FLUORIDE VARNISH PRODUCTION

Karen Geraldine & Dhea Putriani

PATENT WO2014127178A1

Dental varnishes are composed of:

1. Rosin
2. Resin
3. A fluoridizing agent
4. A solvent
5. An optional remineralization agent
6. An optional flavor additive
7. An optional sweetener
8. An optional oxide

INGREDIENTS

Rosin Preparation

Examples of suitable rosins:

● FORAL AX-E (hydrogenated gum rosin; AN 165)

● STAYB ELITE Resin-E (partially hydrogenated gum rosin); AN 162)
● PAMITE 79 (tall oil rosin; AN 158)
● PAMITE 90 (tall oil rosin; AN 175)
● POLY-PALE (partially dimerized rosin; AN 142)
● DYM EREX (dimerized rosin; AN 140)
● POLYSTIX 90 (partially dimerized rosin; AN 150)
● DRESINATE (rosin soap)
● PERMALYN NC-11 (noncrystalline rosin; AN 157)

Further examples of rosins suitable for use may be any of the commercially available types of rosin are
as follows:

● Wood rosin
● Gum rosin
● Tall oil rosin
● Mixtures in their crude or refined state
○ Methyl ester of hydrogenated rosin
○ Triethylene glycol ester of hydrogenated rosin
○ Diethylene glycol ester of hydrogenated rosin
○ Ethylene glycol ester of hydrogenated rosin
○ Mixtures with each other or with the glycerol ester of hydrogenated rosin
Rosin suitable for use is partially hydrogenated rosin to fully hydrogenated rosin. The more hydrogenated
the rosin, the more colorless it will be. The rosin is necessary to the dental varnish because the rosin
provides adhesive qualities to the teeth upon application.

The rosin in varnish should be from 5 to 75 wt %, 18 to 60 wt %, 29 to 35 wt %.

Resin Preparation

Examples of suitable resins are vinyl type resins such as acrylic type resins and styrene type resins, such
as:

● 4-methacryloxyethyl trimellitic acid and its anhydride

● Bisphenol type epoxy acrylates and their oligomers
● Urethane dimethacrylates
● Methyl acrylate
● Methyl methacrylate
● Ethyl methacrylate
● Butyl methacrylate
● Polyethyleneglycol dimethacrylates
● Vinyl acetate
● Styrene
● Divinyl benzene

These vinyl monomers can be used alone or in any mixture thereof.

The resin in varnish may be from 20 to 75 wt %, 25 to 60 wt %, 35 to 45 wt %.

To create a colorless resin, synthesize the resin with a reaction between:

● 2,2’bis[p-(2’-hydroxy-3’methacry oxypropoxy)phenyl]propane (BisGMA) about 75 to 95 wt %

● Hexamethylene diisocyanate (HMDI) about 5 to 25 wt %

Mixing is done from 6 to 8 hours in a mixer at a mixing speed of 10 to 35 rpm. Catalyst used is Dabco T-
9 (0.01 to 0.1 wt %) and stabilizer used is butylated hydroxy toluene (BHT) (0.01 to 0.1 wt %). This
synthesized resin combined with hydrogenated rosin provides a colorless dental varnish as both rosin
and resin are colorless.

Fluoridizing Agent

Fluoridizing agents suitable for varnish:

● Sodium fluoride
● Stannous fluoride
● Sodium monofluorophosphate
● Zinc
● Hexafluorosilicate
● Sodium hexafluorosilicate

The fluoridizing agent in varnish may be 0.1 to 8 wt %, 1 to 7.5 wt %, or 2 to 7 wt %.

Solvent
The solvent is typically selected so that it evaporates relatively quickly after the varnish is applied to the
teeth to form a film of solid varnish material on the tooth surface.

Solvents that can be used:

● Individual alcohols
○ Ethyl alcohol
○ Propyl alcohol
○ Butyl alcohol
● Mixture of alcohols
● Individual hydrocarbons
Suitable hydrocarbons include C5-C7 (linear/branched/cyclic, alkanes/alkenes)
Examples: Isopentane, n-pentane, isohexane, n-hexane, cyclohexane, 2,5-dimethylhexane, etc.
● Mixtures hydrocarbons
● Mixture of alcohols with hydrocarbons

The solvent may be present in the dental varnish in amounts of from about 10 to 35 wt %, 15 to 30 wt %,
or 20 tp 25 wt%.

Flavor Additive and Sweetener

Example of flavor additives:

● Peppermint
● Watermelon
● Spearmint
● Cherry
● Citric acid
● Orange
● Strawberry
● Vanilla
● Coconut
● Bubble Gum

Such flavoring additives may be in the dental varnish in amounts of from about 0.01 to 5 wt %, 0,1 to 4
wt%, or 0.7 to 3 wt%t.

Example of sweeteners:

● Xylitol
● Sorbitol
● Sucralose
● Aspartam
● Sodium Saccharine

Such sweeteners may be in the dental varnish in amounts of from about 0.01 to 2 wt %, 0.05 to 1.5 wt%,
or 0.08 to 1 wt%

Oxide
Dental varnish may include a white or substantially white tint from at least one oxide, such as:

● Titanium
● Zirconium
● Germanium
● Zinc
● Iron
● Chromium
● Vanadium
● Tantalum
● Niobium

The oxide may be present in the dental varnish in amounts of from about 0 to 2 wt %, 0.01 tp 1 wt %,
0.08 to 1 wt %.

PROCEDURE

1. Preparation of the following:

a. 285 grams of 2-propanol
b. 520 grams of resin (derived from BisGMA, HDMI, BHT, and T-9 catalyst)
Resin is synthesized by charging a mixture of the following ingredients into a Ross mixer
equipped with a water jacket and two agitators. Temperature of water jacket is increased
to 50oC. The mixture is agitated for 7 hours.
● 1000 grams of BisGMA
● 171 grams of HDMI
● 0.57 grams of T-9
c. 400 grams of fully hydrogenated rosin
d. 65 grams of sodium fluoride
e. 1.5 grams of sweetener
f. 20 grams of flavoring
2. Mixing of ingredients propanol, resin, and rosin from 2 to 14 hours until all of the resin and rosin
is dissolved, thereby creating solution 1.
3. Mixing of ingredients sodium fluoride, sweetener, and flavoring to solution 1 from 1 to 2 hours
until a uniform suspension is formed.
 PATENT US20180071180A1

Dental varnishes are composed of:

1. Hydrogenated rosin
2. Fluoride compound
3. A solvent
4. An antibacterial substance
5. An optional polymerization inhibitor
6. An optional pigment
7. An optional coloring agent
8. An optional fluorescent agent
9. An optional sweetener
10. An optional flavor
11. Optional wax
12. Optional xylitol for neutralization of pH
13. Optional carbonate apatite and calcium phosphate for remineralization of teeth

INGREDIENTS

Hydrogenated Rosin

Hydrogenated rosin refers to a rosin with hydrogen added, combined with hydrogen, or cured with
hydrogen. In this patent, hydrogenated rosin used is Pinecrystal KR-610 (ARAKAWA).

Fluoride Compound

Fluoride compounds suitable for varnish:

● HF
● NH4F
● NaF
● KF
● Na2FPO4
● K2FPO4
● CaF2
● TiF4
● Ca5(PO4)3F
● H2F2Si
● C16H36FN
● SnF2

The fluoridizing agent in varnish may be used alone or as a mixture of two or more thereof.

Solvent

The solvent may be one or more from the following:

● Distilled water
 ● Dimethyl sulfoxide (DMSO)
● Isoamyl propionate
● Hydrogen fluoride (HF)
● Ethanol
● Ethyl acetate

Antibacterial Substance

Suitable antibacterial substances used are as follows:

● Bakuchiol
● Bavachalcone
● Isobavachromene
● Bavachromene
● Xanthorrhizol

PROCEDURE

1. Preparation of the following:

a. 45 wt % of hydrogenated rosin (9 grams)
b. 50 wt % of ethanol (10 grams)
c. 5 wt % of NaF (1 gram)
d. Antibacterial substance powders
e. DMSO
2. Mixing of hydrogenated rosin, ethanol, and NaF for 30 minutes at 240 rpm with an overhead
stirrer on a hot plate for heating in a water bath at 90oC, forming solution 1.
3. Dissolving of antibacterial substance powders in DMSO to 100 mM and stored, forming
solution 2.
4. Dilution is done to solution 2 using DMSO to prepare 20 mM and 2 mM antibacterial substances,
resulting in solution 3 (20 mM) and solution 4 (2mM).
5. Solution 3 and solution 4 are each mixed with solution 1 with a ratio of 1:1. Specifically the
volume used for each solution is 10 μL. This results in two types of fluoride varnish with different
antibacterial concentrations.

EVALUATION OF ANTIBACTERIAL PROPERTIES

Antibacterial properties of antibacterial substances were evaluated using S. mutans as a strain, according
to the agar diffusion test between 0.1 mM, 1 mM, 10 mM antibacterial substances, ampicillin as
positive control, and PBS as negative control.

1. S. mutans is primarily cultured in a BHI medium in a CO2 incubator at 37oC for 24 hours.
2. 200 μL of a suspension of S. mutans is inoculated into BHI and secondarily cultured for 6 hours.
3. OD value is measured with Eppendorf Biophotometer plus.
4. After measurement, bacteria are mixed with top agar and then inoculated into the agar medium
containing base agar.
5. After the top agar hardened, a 6 mm diameter paper disc is placed on the agar medium.
6. 5 μL of each of 0.1 mM, 1 mM and 10 mM antibacterial substances is dropped on the paper disc.
7. After culturing in a CO2 incubator at 37oC for 24 hours, the diameter of S. mutans inhibition zone
is formed around the paper disc. It is measured in two perpendicular locations and the average is
calculated to evaluate the antibacterial activities. The average is expressed in mm.