Hydromer Inc

Transparent anti-fog coating compositions

Patent number:4467073
Type:Grant
Fileed:October 20,1982
Date of Patentt:August 21,1984
Assignee:Hydromer,Inc
Inventor:Walter S.Creasy

<Example I>
↓2.5g Polyvinylpyrrolidone, PVP-K90/ 100 ml  75% diacetone alcohol and 25% cyclohexane,
↓1.0 g dioctyl sodium sulfosuccinate surfactant
↓5.0 g Tycel 7351 isocyanate prepolymer (Hughson Chemicals, Lord Corporation)
↓Coatings
↓24 hours at 72.degree.

＜Example II>
2.5gPVP-K90　/ 100 ml 50%ethyl lactate and 50% methyl ethyl Ketone
1.5 g alkylphenoxypolyethyleneoxy sodium sulfate surfactant
2.5 g Spenlite P25-60cx isocyanate prepolymer (Spencer-Kellogg Corp.)
Coatings
72 hours at 72.degree.

＜Example III＞
7.5gTycel 7351 isocyanate prepolymer (Hughson Chemicals)/100 ml 75% diacetone alcohol and 25% cyclohexane, 1.5 g sodium dioctyl sulfosuccinate
effectiveness was greatly reduced or lost after soaking in water.

＜Example IV＞
2.5ｇ　Polyvinylpyrrolidone　/ 100 ml 75% tertbutyl alcohol and 25% xylene
5.0 g of Tycel 7351 isocyanate prepolymer (Hughson Chemicals)
1.0 g dioctyl sodium sulfosuccinate

＜Example V＞
A vinyl pyrrolidone/vinyl acetate 70/30 copolymer is substituted for the polyvinylpyrrolidone in Example I.

＜Example VI＞
Polydimethylacrylamide was substituted for the polyvinylpyrrolidone in Example I.

＜Example VI＞I
To the solution in Example I was added 0.05 g (1% based on isocyanate prepolymer) dibutyltin dilaurate catalyst. Cure is complete after 10 mins. at 60.degree.

＜Example VIII＞
2.5ｇ　Polyvinylpyrrolidone (K90)/100 ml 75% diacetone alcohol and 25% mineral spirits
5.0 g of Tycel 7351 isocyanate prepolymer
3.0 g of polyethoxylated nonyl phenol surfactant (Triton X-100 of Rohm and Haas)
0.05 g dibutyltin dilaurate catalyst
Coating
30 mins. at 60.degree
The surfactant is chemically bound in this case to the PVP-isocyanate coating matrix.

＜Example IX＞
even much higher Triton X-100 concentrations fail to impart satisfactory fog-resisting qualities.

＜Example X＞
1.0ｇ　Polyvinylpyrrolidone (K90)　85 g diacetone alcohol, 40 g cyclohexane and 10 g n-butyl acetate
2.0 g hexamethylene diisocyanate biuret (Desmodur N-100 made by Mobay Corp.).
2.5 g Acryloid AU608 polyol (Made by Rohm and Haas)
0.7 g dioctyl sodium sulfosuccinate
Coating
72 hours at R.T.

＜Example XI＞
A dibutyltin dilaurate catalyst is added to the composition in Example X.
The resulting coatings cure (0.5% on polymer solids) within 20 mins. at 60.degree. C.

＜Example XII＞
The composition of Example X was prepared without the polyvinylpyrrolidone.
However, utility is limited as much of the anti-fog property is lost after soaking in water.

＜Example XIII＞
1.0ｇ　Polyvinylpyrrolidone (K90)/ 85 g diacetone alcohol, 40 g cyclohexane and 10 g n-butyl acetate
4.0 g hexamethylene diisocyanate biuret (Desmodur N-100 made by Mobay Corp.)
4.0 g Acryloid polyol (Made by Rohm and Haas) AU608
3.0 g perfluorinated (polyethyleneoxy) ethanol (Fluorad FC170C made by 3M).
this coating are particularly inert to long term immersion in water.

＜Example XIV＞
A polyvinyl pyrrolidone-vinyl acetate copolymer is substituted for the polyvinylpyrrolidone in Example X with essentially equivalent results.

＜Example XV＞
A dimethylacrylamide polymer is substituted for the polyvinylpyrrolidone in Example X with essentially equivalent results.

US4642267A
Inventor　Walter S. CreasyDonald H. LorenzRobert G. LaCasseSalvatore A. MalagrecaCurrent
Assignee　.Hydromer Inc Cabot Technology Corp
Date of Patent: Feb. 10, 1987
EXAMPLE 1
To a mixture of
75 g diacetone alcohol
25 g methyl ethyl ketone
4 g polyvinylpyrrolidone (Kollidon 90, BASF Corp.)
2 g linear polyurethane (Estane 5703, B. F. Goodrich Co.)

EXAMPLE 2

47 g of water
10 g N-methylpyrrolidone
10 g of polyvinylpyrrolidone (Kollidon 90, BASF Corp.)
33 g of linear polyurethane aqueous dispersion (Neorez R940, Polyvinyl Chemical Industries).
NeoRez® R-9340 | Covestro

produce hydrophilic foams via either mechanical frothing or casting films with added acetone and drying with heat in vacuo

.EXAMPLE 3

Films cast as in Example 2
and containing 2% chlorohexidine acetate (w/w/ based on polymer)
Other substances which were successfully combined with the blends include cephalosporin, ampicillin, oxytetracycline, metaproterenol sulfate, salicylic acid and phenolphthalein.

Coating composition for multiple hydrophilic applications

Filed: September 27, 2002
Publication date: October 30, 2003
Applicant: Hydromer, Inc.
Inventors: Thomas C. Schottman, Patrick M. Hennessey, Rainer Gruening
＜Example 1＞
87 g　water
189 g　isopropanol and N-methylpyrrolidone,
40 g　polyvinylpyrrolidone solution (20% of Kollidone K90, BASF),
40 g　aqueous polyurethane dispersion 911 (Alberdinck&Boley),
Polyurethane dispersions | Alberdingk Boley (alberdingk-boley.de)
Aliphatic polycarbonate-polyurethane
1.6 g　aziridine cross linker NeoCryl CX 100 (Zeneca Resin)
CROSSLINKER CX-100 | Covestro
23 g　aqueous colloidal silica solution N 5110 (Eka-Akzo).
※The polyurethane dispersion 911 is an aliphatic polycarbonate modified polyurethane dispersion.
＜Example 2＞
281 g of water
89 g isopropanol and diacetone alcohol,
19 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF),
19 g aqueous aromatic polyurethane dispersion NeoRez R-940 (NeoResins),
NeoRez R-940 – Covestro (specialchem.com)
0.8 g aziridine crosslinker NeoCryl CX 100 (Zeneca Resin)
Microsoft Word – Crosslinker CX-100 pds.doc (audax.com.ar)
11 g aqueous colloidal silica solution N5110 (Eka-Akzo).
＜Example 3＞
94 g water
152 g isopropanol and N-methylpyrrolidone,
31.7 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF),
32.2 g aqueous polyurethane dispersion Sancure 898 (BF Goodrich),
Sancure 898 – Lubrizol (specialchem.com)
Lubrizol(ポリウレタンディスパージョン) | 塗料原料 | ケミカル | 事業紹介 | 株式会社ＧＳＩクレオス (gsi.co.jp)
1.3 g aziridine cross linker NeoCryl CX 100 (NeoResins)
18.4 g aqueous colloidal silica solution N 5110 (Eka-Akzo).

＜Example 4＞
173 g water
115 g isopropanol and N-methylpyrrolidone
23 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
24 g aqueous aliphatic polyurethane dispersion NeoRez R-960 (NeoResins)
0.95 g aziridine cross linker NeoCryl CX 100 (NeoResins)
13.5 g aqueous colloidal silica solution N 5110 (Eka-Akzo)
＜Example 5＞
326 g water
79 g isopropanol and N-methylpyrrolidone
１7 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
17 g aqueous polyurethane dispersion 600 (Alberdinck&Boley)
0.68 g aziridine cross linker NeoCryl CX 100 (NeoResins)
10 g aqueous colloidal silica solution N 5110 (Eka-Akzo)
The polyurethane dispersion 600 is an aliphatic polyether modified polyurethane dispersion.
The hydrophilic formulation was mixed and revealed good shelf life.
＜Example 6＞
246 g water
103 g isopropanol and N-methylpyrrolidone
21 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
22 g aqueous polyurethane dispersion 915 (Alberdinck&Boley)
0.87 g aziridine cross linker NeoCryl CX 100 (NeoResins)
12.6 g aqueous colloidal silica solution N 5110 (Eka-Akzo).
The polyurethane dispersion 915 is an aliphatic polyester modified polyurethane dispersion.
The hydrophilic formulation was mixed and revealed good shelf life.
＜Example 7＞
293 g water
72 g isopropanol and N-methylpyrrolidone
15 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
15 g aqueous polyurethane dispersion 910 (Alberdinck&Boley)
0.6 g aziridine cross linker NeoCryl CX 100 (NeoResins)
8.7 g aqueous colloidal silica solution N 5110 (Eka-Akzo)
The polyurethane dispersion 910 is an aliphatic polyester modified polyurethane dispersion.
The hydrophilic formulation was mixed and revealed good shelf life.
＜Example 8 (Comparative Sample)＞
110 g water
189 g isopropanol and N-methylpyrrolidone
40 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
40 g aqueous polyurethane dispersion 911 (Alberdinck&Boley)
1.6 g aziridine cross linker NeoCryl CX 100 (NeoResins)
no silica
reasonable shelf life.
＜Example 9 (Comparative Sample)＞
292 g water
89 g isopropanol and diacetone alcohol
19 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
19 g of aqueous polyurethane dispersion NeoRez R-940 (NeoResins)
0.8 g aziridine crosslinker NeoCryl CX100 (NeoResins)
no colloidal silica
revealed good shelf life.
＜Example 10 (Comparative Sample)＞
112 g water
152 g isopropanol and N-methylpyrrolidone
31.7 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
32.2 g aqueous polyurethane dispersion Sancure 898 (BF Goodrich)
1.3 g aziridine cross linker NeoCryl CX 100 (NeoResins)
no colloidal silica
revealed reasonable shelf life.
＜Example 11 (Comparative Sample)＞
190 g water
112 g isopropanol and N-methylpyrrolidone
23 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
24 g aqueous polyurethane dispersion NeoResin R-960 (NeoResins)
0.95 g aziridine cross linker NeoCryl CX 100 (NeoResins)
no colloidal silica
revealed good shelf life.
＜Example 12 (Comparative Sample)＞
336 g water
79 g isopropanol and N-methylpyrrolidone
17 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
17 g aqueous polyurethane dispersion 600 (Alberdinck&Boley)
0.68 g aziridine cross linker NeoCryl CX 100 (NeoResins)
no colloidal silica.
rvealed good shelf life.
＜Example 13 (Comparative Sample)＞
257 g water
103 g isopropanol and N-methylpyrrolidone
22 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
22 g aqueous polyurethane dispersion 915 (Alberdinck&Boley)
0.87 g aziridine cross linker NeoCryl CX 100 (NeoResins)
no colloidal silica
rvealed good shelf life.
＜Example 14 (Comparative Sample)＞
302 g water
72 g isopropanol and N-methylpyrrolidone
15 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
15 g aqueous polyurethane dispersion 910 (Alberdinck&Boley)
0.6 g aziridine cross linker NeoCryl CX 100 (NeoResins)
no colloidal silica
revealed good shelf life.

<Example 15 (Comparative Sample)>
112 g water
189 g isopropanol and N-methylpyrrolidone
40 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
40 g aqueous polyurethane dispersion 911 (Alberdinck&Boley)
no aziridine cross linker
no colloidal silica

<Example 16 (Comparative Sample)>
293 g water
89 g isopropanol and diacetone alcohol
19 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
19 g aqueous polyurethane dispersion NeoRez R-940 (NeoResins)
no aziridine crosslinker
no colloidal silica

<Example 17 (Comparative Sample)>
112 g water
152 g isopropanol and N-methylpyrrolidone
31.7 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
32.2 g aqueous polyurethane dispersion Sancure 898 (BF Goodrich)
no aziridine cross linker
no colloidal silica
<Example 18 (Comparative Sample)>
191 g water
112 g isopropanol and N-methylpyrrolidone
23 g polyvinylpyrrolidone solution (20% of Kollidone K90, BASF)
24 g aqueous polyurethane dispersion NeoRez R-960 (NeoResins)
no aziridine cross linker
no colloidal silica
<Example 19>
3.4 parts of an aqueous aromatic based polyurethane dispersion (component A),
3.2 parts of an aqueous aliphatic polyester modified polyurethane (component B)
7 parts of a 20% aqueous polyvinylpyrrolidone were combined with
1.5 parts of a colloidal silica,
0.2 parts of crosslinker and
0.3 parts of surfactant in
84.4 parts water-isopropyl alcohol mix.
<Example 20 (Comparative Example from U.S. Pat. No. 4,662,267)>
47 g water
10 g N-methylpyrrolidone
10 g of polyvinylpyrrolidone
33 g of linear polyurethane aqueous dispersion
<Example 21 (Comparative Example)>
75 g diacetone alcohol
25 g methyl ethyl ketone
4 g polyvinylpyrrolidone (Kollidon 90, BASF Corp.)
2 g linear polyurethane (Estane 5703, B. F. Goodrich Co.)
<Example 22>
13 parts of an aqueous aromatic based polyurethane dispersion (component A),
14 parts of an aqueous aliphatic polyester modified polyurethane (component B)
26 parts of a 20% aqueous polyvinylpyrrolidone
17 parts of a colloidal silica
0.5 parts of aziridine crosslinker
0.6 parts of surfactant
115 parts water
128 parts of isopropyl alcohol/NMP mix
<Example 23 (Comparative Sample from U.S. patent application Ser. No. 20020018898)>
a melamine formaldehyde crosslinking agent (hexamethoxy melamine/formaldehyde, Cymel 303, Cytec Corp.) at 2.0 times

<Example 24 (Controlled Release)>

<Example 25 (Controlled Release, Comparative Sample)>

<Example 26>
15 parts of an aqueous aromatic based polyurethane dispersion
39 parts of a 20% aqueous polyvinylpyrrolidone solution
13 parts of a colloidal silica
0.6 parts of an aziridine crosslinker
137 parts of an isopropyl alcohol/NMP/diaceton alcohol
146 parts of water.
<Example 27>
13 parts of an aqueous aromatic based polyurethane dispersion,
64 parts of a 20% aqueous polyvinylpyrrolidone solution,
9 parts of a colloidal silica,
0.6 parts of an aziridine crosslinker,
152 parts of an isopropyl alcohol/NMP/diaceton alcohol
90 parts of water.

<Example 28>
8 parts of an aqueous aromatic based polyurethane dispersion,
8 parts of a polyester modified polyurethane dispersion,
42 parts of a 20% aqueous polyvinylpyrrolidone solution,
14 parts of a colloidal silica solution,
0.6 parts of an aziridine crosslinker,
149 parts of an isopropyl alcohol/diaceton alcohol solvent mix
128 parts of water.
<Example 29>
11 parts of an aqueous aromatic based polyurethane dispersion (component A),
11 parts of an aqueous aliphatic polyester modified polyurethane (component B)
1 part of an aqueous polycarbonate modified polyurethane (component C)
23 parts of a 20% aqueous polyvinylpyrrolidone
15 parts of a commercial colloidal silica solution
0.2 parts of aziridine crosslinker
5 parts of surfactant i
111 parts of isopropyl alcohol/diacetone alcohol
154 of water.
 

<Example 30 (Comparative Sample from U.S. Pat. No. 4,662,267)>
47 g of water
10 g N-methylpyrrolidone
10 g of polyvinylpyrrolidone
33 g of linear polyurethane aqueous dispersion.
<Example 31>
11 parts of an aqueous aromatic based polyurethane dispersion (component A)
11 parts of an aqueous aliphatic polyester modified polyurethane (component B)
1 part of an aqueous polycarbonate modified polyurethane (component C)
23 parts of a 20% aqueous polyvinylpyrrolidone
15 parts of a commercial colloidal silica solution,
2 parts of sodium aluminate,
0.2 parts of aziridine crosslinker
5 parts of surfactant
111 parts of isopropyl alcohol/diacetone alcohol
152 of water.

<Example 32>
118 g of water was added a solvent
133 g which consisted of isopropanol and N-methylpyrrolidone,
28 g of a 20% aqueous polyvinylpyrrolidone solution
14 g aqueous aromatic modified polyurethane dispersion
1 g aqueous polycarbonate modified polyurethane dispersion
13 g aqueous aliphatic modified polyurethane
0.5 g aziridine cross linker
18 g of a commercial colloidal silica solution
<Example 33 (Comparative Sample)>
200 g of water
94 g which consisted of isopropanol and diacetone alcohol,
19 g of a 20% aqueous polyvinylpyrrolidone solution,
20 g aqueous polyester modified polyurethane dispersion,
no aziridine cross linker
13 g of a commercial colloidal silica solution.
<Example 34>
200 g of water
4 g of surfactant was added a solvent
94 g which consisted of isopropanol, and diaceton alcohol,
19 g of a 20% aqueous polyvinylpyrrolidone solution,
10 g aqueous aromatic modified polyurethane dispersion,
9 g aqueous polyester modified polyurethane dispersion
1 g aqueous polycarbonate modified polyurethane dispersion,
0.4 g of an alternative aziridine cross linker
13 g of a commercial colloidal silica solution.
<Example 35>
143 g of water
6 g of surfactant
129 g which consisted of isopropanol, diaceton alcohol and N-methylpyrrolidone,
27 g of a 20% aqueous polyvinylpyrrolidone solution,
15 g aqueous aromatic modified polyurethane dispersion
13 g aqueous aliphatic polyester modified polyurethane dispersion,
0.5 g aziridine cross linker
17 g of a commercial colloidal silica solution.
<Example 36>
118 g of water
6 g of surfactant
133 g which consisted of isopropanol, diaceton alcohol and N-methylpyrrolidone,
28 g of a 20% aqueous polyvinylpyrrolidone solution,
14 g aqueous aromatic modified polyurethane dispersion
13 g aqueous aliphatic polyester modified polyurethane dispersion,
1 g aqueous polycarbonate modified polyurethane dispersion,
0.5 g aziridine cross linker
18 g of a commercial colloidal silica solution.
<Example 37>
200 g of water and
4 g of surfactant
94 g which consisted of isopropanol, and diaceton alcohol,
19 g of a 20% aqueous polyvinylpyrrolidone solution,
9 g aqueous polyester modified polyurethane dispersion
11 g aqueous polycarbonate modified polyurethane dispersion,
0.3 g aziridine cross linker
13 g of a commercial colloidal silica solution.
 

<Example 38>
200 g water
4 g surfactant
94 g isopropanol, diaceton alcohol and N-methylpyrrolidone
19 g of a 20% aqueous polyvinylpyrrolidone solution
10 g aqueous aromatic modified polyurethane dispersion
9 g aqueous aliphatic polyester modified polyurethane dispersion
1 g aqueous polycarbonate modified polyurethane dispersion
0.4 g aziridine cross linker
13 g of a commercial colloidal silica solution
 

<Example 39>
200 g water
4 g of surfactant
94 g isopropanol, diaceton alcohol and N-methylpyrrolidone
19 g of a 20% aqueous polyvinylpyrrolidone solution
10 g aqueous aromatic modified polyurethane dispersion
9 g aqueous aliphatic polyester modified polyurethane dispersion
1 g aqueous polycarbonate modified polyurethane dispersion
0.4 g aziridine cross linker
13 g of an alternative commercial colloidal silica solution
 

<Example 40 (Comparative Sample)>
200 g water
94 g which consisted of isopropanol and diacetone alcohol, 19 g of a 20% aqueous polyvinylpyrrolidone solution
10 g aqueous aromatic modified polyurethane dispersion
9 g aqueous aliphatic polyester modified polyurethane dispersion
1 g aqueous polycarbonate modified polyurethane dispersion
no aziridine cross linker
13 g of an alternative commercial colloidal silica solution
<Example 41>
200 g water
94 g which consisted of isopropanol and diacetone alcohol
19 g of a 20% aqueous polyvinylpyrrolidone solution
10 g aqueous aromatic modified polyurethane dispersion
9 g aqueous aliphatic polyester modified polyurethane dispersion
1 g aqueous polycarbonate modified polyurethane dispersion
0.4 g melamine cross linker
13 g of an alternative commercial colloidal silica solution
 

<Example 42>
<Example 43>
<Example 44>
after 24 hrs the weight reached 10.3 times its original weight.
<Example 45>
30 min in various sodium chloride solutions as electrolytes.
A pure 2 cm×1 cm sample showed a resistance of about 4000 Ohm
0.5% NaCl had 1500 Ohm
1% has 1500 Ohm
2% had 1100 Ohm.

<Example 46 (Comparative Anti-Fog from U.S. Pat. No. 4,467,073)>
2.5g Polyvinylpyrrolidone, PVP-K90
100 ml  75% diacetone alcohol and 25% cyclohexane, followed
1.0 g dioctyl sodium sulfosuccinate surfactant
5.0 g Tycel 7351 isocyanate prepolymer (Hughson Chemicals, Lord Corporation).
cured 24 hours at 72° F

<Example 47>
Example 19
coat polycarbonate
120° C. for 3 min.

<Example 48 (Comparative Sample from U.S. Pat. No. 4,789,720)>
A latex Foley urinary catheter was dip-coated
3 parts of polymer from Example 1
97 parts of dichloroethane.
After air drying, the dipping was repeated.
The coating was cured at 80° C. for 5 minutes.
<Example 49>

Example 19
The coating was done in a one-step process
<Example 50>
Example 19 was modified with 25% commercially available antimicrobial colloidal silver (Millike

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