JPH02252775A - Photopolymerizable adhesive composition - Google Patents

Abstract

PURPOSE:To prepare a one-component photopolymerizable adhesive compsn. which adheres well even without using a primer and is suitable for dental use by compounding a specific polymerizable monomer, a filler, and a photopolymn. initiator comprising camphorquinone and/or benzil. CONSTITUTION:The title composition comprises 30-50wt.% polymerizable monomer e.g. comprising an addition product of two molecules of hydroxyalkyl methacrylate to one molecule of diisocyanate deriv. comprising an addition product of two molecules of hydroxyethyl methacrylate to one molecule of trimethyhexamethylene diisocyanate; 50-70wt.% filler (e.g. a colloidal silica) which is pref. coated with an org. compd. and insol. in the polymerizable monomer and contains 70-100wt.% particles with a mean particle diameter of 1-30mum; 0.0005-1wt.% photopolymn. initiator comprising camphorquinone and/or benzil; and, if necessary, a reducing agent, a silane coupling agent, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive composition, and more particularly to a visible light polymerizable adhesive composition useful as a dental adhesive.

In medical fields such as dentistry, it is necessary to firmly bond tooth tissue, especially dentin, to other materials, such as plastics, metals, and dental porcelain, and adhesives for this purpose have been developed. .

Such dental adhesives include: i) a polymerizable monomer such as methyl methacrylate (MMA); 11) a photosensitizer such as camphorquinone;
, dimethylaminoethyl methacrylate, etc., and 1ii) a filler such as polymethyl methacrylate (PMMA); With polymerizable monomers such as ^).

1i) with adhesion-promoting monomers such as 4-methacryloyloxyethoxycarbonylphthalic anhydride (4-ME-A).

1ii)) So n-butyl boron oxide (TBBO)
With photoinitiators such as.

iv) An adhesive composition comprising a filler such as polymethyl methacrylate (PMMA) has been proposed.

All of these adhesive compositions are two-component adhesives, and therefore, such adhesive compositions consist of a powder consisting of a filler, a photoinitiator, and a reducing agent, and a polymerizable monomer. It is used by mixing the liquid agent immediately before use.

However, with these adhesives that are used by mixing powder and liquid immediately before use, the mixing time is labor intensive and -
There was a problem that once they were mixed together, the usable time spells were short.

To solve these problems, two-component adhesives containing fillers and photoinitiators have been developed.

With this wave-type adhesive, it is not necessary to mix the powder and liquid immediately before use, but in order to increase the adhesive strength, it is necessary to apply a primer to the bonding surface of the adherend in advance. However, there was still the problem that it was time-consuming to use.

The present inventors conducted research to solve the above-mentioned problems and found that camphorquinone and/or
Alternatively, the inventors discovered that a two-component adhesive composition using benzyl as a photopolymerization initiator exhibits sufficient adhesive strength without applying a primer to the surface of the adherend, thereby completing the present invention. reached.

11 1j The present invention aims to solve the problems associated with the prior art as described above. The purpose of the present invention is to provide a two-component adhesive composition having the following characteristics.

11 11 The photopolymerizable adhesive composition according to the present invention comprises (A) one molecule of a diisocyanate derivative as a polymerizable monomer, and two
Addition compound of the molecule with hydroxyalkyl methacrylate; 30 to 50% by weight (B) A filler containing 70 to 100% by weight of particles that are insoluble in the above polymerizable monomer and have an average particle size of 1 to 30 μl; 50 to 70% by weight and.

(C) A photopolymerization initiator consisting of camphorquinone and/or benzyl; characterized by comprising 0.0005 to 1% by weight.

The photopolymerizable adhesive according to the present invention exhibits sufficient adhesion to adherends without using an undercoat, and can be cured by visible light irradiation.

1, I The photopolymerizable adhesive composition according to the present invention will be explained below.

The photopolymerizable adhesive composition according to the present invention comprises a polymerizable monomer, a filler, and a photopolymerization initiator.

Each component will be explained below.

The polymerizable monomer used in the present invention is an addition compound of one molecule of a diisocyanate derivative and two molecules of hydroxyalkyl methacrylate.

Diisocyanate derivatives include polyalkylene diisocyanates, such as 2,2.4-trimethylhexamethylene diisocyanate, 2,4.4-)trimethylhexamethylene diisocyanate, or mixtures thereof;
Hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, etc. are used.

Among these, trimethylhexamethylene diisocyanate or isophorone diisocyanate is particularly preferred.

Further, as the hydroxyalkyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl methacrylate, etc. are used. Among these, hydroxyethyl methacrylate is particularly preferred.

Among such polymerizable monomers, for example, an addition compound of one molecule of trimethylhexamethylene diisocyanate and two molecules of hydroxyethyl methacrylate is
One molecule of such a diisocyanate derivative can be represented by the following formula.

The addition compound with two molecules of hydroxyalkyl methacrylate has a double bond at both ends of the molecule, and is used as a polymerizable monomer.

This polymerizable monomer is added to the photopolymerizable adhesive composition at 30%
It is used in an amount of ~50% by weight, preferably 34-46% by weight.

In the present invention, the polymerizable monomer is one molecule of the above-mentioned isocyanate derivative.

Any polymerizable monomer containing a small amount of a monomer component other than the above-mentioned addition compound may be used, as long as the main component is an addition compound with two molecules of hydroxyalkyl methacrylate. For example, the polymerizable monomer may contain monomer components other than the above-mentioned addition compounds, such as 4-methacryloxy and ethoxy trimellitic anhydride, within 5% by weight.

Next, the filler will be explained.

Fillers are added to prevent polymerization shrinkage and further adjust the viscosity of the composition.

This filler is a particle that is insoluble in the above polymerizable monomer.

These fillers have an average particle size in the range of 1 to 30 μm, preferably in the range of 3 to 15 μm.

The filler having the average particle diameter as described above is dispersed in the polymerizable monomer solution to form a -wave type adhesive composition.

By blending the filler as described above, polymerization shrinkage when the resin composition is cured can be prevented, and the viscosity of the composition can be adjusted.

Specific examples of such fillers include organic fillers such as polymethyl methacrylate and polyethyl methacrylate, and glass beads.

Inorganic fillers such as alumina oxide, alpha-quartz powder and colloidal silica are used.

In the present invention, it is preferable to use such a filler by coating it with an organic compound. Specifically, the filler as described above is coated with a compound having an ethylenically unsaturated group such as trimethylolpropane trimethacrylate, Alternatively, a polymerizable monomer such as an adduct of one molecule of a diisocyanate derivative and two molecules of hydroxyalkyl methacrylate used as a polymerizable monomer in the present invention is polymerized in the presence of a radical generator, and then pulverized. It is preferable to use it.

The filler used in the present invention contains 70 to 100% by weight of particles that are insoluble in the polymerizable monomers mentioned above and have a specific particle size as mentioned above.

Note that the filler used in the present invention may contain particles outside the specific particle size range as described above or other particles in an amount of 30% by weight or less.

Such fillers are used in the composition in an amount of 50-70% by weight, or 53-66% by weight.

The photopolymerizable adhesive composition of the present invention uses camphorquinone and/or benzyl as a polymerization initiator.

Camphorquinone used as a polymerization initiator in the present invention is represented by the following formula.

Moreover, benzyl is represented by the following formula.

In the present invention, the above-mentioned camphorquinone and benzyl can be used alone or in combination.

Both camphorquinone and benzyl are α-diketone compounds as described above, and by using such compounds as polymerization initiators, one molecule of the diisocyanate derivative as described above can be produced.

A polymerizable monomer consisting of an addition compound with two molecules of hydroxyalkyl methacrylate can be cured well, and can be used well as a one-component photopolymerizable resin composition.

These photopolymerization initiators are contained in the composition in an amount of 0.0005 to 1% by weight, preferably 0.01 to 0.5% by weight.
Used in amounts of % by weight.

The photopolymerizable adhesive an composition according to the present invention has a composition in which the above-mentioned polymerizable monomer, filler, and photopolymerization initiator are blended in predetermined amounts, and a reducing agent or silane coupling agent is further blended. may have been done.

Examples of reducing agents that can be blended into the photopolymerizable resin composition of the present invention include N,N-dimethyl para-toluidine (DMPT), N,N-jethanol para-toluidine,
Examples include dimethylaminoethyl methacrylate.

When using a reducing agent, the reducing agent is used in an amount of usually 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the polymerizable monomer in the composition.

Silane coupling agents that can be blended into the photopolymerizable resin composition according to the present invention include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri(trimethylsiloxy)silane, γ-
Examples include methacryloxypropylpentamethyldisiloxane.

By using such a silane coupling agent, for example, the adhesiveness between metal and tooth substance is improved.

The silane coupling agent is the polymerizable monomer 1 in the composition.
00 parts by weight, usually 0.01 to 10 parts by weight,
Preferably 0. It is used in an amount of 1 to 3x parts.

Although there is no particular restriction on the method of blending the reducing agent and silane coupling agent as described above, it is preferable, for example, that the silane coupling agent is mixed in advance with a polymerizable monomer and then mixed with other components.

The adhesive composition according to the present invention can be produced, for example, by the following method.

First, a photoinitiator and, if desired, a silane coupling agent are dissolved in a polymerizable monomer. Next, a filler and, if desired, a reducing agent are added to this solution. The mixture thus obtained is kneaded to disperse the blended filler.

The photopolymerizable resin composition according to the present invention can be obtained by vacuum defoaming the dispersion thus obtained.

The photopolymerizable resin composition according to the present invention thus obtained is usually in the form of a paste.

In addition, in the photopolymerizable resin composition according to the present invention, since the polymerization reaction proceeds by irradiation with light, the above-mentioned mixing of the components is performed under conditions such that the photopolymerization reactant does not proceed.

The adhesive composition of the present invention thus produced can be stored stably for a long period of time by being filled and stored in a light-shielding container.

When the photopolymerizable resin composition obtained as described above is irradiated with visible light, the photopolymerizable resin composition has 0. Hardens in 2-3 minutes. As the visible light used for curing the resin composition, it is preferable to use light with a wavelength of 400 to 800 nm.

The adhesive composition according to the present invention exhibits excellent adhesion between dentin and metal, and is therefore preferably used as an adhesive for dental treatment, and particularly preferably used as an adhesive for orthodontic treatment.

However, the photopolymerizable adhesive composition according to the present invention can be used not only as an adhesive for dental treatment but also as an adhesive for bonding metals, for example.

The adhesive composition according to the present invention exhibits sufficient adhesion to adherends without the use of a primer, and can be cured by irradiation with visible light.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited by these Examples.

In addition, in the examples, comparative examples, and reference examples shown below,
The expression "1 part" means "part by weight" unless otherwise specified.

A filler-forming composition having the following composition was prepared.

) --n Aerosil (manufactured by Nippon Aerosil ■, R972) 40 parts Aerosil (manufactured by Nippon Aerosil ■, 0X50) 8
0 parts Trimethylolpropane trimethacrylate 50 parts 2.2.4-) Addition compound of 1 molecule of dimethylhexamethylene diisocyanate and 2 molecules of hydroxyethyl methacrylate (UDMA) 50 parts Benzoyl peroxide 0.5 part Above-mentioned filler The forming composition was mixed using a kneader.

This mixture was heated on a hot press at 120'C for 10
Polymerization was carried out for 10 minutes under pressure of 0 K g G/cm 2 .

Next, the polymer obtained by polymerization as described above was pulverized using an alumina ball mill to prepare an organic composite filler (TU filler) having an average particle size of 9 and 10 μm.

Actually, 1 case.

Eleven adhesive compositions having the following compositions were prepared.

[After] L 肚I' [Material polymerizable monomer (UDMA: addition compound of 1 molecule of 2,2.4-trimethylhexamethylene diisocyanate and 2 molecules of hydroxyethyl methacrylate) 100 parts Filler (TU filler) 160 parts light Polymerization initiator (camphorquinone) 0.3 parts Reducing agent (DMPT; N,N-dimethylaminopara-toluidine)
0.55 parts Silane coupling agent (γ-Metz) 3 parts The obtained composition was kneaded on a glass plate using a spanula, and then this kneaded product was defoamed using a vacuum stirring defoaming machine. It was made into a photopolymerizable paste. All of these steps were performed in a dark room.

Using the adhesive composition thus obtained.

Photocuring strength and adhesion depth were measured by the methods described below. M fruits are shown in Table 1.

11 Nu1 Bovine front teeth that were frozen and stored immediately after extraction were used as adherents. Bovine anterior teeth were thawed and the crowns were cut in the axial direction with a low-speed cutter. The labial dentin was used for the adhesion test.

The adhesion area was set at 5 m2, and the metal rods were adhered using the brush stacking method.

The adhesive was left at room temperature for 10-30 minutes.

After standing, this adhesive was immersed in water at 37° C. for 24 hours.

After the end of immersion Y, the adhesive strength between the metal rod and the adherend (K to f/
cm2).

Stop 11 Photocuring depth was measured as follows.

10II with carbon incorporated and essentially non-light transparent
A 4 mm diameter hole was made in a polyethylene plate with a thickness of I11, and the adhesive was placed in a bottle, being careful not to introduce air bubbles, and after irradiation with light for 12 seconds using a commercially available light irradiator (WhiteLite manufactured by Kuraray), The unpolymerized portion was scraped off with a spatula, and the length of the cured product was measured.

Example 1 was carried out in the same manner as in Example 1 except that the composition of the adhesive composition was changed as described below.

11 plates 1 Polymerizable monomer CUDMA; 2,2.4-) Addition compound of 1 molecule of dimethyl hexamethylene diisocyanate and 2 molecules of hydroxyethyl methacrylate) 100 parts Filler (TU filler) 120 parts Photoinitiator (Camphorquinone) 0.3 parts Reducing agent (DMPT; N,N-dimethyladenovalatluidine)
Table 1 shows the adhesive strength and photocuring depth measured in the same manner as in Example 1 using 0.55 parts of the above adhesive composition.

For example, Example 1 was carried out in the same manner as in Example 1 except that the composition of the adhesive composition was changed as described below.

Post-IL dish" [Depolymerizable monomer CUDMA; 2,2.4-) Addition compound of 1 molecule of dimethyl hexamethylene diisocyanate and 2 molecules of hydroxyethyl methacrylate) 100 parts Filler (TU filler) 190 parts Light initiation Agent (camphorquinone) 0.3 parts Reducing agent (DMPT; N,N-dimethylaminopara-toluidine)
0.55 parts Silane coupling agent (γ-Menz) 3 parts The adhesive strength and photocuring depth measured in the same manner as in Example 1 using the above adhesive composition are shown in Table 1.

Shuchiko 1 Example 1 was carried out in the same manner as in Example 1, except that the composition of the adhesive composition was changed as described below.

94 parts polymerizable monomer (addition compound of 1 molecule of 2,2,4-)dimethylhexamethylene diisocyanate and 2 molecules of hydroxyethyl methacrylate) -xyethoxytrimellitic anhydride)
6 parts filler (TU filler) 160 parts photoinitiator (campurquinone) 0.3 parts reducing agent (DMPT; N,N-dimethylamino para-toluidine)
0.55 parts Silane coupling agent (γ-mentz) 3 parts The adhesive strength and σ light curing depth measured in the same manner as in Example 1 using the above adhesive composition are shown in Table 1.

[Example 1] Example 1 was carried out in the same manner as in Example 1 except that the composition of the adhesive composition was changed as described below.

After] b-arc JLt polymerizable monomer (TEGDMA; ) lyethylene glycol dimethacrylate) 100
Part filler (TU filler) 120 parts Photoinitiator (camphorquinone) 0.3 part Reducing agent (DMPT; N,N-dimethylamino para-toluidine)
Table 1 shows the adhesive strength and photocuring depth measured in the same manner as in Example 1 using 0.55 parts of the above adhesive composition.

Ratio 11 Example 1 was carried out in the same manner as in Example 1 except that the composition of the adhesive composition was changed as described below.

80 parts Polymerizable monomer (MMA; methyl methacrylate) 20 0.3 parts photoinitiator (camphorquinone) reducing agent (DMPT; N,N-dimethylamino para-toluidine)
0.55 parts Silane coupling agent (γ-Menz) 3 parts The adhesive strength and photocuring depth measured in the same manner as in Example 1 using the above adhesive composition are shown in Table 1.

Example 1 was carried out in the same manner as in Example 1, except that the composition of the adhesive composition was changed as described below.

Polymerizable monomer (2,2-bis[4''-(methacryloxypolyethoxy)phenyl]propane) 30 parts Polymerizable monomer (MMA; methyl methacrylate) 50
Part polymerizable monomer (hydroxyethyl methacrylate) 10 parts polymerizable monomer (4-methacryloxyethoxytrimellitic anhydride)
10 parts Photoinitiator (camphorquinone) 0.3 parts Reducing agent (DMPT; N,N-dimethylamino para-toluidine)
0.55 parts Silane coupling agent (γ-Menz) 3 parts The adhesive strength and photocuring depth measured in the same manner as in Example 1 using the above adhesive composition are shown in Table 1.

1 monster-”-

Claims (4)

[Claims] (1) (A) An addition compound of one molecule of diisocyanate derivative and two molecules of hydroxyalkyl methacrylate as a polymerizable monomer; 30 to 50% by weight, (B) Insoluble in the above polymerizable monomer, and A filler containing 70 to 100% by weight of particles having an average particle size of 1 to 30 μm; 50 to 70% by weight, and (C) a photopolymerization initiator consisting of camphorquinone and/or benzyl; 0.0005 to 1% by weight %. (2) The composition according to claim 1, wherein the diisocyanate derivative is trimethylhexamethylene diisocyanate. (3) The composition according to claim 1, wherein the diisocyanate derivative is isophorone diisocyanate. (4) The composition according to claim 1, wherein the hydroxyalkyl methacrylate is hydroxyethyl methacrylate.