Surface modification method and surface-modified elastic body

Patent metadata

Field	Value
Publication number	US-9321872-B2
Application number	US-201313756837-A
Country	US
Kind code	B2
Filing date	Feb 1, 2013
Priority date	Feb 2, 2012
Publication date	Apr 26, 2016
Grant date	Apr 26, 2016

Abstract

The present invention aims to provide a surface modification method for a rubber vulcanizate or a thermoplastic elastomer, which can impart various functions such as sliding properties and biocompatibility according to its use. The present invention relates to a surface modification method for modifying a rubber vulcanizate or a thermoplastic elastomer as an object to be modified, the method including: Step 1 of forming polymerization initiation points on a surface of the object to be modified; Step 2 of radical polymerizing monomers starting from the polymerization initiation points to grow polymer chains on the surface of the object to be modified; and Step 3 of functionalizing the polymer chains.

First claim

The invention claimed is:

1. A surface modification method for modifying a rubber vulcanizate or a thermoplastic elastomer as an object to be modified, the method comprising:
Step 1 of forming polymerization initiation points on a surface of the object to be modified;
Step 2 of radical polymerizing monomers starting from the polymerization initiation points to grow polymer chains on the surface of the object to be modified; and
Step 3 of functionalizing the polymer chains,
wherein the rubber vulcanizate or the thermoplastic elastomer contains an allylic carbon atom which is a carbon atom adjacent to a double bond.

2. The surface modification method according to claim 1 ,
wherein the Step 1 comprises irradiating the surface of the object to be modified with LED light at 300 to 400 nm to form the polymerization initiation points from a photosensitizer on the surface, and
the Step 2 comprises irradiating the monomers with LED light at 300 to 400 nm to radical polymerize the monomers starting from the polymerization initiation points to grow the polymer chains.

3. The surface modification method according to claim 2 ,
wherein the photosensitizer is a benzophenone compound represented by the following formula (1):

wherein R 1 to R 5 and R 1 ′ to R 5 ′ are the same as or different from each other and each represent a hydrogen atom, an alkyl group, a halogen, a hydroxy group, a primary, secondary, or tertiary amino group, a mercapto group, or a hydrocarbon group that may contain an oxygen atom, a nitrogen atom, or a sulfur atom; and any two adjacent groups thereof may be joined to each other to form a cyclic structure together with the carbon atoms to which they are bonded.

4. The surface modification method according to claim 1 ,
wherein the Step 2 comprises adding a reducing agent or an antioxidant for radical polymerization of the monomers.

5. The surface modification method according to claim 4 ,
wherein the reducing agent or the antioxidant is at least one selected from the group consisting of riboflavin, ascorbic acid, α-tocopherol, β-carotene, and uric acid.

6. The surface modification method according to claim 2 ,
wherein during or before the light irradiation, an inert gas is inserted into a reaction container and a reaction solution to replace the atmosphere therein with the inert gas, followed by polymerization.

7. The surface modification method according to claim 1 ,
wherein the Step 3 comprises salifying side chains of the polymer chains.

8. The surface modification method according to claim 1 ,
the Step 3 comprises salifying side chains of the polymer chains using an alkali metal salt or an antibacterial metal salt.

9. The surface modification method according to claim 1 ,
wherein the Step 3 comprises bringing side chains of the polymer chains into contact with aqueous ammonia and then salifying the side chains.

10. The surface modification method according to claim 1 ,
wherein the Step 3 comprises salifying side chains of the polymer chains using an alkaline salt.

11. The surface modification method according to claim 1 ,
wherein the Step 3 comprises salifying side chains of the polymer chains using a nitrate, a carbonate, or a halogenated salt.

12. The surface modification method according to claim 1 ,
wherein the Step 3 comprises salifying side chains of the polymer chains using silver nitrate, silver carbonate, or silver chloride.

13. The surface modification method according to claim 1 ,
wherein the Step 3 comprises reacting a carboxylic group in side chains of the polymer chains with an amine compound to form an amide bond so that a functionalized group is introduced.

14. The surface modification method according to claim 1 ,
wherein the Step 3 comprises reacting a carboxylic group in side chains of the polymer chains with a hydroxy group-containing compound to form an ester bond so that a functionalized group is introduced.

15. The surface modification method according to claim 13 ,
wherein the functionalized group is a fluoroalkyl group.

16. The surface modification method according to claim 13 ,
wherein the amine compound is a compound represented by the following formula:
CF 3 (CF 2 ) n —(CX 2 ) p —NH 2-m ((CF 2 ) n CF 3 ) m

wherein X represents hydrogen or fluorine; the n's are the same as or different from each other and each represent an integer of 1 to 10; m represents an integer of 0 to 2; and p represents an integer of 0 to 4.

17. The surface modification method according to claim 1 ,
wherein the (liquid) radical polymerizable monomers or a solution thereof contains a polymerization inhibitor, and the monomers are polymerized in the presence of the polymerization inhibitor.

18. The surface modification method according to claim 17 ,
wherein the polymerization inhibitor is 4-methylphenol.

19. The surface modification method according to claim 1 ,
wherein the polymer chains are 10 to 50000 nm in length.

20. A surface-modified elastic body, which is obtained by the surface modification method according to claim 1 .

21. A surface-modified elastic body, which needs to have sliding properties, low friction, or low water drag in the presence of water or in a dry state, and which is obtained by the surface modification method according to claim 1 .

22. A surface-modified elastic body, which needs to have antibacterial properties and which is obtained by the surface modification method according to claim 1 .

23. A surface-modified elastic body, which comprises a three-dimensional solid and has at least partially a surface modified by the surface modification method according to claim 1 .

24. The surface-modified elastic body according to claim 20 , which is a polymer brush.

25. A gasket for syringes, which has at least partially a surface modified by the surface modification method according to claim 1 .

26. A catheter, which has at least partially a surface modified by the surface modification method according to claim 1 .

27. A tire, which has at least partially a groove surface modified by the surface modification method according to claim 1 .

Assignees

• Sumitomo Rubber Ind

Inventors

• Minagawa Yasuhisa

Classifications

• C08F255/10

  on to butene polymers · CPC title

• C08J2433/02

  Homopolymers or copolymers of acids; Metal or ammonium salts thereof · CPC title

• B60C2011/0369

  with varying depth of the groove · CPC title

• B60C11/1346

  covered by a rubber different from the tread rubber · CPC title

• C08F291/18

  on to irradiated or oxidised macromolecules (epoxidised C08F291/10) · CPC title