Polyorganosilsesquioxane, hard coat film, adhesive sheet, and laminate

Patent metadata

Field	Value
Publication number	US-11111337-B2
Application number	US-201816000313-A
Country	US
Kind code	B2
Filing date	Jun 5, 2018
Priority date	Dec 13, 2013
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

Provided is a polyorganosilsesquioxane capable of forming, when cured, a cured product that offers high surface hardness and good heat resistance, is highly flexible, and has excellent processability. The present invention relates to a polyorganosilsesquioxane including a constitutional unit represented by Formula (1). The polyorganosilsesquioxane includes a constitutional unit represented by Formula (I) and a constitutional unit represented by Formula (II) in a mole ratio of the constitutional unit represented by Formula (I) to the constitutional unit represented by Formula (II) of 5 or more. The polyorganosilsesquioxane has a total proportion of the constitutional unit represented by Formula (1) and a constitutional unit represented by Formula (4) of 55% to 100% by mole based on the total amount (100% by mole) of all siloxane constitutional units. The polyorganosilsesquioxane has a number-average molecular weight of 1,000 to 3,000 and a molecular-weight dispersity (weight-average molecular weight to number-average molecular weight ratio) of 1.0 to 3.0.[R1SiO3/2]  (1)[Chem. 2][RaSiO3/2]  (I)[Chem. 3][RbSiO(ORc)]  (II)[Chem. 4][R1SiO(ORc)]  (4).

First claim

The invention claimed is:

1. A hard coat layer comprising a cured product of a curable composition comprising a polyorganosilsesquioxane,
the polyorganosilsesquioxane comprising:
a constitutional unit represented by Formula (I); and
a constitutional unit represented by Formula (II), in a mole ratio of the constitutional unit represented by Formula (I) to the constitutional unit represented by Formula (II) of from 5 to 18,
a constitutional unit represented by Formula (2), and
an optional constitutional unit represented by Formula (5),

the polyorganosilsesquioxane having a total proportion of the constitutional unit represented by Formula (I) and a constitutional unit represented by Formula (II) of 95% to 99% by mole based on a total amount (100% by mole) of all siloxane constitutional units,
the polyorganosilsesquioxane having a total proportion of the constitutional unit represented by Formula (2) and a constitutional unit represented by Formula (5) of 1% to 5% by mole based on a total amount (100% by mole) of all siloxane constitutional units,
the polyorganosilsesquioxane having a number-average molecular weight of 1100 to 2600 and a molecular-weight dispersity (weight-average molecular weight to number-average molecular weight ratio) of 1.1 to 2.0,
Formulae (I), (II), (2), and (5) expressed as follows:
[R a SiO 3/2 ]  (I)

wherein R a is selected from:
a group represented by Formula (1a);
a group represented by Formula (1d),

Formulae (1a) and (1d) expressed as follows:

wherein R 1a represents an ethylene group,

wherein R 1d represents an ethylene group,
[R b SiO(OR c )]  (II)

wherein R b is selected from:
a group represented by Formula (1a); and
a group represented by Formula (1d),

Formulae (1a) and (1d) expressed as follows:

wherein R 1a represents an ethylene group,

wherein R 1d represents an ethylene group;
and R c is selected from a hydrogen atom and a C 1 -C 4 alkyl group,
[R 2 SiO 3/2 ]  (2)

wherein R 2 is an unsubstituted phenyl group, and
[R 2 SiO(OR c )]  (5)

wherein R 2 is as defined in Formula (2); and R c is as defined in Formula (II).

2. The hard coat layer according to claim 1 ,
the curable composition further comprising
a curing catalyst.

3. The hard coat layer according to claim 2 ,
wherein the curing catalyst comprises a cationic photoinitiator.

4. The hard coat layer according to claim 2 ,
wherein the curing catalyst comprises a cationic thermal initiator.

5. The hard coat layer according to claim 1 ,
the curable composition further comprising
a vinyl ether compound.

6. The hard coat layer according to claim 1 ,
the curable composition further comprising
a vinyl ether compound containing a hydroxy group in molecule.

7. A hard coat film comprising:
a substrate; and
the hard coat layer according to claim 1 disposed on or over at least one side of the substrate.

8. The hard coat film according to claim 7 ,
wherein the hard coat layer has a thickness of 1 to 200 μm.

9. The hard coat film according to claim 7 ,
wherein the hard coat film is produced by a roll-to-roll process.

10. The hard coat film according to claim 7 , further comprising
a surface-protecting film on or over the hard coat layer.

11. A method for producing a hard coat film, the method comprising the step of:
(B) applying a curable composition to at least one side of a substrate, and curing the applied curable composition to form a hard coat layer on the substrate to thereby give a hard coat film,
the curable composition comprising a polyorganosilsesquioxane,
the polyorganosilsesquioxane comprising:
a constitutional unit represented by Formula (I); and
a constitutional unit represented by Formula (II), in a mole ratio of the constitutional unit represented by Formula (I) to the constitutional unit represented by Formula (II) of from 5 to 18,
the polyorganosilsesquioxane comprising
a constitutional unit represented by Formula (2), and
an optional constitutional unit represented by Formula (5),

the polyorganosilsesquioxane having a total proportion of the constitutional unit represented by Formula (I) and a constitutional unit represented by Formula (II) of 95% to 99% by mole based on a total amount (100% by mole) of all siloxane constitutional units,
the polyorganosilsesquioxane having a total proportion of the constitutional unit represented by Formula (2) and a constitutional unit represented by Formula (5) of 1% to 5% by mole based on a total amount (100% by mole) of all siloxane constitutional units,
the polyorganosilsesquioxane having a number-average molecular weight of 1100 to 2600 and a molecular-weight dispersity (weight-average molecular weight to number-average molecular weight ratio) of 1.1 to 2.0,
Formulae (I), (II), (2), and (5) expressed as follows:
[R a SiO 3/2 ]  (I)

wherein R a is selected from:
a group represented by Formula (1a);
a group represented by Formula (1d),

Formulae (1a) and (1d) expressed as follows:

wherein R 1a represents an ethylene group,

wherein R 1d represents an ethylene group,
[R b SiO(OR c )]  (II)

wherein R b is selected from:
a group represented by Formula (1a); and
a group represented by Formula (1d),

Formulae (1a) and (1d) expressed as follows:

wherein R 1a represents an ethylene group,

wherein R 1d represents an ethylene group; and
R c is selected from a hydrogen atom and a C 1 -C 4 alkyl group,
[R 2 SiO 3/2 ]  (2)

wherein R 2 is an unsubstituted phenyl group, and
[R 2 SiO(OR c )]  (5)

wherein R 2 is as defined in Formula (2); and R c is as defined in Formula (II).

12. The method for producing a hard coat film according to claim 11 , the method further comprising the step of:
(A) unwinding a wound, rolled substrate,
the steps (A) and (B) being performed successively.

13. The method for producing a hard coat film according to claim 12 , the method further comprising the step of:
(C) rewinding the hard coat film into a roll,
the steps (A), (B), and (C) being performed successively.

Assignees

• Daicel Corp

Inventors

• Kuwana Akihiro
• Harada Nobuhiko
• Masui Maya
• Takase Ichiro
• Maetani Shinji
• Tsuji Naoko

Classifications

• B32B2307/306

  Resistant to heat · CPC title

• C09J7/20

  characterised by their carriers · CPC title

• C09D183/06

  containing silicon bound to oxygen-containing groups (C09D183/12 takes precedence) · CPC title

• B32B2307/536

  Hardness · CPC title

• B32B9/045

  of synthetic resin · CPC title