoxide is contained in the chemical polymerization initiator to the extent that there is no obvious significant difference in storage stability and polymerization activity when compared to the case where hydroperoxide is not contained, means. Here, the minute amount of hydroperoxide in the above (2) cannot be categorically defined because it depends on the type and amount of the acidic monomer in the second partial composition. (b) Molar ratio of peroxyester (PE) and hydroperoxide (HP) contained in the initiator composition: expressed as HP/PE, usually in the range of more than 0 to about 2/100 or less, More preferably, it is in the range of more than 0 and about 1/300 or less.

Although the reason why the above-mentioned high polymerization activity is obtained in the chemical polymerization initiator of the present embodiment is not necessarily clear, the present inventors presume as follows. First, the present inventors found that when only a monovalent copper compound is used as the copper compound, (i) the chemical polymerization initiator and various components constituting the adhesive composition using the same are combined in any combination. (ii) a first partial composition comprising a first partial initiator composition and a second partial composition comprising a second partial initiator composition; It was confirmed that sufficient adhesiveness tends not to be obtained when mixing immediately after preparing each.

Based on this fact, the reason why the chemical polymerization initiator of the present embodiment exhibits high polymerization activity is presumed to be as follows. First, in the absence of water or in an environment where the amount of water present is extremely small, the first partial initiator composition (or first partial composition) and the second partial initiator composition (or second partial composition), first, the thiourea compound is coordinated with the divalent copper atoms constituting the divalent copper compound by contacting the divalent copper compound, and at the same time the divalent It reduces the copper atom to monovalent. Next, the copper complex obtained by this reduction reaction is brought into contact with the highly hydrophobic peroxyester to form a highly active complex (easily generating radicals). Then, the monovalent copper atom is oxidized to divalent again by a redox reaction accompanied by radical generation. In this way, the copper atoms that have been once reduced to monovalent are again oxidized to divalent and reused (catalytically without being deactivated or consumed) to form the active complex. It is presumed that the chemical polymerization initiator of the present embodiment exhibits high polymerization activity because the circulation process of Since peroxyesters are poorly hydrophilic, the above mechanism is less likely to work in an environment where there is a relatively large amount of water. It is presumed that by forming an active complex, high polymerization activity is exhibited even in the presence of water. That is, it is considered that the peroxyester mainly functions in the part with less water and the inorganic peroxide mainly functions in the part with more water, resulting in high activity regardless of the amount of water present. .

Further, the chemical polymerization initiator of this embodiment contains an arylborate compound. Therefore, in the adhesive composition (curable composition) or adhesive composition kit (curable composition kit) containing the chemical polymerization initiator of the present embodiment, the adhesive composition is caused by the aryl borate compound. Alternatively, the curability and/or adhesiveness of the adhesive composition kit can be further improved.

Further, when the present inventors have studied, compared with the chemical polymerization initiator disclosed in Patent Document 5 and the curable composition using the same, the chemical polymerization initiator of the present embodiment and the adhesiveness using the same It was confirmed that the composition or the adhesive composition kit also has excellent storage stability. In particular, the adhesive composition of the present embodiment is composed of a combination of a first partial composition containing the first partial initiator composition and a second partial composition containing the second partial initiator composition. The product or adhesive composition kit exhibits particularly high storage stability among various possible combinations when each component constituting the adhesive composition of the present embodiment is divided into two partial compositions. The chemical polymerization initiator of the present embodiment and the adhesive composition and the adhesive composition kit using the same have high storage stability. It seems that the reason is that peroxyester, which has the specificity of "", was used instead of hydroperoxide. It should be noted that inorganic peroxides are considered to be almost inert in systems in the absence of water. In addition, even if it contains water due to intentional addition or absorption of moisture from the atmosphere, storage stability is hardly affected unless there is a reducing agent in the surroundings. do not have. However, when a reducing agent such as a thiourea compound coexists in an aqueous system, it reacts slightly and may cause gelation.

Next, (a) a thiourea compound, (b) a peroxy ester, (c) an inorganic peroxide, (d) a divalent copper compound, and (e) an aryl borate used as the chemical polymerization initiator of the present embodiment In addition to the compounds, further components other than the components (a) to (e), which can be added as necessary, will be described in detail below.

<(a) thiourea compound>
A thiourea compound refers to a compound having the structure =NC(=S)-N=. Among them, a thiourea compound represented by the following general formula (1) is used .

Here, in general formula (1), R ¹ , R ² and R ³ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group , a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkenyl group, and R ² is selected from R ¹ and R ³ may be combined with any group to form a ring.

The substituted or unsubstituted alkyl group may be either a linear alkyl group or a branched alkyl group, but an alkyl group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is preferable. more preferred. Further, when a hydrogen atom constituting the alkyl group is substituted with a substituent, the substituent includes (a) a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, (b) a hydroxyl group, and (c) nitro group, (d) cyano group, (e) aryl group having 6 to 10 carbon atoms such as phenyl group, nitrophenyl group and chlorophenyl group, (f) 1 to 5 carbon atoms such as methoxy group, ethoxy group and propoxy group (g) an acyl group having 2 to 5 carbon atoms such as an acetyl group; (h) a tetrahydrofuran group; Also, the number and positions of the substituents are not particularly limited, but the number of the substituents is preferably three or less, more preferably one.

The substituted or unsubstituted cycloalkyl group has any ring structure selected from a monocyclic structure and a polycyclic structure in which 2 or 3 monocyclic rings are bonded, and has 3 to 14 carbon atoms. (However, the carbon atoms constituting the substituent are excluded from the number of carbon atoms). In addition, when the hydrogen atoms constituting the cycloalkyl group are substituted with substituents, the substituents include the groups (a) to (h) and (i ) alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group and butyl group. Also, the number and positions of the substituents are not particularly limited, but the number of the substituents is preferably three or less, more preferably one.

The substituted or unsubstituted aryl group has a ring structure selected from a monocyclic structure and a condensed polycyclic structure in which 2 or 3 monocyclic rings are condensed, and has 6 to 14 carbon atoms. (However, the carbon atoms constituting the substituent are excluded from the number of carbon atoms). When a hydrogen atom constituting the aryl group is substituted with a substituent, examples of the substituent include the groups (a) to (i) exemplified as the substituent of the cycloalkyl group. Also, the number and positions of the substituents are not particularly limited, but the number of the substituents is preferably three or less, more preferably one.

The substituted or unsubstituted heterocyclic group has any ring structure selected from a monocyclic structure and a condensed polycyclic structure in which two or three monocyclic rings are condensed, and the skeleton of the ring structure A heterocyclic group having 3 to 14 atoms constituting is preferable. When a hydrogen atom constituting the heterocyclic group is substituted with a substituent, examples of the substituent include the groups exemplified as the substituents (a) to (i) of the cycloalkyl group. Also, the number and positions of the substituents are not particularly limited, but the number of the substituents is preferably three or less, more preferably one.

Also, the substituted or unsubstituted acyl group preferably has 2 to 20 carbon atoms. When a hydrogen atom constituting the acyl group is substituted with a substituent, examples of the substituent include the substituents (a) to (i) exemplified for the cycloalkyl group.

As the substituted or unsubstituted aralkyl group, those having 7 to 20 carbon atoms are preferable (however, the carbon atoms constituting the substituent are excluded from the number of carbon atoms). When a hydrogen atom constituting the aralkyl group is substituted with a substituent, examples of the substituent include the substituents (a) to (i) exemplified for the cycloalkyl group.

Also, the substituted or unsubstituted alkenyl group preferably has 7 to 20 carbon atoms (the number of carbon atoms excludes the carbon atoms constituting the substituents). When a hydrogen atom constituting the alkenyl group is substituted with a substituent, examples of the substituent include the substituents (a) to (i) exemplified for the cycloalkyl group.

Examples of the ring formed by combining R ¹ and R ² include ethyleneimine, azacyclobutane, pyrrolidine, piperidine, hexamethyleneimine and the like. Examples of the ring formed by combining R ¹ and R ³ include ethylenethiourea, propylenethiourea, and butylenethiourea.

Among the thiourea compounds represented by the general formula (1), from the viewpoint of storage stability, at least two groups among R ¹ , R ² and R ³ are hydrogen atoms, and the remaining one group is a substituent. Preferably. For example, thiourea compounds in which R ² and R ³ are hydrogen atoms and R ¹ is an acyl group are most preferred.

Preferred thiourea compounds include thiourea, methylthiourea, ethylthiourea, n-propylthiourea, isopropylthiourea, cyclohexylthiourea, benzylthiourea, phenylthiourea, acetylthiourea, benzoylthiourea, adamantylthiourea, 1 -(2-pyridyl)-2-thiourea, 1-(2-tetrahydrofurfuryl)-2-thiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di- n-propylthiourea, N,N'-di-isopropylthiourea, N,N'-dicyclohexylthiourea, N,N'-diphenylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tri Isopropylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetraisopropylthiourea, tetracyclohexylthiourea, ethylenethiourea, 4,4'-dimethylethylenethiourea, etc. can be done. Specific examples of most suitable thiourea compounds include acetylthiourea or benzoylthiourea.

Moreover, a thiourea compound may use only one type, and may use it in combination of 2 or more types. When two or more thiourea compounds are used, the reference mass is the total mass of those thiourea compounds.

In the chemical polymerization initiator of the present embodiment, the amount of the (a) thiourea compound is not particularly limited, but (b) per 100 parts by mass of the peroxyester, 4 parts by mass to 4800 parts by mass. preferably. By satisfying this range, high polymerization activity and high storage stability can be exhibited. In order to exhibit higher polymerization activity and higher storage stability, it is more preferably 13 parts by mass to 875 parts by mass, more preferably 27 parts by mass to 600 parts by mass, per 100 parts by mass of the peroxyester. is more preferred.

<(b) Peroxyester>
(b) Peroxyester means R—C(=O)—O—O—R′ (wherein R and R′ are arbitrary organic groups) or R—O—C(=O)—O—O It is a compound having a structure represented by -R' (R and R' are arbitrary organic groups). In the chemical polymerization initiator of the present embodiment, peroxyesters having such structures can be used without particular limitation. Specific examples of peroxyesters that can be preferably used include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxydecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5 -dimethyl 2,5-di(2-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate, t -hexylperoxybenzoate, 2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, t-butylperoxy-3-methylbenzoate, t-butylperoxybenzoate and the like. Among these, from the viewpoint of polymerization activity and storage stability, peroxy esters having a 10-hour half-life temperature of 80° C. or higher are preferably used. t-Butyl peroxylaurate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxy acetate, t-butyl peroxy benzoate and the like are particularly preferably used.

The (b) peroxyester may be used alone or in combination of two or more. When two or more (b) peroxyesters are used, the reference mass is the total mass of the (b) peroxyesters.

<(c) inorganic peroxide>
(c) Inorganic peroxides include known inorganic peroxides such as lithium peroxide, potassium peroxide, magnesium peroxide, calcium peroxide, barium peroxide, zinc peroxide, peroxodisulfate, and peroxodiphosphate. Oxides can be used without particular restrictions. From the viewpoint of polymerization activity, peroxodisulfates such as sodium peroxodisulfate, potassium peroxodisulfate and ammonium peroxodisulfate are preferably used, and potassium peroxodisulfate and sodium peroxodisulfate are particularly preferred. preferable.
In the chemical polymerization initiator of the present invention, the compounding amount of the inorganic peroxide (c) can exhibit high polymerization activity and high adhesive strength. 7 to 20,000 parts by mass, preferably 17 to 3,300 parts by mass, most preferably 55 to 1,300 parts by mass.

<(d) divalent copper compound>
In the chemical polymerization initiator of this embodiment, a divalent copper compound is used as the copper compound. In addition, in the chemical polymerization initiator of the present embodiment, a monovalent copper compound can be used together with the divalent copper compound. It is preferable that the copper compound containing a valence is contained in such a small amount that it does not affect the storage stability, or that it is not substantially contained. In this case, it is particularly preferred that the second partial initiator composition contains substantially no monovalent copper compound. When a monovalent copper compound is contained in the second partial initiator composition, the monovalent copper compound may act as a reducing agent for the peroxyester, degrading the storage stability.

(d) The divalent copper compound may be either a hydrate or an anhydride. Examples of divalent copper compounds that can be preferably used include copper(II) chloride, copper(II) sulfate pentahydrate, copper(II) nitrate, copper(II) trifluoromethanesulfate, copper(II) acetate. hydrate, copper(II) acetylacetone, copper(II) naphthenate, copper(II) salicylate, copper(II) benzoate, copper(II) methacrylate, copper(II) butyl phthalate, copper(II) gluconate ), dichloro(1,10-phenanthroline) copper (II), copper (II) ethylenediaminetetraacetate disodium tetrahydrate, copper (II) dimethyldithiocarbamate, copper (II) diethylthiocarbamate, hexafluoroacetylaceto natocopper(II), bis(1,3-propanediamine)copper(II) dichloride, bis(8-quinolinolato)copper(II), and the like. These divalent copper compounds may be used alone or in combination of two or more.

Among these divalent copper compounds, due to the high storage stability and the high activity with the (b) thiourea compound, the coordination that coordinates to the divalent copper atoms that constitute the divalent copper compound It is preferred that the child is (i) a halogen atom, (ii) a group containing an oxygen atom, or (iii) a group containing a nitrogen atom. In particular, the ligand (ii) is more preferably an atomic group containing an oxygen atom. Examples of the divalent copper compound having such a ligand include copper (II) sulfate, copper acetate (II) Monohydrate, acetylacetonate copper (II). In addition, (ii) when the ligand is an atomic group containing an oxygen atom, the atomic group containing an oxygen atom is coordinated to the divalent copper atom via the oxygen atom, and (iii) the ligand is a nitrogen atom-containing atomic group, the nitrogen atom-containing atomic group is coordinated to the divalent copper atom via the nitrogen atom.

In the chemical polymerization initiator of the present embodiment, the compounding amount of the ( d ) divalent copper compound (the total compounding amount when two or more compounds are included) is not particularly limited, but (b) It is preferably 0.002 to 250 parts by mass per 100 parts by mass of peroxyester. By satisfying this range, high polymerization activity and high storage stability can be exhibited. In order to exhibit higher polymerization activity and higher storage stability, per 100 parts by weight of peroxyester, it is more preferably 0.008 to 20 parts by weight, and 0.03 to 8 parts by weight. Part by mass is more preferable.

<(e) Aryl borate compound>
The arylborate compound is not particularly limited as long as it is a compound having at least one boron-aryl bond in the molecule, but it is preferable to use a compound represented by the following general formula (2).

In general formula (2), R ¹⁰ , R ²⁰ and R ³⁰ are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted an alkenyl group, R ⁴⁰ and R ⁵⁰ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group, and L ⁺ is a metal cation , quaternary ammonium ion, quaternary pyridinium ion, quaternary quinolinium ion, or phosphonium ion.

In the general formula (2), the substituted or unsubstituted alkyl group selected as R ¹⁰ , R ²⁰ and R ³⁰ may be either a straight-chain alkyl group or a branched alkyl group, and has 3 to 30 carbon atoms. , and particularly preferably a straight-chain alkyl group having 4 to 20 carbon atoms. Further, when a hydrogen atom constituting the alkyl group is substituted with a substituent, the substituent includes (a) a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, (b) a hydroxyl group, and (c) nitro group, (d) cyano group, (e) aryl group having 6 to 10 carbon atoms such as phenyl group, nitrophenyl group and chlorophenyl group, (f) 1 to 5 carbon atoms such as methoxy group, ethoxy group and propoxy group and (g) an acyl group having 2 to 5 carbon atoms such as an acetyl group. Also, the number and positions of the substituents are not particularly limited, but the number of the substituents is preferably three or less, more preferably one.

The substituted or unsubstituted aryl group selected as R ¹⁰ , R ²⁰ and R ³⁰ is any ring structure selected from a monocyclic structure and a condensed polycyclic structure in which 2 or 3 monocyclic rings are condensed. and having 6 to 14 carbon atoms (the number of carbon atoms excludes the carbon atoms constituting the substituents). When a hydrogen atom constituting the aryl group is substituted with a substituent, the substituent includes the groups (a) to (g) exemplified as the substituent of the alkyl group, and (h) a methyl group. , ethyl group, butyl group and other alkyl groups having 1 to 5 carbon atoms are exemplified. Also, the number and positions of the substituents are not particularly limited, but the number of the substituents is preferably three or less, more preferably one.

The substituted or unsubstituted aralkyl group selected as R ¹⁰ , R ²⁰ and R ³⁰ includes an aralkyl group having 7 to 20 carbon atoms (however, the number of carbon atoms excludes the carbon atoms constituting the substituents). is preferred. When a hydrogen atom constituting the aralkyl group is substituted with a substituent, examples of the substituent include the groups (a) to (h) exemplified as the substituent of the aryl group.

The substituted or unsubstituted alkenyl group selected as R ¹⁰ , R ²⁰ and R ³⁰ is preferably an alkenyl group having 4 to 20 carbon atoms (however, the number of carbon atoms excludes the carbon atoms constituting the substituents). . When a hydrogen atom constituting the alkenyl group is substituted with a substituent, examples of the substituent include the groups (a) to (g) exemplified as the substituent of the alkyl group.

In the general formula (2), the substituted or unsubstituted alkyl group selected as R ⁴⁰ and R ⁵⁰ includes a Alkyl groups are preferred. When a hydrogen atom constituting the alkyl group is substituted with a substituent, the substituent includes the groups exemplified as the substituents of the alkyl group represented by R ¹ to R ³ in the general formula (1) ( a) to (h).

Further, when a hydrogen atom constituting a substituted or unsubstituted phenyl group selected as R ⁴⁰ and R ⁵⁰ is substituted by a substituent, the substituent is selected as R ¹⁰ , R ²⁰ and R ³⁰ Groups (a) to (h) exemplified as substituents of the aryl group can be mentioned.

Further, L ⁺ in the general formula (2) includes a metal cation, a quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a phosphonium ion. Here, (i) metal cations are preferably (ia) alkali metal cations such as sodium ions, lithium ions and potassium ions, or (ib) alkaline earth metal cations such as magnesium ions. (ii) quaternary ammonium ions such as tetrabutylammonium ion, tetramethylammonium ion and tetraethylammonium ion are suitable; (iii) quaternary pyridinium ions such as methylpyridinium ion and ethylpyridinium ion (iv) the quaternary quinolinium ion is preferably methylquinolinium ion, ethylquinolinium ion, butylquinolinium ion, or the like; (v) the phosphonium ion is preferably tetra Quaternary phosphonium ions such as butylphosphonium ion and methyltriphenylphosphonium ion are preferred.

Suitable examples of the arylborate compound represented by the general formula (2) include sodium salt, lithium salt, potassium salt, triethanolammonium salt, tetrabutylammonium salt and the like of tetraphenylborate.

In the chemical polymerization initiator of the present embodiment, the amount of the (e) aryl borate compound is not particularly limited, but (b) per 100 parts by mass of the peroxyester, 10 parts by mass to 2000 parts by mass, In particular, it is preferably 30 parts by mass to 1000 parts by mass. By setting the compounding amount within such a range, high curability and/or adhesiveness can be obtained when the chemical polymerization initiator of the present embodiment is used in an adhesive composition or an adhesive composition kit. .

<Other polymerization accelerators>
In the chemical polymerization initiator of the present embodiment, in addition to the five components shown in (a) to (e) described above, other optional components may be used in combination as necessary. Such optional components include aromatic sulfinic acid compounds and barbituric acid compounds as polymerization accelerators other than the components (a) and (e). These polymerization accelerators may be used alone or in combination of two or more.

In the chemical polymerization initiator of the present embodiment, the total amount of the other polymerization accelerators, that is, the aromatic sulfinic acid compound and/or the barbituric acid compound is not particularly limited, but (b) per It is preferably 10 to 2,000 parts by mass, more preferably 30 to 1,000 parts by mass, per 100 parts by mass of the oxyester.

Aromatic sulfinic acid compound Examples of aromatic sulfinic acid compounds that can be suitably used include sodium p-toluenesulfinate, sodium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, and 2,6-dimethyl. Benzenesulfinic acid, 2,6-diisopropylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, sodium salt of 2,4,6-triisopropylbenzenesulfinic acid, triethanolammonium salt, tetraethylammonium salt and the like. be able to. Among these aromatic sulfinates, benzenesulfinate and p-toluenesulfinate are preferred because of their high reactivity and high solubility in polymerizable monomers.

- Barbituric acid compounds Suitable examples of barbituric acid compounds include 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, and Sodium salts and calcium salts of these barbiturates can be mentioned.

II. Adhesive Composition and Dental Material The chemical polymerization initiator of the present embodiment is usually used by blending it with a reactive composition containing an acid component, which is used for various purposes. In this case, components other than the chemical polymerization initiator (non-chemical polymerization initiator components) in the reactive composition are appropriately selected depending on the use of the reactive composition. The acid component may exist in the form of an acid anhydride or the like.

As a reactive composition containing the chemical polymerization initiator of the present embodiment, an adhesive composition containing the chemical polymerization initiator of the present embodiment and (f) an acidic group-containing polymerizable monomer (acidic monomer) is particularly preferred. The adhesive composition of the present embodiment usually contains (f) an acidic group-containing polymerizable monomer and (g) an acidic group-free polymerizable monomer as a polymerizable monomer component. (Non-acidic monomer) is preferably included. In this case, (g) the polymerizable monomer not containing an acidic group may be contained in at least one of the first partial composition and the second partial composition, but at least the first partial composition It is preferably contained, and may be contained in both the first partial composition and the second partial composition.

The adhesive composition of the present embodiment can be suitably used as a dental material, and among dental materials, it can be particularly suitably used as a dental cement or a dental adhesive. The adhesive composition of the present embodiment may further contain (h) a filler or the like, if necessary. (h) The filler may be contained in at least one of the first partial composition and the second partial composition. The amount of each component blended in the adhesive composition of the present embodiment can be appropriately selected according to the application of the adhesive composition.

The adhesive composition of the present embodiment is composed of two or more parts in which each component constituting the adhesive composition is kept in a state of being chemically incapable of contact with each other before the adhesive composition is used. It consists of a combination of compositions. When using an adhesive composition, all kinds of partial compositions constituting the adhesive composition are mixed. In the adhesive composition of the present embodiment, excellent storage stability can be ensured by appropriately selecting the types of components to be blended in each partial composition. However, when the adhesive composition of the present embodiment is composed of two or more partial compositions, from the viewpoint of storage stability, among the plurality of types of partial compositions, (b) peroxyester and (f ) It is preferred that the partial composition containing at least the acidic group-containing polymerizable monomer substantially does not contain hydroperoxide. Moreover, since the adhesive composition of the present embodiment contains the chemical polymerization initiator of the present embodiment having high polymerization activity, it has excellent curability and/or adhesiveness.

The adhesive composition of the present embodiment may be composed of a combination of two or more partial compositions, but practically it is preferably composed of a combination of two partial compositions. be. Therefore, in the following description, it is assumed that the adhesive composition of this embodiment is composed of a combination of two partial compositions.

In this case, in the adhesive composition of the present embodiment, the combination of partial compositions that provide high storage stability is not particularly limited, but for example, a first partial composition having the composition shown below A combination of a product and a second part composition is particularly preferred.

<First partial composition>
1. Components contained as main components (a) thiourea compound (e) aryl borate compound 2. Ingredients that are not substantially contained ・Organic peroxide <Second partial composition>
1. Components contained as main components (b) Peroxyester (c) Inorganic peroxide (d) Divalent copper compound (f) Acidic group-containing polymerizable monomer 2. Ingredients that are practically not included Hydroperoxide.

The (f) acidic group-containing polymerizable monomer used in the adhesive composition of the present embodiment, which is composed of a combination of the first partial composition and the second partial composition, is the second partial composition Since it is blended as a main component in the product, it is substantially not contained in the first partial composition. From the viewpoint of storage stability, the second partial composition more preferably does not substantially contain organic peroxides other than (b) peroxyester and hydroperoxide.

In the specification of the present application, "substantially free of organic peroxides other than peroxyesters and hydroperoxides" means that (1) peroxyesters and hydroperoxides in the second partial composition If it does not contain an organic peroxide other than (hereinafter abbreviated as "organic peroxide" or "OP" only in this paragraph) (the content of organic peroxide is 0% by mass), or (2) ( 1) When a trace amount of organic peroxide is contained in the chemical polymerization initiator within a range where no significant difference is clearly observed in terms of storage stability and polymerization activity when compared with the case where the organic peroxide is not contained, means Here, in the case shown in the above (2), the content of the organic peroxide (OP) (two or more types of In the case of organic peroxides, the total content) is preferably more than 0 and 2/100 or less, more preferably more than 0 and 1/300 or less in terms of molar ratio OP/PE. From a similar point of view, when the second partial composition contains trace amounts of both hydroperoxide (HP) and organic peroxide (OP), (b) peroxy ester ( The total content of hydroperoxide (HP) and organic peroxide (OP) relative to the content of PE) is preferably more than 0 and 2/100 or less at a molar ratio of (HP + OP) / PE. , more preferably greater than 0 and less than or equal to 1/300.

Further, when the adhesive composition of the present embodiment further contains (g) an acidic group-free polymerizable monomer and (h) a filler, these components are added to the first partial composition and the second It may be blended in either one of the partial compositions or may be blended in both.

The compounding amount of the chemical polymerization initiator of the present embodiment contained in the adhesive composition of the present embodiment may be an effective amount that allows polymerization to proceed appropriately. However, usually, <I> 0.05 parts by mass to 2.5 parts by mass of (a) a thiourea compound with respect to 100 parts by mass of the polymerizable monomer component contained in the adhesive composition of the present embodiment The (b) peroxyester is 0.005 parts by mass to 5 parts by mass, (c) the inorganic peroxide is 0.5 parts by mass to 20 parts by mass, and (d) the divalent copper compound is 0.00005 parts by mass to 0.05 parts by mass, and (e) the aryl borate compound is 0.05 parts by mass to 6.5 parts by mass.

Further, when the adhesive composition of the present embodiment is used as a dental material (in particular, dental cement), the following compounding composition is suitable. That is, <II> it is preferable that (a) the thiourea compound is 0.15 parts by mass to 2 parts by mass with respect to 100 parts by mass of the polymerizable monomer component contained in the adhesive composition of the present embodiment. , (b) preferably 0.05 to 2.5 parts by mass of peroxyester, (c) 1.0 to 10 parts by mass of inorganic peroxide, and (d) divalent copper The compound is preferably 0.00025 parts by mass to 0.0025 parts by mass, and (e) the aryl borate compound is preferably 0.25 parts by mass to 2.5 parts by mass. By adopting such a compounding amount, it becomes easier to secure the curability of the cured dental material and to secure the adhesive strength and the mechanical strength of the cured dental material.

However, in any of the formulations shown in <I> and <II> above, the blending ratio of each component of the chemical polymerization initiator of the present embodiment contained in the adhesive composition of the present embodiment is (b ) With respect to 100 parts by mass of the peroxyester, (a) the thiourea compound is in the range of 4 parts by mass to 4800 parts by mass, (c) the inorganic peroxide is 0.01 parts by mass to 10 parts by mass, (d ) the divalent copper compound in the range of 0.002 parts by mass to 250 parts by mass, and (e) the aryl borate compound in the range of 10 parts by mass to 2000 parts by mass.

The polymerizable monomer component used in the adhesive composition of this embodiment will be described below.
<(f) Acidic group-containing polymerizable monomer (acidic monomer)>
As the acidic monomer, a known polymerizable monomer having at least one acidic group and at least one radically polymerizable unsaturated group can be used. Here _, the acidic group means that an aqueous solution or aqueous suspension of a radically polymerizable monomer having this group exhibits acidity. H), a phosphinico group {=P(=O)OH}, a phosphono group {-P(=O)(OH) ₂ } and the like having a hydroxyl group. In addition to such a hydroxyl group-containing acidic group, an acid anhydride group having a structure in which two hydroxyl-containing acidic groups are dehydrated and condensed, an acid halide group in which the hydroxyl group of a hydroxyl group-containing acidic group is substituted with a halogen, etc. can be mentioned. Also, the radically polymerizable unsaturated group is not particularly limited, and may be a known one. Examples include (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamino group, (meth)acryloylthio group and other (meth)acryloyl groups, vinyl group, allyl group, styryl group, and the like. .

As the acidic monomer, a (meth)acrylic acid ester-based acidic group-containing polymerizable monomer is preferably used from the viewpoint of polymerizability. This (meth)acrylic acid ester-based acidic group-containing polymerizable monomer is particularly suitable for use in dental materials from the viewpoint of safety to the living body. Only one type of acidic monomer may be used, or two or more types may be used in combination.

Suitable acidic monomers include 2-(meth)acryloyloxyethyl dihydrogenphosphate, bis[2-(meth)acryloyloxyethyl]hydrogenphosphate, 2-(meth)acryloyloxyethylphenylhydrogenphosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 6-(meth) acryloyloxyhexylphenyl hydrogen phosphate, 10-(meth) acryloyloxydecyl dihydrogen phosphate, 1,3-di(meth) acryloylpropane- 2-dihydrogen phosphate, 1,3-di(meth)acryloylpropane-2-phenyl hydrogen phosphate, bis[5-{2-(meth)acryloyloxyethoxycarbonyl}heptyl] hydrogen phosphate and the like. can.

<(g) Acidic group-free polymerizable monomer (non-acidic monomer)>
The non-acidic monomer is not particularly limited as long as it has at least one radically polymerizable unsaturated group in the molecule and does not have an acidic group. From the viewpoint of polymerizability and safety to living bodies, (meth)acrylic acid ester-based polymerizable monomers containing no acidic groups are preferably used. Only one type of non-acidic monomer may be used, or two or more types may be used in combination. Suitable non-acidic monomers include methyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 2,2-bis[4-( 3-methacryloyloxy)-2-hydroxypropoxyphenyl]propane, 2,2-bis(methacryloyloxypolyethoxyphenyl)propane, 2-hydroxyethyl methacrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl ) dimethacrylate, 1,10-decanediol di(meth)acrylate and the like.

As in the case where the adhesive composition of the present embodiment is used as a dental material, the cured adhesive composition may be required to have higher mechanical strength. In this case, as the non-acidic monomer, it is preferable to use a di-, tri- or tetra-functional radically polymerizable monomer having a plurality of radically polymerizable groups.

The blending ratio of (f) acidic monomer and (g) non-acidic monomer in the polymerizable monomer component of the adhesive composition of the present embodiment is not particularly limited. is the same as in conventional dental materials containing acidic monomers. General blending ratios for use as dental cements and dental adhesives are as follows, and these also apply to the adhesive composition of the present embodiment.

That is, when the adhesive composition of this embodiment is used as a dental cement, it generally contains (h) a filler as described above. The composition of the polymerizable monomer component contained in this dental cement is usually 0.1% by mass or more and 50% by mass or less of the (f) acidic monomer based on the total mass of the polymerizable monomer component. The remainder is (g) non-acidic monomer, preferably 1% by mass or more and 30% by mass or less is (f) acidic monomer, and the remainder is (g) non-acidic monomer. A dental cement that employs such a composition of polymerizable monomer components is expected to have stronger adhesiveness to tooth structure and to further improve adhesion durability to tooth structure and prostheses made of various materials. can be done.

Next, compounding agents that can be suitably compounded in the adhesive composition of the present embodiment will be described.
<(h) Filler>
As fillers that can be used in the adhesive composition of the present embodiment, inorganic fillers, organic fillers, organic-inorganic composite fillers and the like used in conventional dental materials can be used without particular limitation. From the viewpoint of the mechanical strength of the cured body, it is preferable to use an inorganic filler or an organic-inorganic composite filler. Only one type of filler may be used, or two or more types may be used in combination.

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

(g) The total blending amount of the filler may be appropriately determined according to the intended use. Above all, when it is used for dental materials, particularly dental cement, it is preferable to blend 65 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer component contained in the dental cement. From the viewpoint of kneadability and mechanical strength of the cured product, it is more preferable to use 150 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer component contained in the dental cement.

Various fillers are described below.
Inorganic filler In the adhesive composition of the present embodiment, examples of inorganic fillers that are particularly preferably used include various types of silica; silica-titania, silica-composite oxides containing silicon such as zirconia as a constituent element; Clay minerals or silicates containing silicon as a constituent element such as talc, montmorillonite, zeolite, calcium silicate (hereinafter referred to as silica-based fillers); ytterbium fluoride, yttrium fluoride, silicate glass, fluoroalumino silicate glass, lanthanum glass, barium glass, strontium glass, etc.; These inorganic fillers are used after being surface-treated with a surface treatment agent such as a silane coupling agent in order to improve compatibility with the polymerizable monomer and improve the mechanical strength and water resistance of the resulting cured product. Sometimes it is done. The silica-based filler has excellent chemical stability and can be easily surface-treated with a silane coupling agent or the like.

・Organic filler Organic fillers that can be suitably used include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, and ethylene. -vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer and the like.

・Organic-inorganic composite filler The organic-inorganic composite filler is an organic-inorganic composite filler obtained by combining a polymerizable monomer that can be used as (e) an acidic monomer or (f) a non-acidic monomer with an inorganic filler. material can be preferably used. The method of forming the composite is not particularly limited, and the composite may be solid or have pores. From the viewpoint of the mechanical strength of the cured product, the surface of the inorganic aggregated particles is coated with an organic polymer, and an organic-inorganic composite filling having pores, as described in the pamphlet of International Publication No. 2013/039169. It is preferable to use wood.

III. Adhesive Composition Kit, Dental Material Kit, and Adhesive Composition Storage Method The adhesive composition kit (or dental material kit) of the present embodiment contains the adhesive composition (or dental material) of the present embodiment. In order to facilitate handling of the adhesive composition (or dental material) of the present embodiment, the first partial composition and the first partial composition in a state where physical contact is impossible The main feature is that it is limited to combination with two part compositions. In other respects, the adhesive composition kit (or dental material kit) of this embodiment can be the same as the adhesive composition (or dental material) of this embodiment. The adhesive composition kit and dental material kit of the present embodiment and the method for storing the adhesive composition of the present embodiment are described in more detail below.

The adhesive composition kit of the present embodiment comprises a combination of a first partial composition and a second partial composition that cannot physically contact the first partial composition. and the second partial composition are composed of (a) a thiourea compound, (b) a peroxyester, (c) an inorganic peroxide, and (d) a divalent It contains at least six components consisting of a copper compound, (e) an aryl borate compound, and (f) an acidic group-containing polymerizable monomer.

Here, the first partial composition (hereinafter sometimes referred to as "first agent") contains (a) a thiourea compound and (e) an arylborate compound as main components among the above six components. and substantially free of organic peroxides. In addition, the second partial composition (hereinafter sometimes referred to as "second agent") is composed of (b) peroxyester, (c) inorganic peroxide, and (d ) a divalent copper compound and (f) an acidic group-containing polymerizable monomer as main components, and substantially free of hydroperoxide.

The first partial composition contains only (a) a thiourea compound and (e) an arylborate compound among the above six components , and the second partial composition contains , (b) a peroxyester, (c) an inorganic peroxide, (d) a divalent copper compound, and (f) an acidic group-containing polymerizable monomer.

The adhesive composition kit of the present embodiment can be suitably used as a dental material kit, and among dental material kits, it can be particularly suitably used as a dental cement kit or a dental adhesive kit.

Further, in the adhesive composition kit of the present embodiment, for example, the first partial composition and the second partial composition are substantially composed only of the components listed in Composition Examples A, B, or C below. More preferably, it is composed only of the components listed in Composition Examples A, B, or C below. An adhesive composition kit consisting essentially of only the components listed in Composition Examples A, B or C below, or an adhesive composition kit consisting only of the components listed in Composition Examples A, B or C below is particularly suitable as a dental cement kit.

<<Composition example A>>
<First partial composition>
(a) Thiourea compound (e) Arylborate compound (g) Acidic group-free polymerizable monomer (h) Filler <Second partial composition>
(b) Peroxyester (c) Inorganic peroxide (d) Divalent copper compound (f) Acid group-polymerizable monomer (g) Acid group-free polymerizable monomer (h) Filler.

<<Composition example B>>
<First partial composition>
(a) Acetylthiourea as a thiourea compound (e) Sodium salt of tetraphenylboron as an arylborate compound (g) Polymerizable monomer containing no acidic group (h) Filler <Second partial composition>
(b) t-butyl peroxy-3,5,5-trimethylhexanoate as a peroxyester (c) sodium peroxodisulfate as an inorganic peroxide (d) copper (II) acetate as a divalent copper compound hydrate (f) acidic group polymerizable monomer (g) acidic group-free polymerizable monomer (h) filler.

<<Composition example C>>
<First partial composition>
(a) Benzoylthiourea as a thiourea compound (e) Sodium salt of tetraphenylboron as an arylborate compound (g) Polymerizable monomer containing no acidic group (h) Filler <Second partial composition>
(b) t-butyl peroxy-3,5,5-trimethylhexanoate as a peroxyester (c) sodium peroxodisulfate as an inorganic peroxide (d) copper (II) acetate as a divalent copper compound hydrate (f) acidic group polymerizable monomer (g) acidic group-free polymerizable monomer (h) filler.

In the adhesive composition kit of the present embodiment, when the first partial composition and the second partial composition are in a state before use (during storage), physical contact with each other is particularly difficult. Although not limited, from a practical point of view such as handleability, each of the first partial composition and the second partial composition is placed (packaged) in various containers such as syringes, bags, and bottles. preferably stored. In other words, the adhesive composition of the present embodiment is preferably stored in a state in which it is divided into the first partial composition and the second partial composition. Then, at the time of use, the first partial composition and the second partial composition are mixed. Of course, the adhesive composition kit of the present embodiment can be distributed as a product in the market before use (at the time of storage).

When the chemical polymerization initiator of the present embodiment contained in the adhesive composition or the adhesive composition kit of the present embodiment contains an aromatic sulfinic acid compound and/or a barbituric acid compound, these compounds are first It is preferably blended with the agent. In addition, when the adhesive composition or adhesive composition kit of the present embodiment contains (h) a filler, these components may be blended in either the first agent or the second agent, but both are mixed. It is preferable to mix both because it is easy to blend in and uniformity can be achieved easily.

The composition of each of the first partial composition (first agent) and the second partial composition (second agent) is basically the same when both are mixed in equal amounts {first agent and second agent Mixing ratio (amount of first agent / amount of second agent): 1/1, or mixing ratio of first agent and second agent (100 × amount of first agent / amount of second agent): When mixed at 100%], the composition of the adhesive composition or adhesive composition kit of the present embodiment is determined. Here, "equivalent amount" usually means an equivalent amount on a mass basis, but may be an equivalent amount on a volume basis when the composition is liquid. At this time, the distribution ratios of (g) non-acidic monomer and (h) filler, which can be appropriately blended with the first agent and/or the second agent as necessary, should be set so as to satisfy the above conditions. is preferred.

However, depending on the specific composition of the adhesive composition or adhesive composition kit of the present embodiment, the mixing ratio may not be 1/1. In this case, the adhesive composition or adhesive composition kit of the present embodiment having a desired composition when mixed at a mixing ratio other than 1/1 (hereinafter also referred to as a “designated mixing ratio”) can be obtained. It is preferable to In addition, it is necessary to make the first and second agents uniform compositions in consideration of the solubility of each component, or to make the properties (paste viscosity, etc.) of the first and second agents easy to handle. Even if there is, it is also preferable to obtain the adhesive composition or adhesive composition kit of the present embodiment having the desired composition when mixed at the specified mixing ratio.

The specified mixing ratio (this value expressed in % is also referred to as "specified mixing ratio") may be appropriately determined within a range that does not significantly impair the polymerization activity and operability. However, from a practical point of view such as ease of handling and product packaging, the specified mixing ratio (ratio) is 1/5 of the mass-based (or volume-based) mixing ratio (first agent/second agent). It is preferable to be within the range of ~ 5/1 (mixing ratio: 20% to 500%), and it is preferable to be within the range of 1/3 to 3/1 (mixing ratio: 33% to 300%). more preferred.

The specified mixing ratio (ratio) can be displayed on the mixing ratio (ratio) information display medium. The mixing ratio (ratio) information display medium includes, for example, i) a product package made of a paper box or the like, ii) a product instruction manual provided as a paper medium and/or electronic data, iii) a first agent and a second agent Containers (bottles, syringes, packaging bags, etc.) that store each agent in a sealed state, iv) Product catalogs provided as paper media and/or electronic data, v) Product use by e-mail, postal mail, etc. separately from the product You can use the correspondence sent to the person. In addition, the specified mixing ratio may be provided to the product user in a form other than those shown in i) to v) above so that the product user can perceive it.

In the adhesive composition and adhesive composition kit of the present embodiment, the first agent and the second agent can be easily prepared by weighing and mixing each component. In the adhesive composition kit of the present embodiment, each prepared partial composition (agent) is stored (preserved) in a container such as a bottle, tube, or syringe. Then, by taking out and mixing the necessary amount of these compositions immediately before use, a mixed composition in which all the components constituting the adhesive composition (or adhesive composition kit) of the present embodiment are mixed is manufactured. can be done. The mixing method for producing the mixed composition is not particularly limited, i) a method of applying appropriate amounts of the first agent and the second agent on kneading paper and kneading them with a spatula, ii) the first agent and when the second agent is a paste, a method of simultaneously extruding the first agent and the second agent from a syringe having a mixing tip connected to the tip, iii) when the first agent and the second agent are liquid , a method of collecting the first agent and the second agent in the same mixing dish, or the like can be adopted.

The mixed composition obtained by mixing in this way contains all types of chemical polymerization initiator components and polymerizable monomer components, so that it polymerizes and cures quickly or with a preset operation margin time. . And thereby, a hardening body can be obtained. A known method can be employed as a method for polymerizing and curing the mixed composition. For example, the mixed composition may be applied to the area where curing is required and allowed to stand. In this case, the applied mixed composition can be sufficiently cured by maintaining it in the temperature range of 10 to 37°C.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited only to the following examples.

1. Abbreviations of Substances Used First, abbreviations of substances used in chemical polymerization initiators and compositions containing the same in Examples and Comparative Examples are described below.

<(a) thiourea compound>
AcTU; acetylthiourea BzTU; benzoylthiourea PTU; pyridylthiourea.

<(b) Peroxyester>
BPT; t-butyl peroxy-3,5,5-trimethylhexanoate BPB; t-butyl peroxybenzoate BPE; t-butyl peroxy-2-ethylhexyl monocarbonate BPL; t-butyl peroxylaurate.

<(c) inorganic peroxide>
NPS; sodium peroxodisulfate KPS; potassium peroxodisulfate APS; ammonium peroxodisulfate.

<(d) divalent copper compound>
CuA; copper (II) acetate monohydrate CuAA; copper (II) acetylacetone
CuCl2; copper (II) chloride.

<Monovalent copper compound>
CuCl; copper (I) chloride
CuSO4; copper(I) sulfate.

<(e) Aryl borate compound>
PhBNa; sodium salt of tetraphenylboron PhBTEOA; triethanolammonium salt of tetraphenylboron.

<(f) Acidic group-containing polymerizable monomer (acidic monomer)>
MDP: 10-methacryloxydecyl dihydrogen phosphate SPM: a mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis(2-methacryloyloxyethyl) hydrogen phosphate at a molar ratio of 1:1.

<(g) Acidic group-free polymerizable monomer (non-acidic monomer)>
BisGMA; 2,2-bis[4-(3-methacryloyloxy)-2-hydroxypropoxyphenyl]propane D-2.6G; 2,2-bis(methacryloyloxypolyethoxyphenyl)propane 3G; triethylene glycol dimethacrylate HEMA; 2-hydroxyethyl methacrylate UDMA; 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate.

<(h) Filler>
F1: Silica-zirconia filler with an average particle size of 3 μm F2: Silica-zirconia filler with an average particle size of 0.2 μm.

<Organic peroxide other than peroxyester>
• Hydroperoxide CHP; cumene hydroperoxide TMBHP; 1,1,3,3-tetramethylbutyl hydroperoxide • Diacyl peroxide BPO; benzoyl peroxide.

<Others>
・Vanadium compound VOAA; vanadium oxide acetylacetonate (V)
Amine compound DEPT; p-tolyldiethanolamine.

2. Examples 1-47 and Comparative Examples 1-16
Adhesive compositions of Examples 1-47 and Comparative Examples 1-16 were prepared and evaluated. These adhesive compositions contain a filler, and the adhesive compositions of Examples 1 to 47 can also be suitably used as dental cement.

[Example 1]
<Preparation of adhesive compositions (first agent and second agent)>
An adhesive composition consisting of a combination of the first agent and the second agent was prepared by the following procedure. That is, first, polymerizable monomers having the compositions shown below were blended to prepare a polymerizable monomer component for the first agent and a polymerizable monomer component for the second agent (both polymerizable monomer components are blended so that the total of is 100 parts by mass.).

(1) Polymerizable monomer component for first agent (g) BisGMA: 30 parts by mass (g) 3G: 20 parts by mass (2) Polymerizable monomer component for second agent (f) MDP: 12.5 parts by mass (g) HEMA: 5 parts by mass (g) D-2.6E: 20 parts by mass (g) 3G: 12.5 parts by mass.

Next, the polymerizable monomer component for the first agent in (1) above and each component of the chemical polymerization initiator shown in the column of the first agent in Table 1 are mixed and completely dissolved to form the first agent. A base composition was prepared for Separately from this, each of the above (2) polymerizable monomer component for the second agent and (c) a chemical polymerization initiator other than an inorganic peroxide shown in the column of the second agent in Table 1 The ingredients were mixed and dissolved to prepare the base composition for the second part.

After that, (c) an inorganic peroxide and fillers F1 and F2 are added to the obtained basic composition for the first agent and the basic composition for the second agent in the amounts shown below, respectively, to obtain the first agent and the second agent. Two agents were prepared.
・Inorganic peroxide Second agent: 3.3 parts by mass ・F1 (93 parts by mass in total) First agent: 46.5 parts by mass, Second agent: 46.5 parts by mass ・F2 (140 parts by mass in total) First agent: 70 parts by mass, Second agent: 70 parts by mass.

Table 1 shows the compounding ratio of each component of the chemical polymerization initiator when divided into the first agent and the second agent, and (b) the compounding amount of each component when the peroxyester is 100 parts by mass. [(a) 50 parts by mass of thiourea compound, (c) 330 parts by mass of inorganic peroxide, (d) 0.10 parts by mass of divalent copper compound, (e) 150 parts by mass of aryl borate compound] .

Table 3 shows the compositions of the finally obtained first agent and second agent. In Table 3, on the premise that the mixed composition is prepared by mixing the total amount of the first agent and the total amount of the second agent, the total mass of the polymerizable monomer components of both agents is set to 100 parts by mass. Parts by mass of each component are shown. Incidentally, in Examples 1-10 in Table 3, the amount of (b) the peroxyester compounded is 1 part by mass, so the compounded amount of each component constituting the chemical polymerization initiator is the compounded amount shown in Table 1. 1/100 of

<Various evaluation methods>
Adhesion strength and surface strength of the mixed composition obtained by mixing the first part and the second part prepared as described above at a mass ratio of 1:1 and the cured product thereof were evaluated. In addition, in order to examine the storage stability of the first agent and the second agent, the two types of adhesive compositions shown in (a) and (b) below were used to determine the bending strength and adhesion to dentin (including moisture). evaluated strength. Some of the adhesive compositions were also evaluated for bond strength to cobalt-chromium alloys (water free). Details of measurement of bending strength, measurement of adhesion strength to dentin, and measurement of adhesion strength to cobalt-chromium alloy are shown below.
(a) Adhesive composition "immediately after preparation" Adhesive composition consisting of a combination of the first part and the second part within 3 hours after preparation.
(b) Adhesive composition "after storage" At 50 ° C., the first agent and second agent constituting the adhesive composition immediately after preparation shown in (a) above are placed in separate containers. Adhesive composition after 2 weeks of storage.

・<Measurement of bending strength>
A polyacetal mold having a rectangular hole with a length of 25 mm, a width of 2 mm, and a thickness of 2 mm was filled with the adhesive composition prepared by the above method and allowed to stand for 60 minutes in a constant temperature bath under moist conditions at 37° C. to cure. rice field. The obtained cured body was immersed in water at 37° C. for 24 hours, and then water-resistant abrasive paper was used to remove burrs, thereby obtaining a measurement sample. Next, using a universal testing machine (AG-I type, manufactured by Shimadzu Corporation), load is started at a crosshead speed of 1 mm/mm, and the load is applied to the test sample until the test sample breaks, and the maximum Bending strength was obtained from the load using the following formula (1). Table 8 shows the results.
・Formula (1) Bending strength (MPa) = 3 × maximum load (N) × distance between fulcrum centers / (2 × width of test piece (mm) × thickness of test piece (mm) × thickness of test piece (mm)).
In addition, since this test is performed in an environment where water is scarcely present, the initiator activity is evaluated in the case where water is almost absent.

・ <Measurement of adhesion strength to dentin>
The extracted bovine mandibular anterior tooth was polished with #600 water-resistant abrasive paper under water injection, and the dentin plane was scraped out so as to be parallel to the lip surface. After blowing compressed air onto the dentin plane to dry it, double-faced tapes having circular holes with a diameter of 3 mm were fixed to define the bonding area. Subsequently, the adhesive composition prepared by the above method is applied to a cylindrical metal attachment with a diameter of 8 mm, and the surface of the adhesive composition is applied so that the hole of the double-sided tape and the surface of the metal attachment are concentric. was pressed against the dentin surface. After immersing this test sample in water at 37° C. for 24 hours, a universal testing machine (AG-I type, manufactured by Shimadzu Corporation) was used to apply a load at a crosshead speed of 1 mm/mm. A load was applied to the test sample until it broke, and the bond strength was obtained from the maximum load using the following formula (2).
- Formula (2) Adhesion strength (MPa) = maximum load (N) / adhesion area (mm< ² >).

In order to exhibit high adhesive strength to dentin, the adhesive composition should be separated from a portion of the adhesive composition in contact with dentin that contains a large amount of water and a portion that is distant from dentin and contains little water (a metal It is necessary that the portion close to the attachment) is fully polymerized.
Therefore, this test serves as an evaluation of whether the polymerization activity is sufficient both in a system in which a lot of water exists and in a system in which little water exists.

・ <Measurement of adhesion strength to cobalt-chromium alloy>
In order to more directly confirm the effect of moisture on the bond strength, test samples were prepared as follows for the bond strength to the cobalt-chromium alloy in a system in which water was not present and a system in which water was present.
・System without water: After polishing a cobalt-chromium alloy plate with #800 and #1500 water-resistant abrasive paper under water injection, high-pressure sandblasting (4-5 kgf/cm ² from a distance of 0.5-1 cm). and then ultrasonically cleaned twice with deionized water and once with acetone. Next, after blowing compressed air onto the surface of the washed plate to dry it, a double-faced tape having a circular hole with a diameter of 3 mm was fixed. Here, the area inside the circular hole with a diameter of 3 mm is the bonding area. Subsequently, a mixed composition obtained by mixing the first agent and the second agent constituting the adhesive composition immediately after preparation or after storage was applied to the end face of a cylindrical metal attachment having a diameter of 8 mm. Then, a test sample was obtained by press-contacting the circular hole of the double-sided tape and the end face of the metal attachment coated with the mixed composition so that the center axes of both coincided.
- System in which water exists: After fixing a double-sided tape with a circular hole with a diameter of 3 mm in the same manner as above, the test is performed in the same manner as the above system except that water is applied to the hole using a cotton ball. A sample was made.
Next, after immersing these test samples in water at 37° C. for 24 hours, using a universal testing machine (AG-I type, manufactured by Shimadzu Corporation), tensile strength was applied at a crosshead speed of 1 mm/mm. Added load. At this time, the tensile load applied to the test sample was gradually increased until the adhesive surface of the test sample broke, and the bond strength was obtained from the maximum load at the time of breakage using the above formula (1).
In this test, when water is applied in the circular holes, it is evaluated whether the polymerization activity is sufficient in both a system in which a lot of water exists and a system in which little water exists. It is an evaluation of whether the polymerization activity is sufficient in a system in which there is almost no

<Evaluation results>
The results of evaluation based on the evaluation method described above are shown below.
・Bending strength (MPa); immediately after preparation: 130, after storage: 130
- Adhesion strength to dentin (MPa); immediately after preparation: 51, after storage: 49
・Adhesion strength to cobalt-chromium alloy (MPa); without water application: 23, with water application: 22
As shown above, the adhesive composition of Example 1 showed good results in both flexural strength and adhesive strength to dentin both immediately after preparation and after storage. Furthermore, the adhesion strength to the cobalt-chromium alloy also showed high adhesion strength regardless of the presence or absence of water application. From these results, it was found that the adhesive composition of Example 1 had excellent curability and storage stability, and exhibited high adhesive strength regardless of the presence of water.

[Examples 2 to 47]
<Preparation and Evaluation Method of Adhesive Composition>
In Example 1, the compounding ratio of the chemical polymerization initiator was changed to the ratio shown in Table 1 or Table 2, and the acidic monomers and non-acidic monomers used as the polymerizable monomer component and their compounding amounts were shown in Table 3 ( Examples 2-10), Table 4 (Examples 11-20), Table 5 (Examples 21-30), Table 6 (Examples 31-40) and Table 7 (Examples 41-47) Adhesive compositions immediately after preparation and after storage were prepared in the same manner as in Example 1 except for the changes, and bending strength and adhesive strength to dentin were measured. For Examples 2, 5, 7 and 8, the adhesion strength to the cobalt-chromium alloy was also measured in the same manner as in Example 1.

<Evaluation results of Examples 2 to 47>
Table 8 shows the results of evaluation of bending strength and adhesive strength to dentin together with the results of Example 1. The adhesive compositions of Examples 2 to 47 also showed good results in both bending strength and adhesive strength to dentin both immediately after preparation and after storage, as in Example 1. From these results, it was found that the adhesive compositions of Examples 2 to 47 also had excellent curability, adhesive strength and storage stability.

The adhesive compositions of Examples 46 and 47 differ from the adhesive composition of Example 1 in that only the combination of the main components (a) to (e) constituting the first agent and the second agent are used. It is a modified composition. Although the flexural strength and adhesive strength immediately after preparation of Examples 46 and 47 are as high as in Example 1, the flexural strength and adhesive strength after storage show relatively high values, and are practically acceptable. Although it is within the range of , the value is lower than that of Example 1.

Table 9 also shows the adhesion strength to the cobalt-chromium alloy together with the results of Example 1. Examples 2, 5, 7 and 8, which were evaluated, all exhibited high adhesive strength, as in Example 1, regardless of the presence or absence of water application. This result shows that a high adhesive strength cannot be obtained unless a high adhesive strength is obtained in both the portion where water exists and the portion where water does not exist (if either one is low, the value will be the evaluation result. ), which is in line with the above measurement results of adhesion strength to dentin.
Table 9 also shows the results of Comparative Examples 5 to 9 corresponding to each Example (these Comparative Examples do not contain an inorganic peroxide, as will be described later).

[Comparative Examples 1 to 9]
These comparative examples are examples lacking any of the components (a) to (e) as the chemical polymerization initiator. Adhesion immediately after preparation and after storage in the same manner as in Example 1 except that the acidic monomers and non-acidic monomers used as the polymerizable monomer components and the blending amounts thereof were changed as shown in Table 11. Compositions were prepared and measured for flexural strength and adhesive strength to dentin. Further, for Comparative Examples 5 to 9, an adhesive composition immediately after preparation was prepared and cobalt chromium Further measurements of bond strength to the alloy were made. Evaluation results will be shown later together with evaluation results of other comparative examples.
Comparative Examples 5 to 9 are comparative examples to Examples 1, 2, 5, 7 and 8, respectively. In Examples 5 to 9, no inorganic peroxide was blended (this is the only difference from the Examples). The evaluation results are shown in Table 9. As shown in Table 9, these Comparative Examples 5 to 9 do not contain inorganic peroxide, so they exhibit high adhesive strength when no water is applied, but when water is applied, the adhesion strength is high. Strength was greatly reduced.

[Comparative Examples 10 to 13]
These comparative examples are examples in which a monovalent copper compound is used in place of the divalent copper compound. , In the same manner as in Example 1 except that the acidic monomers and non-acidic monomers used as polymerizable monomer components and the blending amounts thereof were changed as shown in Tables 11 and 12, the first agent and the second agent and the adhesive composition were prepared, the adhesive composition was prepared immediately after preparation and after storage, and the bending strength and adhesive strength to dentin were measured.

[Comparative Examples 14 to 17]
These comparative examples are examples in which hydroperoxide is used instead of the component (b). An adhesive composition immediately after preparation and after storage was prepared in the same manner as in Example 1, except that the acidic monomers and non-acidic monomers used as monomer components and their blending amounts were changed as shown in Table 12. , flexural strength and adhesive strength to dentin were measured.
Comparative Examples 14 and 15 are examples in which hydroperoxide is simply used instead of (b) peroxyester, and Comparative Example 16 uses hydroperoxide instead of (b) peroxyester. Comparative Example 17 is an example in which (a) the thiourea compound was removed from Comparative Example 16.

[Comparative Examples 18 to 20]
In Example 1, the components and blending ratios of the chemical polymerization initiator used were changed to the proportions shown in Table 10, and the acidic monomers and non-acidic monomers used as polymerizable monomer components and their blending amounts are shown in Table 12. Adhesive compositions immediately after preparation and after storage were prepared in the same manner as in Example 1 except for the changes shown, and bending strength and adhesive strength to dentin were measured.
Comparative Example 18 is an example in which diacyl peroxide was used instead of (b) peroxyester, and Comparative Example 19 is an example in which ( d ) a vanadium compound was added instead of a divalent copper compound. , Comparative Example 20 is an example using a benzoyl peroxide/amine compound as a chemical polymerization initiator.

<Evaluation results of Comparative Examples 1 to 20>
Table 13 shows the evaluation results of bending strength and adhesive strength to dentin. As shown in Table 13, Comparative Examples 1 to 9 were not sufficiently cured, or even when cured, the adhesive strength was low and insufficient. In Comparative Examples 10 to 13, even when gelation occurred or cured, the flexural strength and adhesive strength were greatly reduced after storage, indicating low storage stability. Comparative Examples 14 to 16 were gelled after storage and had low storage stability.
In Comparative Example 17, gelation did not occur, but sufficient flexural strength and adhesive strength were not exhibited immediately after preparation, and the flexural strength after preparation was significantly lower than that immediately after preparation. In Comparative Example 18, the storage stability was insufficient. In Comparative Example 19, the second agent gelled immediately after preparation. did not harden.

Claims (13)

(a) a thiourea compound, (b) a peroxyester, (c) an inorganic peroxide, (d) a divalent copper compound and (e) an arylborate compound, and substantially free of hydroperoxide A chemical polymerization initiator, wherein the (a) thiourea compound is a compound represented by the following general formula (1) .

[In formula (1), R ¹ , R ² and R ³ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted a substituted heterocyclic group, a substituted or unsubstituted acyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkenyl group, and R ² is any one selected from R ¹ and R ³ It may combine with the group to form a ring. ] 2. The chemical polymerization initiator according to claim 1, wherein (a) the thiourea compound represented by the general formula (1) is at least one compound selected from the group consisting of acetylthiourea, benzoylthiourea and pyridylthiourea . 3. The chemical polymerization initiator according to claim 1, wherein the peroxyester (b) has a 10-hour half-life temperature of 80[deg.] C. or higher. 4. The chemical polymerization initiator according to any one of claims 1 to 3, wherein the inorganic peroxide (c) is a peroxodisulfate. The (d) divalent copper compound comprises a divalent copper atom and a ligand that coordinates to the divalent copper atom,
the ligand is selected from the group consisting of a halogen atom, an atomic group containing an oxygen atom, and an atomic group containing a nitrogen atom;
When the ligand is an atomic group containing the oxygen atom, the atomic group containing the oxygen atom is coordinated to the divalent copper atom via the oxygen atom,
When the ligand is an atomic group containing the nitrogen atom, the atomic group containing the nitrogen atom is coordinated to the divalent copper atom via the nitrogen atom. Item 5. The chemical polymerization initiator according to any one of items 1 to 4. 2. An adhesive composition comprising the chemical polymerization initiator according to claim 1 , (f) an acidic group-containing polymerizable monomer , and substantially free of hydroperoxide . 7. The adhesive composition according to claim 6, further comprising (g) an acidic group-free polymerizable monomer. Composed of a combination of a first partial composition and a second partial composition that is physically inaccessible from the first partial composition,
The entire combination of the first partial composition and the second partial composition constitutes the adhesive composition according to claim 6,
The first partial composition comprises the six components of the adhesive composition according to claim 6 : (a ) the thiourea compound and (e) the aryl containing a borate compound as a main component and substantially free of organic peroxides,
The second partial composition comprises, among the six components, the (b) peroxyester, the (c) inorganic peroxide, the (d) divalent copper compound, and the (f) containing an acidic group-containing polymerizable monomer as a main component and substantially free of hydroperoxide,
An adhesive composition kit characterized by: 9. The composition according to claim 8, wherein at least one composition selected from the first partial composition and the second partial composition further contains (g) an acidic group-free polymerizable monomer. Adhesive composition kit as described. 10. The adhesive composition according to claim 8 or 9, wherein at least one composition selected from the first partial composition and the second partial composition further comprises (h) a filler. things kit. A dental material comprising the adhesive composition according to claim 6 or 7. A dental material kit, characterized in that it comprises an adhesive composition kit according to claim 8 or 9. The adhesive composition according to claim 6 or 7 is stored in a state of being divided into a first partial composition and a second partial composition,
The first partial composition comprises the (a) thiourea compound, the (b) peroxyester, the (c) inorganic peroxide, the (d) divalent copper compound, and the ( Among the six components consisting of e) the arylborate compound and the (f) acidic group-containing polymerizable monomer, the (a) thiourea compound and the (e) arylborate compound are included as main components. and substantially free of organic peroxides,
The second partial composition comprises, among the six components, the (b) peroxyester, the (c) inorganic peroxide, the (d) divalent copper compound, and the (f) containing an acidic group-containing polymerizable monomer as a main component and substantially free of hydroperoxide,
A method for storing an adhesive composition, characterized by: