JP3143804B2 - Cast film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cast film containing a hydrogenated norbornene resin as a main component, having excellent heat resistance, electrical properties and light resistance, and being freely colored.

[0002]

2. Description of the Related Art Hydrogenated norbornene resins have excellent properties such as heat resistance, light resistance, transparency, and electrical properties.
Its application as a film to optical parts and building materials is being studied. A film is manufactured by extrusion molding and blowing of a hydrogenated norbornene resin, but the molding temperature is high because the softening temperature of the resin is high. For this reason, the film may be colored due to thermal deterioration and physical properties may be reduced, and it is difficult to obtain a good film. Further, when a composition having a high glass transition point such as a hydrogenated norbornene resin is formed into a film, it is necessary to cast at a high temperature in order to sufficiently evaporate the solvent. However, there is a problem that thermal deterioration is apt to occur.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a film having a uniform thickness without coloring and deterioration of physical properties, which are the problems described above.

[0004]

That is, the present invention relates to the present invention, wherein 50% to 100% by weight of the following component (a) and (b)
A film formed by casting a liquid obtained by dissolving or dispersing a polymer containing components in a solvent. Component (a): obtained by subjecting a monomer comprising at least one kind of norbornene derivative represented by the following general formula (I) or a monomer and a copolymerizable monomer copolymerizable therewith to ring-opening polymerization. A hydrogenated polymer obtained by further hydrogenating the resulting ring-opened polymer. General formula (I)

[0005]

Embedded image [In the formula, A and B are a hydrogen atom or a hydrocarbon group having a simplex of 1 to 10, X and Y are a hydrogen atom, a halogen atom or a monovalent organic group, and m is 0 or 1. ] Is provided. Component (b): a rubbery polymer and / or a thermoplastic resin other than component (a). Hereinafter, the present invention will be described specifically. <Component (a)> The component (a) forming the resin component in the film of the present invention is a monomer (hereinafter, referred to as “specific monomer”) composed of the norbornene derivative represented by the above general formula (I). A ring-opening polymer obtained by ring-opening copolymerization alone or with a copolymerizable monomer copolymerizable with a specific monomer using a metathesis polymerization catalyst, and further obtained by hydrogenation It is a hydrogenated polymer and is also referred to as “hydrogenated polymer (a)” below.

The molecular weight of the hydrogenated polymer (a) is a weight average molecular weight in terms of polystyrene and is usually 20,000 or less.
00 to 700,000, especially 30,000 to 50
Preferably it is 000. In the present invention, as the hydrogenated polymer (a), for example, JP-A-1-132
No. 626, a polymer obtained by hydrogenating a ring-opened (co) polymer of a compound having a norbornene ring. Among these specific monomers, X or Y in the above general formula (I) has the formula-(CH ₂ ) nC
The specific monomer which is a group represented by OOR ¹ is preferable in that the resulting polymer has a high glass transition temperature and a low hygroscopicity. In particular, this formula - (CH ₂₎ nCOO
It is preferable that ^one polar substituent consisting of the group represented by R ¹ be contained per molecule of the specific monomer, since the hygroscopicity of the obtained polymer is reduced. Also, the formula-(CH
₂₎ Among the groups represented by NCOOR ^1, preferably the glass transition temperature of the polymer obtained as those small values of n is increased, further n has a particular monomer is 0, its synthesis is easy This is preferred in that the obtained polymer has good properties.

In the above formula, R ¹ is a simple prime number 1 to 20
However, it is preferable in terms of decreasing the hygroscopicity of the obtained polymer as the number of simple elements increases. But,
From the viewpoint of the balance with the glass transition temperature of the obtained polymer, a chain alkyl group having 1 to 4 carbon atoms or a single prime number of 5
The above (poly) cyclic alkyl group is preferable, and a methyl group is particularly preferable. Further, the formula-(CH
₂ ) The specific monomer in which a hydrocarbon group having 1 to 10 units is simultaneously bonded as a substituent to the carbon atom to which the group represented by nCOOR ¹ is bonded decreases the glass transition temperature of the obtained polymer. This is preferable because it reduces the hygroscopicity without using any of them. In particular, the specific monomer in which the substituent is a methyl group is preferable in that the synthesis is easy. The ring-opening polymer according to the hydrogenated polymer (a) used in the present invention may be one obtained by subjecting a specific monomer to ring-opening polymerization alone. It may be one obtained by ring-opening copolymerization with a body. When a copolymerizable monomer is used as described above, the ratio of the specific monomer in the ring-opening polymer is at least 5 mol%, preferably at least 20 mol%. Examples of the copolymerizable monomer used include a monomer capable of ring-opening polymerization by a metathesis polymerization catalyst, and a partially polymerized low-polymer having a carbon-carbon double bond in a main chain of the polymer. Can be mentioned.

Among the above-mentioned specific monomers, a tetracyclododecene derivative in which m is 1 in the above general formula (I) is preferable in that a polymer having a high glass transition point can be obtained. In the general formula (I), among the tetracyclododecene derivatives in which m is 1, a preferred compound is
Carboxymethyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene, 5-carboxymethyl-bicyclo [2.
2.1] -2-heptene and the like. The specific monomer can also be copolymerized with a cyclic olefin compound. Specific examples of such a cyclic olefin compound include:
Cycloolefins such as cyclopentene, cyclooctene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene; bicyclo [2.2.1] -2-heptene, tricyclo [5.2.1.0 ^2,6 ] -8-decene, tricyclo [5.2.1.0 ^2,6 ] -3-decene,
Tricyclo [6.2.1.0 ^1,8 ] -9-undecene,
Tricyclo [6.2.1.0 ^1,8 ] -4-undecene,
Tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 .
0 ^9,13 ] -4-pentadecene, pentacyclo [6.6.
1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] −
11-pentadecene, dicyclopentadiene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] - pentadeca-4,11 poly cycloalkenes diene may be mentioned.

Further, the specific monomer is a carbon-carbon double bond in the main chain of a polymer such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene non-conjugated diene copolymer rubber, polynorbornene, and polypentenamer. Ring-opening polymerization in the presence of an unsaturated hydrocarbon polymer containing The method of ring-opening polymerization of a specific monomer and a copolymerizable monomer copolymerizable therewith and the method of hydrogenation include the same methods as those described in JP-A-1-132626. Can be. The hydrogenation rate of the resulting hydrogenated polymer (a) is usually 50% or more,
It is preferably at least 70%, more preferably at least 80%. A polymer having a hydrogenation ratio of less than 50% has a low light resistance of a film obtained due to a low hydrogenation ratio.

<Component (b)> In the present invention, in the hydrogenated polymer solution, a rubbery polymer and / or a thermoplastic resin other than the above-mentioned component (a) (hereinafter, collectively referred to as “component (b)”) ") May be added. The rubbery polymer used as the component (b) has a glass transition temperature of 0.
It is a polymer having a temperature of not more than 0 ° C. and includes a usual rubbery polymer and a thermoplastic elastomer. Examples of the rubbery polymer include an ethylene-α-olefin rubbery polymer;
Ethylene-α-olefin-polyene copolymer rubber; Copolymer of ethylene and unsaturated carboxylic acid ester such as ethylene-methyl methacrylate and ethylene-butyl acrylate; Copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate Polymers of alkyl acrylates such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate; polybutadiene, polyisoprene,
Styrene-butadiene or styrene-isoprene random copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene-
Diene rubbers such as (meth) acrylic acid alkyl ester copolymer, butadiene- (meth) acrylic acid alkyl ester-acrylonitrile copolymer, butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymer; butylene- There are isoprene copolymers and the like, and not only one kind thereof but also two or more kinds thereof can be used.

The rubbery polymer comprising the above rubbery polymer has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 5 to 2
00 is preferred. Examples of the thermoplastic elastomer used as the rubbery polymer include styrene-
Aromatic vinyl-conjugated diene block copolymers such as butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, low crystallinity Polybutadiene resin, ethylene-propylene elastomer, styrene-grafted ethylene-propylene elastomer, thermoplastic polyester elastomer,
Examples thereof include an ethylene ionomer resin. Of these thermoplastic elastomers, preferred are hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, and the like. JP-A-305814, JP-A-3-72512, JP-A-3-74409, and the like. The rubbery polymer is modified with a specific functional group such as an epoxy group, a carboxyl group, a hydroxyl group, an amino group, an acid anhydride group, an oxazoline group for the purpose of improving compatibility with the hydrogenated polymer (a). May be done. By including the rubbery polymer as the component (b), the finally obtained film can have more excellent impact resistance and ductility.

The thermoplastic resin used as the component (b) is a polymer having a glass transition temperature of 25 ° C. or higher. Specific examples include styrene-based resins (polystyrene, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer), acrylic resins, polycarbonate resins, and the like. By including the above thermoplastic resin as the component (b), the finally obtained film has excellent electric properties and light resistance. The amount of the component (b) that can be used is usually 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less of the hydrogenated polymer (a).
% By weight or less. In addition to the components (a) and (b), antioxidants such as 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,
6, dimethylphenol, 2,2-methylene-bis-
(4-ethyl-6-t-butylphenol), tris (di-nonylphenyl phosphite), an ultraviolet absorber,
For example, pt-butylphenyl salicylate, 2,2 '
-Dihydroxy-4-methoxy-benzophenone, 2-
(2'-dihydroxy-4'-m-octoxyphenyl) benzotriazole, lubricant (paraffinphenos,
Hardened oil), and an antistatic agent such as stearoazitopropyldimethyl-β-hydroxyethylammonium tolate can be added as necessary.

In the present invention, if necessary, the above hydrogenated polymer (a) mixed with the component (b) and additives is dissolved or dispersed in a solvent to form a liquid having an appropriate concentration, and then poured onto a suitable carrier. A film is produced by a cast molding method in which the film is applied or coated, dried, and then separated from the carrier. Here, depending on the thickness of the film, the proportion of the hydrogenated polymer (a) in the solution is usually 0.01 to 30% by weight, preferably 0.1 to 20% by weight. Examples of the solvent include aromatic compounds such as benzene, toluene and xylene, butyl acetate, tetrahydrofuran, dimethoxyethane, chloroform, methylene dichloride, and methyl ethyl ketone, which are generally used as solvents. Further, a mixed solvent thereof may be used. Further, a mixture of a solvent that dissolves the hydrogenated polymer (a) and a solvent that does not dissolve the hydrogenated polymer (a) may be used. In addition, water and oils and fats may be used as those which do not dissolve the hydrogenated polymer (a). When the hydrogenated polymer (a) is dissolved in a solvent, it may be at room temperature or at a high temperature. A thorough stirring results in a homogeneous solution.
In the case of coloring, a color may be added to the solution.

As a method for producing a film having a uniform thickness, the above solution is extruded from a die having a constant width onto a metal drum, a steel vent, a polyester film, a Teflon belt or the like, and dried at a temperature and for a time. In addition, a solution having a uniform thickness is produced by applying the solution by spraying, brushing, rolling, spin coating, dipping or the like, and arbitrarily applying temperature and time. In addition, when a desired film thickness cannot be obtained by one application, it is necessary to repeatedly apply. The thickness of the film of the present invention is usually 0.5 μm
To 5 mm, preferably 1 μm to 2 mm, and more preferably 5 μm to 0.5 mm.

In the present invention, a more favorable cast film can be formed by subjecting the cast film obtained as described above to the following treatment. That is, after contacting the cast film with a mixed solvent consisting of 25 to 100% by weight of a good solvent with respect to the hydrogenated polymer (a) and 0 to 75% by weight of a poor solvent with respect to the hydrogenated polymer (a), This is a step of bringing into contact with a solvent composed of a poor solvent for (a). Here, as the good solvent for the hydrogenated polymer (a), a solvent having a boiling point of 100 ° C. or lower is preferable, and examples thereof include chloroform and tetrahydrofuran. Ethanol and the like can be mentioned.

The temperature at which the cast film is brought into contact with a mixture of a good solvent and a poor solvent or a poor solution is usually 2
The temperature is 5 to 80C, preferably 25 to 60C, and the immersion time is usually about 1 to 60 seconds. In the present invention, the cast film is swelled by bringing the cast film into contact with a mixed solution composed of a good solvent and a poor solvent, so that the molecules of the polymer forming the cast film can be spread. As a result, a low molecular weight compound can be transferred from a polymer molecule to a mixture of a poor solvent and a good solvent. After transferring the low molecular weight compound to the mixture of the poor solvent and the good solvent, the spread between the polymer molecules can be restored by contacting the cast film with the poor solvent. By performing this operation, a cast film having higher heat resistance can be formed.

[0017]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these. The measurement and evaluation of each characteristic were performed according to the following conditions. Tensile strength and elongation (TS, TE): ASTM D63
8 Total light transmittance (Tt): ASTM D1003 Yellowness (YI) Heat resistance: DSe method (Differntial Scanning Calorymeter)
), The glass transition temperature was measured at a temperature rise of 20 ° C./min. Electrical properties: Volume resistivity (Ωcm) ASTM D257 Lightfastness: Discoloration (ΔE) after 500 hours of fade meter (63 ° C., no rain) was measured.

Examples 1-2 Preparation of Component (a) Polymer a-1 A specific monomer represented by the following structural formula (1), 8-methyl-8-carboxymethyl, was placed in a reaction vessel purged with nitrogen gas. Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 500 g and 1,2-dichloroethane 200 ml
3.8 g of 1-hexene as a molecular weight regulator, 91.6 ml of a chlorobenzene solution having a concentration of 0.05 M / liter of tungsten hexachloride as a catalyst, and 1,2- (a) of a concentration of 0.1 M / liter of paraaldehyde as a catalyst. 68.7 ml of a dichloroethane solution and 37 ml of a toluene solution having a concentration of 0.5 M / liter of triisobutylaluminum were added and reacted at 60 ° C. for 10 hours to obtain an intrinsic viscosity (η _inh ) of 0.56 dl / g (in chloroform. 30
(C, 0.5 g / dl) 450 g of a ring-opened polymer was obtained. This ring-opened polymer was dissolved in 9000 ml of tetrahydrofuran, and the palladium concentration was 5% by polymerization of palladium-polymer.
45 g of alumina catalyst was added, and the pressure of hydrogen gas was increased to 100 k.
g / cm ² and hydrogenated at 150 ° C. for 5 hours. After the hydrogenation reaction, the catalyst was filtered off, and the filtrate was poured into a large excess of methanol acidic with hydrochloric acid to produce a hydrogenated polymer a-1. The hydrogenation rate of this polymer a-1 was substantially 100%. Structural formula (1)

[0019]

Embedded image A cyclohexane solution (concentration: 4% by weight) of the polymer (a-1) is passed through a die to form a liquid having a uniform thickness.
To produce a film having a thickness of 25 μm. Also,
A film having a thickness of 260 μm was manufactured by changing the width of the dice. Test pieces were cut off from these films, and physical properties were measured (Table 1). Comparative Examples 1-2 Using a 50 m / m extruder, a film of the polymer (a-1) having a thickness of 25 µm and 260 µm was formed at a forming temperature of 310 ° C, and physical properties were measured. Example 3 Polymer (a-1) / thermoplastic elastomer = 90/10
From a cyclohexane solution (concentration: 5%) of (wt%), a film having a thickness of 30 µm was produced. Thermoplastic elastomer: Septon 2002 (made by Kuraray)

Comparative Example 3 In the same manner as in Comparative Example 1, a film was produced from the material of Example 3. Example 4 Polymer (a-1) / polypropylene (manufactured by Mitsubishi Yuka, J5
010B) = 80/20 (% by weight) in xylene to 110
A 5% by weight solution was prepared at 5 ° C., and a 15 μm film was formed by spin coating, and physical properties were measured. Comparative Example 4 A film was prepared from the polymer (a-1) / polypropylene = 40/60 (% by weight) in the same manner as in Example 4.

[0021]

[Table 1]

Examples 5 and 6 A 6% by weight toluene solution of the polymer (a-1) was passed through a die to obtain a liquid having a uniform thickness, which was dried at 200 ° C. to have a thickness of 30 μm (Example 5) and 150 μm. (Example 6)
Was formed. Next, the cast film was immersed in a mixed solvent of 50% by weight of tetrahydrofuran and 50% by weight of methanol at 60 ° C. for 5 minutes, and then immersed in methanol at 60 ° C. for 5 minutes and dried. The tensile strength, total light transmittance, yellowness, and heat resistance of the obtained cast film were measured. Table 2 shows the results.

Example 7 A 5% by weight toluene solution of a polymer component composed of 90% by weight of the polymer (a-1) and 10% by weight of a hydrogenated product of a styrene-isoprene block copolymer was passed through a die to obtain a uniform thickness. And dried at 200 ° C to a thickness of 35μ.
m of cast film was formed. Next, the cast film was immersed in a mixed solvent composed of a good solvent and a poor solvent and a poor solvent in the same manner as in Example 5, and dried. Tensile strength of the obtained cast film, total light transmittance, yellowness,
And heat resistance were measured. Table 2 shows the results.

[0024]

[0025]

The film of the present invention containing a hydrogenated norbornene resin as a main component has excellent heat resistance, electrical properties, light resistance, and mechanical properties, and is used as an insulating material for optical parts and electric / electronic related materials. It is valid.

Claims (1)

(57) [Claims] 1. A film formed by casting a liquid in which a polymer containing 50 to 100% by weight of the following component (a) and 0 to 50% by weight of the component (b) is dissolved or dispersed in a solvent. Component (a): obtained by subjecting a monomer comprising at least one kind of norbornene derivative represented by the following general formula (I) or a monomer and a copolymerizable monomer copolymerizable therewith to ring-opening polymerization. A hydrogenated polymer obtained by further hydrogenating the resulting ring-opened polymer. General formula (I) [In the formula, A and B are a hydrogen atom or a hydrocarbon group having a simplex of 1 to 10, X and Y are a hydrogen atom, a halogen atom or a monovalent organic group, and m is 0 or 1. Component (b): a rubbery polymer and / or a thermoplastic resin other than component (a).