Fluorine-containing cyclic olefin polymer composition, imprint product obtained using the composition, and method for producing the same

Patent metadata

Field	Value
Publication number	US-10000633-B2
Application number	US-201514739164-A
Country	US
Kind code	B2
Filing date	Jun 15, 2015
Priority date	Aug 26, 2009
Publication date	Jun 19, 2018
Grant date	Jun 19, 2018

Abstract

A fluorine-containing cyclic olefin polymer composition of the present invention includes a fluorine-containing cyclic olefin polymer (A) containing a repeating structural unit represented by the general formula (1) and having a fluorine atom content rate of 40 to 75% by mass; a photocurable compound (B); and a photocuring initiator (C).

First claim

The invention claimed is:

1. An imprint product having a fine pattern of a mold surface transcribed, wherein the imprint product comprises:
a fluorine-containing cyclic olefin polymer (A) containing a repeating structural unit represented by the general formula (1) and having a fluorine atom content rate of 40 to 75% by mass; a photocurable compound (B); and a photocuring initiator (C);

wherein, at least one of R 1 to R 4 is fluorine, fluorine-containing alkyl having 1 to 10 carbon atoms, fluorine-containing alkoxy having 1 to 10 carbon atoms, or fluorine-containing alkoxyalkyl having 2 to 10 carbon atoms; wherein when R 1 to R 4 are fluorine-free groups, R 1 to R 4 are selected from hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms; R 1 to R 4 are the same as or different from each other; R 1 to R 4 are optionally combined with one another to form a ring structure;
wherein the mass ratio (A)/(B) of said fluorine-containing cyclic olefin polymer (A) and said photocurable compound (B) is in the range from 99.9/0.1 to 80/20 and
wherein said photocurable compound (B) is a (meth)acrylate monomer having a trifunctional or higher reactive double bond group and/or an epoxy monomer having a trifunctional or higher cationically ring-opening polymerizable linking group.

2. The imprint product as set forth in claim 1 ,
wherein the storage modulus or loss modulus of said fluorine-containing cyclic olefin polymer (A) in the measurement of a dynamic mechanical analysis by tensile mode at a frequency of 1 Hz and a temperature increase rate of 3° C./minute has a variable region in the range from −1 to 0 MPa/° C. with respect to a temperature varying in the temperature region of the glass transition temperature or higher.

3. The imprint product as set forth in claim 1 ,
wherein the variable region of the storage modulus or loss modulus in the temperature region of the glass transition temperature or higher of said fluorine-containing cyclic olefin polymer (A) is in the storage modulus region or loss modulus region of 0.1 MPa or more.

4. The imprint product as set forth in claim 1 ,
wherein said fluorine-containing cyclic olefin polymer (A) comprises a repeating structural unit [I] represented by the general formula (1) and a repeating structural unit [II] represented by the general formula (2), the molar ratio thereof is [I]/[II]=95/5 to 25/75, and the fluorine atom content rate is 40 to 75% by mass;

wherein at least one of R 5 to R 8 is fluorine, fluorine-containing alkyl having 1 to 10 carbon atoms, fluorine-containing alkoxy having 1 to 10 carbon atoms, or fluorine-containing alkoxyalkyl having 2 to 10 carbon atoms; wherein when R 5 to R 8 are fluorine-free groups, R 5 to R 8 are selected from hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms; R 5 to R 8 are the same as or different from each other; R 5 to R 8 are optionally combined with one another to form a ring structure; n represents an integer of 1 or 2.

5. The imprint product as set forth in claim 1 ,
wherein said photocurable compound (B) is at least one compound selected from the group of compounds represented by the following general formulae (5), (6), (7), (8) and (9);

wherein, in the formula (5), R 12 represents tolylene, diphenylmethane, hexamethylene, norbornane dimethylene, dicyclohexylenemethane, trimethylcyclohexylene, cyclohexane dimethylene, N,N′,N″-tris(hexamethylene)-isocyanurate, N,N′-dihexamethyleneurea, N,N,N′-tris(hexamethylene)-urea, N,N,N′,N′-tetrakis(hexamethylene)-urea, or xylene; R 9 , R 10 , and R 11 independently represent H or CH 3 ; W 1 and W 2 represent H, CH 3 , OH, or V 1 ; X 1 represents an integer of 2 to 4; Y 1 represents an integer of 0 to 2 and Y 2 represents an integer of 0 to 5;

wherein, in the formula (6), R 16 represents tolylene, diphenyl methane, hexamethylene, norbornanedimethylene, dicyclohexylenemethane, trimethylcyclohexylene, cyclohexane dimethylene, N,N′,N″-tris(hexamethylene)-isocyanurate, N,N′-dihexamethyleneurea, N,N,N′-tris(hexamethylene)-urea, N,N,N′,N′-tetrakis(hexamethylene)-urea, or xylene; R 13 , R 14 , and R 15 independently represent H or CH 3 ; W 3 and W 4 represent H, CH 3 , OH, or V 2 ; X 2 represents an integer of 2 to 4; Y 3 represents an integer of 0 to 2 and Y 4 represents an integer of 0 to 5;

wherein, in the formula (7), W 5 represents H, CH 3 , OH, or V 3 ; R 17 , R 18 , and R 19 independently represent H or CH 3 , and Y 5 represents an integer of 0 to 20;

wherein, in the formula (8), W 6 and W 7 represent H, CH 3 , OH, or V 4 ; R 20 , R 21 , and R 22 represent H or CH 3 , and Y 6 represents an integer of 0 to 3;

wherein, in the formula (9), W 8 represents H, alkyl having 1 to 3 carbon atoms, OH, or V 5 , and Y 7 represents an integer of 1 to 20.

6. A method for producing a cured body using the imprint product as set forth in claim 1 as a mold, wherein the method comprises a step of bringing a surface having the fine pattern of said imprint product into contact with a photocurable monomer composition,
a step of curing said photocurable monomer composition with light irradiation to obtain a cured product, and
a step of releasing said cured product from said imprint product.

7. A resin composition for obtaining imprint product transcribed a fine pattern of a mold surface, wherein the composition comprising:
a fluorine-containing cyclic olefin polymer (A) containing a repeating structural unit represented by the general formula (1) and having a fluorine atom content rate of 40 to 75% by mass; a photocurable compound (B); and a photocuring initiator (C);

wherein, at least one of R 1 to R 4 is fluorine, fluorine-containing alkyl having 1 to 10 carbon atoms, fluorine-containing alkoxy having 1 to 10 carbon atoms, or fluorine-containing alkoxyalkyl having 2 to 10 carbon atoms; wherein when R 1 to R 4 are fluorine-free groups, R 1 to R 4 are selected from hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms; R 1 to R 4 are the same as or different from each other; R 1 to R 4 are optionally combined with one another to form a ring structure;
wherein the mass ratio (A)/(B) of said fluorine-containing cyclic olefin polymer (A) and said photocurable compound (B) is in the range from 99.9/0.1 to 80/20 and
wherein said photocurable compound (B) is a (meth)acrylate monomer having a trifunctional or higher reactive double bond group and/or an epoxy monomer having a trifunctional or higher cationically ring-opening polymerizable linking group.

8. The resin composition for transcription as set forth in claim 7 ,
wherein the mass ratio (A)/(B) of said fluorine-containing c

Assignees

• Mitsui Chemicals Inc

Inventors

• Sunaga Tadahiro
• Oda Takashi

Classifications

• C08F283/14 Primary

  on to polymers obtained by ring-opening polymerisation of carbocyclic compounds having one or more carbon-to-carbon double bonds in the carbocyclic ring, i.e. polyalkeneamers {(C08F283/004 takes precedence)} · CPC title

• B29C59/022

  characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor · CPC title

• B29C33/38

  characterised by the material or the manufacturing process (B29C33/44 takes precedence) · CPC title

• B29K2885/00

  Use of polymers having other elements than silicon, sulfur, nitrogen, oxygen, and carbon in the main chain, as mould material · CPC title

• Y10T428/24802

  Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] · CPC title