Polymerizable composition

Abstract: Provided are polymerizable compositions comprising: (a) a sulfinate represented by the general formula [I] wherein R¹ and R⁵ each represents a substituent having 2 to 6 carbon atoms, R², R³ and R⁴ each represents an atom or substituent inert to the monomer (b) referred to below, M n+ represents a n-valent cation, and n represents an integer of 1 to 4; and (b) a monomer. (a) is an aromatic sulfinate substituted with bulky groups at its positions 2 and 6. Since the bulky substi­ tuents dramatically suppress the addition of the sulfinate to the double bond of the monomers, e.g. (meth)acrylates, (meth)acrylamides and derivatives thereof, the compositions can be stored at room temperature for at least 1 year and thus are of great industrial value and, in particular very useful as dental adhesive compositions.

Description: The present invention relates to polymerizable compositions, and more specifically provides polymerizable compositions with good storage stability comprising an aromatic sulfinate as polymerization activator. Description of prior art It has been proposed to use a sulfinic acid or a salt thereof as a component of polymerization initiators for polymerizing radical-polymerizable monomers, for example a sulfinic acid, a sulfinic acid (or its salt)-oxidizer system, and a sulfinic acid (or its salt)-amine-peroxide system. For example. Japanese Patent Application Laid-open No. 30193/1978 discloses a process comprising the use of a sulfinate-amine-peroxide system as a polymerization initiator for radical-polymerizable monomers. Further, Japanese Patent Application Laid-open No. 75907/1982 discloses that this sulfinate-amine-peroxide system is particularly useful for the polymerization of dental adhesives comprising an acidic monomer. However, since aromatic sulfinates which have hitherto been used, e.g. benzenesulfinate and toluenesulfinate, add, when contacted with a (meth)acrylate, (meth)acrylamide or a (meth)acrylamide derivative, gradually to the double bond of the monomer, compositions comprising the sulfinate dissolved or suspended in the monomer will, when stored at room temperature, lose polymerization activity in a few weeks. The two components therefore must be stored in separate packages so that they will not be in contact with each other, which is a disadvantage in comparison with other systems in which the initiator and monomer can be packed and stored together. SUMMARY OF THE INVENTION Accordingly, the present applicants sought to provide a composition comprising a sulfinate and a polymerizable monomer, which has a long pot life (e.g. at least one year). As a result of an intensive study to solve the above problem, it was found that introduction of bulky substituents into positions 2 and 6 of aromatic sulfinates dramatically suppress the addition of these sulfinates to the double bond of (meth)acrylates, (meth)acrylamides or derivatives thereof. Thus, the present invention provides a composition comprising: (a) a sulfinate represented by the general formula [I] wherein R¹ and R⁵ each represents a substituent having 2 to 6 carbon atoms, R², R³ and R⁴ each represents an atom or substituent inert to the monomer (b) referred to below, M n+ represents a n-valent cation, and n represents an integer of 1 to 4, in an amount of 0.01 to 10% by weight based on the weight of the composition; and (b) a monomer which has at least one ethylenically unsaturated group therein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention employs aromatic sulfinates represented by the general formula (I) having bulky substituents in their positions 2 and 6. In the above-mentioned general formula [I], R¹ and R⁵ each is a substituent located in the ortho-position to the sulfinate group of the aromatic sulfinate and having sufficient bulkiness for exerting steric hindrance to addition of the sulfinate group to carbon-to-carbon double bond of a monomer. It is important that both R¹ and R⁵ be bulky groups. If only one of the two groups is bulky, sufficient steric hindrance to the addition of the sulfinate group to the double bond will not be achieved. With respect to the bulkiness of the groups, although a carbon atom number of 1, e.g. a methyl group, may suppress the addition reaction, for practical purposes the effect is attained with a carbon atom number of at least 2, preferably at least 3. While the addition is suppressed to a larger extent with an increasing number of carbon atoms, the effect of the suppression will become smaller once the substituent has a bulkiness of a certain degree. In view of this and commercial availability of raw material, the number of carbon atoms is up to 6 for practical purposes. R¹ and R⁵ should, naturally, be inert to the double bond of monomers. Generally, R¹ and R⁵ each is a hydrocarbon group which has 2 to 6 carbon atoms and may be substituted with one or more halogen atoms. Examples of the group are ethyl, 2-chloroethyl, 2-bromo-2-chloroethyl, propyl, isopropyl, perfluoropropyl, allyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclohexyl, phenyl, 4-bromophenyl and the like. R², R³ and R⁴ may be any atoms and/or groups as long as they are inert to the double bond of monomers. Examples are hydrogen, fluoro, chloro, bromo, iodo, methyl, ethyl, 2-chloroethyl, 2-bromo-2-chloroethyl, propyl, isopropyl, per-fluoropropyl, allyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclohexyl, phenyl and 4-bromophenyl. M n+ is a cation with monovalency to 4-valency that can, as a counter ion for a sulfinic acid anion, form the sulfinate. Examples of M n+ are alkali metal ions, such as Li⁺, Na⁺, K⁺, Rb⁺, and Cs⁺, alkaline earth metal ions, such as Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺, transition metal ions such as Cr²⁺, Cr³⁺, Mn²⁺, Fe²⁺, Fe³⁺, Co²⁺, CO³⁺, Ni²⁺, Cu²⁺, Zn²⁺, Rh³⁺, Pd²⁺, Ag⁺, Cd²⁺, Ir³⁺, Ir⁴⁺ and Hg²⁺, and ammonium ions, such as NH₄⁺, (CH₃CH₂)₃NH⁺, Preferred counter ions among these ions are Li⁺, Na⁺, K⁺, Mg²⁺ and Ca²⁺, since sulfinates thereof have good stability when stored in monomers and have good solubility in the monomers. Examples of sulfinates represented by general formula [I] are as follows. The advantage of the present invention is most apparent when using monomers having a carbon-to-carbon double bond directly linked to an electron-attracting group such as -F, -Cl, -Br, -I, -CN, -NO₂, -NO, -CO-, -CS-, -COO-, -COS-, -CSO-, -CSS-, -CONH₂, -CONH- or Where monomers without the above electron-attracting groups, such as styrene, butadiene and allyl alcohol are used, sufficient storage stability is secured with conventional benzenesulfinates and toluenesulfinates. With monomers having the above electron-attracting groups, these conventional sulfinates, however, cannot achieve practical storage stability because of the occurrence of the addition reaction. Among monomers having carbon-to-carbon double bonds directly linked to an electron-attracting group, particularly suited for the purpose of the present invention are (meth)acrylates, α-haloacrylates, (meth)acrylamides and derivatives thereof, represented by the general formula wherein R⁶ represents a hydrogen atom, methyl group or halogen atom, R⁷ and R⁸ each represents a hydrogen atom or an organic group which may contain X represents an oxygen atom or nitrogen atom and m represents 0 where X is an oxygen atom and represents 1 where X is a nitrogen atom. Examples of the monomer represented by the above general formula are as follows. In the present invention the expression "(meth)acryl" means both methacryl and acryl. (a) Monofunctional (meth)acrylates Methyl (meth)acrylate, ethyl (meth)acrylate, iso-butyl (meth)acrylate, n-hexyl (meth)acrylate, benzyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(N,N-dimethylamino)ethyl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, oxiranylmethyl (meth)acrylate, 3-methacryloyloxypropyltrimethoxysilane and the like. (b) Bifunctional (meth)acrylates Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, bisphenol-A-di(meth)acrylate, 2,2-bis((meth)acryloyloxyethoxyphenyl)propane, 2,2-bis((meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane, 1,2-bis(3-(meth)acryloyloxy-2-hydroxypropoxy)ethane and the like. (c) Tri- or more functional (meth)acrylates Trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and the like. (d) α-Haloacrylates α-Fluoromethyl acrylate, α-chloromethyl acrylate, α-fluoroethyl acrylate, α-chlorobutyl acrylate, α-fluoro-2,2,2-trifuloroethyl acrylate, and the like. (e) (Meth)acrylamide derivatives (Meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-n-octyl(meth)acrylamide, N-benzyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-dimethylaminoethyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-dicyclohexyl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, N,N'-methylenebis(meth)acrylamide, 1,6-bis(meth)acrylamidehexane, and the like. These copolymerizable monomers may be used singly or in combination. The composition of the present invention is obtained by dissolving or suspending the compound represented by general foumula [I] in the above monomer. The sulfinate represented by formula [1] is generally used in an amount of 0.01 to 10% by weight based on the weight of the composition, preferably in an amount of 0.03 to 5% by weight on the same basis. Since the composition of the present invention is by itself extremely slow in initiating polymerization at room temperature, polymerization is effected by adding an organic peroxide or by adding a photoinitiator, followed by photoradiation. As the organic peroxide used in the invention, organic peroxides capable of initiating polymerization by redox reaction with sulfinates may be employed, and diacyl peroxides are preferred. Examples of the diacyl peroxides include, among others, benzoyl peroxide, m-toluoyl peroxide, 2,4-dichloro-benzoyl peroxide, octanoyl peroxide, lauroyl peroxide and succinoyl peroxide, among which particularly preferred are aromatic peroxides such as benzoyl peroxide and m-toluoyl peroxide. The oxidizer is stored in a package avoiding contact with the sulfinate represented by formula [I], and is, in polymerizing the composition of the present invention, added to the sulfinate generally in an amount of 0.01 to 500 parts by weight based on 1 parts by weight of the sulfinate. An amine may further be added to the sulfinate and organic peroxide system to form a ternary initiator, whereby polymerization is much more accelerated. In this case, while the amine can be stored in contact with the sulfinate with no problem, the amine must not contact the organic peroxide to avoid premature polymerization. When packaging the sulfinate and the organic peroxide separately, the amine is therefore packed together with the sulfinate. Aromatic secondary or tertiary amines are preferred for this purpose, and examples are N,N-dimethylaniline, N,N-dimethyl-p-toluidine, ethyl m-N,N-dimethylaminobenzoate, ethyl p-N,N-dimethylaminobenzoate, N,N-diethanolaniline, N,N-diethanol-p-toluidine, N,N-diethanol-m-chloroaniline, N,N-bis(3-hydroxypropyl)aniline, N,N-bis(3-hydroxypropyl)-p-toluidine, N,N-bis(2,3-dihydroxypropyl)aniline, N,N-bis(2,3-dihydroxypropyl)-p-toluidine, ethyl m-N,N-bis(2,3-dihydroxypropyl)aminobenzoate, N-methylaniline and N-methyl-p-toluidine. The amine is generally added in an amount of 0.01 to 500 parts by weight based on 1 part by weight of the compound represented by formula [I]. Suitable photoinitiators are photosensitive dyes and α-diketones, and examples are Methylene blue, Eosin YS, diacetyl, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, camphorquinone, bicyclo-[2.2.1]heptane-2,3-dione, acenaphthenequinone, 9,10-phenanthraquinone, 9,10-anthraquinone and the like. The photoinitiator is generally added in an amount of 0.01 to 500 parts by weight based on 1 part by weight of the compound of formula [I]. The composition of the present invention can comprise both the organic peroxide and the photoinitiator and be subjected to both redox and photopolymerization. On the other hand, where the composition of the present invention is used as a primer, on which another polymerizable composition is applied, polymerization may be effected by an initiator which has been contained in the other polymerizable composition and has migrated to the composition of the present invention, even when the composition of the present invention has not originally contained an organic peroxide or photoinitiator. The composition of the present invention may further comprise, as required, additives other than the above components, such as an inorganic filler, polymer, organic solvent, polymerization inhibitor, antioxidant, ultraviolet absorber, pigment, dye and the like. When a polymer is added, it can be added either as an insoluble filler or as a thickener which is soluble in the composition. As stated heretofore, introduction of bulky groups into positions 2 and 6 of a benzenesulfinate can suppress the rate of addition reaction of the sulfinate to the double bond of the monomer to below 1/10 the rate when conventional benzenesulfinates or toluenesulfinates are used. While compositions comprising conventional sulfinates can be stored at room temperature stably only for a few weeks, compositions of the present invention may be stored at room temperature stably for at least one year and thus have significant practical advantages. The polymerizable composition of the present invention can polymerize rapidly on addition of an organic peroxide or on addition of a photoinitiator, followed by photoradiation. The present compositions can be used as adhesives for various industrial uses and as moldable resins. One suitable use of the composition is in the dental field, where it is used as a dental adhesive. The invention also extends to multi-package systems for preparing polymerizable compositions of the invention, as hereinafter set out in the claims. EXAMPLES Examples 1 to 7 and Comparative Examples 1 to 8 There were used as the sulfinates, sodium 2,4,6-triethylbenzenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesufinate, calcium 2,6-diisopropylbenzenesulfinate, lithium 2,4,6-tri-tert-butylbenzenesulfinate and sodium 2,4,6-triphenylbenzenesulfinate, and, as the polymerizable monomers, 2-hydroxyethyl methacrylate and a mixture of 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane, triethylene glycol dimethacrylate and 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, to prepare compositions of Examples 1 to 7 as shown in Table 1. These compositions were each placed in a glass ampoule tube, which was then sealed by fusion, and the tubes with their contents were stored at 37°C for 14 days. The amounts of the sulfinates before and after the storage were determined by high-performance liquid chromatography, and the ratios of remaining sulfinates after the storage at 37°C for 14 days were calculated. The results are shown in Table 1. The above procedures were repeated except for using, instead of the sulfinates used in Examples 1 to 7, sodium benzenesulfinate, sodium p-toluenesulfinate, sodium p-ethylbenzenesulfinate, sodium p-isopropylbenzenesulfinate, calcium p-isopropylbenzenesulfinate, calcium o-isopropylbenzenesulfinate and sodium 2,4,6-trimethylbenzenesulfinate, to prepare compositions of Comparative Examples 1 to 8. Regardless of absence or presence, or the type, of substituent in position 4, introduction of substituents having at least 2 carbon atoms into positions 2 and 6 significantly increased the retention of sulfinate. Where a substituent having at least 2 carbon atoms was introduced into only position 2 and where methyl groups were introduced into positions 2 and 6, there was observed some improvement in retention, which fell, however, far short of the retention achieved in the case where substituents having at least 2 carbon atoms were introduced in both positions 2 and 6. Example 8 and Comparative Example 9 The following compositions A and B were prepared. The composition A just after preparation and after having been stored at 25°C for 1 year were each subjected to the following Test 1. Then the two samples were combined with composition B and subjected to the following Tests 2, 3 and 4. Test 1 To 0.5 g of composition A 5 ml of methanol was added, the mixture was stirred well and the quartz powder was removed from the mixture by filtration. The amount of sodium 2,4,6-triisopropylbenzenesulfinate in the methanol solution was determined by high-performance liquid chromatography. The ratio of the amount of sodium 2,4,6-triisopropylbenzenesulfinate after storage to that just after preparation was calculated. The results are shown in Table 2. Test 2 Equal amounts of compositions A and B were kneaded together for 30 seconds, and the mixture was placed in a Teflon® container having an inside diameter of 5 mm and a depth of 7 mm, and tested for curing or hardening time. A thermocouple was inserted in the kneaded mixture and temperature change was recorded. The time required until the cessation of temperature increase due to polymerization heat was taken as the curing time. The results are shown in Table 2. Test 3 A test surface to be bonded was prepared by patching an adhesive tape with a hole having a diameter of 5 mm to the surface of a nickel-chrome alloy plate (Now Chrom (I)®, made by Towa Giken Co.) ground with 1000-grit silicon-carbide abrasive paper. Round rods of SUS (Stainless Steel) 304 and having a diameter of 7 mm and a length of 25 mm were sand blasted on their end surface with alumina abrasive powder of particle size of 50µm. On the blasted end a paste obtained by kneading equal amounts of compositions A and B was heaped and the paste was pressed onto the test surface to bond the rod to the surface. After 1 hour the test piece thus prepared was immersed in water at 37°C and kept therein for 24 hours, and then tested for tensile bond strength using a universal tensile testing machine (Instron®) at a crosshead speed of 2 mm/min. An average of measurements on 10 test pieces was calculated. The results are shown in Table 2. Test 4 A labial enamel surface of bovine tooth was ground with silicon-carbide abrasive paper so that it was flat, and the flat surface was etched with a 40% aqueous phosphoric acid solution for 1 minute. On the etched surface an adhesive tape with a hole having a diameter of 5 mm was patched to prepare a test surface to be bonded. Round rods of SUS304 and having a diameter of 7 mm and a length of 25 mm were sand blasted on their end surface with alumina abrasive powder of particle size of 50µm. On the blasted end a paste obtained by kneading equal amounts of compositions A and B was heaped and the paste was pressed onto the test surface to bond the rod to the surface. After 1 hour the test piece thus prepared was immersed in water at 37°C and kept therein for 24 hours, and then tested for tensile bond strength using Instron® at a crosshead speed of 2 mm/min. An average of measurements on 10 test pieces was calculated. The results are shown in Table 2. Example 8 was repeated except that sodium benzenesfulfinate was used instead of sodium 2,4,6-triisopropylbenzenesulfinate in composition A. This is Comparative Example 9 in Table 2. Example 9 The following composition C was prepared. A glass cylindrical sample tube having an inside diameter of 10 mm and a wall thickness of 0.8 mm was charged with 0.25 ml of the composition. The tube with its contents was irradiated from below through a visible light irradiator (Quick light®, made by Kuraray Co., Ltd.); the contents hardened in 32 seconds. A part of the above composition was stored at room temperature for 1 year, and then subjected to the same irradiation test; it hardened in 35 seconds. In determining the curing time, a thermocouple was inserted in the composition and temperature change was recorded. The time required until the cessation of temperature increase due to polymerization heat was taken as the curing time. Example 10 The following compositions D and E were prepared, and, after being stored at room temperature for 1 year, tested for adhesiveness to human tooth dentine. Human molar tooth was ground with a silicon-carbide abrasive paper to expose the dentine, and then acid-etched with a 40% aqueous phosphoric acid solution for 1 minute. An adhesive tape with a hole having a diameter of 5 mm was patched on this etched surface to prepare a test surface to be bonded. Separately, pieces of round rod of SUS304 and having a diameter of 7 mm and a length of 25 mm were sand blasted on their end surface with alumina abrasive powder of particle size of 50µm. A paste obtained by kneading equal amounts of compositions D and E was applied both on this blasted end surface and on the human tooth test surface prepared above. Kneaded paste of a commercially available dental composite resin (CLEARFIL FII®, made by Kuraray Co.) was heaped on the end surface of the rod and the paste was pressed onto the human tooth test surface to bond the rod to the surface. After 1 hour the test piece thus prepared was immersed in water at 37°C and kept therein for 24 hours, and then tested for tensile bond strength using Instron® at a crosshead speed of 2 mm/min. An average of measurements on 8 test pieces was calculated to give 130 kg/cm². Example 11 The compositions D and E stored at room temperature for 1 year as used in Example 10 were tested for metal-to-metal adhesiveness as follows. Two pieces of round rod of SUS304 and having a diameter of 7 mm and a length of 25 mm were sand blasted on their end surface with alumina grinding powder of particle size of 50µm. Composition D was applied to the blasted end surface of one rod, while composition E to that of the other rod. The two surfaces were pressed with each other to bond, to prepare a test piece. The test piece was kept at 25°C for 24 hours, and then tested for tensile bond strength with Instron at a crosshead speed of 2 mm/min. An average of measurements on 10 test pieces was 382 kg/cm².

Claims: A polymerizable composition comprising: (a) a sulfinate represented by the general formula [I] wherein R¹ and R⁵ each represents a substituent having 2 to 6 carbon atoms, R², R³ and R⁴ each represents an atom or substituent inert to monomer (b) referred to below, M n+ represents a n-valent cation, and n represents an integer of 1 to 4, in an amount of 0.01 to 10% by weight based on the weight of the composition; and (b) a monomer which has at least one ethylenically unsaturated group therein. A polymerizable composition according to Claim 1, wherein said sulfinate is represented by the general formula wherein R¹ and R⁵ each represents a substituent having 2 to 6 carbon atoms, R³ represents a substituent having 1 to 6 carbon atoms, a hydrogen atom or a halogen, M n+ represents an alkali metal ion, an alkali earth metal ion, a transition metal ion or an ammonium ion, and n represents an integer of 1 to 4. A polymerizable composition according to Claim 1, wherein said sulfinate is a sulfinate represented by the general formula wherein M n+ represents Li⁺, Na⁺, K⁺, Mg²⁺ or Ca²⁺. A polymerizable composition according to any preceding claim, wherein said monomer has a carbon-to-carbon double bond directly linked to an electron-attracting group. A polymerizable composition according to any one of Claims 1-3, wherein said monomer is an acrylate, a methacrylate, an α-haloacrylate, an acrylamide, a methacrylamide, an acrylamide derivative or a methacrylamide derivative. A multiple-package system for preparing a polymerizable composition according to any one of Claims 1-5 comprising: (a) said sulfinate represented by the general formula [I], (b) said monomer, and (c) an organic peroxide; said (a) and (c) being stored in separate packages and mixed with each other to effect polymerization. A system according to Claim 6, wherein said organic peroxide is an aromatic diacyl peroxide. A polymerizable composition according to any one of Claims 1-5 comprising: (a) said sulfinate represented by the general formula [I], (b) said monomer, and (c) a photoinitiator. A polymerizable composition according to Claim 8, wherein said photoinitiator is a photosensitive dye or an α-diketone. A multiple-package system for preparing a polymerizable composition according to any one of Claims 1-5 comprising: (a) said sulfinate represented by the general formula [I], (b) said monomer, (c) an organic peroxide, and (d) an amine, said organic peroxide being stored in a separate package from (a) and (d). A system according to Claim 10, wherein said amine is an aromatic secondary or tertiary amine.

Inventors: KAWASHIMA MITSUNOBU, OMURA IKUO, KAWASHIMA, MITSUNOBU, OMURA, IKUO
Applicants: KURARAY CO, KURARAY CO., LTD.
Application year: 1990
Main classification: C08F2
IPC codes: A61K6, C09J4, C08F2, C08F4