JP2009084332A - Film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film for a substrate plate excellent in moisture proof property and solvent resistance, which is mounted with functional elements such as a displaying element, for example, an LCD element, an organic EL element, or an inorganic EL element, and a solar cell element. <P>SOLUTION: This film comprises a norbornene-based ring-opened and hydrogenated material having been prepared by performing the ring-opening polymerization of a monomer mixture containing at least 90 to 100 wt.% 2-norbornene and 10 to 0 wt.% substituent norbornenes, followed by hydrogenation, and having 110 to 145°C melting point, 50,000 to 200,000 weight-average molecular weight (Mw) and 1.5 to 10.0 molecular weight distribution (Mw/Mn) by the gel permeation chromatography (GPC), and has ≤0.40 g/m<SP>2</SP>day water vapor permeability at 100 μm thickness and ≤20% haze at 100 μm thickness. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is a norbornene-based ring-opening that is excellent in water vapor barrier properties, heat resistance, oil resistance, mechanical properties, transparency, processability, etc., which are required in recent information fields, food fields, medical fields, civil engineering fields, etc. The present invention relates to a resin film obtained by molding a copolymer hydride.

  Since the norbornene-based ring-opening (co) polymer hydride is excellent in transparency and has low birefringence, use as a resin material for optical lenses and optical sheets has been proposed (Patent Documents 1 and 2). . In addition, it has excellent fluidity when melted, and also has excellent dissolution properties and chemical resistance, so it is useful as various resin materials other than optical applications, including packaging films and medical containers. Has also been proposed (Patent Documents 3 and 4).

  However, since most of norbornene-based ring-opening (co) polymer hydrides are amorphous, moisture resistance, sebum resistance, solvent resistance, etc. are insufficient depending on the application, and further improvements in physical properties Was desired.

  On the other hand, the hydride of norbornene-based ring-opening polymer having crystallinity (that is, having a melting point) contains a repeating unit of norbornene-based monomer having three or more rings described in Patent Documents 5 to 7. Crystalline norbornene-based ring-opening polymer hydrides are known. The resin film or sheet obtained from the norbornene-based ring-opening polymer hydride described in these documents is excellent in transparency, heat resistance and chemical resistance, and excellent in mechanical strength.

  However, these crystalline norbornene-based ring-opening polymer hydrides are poorly soluble in solvents, and after hydrogenation of the ring-opening copolymer, they are precipitated from the solvent, and polymer purification such as removal of catalyst residues is sufficient. There was a case that could not be done. Further, the moisture permeability of a film formed using the norbornene-based ring-opening copolymer hydride did not sufficiently satisfy the requirements.

  Non-Patent Documents 1 and 2 disclose a ring-opening copolymer hydride of a norbornene monomer having a certain crystallinity.

  However, these documents do not specifically describe the polymer physical properties of the polymer. Further, among the specifically disclosed polymers, a polymer having a large molecular weight and a narrow molecular weight distribution is difficult to control the film thickness during film forming. Further, a polymer having a small molecular weight has a small tensile elongation at break of the molded film, and has a problem in mechanical properties when formed into a film. Furthermore, since the hydrogenation rate is not always sufficient, there is a problem that the molded product obtained by molding this polymer is easily burnt.

JP 60-26024 A JP-A-9-263627 JP 2000-313090 A JP 2003-183361 A JP 2000-201826 A JP 2000-393316 A JP 2006-52333 A Polymer International, 1994, 34, 49-57. Macromolecules, 2004, 37, 7278-7284.

  The present invention has been made in view of the situation of such prior art, and in recent information fields, food fields, medical fields, civil engineering fields, etc., water vapor barrier properties, heat resistance, oil resistance, mechanical properties, It is an object of the present invention to provide a film that satisfies demands for better performance such as transparency and workability.

Thus, according to the present invention, a monomer containing at least 90 to 100% by weight of 2-norbornene and 10 to 0% by weight of substituent-containing norbornene is subjected to ring-opening polymerization and hydrogenated, and the melting point is 110 to 110%. Norbornene-based ring opening having a weight average molecular weight (Mw) of 50,000 to 200,000 and a molecular weight distribution (Mw / Mn) of 1.5 to 10.0 by 145 ° C., gel permeation chromatography (GPC) A film comprising a hydride and having a water vapor permeability of 0.40 g / m ² · day or less at a thickness of 100 μm and a haze of 20% or less at a thickness of 100 μm is provided.
This film can be easily obtained by using a norbornene-based ring-opening polymer hydride crystallized in the presence of a nucleating agent having an average major axis of 20 μm or less.

  In the film of the present invention, the norbornene-based ring-opening polymer hydride has a weight average molecular weight in terms of standard polystyrene by gel permeation chromatography of 50,000 to 200,000, and a molecular weight. A polymer having a distribution of 1.5 to 7.0 is preferred.

  According to the present invention, a film having low moisture permeability and low haze is provided.

Hereinafter, the present invention will be described in detail.
The film of the present invention is derived from 2-norbornene obtained by ring-opening polymerization of a monomer containing at least 90 to 100% by weight of 2-norbornene and 10 to 0% by weight of a substituent-containing norbornene and hydrogenating the monomer. The abundance ratio of the repeating unit (A) with respect to all repeating units is 90 to 100% by weight, and the abundance ratio with respect to all repeating units of the repeating unit (B) derived from the substituent-containing norbornene monomer is 0 to 10% by weight. And a norbornene-based ring-opening polymer hydride having a melting point in the range of 110 to 145 ° C.

(Norbornene ring-opening polymer hydride)
The norbornene-based ring-opening polymer hydride used in the present invention is obtained after (i) 2-norbornene is obtained by ring-opening polymerization of 2-norbornene in the presence of a metathesis polymerization catalyst. Or (ii) a monomer mixture comprising 2-norbornene and a substituent-containing norbornene-based monomer, obtained by hydrogenating 80% or more of the carbon-carbon double bonds of the ring-opening polymer obtained A ring-opening copolymer of 2-norbornene and a substituent-containing norbornene monomer is obtained by ring-opening polymerization in the presence of a metathesis polymerization catalyst, and then the carbon-carbon double of the resulting ring-opening copolymer is obtained. It is obtained by hydrogenating 80% or more of the bonds.

  2-norbornene (bicyclo [2.2.1] hept-2-ene) is a known compound and can be obtained, for example, by reacting cyclopentadiene with ethylene.

  The substituent-containing norbornene-based monomer is a compound having a norbornene skeleton in the molecule (excluding 2-norbornene). The “substituent-containing norbornene monomer” used in the present invention includes a norbornene compound having a condensed ring in addition to a 2-norbornene derivative having a substituent.

  Examples of the substituent-containing norbornene monomer include a norbornene monomer that does not have a ring condensed with a norbornene ring in the molecule, and a polycyclic norbornene monomer having three or more rings.

  Specific examples of the norbornene-based monomer having no ring condensed with the norbornene ring in the molecule include 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5- Norbornenes having an alkyl group such as hexyl-2-norbornene, 5-decyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-cyclopentyl-2-norbornene; 5-ethylidene-2-norbornene, 5-vinyl- Norbornenes having an alkenyl group such as 2-norbornene, 5-propenyl-2-norbornene, 5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2-norbornene; aromatic rings such as 5-phenyl-2-norbornene Having norbornenes; 5-methoxycarbonyl-2-norbol , 5-ethoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-methyl-5-ethoxycarbonyl-2-norbornene, norbornenyl-2-methylpropionate, norbornenyl-2- Methyl octanate, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) -2-norbornene, 5,5-di (hydroxymethyl) -2-norbornene, 5-hydroxyisopropyl-2-norbornene, 5,6 -Norbornenes having a polar group containing an oxygen atom such as dicarboxy-2-norbornene and 5-methoxycarbonyl-6-carboxy-2-norbornene; having a polar group containing a nitrogen atom such as 5-cyano-2-norbornene Norbornenes; and the like.

  The polycyclic norbornene monomer having three or more rings is a norbornene monomer having a norbornene ring and one or more rings condensed with the norbornene ring in the molecule. Specific examples thereof include monomers represented by the following formula (1) or formula (2).

(Wherein R ¹ and R ² are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

(Wherein R ^{4 to} R ⁷ are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ⁴ and R ⁶ may be bonded to each other to form a ring, and m is 1 or 2.)

Specific examples of the monomer represented by the formula (1) include dicyclopentadiene (tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene), methyldicyclopentadiene, dimethyl Examples include dicyclopentadiene and tricyclo [5.2.1.0 ^2,6 ] dec-8-ene. In addition, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0 ^{2 , 11} . Norbornene derivatives having an aromatic ring such as 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene) Can be mentioned.

  Examples of the monomer represented by the formula (2) include tetracyclododecenes in which m is 1 and hexacycloheptadecenes in which m is 2.

Specific examples of the tetracyclododecenes include tetracyclododecene (tetracyclo [4.4.0.1 ^2,5 .1, ^7,10 ] dodec-3-ene), 8-methyltetracyclododecene, 8 -Unsubstituted or alkyl-containing tetracyclododecenes such as ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyltetracyclododecene; 8-methylidenetetracyclododecene, 8-ethylidenetetra Tetracyclodo having a double bond outside the ring, such as cyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, 8-cyclopentenyltetracyclododecene, etc. Decenes: tetracyclodo having an aromatic ring such as 8-phenyltetracyclododecene Decenes; 8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9 -Tetracyclododecenes having a substituent containing an oxygen atom such as dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride; 8-cyanotetracyclododecene, tetracyclododecene-8,9- Tetracyclododecenes having a substituent containing a nitrogen atom such as dicarboxylic imide; tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; 8-trimethoxysilyltetracyclod Examples include tetracyclododecenes having a substituent containing a silicon atom such as decene. It is.

  Specific examples of hexacycloheptadecenes include hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene. Hexacycloheptadecenes having a substituted or alkyl group; 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexa Hexacycloheptadecenes having a double bond outside the ring such as cycloheptadecene, 12-cyclopentenylhexacycloheptadecene, etc .; Heterocyclic rings such as 12-phenylhexacycloheptadecene Sacycloheptadecenes; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene 12 , 13-dicarboxylic acid, hexacycloheptadecene 12,13-dicarboxylic anhydride, etc., hexacycloheptadecenes having a substituent containing an oxygen atom; 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13- Hexacycloheptadecenes having a substituent containing a nitrogen atom such as dicarboxylic acid imide; Hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; Hexa cycloheptanone decene and the like having a substituent containing a Le hexa cycloheptanone de silicon atoms Sen and the like. These norbornene monomers can be used alone or in combination of two or more.

  In the present invention, the aforementioned 2-norbornene and / or substituent-containing norbornene-based monomer and other monomers capable of ring-opening copolymerization can be used in combination.

  Other monomers capable of ring-opening copolymerization with 2-norbornene and / or substituent-containing norbornene-based monomers include monocyclic olefins such as cyclohexene, cycloheptene, cyclooctene and their derivatives; cyclohexadiene, cyclohepta Cyclic dienes such as dienes and derivatives thereof; and the like.

  The composition of the monomer mixture comprising 2-norbornene or 2-norbornene and a substituent-containing norbornene-based monomer is such that 2-norbornene is usually 90 to 100% by weight, preferably 95 to 99% by weight, more preferably It is 97 to 99% by weight, and the substituent-containing norbornene monomer is usually 0 to 10% by weight, preferably 1 to 5% by weight, and more preferably 1 to 3% by weight.

  Examples of the metathesis polymerization catalyst include, for example, Japanese Patent Publication No. Sho 41-20111, Japanese Patent Publication No. Sho 46-14910, Japanese Patent Publication No. Sho 57-17883, Japanese Patent Publication No. Sho 57-61044, Japanese Patent Publication No. Sho 54-86600, A general metathesis polymerization catalyst consisting essentially of (a) a transition metal compound catalyst component and (b) a metal compound co-catalyst component as described in JP-A-58-127728 and JP-A-1-240517; Schrock type polymerization catalyst (JP-A-7-179575, Schrock et al., J. Am. Chem. Soc., 1990, Vol. 112, page 3875-) and Grubbs type polymerization catalyst (Fu et al. Nguyen et al., J. Am. Chem., 1993, 115, 9856 et seq., J. Am. . Soc, 1992 years, 114th volume, 3974 pp ~;., And the like; Grubbs et al, living ring-opening metathesis catalyst brochures etc.) and No. WO98 / 21214.

  Among these, a metathesis polymerization catalyst comprising (a) a transition metal compound catalyst component and (b) a metal compound promoter component is preferable in order to adjust the molecular weight distribution of the obtained polymer to a suitable range.

The (a) transition metal compound catalyst component is a compound of a transition metal of Groups 3 to 11 of the periodic table. For example, halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, derivatives of these, or derivatives of these transition metals. A complexed product of a complexing agent such as P (C ₆ H ₅ ) ₅ may be mentioned.

Specific examples include TiCl ₄ , TiBr ₄ , VOCl ₃ , WBr ₃ , WCl ₆ , WOCl ₄ , MoCl ₅ , MoOCl ₄ , WO ₂ and H ₂ WO ₄ . Of these, W, Mo, Ti, or V is preferable from the viewpoint of polymerization activity and the like, and these halides, oxyhalides, and alkoxy halides are particularly preferable.

  The (b) metal compound promoter component is a metal compound of Groups 1 to 2 and Groups 12 to 14 of the periodic table, and has at least one metal element-carbon bond or metal element-hydrogen bond. is there. Examples thereof include organic compounds such as Al, Sn, Li, Na, Mg, Zn, Cd, and B.

  Specific examples include organoaluminum compounds such as trimethylaluminum, triisobutylaluminum, diethylaluminum monochloride, methylaluminum sesquichloride, and ethylaluminum dichloride; organotin compounds such as tetramethyltin, diethyldimethyltin, tetrabutyltin, and tetraphenyltin. Organic lithium compounds such as n-butyl lithium; organic sodium compounds such as n-pentyl sodium; organic magnesium compounds such as methyl magnesium iodide; organic zinc compounds such as diethyl zinc; organic cadmium compounds such as diethyl cadmium; Organic boron compounds; and the like. Of these, Group 13 metal compounds are preferred, and Al organic compounds are particularly preferred.

  In addition to the components (a) and (b), a metathesis polymerization activity can be increased by adding a third component. As the third component to be used, aliphatic tertiary amine, aromatic tertiary amine, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound , Halogen-containing compounds, and other Lewis acids.

  The compounding ratio of these components is the molar ratio of the (a) component: (b) component to the metal element, and is usually in the range of 1: 1 to 1: 100, preferably 1: 2 to 1:10. Moreover, (a) component: 3rd component is the range of 1: 0.005-1: 50 normally by molar ratio, Preferably it is the range of 1: 1-1: 10.

  The polymerization catalyst is used in a molar ratio of (transition metal in the polymerization catalyst) :( total monomer), usually 1: 100 to 1: 2,000,000, preferably 1: 1,000 to 1: 20,000, more preferably 1: 5,000 to 1: 8,000. If the amount of catalyst is too large, it may be difficult to remove the catalyst after the polymerization reaction, and the molecular weight distribution may be widened. On the other hand, if the amount is too small, sufficient polymerization activity cannot be obtained.

  The ring-opening polymerization can be carried out without a solvent, but is preferably carried out in a suitable solvent. The organic solvent to be used is not particularly limited as long as the polymer and the polymer hydride are dissolved or dispersed under predetermined conditions and do not affect the polymerization and the hydrogenation reaction. Is preferred.

  Examples of such organic solvents include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, Cycloaliphatic hydrocarbons such as cyclodecane, hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene, Halogen-based aromatic hydrocarbons such as dichlorobenzene; Nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; Ethers such as diethyl ether and tetrahydrofuran The solvent etc. can be used. These organic solvents can be used alone or in combination of two or more.

  Among these, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and ethers that are widely used in industry are preferable.

  When polymerization is carried out in an organic solvent, 2-norbornene and optionally other monomers capable of ring-opening copolymerization with 2-norbornene, or a single monomer comprising 2-norbornene and a substituent-containing norbornene-based monomer The concentration of the body mixture and other monomers capable of ring-opening copolymerization therewith (hereinafter sometimes collectively referred to as “monomer”) is preferably 1 to 50% by weight. -45 wt% is more preferable, and 3-40 wt% is particularly preferable. If the concentration of the monomer is less than 1% by weight, the productivity may be lowered, and if it is more than 50% by weight, the solution viscosity after polymerization may be too high, and the subsequent hydrogenation reaction may be difficult. .

  In the ring-opening polymerization, a molecular weight regulator can be added to the reaction system. The molecular weight of the resulting ring-opening polymer can be adjusted by adding a molecular weight regulator.

  It does not specifically limit as a molecular weight regulator to be used, A conventionally well-known thing can be used. For example, α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; allyl chloride and the like A halogen-containing vinyl compound such as glycidyl methacrylate; a nitrogen-containing vinyl compound such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl- Non-conjugated dienes such as 1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene, or 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3- Conjugates such as butadiene, 1,3-pentadiene, 1,3-hexadiene Mention may be made of the ene or the like. Among these, α-olefins are preferable because of easy molecular weight adjustment.

  The addition amount of the molecular weight regulator may be an amount sufficient to obtain a polymer having a desired molecular weight, and is usually 1:50 to 1: 1 in a molar ratio of (molecular weight regulator) :( total monomer). 1,000,000, preferably 1: 100 to 1: 5,000, more preferably 1: 300 to 1: 3,000.

Ring-opening polymerization is initiated by mixing the monomer and the polymerization catalyst.
Although the temperature which performs ring-opening polymerization is not specifically limited, Usually, -20- + 100 degreeC, Preferably it is 10-80 degreeC. If the temperature at which the ring-opening polymerization is carried out is too low, the reaction rate decreases.
The polymerization time is not particularly limited, and is usually 1 minute to 100 hours.
Although the pressure conditions at the time of superposition | polymerization are not specifically limited, Usually, superposition | polymerization is performed under the pressurization of 0-1 Mpa.

  After completion of the reaction, the desired norbornene-based ring-opening polymer can be isolated by ordinary post-treatment operation.

The obtained norbornene-based ring-opening polymer is subjected to the next hydrogenation reaction step.
Further, as described later, the hydrogenation catalyst can be continuously performed without adding a hydrogenation catalyst to the reaction solution subjected to the ring-opening polymerization and isolating the norbornene-based ring-opening polymer.

  The hydrogenation reaction of the norbornene-based ring-opening polymer is a reaction in which the norbornene-based ring-opening polymer is hydrogenated to a carbon-carbon double bond existing in the main chain and / or side chain. This hydrogenation reaction is performed by adding a hydrogenation catalyst to an inert solvent solution of a norbornene-based ring-opening polymer and supplying hydrogen into the reaction system.

  As the hydrogenation catalyst, any one of a homogeneous catalyst and a heterogeneous catalyst can be used as long as it is generally used for hydrogenation of an olefin compound. Considering the removal of residual metals in the resulting polymer, a heterogeneous catalyst is preferable.

  Examples of homogeneous catalysts include combinations of cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, etc. Catalyst systems comprising combinations of transition metal compounds and alkali metal compounds; noble metal complex catalysts such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, etc. .

  Examples of heterogeneous catalysts include nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, nickel, palladium, platinum, rhodium, ruthenium, Alternatively, a solid catalyst system in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, or titanium oxide can be used.

  The usage-amount of a hydrogenation catalyst is 0.05-10 weight part normally with respect to 100 weight part of norbornene-type ring-opening polymers.

As the inert organic solvent used for the hydrogenation reaction, the same aliphatic hydrocarbons as those exemplified as the organic solvent that can be used in the ring-opening polymerization of 2-norbornene and a substituent-containing norbornene monomer described above. , Alicyclic hydrocarbons, aromatic hydrocarbons, halogenated aromatic hydrocarbons, nitrogen-containing hydrocarbons, ethers and the like.

  The temperature range of the hydrogenation reaction varies depending on the hydrogenation catalyst used, but the hydrogenation temperature is usually -20 ° C to + 300 ° C, preferably 0 ° C to + 250 ° C. If the hydrogenation temperature is too low, the reaction rate may be slow, and if it is too high, side reactions may occur.

  The hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.1 to 10 MPa, more preferably 1 to 5 MPa. If the hydrogen pressure is too low, the hydrogenation rate is slow, and if it is too high, a high pressure reactor is required, which is not preferable.

  Norbornene-based ring-opening polymer hydride (hereinafter sometimes referred to as “ring-opening polymer hydride”) has a hydrogenation rate of carbon-carbon double bonds in the polymer of 80% or more, preferably 90% or more. More preferably, it is 95% or more, more preferably 99% or more, and particularly preferably 99.9% or more. When it exists in said range, the film obtained is excellent in moisture resistance and solvent resistance.

The hydrogenation rate of the ring-opened polymer hydride can be determined by measuring by ¹ H-NMR using deuterated chloroform as a solvent.

  After completion of the hydrogenation reaction, the hydrogenation catalyst and the like are filtered off from the reaction solution, and the target ring-opening polymer hydride is obtained by removing volatile components such as a solvent from the polymer solution after the filtration. Can do.

As a method for removing volatile components such as a solvent, a known method such as a coagulation method or a direct drying method can be employed.
The coagulation method is a method in which a polymer is precipitated by mixing a polymer solution with a poor solvent for the polymer. Examples of the poor solvent to be used include polar solvents such as alcohols such as ethyl alcohol, n-propyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate;

  The particulate component obtained by solidification is dried by heating, for example, in vacuum, nitrogen or air, or is extruded into a pellet from a melt extruder as necessary. be able to.

  The direct drying method is a method in which the polymer solution is heated under reduced pressure to remove the solvent. This method can be carried out using a known apparatus such as a centrifugal thin film continuous evaporation dryer, a scratched heat exchange type continuous reactor type dryer, a high viscosity reactor device or the like. The degree of vacuum and temperature are appropriately selected depending on the device and are not limited.

  The abundance ratio of the repeating unit (A) derived from 2-norbornene of the ring-opening polymer hydride obtained as described above is 90 to 100% by weight, preferably 95 to 99% by weight, more preferably The proportion of the repeating unit (B) derived from the substituent-containing norbornene monomer is 97 to 99% by weight, based on all repeating units, 0 to 10% by weight, preferably 1 to 5% by weight, more preferably 1 ~ 3 wt%.

  It is excellent in the mechanical characteristics of a film that the presence rate of a repeating unit (B) is the said range, and preferable. When the proportion of the repeating unit (B) is too large, the heat resistance of the film may be deteriorated. On the other hand, if the proportion of the repeating unit (B) is too small, the mechanical properties of the film may be deteriorated.

  The obtained ring-opened polymer hydride has a weight average molecular weight (Mw) of usually 50, in terms of standard polystyrene by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as an eluent. 000 to 200,000, preferably 70,000 to 180,000, more preferably 80,000 to 150,000.

  If Mw is too high, the processability of the film may be deteriorated. On the other hand, if Mw is too low, the mechanical properties and heat resistance of the film may be reduced, and the ring-opened polymer hydride is likely to precipitate from the solvent, which may make it difficult to purify the polymer.

The molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the ring-opening polymer hydride is usually 1.5 to 7.0, preferably 2.0. It is -6.5, More preferably, it is 2.5-6.0, More preferably, it is 2.5-5.5.
If Mw / Mn is too narrow, the processability of the film may be deteriorated. On the other hand, if Mw / Mn is too wide, the mechanical properties may deteriorate.

  Incidentally, Mn is a number average molecular weight measured as standard polystyrene conversion by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as an eluent.

The melting point of the ring-opening polymer hydride is 110 to 145 ° C, preferably 120 to 145 ° C, more preferably 130 ° C to 145 ° C. It is preferable for it to be in the above range since the film has excellent heat resistance.
Incidentally, the melting point of the ring-opened polymer hydride varies depending on the molecular weight, molecular weight distribution, isomerization rate, composition ratio, etc. of the ring-opened polymer hydride.

  The isomerization rate of the ring-opened polymer hydride is usually 0 to 40%, preferably 0 to 20%, more preferably 1 to 10%, and particularly preferably 3 to 9%.

The isomerization rate can be calculated from 33.0 ppm peak integrated value / (31.8 ppm peak integrated value + 33.0 ppm peak integrated value) × 100 measured by ¹³ C-NMR using deuterated chloroform as a solvent.

  By the way, the 31.8 ppm peak is derived from the cis isomer of 2-norbornene repeating units in the polymer, and the 33.0 ppm peak is derived from the trans isomer of 2-norbornene repeating units in the polymer. is there.

  In the present invention, it is preferable to synthesize a ring-opened polymer that is substantially a cis-form by ring-opening polymerization, and hydrogenate this to obtain a hydrogenated ring-opened polymer. In the hydrogenation reaction, isomerization to the trans isomer usually occurs, but it is preferable to suppress this isomerization and to keep the content of the trans isomer low.

  If the isomerization rate of the ring-opened polymer hydride is too high, the heat resistance may decrease. On the other hand, if the isomerization rate is too low, the solubility of the ring-opened polymer hydride in the organic solvent is lowered and may be precipitated. Therefore, the isomerization rate of the ring-opened polymer hydride may be 0%, but preferably exhibits a certain degree of isomerization within a range of 10% or less.

  In order to make the isomerization ratio within the above range, in the hydrogenation reaction of the ring-opening polymer, the reaction temperature is preferably 120 to 170 ° C., more preferably 130 to 160 ° C., and the use of the hydrogenation catalyst to be used The amount is preferably 0.2 to 5 parts by weight, more preferably 0.2 to 1 part by weight with respect to 100 parts by weight of the ring-opening polymer.

  It is preferable that the ring-opening polymer hydride to be used has few foreign matters. Metal residues, foreign matters, and the like in the film may cause a decrease in electrical characteristics when applied to electronic components. After the polymerization reaction or after the hydrogenation reaction, metal residues and foreign matters can be precisely removed by filtering the polymer solution with a filter having a pore size of 0.2 μm or less.

  Since the ring-opening copolymer hydride used in the present invention is a polymer having a melting point, that is, a polymer that forms a crystal structure, a crystal portion is formed (crystallized) inside the molded body of the film and sheet. Combined with the amorphous part, mechanical properties such as tensile elongation at break of the molded product are improved.

In order for the film to have a water vapor permeability of 0.40 g / m ² · day or less at a thickness of 100 μm and a haze at a thickness of 100 μm of 20% or less, the ring-opening polymer hydride is crystallized. In doing so, it is important to control the spherulite size by the presence of a nucleating agent. The spherulite size is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. The spherulite size is preferably ½ or less, more preferably 1/3 of the spherulite when the above-described ring-opened polymer hydride is crystallized without a nucleating agent. Here, the spherulite size is measured by observing the crystal using a polarizing microscope.

The nucleating agent is not particularly limited as long as it is a particle having a melting point higher than the melting point of the ring-opening polymer hydride to be crystallized, and includes talc, sorbitol compound, hindered amine compound, hindered phenol compound, and organic phosphoric acid. Examples thereof include metal salts, metal salts of organic carboxylic acids, clays such as mica or clay, and clay. These may be used alone or in combination of at least two.
Among these, the major axis of the nucleating agent is preferably 20 μm or less, more preferably 15 μm or less, particularly preferably 10 μm or less, and the water vapor permeability at a thickness of 100 μm is 0.40 g / m ² · day or less. In addition, a film having a haze of 20% or less at a thickness of 100 μm can be obtained.

  Moreover, a nucleating agent is a ratio of 0.005-10 weight part normally with respect to 100 weight part of ring-opening polymer hydrides, Preferably it is 0.01-5 weight part, More preferably, it is a ratio of 0.05-1 weight part. Add in.

In addition, the film of the present invention may contain an antioxidant (stabilizer), a crosslinking agent, a foaming agent, a flame retardant, a compound such as a thermoplastic resin or a soft polymer, a compounding agent such as a lubricant, if necessary. , Dyes, antistatic agents, ultraviolet absorbers, light-resistant stabilizers, waxes and other compounding agents usually used in the resin industry.
In addition, the ratio of the ring-opened polymer hydride is generally 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more with respect to the entire polymer constituting the film of the present invention.

  A resin composition is prepared by mixing a ring-opening polymer hydride with a nucleating agent and a compounding agent used as necessary. There are no particular restrictions on the method for preparing the resin composition, but the ring-opening polymer hydride, nucleating agent and compounding agent are melt-mixed by a kneader such as a single-screw extruder, twin-screw extruder, roll, or Banbury mixer. Is preferable from the viewpoint of productivity.

  The ring-opening polymer hydride when mixed with the compounding agent is a solution obtained by filtering insoluble matter from the reaction liquid, even if it is isolated from a reaction liquid containing the ring-opening polymer hydride. Alternatively, it may be a reaction solution before filtration. The compounding agents may be those dissolved in an appropriate solvent. The ring-opening polymer hydride solution and / or the compounding agent solution may be heated and used as necessary.

  The resin composition obtained as described above is usually subjected to film production after being processed into a size of about the size of rice grains called pellets so as to be easy to handle.

  There is no restriction | limiting in particular in the method of manufacturing the film of this invention, Both a heat-melt-molding method and a solution casting method can be used.

  The hot melt molding method is a method in which the above pellets are heated to a temperature equal to or higher than the melting point (Tm) of the polymer and lower than the thermal decomposition temperature to form a fluidized film.

Examples of the heat-melt molding method include an extrusion molding method, a calendar molding method, a compression molding method, an inflation molding method, an injection molding method, a blow molding method, and a stretch molding method.
Further, after forming a film by an extrusion molding method, a calendar molding method, an inflation molding method, or the like, a stretch molding method may be performed.

The heating and pressurizing conditions in the hot melt molding method may be appropriately selected depending on the characteristics of the molding machine, the ring-opening polymer hydride used, and the temperature is usually Tm to (Tm + 100 ° C.), preferably (Tm + 20 ° C.). To (Tm + 50 ° C.).
The pressure at the time of molding is usually 0.5 to 100 MPa, preferably 1 to 50 MPa.
The pressurizing time is usually about several seconds to several tens of minutes.

The ring-opening copolymer hydride used in the present invention has a characteristic that the Tm is relatively high and the heat resistance is high, but the viscosity becomes extremely low between 200 to 400 ° C. and becomes fluid.
The reason for this is not clear, but it is considered that since it has crystallinity, it becomes a liquid crystal state and the viscosity rapidly decreases. Therefore, although the ring-opening copolymer hydride of the present invention flows well even though it is a resin having a high melting temperature, it can be formed into a film in a short time.

  On the other hand, the solution casting method is a method in which the resin composition of the present invention is dissolved in an organic solvent, this is cast on a flat surface or a roll, and the solvent is removed by heating to form a film and a sheet. is there.

  As the solvent to be used, the same aliphatic hydrocarbons and alicyclic rings as those exemplified as the solvent for the ring-opening polymerization reaction of 2-norbornene and a substituent-containing norbornene-based monomer and the hydrogenation reaction of the ring-opening copolymer Aromatic hydrocarbons, aromatic hydrocarbons, halogenated aromatic hydrocarbons, nitrogen-containing hydrocarbons, ethers and the like.

  In the solution casting method, the temperature at which the solvent is volatilized becomes the molding temperature, and the temperature is appropriately set depending on the type of solvent used.

  Further, the molded body may be annealed after the molding in order to reveal the crystallinity of the molded product more strongly.

The thickness of the resin film of the present invention is not particularly limited, but is usually 1 μm to 20 mm, preferably 5 μm to 5 mm, more preferably 10 μm to 2 mm. There is no special rule for the distinction between film and sheet, and there are cases where they are differentiated by thickness, but the actual situation is that the name changes depending on the usage and customs in the industry.

  In order to increase the mechanical strength and water vapor barrier property of the film, the film may be stretched to increase the crystallinity. Stretching means that the formed film is subsequently stretched by about 1.1 to 10 times to give plastic deformation. This plastic deformation has an effect of stretching and aligning not only the crystal chain but also the amorphous chain by internal friction.

  The film of the present invention may be a laminate having a layer containing a hydrogenated ring-opening copolymer and a layer containing another polymer.

  Other polymers include rubbery polymers or other resins, and specific examples thereof are the same as those described above as those that can be used by blending with the ring-opening copolymer hydride of the present invention. It is.

  The number of layers to be laminated is usually two or three, but it may be a multi-layer laminate. The arrangement order of the layers depending on the polymer species in three or more layers can be appropriately set depending on the purpose and application.

  In addition, a layer of the same kind of polymer may be arranged with a layer of another polymer being separated, for example, a layer containing polystyrene between two layers containing the hydrogenated ring-opening copolymer of the present invention. A three-layer laminate sandwiched between the layers, a four-layer laminate in which a layer containing a hydrogenated styrene-isoprene block copolymer is laminated on one outer side, and the like are possible.

  Lamination methods include methods of applying and bonding adhesive between layers, methods of fusing single-layer or multiple-layer films or sheets by heating or heating to a melting point or higher, ring opening co-polymerization There is a method in which an organic solvent in which another polymer or a ring-opening copolymer hydride is dispersed or dissolved is applied to the surface of a film or sheet of a polymer hydride or other polymer and dried.

  Moreover, a ring-opening copolymer hydride and other polymers can be coextruded with an extruder to produce a laminate.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In the following Examples and Comparative Examples, “part” or “%” is based on weight unless otherwise specified.

In the following Examples and Comparative Examples, various physical properties are measured as follows.
(1) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening (co) polymer were measured as standard polystyrene conversion values by gel permeation chromatography (GPC) using toluene as an eluent. .

GPC-8020 series (DP8020, SD8022, AS8020, CO8020, RI8020, manufactured by Tosoh Corporation) was used as a measuring apparatus.
As the standard polystyrene, standard polystyrene manufactured by Tosoh Corporation (total 8 points of Mw of 500, 2630, 10200, 37900, 96400, 427000, 1090000, 5480000) were used.

  The sample was prepared by dissolving the measurement sample in toluene so as to have a sample concentration of 1 mg / ml, and then filtering with a cartridge filter (polytetrafluoroethylene, pore size 0.5 μm).

  The measurement was performed using two TSKgel GMHHR · H (manufactured by Tosoh Corporation) connected in series to the column under the conditions of a flow rate of 1.0 ml / min, a sample injection amount of 100 μml, and a column temperature of 40 ° C.

(2) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening (co) polymer hydride were determined by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as an eluent. ) As a standard polystyrene equivalent value.

As a measuring device, HLC8121GPC / HT (manufactured by Tosoh Corporation) was used.
As the standard polystyrene, standard polystyrene manufactured by Tosoh Corporation (Mw of 988, 2580, 5910, 9010, 18000, 37700, 95900, 186000, 351000, 889000, 1050,000, 2770000, 5110000, 7790,000, 20000000) is used. It was.

  The sample was prepared by heating and dissolving the measurement sample in 1,2,4-trichlorobenzene at 140 ° C. so that the sample concentration was 1 mg / ml.

  The measurement was performed using three TSKgel GMHHR · H (20) HT (manufactured by Tosoh Corporation) connected in series to the column under the conditions of a flow rate of 1.0 ml / min, a sample injection amount of 300 μml, and a column temperature of 140 ° C.

(3) The hydrogenation rate of the ring-opening copolymer hydride was determined by measuring by ¹ H-NMR using deuterated chloroform as a solvent.

(4) The isomerization rate is obtained by calculating from 33.0 ppm peak integrated value / (31.8 ppm peak integrated value + 33.0 ppm peak integrated value) × 100 measured by ¹³ C-NMR using deuterated chloroform as a solvent. It was.
By the way, the 31.8 ppm peak is derived from the cis isomer of 2-norbornene repeating units in the polymer, and the 33.0 ppm peak is derived from the trans isomer of 2-norbornene repeating units in the polymer. is there.

(5) The melting point is determined by using a differential scanning calorimeter (DSC 6220, manufactured by SII Nanotechnology) based on JIS K 7121. After heating the sample to 30 ° C. or higher from the melting point, the cooling rate is −10 ° C./min. After cooling to room temperature, the temperature was measured at a rate of temperature increase of 10 ° C./min.

(6) The glass transition temperature was measured based on JIS K 6911 using a differential scanning calorimeter (DSC 6220, manufactured by SII Nanotechnology).
(7) The average major axis of the crystal nucleating agent is obtained by embedding a sample with an epoxy resin, performing a surface operation with an ultramicrotome (ULTRACUT UCT, manufactured by LEICA), and performing a field emission scanning electron microscope (FE-). SEM S-4700, manufactured by Hitachi, Ltd.), and the values were averaged from 100 crystal nucleating agents.
(8) The average major axis of the spherulite is a value obtained from 100 spherulites observed by observing the spherulites formed when the sample is melted at 180 ° C. for 5 minutes under a polarizing microscope with a hot stage and then crystallized at 90 ° C. Were averaged.
(9) The haze of a 100 μm thick film was measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.).
(10) Water vapor transmission rate (moisture permeability) is determined based on JIS K 7129 (Method A) using a film having a thickness of 100 μm and the water vapor transmission rate under the conditions of temperature: 40 ° C. and humidity: 90% RH. It was measured with a degree tester (L80-5000 type, manufactured by LYSSY). If the moisture permeability (water vapor permeability, [g / (m ² · 24 h)]) is small, the water vapor barrier property is good.

Example 1
(Ring-opening polymerization)
Under nitrogen atmosphere, 500 parts of dehydrated cyclohexane was mixed with 0.55 part of 1-hexene, 0.30 part of diisopropyl ether, 0.20 part of triisobutylaluminum, and 0.075 part of isobutyl alcohol at room temperature. . Thereto, 250 parts of 2-norbornene (hereinafter sometimes referred to as “2-NB”) and 15 parts of tungsten hexachloride 1.0% toluene solution were continuously added over 2 hours while maintaining at 55 ° C. Then, polymerization was performed.
The resulting ring-opening polymer (A) had a weight average molecular weight (Mw) of 83,000 and a molecular weight distribution (Mw / Mn) of 1.8. The polymerization conversion rate was almost 100%.
(Hydrogenation reaction)
The polymerization reaction liquid obtained above was transferred to a pressure-resistant hydrogenation reactor, to which 0.5 parts of a diatomaceous earth-supported nickel catalyst (T8400, nickel support rate 58%, manufactured by Nissan Zudhemy) was added, at 160 ° C, The reaction was performed at a hydrogen pressure of 4.5 MPa for 6 hours. This solution was filtered under pressure at a pressure of 0.25 MPa using a pressure filter (Hunda filter, manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.) using Radiolite # 500 (manufactured by Showa Chemical Co., Ltd.) as a filter bed, and opened the ring A colorless and transparent solution of the polymer hydride (A) was obtained.
(Polymer physical properties)
The hydrogenation rate of the obtained ring-opened polymer hydride (A) was 99.9%, the weight average molecular weight (Mw) was 82,200, the molecular weight distribution (Mw / Mn) was 2.9, and the isomerization rate was It was 5% and the melting point was 140 ° C.
(Preparation of resin composition)
To the resulting solution, an antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, Irganox 1010 per 100 parts of polymer solids). 0.1 parts by weight (hereinafter referred to as “Antioxidant (A)”) and 0.5 parts by weight of a crystal nucleating agent (manufactured by Nippon Talc; MS, food-added talc; major axis 15 μm), Dissolved.
(Dry)
After filtering this solution through a metal fiber filter (pore size 0.5 μm, manufactured by Nichidai), the filtrate was filtered through “Zeta Plus Filter 30S” (pore size 0.5-1 μm, manufactured by Cuno), Foreign matter was removed by filtering with a metal fiber filter (pore size 0.2 μm, manufactured by Nichidai). The obtained filtrate was heated to 200 ° C. with a preheating device and continuously supplied to a thin film dryer (manufactured by Hitachi, Ltd.) at a pressure of 3 MPa. The operating conditions of the thin film dryer were a pressure of 13.4 kPa and a temperature of the polymer solution concentrated inside was 240 ° C. (first stage drying).
Next, the concentrated solution was continuously led out from the thin film dryer, and further supplied to the same type of thin film dryer at a pressure of 1.5 MPa while maintaining the temperature at 240 ° C. The operating conditions were a pressure of 0.7 kPa and a temperature of 240 ° C. (second stage drying).
(Pelletized)
The polymer in a molten state is continuously derived from a thin film dryer, extruded from a die in a class 100 clean room, cooled with water, and then cut with a pelletizer (OSP-2, manufactured by Nagata Seisakusho) to form a resin composition (A ) Was obtained.
(Film forming)
A pellet of the resin composition (A) is a hanger manifold type T-die type melt extrusion molding machine (stationary type, manufactured by GSI Creos Co., Ltd.) equipped with a screw having a screw diameter of 20 mmφ, a compression ratio of 3.1, and L / D = 30. ) Was used to perform T-die molding under the following conditions to obtain a single-layer sheet (A) (thickness: 100 μm, haze: 17%).
<Molding conditions>
Die lip: 0.8mm
Molten resin temperature: 170 ° C
T die width: 300mm
T die temperature: 200 ° C
Cooling roll: 10 ° C
Cast roll: 10 ° C
Sheet take-up speed: 2.5 m / min Screw compression ratio: 3.1
From the obtained single layer sheet (A), the average major axis of the crystal nucleating agent, the average major axis of the spherulites, the water vapor barrier property, and the haze were evaluated. The evaluation results are shown in Table 1.

Example 2
In Example 1, instead of the crystal nucleating agent MS dietary talc, the crystal nucleating agent (manufactured by Ciba Specialty Chemicals; product name TINUVIN 144 (hindered amine compound); major axis 1 μm or less) 0.5 parts by weight was used. A film was produced and evaluated in the same manner as in Example 1.

Comparative Example 1
In Example 1, a film was produced and evaluated in the same manner as in Example 1 except that the crystal nucleating agent was not used.
Comparative Example 2
In Example 1, it replaced with the crystal nucleating agent MS food addition talc, and it carried out similarly to Example 1 except having set it as 0.5 weight part of crystal nucleating agents (Nippon Talc company make; MS-KY, talc; 24 micrometers in long diameters). Films were manufactured and evaluated.
The evaluation results of Examples and Comparative Examples are shown in Table 1.

From Table 1, the spherulite size is reduced by adding a predetermined crystal nucleating agent, and the water vapor permeability per 100 μm thickness is 0.40 g / m ² · day or less without deteriorating the haze, and the water vapor barrier It can be seen that a film having excellent properties can be obtained.

Claims (2)

A ring-opening polymerization of a monomer containing at least 90 to 100% by weight of 2-norbornene and 10 to 0% by weight of a substituent-containing norbornene, and obtained by hydrogenation, has a melting point of 110 to 145 ° C., gel permeation -Thickness composed of a norbornene-based ring-opening hydride having a weight average molecular weight (Mw) of 50,000 to 200,000 and a molecular weight distribution (Mw / Mn) of 1.5 to 10.0 by chromatography (GPC) A film having a water vapor transmission rate of 0.40 g / m ² · day or less at 100 μm and a haze of 20% or less at a thickness of 100 μm. The film according to claim 1, wherein the hydride of the norbornene-based ring-opening polymer is crystallized in the presence of a nucleating agent having an average major axis of 20 µm or less.