Fluorescent degree of cure monitors

• US 5,182,316 A
• Filed: 11/26/1991
• Issued: 01/26/1993
• Est. Priority Date: 05/31/1989
• Status: Expired due to Fees

• Current Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: DeVoe, Robert J., Tiers, George V. D., Brown-Wensley, Katherine A.
• Primary Examiner(s): Mc Camish, Marion E.
• Assistant Examiner(s): BERMAN, SUSAN W
• Application Number:
  US07/798,582
• Time in Patent Office: 427 Days
• Field of Search: 522/99, 522/100, 522/103, 522/182, 522/65, 522/70, 522/75, 526/93, 526/103, 526/284, 526/280, 526/256, 526/259, 526/268, 526/279, 528/15, 528/25, 528/27, 528/28, 528/32, 428/262, 428/264, 428/266, 428/290
• US Class Current: 522/99
• CPC Class Codes: C08F 283/12 on to polysiloxanes
• CPC Class Codes: C08G 85/00 General processes for preparing compounds provided for in this subclass
• CPC Class Codes: C08J 3/20 Compounding polymers with additives, e.g. colouring
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: G01N 21/643 non-biological material
• CPC Class Codes: G03F 7/105 having substances, e.g. indicators, for forming visible images

Abstract

A curable composition, the cure of which can be monitored optically, comprises at least one of a hydride curable silicone, an ethylenically unsaturated compound, and a cationically polymerizable monomer, and as cure monitor dibenzofulvene or derivative thereof. The cure monitor is a latent fluorophore which reacts under the cure conditions to form a UV-detectable fluorophore.

The invention also provides a method for measuring degree of cure of a polymeric material which can be a coating or an article.

Claims

1. A method for measuring the degree of cure of a polymeric composition comprising the steps of:

a) reacting a mixture comprising a polymerizable composition comprising at least one of

     1) a hydride curable silicone,

     2) an ethyleneically unsaturated compound,

     3) a cationically sensitive compound, and a spectroscopically detectable amount of a latent uvaphore comprising at least one of dibenzofulvene or derivative thereof, to provide an at least partially polymerized composition comprising a uvaphore, which differs chemically from said latent uvaphore, that absorbs radiant energy of a wavelength range centered around λ

₁ and emits radiant energy of a wavelength range centered around λ

₂, λ

₁ and λ

₂ each being a wavelength within the ultraviolet portion of the electromagnetic spectrum; and

the mean of the range of λ

₁ being below the mean of the range of λ

₂ ; and

b) measuring uvescence intensity at a wavelength centered around λ

₂ emitted by said composition during or after polymerization to provide an indication of degree of cure.

2. The method according to claim 1 wherein said latent uvaphore is a 9-fluorenone.

3. The method according to claim 1 wherein said polymerizable mixture further comprises at least one of a polymerization promoter, a solvent, and a polymerization inhibitor.

4. The method according to claim 1 further comprising the step of applying said polymerizable composition to at least one surface of a support prior to effecting polymerization.

5. The method according to claim 1 further comprising the step of adding energy to effect polymerization.

6. The cured composition prepared by the method according to claim 5.

7. The cured composition prepared by the method according to claim 5 wherein said uvaphore has the formula ##STR7## wherein X is as previously defined, and

Y and Z are chain atoms in the backbone of said cured composition.

8. A method for measuring the degree of cure of a polymeric composition comprising the steps of:

a) reacting a mixture comprising a polymerizable composition comprising at least one of

     1) a hydride curable silicone,

     2) an ethylenically unsaturated compound,

     3) a cationically sensitive compound, and a spectroscopically detectable amount of a latent uvaphore comprising at least one of dibenzofulvene or derivative thereof,

said dibenzofulvene or derivative thereof having the formula ##STR8## wherein X is Cr¹ R² or NR¹, wherein R¹ and R² each independently is a hydrogen atom, or an alkyl, aryl, alkenyl, aralkenyl, alkynyl, aralkynyl, alkaryl, or aralkyl group, or R¹ and R² together are a cycloaliphatic group of ring size 3 to 12 atoms, all of which can include up to 50 carbon atoms and 0 to 30 heteroatoms selected from the group consisting of unitary N, Si, S and nonperoxidic O;

or wherein aromatic groups designated A and B together or each independently can contain up to two ring nitrogen atoms, and together or independently can be a single or fused aromatic ring system having 1 to 4 rings, and each aromatic ring designated A and B in formula I can be substituted with up to four substituents, which are chosen from

     1) alkyl, aryl, aralkyl, alkaryl, acyl, acylamido, amino, hydroxycarbonyl, alkoxycarbonyl, alkoxy, aryloxy groups of up to 50 carbon atoms and 0 to 30 unitary fluoro, chloro, bromo, nitrogen, silicon, sulfur, and nonperoxidic oxygen atoms,

     2) cyano groups, bromo, chloro, and fluoro atoms, and

     3) silyl and siloxy groups containing up to 200 silicon atoms and up to 200 unitary nitrogen, sulfur, and nonperoxidic oxygen atoms,

to provide an at least partially polymerized composition comprising a uvaphore that absorbs radiant energy of a wavelength range centered around λ

₁ and emits radiant energy of a wavelength range centered around λ

₂, λ

₁ and λ

₂ each being a wavelength within the ultraviolet portion of the electromagnetic spectrum; and

the mean of the range of λ

₁ being below the mean of the range of λ

₂ ; and

b) measuring uvescence intensity at a wavelength centered around λ

₂ emitted by said composition during or after polymerization to provide an indication of degree of cure.

9. The method according to claim 8 wherein the aromatic groups designated A and B of formula I are substituted by 1 to 4 substituents chosen from 1) alkyl, aryl, aralkyl, alkaryl, acylamido, acyl, amino, alkoxycarbonyl, alkoxy, aryloxy, and hydroxycarbonyl groups of up to 50 carbon atoms and 0 to 30 unitary fluoro, chloro, bromo, nitrogen, silicon, sulfur, and nonperoxidic oxygen atoms, 2)cyano, chloro, bromo, fluoro groups, and 3) silyl and siloxy groups containing up to 200 silicon atoms and up to 200 unitary nitrogen, sulfur, and nonperoxidic oxygen atoms.

10. The method according to claim 8 wherein said latent uvaphore is selected from the group consisting of dibenzofulvene, methyldibenzofulvene, and vinyldibenzofulvene.

11. The method according to claim 8 wherein said latent uvaphore is present in the range of 0.001 to 10 weight percent of the solids content of the curable composition.

12. The method according to claim 8 wherein said composition further comprises at least one adjuvant selected from the group consisting of fillers, plasticizers, flowing agents, colorants, and pigments.

13. The method according to claim 8 wherein said composition further comprises an effective amount of a thermally or photochemically activated catalyst.

14. The method according to claim 13 wherein said catalyst is a Pt(O) catalyst.

15. The method according to claim 13 wherein said composition further comprises an inhibitor.

16. The method according to claim 8 wherein said composition further comprises an inhibitor.

17. The method according to claim 16 wherein said inhibitor is a maleate inhibitor.