Two-photon absorbing polymerizable composition and polymerization process thereof

1. A two-photon absorbing polymerizable composition comprising at least a two-photon absorbing compound, a polymerization initiator and a polymerizable compound, said composition being photopolymerizable upon non-resonant two-photon absorption, wherein said two-photon absorbing compound is a cyanine dye represented by the following formula (3), a merocyanine dye represented by the following formula (4), an oxonol dye represented by the following formula (5) or a dye compound represented by the following formula (1):

wherein R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a substituent and some of R 1 , R 2 , R 3 and R 4 may combine with each other to form a ring; n and m each independently represents an integer of 0 to 4 and when n and m each is 2 or more, the plurality of R 1 s, R 2 s, R 3 s or R 4 s may be the same or different, provided that n and m are not 0 at the same time; and X 1 and X 2 each independently represents an aryl group, a heterocyclic group or a group represented by formula (2):

wherein R 5 represents a hydrogen atom or a substituent, R 6 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and Z 1 represents an atomic group for forming a 5- or 6-membered ring;

wherein Za 1 , Za 2 and Za 3 each represents an atomic group for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, Za 4 , Za 5 and Za 6 each represents an atomic group for forming a 5- or 6-membered ring, Ra 1 , Ra 2 and Ra 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, Ma 1 to Ma 14 each independently represents a methine group, which may have a substituent or may form a ring together with another methine group, na 1 , na 2 and na 3 each represents 0 or 1, ka 1 and ka 3 each represents an integer of 0 to 3, provided that when ka 1 is 2 or more, multiple Ma 3 s or Ma 4 s may be the same or different and when ka 3 is 2 or more, multiple Ma 12 s or Ma 13 s may be the same or different, ka 2 represents an integer of 0 to 8, provided that when ka 2 is 2 or more, multiple Ma 10 s or Ma 11 s may be the same or different, CI represents an ion for neutralizing the electric charge, and y represents a number necessary for the neutralization of electric charge.

2. The two-photon absorbing polymerizable composition as claimed in claim 1 , wherein in the compound represented by formula (1), X 1 and X 2 each is a group represented by formula (2).

3. The two-photon absorbing polymerizable composition as claimed in claim 1 , wherein the polymerization initiator is 1) ketone containing polymerization initiator, 2) an organic peroxide containing polymerization initiator, 3) a bisimidazole containing polymerization initiator, 4) a trihalomethyl-substituted triazine containing polymerization initiator, 5) a diazonium salt containing polymerization initiator, 6) a diaryliodonium salt containing polymerization initiator, 7) a sulfonium salt containing polymerization initiator, 8) a triphenylalkylborate containing polymerization initiator, 9) a diaryliodonium organic boron complex containing polymerization initiator, 10) a sulfonium organic boron complex containing polymerization initiator, 11) a cationic two-photon absorbing and organic boron complex containing polymerization initiator, 12) an anionic two-photon absorbing and onium salt complex containing polymerization initiator, 13) a metal arene complex containing polymerization initiator or 14) a sulfonic acid ester-base polymerization initiator.

4. The two-photon absorbing polymerizable composition as claimed in claim 1 , wherein the polymerization initiator contains a polymerization initiator capable of generating at least one radical and the polymerizable compound contains a radical polymerizable compound capable of undergoing polymerization under the action of at least one radical.

5. The two-photon absorbing polymerizable composition as claimed in claim 1 , wherein the polymerization initiator contains a polymerization initiator capable of generating an acid without generating at least one radical and the polymerizable compound contains a cationic polymerizable compound capable of undergoing polymerization under the action of at least one acid.

6. The two-photon absorbing polymerizable composition as claimed in claim 1 , wherein the polymerization initiator contains a polymerization initiator capable of generating both at least one radical and at least one acid and the polymerizable compound contains either one or both of a radical polymerizable compound capable of undergoing polymerization under the action of at least one radical and a cationic polymerizable compound capable of undergoing polymerization under the action of at least one acid.

7. A polymerization process comprising irradiating the two-photon absorbing polymerizable composition claimed in claim 1 with a laser ray at a wavelength being longer than the linear absorption band of the two-photon absorbing compound and not having linear absorption, and causing a polymerization reaction by using the two-photon absorption induced.

8. A three-dimensional optical recording medium comprising the two-photon absorbing polymerizable composition claimed in claim 1 .

9. A stereolithography composition comprising the two-photon absorbing polymerizable composition claimed in claim 1 .

10. A two-photon absorbing polymerizable composition comprising at least a two-photon absorbing compound and a polymerizable compound, said composition being photopolymerizable upon non-resonant two-photon absorption, wherein said two-photon absorbing compound is a cyanine dye represented by the following formula (3), a merocyanine dye represented by the following formula (4), an oxonol dye represented by the following formula (5) or a dye compound represented by the following formula (1):

wherein R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a substituent and some of R 1 , R 2 , R 3 and R 4 may combine with each other to form a ring; n and m each independently represents an integer of 0 to 4 and when n and m each is 2 or more, the plurality of R 1 s, R 2 s, R 3 s or R 4 s may be the same or different, provided that n and m are not 0 at the same time; and X 1 and X 2 each independently represents an aryl group, a heterocyclic group or a group represented by formula (2):

wherein R 5 represents a hydrogen atom or a substituent, R 6 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and Z 1 represents an atomic group for forming a 5- or 6-membered ring;

wherein Za 1 , Za 2 and Za 3 each represents an atomic group for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, Za 4 , Za 5 and Za 6 each represents an atomic group for forming a 5- or 6-membered ring, Ra 1 , Ra 2 and Ra 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, Ma 1 to Ma 14 each independently represents a methine group, which may have a substituent or may form a ring together with another methine group, na 1 , na 2 and na 3 each represents 0 or 1, ka 1 and ka 3 each represents an integer of 0 to 3, provided that when ka 1 is 2 or more, multiple Ma 3 s or Ma 4 s may be the same or different and when ka 3 is 2 or more, multiple Ma 12 s or Ma 13 s may be the same or different, ka 2 represents an integer of 0 to 8, provided that when ka 2 is 2 or more, multiple Ma 10 s or Ma 11 s may be the same or different, CI represents an ion for neutralizing the electric charge, and y represents a number necessary for the neutralization of electric charge.

11. The two-photon absorbing polymerizable composition as claimed in claim 10 , wherein in the compound represented by formula (1) X 1 and X 2 each is a group represented by formula (2).

12. A polymerization process comprising irradiating the two-photon absorbing polymerizable composition claimed in claim 10 with a laser ray at a wavelength being longer than the linear absorption band of the two-photon absorbing compound and not having linear absorption, and causing a polymerization reaction by using the two-photon absorption induced.

13. A three-dimensional optical recording medium comprising the two-photon absorbing polymerizable composition claimed in claim 10 .

14. A stereolithography composition comprising the two-photon absorbing polymerizable composition claimed in claim 10 .

15. A two-photon absorbing polymerizable composition comprising at least two-photon absorbing compound, a polymerization initiator and a polymerizable compound, said composition being photopolymerizable upon non-resonant two-photon absorption,

wherein the polymerization initiator is 1) an organic peroxide containing polymerization initiator, 2) a bisimidazole containing polymerization initiator, 3) a trihalomethyl-substituted triazine containing polymerization initiator, 4) a diazonium salt containing polymerization initiator, 5) a sulfonium salt containing polymerization initiator, 6) a borate containing polymerization initiator, 7) a diaryliodonium organic boron complex containing polymerization initiator, 8) a sulfonium organic boron complex containing polymerization initiator, 9) a cationic two-photon absorbing compound organic boron complex containing polymerization initiator, 10) an anionic two-photon absorbing compound onium salt complex containing polymerization initiator, 11) a metal arene complex containing polymerization initiator or 12) a sulfonic acid ester-base polymerization initiator and

wherein said two-photon absorbing compound is a cyanine dye represented by the following formula (3), a merocyanine dye represented by the following formula (4), an oxonol dye represented by the following formula (5) or a dye compound represented by the following formula (1):

wherein R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a substituent and some of R 1 , R 2 , R 3 and R 4 may combine with each other to form a ring; n and m each independently represents an integer of 0 to 4 and when n and m each is 2 or more, the plurality of R 1 s, R 2 s, R 3 s or R 4 s may be the same or different, provided that n and m are not 0 at the same time; and X 1 and X 2 each independently represents an aryl group, a heterocyclic group or a group represented by formula (2):

wherein R 5 represents a hydrogen atom or a substituent, R 6 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and Z 1 represents an atomic group for forming a 5- or 6-membered ring;

wherein Za 1 , Za 2 and Za 3 each represents an atomic group for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, Za 4 , Za 5 and Za 6 each represents an atomic group for forming a 5- or 6-membered ring, Ra 1 , Ra 2 and Ra 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, Ma 1 to Ma 14 each independently represents a methine group, which may have a substituent or may form a ring together with another methine group, na 1 , na 2 ,and na 3 each represents 0 or 1, ka 1 and ka 3 each represents an integer of 0 to 3, provided that when ka 1 is 2 or more, multiple Ma 3 s or Ma 4 s may be the same or different and when ka 3 is 2 or more, multiple Ma, 12 s or Ma 13 s may be the same or different, ka 2 represents an integer of 0 to 8, provided that when ka 2 is 2 or more, multiple Ma 10 s or Ma 11 s may be the same or different, CI represents an ion for neutralizing the electric charge, and y represents a number necessary for the neutralization of electric charge.