JPH0967222A - Curing retarder for normal-temperature-polymerizable resin for dental use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject retarder capable of retarding the curing time of a normal-temperature-polymerizable resin along with controlling the retardation time. SOLUTION: This retarder is to be used for a normal-temperature- polymerizable resin for dental use composed of a liquid predominant in methyl methacrylate and powder predominant in polymethyl methacrylate or polymethyl-ethyl methacrylate and curable by radical polymerization, and comprises 100 pts.wt. of a radical-polymerizable compound containing at least one ethylenic unsaturated double bond and 1-10 pts.wt. of a phenolic polymerization inhibitor.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a delay of curing time and control of a delay time of a room temperature dental resin used for temporary prostheses, repair of broken denture bases and artificial teeth, orthodontic beds, splints and the like. The present invention relates to a curing retarder for a room temperature dental resin for dental treatment.

[0002]

2. Description of the Related Art A dental room temperature polymerization resin is composed of a liquid agent containing methylmethacrylate as a main component and a powder agent containing polymethylmethacrylate or polymethylethylmethacrylate as a main component. A resin material that undergoes a radical polymerization reaction between a polymerization initiator such as an oxide and a polymerization accelerator such as a tertiary amine to polymerize and cure at room temperature. And, it is used by the usage methods such as the pen-stacking method, the mixing method, the free-fake method, etc., depending on the purpose of use and the site of use. With the brush-loading method, the liquid agent is soaked in the tip of a small brush made of pig hair or nylon, and this is put in the powder agent and the powder agent is attached to the tip of the brush. At this time, the liquid agent contained in the brush penetrates into the gap of the powder agent by the capillary phenomenon. This is a method in which the powder agent and the liquid agent are brought into contact with each other to initiate a reaction and start polymerization, which is a method suitable for use in a fine work site.

The mixing method is a method in which a fixed amount of a liquid agent and a powder agent are taken and mixed in a rubber cup, whereby the powder agent and the liquid agent are brought into contact with each other to initiate a reaction and start polymerization, and like a large prosthesis or the like. This method is suitable when using a large amount of resin. According to the Furikake method, when a liquid agent is thinly applied or dipped on a gypsum model and a powder agent is sprayed thereon, the liquid agent penetrates into the gaps of the powder agent by a capillary phenomenon. This is a method in which the powder agent and the liquid agent are brought into contact with each other to start a reaction and start polymerization, and is a method suitable for use when precision such as preparation and repair of a denture base or an orthodontic bed is required. However, the curing time of the cold-curing dental resin is determined by the manufacturer of the product and cannot be adjusted by the user. Therefore, in the case of producing a large prosthesis or the like, the operation time is insufficient and sufficient morphology cannot be imparted regardless of which of the writing method, the mixing method and the free flake method is used.

Further, in any of the writing method, the mixing method, and the free-flake method, air bubbles are liable to be mixed when the powder agent and the liquid agent come into contact with each other, and the strength and aesthetic property of the cured product after completion of the polymerization may be deteriorated. It often happens. Therefore, a dentist or a dental technician uses a pressure pot to apply a pressure of about 2 atm to the resin before curing to perform defoaming. However, before the room-temperature dental resin is polymerized and hardened, it is necessary to apply a form, put it in a pressure pot and apply a pressure of about 2 atm. In this case, the time available for the form application is further shortened, It is not possible to give sufficient morphology or sufficient defoaming. As a method of delaying the operation time, some dentists and dental technicians have slowed the polymerization reaction by cooling the liquid or powder in a refrigerator. However, in this method, the operation time cannot be controlled as desired, and the operation time is unnecessarily delayed, and the curing time cannot be adjusted appropriately.

[0005]

In view of the above situation, the present invention makes it possible for a user to easily delay the curing time of a dental cold polymerization resin at the time of use and to reduce the delay time. The subject was to develop a curing retarder for a room temperature dental resin that can be freely controlled.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above-mentioned problems, the present invention has shown that a phenol-based polymerization inhibitor is added to a radical-polymerizable compound containing at least one ethylenically unsaturated double bond. It was determined that a retarder having a composition containing is effective in delaying the polymerization and curing reaction of a dental room temperature polymerization resin, and when using the dental room temperature polymerization resin, this retarder is used as a liquid agent. The present invention has been completed by clarifying that it is possible to freely set the curing delay time by adding a predetermined amount (about 1 to 6 parts by weight).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION That is, as a hardening retarder for a dental room temperature polymerization resin according to the present invention, a liquid agent containing methyl methacrylate as a main component, and a powder agent containing polymethyl methacrylate or polymethyl ethyl methacrylate as a main component. A curing retarder for a room-temperature polymerization resin for dental use, which cures by a radical polymerization reaction, is a phenol-based polymerization inhibitor for 100 parts by weight of a radical-polymerizable compound containing at least one ethylenically unsaturated double bond. Agents 1 to 1
It is characterized by being mixed with 0 part by weight. Then, at the time of using the dental cold polymerization resin, it is possible to delay the hardening of the dental cold polymerization resin by adding a small amount of this hardening retarder to the liquid agent, and by adjusting the addition amount of the hardening retarder. The curing delay time can be adjusted.

Ethylenic Unsaturation 2 Used in the Present Invention
As the radically polymerizable compound containing at least one heavy bond, monofunctional methacrylate, monofunctional acrylate, polyfunctional methacrylate, or polyfunctional acrylate can be used. Specifically, methyl methacrylate, 2
-Hydroxyethyl methacrylate, ethyl methacrylate, isopropyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3 butanediol Dimethacrylate, 1,4 butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 2,2-bis (methacryloxyphenyl) propane, 2,2-bis [4- (2-hydroxy-3-methacryloxyphenyl] )] Propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-methacrylate) Xydiethoxyphenyl) propane, 2,2-bis (4-methacryloxypropoxyphenyl) propane, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, pentaerythritol tetramethacrylate and acrylates thereof. There is. These may be used alone or in combination of two or more. Among these, methyl methacrylate is preferable because it is the main component of the liquid agent for the room temperature dental resin.

The phenolic polymerization inhibitor is required to act as a radical chain reaction inhibitor during the radical polymerization reaction of the dental room temperature polymerization resin and to impart a curing retarding effect by inhibiting the radical polymerization reaction. Specifically, 2,6-di-t-butyl-p-cresol, 2,4-dimethyl-6-t-butylphenol,
p-methoxyphenol, 1,4-benzenediol,
Butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, sterial-β- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-ethyl-6)
-T-butylphenol), 4,4'-thiobis- (3
-Methyl-6-t-butylphenol), 4,4'-butylidene-bis- (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- [β-
(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-
Tetraoxaspiro [5,5] undecane, 1,1,3
-Tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3
-(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis (3,3'-bis- (4'-hydroxy-3'-t-butylphenyl)
Futilic acid] glycol ester, 1,3,5
-Tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6,-(1
(H, 3H, 5H) trione, vitamin E and the like. These phenolic polymerization inhibitors may be used alone or in combination of two or more. Among these, 2,4-dimethyl-6-t-butylphenol is preferable because it has an excellent curing delaying effect on the dental room temperature polymerization resin and has a good controllability of the delaying time.

The compounding amount of the phenolic polymerization inhibitor is appropriately 1 to 10 parts by weight with respect to 100 parts by weight of the radically polymerizable compound containing at least one ethylenically unsaturated double bond. If the amount is less than 1 part by weight, the effect of the room temperature polymerization resin for dental treatment is not sufficient, whereas if it exceeds 10 parts by weight, the delay time becomes too long and the controllability of the delay time becomes poor.

[0011]

EXAMPLES Next, the present invention will be described in detail with reference to examples. The present invention is not limited to these.

<Evaluation method of delay effect and controllability of delay time> As a dental room temperature polymerization resin, product name "UNIFAST II" manufactured by GC Co., Ltd. -Ethyl methacrylate, which is a room-temperature dental resin that cures by radical polymerization, was used to precisely weigh 2 g of the powder in a rubber cup and 1 g of the liquid in a glass container based on the ratio of the powder and the liquid specified by the product. A predetermined amount of a curing retarder for dental room temperature polymerization resin was added to the precisely weighed liquid agent, and the powder agent and the liquid agent were brought into contact in the rubber cup and mixed for 15 seconds, and at the same time, the time until the exothermic peak was reached using a thermistor thermometer. Was measured as the curing time, and the delay effect and controllability of the delay time were evaluated. The temperature is 23 ± 2 ℃ and the relative humidity is 50 ± 5.
% In a constant temperature chamber.

Example 1 Methyl methacrylate was used as a radically polymerizable compound containing at least one ethylenically unsaturated double bond.
100 parts by weight, 5 parts by weight of 2,4-dimethyl-6-t-butylphenol as a phenolic polymerization inhibitor were blended to prepare a curing retarder for a dental room temperature polymerization resin, and a retarding effect was obtained based on the above evaluation method. The controllability of delay time was evaluated. The results are summarized in Table 1. Curing time was delayed by adding 1 drop (0.018g) for 30 seconds in a special container, and
Add 60 drops with drop addition (0.036g) and add 3 drops (0.054g)
g) 1 minute and 30 seconds, depending on the amount of the curing retarder added,
It was confirmed that the delay time could be adjusted.

Example 2 Methyl methacrylate was used as a radically polymerizable compound containing at least one ethylenically unsaturated double bond.
100 parts by weight, 2 parts by weight of 2,4-dimethyl-6-t-butylphenol as a phenolic polymerization inhibitor were mixed to prepare a curing retarder for a dental room temperature polymerization resin, and a retarding effect was obtained based on the above evaluation method. The controllability of delay time was evaluated. The results are summarized in Table 1. The curing time was delayed by 15 seconds with the addition of 1 drop (0.018g) in a special container, and 2
Add a drop (0.036g) for 30 seconds, add 3 drops (0.054g)
It was confirmed that it was possible to adjust the delay time depending on the addition amount of the setting retarder by delaying 45 seconds with g).

Example 3 Methyl methacrylate was used as a radically polymerizable compound containing at least one ethylenically unsaturated double bond.
100 parts by weight, 9 parts by weight of 2,4-dimethyl-6-t-butylphenol as a phenolic polymerization inhibitor were mixed to prepare a curing retarder for a dental room temperature polymerization resin, and a retarding effect was obtained based on the above evaluation method. The controllability of delay time was evaluated. The results are summarized in Table 1. Curing time was delayed by adding 1 drop (0.018g) for 1 minute 30 seconds, adding 2 drops (0.036g) for 3 minutes 30 seconds, and adding 3 drops (0.054g) in a dedicated container. After a delay of 9 minutes and 30 seconds, it was confirmed that the delay time could be adjusted according to the amount of the curing retarder added.

Example 4 Methyl methacrylate was used as a radically polymerizable compound containing at least one ethylenically unsaturated double bond.
100 parts by weight, 5 parts by weight of 2,6-di-t-butyl-p-cresol as a phenol-based polymerization inhibitor were mixed to prepare a curing retarder for a dental room temperature polymerization resin, and the retardation was delayed based on the above evaluation method. The effect and controllability of delay time were evaluated. The results are summarized in Table 1. Curing time was delayed by adding 1 drop (0.018g) for 10 seconds, adding 2 drops (0.036g) for 20 seconds, and adding 3 drops (0.054g) in a special container.
It was confirmed that it was possible to adjust the delay time depending on the addition amount of the curing retarder by 30 seconds.

Example 5 Methyl methacrylate was used as a radically polymerizable compound containing at least one ethylenically unsaturated double bond.
100 parts by weight, 2.5 parts by weight of 2,6-di-t-butyl-p-cresol as a phenol-based polymerization inhibitor, 2,4-
2.5 parts by weight of dimethyl-6-t-butylphenol was blended to prepare a curing retarder for a dental room temperature polymerization resin, and the retarding effect and the controllability of the retarding time were evaluated based on the above evaluation method. The results are summarized in Table 1. Curing time was delayed by adding 1 drop (0.018g) for 40 seconds, adding 2 drops (0.036g) by 55 seconds, and adding 3 drops (0.054g) by 1 minute 15 seconds. It was confirmed that it was possible to adjust the delay time depending on the amount of the retarder added.

Example 6 100 parts by weight of ethylene glycol dimethacrylate as a radically polymerizable compound containing at least one ethylenically unsaturated double bond, and 2,4-dimethyl-6-t-as a phenolic polymerization inhibitor. 5 parts by weight of butylphenol was blended to prepare a curing retarder for a dental room temperature polymerization resin, and the retardation effect and the controllability of the delay time were evaluated based on the above evaluation method. The results are summarized in Table 1. Curing time is 30 by adding 1 drop (0.018g) in a special container.
Delay by 2 seconds, add 2 drops (0.036g) for 55 seconds, add 3 drops (0.054g) for 1 minute 45 seconds, and adjust the delay time according to the amount of curing retarder added. Was confirmed to be possible.

Example 7 100 parts by weight of ethylene glycol dimethacrylate as a radically polymerizable compound containing at least one ethylenically unsaturated double bond, and 2,4-dimethyl-6-t-as a phenolic polymerization inhibitor. 1 part by weight of butylphenol was blended to prepare a curing retarder for a dental room temperature polymerization resin, and the retarding effect and the controllability of the retarding time were evaluated based on the above evaluation method. The results are summarized in Table 1. Curing time is 10 by adding 1 drop (0.018g) in a special container.
Delay by 20 seconds, by adding 2 drops (0.036g), delay by 20 seconds, by adding 3 drops (0.054g), delay by 30 seconds. Delay time can be adjusted according to the amount of curing retarder added. Was confirmed.

Example 8 100 parts by weight of ethylene glycol dimethacrylate as a radically polymerizable compound containing at least one ethylenically unsaturated double bond, and 2,4-dimethyl-6-t-as a phenolic polymerization inhibitor. 10 parts by weight of butylphenol was blended to prepare a hardening retarder for a dental room temperature polymerization resin, and the delay effect and controllability of delay time were evaluated based on the above evaluation method. The results are summarized in Table 1. Curing time is 1 by adding 1 drop (0.018g) in a special container.
Delay 30 minutes, add 2 drops (0.036g) for 3 minutes 30 seconds, add 3 drops (0.054g) for 9 minutes 30 seconds, depending on the amount of curing retarder It was confirmed that it is possible to adjust.

Comparative Example 1 Methyl methacrylate was used as a radically polymerizable compound containing at least one ethylenically unsaturated double bond.
100 parts by weight, 0.1 parts by weight of 2,4-dimethyl-6-t-butylphenol as a phenol-based polymerization inhibitor were mixed to prepare a curing retarder for a dental room temperature polymerization resin, and a retarding effect was obtained based on the evaluation method. The controllability of delay time was evaluated. The results are summarized in Table 2. The curing time is
Addition of 1 drop (0.018g) and 2 drops (0.036g) in a special container did not delay at all, and 3 drops (0.054g)
It was delayed for 10 seconds and could not be used as a dental room temperature polymerization resin hardening retarder.

Comparative Example 2 Methyl methacrylate was used as a radically polymerizable compound containing at least one ethylenically unsaturated double bond.
100 parts by weight, 20 parts by weight of 2,4-dimethyl-6-t-butylphenol as a phenol-based polymerization inhibitor were mixed to prepare a curing retarder for a dental room temperature polymerization resin, and a retarding effect was obtained based on the above evaluation method. The controllability of delay time was evaluated. The results are summarized in Table 2. Curing time was delayed by adding 1 drop (0.018g) for 1 minute 30 seconds, adding 2 drops (0.036g) for 9 minutes 30 seconds, and adding 3 drops (0.054g) in a special container. Did not cure. The delay time of the curing time was too long, the controllability of the delay time could not be achieved, and it was unsuitable as a dental room temperature polymerization resin curing retarder.

Comparative Example 3 Methyl methacrylate was used as a radically polymerizable compound containing at least one ethylenically unsaturated double bond.
100 parts by weight, 0.1 parts by weight of 2,6-di-t-butyl-p-cresol as a phenolic polymerization inhibitor were mixed to prepare a curing retarder for a dental room temperature polymerization resin, and the retardation was delayed based on the above evaluation method. The effect and controllability of delay time were evaluated. The results are summarized in Table 2. Curing time is 1 drop (0.018g) and 2 drops (0.0
36g) did not delay at all, and 3 drops (0.054g) gave 5
It was delayed for only 2 seconds and could not be used as a dental room temperature polymerization resin curing retarder.

Comparative Example 4 Methyl methacrylate was used as a radically polymerizable compound containing at least one ethylenically unsaturated double bond.
100 parts by weight, 20 parts by weight of 2,6-di-t-butyl-p-cresol as a phenol-based polymerization inhibitor were mixed to prepare a curing retarder for a dental room temperature polymerization resin, and the retardation was delayed based on the above evaluation method. The effect and controllability of delay time were evaluated. The results are summarized in Table 2. Curing time was delayed by adding 1 drop (0.018g) for 30 seconds, adding 2 drops (0.036g) for 55 seconds, and adding 3 drops (0.054g) in a dedicated container.
I was delayed by 1 minute. Even if two or more drops of curing time were delayed, there was almost no change, and it could not be used as a dental room temperature polymerization resin curing retarder.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

As described above, when the curing retardant for a dental room temperature polymerization resin of the present invention is used, the curing time of the dental room temperature polymerization resin is delayed or controlled according to the purpose and application. This makes it possible to delay and adjust the curing time so that there is enough morphing time even for large prostheses, etc., and it has sophisticated morphing and excellent compatibility. It is now possible to manufacture prostheses. Further, it becomes possible to sufficiently perform the defoaming work in the pressure cooker, and it is possible to obtain a prosthesis which is excellent in aesthetics and has sufficient mechanical properties such as strength. Even when the curing time of the dental room temperature polymerization resin is shortened due to the rise in temperature, it is possible to easily adjust the curing time to a desired one without performing operations such as cooling in the refrigerator. As described above, the curing retardant for the dental room temperature polymerization resin of the present invention greatly improves the operability of the dental room temperature polymerization resin, and the prosthesis produced has excellent aesthetic properties such as the function expression of the dental room temperature polymerization resin. It is extremely useful and has a great place to contribute to dental care.

Claims (2)

[Claims] 1. A liquid agent containing methyl methacrylate as a main component, and polymethyl methacrylate or polymethyl.
A radically-polymerizable compound containing at least one ethylenically unsaturated double bond as a curing retarder used in a dental room temperature polymerization resin, which comprises a powder having ethyl methacrylate as a main component and is cured by a radical polymerization reaction. A hardening retarder for a dental room temperature polymerization resin, characterized in that 1 to 10 parts by weight of a phenolic polymerization inhibitor is blended with respect to parts by weight. 2. The radically polymerizable compound containing at least one ethylenically unsaturated double bond is selected from the group consisting of monofunctional methacrylate, monofunctional acrylate, polyfunctional methacrylate and polyfunctional acrylate, or The hardening retarder for a dental room temperature polymerization resin according to claim 1, which comprises two or more kinds.