Method of forming thin film of vinylidene fluoride homopolymer

• US 20070190334A1
• Filed: 03/09/2005
• Published: 08/16/2007
• Est. Priority Date: 03/22/2004
• Status: Abandoned Application

• Current Assignee: Daikin Industries Ltd
• Original Assignee: Daikin Industries Ltd
• Inventors: Araki, Takayuki, Kodani, Tetsuhiro
• Application Number:
  US10/593,299
• Publication Number:
  US 20070190334A1
• Time in Patent Office: Days
• US Class Current: 428/421
• CPC Class Codes: B32B 27/30 comprising vinyl (co)polymers; comprising acrylic (co)polymers
• CPC Class Codes: C08F 114/22 Vinylidene fluoride
• CPC Class Codes: C08F 2810/30 leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
• CPC Class Codes: C08F 2810/40 taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C
• CPC Class Codes: C08F 8/14 Esterification
• CPC Class Codes: C08F 8/42 Introducing metal atoms or metal-containing groups
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31544 Addition polymer is perhalogenated

Abstract

There is provided the method of forming a thin film of vinylidene fluoride homopolymer of I-form crystal structure having functional group at its end which can be applied to various substrates, by relatively easy method (applying conditions, manner, etc.). The method is a method of forming a thin film of vinylidene fluoride homopolymer by applying, on a substrate, a vinylidene fluoride homopolymer which contains, at one end or both ends thereof, a moiety represented by the formula (1):
—(R¹)_n—Y  (1)
wherein R¹ is a divalent organic group but does not contain a structural unit of the vinylidene fluoride homopolymer; n is 0 or 1; Y is a functional group, and has from 3 to 100 repeat units of vinylidene fluoride, to form a thin film of vinylidene fluoride homopolymer comprising I-form crystal structure alone or as main component.

Claims

1. A method of forming a thin film of vinylidene fluoride homopolymer comprising I-form crystal structure alone or as main component, the method comprises applying, on a substrate, a vinylidene fluoride homopolymer which contains, at one end or both ends thereof, a moiety represented by the formula (1):

—

(R¹)_n—

Y 

 

(1)

wherein R¹ is a divalent organic group but does not contain a structural unit of the vinylidene fluoride homopolymer;

n is 0 or 1;

Y is a functional group, and has a number average degree of polymerization of vinylidene fluoride homopolymer unit of 3 to 100, to form a thin film of the vinylidene fluoride homopolymer comprising I-form crystal structure alone or as main component.

2. The method of forming a thin film of claim 1, wherein in the vinylidene fluoride homopolymers comprising I-form crystal structure alone or as main component, when attention is given to proportions of the respective vinylidene fluoride homopolymers having I-, II- or III-form crystal structure in the thin film of vinylidene fluoride homopolymer which are calculated by IR analysis, the proportion of vinylidene fluoride homopolymers having I-form crystal structure satisfies both of (Equation 1):

100≧

I-form/(I-form+II-form)>

50% by weight 

 

(Equation

     1)

and (Equation

     2);

100≧

I-form/(I-form+III-form)>

50% by weight 

 

(Equation

     2).

3. The method of forming a thin film of claim 1, wherein Y in the formula (1) is a functional group which can impart, to the vinylidene fluoride homopolymer, adhesion to the substrate of organic material and/or inorganic material.

4. The method of forming a thin film of claim 1, wherein Y in the formula (1) is a functional group which can make self-organization of vinylidene fluoride homopolymer possible on the surface of the substrate of organic material and/or inorganic material.

5. The method of forming a thin film of claim 1, wherein Y in the formula (1) is a functional group which can bond vinylidene fluoride homopolymers each other.

6. The method of forming a thin film of claim 4, wherein Y in the formula (1) is —

CH═

CH₂, —

SH and/or —

SiX_3-nR⁶_n (n is 0 or an integer of 1 or 2;

R⁶ is CH₃ or C₂H₅;

X is —

OR⁷, —

COOH, —

COOR⁷, —

NH_3-mR⁷_m, —

OCN or halogen atom (R⁷ is CH₃, C₂H₅ or C₃H₇, m is 0 or an integer of 1 to

     3)).

7. The method of forming a thin film of claim 5, wherein Y in the formula (1) is —

CH═

CH₂, —

OCOCH═

CH₂, —

OCOCF═

CH₂, —

OCOC(CH₃)═

CH₂ or −

OCOCCl═

CH₂.

16. The method of forming a thin film of claim 2, wherein Y in the formula (1) is a functional group which can impart, to the vinylidene fluoride homopolymer, adhesion to the substrate of organic material and/or inorganic material.

17. The method of forming a thin film of claim 2, wherein Y in the formula (1) is a functional group which can make self-organization of vinylidene fluoride homopolymer possible on the surface of the substrate of organic material and/or inorganic material.

18. The method of forming a thin film of claim 2, wherein Y in the formula (1) is a functional group which can bond vinylidene fluoride homopolymers each other.

8. A laminated article which has, on a substrate, a self-organized thin film formed by using vinylidene fluoride homopolymers comprising I-form crystal structure alone or as main component and having a number average degree of polymerization of vinylidene fluoride homopolymer unit of 3 to 100.

10. The laminated article of claim 8, wherein in the vinylidene fluoride homopolymers comprising I-form crystal structure alone or as main component, when attention is given to proportions of the respective vinylidene fluoride homopolymers having I-, II- or III-form crystal structure in the thin film of vinylidene fluoride homopolymer which are calculated by IR analysis, the proportion of vinylidene fluoride homopolymers having I-form crystal structure satisfies both of (Equation 1):

100≧

I-form/(I-form+II-form)>

50% by weight 

 

(Equation

     1)

and (Equation

     2);

100≧

I-form/(I-form+III-form)>

50% by weight 

 

(Equation

     2).

11. The laminated article of claim 8, wherein the self-organized film formed by using the vinylidene fluoride homopolymers comprising I-form crystal structure alone or as main component is formed by using vinylidene fluoride homopolymers having a number average degree of polymerization of vinylidene fluoride homopolymer unit of 3 to 100 and containing, at one end or both ends thereof, a moiety represented by the formula (1-1):

—

(R¹)_n—

Y¹ 

 

(1-1)

wherein R¹ is a divalent organic group but does not contain a structural unit of the vinylidene fluoride homopolymer;

n is 0 or 1;

Y¹ is —

SH and/or —

SiX_3-nR⁶_n (n is 0 or an integer of 1 or 2;

R⁶ is CH₃ or C₂H₅;

X is —

OR⁷, —

COOH, —

COOR⁷, —

NH_3-mR⁷_m, —

OCN or halogen atom (R⁷ is CH₃, C₂H₅ or C₃H₇, m is 0 or an integer of 1 to

     3)).

13. A ferroelectric device comprising the laminated article of claim 8.

9. A laminated article which has, on a substrate, a thin film formed by bonding of vinylidene fluoride homopolymers comprising I-form crystal structure alone or as main component and having a number average degree of polymerization of vinylidene fluoride homopolymer unit of 3 to 100.

12. The laminated article of claim 9, wherein the thin film formed by bonding of the vinylidene fluoride homopolymers comprising I-form crystal structure alone or as main component is formed by using vinylidene fluoride homopolymers having a number average degree of polymerization of vinylidene fluoride homopolymer unit of 3 to 100 and containing, at one end or both ends thereof, a moiety represented by the formula (1-2):

—

(R¹)_n—

Y² 

 

(1-2)

wherein R¹ is a divalent organic group but does not contain a structural unit of the vinylidene fluoride homopolymer;

n is 0 or 1;

Y² is —

CH═

CH₂, —

OCOCH═

CH₂, —

OCOCF═

CH₂, —

OCOC(CH₃)═

CH₂ or —

OCOCCl═

CH₂.

19. The laminated article of claim 9, wherein in the vinylidene fluoride homopolymers comprising I-form crystal structure alone or as main component, when attention is given to proportions of the respective vinylidene fluoride homopolymers having I-, II- or III-form crystal structure in the thin film of vinylidene fluoride homopolymer which are calculated by IR analysis, the proportion of vinylidene fluoride homopolymers having I-form crystal structure satisfies Both of (Equation 1):

100≧

I-form/(I-form+II-form)>

50% by weight 

 

(Equation

     1)

and (Equation

     2);

100≧

I-form/(I-form+III-form)>

50% by weight 

 

(Equation

     2).

20. A ferroelectric device comprising the laminated article of claim 9.

14. A vinylidene fluoride homopolymer represented by the formula (IA-2):

Z¹-(R¹⁰)_n1-A¹-(R¹¹)_n2—

S-M¹ 

 

(IA-2)

wherein A¹ is a structural unit of vinylidene fluoride homopolymers having a number average degree of polymerization of 3 to 100;

Z¹ is a polyfluoroalkyl group or an alkyl group;

R¹⁰ and R¹¹ are the same or different and each is a divalent organic group but does not contain a vinylidene fluoride homopolymer unit comprising I-form crystal structure alone or as main component;

n1 and n2 are the same or different and each is 0 or 1;

M¹ is hydrogen atom or alkali metal atom.

15. A vinylidene fluoride homopolymer represented by the formula (IB-3):

M²-S—

(R¹²)_n3-A²-R²-A³-(R¹³)_n4—

S-M³ 

 

(IB-3)

wherein A² and A³ are the same or different and each is a structural unit of vinylidene fluoride homopolymers and a total number average degree of polymerization of A² and A³ is from 3 to 100;

R² is a divalent organic group but does not contain a structural unit of the vinylidene fluoride homopolymer;

R¹² and R¹³ are the same or different and each is a divalent organic group but does not contain a structural unit of the vinylidene fluoride homopolymer;

n3 and n4 are the same or different and each is 0 or 1;

M² and M³ are the same or different and each is hydrogen atom or alkali metal atom.