JP2006178191A - Manufacturing method of polarizing film and polarizing film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a polarizing film which is excellent in adhesiveness between a substrate and a polarizing plate, is excellent in characteristics such as heat resistance and chemical resistance, hardly causes peeling, deformation and the like even when being used for a long term and has high reliability, and also to provide a polarizing film obtained according to the manufacturing method of polarizing film. <P>SOLUTION: The manufacturing method of polarizing film comprises processes of: subjecting at least one surface of the substrate consisting of norbornene resin to plasma treatment; and bonding the polarizing film to the surface subjected to the plasma treatment of the substrate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polarizing film manufacturing method and a polarizing film. Specifically, the present invention relates to a polarizing film manufacturing method and a polarizing film in which a norbornene resin substrate and a polarizing film are bonded with high strength.

A polarizing film (polarizing plate) used for a liquid crystal display or the like is usually formed from a substrate (optical film) excellent in transparency and a polarizing film (polarizer).
Conventionally, polycarbonate films, polyester films, acetate films, etc. have been used as substrates that make up polarizing films, but polarizing films using polycarbonate films or polyester films have a large photoelastic coefficient and small changes in stress. In some cases, the phase difference given to transmitted light may be changed due to factors such as the fact that acetate films have low heat resistance and high water absorption. there were.

  By the way, norbornene-based resins are attracting attention as materials for various optical components because they are excellent in transparency, heat resistance, chemical resistance, and the like. Patent Document 1 proposes a polarizing film in which a norbornene resin sheet is laminated as a protective layer on a polarizing film.

However, since the norbornene-based resin and other resin materials have poor adhesiveness, it is difficult to produce a polarizing plate using a norbornene resin substrate, and there is a problem that peeling is likely to occur during long-term use. For this reason, the appearance of a polarizing film using a norbornene-based resin substrate and having excellent adhesiveness has been strongly demanded.
JP-A-6-511117

  The present invention provides a highly reliable polarizing film having excellent adhesion between a substrate and a polarizing plate, excellent properties such as heat resistance and chemical resistance, and being resistant to peeling and deformation even in long-term use. It is an object to provide a method and a polarizing film.

The method for producing the polarizing film of the present invention comprises:
Plasma treatment of at least one surface of a substrate made of norbornene-based resin;
And a step of adhering a polarizing film to the plasma-treated surface of the substrate.

  In such a method for producing a polarizing film of the present invention, the norbornene-based resin is a resin obtained by (co) polymerizing a monomer containing at least one compound represented by the following general formula (1) It is preferable that

[In the formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom; a halogen atom; or a substituted or unsubstituted carbon atom which may have a linking group containing oxygen, nitrogen, sulfur or silicon. 1 to 15 hydrocarbon groups or other monovalent organic groups are represented. R ¹ and R ² , or R ³ and R ⁴ may be bonded to each other to form an alkylidene group, and R ¹ and R ² may be R ³ and R ⁴ , or R ² And R ³ are bonded to each other to form a carbocycle or heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure). It may be formed. The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. X represents an integer of 0 to 3, and y represents 0 or 1. When x is 0, y is also 0. ]
In the manufacturing method of the polarizing film of this invention, it is preferable that the said plasma processing is a process which introduce | transduces a functional group into the surface of the said board | substrate consisting of norbornene-type resin.

In the manufacturing method of the polarizing film of this invention, it is preferable that the functional group introduce | transduced into the surface of the said board | substrate is a hydroxyl group.
Furthermore, in the manufacturing method of the polarizing film of this invention, it is preferable that the process of adhere | attaching the said polarizing film is a process of adhere | attaching a polarizing film through a urethane type adhesive agent.

The polarizing film of this invention is obtained by the manufacturing method of the polarizing film of the said invention.
The polarizing film of the present invention is characterized by comprising a plasma-treated norbornene-based resin substrate, a urethane-based adhesive, and a polarizing film.

  According to the present invention, it has a good polarizing function, excellent adhesion between the substrate and the polarizing film, excellent properties such as heat resistance and chemical resistance, and peeling and deformation occur even in long-term use. It is possible to provide a polarizing film production method and a polarizing film which are difficult to use and have excellent durability and high reliability.

Hereinafter, the present invention will be specifically described.
In the method for producing a polarizing film of the present invention, a substrate made of a norbornene resin is used.
<Norbornene resin>
The norbornene-based resin used in the present invention is a resin obtained by polymerizing a monomer composition containing at least one norbornene-based compound and, if necessary, further hydrogenating.

<Monomer composition>
As a norbornene-type compound used for the said monomer composition, the norbornene-type compound represented by following General formula (1) can be mentioned, for example.

[In the formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom; a halogen atom; or a substituted or unsubstituted carbon atom which may have a linking group containing oxygen, nitrogen, sulfur or silicon. 1-15 hydrocarbon groups or other monovalent organic groups are represented. R ¹ and R ² , or R ³ and R ⁴ may be bonded to each other to form an alkylidene group, and R ¹ and R ² are R ³ and R ⁴ or R ² And R ³ are bonded to each other to form a carbocyclic or heterocyclic ring (these carbocyclic or heterocyclic rings may be monocyclic structures or other rings may be condensed to form a polycyclic structure). You may form. The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. X represents an integer of 0 to 3, y represents 0 or 1, and when x is 0, y is also 0. ]
Specific examples of the norbornene-based monomer represented by the general formula (1) include, for example, the compounds shown below, but are not limited to these examples.
Bicyclo [2.2.1] hept-2-ene (norbornene)
5-methyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept 2-ene-5-phenyl-bicyclo [2.2.1] hept-2-ene-5- (4-biphenyl) -bicyclo [2.2.1] hept-2-ene-5-methoxycarbonyl- Bicyclo [2.2.1] hept-2-ene · 5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene · 5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2 -Ene, 5-phenylcarbonyloxy-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl- 5-phenoxycarboni -Bicyclo [2.2.1] hept-2-ene.5-methyl-5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene.5-vinyl-bicyclo [2.2.1] ] Hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5,5-dimethyl-bicyclo [2.2.1] hept-2-ene, 5,6-dimethyl -Bicyclo [2.2.1] hept-2-ene, 5-fluoro-bicyclo [2.2.1] hept-2-ene, 5-chloro-bicyclo [2.2.1] hept-2-ene 5-bromo-bicyclo [2.2.1] hept-2-ene5,6-difluoro-bicyclo [2.2.1] hept-2-ene5,6-dichloro-bicyclo [2.2 .1] Hept-2-ene-5,6-dibromo-bicyclo [2.2.1 Hept-2-ene, 5-hydroxy-bicyclo [2.2.1] hept-2-ene, 5-hydroxyethyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2 2.1] hept-2-ene, 5-amino-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, tricyclo [ 4.4.0.1 ^2,5 ] Undec-3-ene.7-methyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene.7-ethyl-tricyclo [4.3. 0.1 ^2,5] dec-3-ene-7-cyclohexyl - tricyclo [4.3.0.1 ^2,5] dec-3-ene-7-phenyl - tricyclo [4.3.0.1 ^{2 , 5]} dec-3-ene-7- (4-biphenyl) - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-7,8 Methyl - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-7,8,9- trimethyl - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-8- Methyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene · 8-phenyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene · 7-fluoro-tricyclo [ 4.3.0.1 ^2,5 ] dec-3-ene.7-chloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene.7-bromo-tricyclo [4.3. 0.1 ^2,5] dec-3-ene-7,8-dichloro - tricyclo [4.3.0.1 ^2,5] dec-3-ene-7,8,9- trichloro - tricyclo [4. 3.0.1 ^2,5 ] dec-3-ene · 7-chloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene · 7-dichloromethyl-tricycl B [4.3.0.1 ^2,5 ] dec-3-ene · 7-trichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene · 7-hydroxy-tricyclo [4 .3.0.1 ^2,5 ] dec-3-ene · 7-cyano-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene · 7-amino-tricyclo [4.3.0 .1 ^2,5] deca-3-ene-tetracyclo [4.4.0.1 ^2,5. 1 ^7,10 ] dodec-3-ene pentacyclo [7.4.0.1 ^2,5 . 1 ^8,11 . 0 ^7,12] pentadeca-3-ene-hexacyclo [8.4.0.1 ^2,5. 1 ^7,14 . 1 ^9,12 . 0 ^8,13] heptadec-3-en-8-methyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8-ethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8-cyclohexyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8- (4-biphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-
Ene-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-
Ene-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodec-3-ene-8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodec-3-ene-8-methyl-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodec-3-ene-8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-ethylidene - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8,8-dimethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8,9-dimethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-fluoro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-chloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-bromo - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene.8,8-dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene.8,9-dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene. 8,8,9,9-tetrachloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-hydroxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-cyano - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-amino-tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] dodec-3-ene These norbornene compounds may be used alone or in combination of two or more.

The kind and amount of the norbornene-based compound used in the present invention are appropriately selected depending on the properties required for the obtained resin.
Of these, when a compound having a structure containing at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom in the molecule (hereinafter referred to as “polar structure”) is used. It is preferable because of excellent adhesion and adhesion to other materials. In particular, in the formula (1), R ¹ and R ³ are a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and any one of R ^{2 and} R ⁴ is A compound having a polar structure and the other one being a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable because the water absorption (wet) property of the resin is low. Furthermore, a norbornene compound in which the group having a polar structure is a group represented by the following general formula (2) is easy to balance the heat resistance and water absorption (wet) property of the resulting resin and can be preferably used.

_{- (CH 2) z COOR ...} (2)
(In formula (2), R represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and z represents 0 or an integer of 1 to 10)
In the general formula (2), the smaller the value of z, the higher the glass transition temperature of the resulting hydrogenated product and the better the heat resistance, so z is preferably an integer of 0 or 1 to 3, A monomer in which z is 0 is preferable in that its synthesis is easy. Further, R in the general formula (2) tends to decrease the water absorption (wet) property of the hydrogenated polymer obtained as the number of carbon atoms increases, but also tends to decrease the glass transition temperature. From the viewpoint of maintaining heat resistance, a hydrocarbon group having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 to 6 carbon atoms is particularly preferable.

  In the general formula (1), when an alkyl group having 1 to 3 carbon atoms, particularly a methyl group, is bonded to the carbon atom to which the group represented by the general formula (2) is bonded, heat resistance and water absorption It is preferable in terms of balance with (wet) property. Further, in the general formula (1), a compound in which x is 0 or 1 and y is 0 has high reactivity, a polymer can be obtained in a high yield, and polymer hydrogen having high heat resistance. It is preferably used because an additive is obtained and it is industrially easily available.

  In obtaining the norbornene-based resin used in the present invention, a monomer that can be copolymerized with the norbornene-based compound can be included in the monomer composition and polymerized as long as the effects of the present invention are not impaired.

  Examples of these copolymerizable monomers include cyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and cyclododecene, and non-conjugated cyclic polyenes such as 1,4-cyclooctadiene, dicyclopentadiene, and cyclododecatriene. Can be mentioned.

These copolymerizable monomers may be used alone or in combination of two or more.
<Polymerization method>
The method for polymerizing the monomer composition containing the norbornene-based compound is not particularly limited as long as the monomer composition can be polymerized. For example, the polymerization is performed by ring-opening polymerization or addition polymerization. be able to.

(A) Ring-opening polymerization Production of a polymer by ring-opening polymerization can be performed by a known ring-opening polymerization reaction for a norbornene-based compound, and a monomer composition containing the norbornene-based compound is used as a polymerization catalyst and a polymerization reaction. It can manufacture by carrying out ring-opening polymerization using the solvent for use, and a molecular weight regulator as needed.

(A) Polymerization catalyst In this invention, when superposing | polymerizing a monomer composition by ring-opening (co) polymerization reaction, superposition | polymerization is performed in presence of a metathesis catalyst.

This metathesis catalyst is
(A) at least one compound selected from compounds having W, Mo and Re (hereinafter referred to as compound (A));
(B) Deming periodic table group IA elements (for example, Li, Na, K, etc.), group IIA elements (for example, Mg, Ca, etc.), group IIB elements (for example, Zn, Cd, Hg, etc.), group IIIA elements (For example, B, Al, etc.), a compound having a group IVA element (for example, Si, Sn, Pb, etc.), or a group IVB element (for example, Ti, Zr, etc.), The catalyst comprises a combination of at least one compound selected from compounds having at least one bond between this element and hydrogen (hereinafter referred to as compound (B)). Moreover, in order to improve the activity of a catalyst, the below-mentioned additive (C) may further be added.

Compound (A) includes W, Mo or Re halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, and derivatives thereof. Alternatively, a combination thereof may be mentioned, and W and Mo compounds, particularly their halides, oxyhalides and alkoxyhalides are preferred from the viewpoint of polymerization activity and practicality. Moreover, you may use the mixture of 2 or more types of compounds which produce | generate the said compound by reaction. Further, these compounds may be complexed with an appropriate complexing agent such as P (C ₆ H ₅ ) ₅ or C ₅ H ₅ N.

Specific examples of the compound (A) include WCl ₆ , WCl ₅ , WCl ₄ , WBr ₆ , WF ₆ , WI ₆ , MoCl ₅ , MoCl ₄ , MoCl ₃ , ReCl ₃ , WOCl ₄ , MoOCl ₃ , ReOCl ₃ , ReOBr ₃ , W (OC ₆ H ₅ ) ₆ , WCl ₂ (OC ₆ H ₅ ) ₄ , Mo (OC ₂ H ₅ ) ₂ Cl ₃ , Mo (OC ₂ H ₅ ) ₅ , MoO ₂ (acac) ₂ , W (OCOR) ₅ , W (OC ₂ H ₅ ) ₂ Cl ₃ , W (CO) ₆ , Mo (CO) ₆ , Re ₂ (CO) ₁₀ , ReOBr ₃・ P (C ₆ H ₅ ) ₃ , WCl _{5 · P (C 6 H 5)} 3, WCl 6 · C 5 H 5 N, such as _{W (CO) 5 · P (} C 6 H 5) 3, W (CO) 3 · (CH 3 CN) 3 and the like . Among the above compounds, particularly preferred compounds include MoCl ₅ , Mo (OC ₂ H ₅ ) ₂ Cl ₃ , WCl ₆ , W (OC ₂ H ₅ ) ₂ Cl _{3 and the} like.

Specific examples of the compound _{(B), n-C 4 H 5 Li} , n-C 5 H 11 Na, C 5 H 5 Na, CH 3 MgI, C 2 H 5 MgBr, CH 3 MgBr, n- C ₃ H ₇ MgCl, (C ₆ H ₅ ) ₃ Al, t-C ₄ H ₉ MgCl, CH ₂ = CHCH ₂ MgCl, (C ₂ H ₅ ) ₂ Zn, (C ₂ H ₅ ) ₂ Cd, CaZn ( C ₂ H ₅ ) ₄ , (CH ₃ ) ₃ B, (C ₂ H ₅ ) ₃ B, (nC ₄ H ₉ ) ₃ B, (CH ₃ ) ₃ Al, (CH ₃ ) ₂ AlCl, (CH ₃ ) ₃ Al ₂ Cl ₃ , CH ₃ AlCl ₂ , (C ₂ H ₅ ) ₃ Al, LiAl (C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₃ Al-O (C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₂ AlCl, C ₂ H ₅ AlCl ₂ , (C ₂ H ₅ ) ₂ AlH, (iso-C ₄ H ₉ ) ₂ AlH, (C ₂ H ₅ ) ₂ AlOC ₂ H ₅ , (iso-C ₄ H ₉ ) ₃ Al, (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ , (CH ₃ ) ₄ Ga, (CH ₃ ) ₄ Sn, (n−C ₄ H ₉ ) ₄ Sn, (C ₂ H ₅ ) ₃ include _{SiH, (n-C 6 H} 13) 3 Al, (n-C 4 H 17) 3 Al, LiH, NaH, etc. _{B 2 H 6, NaBH 4,} AlH 3, LiAlH 4, BiH 4 and TiH ₄ is It is done. Moreover, the mixture of 2 or more types of compounds which produce | generate these compounds by reaction can also be used. Preferred examples of these include (CH ₃ ) ₃ Al, (CH ₃ ) ₂ AlCl, (CH ₃ ) ₃ Al ₂ Cl ₃ , CH ₃ AlCl ₂ , (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , C ₂ H ₅ AlCl ₂ , (C ₂ H ₅ ) ₂ AlH, (C ₂ H ₅ ) ₂ AlOC ₂ H ₅ , (C ₂ H ₅ ) ₂ AlCN, (C ₃ H ₇ ) ₃ Al, (iso-C ₄ H ₉ ) ₃ Al, (iso-C ₄ H ₉ ) ₂ AlH, (C ₆ H ₁₃ ) ₃ Al, (C ₈ H ₁₇ ) ₃ Al, (C ₆ H ₅ ) ₅ Al and the like can be mentioned.

As the additive (C) that can be used together with the compound (A) and the compound (B), alcohols, aldehydes, ketones, amines and the like can be suitably used. For example, the following (1) to (1) to (9) can be exemplified.
(1) Non-organometallic compounds of boron such as simple boron, BF ₃ , BCl ₃ , B (OnC ₄ H ₉ ) ₃ , (C ₂ H ₅ O ₃ ) ₂ , BF, B ₂ O ₃ , H ₃ BO ₃ Silicon non-organometallic compounds such as Si (OC ₂ H ₅ ) ₄ ;
(2) alcohols, hydroperoxides and peroxides;
(3) water;
(4) oxygen;
(5) Carbonyl compounds such as aldehydes and ketones and polymers thereof;
(6) cyclic ethers such as ethylene oxide, epichlorohydrin, oxetane;
(7) Amides such as N, N-diethylformamide and N, N-dimethylacetamide, amines such as aniline, morpholine and piperidine, and azo compounds such as azobenzene;
(8) N-nitroso compounds such as N-nitrosodimethylamine and N-nitrosodiphenylamine;
(9) Compounds containing an S-Cl or N-Cl group such as trichloromelamine, N-chlorosuccinimide, phenylsulfenyl chloride and the like.

  The amount of the metathesis catalyst used is such that the molar ratio (compound: total monomer) of the compound (A) and all monomers used for polymerization is usually 1: 500 to 1: 50,000, preferably 1: An amount of 1,000 to 1: 10,000 is desirable.

The ratio of the compound (A) to the compound (B) (compound (A): compound (B)) is 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atom ratio.
The ratio of the compound (A) to the compound (C) (compound (C): compound (A)) is 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1 in molar ratio. desirable.

(B) Polymerization solvent As the solvent used in the ring-opening polymerization reaction, the monomer composition or catalyst to be used for polymerization is not dissolved and the catalyst is not deactivated. Although it will not specifically limit if a compound melt | dissolves, For example, alkanes, such as pentane, hexane, heptane, octane, nonane, decane; Cycloalkanes, such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; benzene, Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene; halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chloroform, tetrachloroethylene; halogenated aryl compounds such as chlorobenzene; ethyl acetate, acetic acid n-butyl, Examples thereof include saturated carboxylic acid esters such as iso-butyl acetate, methyl propionate and dimethoxyethane; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane. These can be used alone or in admixture of two or more. Such a solvent is used as a solvent for dissolving the solvent constituting the molecular weight regulator solution, the norbornene compound, the copolymerizable monomer and / or the metathesis catalyst.

The amount of the solvent used is such that the weight ratio of the solvent to the monomer composition used for polymerization (solvent: monomer composition) is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. Is desirable.
(C) Molecular weight regulator The molecular weight of the resulting ring-opening polymer can be controlled by the polymerization temperature, the type of catalyst, and the type of solvent, but it can also be adjusted by allowing a molecular weight regulator to coexist in the reaction system. be able to.

  Suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and styrene, 4 -Methylstyrene, 2-methylstyrene, 4-ethylstyrene can be mentioned, and among these, 1-butene and 1-hexene are particularly preferable. These molecular weight regulators can be used alone or in admixture of two or more.

The usage-amount of a molecular weight modifier is 0.005-0.6 mol normally with respect to 1 mol of monomers with which a ring-opening polymerization reaction is provided, Preferably it is 0.01-0.5 mol.
(D) Other polymerization conditions The ring-opening polymer can be obtained by ring-opening polymerization of the norbornene compound alone or the norbornene compound and a copolymerizable monomer. Polybutadiene, polyisoprene. Presence of unsaturated hydrocarbon polymers containing two or more carbon-carbon double bonds in the main chain, such as conjugated diene compounds such as styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, and polynorbornene A monomer composition containing a norbornene compound may be subjected to ring-opening polymerization.

(B) Addition polymerization The production of a polymer by addition (co) polymerization can be performed by a known addition polymerization reaction for a norbornene compound, and a monomer composition containing the norbornene compound is used as a polymerization catalyst. Accordingly, it can be produced by addition polymerization using a solvent for polymerization reaction and, if necessary, a molecular weight regulator.

(A) Polymerization catalyst Examples of the polymerization catalyst for addition polymerization include single catalysts and multi-component catalysts such as palladium, nickel, cobalt, titanium and zirconium mentioned in the following (a-1) to (a-3). However, the polymerization catalyst used in the present invention is not limited thereto.

(A-1) Single catalyst system [Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ , [Pd (PhCN) ₄ ] [SbF ₆ ]
[(Η ³ -crotyl) Pd (cycloocta-1,5-diene)] [PF ₆ ],
[(Η ³ -crotyl) Ni (cycloocta-1,5-diene)] [B (3
, 5- (CF ₃ ) ₂ C ₆ F ₃ ) ₄ ],
[(Η ³ -crotyl) Ni (cycloocta-1,5-diene)] [PF ₆ ],
[(Η ³ -allyl) Ni (cycloclota-1,5-diene)] [B (C ₆ F ₅ ) ₄ ],
[(Η ³ -crotyl) Ni (cycloocta-1,5-diene)] [SbF ₆ ],
Toluene · Ni (C ₆ F ₅ ) ₂ , Benzene · Ni (C ₆ F ₅ ) ₂ , Mestinene · Ni (C ₆ F ₅ ) ₂ , Ethylether · Ni (C ₆ F ₅ ) ₂
Etc.

(A-2) Multi-component catalyst system (1)
A combination of a palladium complex having a σ or σ, π bond and an organoaluminum or super strong acid salt.
Di-μ-chloro-bis (6-methoxybicyclo [2.2.1] hept-2-ene-endo-5σ, 2π) Pd, methylalumoxane (abbreviated as MAO), AgSbF6 or AgBF4 Combinations with different compounds,
A combination of [(η ³ -aryl) PdCl] ₂ and AgSbF ₆ or AgBF ₄ ;
A combination of [(cycloocta-1,5-diene) Pd (CH ₃ ) Cl], PPh ₃ and NaB [3,5- (CF ₃ ) ₂ C ₆ H ₃ ] ₄ may be mentioned.

(A-3) Multi-component catalyst system (2)
(I) transition metal compounds selected from nickel compounds, cobalt compounds, titanium compounds or zirconium compounds,
(II) a compound selected from super strong acids, Lewis acids and ionic boron compounds,
(III) A combination comprising three components of an organoaluminum compound.

(I) Examples of transition metal compounds (I-1) Examples of nickel compounds and cobalt compounds:
Compounds selected from nickel or cobalt organic carboxylates, organic phosphites, organic phosphates, organic sulfonates, β-diketone compounds,
For example, nickel 2-ethylhexanoate, nickel naphthenate, cobalt naphthenate, nickel oleate, nickel dodecanoate, cobalt dodecanoate, cobalt neodecanoate, nickel dibutyl phosphite, nickel dibutyl phosphate, nickel dioctyl phosphate, phosphoric acid Examples thereof include nickel salts of dibutyl ester, nickel dodecylbenzenesulfonate, nickel p-toluenesulfonate, nickel bis (acetylacetonate), and bis (ethylacetoacetate) nickel.

A compound obtained by modifying the organic carboxylate of nickel with a super strong acid such as hexafluoroantimonic acid, tetrafluoroboric acid, trifluoroacetic acid, hexafluoroacetone,
Nickel diene or triene coordination complexes,
For example, dichloro (1,5-cyclooctadiene) nickel, [(η ³ -crotyl) (
1,5-cyclooctadiene) nickel] hexafluorophosphate, and its tetrafluoroborate, tetrakis [3,5-bis (trifluoromethyl)] borate complex, (1,5,9-cyclododecatriene) nickel, bis Nickel complexes such as (norbornadiene) nickel and bis (1,5-cyclooctadiene) nickel,
A complex in which a ligand having an atom such as P, N, or O is coordinated to nickel.

For example, bis (triphenylphosphine) nickel dichloride, bis (triphenylphosphine) nickel dibromide, bis (triphenylphosphine) cobalt dibromide, bis [tri (2-methylphenyl) phosphine] nickel dichloride, bis [tri (4 - methylphenyl) phosphine] nickel dichloride, bis [N- (3-t- butylsalicylidene) phenyl aminate] nickel, Ni [PhC (O) CH] (Ph), Ni (OC ( C 6 H 4) PPh) (H) (PCy ₃ ), Ni [OC (O) (C ₆ H ₄ ) P]
(H) (PPh ₃ ), bis (1,5-cyclooctadiene) nickel and PhC (O) CH
= Reaction product of PPh _{3, [2,6- (i-Pr) 2 C} 6 H 3 N = CHC 6 H 3 (O) (Anth) ] (Ph) (PPh ₃₎ nickel complex such as Ni (here And Anth is 9-anthr
acenyl and Ph are abbreviations for phenyl and Cy for cyclohexyl. ),
Is mentioned.

(I-2) Examples of titanium and zirconium compounds:
[T-BuNSiMe (Me ₄ Cp)] TiCl ₂ , (Me ₄ Cp) (O—iPr ₂ C ₆ H ₃ ) ₂ TiCl, (Me ₄ Cp) TiCl ₃ , (Me ₄ Cp) Ti (OBu) ₃ , [T-BuNS
iMe ₂ Flu] TiMe ₂ , [t-BuNSiMe ₂ Flu] TiCl ₂ , Et (Ind) ₂ ZrCl ₂ , Ph ₂ C (Ind) (Cp) ZrCl ₂ , iPr (Cp) (Flu) ZrCl ₂ , iPr (3 -tert-But-Cp) (Ind ) ZrCl 2, iPr (Cp) (Ind) ZrCl 2, Me 2 Si (Ind) 2 ZrCl 2, Cp 2 ZrCl 2, (Cp is Cyclopentadienl, Ind is Indenyl, Flu is Fluorenyl (The abbreviation for.)
Etc.

(II) Examples of super strong acids, Lewis acids and ionic boron compounds include:
Examples of super strong acids include hexafluoroantimonic acid, hexafluorophosphoric acid, hexafluoroarsenic acid, trifluoroacetic acid, fluorosulfuric acid, trifluoromethanesulfonic acid, tetrafluoroboric acid, tetrakis (pentafluorophenyl) boric acid, tetrakis [3, 5-bis (trifluoromethyl) phenyl] boric acid, p-toluenesulfonic acid, pentafluoropropionic acid, etc.
Examples of Lewis acid compounds include complexes of boron trifluoride with ethers, amines, phenols, etc., aluminum trifluoride ethers, complexes of amines, phenols, tris (pentafluorophenyl) borane, tris [3,5 Boron compounds such as -bis (trifluoromethyl) phenyl] borane, aluminum compounds such as aluminum trichloride, aluminum tribromide, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum fluoride, tri (pentafluorophenyl) aluminum , Organic halogen compounds exhibiting Lewis acidity such as hexafluoroacetone, hexachloroacetone, chloranil, hexafluoromethyl ethyl ketone, and other Lewis acidity such as titanium tetrachloride and pentafluoroantimony Such as the compounds,
Examples of the ionic boron compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenylcarbeniumtetrakis (2,4 , 6-trifluorophenyl) borate, triphenylcarbenium tetraphenylborate, tributylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (Pentafluorophenyl) borate, N, N-diphenylanilinium tetrakis (pentafluorophenyl) borate and the like.

As an example of the organoaluminum compound (III),
Alkylalumoxane compounds such as methylalumoxane, ethylalumoxane, butylalumoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum chloride, diethylaluminum fluoride, ethylaluminum sesquichloride, ethylaluminum dichloride, etc. The alkylaluminum compound and the halogenated alkylaluminum compound, or a mixture of the alkylalumoxane compound and the alkylaluminum compound are preferably used.

These catalyst components are used, for example, in amounts used within the following ranges.
Transition metal compounds such as nickel compounds, palladium compounds, cobalt compounds, titanium compounds, and zirconium compounds are 0.02 to 100 millimole atoms per mole of monomer, and organoaluminum compounds are per mole of transition metal compound. The amount of non-conjugated diene, Lewis acid, and ionic boron compound is 0 to 100 mol with respect to 1 mol atom of the transition metal compound.

(B) Polymerization solvent As the solvent used in the addition polymerization reaction, the monomer composition or catalyst to be subjected to the polymerization is dissolved and the catalyst is not deactivated. Although it will not specifically limit if it melt | dissolves, For example, alicyclic hydrocarbon solvents, such as cyclohexane, cyclopentane, and methylcyclopentane, Aliphatic hydrocarbon solvents, such as hexane, heptane, and octane, toluene, benzene, xylene, mesitylene And an aromatic hydrocarbon solvent such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, and other solvents selected from dichlorobenzene. These can be used alone or in admixture of two or more.

(C) Molecular Weight Modifier In the present invention, the molecular weight of the norbornene addition polymer to be produced can be adjusted by adding hydrogen or α-olefin as a molecular weight regulator in the polymerization system. The molecular weight of the norbornene-based addition polymer produced decreases as the molecular weight regulator added increases.

《Hydrogenation reaction》
The polymer obtained by the ring-opening polymerization reaction has an olefinically unsaturated bond in the molecule. Moreover, also in the said addition polymerization reaction, a polymer may have an olefinically unsaturated bond in the molecule | numerator. Thus, if an olefinically unsaturated bond is present in the polymer molecule, the olefinically unsaturated bond may cause deterioration over time such as coloring or gelation. It is preferable to carry out a hydrogenation reaction to convert to.

  In the hydrogenation reaction, a known hydrogenation catalyst is added to an ordinary method, that is, a polymer solution having an olefinically unsaturated bond, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added to the solution. The reaction can be carried out at -200 ° C, preferably 20-180 ° C.

The hydrogenation rate of the hydrogenated polymer is typically 50 MHz, as measured by ¹ H-NMR.
% Or more, preferably 70% or more, more preferably 90% or more, particularly preferably 98% or more, and most preferably 99% or more. The higher the hydrogenation rate, the better the stability to heat and light, and it is preferable because stable characteristics can be obtained over a long period when used as a molded product.

  In addition, when the polymer obtained by the above method has an aromatic group in the molecule, the aromatic group does not cause deterioration such as coloring over time or gelation, but rather, mechanical characteristics and optical characteristics. In some cases, such an aromatic group does not necessarily have to be hydrogenated.

  As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. Homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichloro Examples thereof include tris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of the catalyst may be powder or granular.

These hydrogenation catalysts are usually used in a ratio such that the weight ratio of the ring-opening polymer to the hydrogenation catalyst (ring-opening polymer: hydrogenation catalyst) is 1: 1 × 10 ⁻⁶ to 1: 2. The
The norbornene resin used in the present invention has an intrinsic viscosity [η] _inh of preferably 0.2 to 2.0 dl / g, more preferably 0.35 to 1.0 dl / g, and particularly preferably 0.4 to 0. The polystyrene-reduced number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 1.5. A material having a weight average molecular weight (Mw) of 10,000 to 2,000,000, more preferably 20,000 to 1,000,000, particularly preferably 30,000 to 500,000 is suitable. When the intrinsic viscosity [η] _inh , the number average molecular weight, and the weight average molecular weight are in the above ranges, the norbornene resin has excellent mechanical strength, and a norbornene resin substrate that is not easily damaged can be obtained.

  The norbornene resin has a glass transition temperature (Tg) of usually 120 ° C. or higher, preferably 130 ° C. or higher, more preferably 150 ° C. or higher. When Tg is within the above range, the adhesion strength of the dielectric multilayer film to the base material is improved, and a norbornene resin substrate having excellent solder reflow resistance is obtained.

  The saturated water absorption of the norbornene resin is 1% by weight or less, preferably 0.1 to 0.8% by weight. When the saturated water absorption exceeds 1% by weight, there may be a problem in durability such that the resin substrate obtained from the resin is subject to water absorption (wet) deformation over time depending on the environment in which it is used. On the other hand, when the amount is less than 0.1% by weight, there may be a problem in adhesiveness or a problem in dispersibility of the near infrared absorber. Further, when the saturated water absorption is within the above range, it is possible to prevent the norbornene-based resin from being deteriorated due to moisture of the image sensor, particularly when used for a light-transmitting lid of a package for housing a solid-state image sensor. The saturated water absorption is a value obtained by immersing in 23 ° C. water for 1 week and measuring the increased weight according to ASTM D570.

《Other ingredients》
In the present invention, additives such as an antioxidant and an ultraviolet absorber can be further added to the norbornene-based resin as long as the effects of the present invention are not impaired.

  Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [ And methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone. Moreover, when manufacturing a norbornene-type resin-made board | substrate by the solution casting method mentioned later, manufacture of a resin board | substrate can be made easy by adding a leveling agent and an antifoamer.

These additives may be mixed together with a norbornene-based resin or the like when manufacturing the norbornene-based resin substrate used in the present invention, or added in advance when manufacturing the norbornene-based resin. May be. The addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2. parts by weight based on 100 parts by weight of the norbornene resin. 0 part by weight is desirable.

<< Manufacturing Method of Norbornene Resin Substrate >>
The substrate made of norbornene-based resin used in the present invention can be suitably molded by directly melt-molding norbornene-based resin or by a method of dissolving in a solvent and casting (cast molding).

(A) Melt Molding The norbornene resin substrate used in the present invention can be produced by melt molding a norbornene resin or a resin composition containing a norbornene resin and an infrared absorber. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

(B) Casting The norbornene-based resin substrate used in the present invention can also be produced by casting a liquid resin composition obtained by dissolving a norbornene-based resin in a solvent on an appropriate base material and removing the solvent. For example, a norbornene-based resin substrate is formed by applying the above-described liquid resin composition onto a substrate such as a steel belt, a steel drum, or a polyester film, drying the solvent, and then peeling the coating film from the substrate. Can be obtained. Further, a norbornene resin substrate can be formed on the original optical component by coating the above-mentioned liquid composition on an optical component made of glass, quartz or transparent plastic and drying the solvent.

  The amount of residual solvent in the norbornene-based resin substrate obtained by the above method is preferably as small as possible, and is usually 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less. When the residual solvent amount exceeds 3% by weight, the resin substrate may be deformed over time or the characteristics may be changed over time, and a desired function may not be exhibited.

  The thickness of the substrate made of norbornene resin used in the present invention is not particularly limited, but is usually 10 to 300 μm, preferably about 30 to 200 μm. If the substrate made of norbornene resin is too thin, the strength may be insufficient, and if the substrate is too thick, the birefringence may become too high, or the transparency and appearance may deteriorate. .

The substrate made of norbornene-based resin used in the present invention desirably has a light transmittance of usually 80% or more, preferably 85% or more, more preferably 90% or more.
<Plasma treatment>
In the manufacturing method of the polarizing film of this invention, it has the process of plasma-treating at least one surface of the board | substrate which consists of a norbornene-type resin mentioned above.

  The plasma treatment according to the present invention is a treatment performed using plasma (also referred to as non-equilibrium plasma) generated in a region where the electron temperature is high but the gas temperature is low, and the plasma includes active species such as ions, electrons, radicals, This is a technology that activates the surface by applying vacuum ultraviolet rays or the like to the substrate surface to perform surface modification such as etching, implantation, radical generation, and the like. In the implantation, functional groups such as a hydroxyl group, a carbonyl group, and a carboxyl group are introduced on the surface of the material, and an effect of improving adhesion and wettability is obtained.

The plasma treatment according to the present invention is preferably performed at a relatively low temperature at normal pressure or a pressure condition close thereto, for example, under a pressure of 0.1 to 1.1 kg / cm ² , the temperature during the discharge treatment is Usually, it can be carried out in a temperature range of about 10 to 80 ° C., preferably about 25 to 60 ° C.

The gas used for such plasma treatment is not particularly limited as long as plasma is generated under normal pressure or a pressure condition close thereto, but an inert gas such as He, Ar, Ne, Kr, Xe, and Rn, Examples thereof include carbon oxide gases such as CO ₂ and CO, oxidizing gases such as O ₂ , reactive gases such as CF ₄ , polymerizable unsaturated compound gases such as ethylene and propylene, and air. These are appropriately selected according to the purpose and used alone or in combination.

  In the plasma treatment, a functional group such as a hydroxyl group, an amino group, a carbonyl group, or a carboxyl group on the surface of a substrate made of a norbornene resin can be introduced. By introducing these groups, preferably a hydroxyl group or an amino group, onto the substrate surface, the wettability of the substrate surface is improved and the adhesion is improved. In particular, the introduction of a hydroxyl group to the surface of a substrate made of norbornene resin significantly improves the adhesion between the substrate surface and the urethane adhesive, and also improves the wettability. Improved.

  In the plasma treatment, in order to introduce a hydroxyl group on the surface of a substrate made of a norbornene-based resin, it is preferable to perform a plasma treatment in an atmosphere containing water vapor or water, oxygen, etc., and in order to introduce an amino group, ammonia or The plasma treatment is preferably performed in an atmosphere containing nitrogen or further water vapor or hydrogen.

  In the plasma treatment according to the present invention, more preferably, a functional group such as a hydroxyl group or an amino group is formed on the surface of the substrate after the C—C bond or C—H bond of the organic substance existing on the surface of the substrate made of norbornene resin is cut. It is preferable to perform plasma treatment under conditions for introducing a group, whereby more functional groups can be introduced, and a substrate having better adhesiveness can be obtained. Specifically, inert gases such as helium, argon, neon, etc., lower hydrocarbons such as hydrogen, oxygen, ozone, water vapor, carbon dioxide, carbon monoxide, nitrogen, ammonia, nitric oxide, nitrogen dioxide, methane, and ethane It is preferable to perform plasma treatment in the presence of at least two kinds of gases selected from organic compounds having a low boiling point such as ketone and alcohol.

  More preferably, an inert gas such as helium, argon, neon, at least one gas selected from hydrogen, water vapor, hydrogen peroxide, and at least one selected from oxygen, water vapor, hydrogen peroxide, ozone. Adhesiveness can be easily imparted by performing plasma treatment under a reactive gas containing the above gas.

  The discharge treatment can be performed by exposing a surface to be treated of a substrate made of norbornene resin in a predetermined gas atmosphere and applying a high-frequency voltage such as 3 to 40 kHz between the electrodes.

In the present invention, a plasma treatment, preferably carried out under a pressure of 0.1~1.1kg / cm ² at a pressure of atmospheric pressure or atmospheric圧近near which, 0.1 kg / cm ² If it is performed under a pressure lower than that, a special apparatus is required because the system needs to be kept in a vacuum, and the equipment cost is high and the gas density is low, so it is difficult to obtain a uniform and sufficient reformed surface. This is because, and if it exceeds 1.1 kg / cm ² , no further treatment effect can be obtained despite the increase in gas consumption, which is not economical.

The plasma processing according to the present invention can be suitably performed using, for example, an atmospheric pressure plasma processing apparatus as shown in FIG. In the apparatus of FIG. 1, a sample to be plasma-processed is positioned between two opposed electrodes. In order to prevent spark discharge during plasma excitation, it is preferable to provide a dielectric such as glass, ceramic, or polyimide film on the surface of the upper and / or lower electrodes. A plasma-exciting gas such as a mixed gas of argon and helium is introduced into the atmospheric pressure plasma generator from the inflow port, and is discharged from the outflow port by replacing the air inside. Next, a high frequency voltage of 1 to 20 kHz, a voltage of 1 to 10 kV (eg, 3000 Hz, 4200 V) is usually applied between the electrodes, the introduced gas is plasma-excited to generate a glow discharge for a predetermined time, and Modification can be performed. When a substrate made of a norbornene-based resin as a sample is processed while passing through a plasma processing apparatus, it is preferable because plasma processing can be continuously performed.
<Polarizing film>
The polarizing film according to the present invention is formed by bonding a substrate made of norbornene-based resin that has been plasma-treated as described above and a polarizing film.

  The polarizing film used in the present invention has a function as a polarizing film, that is, a function of dividing incident light into two polarization components orthogonal to each other, allowing only one of them to pass, and absorbing or dispersing the other component. Any of these can be used and is not particularly limited. Examples of the polarizing film that can be used in the present invention include polyvinyl alcohol (hereinafter abbreviated as PVA) / iodine polarizing film, PVA / dye polarizing film in which a dichroic dye is adsorbed and oriented on a PVA film, , A polyene polarizing film in which a polyene is formed by inducing a dehydration reaction from a PVA film or by dehydrochlorination reaction of a polyvinyl chloride film, a surface of a PVA film made of a modified PVA containing a cationic group in the molecule, and Examples thereof include a polarizing film having a dichroic dye inside.

  Moreover, the manufacturing method of the polarizing film used in the present invention is not particularly limited. For example, a method of adsorbing iodine ions after stretching on a PVA film, a method of stretching a PVA film after dyeing with a dichroic dye, a method of dyeing a PVA film with a dichroic dye after stretching, a dichroic dye Well-known methods such as a method of stretching after printing on a PVA-based film and a method of printing a dichroic dye after stretching a PVA-based film can be mentioned. More specifically, iodine is dissolved in a potassium iodide solution to form higher-order iodine ions, the ions are adsorbed on a PVA film and stretched, and then a 1 to 4% boric acid aqueous solution has a bath temperature of 30 to 30%. A method for producing a polarizing film by immersing at 40 ° C., or treating a PVA film with boric acid in the same manner and stretching it about 3 to 7 times in a uniaxial direction, and adding a 0.05 to 5% dichroic dye aqueous solution to a bath temperature Examples include a method of producing a polarizing film by immersing at 30 to 40 ° C. to adsorb a dye, drying at 80 to 100 ° C. and heat setting.

Although the polarizing film used by this invention is not specifically limited, It is 10-100 micrometers, Preferably it is desirable that it is 20-80 micrometers in thickness.
These polarizing films may be used as they are for the production of the polarizing film according to the present invention, but can also be used by performing plasma treatment on the surface to be bonded to the substrate made of a norbornene resin. <Adhesion>
In the present invention, a polarizing film is manufactured by adhering a polarizing film to the plasma-treated surface of a substrate made of the above-described norbornene-based resin. Adhesion between the substrate and the polarizing film is usually performed using an adhesive or an adhesive.

  As the pressure-sensitive adhesive, those having excellent transparency, small birefringence, and the like and capable of exhibiting sufficient adhesive force even when used as a thin layer are preferable. Examples of such pressure-sensitive adhesives include natural rubber, synthetic rubber / elastomer, vinyl chloride / vinyl acetate copolymer, polyvinyl alkyl ether, polyacrylate, modified polyolefin resin-based pressure-sensitive adhesive, and the like, and curing such as isocyanate. A curable pressure-sensitive adhesive to which an agent is added is mentioned, and a curable pressure-sensitive adhesive is particularly preferable among the pressure-sensitive adhesives used for adhesion of polyolefin foam or polyester film.

Moreover, as an adhesive agent, any adhesive agent used for adhesion of polyethylene or polypropylene can be used. For example, an adhesive for dry lamination that mixes polyurethane resin solution and polyisocyanate resin solution, styrene butadiene rubber adhesive, epoxy two-component curable adhesive, for example, two-component epoxy resin and polythiol A two-component solution of an epoxy resin and a polyamide can be used, and a solvent-type adhesive and an epoxy-based two-component curable adhesive are particularly preferable, and a transparent one is preferable. Some adhesives can improve the adhesive force by using an appropriate adhesion primer. When using such an adhesive, it is preferable to use an adhesion primer.

  In the present invention, among these pressure-sensitive adhesives or adhesives, it is preferable to use a urethane-based adhesive because it is particularly excellent in adhesion to a plasma-treated surface of a substrate made of a norbornene-based resin.

As the urethane adhesive, MS720, MG4100, and MLT2300A (all manufactured by Etec Co., Ltd.) can be preferably used.
<Polarizing film>
The polarizing film which concerns on this invention is suitably manufactured with the manufacturing method of the polarizing film of this invention mentioned above, Preferably, it consists of a norbornene-type resin substrate by which plasma treatment was carried out, a urethane type adhesive agent, and a polarizing film.

  Such a polarizing film according to the present invention has a good polarizing function, a norbornene-based resin substrate and a polarizing film are firmly bonded, and has excellent characteristics such as heat resistance and chemical resistance. In addition, even when used for a long period of time, peeling, deformation and the like are unlikely to occur, it has high reliability, is excellent in durability, and can be suitably used for applications such as liquid crystal display devices.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

“Parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.
First, a method for measuring each physical property value and a method for evaluating the physical property will be described.
(1) Adhesiveness:
Using an adhesive, a film made of norbornene resin is attached to both sides of the polarizing film and left in a forced-stirred constant temperature bath at 80 ° C. for 10 minutes. Each was grabbed and the norbornene-based resin film was peeled off from the polarizing film. The adhesion between the polarizing film and the norbornene-based resin film when peeled off was visually determined according to the following criteria.
○: No separation between the polarizing film and the norbornene resin film occurs, and material destruction occurs.
Δ: Some material destruction occurs, but at the same time, partial peeling occurs between the polarizing film and the norbornene resin film.
X: Only peeling between the polarizing film and the norbornene-based resin film occurs, and material destruction does not occur.
(2) Wet heat test:
The polarizing film was held for 500 hours in an environment of a temperature of 40 ° C. and a relative humidity of 95%.
(3) Dry heat test:
The polarizing film was held in an environment at a temperature of 80 ° C. for 500 hours.
<Production Example 1>
(Manufacture of norbornene resin A)
8-methyl-8-methoxycarbonyltetracyclo [4,4,0,1 ^2.5, 1 ^7.10] dodeca-3-ene 100 g, 1,2-dimethoxyethane 60 g, cyclohexane 240 g, 1-hexene 9 g, and 0.96 3.4 ml of a toluene solution of mol / liter diethylaluminum chloride was added to an autoclave having an internal volume of 1 liter. On the other hand, 20 ml of a 1,2-dimethoxyethane solution of 0.05 mol / liter tungsten hexachloride and 10 ml of a 1,2-dimethoxyethane solution of 0.1 mol / liter paraaldehyde were mixed in the flask. 4.9 ml of this mixed solution was added to the mixture in the autoclave. After sealing the autoclave, the mixture was heated to 80 ° C. and stirred for 2.5 hours. A mixed solvent of 1,2-dimethoxyethane / cyclohexane having a weight ratio of 2/8 was added to the obtained polymer solution to reduce the weight ratio of the polymer to the solvent (polymer / solvent) to 1/10. Thereafter, 20 g of triethanolamine was added and stirred for 10 minutes. To this polymer solution, 500 g of methanol was added and stirred for 30 minutes and allowed to stand. The upper layer separated into two layers was removed, methanol was added again, the mixture was stirred and allowed to stand, and the upper layer was removed. The same operation was further performed twice, and the obtained lower layer was appropriately diluted with cyclohexane and 1,2-dimethoxyethane to obtain a cyclohexane and 1,2-dimethoxyethane solution having a polymer concentration of 10%. 20 g of palladium / silica magnesia (manufactured by JGC Chemical Co., Ltd., palladium amount = 5%) as a hydrogenation catalyst was added to this solution and reacted at 165 ° C. for 4 hours at a hydrogen pressure of 40 kg / cm ^{2 in} an autoclave. Thereafter, the hydrogenation catalyst was removed by filtration to obtain a hydrogenated polymer solution. Further, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], which is an antioxidant, is added to the hydrogenated polymer solution with respect to the hydrogenated polymer. After adding 1%, the solvent was removed at 380 ° C. under reduced pressure. Next, the molten hydrogenated polymer was pelletized by an extruder under a nitrogen atmosphere, and had an intrinsic viscosity of 0.48 dl / g (30 ° C. in chloroform), a hydrogenation rate of 99.5%, and a glass transition temperature of 168 ° C. A thermoplastic norbornene resin A was obtained.
(Production of film (A) comprising norbornene resin (A))
Using a melt extruder, the thermoplastic norbornene-based resin A was heated and melted at 300 ° C. and extruded from a T-type die to obtain a film (A) as an extruded film having a thickness of 100 μm.
<Production Example 2>
(Manufacture of polarizing film)
A polyvinyl alcohol film having a thickness of 50 μm was uniaxially stretched up to 4 times in about 5 minutes while being immersed in a 40 ° C. bath composed of 5.0 g of iodine, 250 g of potassium iodide, 10 g of boric acid, and 1000 g of water. While maintaining the tension of the obtained film, the surface was washed with alcohol and then air-dried to obtain a polarizing film.
<Example 1>
(Plasma treatment of film (A) 1)
The obtained film (A) was plasma-treated with atmospheric pressure plasma. As an atmospheric gas used for atmospheric pressure plasma, a mixed gas of 69 vol% argon, 30 vol% helium, and 1 vol% oxygen was used. Further, the high voltage electrode and the low voltage electrode were plate-shaped, both of which were 335 mm × 250 mm, and the distance between the electrodes was set to 3 mm. Then, an AC power source having a frequency of 5 kHz was used as a power source, and a voltage of 2.4 kV was applied between the high voltage electrode and the low voltage electrode. The plasma treatment was performed for 30 seconds to obtain a film (B). Film (B) surface pure water contact angle and X-ray photoelectron spectroscopy analysis revealed that the contact angle with pure water was 50 ° and the oxygen atom concentration near the surface was 30%. Compared with the contact angle of 85 ° and oxygen atom concentration of 18% in (A), it was suggested that a hydroxyl group was introduced near the surface of the film (B) by the plasma treatment.
<Example 2>
(Plasma treatment of film (A) 2)
The obtained film (A) was plasma-treated with atmospheric pressure plasma. As an atmospheric gas used for the atmospheric pressure plasma, a mixed gas of 47.5 vol% argon, 47.5 vol% helium, 1 vol% carbon dioxide, and 4 vol% methane was used. Further, the high voltage electrode and the low voltage electrode were plate-shaped, both of which were 335 mm × 250 mm, and the distance between the electrodes was set to 3 mm. Then, an AC power source having a frequency of 5 kHz was used as a power source, and a voltage of 2.3 kV was applied between the high voltage electrode and the low voltage electrode. The plasma treatment was performed for 30 seconds to obtain a film (C).

Film (C) surface pure water contact angle and X-ray photoelectron spectroscopy analysis revealed that the contact angle with pure water was 60 ° and the oxygen atom concentration in the vicinity of the surface was 30%. Compared with the contact angle of 85 ° and the oxygen atom concentration of 18% in (A), it was suggested that a hydroxyl group was introduced near the surface of the film (C) by the plasma treatment. <Example 3>
After applying MS720 (manufactured by Etec Co., Ltd.) as an adhesive to the plasma-treated surface side of the film (B) obtained in Example 1 using an applicator with a gap of 30 microns, a manufacturing example is applied to the adhesive application surface. The polarizing film obtained in Step 2 was attached using a roll laminator, and then held for 10 minutes in a forced stirring dryer set at an internal temperature of 80 ° C., and the polarizing film on which the film (B) was attached Got. Further, after the adhesive (MS720) was applied to the plasma-treated surface side of the new film (B) using an applicator with a gap of 30 microns, the film (B) was applied to the adhesive-applied surface. The polarizing film (1) was obtained by sticking a polarizing film using a roll-type laminator so that the polarizing film side might contact with an adhesive agent, and hold | maintaining for 10 minutes with the forced stirring type dryer set to 80 degreeC.

  The initial adhesiveness of the obtained polarizing film (1) was evaluated. Furthermore, the polarizing film (1) was subjected to a wet heat test and a dry heat test, respectively, and evaluated for adhesiveness and film deformation. The evaluation results for the polarizing film (1) are shown in Table 1.

The obtained polarizing film (1) was excellent in the initial adhesiveness, the film was not deformed even after the wet heat test and the dry heat test, and the adhesive property was equivalent to the initial state (state before the test).
<Example 4>
A polarizing film (2) was obtained in the same manner as in Example 3 except that the film (C) obtained in Example 2 was used instead of the film (B).

  The initial adhesiveness of the obtained polarizing film (2) was evaluated. Further, the polarizing film (2) was subjected to a wet heat test and a dry heat test, respectively, and evaluated for adhesiveness and film deformation. The evaluation results for the polarizing film (2) are shown in Table 1.

The obtained polarizing film (2) was excellent in the initial adhesiveness, the film was not deformed even after the wet heat test and the dry heat test, and the adhesiveness was equivalent to the initial state.
<Example 5>
A polarizing film (3) was obtained in the same manner as in Example 3 except that MG4100 (manufactured by Etec Co., Ltd.) was used as the adhesive.

The initial adhesiveness of the obtained polarizing film (3) was evaluated. Further polarizing film (3)
Were subjected to a wet heat test and a dry heat test, respectively, and evaluated for adhesiveness and deformation of the film. The evaluation results for the polarizing film (3) are shown in Table 1.

The obtained polarizing film (3) was excellent in the initial adhesiveness, the film was not deformed even after the wet heat test and the dry heat test, and the adhesiveness was equivalent to the initial state.
<Example 6>
The same operation as in Example 3 was performed except that MG4100 (manufactured by E-Tech Co., Ltd.) was used as the adhesive and the film (C) obtained in Example 2 was used instead of the film (B). )

The initial adhesiveness of the obtained polarizing film (4) was evaluated. Furthermore, the polarizing film (4) was subjected to a wet heat test and a dry heat test, respectively, and evaluated for adhesiveness and film deformation. The evaluation results for the polarizing film (4) are shown in Table 1.

The obtained polarizing film (4) was excellent in the initial adhesiveness, the film was not deformed even after the wet heat test and the dry heat test, and the adhesiveness was equivalent to the initial state.
<Comparative example>
A polarizing film (5) was obtained in the same manner as in Example 3 except that the film (A) obtained in Production Example 1 was used instead of the film (B).

  The initial adhesiveness of the obtained polarizing film (5) was evaluated. Further, the polarizing film (5) was subjected to a wet heat test and a dry heat test, respectively, and evaluated for adhesiveness and film deformation. The evaluation results for the polarizing film (5) are shown in Table 1.

  Although the obtained polarizing film (5) was excellent in the initial adhesiveness, the adhesiveness decreased from the initial state after the wet heat test and after the dry heat test. In addition, deformation of the film was also confirmed.

FIG. 1 is a schematic cross-sectional view of an atmospheric pressure plasma processing apparatus that can be used for plasma processing according to the present invention.

Explanation of symbols

1 High Voltage Electrode 2 Low Voltage Electrode 3 Gas Inlet 4 Gas Outlet F Film (Sample)

Claims (7)

Plasma treatment of at least one surface of a substrate made of norbornene-based resin;
And a step of bonding a polarizing film to the plasma-treated surface of the substrate. 2. The norbornene-based resin is a resin obtained by (co) polymerizing a monomer containing at least one compound represented by the following general formula (1): Manufacturing method of polarizing film;

[In the formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom; a halogen atom; or a substituted or unsubstituted carbon atom which may have a linking group containing oxygen, nitrogen, sulfur or silicon. 1 to 15 hydrocarbon groups or other monovalent organic groups are represented. R ¹ and R ² , or R ³ and R ⁴ may be bonded to each other to form an alkylidene group, and R ¹ and R ² may be R ³ and R ⁴ , or R ² And R ³ are bonded to each other to form a carbocycle or heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure). It may be formed. The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. X represents an integer of 0 to 3, and y represents 0 or 1. When x is 0, y is also 0. ].   3. The method for producing a polarizing film according to claim 1, wherein the plasma treatment is a treatment for introducing a functional group into the surface of the substrate made of a norbornene resin.   The method for producing a polarizing film according to claim 3, wherein the functional group introduced to the surface of the substrate is a hydroxyl group.   The method for producing a polarizing film according to claim 1, wherein the step of adhering the polarizing film is a step of adhering the polarizing film via a urethane-based adhesive.   A polarizing film obtained by the method for producing a polarizing film according to claim 1.   A polarizing film comprising a plasma-treated norbornene-based resin substrate, a urethane-based adhesive, and a polarizing film.

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