JPH10287732A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. which has a good compatibility and heat stability while retaining properties required of an optical material, such as high clarity, heat resistance, and Tg, by compounding a hydrogenated ring- opening norbornene polymer with a hydrogenated hydrocarbon resin having a low Gardener color vague and a specified softening point. SOLUTION: Examples of a norbornene monomer are nonbornene, dimethanooctahydronaphthalene, trimethanodecahydroanthracene, and their derivs., and when the compsn. is used as the material for optical transparent substrates, a tetra- or pentacyclic compd. having a Tg of 100 deg.C or higher is esp. pref. The ring-opening polymer of a norbornene monomer used pref. has a wt. average mol.wt. of 10,000 or higher, still pref. 20,000-200,000. The method for the polymn. and hydrogenation is not specifically limited. The hydrogenated hydrocarbon resin used, excellent in heat stability, has a Gardner color value (after 24 hr at 180 deg.C) of 1 or lower and a softening point of 105-135 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition. The resin composition of the present invention can be used for various optical transparent substrates, for example, optical disk substrates (substrates, hubs, spacers, etc.) lenses, optical fibers, sealing materials for light-emitting diodes, various cover glasses, window glasses, irons. Water tanks, microwave oven supplies, liquid crystal display substrates, printed circuit boards,
It can be used for transparent conductive sheets, films, syringes, pipettes, animal gauges, housings, films, helmets and the like.

[0002]

2. Description of the Related Art A hydride of a ring-opening polymer of a norbornene-based monomer is a transparent thermoplastic resin, and has a high Tg and excellent heat resistance. Used for transparent substrates and the like.

[0003] In general, such optical transparent substrates are thin and precisely molded by injection molding. Therefore, it is necessary to reduce the melt fracture and raise the resin temperature at the time of injection to sufficiently lower the resin viscosity. In addition, since the thickness is small, the residence time in the cylinder is prolonged, and an excessive heat history is liable to occur. For this reason, the resin is decomposed or deteriorated, resulting in a decrease in mechanical strength of the obtained product, and further, there is a problem that coloring, scorching and the like are mixed. Further, there are problems that minute voids are generated in a substrate obtained by injection molding, a phenomenon called clouding called flash on the surface of the substrate, and silver streaks called silver streaks are generated.

In order to solve this problem, a hydride of a ring-opened polymer of a norbornene monomer is added to a hydride having a molecular weight of 200-3.
A resin composition having improved thin-wall precision moldability by blending a liquid hydrocarbon compound at room temperature of 000 and plasticizing the resin has been proposed (JP-A-63-23102). However, in this resin composition, since a low-molecular-weight liquid hydrocarbon compound is used, the strength and Tg of the resin composition are lower than those of a hydride of a ring-opened polymer of a norbornene-based monomer. There is a problem that the hydrocarbon compound bleeds on the surface of the composition. Further, the hydride of the ring-opened polymer of the norbornene-based monomer has a softening point of 8
A resin composition containing a light-colored hydrocarbon resin at 0 ° C. or higher has also been proposed (JP-A-3-12448). According to this resin composition, the above problem can be solved to some extent. However, there are problems such as a decrease in Tg of the resin composition obtained by this method, insufficient compatibility, a decrease in heating stability, and the like, and a satisfactory resin composition is obtained. I can't say.

[0005]

SUMMARY OF THE INVENTION The present invention uses a hydride of a ring-opening polymer of a norbornene-based monomer as a base resin, has excellent thin-wall precision moldability, has a high Tg similar to that of the base resin, and has a high phase stability. An object is to provide a resin composition having good solubility and heat stability.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, the hydride of a ring-opened polymer of a norbornene-based monomer has the following specific softening points. It has been found that the above object can be achieved by a resin composition containing a specific hydrogenated hydrocarbon resin.

That is, the present invention provides a hydride of a ring-opened polymer of a norbornene-based monomer and a hydrogenated hydrocarbon resin having a softening point of 105 to 135 ° C. which exhibits a Gardner of 1 or less even when left at 180 ° C. for 24 hours. The present invention relates to a resin composition comprising:

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION A hydride of a ring-opened polymer of a norbornene-based monomer of the present invention can be obtained by hydrogenating a polymer obtained by polymerizing a norbornene-based monomer by an ordinary method.

Examples of the norbornene-based monomer include norbornene, dimethanooctahydronaphthalene,
Trimethanododecahydroanthracene, and alkyl-substituted and alkylidene-substituted products thereof; dicyclopentadiene, 2,3-dihydrodicyclopentadiene, dimethanooctahydrobenzoindene, dimethanodecahydrobenzoindene, dimethanodecahydrofluorene, And alkyl-substituted products thereof. Further, these norbornene-based monomers may have a polar substituent such as a halogen atom, an ester-type residue, an ether-type residue, or a cyano group. These norbornene monomers may be used alone or in combination of two or more. Ring opening polymer of norbornene-based monomer and T of its hydride
In order to make g more than 100 ° C., among these norbornene-based monomers, tetracyclic or pentacyclic ones are used, or these are used as a main component and used in combination with bicyclic or tricyclic monomers. Is preferred.

Further, in addition to the norbornene-based monomer, other cycloolefins such as cyclopropene, cyclobutene, cyclopentene, cycloheptene, cyclooctene, and 5,6-dihydrodicyclopentadiene may be used in combination as a copolymer component. Can also. The copolymer component can be used in an amount of usually 30% by weight or less based on the total weight of the monomers constituting the ring-opened polymer of the norbornene-based monomer.

The method for polymerizing the norbornene-based monomer is not particularly limited, but it is preferable to use a well-known metathesis catalyst as a polymerization catalyst. Examples of the metathesis catalyst include, for example, a catalyst system combining a group IV-VII transition metal compound and a group I-III group organometallic compound, a combination of a group VIII metal halide and an alcohol, and various complexes of these metals. And metal carbene. Among such polymerization catalysts, a catalyst system containing a transition metal compound such as titanium tetrahalide and an organic metal such as an organoaluminum compound, and a combination of a third component such as an aliphatic or aromatic tertiary amine with the catalyst system. Catalyst systems are preferred.

The polymerization can be carried out without using a solvent, but usually, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, and alicyclic hydrocarbons such as cyclohexane are usually used. And an inert organic solvent such as a halogenated hydrocarbon such as dichloroethane. Usually, the polymerization temperature is from -20 ° C to 10 ° C.
0 ° C. and the polymerization pressure are selected from the range of 0 to 5 kg / cm ² . In the polymerization, an acyclic olefin may be used as a molecular weight regulator. As the acyclic olefin, α-olefins such as 1-butene, 1-pentene and 1-hexene are preferred.

The ring-opened polymer of the norbornene monomer is
When the hydride is used for the material of the optical transparent substrate,
Usually, Tg is preferably 100 ° C. or higher. The lower limit of Tg is more preferably 120 ° C, furthermore preferably 140 ° C, and the upper limit is more preferably 200 ° C, furthermore preferably 180 ° C.
The weight average molecular weight is about 10,000 or more, preferably 20,000 to 200,000.

The method for hydrogenating the ring-opened polymer of the norbornene-based monomer is not particularly limited, but is usually carried out in the presence of a hydrogenation catalyst. As the hydrogenation catalyst, various catalysts generally used for hydrogenating olefin compounds can be used. For example, Wilkinson complex, cobalt acetate / toluethylaluminum, nickel acetylacetonate /
Triisobutylaluminum, palladium-carbon,
Ruthenium-carbon, nickel-diatomaceous earth and the like can be mentioned. The hydrogenation reaction is carried out in a homogeneous or heterogeneous system depending on the type of the catalyst, usually under a hydrogen pressure of about 1 to 200 kg / cm ^{2 and at} a temperature of about 0 to 250 ° C.

The hydrogenation rate of the ring-opened polymer of the norbornene-based monomer is preferably 90% or more of the olefinic double bond from the viewpoints of heat resistance and light deterioration resistance of the obtained hydride.
It is preferably at least 95%, particularly preferably at least 99%. The hydride of the ring-opened polymer of the norbornene-based monomer thus obtained is substantially amorphous, has excellent transparency, dimensional stability, heat resistance, water absorption, and hardly recognizes moisture permeability.

In the present invention, a hydrogenated hydrocarbon resin exhibiting a Gardner color of 1 or less even when left at 180 ° C. for 24 hours is blended with the hydride of the ring-opened polymer of the norbornene-based monomer to form a resin composition. To manufacture. 18
Having a Gardner color of 1 or less even when left at 0 ° C. for 24 hours means that the composition has excellent heating stability. The hydrogenated hydrocarbon resin of the present invention is obtained by hydrogenating various hydrocarbon resins, and has such heat stability. The hydrogenated hydrocarbon resin of the present invention exhibits a Gardner color of 1 or less even at room temperature.
Preferably, it is a hydrogenated hydrocarbon resin having a Hazen color of 50 or less at room temperature.

Examples of the hydrogenated hydrocarbon resin having excellent heat stability include a hydride of a C9 petroleum resin having a hydrogenation rate of an aromatic ring of 90% or more. Such a C9 petroleum resin is obtained by cationically polymerizing a polymerizable monomer in a C9 fraction obtained by cracking naphtha. Note that C
The nine fractions usually contain about 40% by weight of vinyl toluene and indene as polymerizable monomers, respectively, and the remaining about 20% by weight is composed of styrene, α-methylstyrene, other compounds having a high boiling point, and the like. The reason why the hydrogenation rate of the aromatic ring of the C9 petroleum resin is set to 90% or more is that the C9 petroleum resin satisfies the heating stability and makes the obtained resin composition colorless and transparent.

Examples of the hydrogenated hydrocarbon resin having excellent heat stability include a hydride of a vinyl toluene-rich C9 petroleum resin containing 50% by weight or more and less than 20% by weight of indene as a polymerization monomer component. Can be Such a vinyltoluene-rich C9 petroleum resin is obtained by distilling a normal C9 fraction to remove indenes and high-boiling compounds in the C9 fraction, so that the vinyltoluene content in the polymerizable monomer is 50% by weight. % Or more, and prepared by cationic polymerization of those prepared so that the indene content is 20% by weight or less. The content of vinyltoluene is preferably at least 55% by weight, more preferably at least 60% by weight, and more preferably. The content of indene is preferably at most 15% by weight, more preferably as small as possible. The hydrogenation rate of vinyl toluene-rich C9 petroleum resin is not particularly limited, and the hydrogenation rate of the aromatic ring does not necessarily need to be 90% or more. From the viewpoint of compatibility with the hydride of the ring-opening polymer of the norbornene-based monomer, the hydrogenation rate of the aromatic ring is preferably 30 to 90%. When the vinyl toluene content is higher than the ordinary C9 fraction and the indene content is low, even if the hydrogenation rate of the aromatic ring is low, the color tone and the heat stability are improved because of the homopolymer of indene. It is easier to color by heating than vinyltoluene homopolymer, and further, the fraction on the higher boiling point side than the boiling point of indene is not structurally identified but is inferior in coloring component and thermal stability This is probably because it is likely to be included.

Examples of the hydrogenated hydrocarbon resin having excellent heat stability include hydrides of terpene resins. The hydrogenation rate is not particularly limited.

The hydrogenation of the hydrocarbon resin (C9 petroleum resin, vinyltoluene-rich C9 petroleum resin, terpene resin, etc., hereinafter the same) is carried out by appropriately adjusting the hydrogenation conditions in the presence of a hydrogenation catalyst. Then, the hydrogenation rate of the aromatic ring or the like is set to a predetermined range. As the hydrogenation catalyst, various catalysts such as metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium, rhenium and molybdenum, and metal compounds such as oxides and sulfides thereof can be used. Further, such a hydrogenation catalyst may be used by being supported on a carrier such as alumina, silica (diatomaceous earth), carbon, and titania having a large surface area and being porous. Among these hydrogenation catalysts, a nickel-diatomaceous earth catalyst containing an alkaline earth metal or iron is preferable because the hydrogenation rate can be easily adjusted within a predetermined range, and a catalyst excellent in color tone can be obtained. Examples of such a hydrogenation catalyst include a stabilized nickel-diatomaceous earth catalyst (“N-113”, manufactured by JGC Chemicals, Ltd.). The amount of the hydrogenation catalyst used is 0.1% of the hydrocarbon resin.
It is about 1 to 5% by weight, preferably 0.1 to 3% by weight.

The conditions of the hydrogenation reaction are such that the hydrogenation pressure is usually 3
0~300kg / cm ² in the range of about, the reaction temperature is usually 2
The temperature is adjusted appropriately in the range of about 00 to 300 ° C. Preferably, the hydrogenation pressure is from 100 to 200 kg / cm ² and the reaction temperature is from 240 to 300 ° C. The reaction time is generally about 1 to 7 hours, preferably 2 to 6 hours.
The hydrogenation reaction is carried out while melting the C9 petroleum resin or dissolving it in a solvent. As the solvent, cyclohexane, n-hexane, n-heptane, decalin and the like can be used. In addition, regarding the amount of the catalyst used and the reaction time,
The case where a batch system was adopted as the reaction mode was described, but the reaction system was a flow system (fixed bed system, fluidized bed system, etc.).
Can also be adopted.

The hydrogenated hydrocarbon resin of the present invention has a softening point of 105 to 135 ° C. When the softening point of the hydrogenated hydrocarbon resin is lower than 105 ° C., when the hydrogenated hydrocarbon resin is blended with a hydride of a ring-opening polymer of a norbornene-based monomer, the T of the resulting resin composition is reduced.
g becomes lower than the hydride of the ring-opened polymer of the norbornene-based monomer as the base resin, and the mechanical strength and heat resistance of the resin composition may be reduced. On the other hand, when the softening point exceeds 135 ° C., the compatibility between the hydrogenated hydrocarbon resin and the hydride of the ring-opening polymer of the norbornene-based monomer is poor, and a transparent resin composition cannot be obtained. From these viewpoints, the upper limit of the softening point of the hydrogenated hydrocarbon resin is 1
It is preferably 30 ° C. The weight average molecular weight of the hydrogenated hydrocarbon resin of the present invention is usually 200 to 6000.
Degree, preferably about 250-6000.

The compounding ratio of the hydride of the ring-opening polymer of the norbornene monomer to the hydrogenated hydrocarbon resin is 100
The latter is about 0.01 to 20 parts by weight relative to parts by weight.
Preferably it is 0.1 to 15 parts by weight. If the blending ratio of the hydrogenated hydrocarbon resin is too small, the effect of improving the thin wall precision moldability is small, and if it is too large, the mechanical strength tends to decrease. Further, the resin composition of the present invention may contain additives such as an antioxidant.
For mixing the hydride of the ring-opening polymer of the norbornene-based monomer and the hydrogenated hydrocarbon resin, ordinary methods such as melt-kneading, coprecipitation from a solution, and drying can be used.

[0024]

The resin composition of the present invention is excellent in thin wall precision moldability, has a high Tg similar to that of a hydrogenated ring-opened polymer of a norbornene-based monomer as a base resin, and has compatibility and heat stability. Good nature. Incidentally, the resin composition of the present invention,
In press molding, extrusion molding, thermoplastic resin processing such as rotational molding, it shows excellent properties of surface smoothness and transferability,
Particularly suitable for injection molding, which is an important processing method.

[0025]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following Examples and Comparative Examples, parts and% are by weight unless otherwise specified.

Production Example 1 (Production of hydrogenated hydrocarbon resin) Petrozine 120 (manufactured by Mitsui Petrochemical Co., Ltd., softening point 123 ° C, weight average molecular weight 185) as C9 petroleum resin
0, the composition of the polymerization component in the C9 petroleum resin by pyrolysis gas chromatography was 37 g of vinyl toluene, 39% of indene, 4% of styrene, 3% of α-methylstyrene, and 17% of other) 1000 g of commercially available stabilized nickel Catalyst N
-113 (manufactured by Nikki Chemical Co., Ltd.) was placed in a 2-liter rotary stirring type autoclave, and hydrogen gas pressure was 200 kg.
The reaction was carried out at a reaction temperature of 265 ° C./cm ^{2 for} 7 hours.
After removing the reaction product at room temperature, cyclohexane 400
0 g and the catalyst was filtered off by filtration. The obtained colorless and transparent solution was placed in a 10-liter flask, and finally the low-boiling fraction in cyclohexane and the hydrogenated hydrocarbon resin was removed under the conditions of 200 ° C., 20 Torr and 20 minutes, and the softening point was 125 ° C. 994 g of a hydrogenated hydrocarbon resin (a) having a color tone of 20 Hazen, a weight average molecular weight of 1950, and a hydrogenation ratio of an aromatic ring of 95% were obtained.

The hydrogenation rate was calculated from the H-spectral area of the aromatic ring appearing at about 7 ppm in ¹ H-NMR of the raw material resin and the obtained hydrogenated resin according to the following formula. Hydrogenation rate = ｛1- (spectral area of hydrogenated resin /
Spectral area of raw material resin) x 100 (%). The softening point is based on the ring and ball method of JIS K 2531. In the case of Hazen color, the resin is made 50% in toluene solution, and the color is visually compared with the Hazen standard color (H).
In the case of Gardner color, the resin was melted at 180 ° C. and visually judged by Gardner standard color (G). Pyrolysis gas chromatography is a model "GP-10"
28 (Yanagimoto Manufacturing Co., Ltd.) ", column" DB-5 (J &
W company)), and measured at a thermal decomposition temperature of 600 ° C.

Production Example 2 (Production of Hydrogenated Hydrocarbon Resin) C9 fraction 2000 g (polymerization composition by gas chromatography was 59% vinyltoluene, 10% indene,
Styrene 8%, α-methylstyrene 5%, other 18
%) Is cationically polymerized in the presence of a boron trifluoride catalyst,
1,050 g of a C9 petroleum resin having a softening point of 113 ° C. and a weight average molecular weight of 1910 was obtained. Obtained C9 petroleum resin 100
0 g and 10 g of a commercially available stabilized nickel catalyst N-113 (manufactured by Nikki Chemical Co., Ltd.) were placed in a 2-liter rotary stirring autoclave, and reacted at a hydrogen gas pressure of 200 kg / cm ² and a reaction temperature of 265 ° C. for 7 hours. Was. After the reaction product was taken out at room temperature, it was dissolved in 4000 g of cyclohexane, and the catalyst was separated by filtration. The obtained colorless and transparent solution is
In a 10 liter flask,
Under a condition of 0 Torr and 20 minutes, cyclohexane and low boiling point distillates in the hydrogenated hydrocarbon resin are removed, and the softening point 115
° C, color tone 20 Hazen, weight average molecular weight 2020, hydrogenated hydrocarbon resin (b) 992 having an aromatic ring hydrogenation rate of 65%
g was obtained.

Production Example 3 (Production of Hydrogenated Hydrocarbon Resin) Petrozine 140 (manufactured by Mitsui Petrochemical Co., Ltd., softening point 139 ° C., weight average molecular weight 214) as a C9 petroleum resin
0, the polymerization component composition in the C9 petroleum resin by pyrolysis gas chromatography is 35 g of vinyl toluene, 40% of indene, 3% of styrene, 3% of α-methylstyrene, and 19% of other) 1000 g of commercially available stabilized nickel Catalyst N
-113 (manufactured by Nikki Chemical Co., Ltd.) was placed in a 2-liter rotary stirring type autoclave, and hydrogen gas pressure was 200 kg.
The reaction was carried out at a reaction temperature of 265 ° C./cm ^{2 for} 7 hours.
After removing the reaction product at room temperature, cyclohexane 400
0 g and the catalyst was filtered off by filtration. The obtained colorless and transparent solution was placed in a 10-liter flask, and finally the low-boiling fraction in cyclohexane and the hydrogenated hydrocarbon resin was removed at 220 ° C. and 20 Torr for 20 minutes.
Softening point 141 ° C, color tone 20 Hazen, weight average molecular weight 2
There were obtained 994 g of a hydrogenated hydrocarbon resin (c) having a hydrogenation rate of 150% and an aromatic ring hydrogenation rate of 93%.

Production Example 4 (Production of Hydrogenated Hydrocarbon Resin) Petrozine 100 (manufactured by Mitsui Petrochemical Co., Ltd., softening point 100 ° C., weight average molecular weight 140) was used as a C9 petroleum resin.
0, the composition of the polymerization component in the C9 petroleum resin by pyrolysis gas chromatography was 40 g of vinyl toluene, 35% of indene, 7% of styrene, 4% of α-methylstyrene, and 14% of other) 1000 g of commercially available stabilized nickel Catalyst N
15 g of -113 (manufactured by Nikki Chemical Co., Ltd.) was placed in a 2-liter rotary stirring type autoclave, and hydrogen gas pressure was 200 kg.
The reaction was carried out at a reaction temperature of 290 ° C./cm ^{2 for} 5 hours.
After removing the reaction product at room temperature, cyclohexane 400
0 g and the catalyst was filtered off by filtration. The obtained colorless and transparent solution was placed in a 10-liter flask, and finally the low-boiling fraction in cyclohexane and the hydrogenated hydrocarbon resin was removed at 200 ° C. and 20 Torr for 20 minutes.
Softening point 91 ° C, color tone 20 Hazen, weight average molecular weight 13
20, hydrogenated hydrocarbon resin 9 having a hydrogenation rate of 97% of aromatic ring
94 (d) g were obtained.

Production Example 5 (Production of Hydrogenated Hydrocarbon Resin) Petrozine 120 (manufactured by Mitsui Petrochemical Co., Ltd., softening point 123 ° C., weight average molecular weight 185) was used as a C9 petroleum resin.
0, the polymerization component composition in C9 petroleum resin by pyrolysis gas chromatography is 37 g of vinyltoluene, 39% of indene, 4% of styrene, 3% of α-methylstyrene, and 17% of other) 1000 g of commercially available stabilized nickel Catalyst N
13 g of -113 (manufactured by Nikki Chemical Co., Ltd.) was placed in a 2-liter rotary stirring type autoclave, and hydrogen gas pressure was 200 kg.
The reaction was carried out at a reaction temperature of 265 ° C./cm ^{2 for} 5 hours.
After removing the reaction product at room temperature, cyclohexane 400
0 g and the catalyst was filtered off by filtration. The obtained colorless and transparent solution was placed in a 10-liter flask, and finally the low-boiling fraction in cyclohexane and the hydrogenated hydrocarbon resin was removed under the conditions of 200 ° C., 20 Torr and 20 minutes, and the softening point was 114 ° C. 989 g of a hydrogenated hydrocarbon resin (e) having a color tone of 40 Hazen, a weight average molecular weight of 1820, and a hydrogenation ratio of an aromatic ring of 70% were obtained.

(Heating stability): Hydrogenated hydrocarbon resins (a) to (e) obtained in Production Examples 1 to 5 and hydrides of terpene resins (Clearon P-125, manufactured by Yashara Chemical Co., Ltd., softening A test tube was charged with 5 g each of a point 125 ° C. and a color tone of 20 Hazen, hereinafter referred to as a hydrogenated hydrocarbon resin (f). Table 1 shows the results.

Production Example 6 (Production of hydride of ring-opened polymer of norbornene-based monomer) Under a nitrogen atmosphere, 3.5 liters of dehydrated toluene and 3.5 liters of dehydrated methyltetracyclododecene ( (MTD) 1.5 liter, 1-hexene 100 ml, toluethyl aluminum 0.225 mol, toluethylamine 0.675 mol, titanium tetrachloride 0.045 mol were added and reacted at room temperature for 1 hour. The reaction was stopped with a mixed solution of isopropyl alcohol and aqueous ammonia, and an antioxidant (Irganox 1010,
The product was coagulated with a large amount of isopropyl alcohol in which Ciba Geigy Co., Ltd. was dissolved, and dried at 60 ° C. for one day to obtain a ring-opened polymer. The obtained ring-opened polymer was dissolved in cyclohexane to give a 10% concentration solution, and a 5% palladium-supported
5 parts of a Bonn catalyst was added to 100 parts of the ring-opening polymer,
The hydrogenation reaction was performed at a hydrogen pressure of 60 kg / cm ^{2 at a} temperature of 180 ° C. for 4 hours. After the catalyst was removed by filtration, isopropyl alcohol 5 was added to a 10-liter container equipped with a stirrer.
The polymer was coagulated several times while dropping 2.5 liters of cement over 30 minutes while stirring at 200 rpm, and each was vacuum-dried at 60 ° C. for one day. The hydrogenation rate of the obtained hydride is
It was almost 100%. In addition, from high performance liquid chromatography, the molecular weight of the hydride was 28,000 and the molecular weight distribution was Mw / Mn 2.3. The glass transition temperature (Tg) from DSC is 152 ° C.
In A, the loss on heating up to 350 ° C. was 1%.

Examples 1 to 3 and Comparative Examples 1 to 3 (Preparation of Pellets) As shown in Table 1, 100 parts of the hydride of the ring-opened polymer obtained in Production Example 6 was added to an antioxidant (Irga Knox 10
10, Ciba Geigy) and 5 parts of the hydrogenated hydrocarbon resins (a) to (f) obtained in Production Examples 1 to 5. After sufficiently stirring and mixing the mixture with a Henschel mixer, the mixture was pelletized at 230 ° C. with a twin-screw extruder. The Tg of the resin composition was measured by DSC. Table 1 shows the results.

(Production of Plate Molded Product) Using the above pellets, injection molding was performed at a resin temperature of 300 ° C. and a mold temperature of 110 ° C. to form a plate having a size of 50 × 58 mm and a thickness of 1.0 mm. In addition, a hydride of the ring-opened polymer of the norbornene-based monomer obtained in Production Example 6 was formed into a molded product by the same method. The obtained molded product was subjected to the following tests. Table 2 shows the results.

(Evaluation of Injection Molded Sheet) Mechanical strength: A drop test of the injection molded plate was performed from a height of 1 m, and the presence or absence of cracks and chips was observed. Presence or absence of flash: The surface of the injection-molded product plate was visually determined. Degradability: The degree of degradation of the polymer at the time of injection molding was expressed by gel permeation chromatography (GPC) to determine the rate of change in molecular weight before and after injection molding.

(Appearance) The compatibility and color tone of the resin composition were evaluated by visual judgment. As for transparency, the total light transmittance was measured.

[0038]

[Table 1]

[0039]

[Table 2]

As shown in Tables 1 and 2, the resin compositions of the present invention shown in Examples 1 to 3 have excellent thin film precision moldability, good heat resistance (high Tg), and are colorless and transparent in appearance. Compatibility,
Excellent color tone. On the other hand, the hydrogenated hydrocarbon resin having a higher softening point than the hydrogenated hydrocarbon resin of the present invention (Comparative Example 1) has a low turbidity in appearance due to its low compatibility, and the total light transmittance also decreases. Further, the hydrogenated hydrocarbon resin having a softening point lower than that of the hydrogenated hydrocarbon resin of the present invention (Comparative Example 2) lowers the Tg of the resin composition by 10 ° C. or more, thereby lowering the heat resistance. In addition, the hydrogenated hydrocarbon resin having poor heat stability (Comparative Example 3) causes the film substrate to be somewhat colored, and the total light transmittance also decreases.

Claims (5)

[Claims] 1. A hydride of a ring-opened polymer of a norbornene-based monomer, and a softening point of 105 to 105 having a Gardner color of 1 or less even when left at 180 ° C. for 24 hours.
A resin composition comprising a hydrogenated hydrocarbon resin at 135 ° C. 2. The resin composition according to claim 1, wherein the hydrogenated hydrocarbon resin is a hydride of a C9 petroleum resin having a hydrogenation rate of an aromatic ring of 90% or more. 3. The hydrogenated hydrocarbon resin contains at least 50% by weight of vinyltoluene as a polymerization monomer component and at least 2% of indene.
The resin composition according to claim 1, which is a hydride of a C9 petroleum resin containing less than 0% by weight. 4. The resin composition according to claim 1, wherein the hydrogenated hydrocarbon resin is a hydride of a terpene resin. 5. A hydrogenated hydrocarbon resin is added to 100 parts by weight of a hydride of a ring-opening polymer of a norbornene-based monomer in an amount of 0.01%.
The resin composition according to any one of claims 1 to 4, wherein the resin composition comprises from 20 to 20 parts by weight.