Method for producing a varnish-like cyclic olefin copolymer composition, cyclic olefin copolymer composition, crosslinked material, film or sheet, laminate, circuit board, electronic equipment and prepreg

Abstract

A method for producing a varnish-like cyclic olefin copolymer composition containing a cyclic olefin copolymer (m) and an organic solvent, wherein the method for producing a varnish-like cyclic olefin copolymer composition is characterized in that the cyclic olefin copolymer (m) contains (A) one or more repeating units derived from an olefin, (B) one or more repeating units derived from a cyclic unconjugated diene, and (C) one or more repeating units derived from a cyclic olefin; the method includes a polymerization step that copolymerizes the olefin, cyclic unconjugated diene, and cyclic olefin in the presence of a catalyst for olefin polymerization containing a transition metal compound (A) and a compound (B); the transition metal compound (A) contains one or more selected from transition metal compounds (A-1) and transition metal compounds (A-2); and the compound (B) contains one or more selected from the group consisting of organic metal compounds (B-1), organic aluminum oxy compounds (B-2), and compounds (B-3) that react with the transition metal compound (A) to form an ion pair.

Claims

1. A cyclic olefin copolymer (m), Organic solvents and A method for producing a varnish-like cyclic olefin copolymer composition, comprising: The aforementioned cyclic olefin copolymer (m) is (A) One or more repeating units derived from olefins represented by the following general formula (I), (B) A repeating unit derived from one or more cyclic non-conjugated dienes represented by the following general formula (III), (C) comprising one or more repeating units derived from a cyclic olefin represented by the following general formula (V), 【Chemistry 1】 [In the above general formula (I), R ３００ This represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. 【Chemistry 2】 [In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ６１ ~R ７６ R ａ１ and R ｂ１ These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R １０４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer from 0 to 10, and R ７５ and R ７６ They are connected to each other They may form a monocycle or polycycle. 【Transformation 3】 〔In the above general formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ６１ ~R ７８ as well as R ａ１ and R ｂ１ may be the same as or different from each other, and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms. R ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring.〕 The method described above is The polymerization process comprises copolymerizing an olefin, a cyclic non-conjugated diene, and a cyclic olefin in the presence of an olefin polymerization catalyst containing a transition metal compound (A) and a compound (B). The transition metal compound (A) is The transition metal compound (A-1) represented by the following formula (II), and It contains one or more transition metal compounds selected from the group consisting of (A-2) represented by the following formula (VI), 【Chemistry 4】 [In the above formula (II), M ２ This represents the transition metal atoms of Group 4 of the periodic table. n １ This represents an integer from 1 to 3. Each L independently represents a monovalent anionic ligand in which an atom from Group 15 of the periodic table acts as the coordinating atom. X １ Each of these independently represents a group or atom selected from the group consisting of hydrogen atoms, halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, as well as the group consisting of substituted products thereof. R ５ ~R ９ Each of these independently represents a group or atom selected from the group consisting of hydrogen atoms, halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, as well as the group consisting of substituted products thereof, R ５ ~R ９ Any two or three of these may condense to form a ring, and the formed ring may be aromatic, containing a conjugated double bond. 【Transformation 5】 [In the above formula (VI), M ３ This represents the transition metal atoms of Group 4 of the periodic table. n ２ This represents an integer from 1 to 4. X ２ Each of these independently represents an atom or group selected from the group consisting of hydrogen atoms, halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, as well as the group consisting of substituted products thereof. R １０ ~R １７ Each of these independently represents an atom or group selected from the group consisting of hydrogen atoms, halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, as well as the group consisting of substituted products thereof, R １０ ~R １７ Adjacent elements may be bonded to each other to form a ring, and the formed ring may be aromatic, including a conjugated double bond. The aforementioned compound (B) is organometallic compound (B-1), Organic aluminum oxy compounds (B-2), and It contains one or more compounds selected from the group consisting of compounds (B-3) that react with the transition metal compound (A) to form an ion pair. A method for producing a varnish-like cyclic olefin copolymer composition, characterized by the following:

2. The manufacturing method according to claim 1, wherein the content of the cyclic olefin copolymer (m) in the varnish-like cyclic olefin copolymer composition is 30% by mass or more.

3. The manufacturing method according to claim 1 or 2, wherein the organic solvent comprises at least one selected from the group consisting of aromatic hydrocarbon solvents, cyclic hydrocarbon solvents, linear hydrocarbon solvents, and halogenated aromatic hydrocarbon solvents.

4. The manufacturing method according to claim 1 or 2, wherein, when the total number of moles of repeating units in the cyclic olefin copolymer (m) is taken as 100 mol%, the content of repeating units (A) derived from the olefin is 10 mol% or more and 90 mol% or less, the content of repeating units (B) derived from the cyclic non-conjugated diene is 1 mol% or more and 40 mol% or less, and the content of repeating units (C) derived from the cyclic olefin is 1 mol% or more and 50 mol% or less.

5. The manufacturing method according to claim 1 or 2, wherein the cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene includes 5-vinyl-2-norbornene.

6. The cyclic olefin constituting the structural unit (C) derived from the cyclic olefin is tetracyclo[4.4.0.1 ２，５ 1. ７，１０ The manufacturing method according to claim 1 or 2, comprising at least one selected from the group consisting of ]-3-dodecene and bicyclo[2.2.1]-2-heptene.

7. The manufacturing method according to claim 1 or 2, further comprising a catalyst removal step for removing the olefin polymerization catalyst.

8. The cyclic olefin copolymer (m) １３ In the C-NMR spectrum, The integral value of the signal in the range of 43.8 ppm to 45.0 ppm is X. Ｃ , The integral value of the signal in the range of 40.3 ppm to 41.3 ppm is Y. Ａ , The integral value of the signal in the range of 38.4 ppm to 39.9 ppm is X. Ｂ , When that happens, (X Ｂ -X Ｃ ) / Y Ａ The manufacturing method according to claim 1 or 2, wherein the value of is 0.2 or more and 2.0 or less.

9. The manufacturing method according to claim 1 or 2, wherein the glass transition temperature of the cyclic olefin copolymer (m), as measured by a differential scanning calorimeter (DSC), is 100°C or higher.

10. A cyclic olefin copolymer (m), Organic solvents and A varnish-like cyclic olefin copolymer composition comprising, The aforementioned cyclic olefin copolymer (m) is (A) One or more repeating units derived from olefins represented by the following general formula (I), (B) A repeating unit derived from one or more cyclic non-conjugated dienes represented by the following general formula (III), (C) comprising one or more repeating units derived from a cyclic olefin represented by the following general formula (V), 【Transformation 6】 [In the above general formula (I), R ３００ This represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. 【Transformation 7】 [In the above general formula (III), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ６１ ~R ７６ R ａ１ and R ｂ１ These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R １０４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer from 0 to 10, and R ７５ and R ７６ They are connected to each other They may form a monocycle or polycycle. 【Transformation 8】 [In the above general formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ６１ ~R ７８ R ａ１ and R ｂ１ These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ７５ ~R ７８ These may be bonded to each other to form a monocycle or polycycle. The cyclic olefin copolymer (m) １３ In the C-NMR spectrum, The integral value of the signal in the range of 43.8 ppm to 45.0 ppm is X. Ｃ , The integral value of the signal in the range of 40.3 ppm to 41.3 ppm is Y. Ａ , The sum of the integral values ​​of signals in the range of 38.4 ppm to 39.9 ppm is X. Ｂ , When that happens, (X Ｂ -X Ｃ ) / Y Ａ A varnish-like cyclic olefin copolymer composition in which the value of is 0.2 or more and 2.0 or less.

11. The varnish-like cyclic olefin copolymer composition according to claim 10, wherein the glass transition temperature of the cyclic olefin copolymer (m), as measured by differential scanning calorimeter (DSC), is 100°C or higher.

12. The varnish-like cyclic olefin copolymer composition according to claim 10 or 11, wherein the content of the cyclic olefin copolymer (m) in the varnish-like cyclic olefin copolymer composition is 30% by mass or more.

13. The varnish-like cyclic olefin copolymer composition according to claim 10 or 11, wherein the organic solvent comprises at least one selected from the group consisting of aromatic hydrocarbon solvents, cyclic hydrocarbon solvents, linear hydrocarbon solvents, and halogenated aromatic hydrocarbon solvents.

14. The varnish-like cyclic olefin copolymer composition according to claim 10 or 11, wherein, when the total number of moles of repeating units in the cyclic olefin copolymer (m) is 100 mol%, the content of repeating units (A) derived from the olefin is 10 mol% or more and 90 mol% or less, the content of repeating units (B) derived from the cyclic non-conjugated diene is 1 mol% or more and 40 mol% or less, and the content of repeating units (C) derived from the cyclic olefin is 1 mol% or more and 50 mol% or less.

15. The varnish-like cyclic olefin copolymer composition according to claim 10 or 11, wherein the cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene contains 5-vinyl-2-norbornene.

16. The cyclic olefin constituting the structural unit (C) derived from the cyclic olefin is tetracyclo[4.4.0.1 ２，５ 1. ７，１０ A varnish-like cyclic olefin copolymer composition according to claim 10 or 11, comprising at least one selected from the group consisting of ]-3-dodecene and bicyclo[2.2.1]-2-heptene.

17. The olefin constituting the repeating unit (A) derived from the olefin contains ethylene. The cyclic non-conjugated diene constituting the repeating unit (B) derived from the cyclic non-conjugated diene includes 5-vinyl-2-norbornene. The cyclic olefin constituting the structural unit (C) derived from the cyclic olefin is tetracyclo[4.4.0.1 ２，５ 1. ７，１０ A varnish-like cyclic olefin copolymer composition according to claim 10 or 11, comprising ]-3-dodecene.

18. A crosslinked body obtained by crosslinking the varnish-like cyclic olefin copolymer composition according to claim 10 or 11.

19. A film or sheet comprising the crosslinked material described in claim 18.

20. A laminate comprising a film or sheet as described in claim 19 laminated on a substrate.

21. A circuit board comprising an electrical insulating layer containing a crosslinking body as described in claim 18, and a conductive layer provided on the electrical insulating layer.

22. An electronic device comprising the circuit board described in claim 21.

23. A prepreg comprising a varnish-like cyclic olefin copolymer composition according to claim 10 or 11 and a sheet-like fibrous substrate.

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