TW201607978A - Method of manufacturing cyclic olefin film and cyclic olefin film - Google Patents

Abstract

The method of manufacturing cyclic olefin film comprises: a procedure of preparing resin composition of which containing cyclic olefin resin, phenolic heat stabilizer and sulfide heat stabilizer and a procedure of melting the above-mentioned resin composition and making membrane.

Description

Method for producing cycloolefin film and cycloolefin film

The present invention relates to a method for producing a cycloolefin film and a cycloolefin film.

In recent years, applications such as liquid crystal display devices, organic electroluminescence display devices (organic EL display devices), and touch panels have expanded. In such a device, various resin films are used in a support or a protective film or the like. Among them, a film formed of a cyclic olefin has high heat resistance, low water absorption, and excellent dimensional stability, and therefore a film formed of a cyclic olefin is preferably used. Further, since a cycloolefin can suppress birefringence due to a low photoelastic coefficient, a cyclic olefin is also a material excellent in optical characteristics.

As a method for producing a cycloolefin film, there are a method described in Patent Document 1 and Patent Document 2. Patent Document 1 describes a method of forming a film of a cycloolefin polymer film by a solution film forming method (casting method). In addition, the method for producing an optical film having a method of producing an amorphous thermoplastic resin which is a polymer resin having an alicyclic structure by extrusion is described in the following reference. The machine is melted and extruded into a sheet shape by a die attached to the extruder, and the extruded sheet-shaped amorphous thermoplastic resin is adhered to at least one cooling drum to be molded and removed; In the case where the average value of the surface roughness Ra of the lip is 0.01 μm or less, and the distribution range of the surface roughness Ra of the total lip width is ±0.005 μm or less of the above average value, the mold formed in the longitudinal direction is used. The height of the head line (ダイライン) from the adjacent peak to the bottom of the film is 15 nm to 50 nm over the entire surface of the film.

<Prior Art Document>

<<Patent Literature>>

Patent Document 1: Japanese Laid-Open Patent Publication No. 2002-179875

Patent Document 2: Japanese Patent No. 4442191

<Problems to be solved by the invention>

In Patent Document 1, a film is formed by a solution casting film to form a film of a cycloolefin film. Conventionally, a cycloolefin film is mainly produced by a solution film forming method. However, a solvent for dissolving a cycloolefin resin is limited, and a solvent for dissolving a cycloolefin resin is high in cost, and film formation by a melt film formation method is considered. The environmental impact of the solvent removed afterwards.

On the other hand, in the melt film forming method, the occurrence of the die line is regarded as a problem. The die line here refers to a ruthenium which continuously forms a stripe in the film formation direction of the film, and can be confirmed by visual observation or surface observation. In the melt film forming method, foreign matter adhering or the like occurs at the exit of the die attached to the extruder.

Patent Document 2 describes a content for controlling the surface roughness of a lip in order to reduce the die line. However, although a certain degree of effect is exerted in suppressing the occurrence of the initial die line, it is difficult to suppress the occurrence of frequent occurrence of the die line.

An object of the present invention is to provide a method for producing a cycloolefin film, in which a method for producing a cycloolefin film by a melt film formation method suppresses occurrence of a die line in a obtained cycloolefin film. Further, another object of the present invention is to provide a cycloolefin film obtained by the above production method.

<Means for solving the problem>

The above problems of the present invention are achieved by the means described in the following <1> or <12>. It is described below together with <2> to <11> which are preferred embodiments.

<1> A method for producing a cycloolefin film, comprising the steps of: preparing a resin composition containing a cycloolefin resin, a phenolic heat stabilizer, and a thioether heat stabilizer; a step of melt-forming a film of the resin composition;

(2) The method for producing a cycloolefin film according to the above, wherein the thioether-based heat stabilizer has a molecular weight of 850 or more and 1,400 or less;

(3) The method for producing a cycloolefin film according to the above, wherein the thioether-based heat stabilizer has a group represented by the following formula 1,

<Chemical 1>

In Formula 1, * indicates a portion connected to other structures.

(4) The method for producing a cycloolefin film according to the above, wherein the thioether-based heat stabilizer has three or more groups represented by the above formula 1;

The method for producing a cycloolefin film according to any one of the above aspects, wherein the cycloolefin resin has a polar group;

The method for producing a cycloolefin film according to any one of the above-mentioned, wherein the content of the phenolic heat stabilizer in the resin composition is relative to the total solids of the resin composition. The composition is 2.6 ~ 5.1mmol / kg;

The method for producing a cycloolefin film according to any one of the above-mentioned, wherein the content of the thioether-based heat stabilizer in the resin composition is relative to the total amount of the resin composition. The solid content is 2.2 to 43 mmol/kg;

The method for producing a cycloolefin film according to any one of the above aspects, wherein the content of the phenolic heat stabilizer in the resin composition is relative to the total solids of the resin composition. The composition is 3.0 to 3.8 mmol/kg;

The method for producing a cycloolefin film according to any one of the above-mentioned, wherein the content of the thioether-based heat stabilizer in the resin composition is relative to the total amount of the resin composition. The solid content is 2.2 to 25.8 mmol/kg;

The method for producing a cycloolefin film according to any one of the above aspects, wherein the thioether-based heat stabilizer is a compound represented by Formula 2,

<Chemical 2>

In Formula 2, R represents an alkyl group having 6 to 30 carbon atoms, X represents a group obtained by removing n hydroxyl groups from an n-member or more polyol, and n represents an integer of 3 or more.

The method for producing a cycloolefin film according to any one of the above aspects, wherein the heating temperature in the step of performing the melt film formation is 260 to 300 ° C;

<12> A cycloolefin film obtained by the production method according to any one of <1> to <11>.

<Effect of the invention>

According to the present invention, there is provided a method for producing a cycloolefin film, wherein in the method for producing a cycloolefin film by a melt film formation method, occurrence of a die line in the obtained cycloolefin film is suppressed. Further, according to the present invention, a cycloolefin film obtained by the above production method can be provided.

The contents of the present invention will be described in detail below. The description of the constituent elements described below is based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the specification of the present application, "to" is used in the meaning of including the numerical values described before and after the lower limit and the upper limit.

In the label of the group (atomic group) in the present specification, the unsubstituted and unsubstituted label includes a group having no substituent and a group having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

Further, in the present invention, "% by mass" has the same meaning as "% by weight", and "parts by mass" has the same meaning as "parts by weight".

Further, in the present invention, a combination of preferred modes is a more preferable mode.

The molecular weight of the polymer component is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent.

1. Method for producing cycloolefin film

In the method for producing a cycloolefin film of the present invention, the production method includes a step of preparing a resin composition containing a cycloolefin resin, a phenolic heat stabilizer, and a thioether heat stabilizer, and a combination of the above resins The step of performing melt film formation.

As a result of intensive studies, the present inventors have found that by using a cycloolefin-based resin together with a phenol-based heat stabilizer and a thioether-based heat stabilizer, the occurrence of a die line can be remarkably suppressed, and the present invention has been completed. In addition, the detailed mechanism for producing this effect is not clear, but it is presumed as follows.

The cycloolefin-based resin is considered to have a high melt viscosity and needs to be formed at a high temperature, and has a plurality of tertiary carbon atoms in the structure, so that thermal deterioration is likely to occur. Therefore, it is considered that the resin is thermally deteriorated in the film formation, and the die line deteriorates with the passage of time. On the other hand, in the present invention, it is presumed that such thermal deterioration can be suppressed by using an appropriate heat stabilizer, and as a result, the occurrence of the die line is suppressed. Further, the phenolic heat stabilizer captures radicals generated by heat, particularly peroxidic radicals, and generates hydrogen peroxide. The phenolic heat stabilizer itself changes to a phenoxy radical. The resulting hydroxy peroxide is decomposed into a stable alcohol compound by the action of a thioether-based heat stabilizer. It is understood that the effects of the present invention are exhibited by the synergistic action of such a phenolic heat stabilizer and a thioether heat stabilizer. Further, although the reason is not clear, the inventors have found that when a phosphorus-based heat stabilizer is used in combination with a phenol-based heat stabilizer or a thioether-based stabilizer, the effects of the present invention are not obtained. When a phenolic heat stabilizer is used together with a thioether stabilizer, an excellent effect of suppressing the die line can be obtained.

Hereinafter, each step in the method for producing a cycloolefin film of the present invention will be described.

<Step of preparing resin composition>

The method for producing a cycloolefin film of the present invention includes preparing a resin composition containing a cycloolefin resin, a phenolic heat stabilizer, and a thioether heat stabilizer (hereinafter also referred to as "the resin composition of the present invention"). Process (hereinafter also referred to as "preparation process").

Hereinafter, each component contained in the resin composition of the present invention will be described.

<<Cycloolefin resin>>

The resin composition of the present invention contains a cycloolefin resin. Examples of the cycloolefin-based resin include an addition polymerization type cycloolefin resin (COC) and a ring-opening polymerization type cycloolefin resin (COP). They may be used singly or in combination of two or more. Further, the Tg of the cycloolefin resin is preferably 100 to 200 ° C, more preferably 120 to 190 ° C, still more preferably 125 to 185 ° C. Further, the cycloolefin resin is preferably used after being granulated after the polymerization.

As the ring-opening polymerization type cycloolefin resin (COP), for example, those described in paragraphs 0032 to 0069 of JP-A-2010-164538 or paragraphs 0016 to 0022 of Japanese Patent No. 4492116 can be used.

For the addition polymerization type cycloolefin resin (COC), for example, those described in paragraphs 0014 to 0060 of Japanese Patent No. 3,372,316, and the materials described in paragraphs 0015 to 0062 of Japanese Patent No. 3,683,631, or Japanese Patent No. 3,377,833 can be used. The substances described in paragraphs 0008 to 0093 of the bulletin.

In the present invention, the cycloolefin-based resin is preferably a cycloolefin-based resin having a monomer unit derived from norbornene and a derivative thereof (hereinafter collectively referred to as a norbornene-based monomer). The cycloolefin resin is preferably a saturated norbornene resin-A or a saturated norbornene resin-B described below.

<saturated norbornene resin-A>

As the saturated norbornene resin-A, (1) a ring-opening (co)polymer of a norbornene-based monomer may be subjected to polymerization such as maleic acid addition or cyclopentadiene addition as needed. a resin obtained by further modifying a hydrogenated product; (2) a resin obtained by subjecting a norbornene-based monomer to addition polymerization; (3) a norbornene-based monomer, ethylene, an α-olefin, or the like a resin obtained by subjecting an olefin monomer to addition polymerization; and the like. The polymerization method and the hydrogenation method can be carried out by a conventional method.

Examples of the norbornene-based monomer include norbornene, an alkyl group thereof and/or a secondary alkyl group (for example, 5-methyl-2-norbornene and 5-dimethyl-2-nor Borane, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, etc., and polar group substituents such as halogen; Dicyclopentadiene, 2,3-dihydrodicyclopentadiene, etc.; dimethyl octahydro naphthalene, alkyl and/or alkylidene substituents thereof, and polar group substituents such as halogens thereof (for example, 6- Methyl-1,4:5,8-dimethyl bridge-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-ethyl-1,4:5,8-dimethyl Bridge-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-ethylene-1,4:5,8-dimethyl bridge-1,4,4a,5,6, 7,8,8a-octahydronaphthalene, 6-chloro-1,4:5,8-dimethyl bridge-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-cyano -1,4:5,8-dimethyl bridge-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-pyridyl-1,4:5,8-dimethyl bridge- 1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-methoxycarbonyl-1,4:5,8-dimethyl bridge-1,4,4a,5,6,7 , 8,8a-octahydronaphthalene, etc.; an adduct of cyclopentadiene with tetrahydroanthracene; a 3 to 4 mer of cyclopentadiene (for example, 4,9:5,8-dimethyl -3a,4,4a,5,8,8a,9,9a-octahydro-1H-benzopyrene, 4,11:5,10:6,9-triple bridge-3a,4,4a,5,5a , 6, 9, 9a, 10, 10a, 11, 11a-dodecane-1H-cyclopentaquinone). These norbornene-based monomers may be used singly or in combination of two or more kinds.

<saturated norbornene resin-B>

The saturated norbornene resin-B is represented by the following formulas B1 to B4. Among them, those represented by the following formula B1 are particularly preferred.

<化3>

In the formulae B1 to B4, R ^b1 to R ^b12 each independently represent a hydrogen atom or a monovalent substituent (preferably an organic group).

As the above substituent, a group described in paragraph 0036 of Japanese Patent No. 5009512 can be exemplified. Among them, as the monovalent substituent, a halogen atom, an alkyl group, a methyl decyl group, an aryl group, an alkoxy group, and an aryloxy group are preferable, and a methyl group, a trimethylmethane group, a phenyl group or a methoxy group is more preferable. .

In the formulae B1 to B4, when R ^b1 to R ^b12 are a monovalent substituent (preferably an organic group), at least one of them is preferably a polar group.

The polar group may, for example, be a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, a decylamino group or a cyano group. These polar groups may be bonded by a linking group such as a methylene group. Further, examples of the polar group include a hydrocarbon group to which a divalent organic group having a polar group such as a carbonyl group, an ether group, a carboalkyl ether group, a thioether group or an imino group is bonded, and these divalent organic groups are bonded. The group becomes a linking group. In addition, as the above-mentioned polar group, the group described in paragraph 0037 of Japanese Patent No. 5009512 can be exemplified.

By having a polar group, it is excellent in compatibility with a phenol-based heat stabilizer and/or a thioether-based heat stabilizer to be described later, and it is possible to further suppress the occurrence of a die line.

Among them, the polar group is preferably a carboxyl group or a carboxyalkyl group (the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6), and a carboxyl group (carbon atom of the aryl group) The number is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10).

The weight average molecular weight of these saturated norbornene resins is preferably 5,000 to 1,000,000, more preferably 8,000 to 200,000.

The saturated norbornene resin which can be used in the present invention, for example, is disclosed in JP-A-60-168708, JP-A-62-252406, JP-A-62-252407, and JP-A-62-252407. Resin, etc. described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. .

Among these resins, a hydrogenated polymer obtained by hydrogenating a ring-opening polymer of a norbornene-based monomer is particularly preferable.

In the present invention, as the saturated norbornene resin, a hydrogenated polymer obtained by hydrogenating a polymer which is at least one tetracyclododecene derivative represented by the following formula B5 may be used. The metathesis polymerization is carried out separately, or the tetracyclododecene derivative and the unsaturated cyclic compound copolymerizable therewith are subjected to metathesis polymerization.

<化4>

In the formula B5, R ^b13 to R ^b16 each independently represent a hydrogen atom or a monovalent substituent (preferably an organic group), and at least one of them is preferably a polar group. Specific examples and preferred ranges of the substituents and polar groups referred to herein are the same as those described in the formulae B1 to B4.

In the tetracyclododecene derivative represented by the above formula B5, at least one of R ^b13 to R ^b16 is a polar group, and a phase of a phenol-based heat stabilizer or a thioether-based heat stabilizer described later is used. Excellent in capacity and further suppressing the occurrence of the die line, and thus it is preferable. Further, when the polar group is a group represented by -(CH ₂ ) _n COOR (wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 10), The obtained hydrogenated polymer (substrate of the polarizing film) has a high glass transition temperature and is therefore preferable. From the viewpoint of lowering the water absorption rate, it is particularly preferable to contain one polar substituent represented by the -(CH ₂ ) _n COOR per one molecule of the tetracyclododecene derivative of the formula B5. In the above polar substituent, the more the number of carbon atoms of the hydrocarbon group represented by R, the smaller the hygroscopicity of the obtained hydrogenated polymer. From this point of view, it is preferred that the hydrocarbon group represented by R has a large number of carbon atoms; The hydrocarbon group is preferably a chain alkyl group having 1 to 4 carbon atoms or a (poly)cyclic alkyl group having 5 or more carbon atoms from the viewpoint of balance with the glass transition temperature of the obtained hydrogenated polymer. Particularly preferred are a methyl group, an ethyl group and a cyclohexyl group.

Further, in the tetracyclododecene derivative of the formula B5, when a hydrocarbon group having 1 to 10 carbon atoms is bonded to a carbon atom to which a group represented by -(CH ₂ ) _n COOR is bonded as a substituent The hydrogenated polymer obtained is preferred because it has low hygroscopicity. Particularly, the tetracyclododecene derivative of the formula B5 wherein the substituent is a methyl group or an ethyl group is preferable from the viewpoint of easy synthesis thereof. Specifically, preferably 8-methyl-8-methoxy-carbonyl-tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] dodeca-3-ene. The mixture of the tetracyclododecene derivative and the unsaturated cyclic compound copolymerizable therewith can be, for example, Japanese Patent Application Laid-Open No. Hei 4-77520, page 4, right upper column, 12 rows to sixth page, lower right column, sixth row. The method described is carried out by metathesis polymerization and hydrogenation.

The intrinsic viscosity (ηinh) of these norbornene-based resins measured at 30 ° C in chloroform is preferably 0.1 to 1.5 dl/g, and more preferably 0.4 to 1.2 dl/g. Further, the hydrogenation rate of the hydrogenated polymer is preferably 50% or more, more preferably 90% or more, and still more preferably 98% or more, as measured by 60 MHz and ¹ H-NMR. The higher the hydrogenation rate, the more excellent the stability of the obtained saturated norbornene film to heat or light. The gel content contained in the hydrogenated polymer is preferably 5% by mass or less, and more preferably 1% by mass or less.

<Other cycloolefins capable of ring-opening polymerization>

In the present invention, other cyclic olefins capable of ring-opening polymerization can be used in combination. Specific examples of such a cyclic olefin include, for example, a compound having one reactive double bond such as cyclopentene, cyclooctene or 5,6-dihydrodicyclopentadiene. The content of the cycloolefin which can be subjected to ring-opening polymerization is preferably from 0 mol% to 50 mol%, more preferably from 0.1 mol% to 30 mol%, even more preferably from 0.3 mol% to 10%, based on the norbornene-based monomer. Molar%.

The cycloolefin resin may be a cyclic olefin copolymer containing an ethylene unit and a norbornene unit. The ethylene unit is a repeating unit represented by -CH ₂ CH ₂ -. The ethylene unit is obtained by vinyl polymerization with the above norbornene unit to obtain a cyclic olefin copolymer. The copolymerization molar ratio of the norbornene unit to the ethylene unit is preferably 80:20 to 20:80, more preferably 80:20 to 50:50, still more preferably 80:20 to 60:40.

It should be noted that in the cycloolefin copolymer, in addition to the ethylene unit and the norbornene unit, a repeating unit formed of another copolymerizable vinyl monomer may be contained in a small amount. Specific examples of the other vinyl monomer include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and 1-12. a olefin having 3 to 18 carbon atoms such as carbene, 1-tetradecene, 1-hexadecene or 1-octadecene; cyclobutene, cyclopentene, cyclohexene, a cycloolefin such as 3-methylcyclohexene or cyclooctene. Such a vinyl monomer may be used singly or in combination of two or more, and the repeating unit is preferably 10% by mole or less, more preferably 5% by mole or less based on the whole.

The content of the cycloolefin resin in the resin composition of the present invention is preferably from 50 to 100% by mass, more preferably from 60 to 100% by mass, even more preferably from 70 to 100% by mass, based on the total amount of the solid content.

<Phenolic heat stabilizer>

The phenolic heat stabilizer is not particularly limited as long as it has the ability to capture various radicals, mainly peroxide radicals, and is converted into a phenoxy radical, and can be roughly classified into a hindered type, a semi-blocked type, and a less hindered type.

The phenolic heat stabilizer is appropriately selected from known phenolic heat stabilizers, and specific examples thereof include the following compounds, which are described below together with commercially available product names.

As a less hindered type, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (ADKSTAB AO-30 (manufactured by ADEKA)), Yoshinox 930 can be exemplified. (manufactured by Jifu Pharmaceutical Co., Ltd.), Topanol CA (manufactured by ICI), and 4,4'-butylidene bis(6-tert-butyl-3-methylphenol) (ADKSTAB AO-40 (manufactured by ADEKA Co., Ltd.) , Sumilizer BBM-S (manufactured by Sumitomo Chemical Co., Ltd.), etc.;

As a semi-blocking type, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylene dioxyethylene] (Irganox 245 (manufactured by BASF Corporation), 3 ,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethyl]2,4,8, 10-tetraoxaspiro[5.5]undecane (ADKSTAB AO-80 (manufactured by ADEKA Co., Ltd.), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), etc.;

As a hindered type, 2,6-di-tert-butyl-4-methylphenol (Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.), ANTAGE BHT (manufactured by Kawaguchi Chemical Industry Co., Ltd.), and stearyl-β-(3) can be exemplified. , 5-Bt-Butyl-4-hydroxyphenyl)propionate (ADKSTAB AO-50 (manufactured by ADEKA), Irganox 1076 (manufactured by BASF), Sumilizer BP-76 (manufactured by Sumitomo Chemical Co., Ltd.), Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADKSTAB AO-60 (manufactured by ADEKA), Irganox 1010 (manufactured by BASF), Sumilizer BP-101 (manufactured by Sumitomo Chemical Co., Ltd.), 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione (ADKSTAB AO-20 (manufactured by ADEKA), Irganox 3114 (manufactured by BASF)), 2,4,6-three (3) ',5'-di-tert-butyl-4'-hydroxybenzyl)trimethylbenzene (ADKSTAB AO-330 (manufactured by ADEKA)).

Among them, as the phenolic heat stabilizer, a hindered type is preferable.

The molecular weight of the phenolic heat stabilizer is preferably 850 to 1,400. When the molecular weight of the phenolic heat stabilizer is 850 or more, volatilization or decomposition of the phenolic heat stabilizer is suppressed in the step of melt film formation, which is preferable. Further, when the molecular weight is 1,400 or less, compatibility with a cycloolefin-based resin is excellent, which is preferable.

The molecular weight of the phenolic heat stabilizer is more preferably 900 to 1,350, still more preferably 1,000 to 1,300.

In the present invention, the phenolic heat stabilizer may be used singly or in combination of two or more.

The content of the phenolic heat stabilizer in the resin composition of the present invention is preferably 2.6 to 5.1 mmol/kg. When the content of the phenolic heat stabilizer is 2.6 mmol/kg or more, thermal deterioration of the cycloolefin resin and suppression of occurrence of a die line are sufficiently prevented, which is preferable. In addition, when the content is 5.1 mmol/kg or less, compatibility with a cycloolefin resin is excellent, which is preferable.

The content of the phenolic heat stabilizer is more preferably 3.0 to 3.8 mmol/kg, still more preferably 3.2 to 3.6 mmol/kg.

In addition, the content of the phenolic heat stabilizer in the resin composition is 2.6 mmol/kg, which means that 2.6 mmol of a phenol-based heat stabilizer is contained with respect to 1 kg of the solid content of the resin composition. The same is true in the following description.

<thioether heat stabilizer>

The resin composition of the present invention contains a thioether-based heat stabilizer. The thioether-based heat stabilizer is not particularly limited as long as it has at least one thioether bond (-S-), and is preferably a compound having a group represented by the following formula 1.

<化5>

In Formula 1, * indicates a portion connected to other structures.

The group represented by Formula 1 is preferable because it has excellent compatibility with a cycloolefin-based resin and has a high function as a stabilizer.

In the present invention, the thioether-based heat stabilizer preferably has one or more groups represented by Formula 1, and the group is more preferably two or more, further preferably three or more, and still more preferably four or more. Further, the upper limit thereof is not particularly limited, and from the viewpoint of molecular weight, it is preferably 9 or less. When the number of the groups represented by Formula 1 in one molecule is in the above range, it is excellent in compatibility and has an excellent function as a heat stabilizer, which is preferable.

As a method of synthesizing the compound having a group represented by Formula 1, a known method can be used. For example, a compound having nine groups represented by Formula 1 can be exemplified as the following synthesis method: (1) synthesizing a 9-valent alcohol from dimethyl tartaric acid protected by dimethyl acetal according to the method described in J. Org. Chem., 1993, 58, 5876-5877; (2) according to Japanese special In the method of JP-A-2008-174506, a compound having 9 groups represented by Formula 1 is synthesized using the synthesized 9-membered alcohol and an alkylthiol having 1 carbon atom.

The thioether-based heat stabilizer is preferably a compound represented by the following formula 2.

<Chemical 6>

In Formula 2, R represents an alkyl group having 6 to 30 carbon atoms, X represents a group obtained by removing n hydroxyl groups from an n-member or more polyol, and n represents an integer of 3 or more.

In Formula 2, R represents an alkyl group having 6 to 30 carbon atoms, preferably an alkyl group having 7 to 24 carbon atoms, and more preferably an alkyl group having 8 to 20 carbon atoms. In addition, the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

X represents a group obtained by removing n hydroxyl groups from an n-member or more polyol. X is a trihydric or higher polyhydric alcohol, and examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, and dipentaerythritol.

Among them, X is preferably a group obtained by removing four hydroxyl groups from pentaerythritol.

n represents an integer of 3 or more, preferably an integer of 3 to 8, more preferably an integer of 4 to 6, and further preferably 4.

As the compound represented by Formula 2, a commercially available product can be used, and for example, bis[3-(dodecylthio)propionic acid] 2,2-bis[[3-(dodecylthio)-) can be exemplified. 1-oxopropoxy]methyl]-1,3-propanediester (ADKSTAB AO-412S (manufactured by ADEKA Co., Ltd.).

The compound represented by Formula 2 can be synthesized by referring to JP-A-2008-174506. Specifically, an alkyl sterol having 6 to 30 carbon atoms and an alkyl acrylate (wherein the alkyl group has 1 to 5 carbon atoms) can be reacted to obtain a 3-alkylthio-propionate. It is subjected to transesterification reaction with a trihydric or higher polyhydric alcohol to carry out synthesis.

Further, the thioether-based heat stabilizer is not limited to the above examples, and a known thioether-based heat stabilizer can be used. For example, dilauryl 3,3-thiodipropionate (ADKSTAB AO-503) can be exemplified. (manufactured by ADEKA)), bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy-5-tert-butylphenyl) sulfide (ADKSTAB AO-23 ( (made by ADEKA Co., Ltd.)).

In the present invention, the molecular weight of the thioether-based heat stabilizer is preferably 850 to 1,400. When the molecular weight is 850 or more, thermal decomposition is less likely to occur in the melt film formation step, and the effect can be stably exhibited, which is preferable. Further, when the molecular weight is 1,400 or less, compatibility with a cycloolefin-based resin is excellent, which is preferable.

The molecular weight of the thioether-based heat stabilizer is more preferably 900 to 1,350, still more preferably 1,000 to 1,300, still more preferably 1,100 to 1,250.

The thioether-based heat stabilizer may be used alone or in combination of two or more.

The content of the thioether-based heat stabilizer in the resin composition is preferably 2.2 to 43 mmol/kg. When the content of the thioether-based heat stabilizer is 2.2 mmol/kg or more, the occurrence of the die line can be effectively suppressed, which is preferable. In addition, when the content of the thioether-based heat stabilizer is 43 mmol/kg or less, the compatibility with the cycloolefin-based resin is excellent, which is preferable.

The content of the thioether-based heat stabilizer is more preferably 2.2 to 25.8 mmmol/kg, still more preferably 5 to 20 mmol/kg.

In addition, "the content of the thioether-based heat stabilizer in the resin composition is 2.2 mmol/kg" means that 2.2 mmol of a thioether-based heat stabilizer is contained with respect to 1 kg of the solid content of the resin composition.

<Other additives>

In the present invention, the resin composition may contain other additives in addition to the cycloolefin-based resin, the phenol-based heat stabilizer, and the thioether-based heat stabilizer described above, without departing from the object of the present invention. Examples of other additives include ultraviolet absorbers, lubricants, antistatic agents, fillers, filler dispersants, other resins, colorants (dyes, pigments, etc.), plasticizers, antibacterial agents, deodorants, and deodorizers. Wait.

Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and an acrylonitrile-based ultraviolet absorber.

Further, in addition to the above heat stabilizer, other heat stabilizers may be contained, and examples thereof include phosphorus heat stabilizers and the like.

In the present invention, a lubricant may be added to the resin composition in order to improve the running property of the film at the time of film formation and to reduce scratches occurring on the rolls of the film forming machine. As the lubricant, for example, a lubricant described in paragraph 0032 of JP-A-2009-227932, and the like can be used.

Specifically, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, montanic acid, etc.; stearyl stearate, behenic acid behenic acid Fatty acid esters such as esters, pentaerythritol tristearate, pentaerythritol tetrastearate, glyceryl monostearate, glyceryl monobehenate; stearylamine, palmitosamine, oleylamine, sub a fatty decylamine such as methyl bis-lipidamine or ethylene bis-lipidamine; a metal soap such as calcium stearate or magnesium stearate; a natural wax such as montan wax; and the like. The amount of the lubricant added is preferably less than 0.05% by mass, more preferably less than 0.03% by mass, still more preferably less than 0.01% by mass, based on the mass of the cycloolefin-based resin. By setting the addition amount to less than 0.05% by mass, it is possible to reduce the precipitation of the lubricant on the surface of the film after film formation.

The resin composition in the present invention is obtained by mixing the above-described cycloolefin resin, phenolic heat stabilizer, thioether heat stabilizer, and other components used as necessary.

In this case, it is preferred to dry the cycloolefin resin as needed. The drying may be carried out before mixing the cycloolefin-based resin with other components such as a phenol-based stabilizer, or may be carried out after mixing, or may be carried out before and after mixing, and is not particularly limited. In the case of using a cycloolefin-based resin having a glass transition temperature (Tg) of more than 105 ° C, the drying temperature is preferably "80 ° C or more and Tg or less", more preferably "100 ° C or more, Tg-. Below 5 °C". The drying time is not particularly limited, but is preferably 0.5 hours or longer and 24 hours or shorter, more preferably 1 hour or longer and 10 hours or shorter. By reducing the content of volatile components such as a solvent contained in the resin composition as described above, foaming of the resin composition can be suppressed, and a film of higher quality can be obtained.

The method for producing a cycloolefin film of the present invention includes a step of melt-forming a resin composition prepared as described above (hereinafter also referred to as a melt film forming step). In the melt film forming step, the resin composition obtained as described above is charged into an extruder, the resin is melted, continuously conveyed to a die, and the molten resin extruded from the die onto the sheet is casted in a drum. The film was cooled and solidified to obtain an unstretched cyclic olefin resin film. Filtration is preferably carried out at the outlet of the extruder as required, and a gear pump is provided between the extruder and the die, and a certain amount of resin is supplied from the gear pump.

(1) Extrusion

As a type of extruder, a single screw extruder having a relatively low equipment cost is usually used, and the screw type includes a full thread type, a Maddock type, a Dulmage type, etc., preferably a full thread. type. Further, a twin-screw extruder can be used. In the twin-screw extruder, by changing the screw section, an exhaust port can be provided in the middle, and the unnecessary volatile components can be detached while being extruded. In the twin-screw extruder, there are roughly the same type and the opposite direction, and they can be used. However, it is preferable to use a co-rotating type in which the retained portion is not easily generated and the self-cleaning performance is high.

(2) Filtering

In order to perform foreign matter filtration in the resin or to avoid damage to the gear pump due to foreign matter, it is preferable to perform so-called perforated plate filtration in which a screening filter medium is provided at the outlet of the extruder. Further, in order to further carry out the foreign matter filtration, a filter device in which a so-called vane type rotary screen screening program is installed may be provided after passing through the gear pump. It is possible to provide one filter unit for filtering, and it is also possible to perform multi-stage filtration by providing a plurality of filter units. The filtration accuracy of the screening program filter material is 15 μm to 3 μm. In order to ensure the endurance of the pressure resistance and screening program, the number of sheets can be adjusted. From the viewpoint of use under high temperature and high pressure, it is preferable to use a steel material for the type of the filter material, and stainless steel, steel or the like is particularly preferably used for the iron steel material, and stainless steel is particularly preferably used from the viewpoint of corrosion. As the filter medium, in addition to the filter material obtained by braiding the wire material, for example, a sintered filter material formed by sintering a metal long fiber or a metal powder can be used. From the viewpoint of filtration accuracy and the life of the screening program, a sintered filter material is preferable.

In the present invention, as one of the means for adjusting the amount of the solid granules, a screening program can be used. Since the solid granules are soft and deformable, even if a screening program having a filtration accuracy smaller than the diameter of the solid granules is used, a certain amount can be passed. Therefore, a screening program having a filtration accuracy of 15 to 3 μm which is usually used can be used.

(3) Gear pump

Preferably, a gear pump is provided between the extruder and the die, and a certain amount of resin is supplied from the gear pump. The fluctuation of the discharge pressure can be imparted by varying the number of revolutions. In the gear pump, a pair of gears composed of a drive gear and a driven gear are accommodated in a mutually engaged state, and the drive gear is driven to rotate the two gears to attract the resin in a molten state from the suction port formed in the outer casing. In the cavity, the resin is discharged in a certain amount from a discharge port formed also in the outer casing.

(4) Die

The resin is melted by the extruder configured as described above, and if necessary, the molten resin is continuously conveyed to the die via a filter or a gear pump. The die can be of any type which is generally used as a T-die, a fishtail die, and a coat-type coating die. Further, a static mixer for increasing the uniformity of the resin temperature may be placed directly in front of the die.

(5) Casting

The molten resin extruded from the die onto the sheet was cooled and solidified on the casting drum by the above method to obtain an unstretched film. At this time, it is preferable to increase the adhesion between the casting drum and the sheet after melt extrusion by a method such as an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, or a contact roll method. Such a adhesion improving method may be carried out on the entire surface of the melt-extruded sheet, or may be carried out in a part thereof. In particular, a method called edge pinning and only the both end portions of the film are closely adhered, but is not limited thereto.

Regarding the casting drum, it is more preferable to use a plurality of slow cooling. In particular, it is generally preferred to use three cooling rolls, but it is not limited thereto. The diameter of the roll is preferably 50 mm to 5,000 mm, and when a plurality of rolls are provided, the interval between the rolls is preferably 0.3 mm to 300 mm between the faces.

The temperature of the casting drum is preferably Tg-70 ° C to Tg + 20 ° C of the resin, more preferably Tg - 50 ° C to Tg + 10 ° C, still more preferably Tg - 30 ° C to Tg + 5 ° C.

Further, in the case of using the so-called contact roll method, the surface of the contact roll may be a resin such as rubber or Teflon (registered trademark), or may be a metal roll. Further, a roller called a flexible wand may be used. In the flexible wand, the thickness of the metal roll is reduced, and the surface of the roll is slightly recessed by the pressure at the time of contact to increase the pressure contact area.

The pressure applied to the molten resin to be passed is preferably 20 to 500 MPa, more preferably 30 to 400 MPa, still more preferably 40 to 300 MPa, still more preferably 50 to 200 MPa. The pressure specified here is a value obtained by dividing the force of pressing the nip surface by the contact area between the film and the nip surface. The pressure between the rolls was measured by passing a pressure measuring film (manufactured by Fujifilm Co., Ltd., a pressure sensitive film for medium pressure, etc.) between two rolls at a rate of 5 m/min.

The contact roll temperature is preferably from Tg - 70 ° C to Tg + 20 ° C, more preferably from Tg - 50 ° C to Tg + 10 ° C, still more preferably from Tg - 30 ° C to Tg + 5 ° C.

(6) Surface treatment

In the method for producing a cycloolefin film of the present invention, surface treatment can be performed for the purpose of improving adhesion to the resin layer. Examples of the surface treatment include corona discharge treatment, ultraviolet treatment, glow discharge treatment, atmospheric pressure plasma treatment, flame treatment, and the like (hereinafter referred to as treatment).

The discharge frequency of the corona discharge treatment is preferably 50 Hz to 5,000 kHz, and more preferably 5 kHz to several hundreds kHz. The treatment strength of the material to be treated is preferably 0.001 KV·A·min/m ² to 5 KV·A·min/m from the viewpoint of improving the wettability with respect to a plastic film such as a normal polyester or a polyene hydroxy group. ^{2 is} more preferably 0.01 KV·A·min/m ² to 1 KV·A·min/m ² . The gap clearance between the electrode and the dielectric roller is preferably 0.5 to 2.5 mm, more preferably 1.0 to 2.0 mm.

For the ultraviolet treatment, a conventionally known method can be used. For example, Japanese Patent Publication No. Sho 43-2603, Japanese Patent Publication No. Sho 43-2604, Japanese Patent Publication No. Sho 45-3828, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. The method described.

For details of other processes and the like, the methods described in each of Japanese Patent No. 3,123,872 and Japanese Patent No. 4,958,824 can be used.

(7) Coating

The surface of the film to be produced can be applied, whereby a functional layer such as an easily bonding layer, a resin layer, a conductive layer, a hard coat layer, or an antistatic layer can be imparted.

(8) Stretching treatment

In the present invention, the stretching treatment may be carried out as needed, and specifically, the cast film (undrawn blank film) extruded onto the casting drum may be at least single in the machine direction (MD) or the transverse direction (TD). Stretch in the axial direction. More preferably, biaxial stretching is performed in the machine direction (MD) and the transverse direction (TD). In the case of biaxial stretching in the longitudinal direction and the transverse direction, the stretching may be carried out successively in the longitudinal direction, the transverse direction, the transverse direction and the vertical direction, or may be carried out in two directions at the same time. Further, it is preferable to carry out multistage stretching so as to be, for example, vertical to vertical, horizontal, vertical, horizontal, vertical, vertical, horizontal, and horizontal.

For the longitudinal stretching, two or more pairs of nip rolls are usually provided so that the heated green film passes between them while making the peripheral speed of the outlet side rolls faster than the inlet side, so that the longitudinal stretching can be achieved. At this time, it is preferable to impart a temperature difference to the surface.

Further, the green film is preferably preheated before longitudinal stretching. The preheating temperature is preferably Tg-50 ° C to Tg + 30 ° C, more preferably Tg - 40 ° C to Tg + 15 ° C, and still more preferably Tg - 30 ° C to Tg ° C of the cycloolefin resin. Such preheating may be performed by bringing it into contact with a heating roller, and a radiant heat source (infrared (IR) heater, halogen heater, or the like) may be used, or hot air may be blown.

The longitudinal stretching is preferably carried out at Tg - 10 ° C to Tg + 50 ° C, more preferably Tg ° C to Tg + 40 ° C, still more preferably Tg ° C to Tg + 30 ° C. The draw ratio is preferably 1.1 to 5.5 times, more preferably 1.3 to 3 times. In addition, the draw ratio mentioned here is the value computed by the following formula.

Stretching ratio = (length after stretching - length before stretching) / (length before stretching)

Cooling is preferably carried out after stretching in the longitudinal direction, and the cooling temperature is preferably from Tg to 50 ° C to Tg ° C, more preferably from Tg to 45 ° C to Tg to 5 ° C, still more preferably from Tg to 40 ° C to Tg to 10 ° C. Regarding such cooling, it is possible to contact the cooling roll or to blow cold air.

The transverse stretching is preferably carried out using a tenter. In other words, both ends of the cyclic olefin resin film can be held by a clip while being conveyed in the heat treatment zone, and the clip can be expanded in the width direction to perform the transverse stretching.

The stretching temperature is preferably from 10 g to 10 ° C to Tg + 50 ° C, more preferably from Tg ° C to Tg + 40 ° C, still more preferably from Tg ° C to Tg + 30 ° C. The draw ratio is preferably 1.1 to 5.5 times, more preferably 1.3 to 3 times.

In the stretching step, the film is preferably subjected to heat treatment after the stretching treatment.

The heat treatment means that the film is preferably subjected to a heat treatment of preferably 1 to 60 seconds (more preferably 2 to 30 seconds) at a temperature of preferably about Tg + 10 ° C to Tg + 50 ° C (more preferably Tg + 15 ° C to Tg + 30 ° C). . The heat setting is preferably carried out in a state where the tenter is gripped by the chuck after the transverse stretching, and the gap between the chucks at this time can be performed at the time when the transverse stretching is terminated, and can be further expanded, or Can be reduced in size.

(9) Reeling

After the film formation, it is preferred to trim both ends after stretching and to perform winding. The portion to be trimmed may be reused as a raw material for a film of the same type or as a raw material for a film of a different type after the pulverization treatment or, if necessary, granulation treatment or the like. The trim cutter can be of any type such as a rotary cutter, a shear cutter, a knife, or the like. Regarding the material, any of carbon steel and stainless steel can be used. In general, when a superhard knife or a ceramic knife is used, the life of the blade is long, which is preferable.

Further, it is also preferred to adhere the laminate film (laminated film) to at least one side from the viewpoint of preventing wounds before the winding. The preferred take-up tension is from 1 kg/m to 50 kg/m, more preferably from 2 kg/m to 40 kg/m, and even more preferably from 3 kg/m to 20 kg/m. When the take-up tension is 1 kg/m or more, the film is easily wound up uniformly; when the take-up tension is 50 kg/m or less, the film is not wound tightly, and the appearance of the roll can be kept beautiful.

2. Cyclic olefin film

The cycloolefin film of the present invention is a cycloolefin film obtained by the method for producing a cycloolefin film of the present invention, and is applicable to a laminated film, a hard coat film, a conductive film, a touch panel, an antireflection film, and a polarizing plate. , display device, etc.

The following description will be respectively made.

<Laminated film>

A laminated film can be produced by providing a resin layer on the surface of at least one side of the cycloolefin film of the present invention. In the case of having a conductive layer, by having a resin layer, adhesion to the conductive layer can be improved.

The thickness of the resin layer is preferably 10 to 400 nm, more preferably 10 to 200 nm, still more preferably 10 to 100 nm, and particularly preferably 20 to 100 nm. When the thickness is 10 nm or more, the peeling stress can be absorbed, the adhesion can be improved, and the impact can be absorbed, so that the destruction of the conductive layer can be suppressed, and the increase in the resistivity can be suppressed. On the other hand, when the thickness is 400 nm or less, aggregation in the resin layer can be suppressed, the adhesion can be improved, and the resin layer can be made soft, deformation of the conductive layer can be suppressed, and an increase in resistivity can be suppressed.

The surface roughness (Ra) of the surface of the resin layer opposite to the surface on which the cycloolefin film is laminated is preferably 0.5 to 30 nm, more preferably 0.5 to 25 nm, still more preferably 1 to 25 nm, and particularly preferably 10 to 10 20nm. When the surface roughness (Ra) is 0.5 nm or more, the contact area is increased, and the adhesion can be improved. Further, it is possible to suppress the disconnection of the conductive layer at a position where the adhesion is poor, and it is possible to suppress an increase in the specific resistance. On the other hand, when the surface roughness (Ra) is 30 nm or less, the concentration of the peeling stress due to the unevenness of the resin layer can be suppressed, and the adhesion failure is less likely to occur. Thereby, the conductive layer can follow the unevenness, and it is possible to suppress the defect of the conductive layer and suppress the increase in the specific resistance.

The surface roughness (Ra) can be measured, for example, using a laser microscope.

The raw material of the resin layer may, for example, be a synthetic resin such as a phenol type, an alkyd type, a melamine type, a urea type, a vinyl type, an epoxy type, a polyester type, a polyurethane type or an acrylic type. As a resin other than a synthetic resin, gelatin etc. are mentioned. Commercially available products can also be used, and examples thereof include AS-563A (manufactured by Daicel Finechem Co. Ltd.).

Further, in addition to the resin component, a crosslinking agent, a film forming aid (for example, diethylene glycol monoethyl ether acetate), a matting agent, a lubricant, a surfactant, an antifoaming agent, and a suds suppressor may be contained as needed. , dyes, fluorescent whitening agents, preservatives, water resistance agents, antistatic agents, catalysts for crosslinking agents, and the like.

Carbodilite V-02-L2 (made by Nisshinbo Co., Ltd.), and a catalyst for a crosslinking agent, a catalyst for Elastron (manufactured by Daiichi Kogyo Co., Ltd.: trade name Cat64); as a matting agent; For the lubricant, Cellosol 524 (manufactured by Nippon Oil & Fats Co., Ltd.) can be mentioned, and as a surfactant, Naroacty CL95 (manufactured by Sanyo Chemical Industries, Ltd.) can be mentioned. , RAPISOL A-90 (made by Nippon Oil Co., Ltd.), etc.

<Method of Forming Resin Layer>

The resin layer can be formed by any one of a coating method and a co-extrusion method, and a coating method is preferred from the viewpoint of the breadth of the material selection range and the heat resistance in the melting stage.

In the coating method, a solution containing a resin constituting the resin layer or a coating liquid prepared by mixing an aqueous latex solution is first applied. After coating, it is preferable to apply a temperature difference of 1 to 100 ° C to the coating film (resin layer) and the atmosphere temperature, more preferably a temperature difference of 3 to 80 ° C, and even more preferably a temperature of 5 to 60 ° C. difference. By imparting such a temperature difference, convection occurs inside the coating layer by drying of the solvent, and irregularities are formed on the coating film. The atmosphere temperature refers to the temperature of the outside air at the time of forming the resin layer (30 cm from the coated surface).

After the application, if necessary, the substrate having the unevenness may be embossed on the coated surface to transfer the unevenness, and the resin layer may exhibit a predetermined surface roughness (Ra).

<hard coating film>

The cycloolefin film of the present invention can be used in a hard coat film. In the present invention, the hard coat film preferably has at least the cycloolefin film of the present invention and a hard coat layer.

The hard coat layer may be provided on the surface of the cycloolefin film containing the cycloolefin resin or on the surface of the above resin layer.

The hard coat layer can be formed by any of a wet coating method and a dry coating method (vacuum film formation), and is preferably formed by a wet coating method excellent in productivity.

For the hard coat layer, for example, JP-A-2013-45045, JP-A-2013-43352, JP-A-2012-232459, JP-A-2012-128157, and JP-A-2011-131409 Japanese Laid-Open Patent Publication No. 2011-131, pp., JP-A-2011-126162, JP-A-2011-75705, JP-A-2009-286981, JP-A-2009-263567, and JP-A-2009-263567 Japanese Laid-Open Patent Publication No. 2009-75248, JP-A-2007-164206, JP-A-2006-96811, JP-A-2004-75970, JP-A-2002-156505, and JP-A-2001-272503 The hard coat layer described in the publication, the International Publication No. 12/018087, the International Publication No. 12/098967, the International Publication No. 12/086659, and the International Publication No. 11/105594.

<conductive film>

The cycloolefin film of the present invention can also be used as a conductive film. The conductive film is characterized in that it has a conductive layer on the surface of the cycloolefin film of the present invention. In the present invention, the conductive film is excellent in adhesion and can reduce the visibility of the conductive layer. In addition, it is also possible to suppress an increase in resistance.

The conductive layer may be provided on the surface of the cycloolefin film containing the cycloolefin resin or on the surface of the above resin layer. The conductive layer may be formed in a layer shape, but is preferably formed in such a manner as to have a discontinuous portion. The discontinuous portion refers to a portion where the conductive layer is not provided, and the outer periphery of the discontinuous portion is preferably surrounded by the conductive layer. In the present invention, forming the conductive layer in such a manner as to have a discontinuous portion also means that the conductive layer is formed in a pattern or a mesh shape. For example, Japanese Laid-Open Patent Publication No. 2012-216550, Japanese Laid-Open Patent Publication No. 2012-151095, Japanese Laid-Open Patent Publication No. 2012-151095, No. 2012-25158, and Japanese Laid-Open Patent Publication No. 2011-253546 Japanese Laid-Open Patent Publication No. 2011-197754, JP-A-2011-34806, JP-A-2010-198799, JP-A-2009-277466, JP-A-2012-216550, and JP-A-2012-216550 The conductive layer described in Japanese Laid-Open Patent Publication No. 2010-151095, No. 2010/140275, and No. 2010/114056.

The conductive layer used in the present invention more preferably contains silver and a hydrophilic resin. Examples of the hydrophilic resin include gelatin, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polysaccharides such as starch, cellulose and derivatives thereof, polyethylene oxide, polyvinylamine, and chitosan. , polylysine, polyacrylic acid, polyalginic acid, polyhyaluronic acid, carboxy cellulose, and the like. They have neutral, anionic, and cationic properties depending on the ionicity of the functional group. Among them, gelatin is particularly preferred.

Further, as the conductive layer used in the present invention, a conductive layer of an organic material (for example, a conductive resin such as polythiol) or an inorganic material (for example, a semiconductor such as ITO or a metal such as gold, silver or copper) may be used. Among them, conductive is preferable. A highly conductive inorganic conductive layer is more preferably a metal conductive layer. When a conductive layer of a semiconductor such as ITO is used, since the conductive layer material is transparent, the conductive layer may be provided on the entire surface of the transparent film, or may be patterned into a thin line or the like. In the case of using a conductive layer of silver fiber, since the silver fiber is a fine fiber of the order of nanometers and is transparent as a material of the conductive layer, the conductive layer may be provided on the entire surface of the transparent film, or may be patterned into a thin line or the like. . On the other hand, in the case of using a conductive layer of silver obtained by reducing silver halide, since the material of the conductive layer is a bulk and is opaque, it is necessary to pattern into a thin line in order to form a transparent conductive layer.

Among them, a conductive layer using a silver wiring formed by patterning and developing a silver halide by exposure is excellent in light transmittance and conductivity, and is particularly preferable.

The width of the conductive layer is preferably formed by a fine line of 0.1 to 50 μm, more preferably 0.3 to 30 μm, still more preferably 0.5 to 15 μm. When the width is 0.1 μm or more, breakage of the fine wires can be suppressed, and by making the width 50 μm or less, the visibility of the conductive layer can be reduced.

It is particularly preferable to use a silver halide photographic light-sensitive material in the conductive layer used in the present invention. In the case of using a silver halide photographic light-sensitive material, the method of producing the conductive layer includes three forms as described below depending on the form of the photosensitive material and the development treatment.

(1) A method of chemically developing or thermally developing a photosensitive silver halide black-and-white photosensitive material not containing a physical developing core to form a metallic silver portion on the photosensitive material.

(2) A method in which a photosensitive silver halide black-and-white photosensitive material containing a physical development core in a silver halide emulsion layer is subjected to dissolution physical development to form a metallic silver portion on the photosensitive material.

(3) superimposing a photosensitive silver halide black-and-white photosensitive material not containing a physical development core on an image-receiving sheet having a non-photosensitive layer containing a physical development core, and performing diffusion transfer development on a non-photosensitive image-receiving sheet The way to form the metal silver part.

The aspect of the above (1) is an integrated black-and-white development type, and a light-transmitting conductive film such as a light-transmitting conductive film is formed on the photosensitive material. The resulting developed silver is chemically developed silver or thermally developed silver, and has high activity in subsequent plating or physical development due to filaments having a high specific surface area.

In the aspect of the above (2), in the exposed portion, the silver halide grains which are close to the physical development nucleus are dissolved and deposited on the developing nucleus to form a light-transmitting conductive property such as a light-transmitting conductive film on the photosensitive material. membrane. This method is also an integrated black and white development type. Since the development is a precipitation on the physical development nucleus, the activity is high, but the developed silver is a spherical shape having a small specific surface area.

In the above aspect (3), the silver halide grains are dissolved and diffused in the unexposed portion, and are deposited on the developing core on the image receiving sheet to form a light transmissive conductive film or the like on the image receiving sheet. Conductive film. This method is a so-called separation type, and is a method in which an image receiving sheet is peeled off from a photosensitive material and used.

Any of the negative development processing and the reverse development processing may be selected in all manners. It should be noted that in the case of the diffusion transfer method, the negative development processing can be performed by using a direct positive-type photosensitive material as a photosensitive material.

The chemical development, thermal development, dissolved physical development, and diffusion transfer development referred to herein are meanings as the term is commonly used in the art, and in the general textbook of photochemistry such as Kikuchi, "Photochemistry (Photochemistry) ("Kyoritsu Publishing Co., Ltd., 1955"), and "The Theory of Photographic Processes, 4th ed." edited by CEK Mees (Mcmillan, 1977). The present invention relates to a liquid treatment, but a technique using a thermal development method as another development method can also be referred to. For example, the technique described in each of the publications of JP-A-2004-184693, JP-A-2004-334077, and JP-A-2005-010752 can be applied.

In the present invention, the silver salt emulsion layer serving as the conductive layer may contain an additive such as a solvent or a dye in addition to the silver salt and the binder. Examples of the silver salt include inorganic silver salts such as silver halide and organic silver salts such as silver acetate. In the present invention, silver halide which is excellent in characteristics as a photosensor is preferably used.

The solvent to be used for the formation of the silver salt emulsion layer is not particularly limited, and examples thereof include water and an organic solvent (for example, an alcohol such as methanol, a ketone such as acetone, a guanamine such as formamide or an amidene such as dimethyl hydrazine. Examples, esters such as ethyl acetate, ethers, etc.), ionic liquids, and mixed solvents thereof.

A protective layer may be provided on top of the silver salt emulsion layer. The protective layer in the present invention refers to a layer formed of a binder such as gelatin or a high molecular polymer, and is formed on a photosensitive silver salt emulsion layer in order to exhibit an effect of preventing scratching or improving mechanical properties. The thickness thereof is preferably 0.5 μm or less. The coating method and the formation method of the protective layer are not particularly limited, and a known coating method and formation method can be appropriately selected. For example, the protective layer can be referred to the description of JP-A-2008-250233 or the like.

Further, in the present invention, other functional layers such as an undercoat layer, an antihalation (AH) layer or an antistatic layer may be provided. As the undercoat layer, an undercoat layer of paragraphs 0021 to 0023 of JP-A-2008-250233 can be applied. Further, as the antistatic layer, an antistatic layer of paragraphs 0012 and 0014 to 0020 of JP-A-2008-250233 is applied. As the antihalation (AH) layer, an antihalation layer of paragraphs 0064 to 0068 of JP-A-2012-6377 is used, and among them, the following solid dispersion dye A is preferable.

<化7> Solid disperse dye A

<Control panel>

The cycloolefin film, laminated film and conductive film of the present invention can be used in a touch panel.

The touch panel having the film of the present invention is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include a surface type electrostatic capacitance type touch panel, a projection type electrostatic capacitance type touch panel, and a resistive film type touch panel. It should be noted that the touch panel includes a so-called touch sensor and a touch panel. The layer structure of the touch panel sensor electrode portion in the touch panel may be a bonding method in which two transparent electrodes are bonded, a transparent electrode on both surfaces of one substrate, a single-sided bridging or a through-hole method. Or any one of the single-area layers. Further, in the projection type electrostatic capacitance type touch panel, AC driving is preferable to DC driving, and a driving method in which voltage application time on the electrode is small is more preferable.

<anti-reflection film>

The cycloolefin film or laminated film of the present invention can be used as a support for an antireflection film. In the case of a high-definition, high-quality image display device such as a liquid crystal display (LCD), it is preferable to use an anti-reflection film which has the above-mentioned dustproof property and is also used for prevention. The contrast due to reflection of external light on the display surface is reduced or the reflection of the image is reflected, and the antistatic property is obtained.

<Polarizer>

The cycloolefin film or laminated film of the present invention can be used in a polarizing plate. In the present invention, the polarizing plate has a polarizing element and a protective film provided on both sides of the polarizing element, and as the at least one of the protective films, the cycloolefin film of the present invention can be used. In the cycloolefin film, the surface of the transparent support having the light scattering layer or the antireflection layer on the opposite side, that is, the surface of the surface bonded to the polarizing element is preferably 35 to 50° with respect to water. The scope. For example, an adhesive layer may be provided on one surface of the cycloolefin film of the present invention to be disposed on the outermost surface of the display curtain.

<display device>

The cycloolefin film, laminated film or polarizing plate of the present invention can be used for various types such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD) or a cathode tube display device (CRT). In the display device. The cycloolefin film or polarizing plate of the present invention is preferably disposed on the visible side of the display screen of the image display device.

<Liquid crystal display device>

The cycloolefin film, laminated film or polarizing plate of the present invention is particularly preferably used for the outermost layer of a display screen such as a liquid crystal display device. The liquid crystal display device has a liquid crystal cell and two polarizing plates disposed on both sides thereof, and the liquid crystal cell supports liquid crystal between the two electrode substrates. Further, one optical anisotropic layer is disposed between the liquid crystal cell and one of the polarizing plates, or two optically anisotropic layers are disposed between the liquid crystal cell and the two polarizing plates.

The liquid crystal cell is preferably in TN mode, VA mode, OCB mode, IPS mode or ECB mode.

In the TN mode liquid crystal cell, the rod-like liquid crystalline molecules are substantially horizontally oriented when no voltage is applied, and further twisted at 60 to 120 Å.

The TN mode liquid crystal cell is used at most as a color TFT liquid crystal display device, and is described in many documents.

In the VA mode liquid crystal cell, the rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied.

In the VA mode liquid crystal cell, in addition to (1) a narrow VA mode liquid crystal cell in which a rod-like liquid crystal molecule is substantially vertically oriented when no voltage is applied and substantially horizontally oriented when a voltage is applied (described in Japanese Patent Laid-Open No. 2) In addition to (Japanese Patent No. 176,625), (2) a liquid crystal cell in which the VA mode is multi-domainized (MVA mode) in order to increase the viewing angle (described in SID97, Digest of Tech. Papers 28 (1997). (3) a liquid crystal cell in which a rod-like liquid crystalline molecule is substantially vertically oriented when no voltage is applied, and a twisted multi-domain orientation (n-ASM mode) occurs when a voltage is applied (described in the Japanese Liquid Crystal Symposium). Pre-collections 58-59 (1998); and (4) SURVAIVAL mode liquid crystal cells (published in LCD International 98).

The OCB mode liquid crystal cell is a liquid crystal cell of a bend orientation mode in which rod-like liquid crystal molecules are oriented substantially symmetrically (symmetrically) in the upper and lower portions of the liquid crystal cell, and the liquid crystal cell of this mode is in US Pat. No. 4,538,825. U.S. Patent No. 5,410,422 is disclosed in each specification. Since the rod-like liquid crystalline molecules are symmetrically oriented at the upper and lower portions of the liquid crystal cell, the liquid crystal cell of the bend alignment mode has an optical self-compensation function. Therefore, this liquid crystal mode is called an OCB (Optically Compensatory Bend) liquid crystal mode. The liquid crystal display device of the bend alignment mode has an advantage of a fast response speed.

The IPS mode liquid crystal cell is a method of applying a transverse electric field to a nematic liquid crystal for conversion, and is described in detail in Proc. IDRC (Asia Display' 95), p. 577-580, and p. 707-710 of the same.

In the liquid crystal cell of the ECB mode, the rod-like liquid crystalline molecules are substantially horizontally oriented when no voltage is applied. The ECB mode is one of the liquid crystal display modes having the simplest structure, and is described in detail in Japanese Laid-Open Patent Publication No. Hei 5-203946.

<Plasma Display Panel (PDP)>

A plasma display panel (PDP) is usually composed of a gas, a glass substrate, an electrode, an electrode lead material, a thick film printed material, and a phosphor. The glass substrate is two sheets of a front glass substrate and a rear glass substrate. An electrode and an insulating layer are formed on the two glass substrates. A phosphor layer is further formed on the rear glass substrate. Two glass substrates were assembled, and a gas was sealed therebetween.

A plasma display panel (PDP) can use a commercially available product. The plasma display panel is described in each of the publications of Japanese Laid-Open Patent Publication No. Hei No. 5-205643

The front panel can be placed in front of the plasma display panel. The front panel preferably has sufficient strength for protecting the plasma display panel. The front panel may be used in a gap with the plasma display panel, or may be directly attached to the plasma display panel body for use.

In an image display device such as a plasma display panel, the filter can be directly attached to the surface of the display screen. In addition, in the case where the front panel is provided in front of the display screen, the filter may be attached to the front side (outer side) or the inner side (display side) of the front panel.

<Organic EL element>

The cycloolefin film or laminated film of the present invention can be used as a substrate (base film) such as an organic EL device or a protective film. In the case where the film of the present invention is used in an organic EL device or the like, Japanese Patent Laid-Open No. Hei 11-335661, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. 2001-192651, No. 2001-192651, No. 2001-192652, Japanese Patent Laid-Open No. 2001-192653, Japanese Patent Laid-Open No. 2001-335776, Japanese Patent Laid-Open No. 2001-247859, Japanese Patent Laid-Open No. 2001-181616, Japanese Patent Laid-Open No. 2001-181617, Japanese Patent Application No. 2002-181816, and Japanese Special The contents described in each of the publications such as JP-A-2002-056976 and JP-A-2002-056976 are disclosed. In addition, it is preferably used together with the contents described in each of the publications of JP-A-2001-148291, JP-A-2001-221916, and JP-A-2001-231443.

Example

The invention will be further specifically described below by way of examples. The materials, the amounts, the ratios, the treatment contents, the treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the invention is not limited to the specific examples shown below. It should be noted that “parts” and “%” are quality standards unless otherwise stated.

The components used in the examples and comparative examples are as follows.

<Cycloolefin resin>

・Arton R5000: a cycloolefin resin containing a polar group, manufactured by JSR Corporation

・TOPAS 6017: Norbornene ethylene copolymer (COC obtained by ring-opening metathesis polymerization, non-polar group), manufactured by Topas Advanced Polymer

(phenolic heat stabilizer)

・Ph1: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], ADKSTAB AO-60, manufactured by ADEKA

・Ph2:3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanyloxy]ethyl]2 ,4,8,10-tetraoxaspiro[5.5]undecane, ADKSTAB AO-80, manufactured by ADEKA

・Ph3: stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, ADKSTAB AO-50, manufactured by ADEKA

<化8>

<thioether heat stabilizer>

・ThE1: bis[3-(dodecylthio)propionic acid] 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3- Manufactured by propylene glycol, ADKSTAB AO-412S, ADEKA

-ThE2: a compound of the following structure synthesized from an alkyl sterol having 7 carbon atoms according to the method described in JP-A-2008-174506

-ThE3: a compound of the following structure synthesized from an alkyl sterol having 10 carbon atoms according to the method described in JP-A-2008-174506

-ThE4: a compound of the following structure synthesized from an alkyl sterol having 16 carbon atoms according to the method described in JP-A-2008-174506

-ThE5: a compound of the following structure synthesized from an alkyl sterol having 18 carbon atoms according to the method described in JP-A-2008-174506

・ThE6: manufactured by 2-Lauryl-3,3'-thiodipropionate, ADKSTAB AO-503, and ADEKA Co., Ltd.

・ThE7: bis(2-methyl-4-(3-n-dodecyl) thiopropenyloxy-5-tert-butylphenyl) sulfide, ADKSTAB AO-23, manufactured by ADEKA

In the method of the Japanese Patent Publication No. 55-41654, the compound having the following structure obtained by synthesizing the number of carbon atoms in the dodecyl group to 34 is obtained.

-ThE9: A compound of the following structure obtained by converting pentaerythritol to trimethylolpropane and alkyl sterol having 20 carbon atoms according to the method described in JP-A-2008-174506

<化9>

<Other>

・P1: a phosphorous acid-based heat stabilizer, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9- Manufacture of diphosphorus [5.5] undecane, ADKSTAB PEP-36, and ADEKA

<化10>

<Mastering of heat stabilizer>

The cycloolefin resin was vacuum dried at 110 ° C for 2 hours or more, and the heat stabilizer was vacuum dried at 40 ° C for 2 hours or more. A cycloolefin resin and a heat stabilizer of 10% by mass based on the cycloolefin resin were weighed and placed in a feeder of a twin-screw kneading extruder. The mixture of the cyclic olefin resin and the heat stabilizer was melt-kneaded at 280 ° C using a twin-screw kneading extruder. The melt-melted melt was extruded into water in the form of noodles, taken out from the water, and cut to prepare a masterbatch of a heat stabilizer.

<film making>

The master batch of the cycloolefin-based resin and the heat stabilizer used in the preparation of the masterbatch of the heat stabilizer was vacuum dried at 110 ° C for 2 hours or more. 200 kg of the cycloolefin resin after vacuum drying and 1.6 kg of the master batch of the heat stabilizer were placed in a stirrer, and stirred for 15 minutes to obtain a mixture. The obtained mixture was kneaded and melted at 280 ° C using a single screw kneading extruder to which an extruder/gear pump/screening program/die (width 1,500 mm, lip gap 1 mm) was connected by piping. Extrusion of the body.

The molten body after the extrusion was sandwiched between a contact roll adjusted to 130 ° C and a casting roll set at 135 ° C as described in Example 1 of JP-A-H11-235747, and formed into a sheet shape. Next, the sheet was sequentially brought into contact with two cooling rolls set to 140 ° C and 125 ° C to be cooled.

The cooled sheet was peeled off, and both ends (5% of the full width) were trimmed immediately before the winding, and then a thickening process (knurling) of 10 mm in width and 50 μm in height was applied to both ends to 15 m/ Rolling at the speed of minutes.

An unstretched film having a width of 1.2 m, a length of 500 m, and a thickness of 40 μm was obtained as above.

<Examples 1 to 51 and Comparative Examples 1 to 19>

As shown in Table 1 and Table 2, a cycloolefin-based resin, a phenol-based heat stabilizer, a thioether-based heat stabilizer, and a phosphorous acid-based heat stabilizer were mixed at a content shown in the table. Further, the melt film formation was carried out at the temperatures described in the table.

The following evaluation was performed about the obtained cyclic polyolefin film.

<die line>

The evaluation of the die line was carried out in the following manner.

The obtained cyclic polyolefin-based film was irradiated with light, and the entire width was observed for a portion (die line) where light or dark streaks of light were observed on the screen when the transmitted light was reflected on the screen. . The film of the die line portion was cut into a size of 3 cm square, and the surface of the film was observed using a three-dimensional surface structure analysis microscope (manufactured by Zygo Co., Ltd.). The measurement was performed by causing the unevenness on the film to interfere with the text.

The evaluation criteria are as follows.

A: The occurrence of the die line has not been confirmed.

B: There is a die line, but the height of the die line is less than 100 nm.

C: the height of the die line is 100 nm or more and less than 200 nm.

D: the height of the die line is 200 nm or more and less than 300 nm.

E: the height of the die line is 300 nm or more and less than 500 nm.

F: the height of the die line is 500 nm or more

<thermal deterioration>

The thermal deterioration of the obtained cycloolefin film was evaluated by the coloring of the film as an index.

The cyclic polyolefin resin and the heat stabilizer were heated and kneaded to be pelletized, and 3 g of the particulate matter was placed in an aluminum cup having a diameter of about 5 to 6 cm. After drying under vacuum at 100 ° C for 3 hours, it was placed in an oven heated to 260 ° C for 3 hours. The color of the taken-out polymer was evaluated by visual inspection in four grades.

The evaluation criteria are as follows.

A: Coloring is not confirmed

B: There is a little bit of coloring.

C: a small amount of coloring

D: Confirmed significant coloring

<mould lip dirt>

After the film formation of the film having a length of 9,000 m was completed in 10 hours, the foreign matter adhering to the lip was visually observed in the full width of the die, and evaluation was performed using four grades. The evaluation criteria are as follows.

A: No lip dirt was confirmed

B: Confirm that the lip is slightly dirty.

C: Confirm that a small amount of dirt on the lip

D: The lip is very dirty

<Table 1>

<Table 2>

The above is only a part of the embodiments of the present invention, and is not intended to limit the present invention. It is intended to be included in the scope of the present invention.

In summary, the embodiments of the present invention can achieve the expected use efficiency, and the specific technical means disclosed therein have not been seen in similar products, nor have they been disclosed before the application, and have completely complied with the patent law. The regulations and requirements, the application for invention patents in accordance with the law, and the application for review, and the grant of patents, are truly sensible.

no

no

No

Claims (12)

A method for producing a cycloolefin film, comprising the steps of: preparing a resin composition containing a cycloolefin resin, a phenol heat stabilizer, and a thioether heat stabilizer; And a step of melt-forming the resin composition. The method for producing a cycloolefin film according to the first aspect of the invention, wherein the thioether-based heat stabilizer has a molecular weight of 850 or more and 1,400 or less. The method for producing a cycloolefin film according to the first or second aspect of the invention, wherein the thioether-based heat stabilizer has a group represented by the following formula 1, and In Formula 1, * indicates a portion connected to other structures. The method for producing a cycloolefin film according to the third aspect of the invention, wherein the thioether-based heat stabilizer has three or more groups represented by the above formula 1. The method for producing a cycloolefin film according to the first or second aspect of the invention, wherein the cycloolefin resin has a polar group. The method for producing a cycloolefin film according to the first or second aspect of the invention, wherein the content of the phenolic heat stabilizer in the resin composition is from 2.6 mmol/kg to 5.1 mmol/kg. The method for producing a cycloolefin film according to the first or second aspect of the invention, wherein the content of the thioether-based heat stabilizer in the resin composition is from 2.2 mmol/kg to 43 mmol/kg. The method for producing a cycloolefin film according to the first or second aspect of the invention, wherein the content of the phenolic heat stabilizer in the resin composition is from 3.0 mmol/kg to 3.8 mmol/kg. The method for producing a cycloolefin film according to the first or second aspect of the invention, wherein the content of the thioether-based heat stabilizer in the resin composition is from 2.2 mmol/kg to 25.8 mmol/kg. The method for producing a cycloolefin film according to the first or second aspect of the invention, wherein the thioether-based heat stabilizer is a compound represented by Formula 2, and In Formula 2, R represents an alkyl group having 6 to 30 carbon atoms, X represents a group obtained by removing n hydroxyl groups from an n-member or more polyol, and n represents an integer of 3 or more. The method for producing a cycloolefin film according to the first aspect of the invention, wherein the heating temperature in the step of performing the melt film formation is 260 to 300 °C. A cycloolefin film obtained by the production method according to any one of claims 1 to 11.