A resin composition and a molded article formed by molding the same, and a method for manufacturing a resin composition

Abstract

The resin composition comprises a crystalline polymer having structural units derived from cyclic olefin compounds and an organic solvent. The resin composition has a density of 1.02 g / cm³ or higher, and the content of the organic solvent relative to 100 mass% of the polymer is 0.1 mass% or higher and 10 mass% or lower.

Description

Technology Field

[0001] The present invention relates to a resin composition, a molded article formed by molding the same, and a method for manufacturing a resin composition. Background Technology

[0002] Conventionally, various methods have been considered to obtain resin films having excellent properties. For example, Patent Document 1 proposes a method for producing a resin film with excellent dimensional stability upon heating by stretching a resin film having a crystalline alicyclic structure-containing resin as the main component and then contacting the resulting stretched film with a hydrocarbon solvent. Prior art literature

[0003] Japanese Patent Publication No. 2016-26909 The problem to be solved

[0004] When molding a resin into a desired shape, it is common practice to perform the molding process under heating conditions. Here, a lower heating temperature during the molding process is advantageous because, compared to a higher heating temperature, the time required for heating and cooling the workpiece is shorter, thereby shortening the molding cycle—the time required for a single molding operation—and reducing energy consumption. Furthermore, the molded product obtained by molding the resin into a desired shape requires excellent shape retention, meaning the shape does not collapse. However, with conventional resin materials, it has been difficult to achieve both high shape retention of the resulting molded product and a low heating temperature required during the molding process. Accordingly, the present invention aims to provide a resin composition and a method for manufacturing the same, which has high shape retention when forming a molded product and a reduced heating temperature required during the molding process. Additionally, the present invention aims to provide a molded product with high shape retention. means of solving the problem

[0005] The inventors conducted thorough investigations with the aim of solving the above problem. The inventors discovered that a high-density resin composition can be created by incorporating an organic solvent in a predetermined ratio into a crystalline polymer having structural units derived from cyclic olefin compounds. Furthermore, the inventors newly discovered that such a resin composition has the characteristics of high shape retention when forming a molded article and a low heating temperature required during the molding process.

[0006] That is, the present invention aims to advantageously solve the above problem, wherein the resin composition of the present invention comprises a crystalline polymer having structural units derived from cyclic olefin compounds and an organic solvent, and has a density of 1.02 g / cm³ 3 The above is characterized by the fact that the content of the organic solvent relative to 100 mass% of the polymer is 0.1 mass% or more and 10 mass% or less. This resin composition has high shape retention when a molded article is formed, and also has a low heating temperature required in the molding process.

[0007] In this specification, "crystallinity" of a polymer refers to the ability to observe the melting point by differential scanning calorimetry (DSC) by optimizing measurement conditions, and is a property determined by the stereoregularity of the polymer chains.

[0008] Meanwhile, the content ratio of the organic solvent in the resin composition can be measured by the method described in the examples of this specification.

[0009] Here, in the resin composition of the present invention, it is preferable that the polymer is a hydride. According to the resin composition comprising a polymer that is a hydride, a molded article with excellent heat resistance can be obtained.

[0010] In addition, in the resin composition of the present invention, it is preferable that the hydrogenation rate of the polymer be 90% or higher. According to the resin composition comprising a polymer having a hydrogenation rate of 90% or higher, a molded article with even better heat resistance can be obtained.

[0011] Meanwhile, the “hydrogenation rate” of a polymer refers to the ratio of the carbon-carbon double bonds included in the main chain and side chain of the polymer, which serves as a precursor for the hydrogenation treatment, that are hydrogenated by the hydrogenation treatment. The “hydrogenation rate” of the polymer can be measured according to the method described in the examples of this specification.

[0012] In addition, in the resin composition of the present invention, it is preferable that the organic solvent is a nonpolar solvent. If the organic solvent incorporated into the resin composition is a nonpolar solvent, the shape retention when a molded article is formed using the resin composition can be further enhanced.

[0013] Furthermore, the present invention aims to advantageously solve the above problem, and the molded article of the present invention is formed by molding any one of the resin compositions described above. By using any one of the resin compositions described above, a molded article with high shape retention can be obtained.

[0014] Furthermore, the present invention aims to advantageously solve the above problem. The method for manufacturing a resin composition of the present invention comprises: an immersion process in which a polymer material consisting of a crystalline polymer having structural units derived from a cyclic olefin compound is immersed in an organic solvent; and drying the polymer material that has undergone the immersion process under an atmosphere of pressure of 1,000 Pa or more and 6,000 Pa or less and temperature of 5°C or more and 35°C or less, so as to obtain a density of 1.02 g / cm³ 3At the same time as the above, the method is characterized by including a drying process to obtain a resin composition in which the content of the organic solvent relative to 100 mass% of the polymer is 0.1 mass% or more and 10 mass% or less. According to this manufacturing method, the resin composition of the present invention can be efficiently manufactured.

[0015] Meanwhile, in this specification, "pressure" means gauge pressure. Effects of the invention

[0016] According to the present invention, a resin composition and a method for manufacturing the same can be provided, which have high shape retention when a molded article is formed and also have a reduced heating temperature required in the molding process.

[0017] In addition, according to the present invention, a molded article with high shape retention can be provided. Specific details for implementing the invention

[0018] Hereinafter, embodiments of the present invention will be described in detail.

[0019] The resin composition of the present invention can be used in various fields as a resin material constituting various molded articles. In addition, the resin composition of the present invention can be efficiently manufactured according to the method of manufacturing the resin composition of the present invention.

[0020] (Resin composition)

[0021] The resin composition of the present invention comprises a crystalline polymer having structural units derived from cyclic olefin compounds and an organic solvent. Furthermore, the resin composition of the present invention has a density of 1.02 g / cm³. 3 The above is characterized by the fact that the content of the organic solvent relative to 100 mass% of the polymer is 0.1 mass% or more and 10 mass% or less. The resin composition of the present invention has high shape retention when a molded article is formed, and also has a low heating temperature required in the molding process.

[0022] Polymer

[0023] The polymer included in the resin composition of the present invention is a crystalline polymer having structural units derived from cyclic olefin compounds. Such a polymer may be a polymer comprising only structural units derived from cyclic olefin compounds as repeating units, or it may comprise units other than structural units derived from cyclic olefin compounds. Such other units are not particularly limited and may include any units capable of copolymerizing with structural units derived from cyclic olefin compounds.

[0024] <<Structural unit derived from cyclic olefin compounds>>

[0025] A structural unit derived from a cyclic olefin compound is a structural unit derived from a cyclic olefin compound that is included in a polymer obtained by performing a polymerization reaction using a cyclic olefin compound as a monomer. A cyclic olefin compound is a compound that has a ring structure formed by carbon atoms and possesses a carbon-carbon double bond within that ring structure. Specifically, examples of cyclic olefin compounds include norbornene-based monomers.

[0026] Norbornene monomers are monomers containing a norbornene ring.

[0027] Norbornene-based monomers include dicyclic monomers such as bicyclo[2.2.1]hepto-2-ene (common name: norbornene), 5-ethylidene-bicyclo[2.2.1]hepto-2-ene (common name: ethylidene norbornene), and derivatives thereof (those having substituents on the ring);

[0028] Tricyclo[4.3.0 1,6 .1 2,5 ] Tricyclic monomers such as deca-3,7-diene (common name: dicyclopentadiene) and its derivatives;

[0029] 7,8-Benzotricyclo[4.3.0.1 2,5]Deca-3-en (common name: metannoneterhydrofluorene: also known as 1,4-methano-1,4,4a,9a-tetrahydrofluorene) and its derivatives, tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodeca-3-ene (common name: tetracyclododecene), 8-ethylidenetetracyclo[4.4.0.1 2,5 .1 7,10 Examples include tetracyclic monomers such as ]-3-dodecene and its derivatives; etc.

[0030] Examples of substituents of these monomers include alkyl groups such as methyl and ethyl groups; alkenyl groups such as vinyl groups; alkylidene groups such as propane-2-ylidene; aryl groups such as phenyl groups; hydroxyl groups; acid anhydride groups; carboxyl groups; alkoxycarbonyl groups such as methoxycarbonyl groups; etc.

[0031] When the total repeating unit included in the polymer is 100 mass%, the proportion of structural units derived from cyclic olefin compounds can be appropriately selected according to the purpose of use of the resin composition, typically 30 mass% or more, preferably 50 mass% or more, more preferably 70 mass% or more, and may be 100 mass%.

[0032] <<Hydrogenation Rate of Polymers>>

[0033] It is preferable that the polymer be a hydride. From the perspective of increasing the heat resistance of the resin composition, it is preferable that the hydrogenation rate of the polymer be 98.0% or higher, and more preferable that it be 99.0% or higher.

[0034] <<Melts point of polymer>>

[0035] From the perspective of the heat resistance of the resin composition, the melting point of the polymer is preferably 110°C or higher, more preferably 120°C or higher, and even more preferably 130°C or higher. The upper limit of the polymer's melting point is not particularly limited, but from the perspective of moldability, it is preferably 400°C or lower. Meanwhile, the melting point of the polymer can be adjusted by changing the method of manufacturing the polymer. For example, it can be adjusted by changing the type and / or amount of the polymerization catalyst and molecular weight adjuster used when preparing the polymer.

[0036] In addition, the “melting point” of the polymer can be measured by a differential scanning calorimeter, and, for example, can be measured using the method described in the embodiments of this specification.

[0037] <<Weight-average molecular weight of the polymer>>

[0038] The weight-average molecular weight of the polymer can be appropriately selected depending on the application. For example, the weight-average molecular weight of the polymer is preferably 10,000 or more, more preferably 15,000 or more, even more preferably 20,000 or more, particularly preferably 25,000 or more, preferably 1,000,000 or less, more preferably 500,000 or less, even more preferably 300,000 or less, even more preferably 200,000 or less, and particularly preferably 150,000 or less. If the weight-average molecular weight is 10,000 or more, the mechanical strength of the resin composition can be increased, and if the weight-average molecular weight is 1,000,000 or less, the processability of the resin composition can be increased.

[0039] Meanwhile, the weight-average molecular weight of the polymer can be adjusted by changing the manufacturing method. For example, it can be adjusted by changing the type and / or amount of polymerization catalysts and molecular weight adjusters when preparing the polymer.

[0040] <<Stereoregularity of polymers>>

[0041] The degree of syndiotactic stereoregularity (ratio of racemo-dyads) in the stereostructure of the polymer is not particularly limited as long as the polymer is crystalline, and can be appropriately selected according to the use of the resin composition. For example, the ratio of racemo-dyads in the polymer may be 0% or more and 35% or less, or 65% or more and 100% or less. Meanwhile, the “ratio of racemo-dyads in the polymer” can be measured according to the method described in the examples of this specification.

[0042] <<Isomerization Rate of Polymer>>

[0043] Depending on the structural units derived from cyclic olefin compounds constituting the polymer, cis structural units (I) and trans structural units (II) may be mixed within the polymer. In this case, the ratio of trans structural units (II) to the total sum of cis structural units (I) and trans structural units (II) within the polymer (isomerization rate) is preferably 20% or less, and more preferably 15% or less.

[0044] Meanwhile, the isomerization rate of the polymer can be adjusted by changing the manufacturing method. Specifically, the isomerization rate of the polymer can be adjusted by changing the type and / or amount of the hydrogenation catalyst used when hydrogenating the polymer by providing it to a hydrogenation treatment.

[0045] <<Method for preparing polymer>>

[0046] Polymers are not particularly limited and can be synthesized according to known methods. For example, polymers can be prepared by polymerizing a monomer composition comprising a cyclic olefin compound and any additives, etc., using a known ring-opening polymerization catalyst and a known organometallic reducing agent that may optionally be used in combination with such catalyst (see, for example, Japanese Patent Publication No. 2016-26909). Meanwhile, the polymerization reaction can generally be carried out in an organic solvent. Such organic solvents are not particularly limited and include aliphatic hydrocarbons such as pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindene, and cyclooctane; Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; ethers such as diethyl ether and tetrahydrofuran; and mixed solvents combining these.

[0047] Other additives and polymerization conditions may also be appropriately changed as needed (see, for example, Japanese Patent Publication No. 2016-26909).

[0048] <<Method for Hydrogenating Polymers>>

[0049] A polymer can be converted into a hydride by (a) adding a hydrogenating agent and then heating to react (hydrogen transfer type hydrogenation reaction) to a polymer obtained by polymerizing a cyclic olefin compound; or (b) adding a hydrogenation catalyst and then adding hydrogen to react (catalytic hydrogenation reaction). Meanwhile, the stereoregularity of the polymer is usually unchanged before and after hydrogenation treatment.

[0050] As for the hydrogenating agent used in the hydrogen transfer type hydrogenation reaction (a) described above, any hydrogenating agent capable of hydrogenating carbon-carbon double bonds present in the polymer may be used without particular limitation. Examples include hydrazine and p-toluenesulfonylhydrazide.

[0051] In addition, as the hydrogenation catalyst used in the above-mentioned (b) catalytic hydrogenation reaction, known homogeneous or heterogeneous catalysts may be used as hydrogenation catalysts for olefin compounds (e.g., see Japanese Patent Publication No. 2016-26909).

[0052] When a hydride is used as the polymer to be incorporated into the resin composition of the present invention, it is preferable to perform a drying process to dry the obtained hydride / polymer (unhydrogenated) after the hydrogenation treatment of the polymer; when the synthesized polymer is used without hydrogenation, it is preferable to perform the drying process after the polymerization process. The conditions of the drying process are not particularly limited as long as the organic solvent used as the polymerization solvent and hydrogenation solvent can be removed from the object to be dried. For example, such a drying process can be appropriately carried out in an atmosphere with a temperature of over 35°C, a pressure of 1 Pa or more and 100 Pa or less, and a drying time of 10 hours or more and 48 hours or less.

[0053] Organic Solvents

[0054] The resin composition of the present invention contains an organic solvent. The organic solvent is not particularly limited and may include polar solvents such as alcohols and non-polar solvents. Among these, non-polar solvents may be used appropriately. Examples of non-polar solvents include toluene, xylene, cyclohexane, chloroform, carbon disulfide, benzene, mesitylene, hexane, pentane, chlorobenzene, and anisole. Among these, toluene, xylene, cyclohexane, chloroform, and carbon disulfide are preferred as non-polar solvents. These may be used individually or in a mixture of multiple types.

[0055] <<Organic Solvent Content>>

[0056] The content ratio of the organic solvent in the resin composition needs to be 0.1 mass% or more and 10 mass% or less with respect to 100 mass% of the polymer described above. In addition, the content ratio of the organic solvent is preferably 1.0 mass% or more with respect to 100 mass% of the polymer, and more preferably 2.0 mass% or more. If the content ratio of the organic solvent in the resin composition is above the lower limit value, it is possible to achieve a good balance between increasing the density of the resin composition and lowering the heating temperature required in the molding process. If the content ratio of the organic solvent in the resin composition is below the upper limit value, the shape retention when forming a molded article can be improved. The content ratio of the organic solvent can be adjusted according to the method described in detail in the section (method for manufacturing the resin composition).

[0057] Other ingredients

[0058] Depending on the intended use, the resin composition may optionally contain additives such as antioxidants, crystal nucleating agents, fillers, flame retardants, flame retardant aids, colorants, antistatic agents, ultraviolet absorbers, light stabilizers, near-infrared absorbers, and lubricants. The content of these additives can be appropriately determined according to the purpose, but it is preferable that the content be 50 mass% or less with respect to 100 mass% of the polymer, and more preferable that the content be 30 mass% or less.

[0059] Meanwhile, among general cyclic olefin resins, there are those that contain plasticizers as additives. Conventionally, plasticizers have been added for purposes such as softening the resin and improving moldability. However, it is preferable that the resin composition of the present invention does not contain a plasticizer. By not containing a plasticizer in the resin composition, it is possible to suppress disadvantages caused by the plasticizer, such as bleed-out during resin molding, in a molded article formed using such a resin composition.

[0060] Density of resin composition

[0061] The density of the resin composition of the present invention is 1.02 g / cm³ 3 It needs to be at least 1.12 g / cm³. 3 It may be less than or equal to the above lower limit. If the density of the polymer is greater than or equal to the above lower limit, the shape retention when forming a molded article can be improved. In addition, if the density of the polymer is less than or equal to the above upper limit, the moldability of the resin composition can be improved.

[0062] (Method for manufacturing a resin composition)

[0063] A method for preparing a resin composition of the present invention comprises an immersion process in which a polymer material consisting of a crystalline polymer having structural units derived from a cyclic olefin compound is immersed in an organic solvent, and the polymer material that has undergone the immersion process is dried under an atmosphere of pressure of 1,000 Pa or more and 6,000 Pa or less and temperature of 5°C or more and 35°C or less, so as to have a density of 1.02 g / cm³ 3 At the same time, the method is characterized by including a drying process to obtain a resin composition in which the content of an organic solvent relative to 100 mass% of the polymer is 0.1 mass% or more and 10 mass% or less.

[0064] <Immersion Process>

[0065] In the immersion process, a polymer material composed of the aforementioned "crystalline polymer having structural units derived from cyclic olefin compounds" is immersed in an organic solvent. As the organic solvent, the aforementioned non-polar solvent may be suitably used. The shape of the polymer material provided in this process may be any shape, such as pellets, fragments, and powder. Meanwhile, "fragments" refers to plates cut into any uniform size.

[0066] Among these, from the perspective of obtaining a resin composition with excellent manufacturing efficiency and a uniform organic solvent content, it is desirable to use pellets and small pieces of an appropriate size as the immersion target. If the size of the immersion target is excessively small or in powder form, there is a risk that the moldability of the resulting resin composition will be poor. Conversely, if the size of the immersion target is excessively large, it becomes necessary to extend the immersion time, which may result in a decrease in manufacturing efficiency. When the immersion target is in the form of a pellet, for example, a pellet with a diameter of 0.2 mm or more and 2.5 mm or less and a pellet length of 0.5 mm or more and 5 mm or less can be appropriately used. In addition, when the immersion target is in the form of a small piece, more specifically, a rectangular shape when viewed in planar form, for example, a piece with a side length of 0.5 mm or more and 5 mm or less and a thickness of 0.2 mm or more and 2.5 mm or less can be appropriately used. In addition, the values ​​of the ratio between the pellet diameter and the pellet length (pellet length / pellet diameter) and the ratio between the thickness and the length of one side (length of one side / thickness) may each be greater than 1 and less than or equal to 25 times. Meanwhile, according to the method described above in the items of <<Method for preparing a polymer>> and <<Method for hydrogenating a polymer>>, a powdered polymer (unhydrogenated) / hydride is typically obtained. When molding such a polymer (unhydrogenated) / hydride into any shape, such as a pellet or a fragment, any molding method may be employed. Meanwhile, when carrying out a molding method involving heating, the heating temperature may be, for example, in the range of (melting point + 10)°C or higher and (melting point + 100)°C or lower of the molding target (i.e., polymer (unhydrogenated) or hydride) in the molding method.

[0067] The immersion time in the immersion process may be, for example, 10 minutes or more and 48 hours or less. In addition, the immersion temperature in the immersion process may be, for example, 5°C or more and 35°C or less. Various conditions in these immersion processes can be appropriately adjusted to satisfy the desired density and organic solvent content by taking into account the size of the object to be immersed and the affinity between the composition of the organic solvent used for immersion and the polymer.

[0068] Drying Process

[0069] In the drying process, the polymer material that has undergone the immersion process is dried under predetermined temperature and pressure conditions to obtain a resin composition having a density and an organic solvent content within a predetermined range. The temperature conditions in the drying process need to be 5°C or higher and 35°C or lower, and preferably 10°C or higher and 30°C or lower. In addition, the atmospheric pressure conditions in the drying process need to be 1,000 Pa or higher and 6,000 Pa or lower in gauge pressure. Furthermore, the drying time in the drying process is preferably 3 minutes or higher and less than 30 minutes. The range of density and organic solvent content of the resin composition obtained through the drying process is as described above.

[0070] Meanwhile, in the drying process, prior to exposing the polymer material to a drying atmosphere satisfying the aforementioned temperature and pressure conditions, it is desirable to remove the organic solvent remaining on the surface of the polymer material immediately after the immersion process by wiping the surface of the polymer material that has undergone the immersion process.

[0071] (Plastic Surgery)

[0072] The molded article of the present invention is formed using the resin composition of the present invention described above. Furthermore, since the molded article of the present invention is formed by molding the resin composition of the present invention, it has excellent shape retention properties.

[0073] Meanwhile, the method for manufacturing the molded article is not particularly limited. The resin composition can be formed into a molded article of a desired shape using, for example, known molding means, such as injection molding, compression molding, or extrusion molding. The shape of the molded article can be appropriately selected according to the application.

[0074] Meanwhile, the use of the molded article of the present invention is not particularly limited, but for example,

[0075] Optical materials such as optical discs, optical lenses, prisms, light diffusers, optical cards, optical fibers, optical mirrors, liquid crystal display substrates, light guide plates, polarizing films, phase difference films, etc.;

[0076] Medical materials such as containers for liquid, powder, or solid drugs (containers for liquid drugs for injection, ampoules, vials, pre-filled syringes, intravenous fluid bags, inner layers, middle layers, and outer layers of multilayer films, sealant films, sealed drug pouches, press-through packages, solid drug containers, eye drop containers, etc.), sampling containers (sampling test tubes for blood tests, caps for drug containers, blood collection tubes, specimen containers, etc.), medical instruments (syringes, etc.), sterile containers for medical instruments (for scalpels, forceps, gauze, contact lenses, etc.), laboratory and analytical instruments (beakers, petri dishes, flasks, test tubes, centrifuge tubes, etc.), medical optical components (plastic lenses for medical examination, etc.), piping materials (medical intravenous fluid tubes, tubing, joints, valves, etc.), artificial organs or their parts (denture bases, artificial hearts, artificial tooth roots, etc.);

[0077] Food containers such as bottles, returnable bottles, baby bottles, films, shrink films, etc.;

[0078] Materials for processing electronic components of processing or transfer containers (tank, tray, carrier, case, etc.), protective materials (carrier tape, separation film, etc.), piping (pipe, tube, valve, flow meter, filter, pump, etc.), and liquid containers (sampling container, bottle, ampoule bag, etc.);

[0079] Electrical insulation materials such as sheathing materials (for wires, cables, etc.), casings for consumer and industrial electronic devices (photocopiers, computers, printers, televisions, video decks, video cameras, etc.), and structural members (parabolic antenna structural members, flat antenna structural members, radar dome structural members, etc.);

[0080] Circuit boards such as general circuit boards (rigid printed circuit boards, flexible printed circuit boards, multilayer printed circuit boards, etc.), high-frequency circuit boards (circuit boards for satellite communication devices, etc.); substrates of transparent conductive films (liquid crystal substrates, optical memory, surface heating elements, etc.);

[0081] Encapsulation materials for semiconductors (transistor encapsulation materials, IC encapsulation materials, LSI encapsulation materials, LED encapsulation materials, etc.) and encapsulation materials for electrical and electronic components (motor encapsulation materials, capacitor encapsulation materials, switch encapsulation materials, sensor encapsulation materials, etc.);

[0082] Examples include interior materials for automobiles, such as rearview mirrors and meter covers; and exterior materials for automobiles, such as door mirrors, fender mirrors, beam lenses, and light covers.

[0083] [Example]

[0084] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Meanwhile, in the following description, "%" and "parts" indicating amounts are based on mass unless specifically stated otherwise. In addition, the pressures described in the following description are gauge pressures, and the pressure referred to as "vacuum" is 1 Pa or more and 100 Pa or less, the pressure referred to as "reduced pressure" is 1000 Pa or more and 6000 Pa or less, and the pressure referred to as "atmospheric pressure" is 900 hPa or more and 1100 hPa or less.

[0085] In the examples and comparative examples, the obtained products were measured, analyzed, and evaluated according to the following methods.

[0086] Weight Average Molecular Weight of Ring-Opening Polymer Hydrogenates

[0087] The weight average molecular weight of the polymer hydride (hereinafter also referred to as "ring-opening polymer hydride") obtained by ring-opening polymerization of norbornene-based monomers obtained in Preparation Examples 1 to 5 was measured as a standard polystyrene equivalent value by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as the eluent. An HLC8121GPC / HT (manufactured by Tosho Co., Ltd.) was used as the measuring device. The sample was prepared by heating and dissolving the ring-opening polymer hydride in 1,2,4-trichlorobenzene at 140°C to achieve a sample concentration of 1 mg / ml.

[0088] Measurements were performed by connecting three TSKgelGMHHR·H(20)HT (manufactured by Tosoh Co.) columns in series, with a flow rate of 1.0 ml / min, a sample injection volume of 300 μl, and a column temperature of 140°C.

[0089] Solid Regularity

[0090] The stereoregularity of the ring-opening polymer hydrides obtained in Preparation Examples 1 to 5 is, 13 It was measured by C-NMR. Specifically, using chloroform-d (when norbornene was used as the cyclic olefin compound) or a mixed solvent of 1,3,5-trichlorobenzene-d3 / orthodichlorobenzene-d4 (volume ratio: 2 / 1; when dicyclopentadiene or tetracyclododecene was used as the cyclic olefin compound) as the solvent, the inverse-gated decoupling method was applied at 60°C (when the solvent was chloroform-d) or 200°C (when the solvent was the above mixed solvent) to the ring-opening polymer hydrides 13C-NMR measurements were performed. Based on the obtained measurement results, the ratio (%) of the signal intensity derived from the racemo-dyad to the sum of the signal intensity derived from the meso-dyad and the signal intensity derived from the racemo-dyad was calculated using the 77.0 ppm peak of chloroform-d or the 127.5 ppm peak of orthodichlorobenzene-d4 as a reference shift, and the ratio of the racemo-dyad was determined.

[0091] Hydrogenation rate

[0092] With respect to the ring-opening polymer before hydrogenation and the ring-opening polymer hydride obtained in Preparation Examples 1 to 5, respectively, 1 H-NMR measurements were performed to determine the percentage of hydrogenated carbon-carbon double bonds contained in the main chain and side chains of the polymer.

[0093] Melting Point and Glass Transition Point

[0094] The melting point was measured by increasing the temperature at a rate of 10°C / min using a differential scanning calorimeter (DSC; X-DSC7000, manufactured by SII Nanotechnologies), and the temperature point with the greatest endothermic heat at the first phase transition peak of the crystal melting was taken as the melting point. The glass transition point was measured by melting the resin composition at a high temperature, then rapidly cooling it by immersing it in liquid nitrogen in its molten state to obtain an amorphous sample, and then increasing the temperature at a rate of 10°C / min using a differential scanning calorimeter (DSC).

[0095] - Targets for measuring pre-molding and post-molding melting points -

[0096] "Melting point before molding": The melting points of resin compositions A to H obtained in Examples 1 to 8, and ring-opening polymer hydrides a to d and h obtained in Comparative Examples 1 to 5 were measured according to the above and referred to as "melting point before molding" and shown in Table 1.

[0097] "Melting point after molding": The melt obtained when measuring the "melting point before molding" was cooled and recrystallized, and the melting point was measured again according to the above, and the obtained value was called the "melting point after molding" and shown in Table 1.

[0098] Isomorphism Rate

[0099] The isomerization rate of ring-opening polymer hydrides is, 13 It was calculated by C-NMR measurement (solvent: dichloroform, measurement temperature: 60℃). Specifically, in the obtained NMR spectrum, the isomerization rate (percentage) was calculated by multiplying the value obtained by dividing the signal intensity of the trans-type structural unit (II) by the sum of the signal intensity of the cis-type structural unit (I) and the signal intensity of the trans-type structural unit (II) by 100.

[0100] <Organic Solvent Content>

[0101] In measuring the organic solvent content (based on the mass of ring-opening polymer hydrides) of resin compositions A to H and ring-opening polymer hydrides a to d and h obtained in the examples and comparative examples, the measurement samples were dried for 7 days under conditions of 100°C and 100 Pa. Then, the organic solvent content of the measurement samples before drying was obtained from the mass change of the measurement samples before and after drying.

[0102] Shape retention

[0103] For the small pieces (completed immersion) of the resin compositions obtained in the examples and comparative examples, if the polymer used is crystalline, the temperature was heated to (melting point - 10)°C, and if the polymer used is amorphous (Comparative Example 7), the temperature was heated to (glass transition point + 10)°C, respectively, and the presence or absence of deformation was checked.

[0104] Specifically, first, the sample (completed immersion) was maintained at the above temperature for 10 minutes depending on the presence or absence of crystallinity, and then returned to room temperature (23℃) to obtain a heat-treated sample. Then, the obtained heat-treated sample was visually observed to check for the presence or absence of shape deformation. In addition, the cross-section of the heat-treated sample was placed on a horizontal plane, and the distance between the opposing cross-section and the horizontal plane was measured to check for the presence or absence of curling. The results of the check were evaluated according to the following criteria. The results are shown in Table 1.

[0105] A: No shape deformation or curling.

[0106] B: Occurs in both or one of the shape deformation and curl.

[0107] Temperature Superiority of Molding

[0108] When molding a resin composition comprising a crystalline polymer, it is generally assumed that the molding is performed at (melting point + 20)°C. First, the melting point of the resin composition to be measured was measured in accordance with the above. Starting from a temperature of (melting point + 20)°C, molding was attempted sequentially by lowering the set temperature by 1°C increments, and the temperature superiority of the molding was evaluated according to the following criteria based on the temperature at which molding became impossible. The results are shown in Table 1.

[0109] Compared to cases where the heating temperature required during molding is higher, a lower heating temperature is advantageous in that the time required for heating and cooling the workpiece is shorter, thereby shortening the molding cycle, which is the time required for one molding step, and also in terms of lower energy consumption.

[0110] A: Molding is possible even at (melting point + 13)℃ or lower (i.e., molding was possible at a temperature at least 7℃ lower compared to the general molding temperature).

[0111] B: Molding is possible even at temperatures above (melting point + 13)℃ and below (melting point + 17)℃ (i.e., molding was possible at temperatures 3℃ or more and less than 7℃ lower compared to general molding temperatures).

[0112] C: Molding is possible even at temperatures above (melting point + 17)℃ and below (melting point + 19)℃ (i.e., compared to general molding temperatures, molding was possible at temperatures 1℃ or more and less than 3℃ lower).

[0113] D: The molding temperature was constant, or molding was possible at a temperature less than 1°C lower than the normal molding temperature.

[0114] <Example of preparation of polymer hydride>

[0115] <<Preparation Example 1>>

[0116] 0.028 g of phenylimidetungsten(VI)tetrachloridetetrahydrofuran and 5 ml of toluene were added as ring-opening polymerization catalysts to a glass reactor equipped with a stirrer and stirred. Subsequently, 27 g of cyclohexane, 0.22 g (2.5 mol%) of 1-octene, and 0.022 g of diethylaluminum ethoxide as an organometallic reducing agent dissolved in 1 ml of n-hexane were added to another glass reactor equipped with a stirrer. Next, the toluene solution of phenylimidetungsten(VI)tetrachloridetetrahydrofuran and 7.5 g of norbornene as a cyclic olefin compound were added over a period of 2 hours, and a polymerization reaction was carried out at 50°C for 2 hours. After the start of the polymerization reaction, the viscosity of the reaction mixture gradually increased. After reacting for 2 hours, a polymerization reaction solution was obtained. A large amount of acetone was poured into a portion of the obtained polymerization reaction solution to coagulate the precipitate, and the coagulated material was filtered and collected. The filtered material was washed with methanol and dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 7.4 g. With respect to the obtained ring-opening polymer, according to the above, 1 H-NMR measurements were performed.

[0117] 7.4 g of the polymerization reaction solution obtained above (without the addition of acetone) was transferred without precipitation to an autoclave equipped with a stirrer, equivalent to the mass of the ring-opening polymer. Thereby, 0.075 g of a diatomaceous earth-supported nickel catalyst (T8400, nickel support 58 mass%, manufactured by Nissan Sudscheme Co., Ltd.), which is a heterogeneous catalyst used as a hydrogenation catalyst, was added, and the reaction was carried out at 200°C and a hydrogen pressure of 4.5 MPa for 8 hours. This solution was filtered using a filter equipped with a stainless steel mesh with diatomaceous earth as a filter aid. A large amount of acetone was poured into the obtained reaction solution to coagulate the precipitate, and after filtration, separation, and washing, the solution was dried under reduced pressure at 40°C for 24 hours to obtain 7.5 g of powdered ring-opening polymer hydride. The weight average molecular weight of the obtained ring-opening polymer hydride was 60,000. The ring-opening polymer hydride was syndiotactic, with a hydrogenation rate of 99.7% and a racemo-dyad ratio of 78%. Additionally, the isomerization rate of the ring-opening polymer hydride was 3%. Furthermore, the syndiotactic norbornene ring-opening polymer hydride obtained in this example was found to be crystalline, as its melting point was observed to be 135°C by DSC measurement.

[0118] <<Preparation Example 2>>

[0119] 0.0463 g of bis{3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy}oxymolybdenum(VI) as a ring-opening polymerization catalyst and 4 ml of toluene were added to a glass reactor equipped with a stirrer, and the mixture was cooled to -78°C. To this, 0.00726 g of n-butyllithium dissolved in 1 ml of hexane was added as an organometallic reducing agent, the temperature was returned to room temperature, and the reaction was carried out for 15 minutes. Subsequently, 10.0 g of norbornene, 27 g of cyclohexane, and 0.64 g of 1-hexene were added as cyclic olefin compounds to the obtained reaction mixture, and the polymerization reaction was carried out at 50°C. After the start of the polymerization reaction, the viscosity of the mixture gradually increased. The reaction was carried out for 2 hours to obtain the polymerization reaction solution. A large amount of acetone was poured into a portion of the obtained polymerization reaction solution to coagulate the precipitate, and after filtration, separation, and washing, it was dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 9.8 g. With respect to the obtained ring-opening polymer, according to the above, 1 H-NMR measurements were performed.

[0120] 7.4 g of the ring-opening polymer of the polymerization reaction solution obtained above (without the addition of acetone) was transferred to an autoclave equipped with a stirrer without precipitation, and 0.225 g of a diatomite-supported nickel catalyst (T8400, nickel support 58 mass%, manufactured by Nissan Sudscheme Co., Ltd.) was added thereto and reacted at 200°C and a hydrogen pressure of 4.5 MPa for 8 hours. This solution was filtered using a filter equipped with a stainless steel mesh with diatomite as a filter aid, and a large amount of acetone was poured into the obtained reaction solution to coagulate the precipitate. After filtration, separation, and washing, the solution was dried under reduced pressure at 40°C for 24 hours to obtain 7.5 g of ring-opening polymer hydride in powder form. The weight average molecular weight of the obtained ring-opening polymer hydride was 121,000. In addition, the ring-opening polymer hydride had a hydrogenation rate of 99.8%, and the ratio of racemo-diead was 0% (i.e., the ratio of meso-diead was 100%), and was isotactic. In addition, the isomerization rate of the ring-opening polymer hydride was 10%. In addition, the isotactic norbornene ring-opening polymer hydride obtained in this example was found to be crystalline, as its melting point was observed to be 175°C by DSC measurement.

[0121] <<Preparation Example 3>>

[0122] 0.028 g of phenylimide tungsten(VI) tetrachloride tetrahydrofuran as a ring-opening polymerization catalyst and 5 ml of toluene were added to a glass reactor equipped with a stirrer and stirred. Subsequently, 27 g of cyclohexane, 0.22 g (2.5 mol%) of 1-octene, and 0.022 g of diethylaluminum ethoxide as an organometallic reducing agent dissolved in 1 ml of n-hexane were added to another glass reactor equipped with a stirrer. Next, the toluene solution of phenylimide tungsten(VI) tetrachloride tetrahydrofuran and 7.5 g of dicyclopentadiene as a cyclic olefin compound were added over a period of 2 hours, and a polymerization reaction was carried out at 50°C for 2 hours. After the start of the polymerization reaction, the viscosity of the reaction mixture gradually increased. After reacting for 2 hours, a large amount of acetone was poured into the polymerization reaction mixture to coagulate the precipitate, and the coagulated material was collected by filter. The filtered sample was washed with methanol and dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 7.4 g. With respect to the obtained ring-opening polymer, according to the above, 1 H-NMR measurements were performed.

[0123] 5 g of the obtained ring-opening polymer, 100 g of p-toluenesulfonylhydrazide as a hydrogenating agent, and 200 g of paraxylene were added to a glass reactor equipped with a stirrer, and hydrogenation was performed by heating at 125°C for 5 hours. The resulting reaction solution was poured into a large amount of methanol to coagulate the precipitate, and after filtration, separation, and washing, it was dried under reduced pressure at 40°C for 24 hours to obtain 5.0 g of ring-opening polymer hydride in powder form. The weight average molecular weight of the obtained ring-opening polymer hydride was 50,000. The ring-opening polymer hydride had a hydrogenation rate of 99.8%, a racemo-dyad ratio of 90%, and was syndiotactic. Additionally, the isomerization rate of the ring-opening polymer hydride was 0%. In addition, the syndiotactic dicyclopentadiene ring-opening polymer hydride obtained in this example was found to be crystalline, as its melting point was observed to be 270°C by DSC measurement.

[0124] <<Preparation Example 4>>

[0125] 0.0463 g of bis{3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy}oxymolybdenum(VI) as a ring-opening polymerization catalyst and 4 ml of toluene were added to a glass reactor equipped with a stirrer, and the mixture was cooled to -78°C. To this, 0.00726 g of n-butyllithium dissolved in 1 ml of hexane as an organometallic reducing agent was added, the temperature was returned to room temperature, and the reaction was carried out for 15 minutes. Subsequently, 10.0 g of dicyclopentadiene as a cyclic olefin compound, 27 g of cyclohexane, and 0.64 g of 1-hexene were added to the resulting reaction mixture, and the polymerization reaction was carried out at 50°C. After the start of the polymerization reaction, the viscosity of the mixture gradually increased. After reacting for 2 hours, a large amount of acetone was poured into the polymerization reaction solution to coagulate the precipitate, and after filtration, separation, and washing, it was dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 9.8 g.

[0126] In a glass reactor equipped with a stirrer, 5 g of the obtained ring-opening polymer, 100 g of p-toluenesulfonylhydrazide, and 200 g of paraxylene were added, and hydrogenation was performed by heating at 125°C for 5 hours. The resulting reaction solution was poured into a large amount of methanol to coagulate the precipitate, and after filtration, separation, and washing, it was dried under reduced pressure at 40°C for 24 hours to obtain 5.0 g of ring-opening polymer hydride in powder form. The weight average molecular weight of the obtained ring-opening polymer hydride was 85,000. Furthermore, the ring-opening polymer hydride had a hydrogenation rate of 99.8%, a racemo-dyad ratio of 0% (i.e., a meso-dyad ratio of 100%), and was isotactic. Additionally, the isomerization rate of the ring-opening polymer hydride was 0%. In addition, the isotactic dicyclopentadiene ring-opening polymer hydride obtained in this example was found to be crystalline, as its melting point was observed to be 285°C by DSC measurement.

[0127] <<Preparation Example 5>>

[0128] 0.0745 g of tetrakis(2,6-dimethylphenoxy)oxymolybdenum(VI) as a ring-opening polymerization catalyst and 4 ml of toluene were added to a glass reactor equipped with a stirrer, and the mixture was cooled to -78°C. To this, 0.0160 g of n-butyllithium dissolved in 1 ml of hexane as an organometallic reducing agent was added, the temperature was returned to room temperature, and the reaction was carried out for 15 minutes. Subsequently, 10.0 g of tetracyclododecene, 27 g of cyclohexane, and 0.64 g of 1-hexene were added as cyclic olefin compounds to the resulting reaction mixture, and the polymerization reaction was carried out at 50°C. After the start of the polymerization reaction, the viscosity of the mixture gradually increased. After reacting for 2 hours, a large amount of acetone was poured into the polymerization reaction solution to coagulate the precipitate, and after filtration, separation, and washing, the mixture was dried under reduced pressure at 40°C for 24 hours. The quantity of the obtained ring-opening polymer was 9.8 g. With respect to the obtained ring-opening polymer, according to the above, 1 H-NMR measurements were performed.

[0129] 5 g of the obtained ring-opening polymer, 100 g of p-toluenesulfonylhydrazide as a hydrogenating agent, and 200 g of paraxylene were added to a glass reactor equipped with a stirrer, and hydrogenation was performed by heating at 125°C for 5 hours. The resulting reaction solution was poured into a large amount of methanol to coagulate the precipitate, and after filtration, separation, and washing, it was dried under reduced pressure at 40°C for 24 hours to obtain 5.0 g of ring-opening polymer hydride in powder form. The weight average molecular weight of the obtained ring-opening polymer hydride was 40,000. Furthermore, the ring-opening polymer hydride had a hydrogenation rate of 99.8%, a racemo-dyad ratio of 30%, and was isotactic. Additionally, the isomerization rate of the ring-opening polymer hydride was 0%. In addition, the isotactic tetracyclododecene ring-opening polymer hydride obtained in this example was found to be crystalline, as its melting point was observed to be 310°C by DSC measurement.

[0130] (Example 1)

[0131] The syndiotactic norbornene ring-opening polymer hydride obtained in Preparation Example 1 above was melt-compressed using a vacuum heat press heated to 200°C to form a small piece (syndiotactic norbornene ring-opening polymer hydride a) measuring 2 mm × 2 mm × 1 mm. The density of the small piece (g / cm³) 3 ) was 1.01. Meanwhile, the organic solvent content of the small piece (ring-opening polymer hydride a) was measured according to the above and was 0%. The obtained small piece was immersed in toluene as an organic solvent for 2 hours under conditions of atmospheric pressure and room temperature (23°C), but it did not dissolve at all and did not lose its shape. After removing the small piece from the toluene, the toluene on the surface was wiped off with dry gauze. In addition, the small piece was dried for 10 minutes under a reduced pressure atmosphere at room temperature (23°C). Although no change in shape was observed visually, a mass increase of 8 mass% was observed relative to 100 mass% of norbornene ring-opening polymer hydride. Furthermore, regarding the small piece that underwent the series of operations, the organic solvent content was measured according to the above and was 8 mass% (based on the mass of the ring-opening polymer hydride), which is equivalent to the value of the mass increase. That is, as a result of the above series of operations, a resin composition A was obtained, which is a toluene-containing syndiotactic crystalline norbornene ring-opening polymer hydride containing 8 mass% of toluene as an organic solvent relative to 100 mass% of syndiotactic norbornene ring-opening polymer hydride a. The density of resin composition A (g / cm³) 3 ) was 1.05.

[0132] (Example 2)

[0133] The isotactic norbornene ring-opening polymer hydride obtained in Preparation Example 2 was melt-compressed using a vacuum heat press heated to 200°C to form small pieces (isotactic norbornene ring-opening polymer hydride b) of 2 mm × 2 mm × 1 mm. Density (g / cm³) of isotactic norbornene ring-opening polymer hydride b. 3) was 1.01. Meanwhile, the organic solvent content of the small piece (ring-opening polymer hydride b) was measured according to the above and was 0%. The obtained small piece was immersed in chloroform as an organic solvent for 5 hours under conditions of atmospheric pressure and room temperature (23°C), but it did not dissolve at all and did not lose its shape. After removing the small piece from the chloroform, the chloroform on the surface was wiped off with dry gauze. In addition, the small piece was dried for 10 minutes under a reduced pressure atmosphere at room temperature (23°C), and although no change in shape was visible, a mass increase of 9 mass% was observed. Furthermore, regarding the small piece that underwent the series of operations, the organic solvent content was measured according to the above and was 9 mass% (based on the mass of the ring-opening polymer hydride), which is equivalent to the value of the mass increase. That is, a resin composition B was obtained, which is a chloroform-containing isotactic crystalline norbornene ring-opening polymer hydride, containing 9 mass% of chloroform as an organic solvent relative to 100 mass% of isotactic norbornene ring-opening polymer hydride b. The density of resin composition B (g / cm³) 3 ) was 1.07.

[0134] (Example 3)

[0135] The syndiotactic dicyclopentadiene ring-opening polymer hydride obtained in Preparation Example 3 was melt-compressed using a vacuum heat press heated to 300°C to form a small piece (syndiotactic dicyclopentadiene ring-opening polymer hydride c) measuring 2 mm × 2 mm × 1 mm. The density of the small piece (g / cm³) 3The value was 1.01. Meanwhile, the organic solvent content of the small piece (ring-opening polymer hydride c) was measured according to the above and was 0%. The obtained small piece was immersed in carbon disulfide as an organic solvent for 3 hours under conditions of atmospheric pressure and room temperature (23°C), but it did not dissolve at all and did not lose its shape. After removing the small piece from the carbon disulfide, the carbon disulfide on the surface was wiped off with dry gauze. In addition, the small piece was dried for 10 minutes under a reduced pressure atmosphere at room temperature (23°C). Although no change in shape was observed visually, a mass increase of 10 mass% was observed relative to 100 mass% of the syndiotactic dicyclopentadiene ring-opening polymer hydride. Furthermore, regarding the small piece that underwent the series of operations, the organic solvent content was measured according to the above and was 10 mass% (based on the mass of the ring-opening polymer hydride), which is equivalent to the value of the mass increase. That is, resin composition C was obtained, which is a carbon disulfide-containing syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride containing 10 mass% of carbon disulfide relative to 100 mass% of the syndiotactic dicyclopentadiene ring-opening polymer hydride. The density of resin composition C (g / cm³) 3 ) was 1.06.

[0136] (Example 4)

[0137] The isotactic dicyclopentadiene ring-opening polymer hydride obtained in Preparation Example 4 was melt-compressed using a vacuum heat press heated to 300°C to form a small piece (isotactic dicyclopentadiene ring-opening polymer hydride d) measuring 2 mm × 2 mm × 1 mm. The density of the small piece (g / cm³) 3The value was 1.01. Meanwhile, the organic solvent content of the small piece (ring-opening polymer hydride d) was measured according to the above and was 0%. The obtained small piece was immersed in xylene as an organic solvent for 5 hours under conditions of atmospheric pressure and room temperature (23°C), but it did not dissolve at all and did not lose its shape. After removing the small piece from the xylene, the xylene on the surface was wiped off with dry gauze. In addition, the small piece was dried for 10 minutes under room temperature (23°C) and reduced pressure; although no change in shape was visible, a mass increase of 8 mass% was observed relative to 100 mass% of isotactic dicyclopentadiene ring-opening polymer hydride. Furthermore, regarding the small piece that underwent the series of operations, the organic solvent content was measured according to the above and was 8 mass% (based on the mass of the ring-opening polymer hydride), which is equivalent to the value of the mass increase. That is, a resin composition D was obtained, which is a xylene-containing isotactic crystalline dicyclopentadiene ring-opening polymer hydride containing 8 mass% xylene with respect to 100 mass% of the isotactic dicyclopentadiene ring-opening polymer hydride. The density of resin composition D (g / cm³) 3 ) was 1.04.

[0138] (Example 5)

[0139] The syndiotactic dicyclopentadiene ring-opening polymer hydride obtained in Preparation Example 3 was melt-compressed using a vacuum heat press heated to 300°C to form a small piece (syndiotactic dicyclopentadiene ring-opening polymer hydride c) measuring 2 mm × 2 mm × 1 mm. The density of the small piece (g / cm³) 3The value was 1.00. Meanwhile, the organic solvent content of the small piece (ring-opening polymer hydride c) was measured according to the above and was 0%. The obtained small piece was immersed in toluene as an organic solvent for 15 minutes under conditions of atmospheric pressure and room temperature (23°C), but it did not dissolve at all and did not lose its shape. After removing the small piece from the toluene, the toluene on the surface was wiped off with dry gauze. In addition, the small piece was dried for 10 minutes under a reduced pressure atmosphere at room temperature (23°C). Although no change in shape was observed visually, a mass increase of 1.5 mass% was observed relative to 100 mass% of the syndiotactic dicyclopentadiene ring-opening polymer hydride. Furthermore, regarding the small piece that underwent the series of operations, the organic solvent content was measured according to the above and was 1.5 mass% (based on the mass of the ring-opening polymer hydride), which is equivalent to the value of the mass increase. That is, a resin composition E was obtained, which is a toluene-containing syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride containing 1.5 mass% toluene with respect to 100 mass% of the syndiotactic dicyclopentadiene ring-opening polymer hydride. The density (g / cm³) of resin composition E. 3 ) was 1.02.

[0140] (Example 6)

[0141] The syndiotactic dicyclopentadiene ring-opening polymer hydride obtained in Preparation Example 3 was melt-compressed using a vacuum heat press heated to 300°C to form a small piece (syndiotactic dicyclopentadiene ring-opening polymer hydride c) measuring 2 mm × 2 mm × 1 mm. The density of the small piece (g / cm³) 3The value was 1.01. Meanwhile, the organic solvent content of the small piece (ring-opening polymer hydride c) was measured according to the above and was 0%. The obtained small piece was immersed in cyclohexane as an organic solvent for 24 hours under conditions of atmospheric pressure and room temperature (23°C), but it did not dissolve at all and did not lose its shape. After removing the small piece from the cyclohexane, the cyclohexane on the surface was wiped off with dry gauze. In addition, the small piece was dried for 10 minutes under a reduced pressure atmosphere at room temperature (23°C). Although no change in shape was observed visually, a mass increase of 3 mass% was observed relative to 100 mass% of the syndiotactic dicyclopentadiene ring-opening polymer hydride. Furthermore, regarding the small piece that underwent the series of operations, the organic solvent content was measured according to the above and was 3 mass% (based on the mass of the ring-opening polymer hydride), which is equivalent to the value of the mass increase. That is, a resin composition F was obtained, which is a cyclohexane-containing syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride containing 3 mass% of cyclohexane with respect to 100 mass% of the syndiotactic dicyclopentadiene ring-opening polymer hydride. The density of resin composition F (g / cm³) 3 ) was 1.02.

[0142] (Example 7)

[0143] The syndiotactic dicyclopentadiene ring-opening polymer hydride obtained in Preparation Example 3 was melt-compressed using a vacuum heat press heated to 300°C to form a small piece (syndiotactic dicyclopentadiene ring-opening polymer hydride c) measuring 2 mm × 2 mm × 1 mm. The density of the small piece (g / cm³) 3The value was 1.01. Meanwhile, the organic solvent content of the small piece (ring-opening polymer hydride c) was measured according to the above and was 0%. The obtained small piece was immersed in chloroform as an organic solvent for 5 hours under conditions of atmospheric pressure and room temperature (23°C), but it did not dissolve at all and did not lose its shape. After removing the small piece from the chloroform, the chloroform on the surface was wiped off with dry gauze. In addition, the small piece was dried for 10 minutes under a reduced pressure atmosphere at room temperature (23°C). Although no change in shape was observed visually, a mass increase of 6 mass% was observed relative to 100 mass% of the syndiotactic dicyclopentadiene ring-opening polymer hydride. Furthermore, regarding the small piece that underwent the series of operations, the organic solvent content was measured according to the above and was 6 mass% (based on the mass of the ring-opening polymer hydride), which is equivalent to the value of the mass increase. That is, a resin composition G was obtained, which is a chloroform-containing syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride containing 6 mass% of chloroform relative to 100 mass% of the syndiotactic dicyclopentadiene ring-opening polymer hydride. The density (g / cm³) of resin composition G. 3 ) was 1.03.

[0144] (Example 8)

[0145] The isotactic tetracyclododecene ring-opening polymer hydride obtained in Preparation Example 5 was melt-compressed using a vacuum heat press heated to 330°C to form a small piece (isotactic tetracyclododecene ring-opening polymer hydride h) of 2 mm × 2 mm × 1 mm. The density of the small piece (g / cm³) 3The value was 1.01. Meanwhile, the organic solvent content of the small piece (ring-opening polymer hydride h) was measured according to the above and was 0%. The obtained small piece was immersed in toluene as an organic solvent for 5 hours under conditions of atmospheric pressure and room temperature (23°C), but it did not dissolve at all and did not lose its shape. After removing the small piece from the toluene, the toluene on the surface was wiped off with dry gauze. In addition, the small piece was dried for 10 minutes under a reduced pressure atmosphere at room temperature (23°C). Although no change in shape was observed visually, a mass increase of 7 mass% was observed relative to 100 mass% of the syndiotactic dicyclopentadiene ring-opening polymer hydride. Furthermore, regarding the small piece that underwent the series of operations, the organic solvent content was measured according to the above and was 7 mass% (based on the mass of the ring-opening polymer hydride), which is equivalent to the value of the mass increase. That is, a resin composition H was obtained, which is a toluene-containing isotactic tetracyclododecene ring-opening polymer hydride containing 7 mass% toluene relative to 100 mass% of the isotactic tetracyclododecene ring-opening polymer hydride. The density of resin composition H (g / cm³) 3 ) was 1.04.

[0146] (Comparative Examples 1~5)

[0147] Ring-opening polymer hydrides a to d and h, which are small fragments prepared in Examples 1 to 4 and Example 8, respectively, were used as shown in Table 1. For these small fragments, immersion in an organic solvent and drying following immersion were performed, and the shape retention and temperature superiority of molding were evaluated according to the above. The results are shown in Table 1.

[0148] (Comparative Example 6)

[0149] The syndiotactic dicyclopentadiene ring-opening polymer hydride obtained in Preparation Example 3 was formed into a film with a thickness of 150 μm and a width of 120 mm using a hot melt extrusion film forming machine equipped with a T-die, and wound into a roll at a speed of 2 m / min. The operating conditions of the film forming machine are shown below.

[0150] · Barrel temperature setting: 280~290℃

[0151] · Die temperature: 270℃

[0152] · Screw rotation speed: 30 rpm

[0153] A portion of the obtained resin film was cut to a size of 90 mm × 90 mm, installed in a small stretching machine (manufactured by Toyo Seiki Co., Ltd.: EX10-B type), and stretched film 1 was obtained by performing a stretching process. The operating conditions of the small stretching machine are shown below.

[0154] · Stretching speed: 10,000 mm / min

[0155] · Stretching temperature: 100℃

[0156] · Stretch ratio: 1.8x [Flow direction of resin film (MD)]

[0157] Density of stretched film 1 (g / cm³) 3 ) was 1.01. Meanwhile, the organic solvent content of stretched film 1 was measured according to the above and was 0%.

[0158] As a result of immersing the obtained stretched film 1 in toluene at 23°C for 30 seconds, wiping the surface with dry gauze, and drying it at room temperature (23°C) under reduced pressure for 10 minutes, no change in shape was observed visually, but the stretched film 1 showed only a mass increase of 0.1 mass% relative to 100 mass%. Furthermore, regarding the toluene-containing stretched film 1, the organic solvent content was measured according to the above, and the result was 0.1 mass% (based on the mass of the ring-opening polymer hydride), which is equivalent to the value of the mass increase. The density (g / cm³) of this toluene-containing stretched film 1 3 ) was 1.01.

[0159] (Comparative Example 7)

[0160] 0.006 g of (1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium as a ring-opening polymerization catalyst and 5 ml of toluene were added to a glass reactor equipped with a stirrer and stirred. Subsequently, 27 g of cyclohexane and 0.09 g (1.0 mol%) of 1-octene were added to another glass reactor equipped with a stirrer. Next, 7.5 g of dicyclopentadiene as a cyclic olefin compound was added over a period of 2 hours, and a polymerization reaction was carried out at 50°C for 2 hours. After the start of the polymerization reaction, the viscosity of the reaction mixture gradually increased. After reacting for 2 hours, a large amount of acetone was poured into the polymerization reaction solution to coagulate the precipitate, and the coagulated material was collected by filtration. The filtered material was washed with methanol and dried under reduced pressure at 40°C for 24 hours. The quantity of the obtained ring-opening polymer was 7.4 g. With respect to the obtained ring-opening polymer, according to the above, 1 H-NMR measurements were performed.

[0161] In a glass reactor equipped with a stirrer, 5 g of the obtained ring-opening polymer, 100 g of p-toluenesulfonylhydrazide as a hydrogenating agent, and 200 g of paraxylene were added, and hydrogenation was performed by heating at 125°C for 5 hours. The resulting reaction solution was poured into a large amount of methanol to coagulate the precipitate, and after filtration, separation, and washing, it was dried under reduced pressure at 40°C for 24 hours to obtain 5.0 g of ring-opening polymer hydride in powder form. The weight average molecular weight of the obtained ring-opening polymer hydride was 25,000. The ring-opening polymer hydride had a hydrogenation rate of 99.8%, a racemo-diead ratio of 50%, and was atactic. In addition, the isomerization rate of the ring-opening polymer hydride was 0%. Furthermore, it was found that the atactic dicyclopentadiene ring-opening polymer hydride obtained in this example was amorphous, as no melting point was observed by DSC measurement.

[0162] The obtained atactic dicyclopentadiene ring-opening polymer hydride was melt-compressed using a vacuum heat press heated to 300°C to form small pieces (atactic dicyclopentadiene ring-opening polymer hydride i) measuring 2 mm × 2 mm × 1 mm. The density (g / cm³) of atactic dicyclopentadiene ring-opening polymer hydride i. 3) was 1.00. Meanwhile, the organic solvent content of the fragment (ring-opening polymer hydride i) was measured according to the above and was 0%. The obtained fragment was immersed in xylene for 5 hours under atmospheric pressure and room temperature (23℃), but it swelled from the surface toward the interior, became cloudy, and did not maintain its shape. After removing the fragment from the xylene, the xylene on the surface was wiped off with dry gauze, and it was dried for 10 minutes at room temperature (23℃) under reduced pressure. As a result, a change in shape was clearly visible, and a mass increase of about 80 mass% was observed relative to 100 mass% of atactic dicyclopentadiene ring-opening polymer hydride. That is, xylene-containing atactic dicyclopentadiene ring-opening polymer hydride I was obtained, containing 80 mass% of xylene relative to 100 mass% of atactic dicyclopentadiene ring-opening polymer hydride i. Density of xylene-containing atactic dicyclopentadiene ring-opening polymer hydride I (g / cm³) 3 ) was 0.96.

[0163] Meanwhile, the xylene-containing atactic dicyclopentadiene ring-opening polymer hydride I obtained in this comparative example is amorphous and has no melting point, so the melting point was not measured.

[0164] In Table 1,

[0165] "NB" is Norbornen,

[0166] "DCP" is dicyclopentadiene,

[0167] "TCD" is tetracyclododecene,

[0168] Each represents a different aspect.

[0169]

[0170] According to Examples 1 to 8, it can be seen that resin compositions were produced that have high shape retention when forming a molded article and a reduced heating temperature required during the molding process. In addition, it can be seen that in the resin compositions according to Comparative Examples 1 to 5, which do not contain organic solvents, and in the resin composition according to Comparative Example 6, which has a low content of organic solvent, the heating temperature during molding could not be reduced at all. Furthermore, in the resin composition I according to Comparative Example 7, which consists of an amorphous polymer, it can be seen that introducing an organic solvent into the resin composition did not increase the density of the resin composition, but rather resulted in a decrease in density, making it impossible to even guarantee good shape retention.

[0171] [Industrial Applicability]

[0172] According to the present invention, a resin composition and a method for manufacturing the same can be provided, which have high shape retention when a molded article is formed and also have a reduced heating temperature required in the molding process.

[0173] In addition, according to the present invention, a molded article with high shape retention can be provided.

Claims

Claim 1 A crystalline polymer having structural units derived from cyclic olefin compounds and an organic solvent, comprising a density of 1.02 g / cm³ 3 A resin composition having the above, wherein the content of the organic solvent relative to 100 mass% of the polymer is 1.0 mass% or more and 10 mass% or less. Claim 2 A resin composition according to claim 1, wherein the polymer is a hydride. Claim 3 A resin composition according to paragraph 2, wherein the hydrogenation rate of the polymer is 90% or higher. Claim 4 A resin composition according to claim 1, wherein the organic solvent is a non-polar solvent. Claim 5 A molded article formed by molding a resin composition described in any one of paragraphs 1 to 4. Claim 6 A polymer material comprising a crystalline polymer having structural units derived from cyclic olefin compounds is subjected to an immersion process in which it is immersed in an organic solvent, and the polymer material subjected to the immersion process is dried under an atmosphere of pressure between 1,000 Pa and 6,000 Pa and temperature between 5°C and 35°C, so as to have a density of 1.02 g / cm³ 3 A method for preparing a resin composition, comprising a drying process to obtain a resin composition in which the content of the organic solvent relative to 100 mass% of the polymer is 1.0 mass% or more and 10 mass% or less.

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