JP2001294724A - Resin material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high heat-resistant polyolefin resin material, and to have various forms of resin having environmental safety, chemical resistance and non-hygroscopicity and applicable to various uses. Providing materials. SOLUTION: The molecular structural unit constituting the cyclohexadiene-based polymer has a hydrogenation ratio (molar fraction) of 8 of the molecular structural unit (A) derived from the cyclohexadiene-based monomer.
0% or more, the hydrogenation rate (molar fraction) of the molecular structural unit (B) derived from the chain conjugated diene-based monomer and the molecular structural unit (C) derived from the vinyl-based aromatic monomer is A resin material containing 50% by weight or more of a hydrogenated cyclohexadiene-based polymer which is 80% or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a high heat-resistant polyolefin resin material.

[0002]

2. Description of the Related Art Polyolefin-based materials such as polyethylene and polypropylene can be recycled because they are thermoplastic resins, and because they do not contain halogen molecules or aromatic groups in the molecular structure, they can be discarded and incinerated. It does not generate dioxins or environmental hormones, and is excellent in environmental safety. Furthermore, polyolefin-based materials are excellent in acid resistance, base resistance, and chemical resistance, and are non-hygroscopic, and thus have high utility value. However, these general-purpose polyolefin-based materials have poor heat resistance and cannot be used for heat-resistant applications. For example, the heat resistance (operable temperature) of polypropylene is at most 160 ° C.

On the other hand, as an attempt to improve the heat resistance of a polyolefin material, for example, a cyclic polyolefin using a polycyclic norbornene monomer (for example, Japanese Patent Publication No. 2-9612)
JP, JP-A-60-168708, JP-B-8-
26124) has been proposed. Among resin materials having a porous structure composed of a resin matrix structure and pores, resin materials having a porous structure in which pores communicate with each other are used in a wide range of applications such as filters, absorbents, and separators. In addition, the resin material, which is a foam having pores having a closed cell structure, has properties such as light weight, heat insulating properties, insulating properties, and the like, and is used as a heat insulating material, a packaging material, a cushioning material, a lightweight molded body, an insulating material, and the like. It is used in various fields.

[0004] Further, resin materials in the form of particles are used in the fields of resin fillers, molded product precursors, lubricants, lubricants, mold release materials, coating materials, and the like.
It is used in various fields such as a molded product precursor, a nonwoven fabric, a woven fabric, and a mesh. Film and sheet resin materials include package materials, display element parts, panels, protective plates,
It is used for window materials. However, polyolefin-based resin materials conventionally used in these fields have a relatively low heat-resistant temperature and thus low high-temperature reliability, and the range of use of such resin materials has been limited.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyolefin resin material having high heat resistance.
An object of the present invention is to provide various forms of resin materials having environmental safety, chemical resistance, and non-hygroscopicity and applicable to various uses. Another object of the present invention is to provide a high heat-resistant polyolefin-based resin material and a composite resin material having excellent bonding properties with other materials such as metals, ceramics, and resin materials.

[0006]

According to the present invention, there is provided [1] a hydrogenation ratio (molar fraction) of a molecular structural unit (A) of a cyclohexadiene-based polymer represented by the following formula (1): 80% or more. ,
A resin material comprising a hydrogenated cyclohexadiene-based polymer having a hydrogenation rate (molar fraction) of each of the molecular structural units (B) and (C) of 80% or more, and 50% by weight or more,

[0007]

Embedded image

[Formula (1) represents a composition formula of a polymer.
(A) to (C) represent each molecular structural unit constituting the polymer main chain. i to n represent wt% of each molecular structural unit contained in the polymer main chain. (A): selected from cyclohexadiene-based monomers,
A molecular structural unit derived from one or more monomers. (B): a molecular structural unit derived from one or more monomers selected from linear conjugated diene monomers. (C): it is selected from a vinyl aromatic monomer, one or more kinds of molecular structure units derived from a monomer. However, i + m + n = 100, 50 ≦ i ≦ 100, and the number average molecular weight of the polymer is 10,000 or more and 200,000 or less. [2] The resin material according to [1], which is in a fibrous form; [3] The resin material according to [1] or [2], which is in a particulate form, [4]
The resin material according to [1], which is in the form of a sheet or a film, [5] wherein the resin material according to any of [1] to [4] contains a ceramic, a metal, and / or a semiconductor material. A composite resin material.

Hereinafter, the present invention will be described in detail. The resin material of the present invention is characterized by containing a hydrogenated cyclohexadiene-based polymer obtained by hydrogenating the cyclohexadiene-based polymer of the above formula (1). Since the hydrogenated cyclohexadiene-based polymer has high heat resistance, the resin material of the present invention also has high heat resistance. The resin material of the present invention contains 50% by weight or more of the above hydrogenated cyclohexadiene-based polymer.
It is a resin containing not more than 00% by weight, and is a simple substance of the resin material or a composite material with ceramic, metal, semiconductor material and the like. In addition, as a form of the material, fibrous, particulate,
Sheet or film form is possible.

The heat resistance of the resin material of the present invention is superior to that of a commonly used polyolefin resin (polypropylene has a heat resistance of at most 160 ° C.). Can be.
Further, the hydrogenated cyclohexadiene-based polymer contained as an essential component in the resin material of the present invention has both transparency and non-hygroscopicity, so that it is particularly suitably used for heat resistance applications utilizing these properties. The content of the hydrogenated cyclohexadiene-based polymer obtained by hydrogenating the cyclohexadiene-based polymer of the above formula (1) contained in the resin material of the present invention is 50.
The content is not less than 100% by weight, preferably not less than 60% by weight and not more than 100% by weight, more preferably not less than 70% by weight and not more than 100% by weight. The hydrogenated cyclohexadiene-based polymer has a property of being excellent in heat resistance, and its content can be increased to increase the heat resistance temperature of the resin material.

The cyclohexadiene-based polymer represented by the above formula (1) has one or more monomeric units selected from cyclohexadiene-based monomers as molecular structural units constituting a polymer chain. Contains a molecular structural unit (A) derived from the body. The monomer of the cyclohexadiene polymer is a 6-membered cyclic conjugated diene, and specific examples thereof include 1,3-cyclohexadiene and derivatives thereof. The cyclohexadiene-based polymer in the present invention,
Polymer of only cyclohexadiene monomer (A) or copolymer of monomer (A) with chain conjugated diene monomer (B) and / or vinyl aromatic monomer (C) It is a polymer.

In the present invention, other monomers copolymerized with the cyclohexadiene-based monomer include, for example, 1,3-
Butadiene, isoprene, 2,3-dimethyl-1,3-
Chain conjugated diene-based monomers (B) such as butadiene, 1,3-pentadiene, and 1,3-hexadiene; styrene;
vinyl aromatic monomers (C) such as α-methylstyrene, o-methylstyrene, p-methylstyrene, tert-butylstyrene, 1,3-dimethylstyrene, divinylbenzene, vinylnaphthalene, diphenylethylene and vinylpyridine These monomers may be used alone or in combination of two or more as necessary. In addition, examples of the type of copolymerization include block copolymerization, graft copolymerization, random copolymerization, and alternating copolymerization.

The content of the molecular structural unit (A) derived from the cyclohexadiene monomer of the cyclohexadiene polymer represented by the above formula (1) used in the present invention is based on the total molecular structural unit. , 50% by weight or more and 100% by weight or less, preferably 60% by weight or less and 100% by weight or less,
More preferably, the content is 70% by weight or more and 100% by weight or less. It is preferable that the content of the molecular structural unit derived from the cyclohexadiene-based monomer be high because of high heat resistance.

The hydrogenated cyclohexadiene-based polymer used in the resin material of the present invention is obtained by synthesizing a cyclohexadiene-based polymer and then removing the carbon-carbon remaining in the molecular structural unit (A) derived from the cyclohexadiene-based monomer. The double bond contains a hydrogenated molecular structural unit, and the hydrogenation rate (molar fraction) of the molecular structural unit (A) is 80% or more and 100% or less, preferably 90% or more and 100% or less, and more preferably 95% or less. % To 100%. A high hydrogenation rate leads to high heat resistance of the resin material, which is preferable. In addition, since the transparency of the visible-ultraviolet region is improved by the high hydrogenation rate of the polymer, the polymer is preferable for applications using transparency.

When the cyclohexadiene polymer is a copolymer of a cyclohexadiene monomer and another monomer, the molecular structural unit (A) derived from the cyclohexadiene monomer is In the hydrogenation reaction, a molecular structural unit (B) derived from a linear conjugated diene monomer and / or a molecular structural unit (C) derived from a vinyl aromatic monomer contained in the copolymer. Is also hydrogenated at the same time. Molecular structural units (B) and (C) in the copolymer
Is 80% or more and 100% or less, preferably 90% or more and 100% or less, and more preferably 95% or less.
% To 100%.

The cyclohexadiene polymer represented by the formula (1) of the present invention has a number average molecular weight of 10,000 or more and 2 or more.
It is in the range of 00,000. Number average molecular weight 10,000
If the number average molecular weight is less than 200,000, the polymerization time will be long and the productivity will be poor. The production of the cyclohexadiene-based polymer,
Known methods (for example, WO94-28038, WO
94-29359, WO95-21217, and WO96-16090). As an example of the synthesis method, a polymer can be obtained by living anionic polymerization using an alkali metal ion complex as an initiator. In addition, a copolymer can be produced by sequentially or simultaneously charging and polymerizing a plurality of types of monomers together with an initiator. Hydrogenated cyclohexadiene based on hydrogenation in a hydrogen atmosphere using a hydrogenation catalyst such as a transition metal element or alloy such as palladium, nickel, rhodium, or a transition metal complex such as titanocene or ferrocene on the double bond of the formed polymer. A polymer can be obtained. Alternatively, hydrogenation can be performed by reacting a hydride such as calcium hydride, lithium hydride, or borohydride with a cyclohexadiene-based polymer.

As a specific example, in the case of a nickel catalyst,
Raney nickel manufactured by aluminum etching of nickel aluminum alloy (for example, Nikko Rica Co., Ltd.)
R-200), Raney nickel is mixed with a decaline solution of a cyclohexadiene polymer, and the mixture is subjected to a heat treatment under a hydrogen pressure condition, whereby a hydrogenation reaction of the cyclohexadiene polymer can be performed. As the reaction conditions,
The nickel catalyst is used in a range of 1% by weight or more and 500% by weight or less based on the weight of the cyclohexadiene polymer, a hydrogen pressure is in a range of 1000 hPa to 10 MPa, and a reaction temperature is in a range of room temperature (20 ° C) to 200 ° C. be able to.

A functional group can be introduced into the cyclohexadiene-based polymer of the present invention during and / or after the polymerization. Examples of the functional group include a halogen atom, a C1-C20 alkyl group, a C2-C20 unsaturated aliphatic hydrocarbon,
5 to C20 aryl group, C3 to C20 cycloalkyl group, C4 to C20 cyclodienyl group, 5- to 10-membered heterocyclic group containing at least one nitrogen, oxygen or sulfur as a hetero atom, epoxy group , A hydroxyl group, a sulfonic acid group and a silane group.

Further, the cyclohexadiene polymer used in the present invention may have a reactive functional group in the molecular chain or at the terminal. In order to provide a reactive functional group, a known compound which is generally known to react with an anionic polymerization terminal or a double bond may be added following the polymerization reaction. Examples of such compounds include methyldimethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, phenyldimethoxysilane, dichlorodimethoxysilane, methyltris (ethylmethylketoxime) silane, methyltris (N, N-diethylaminoxy) silane, and the like. Silylate, ethylene oxide,
Oxides such as propylene oxide and butene oxide, titanium compounds such as tetrabutoxytitanium, halogens such as chlorine, bromine, iodine and hydrogen chloride, peroxides such as hydrogen peroxide and metachloroperbenzoic acid, and other aluminum isopropoxides , Triisopropoxy borane, ethyl chloroacetate and the like.

If necessary, a plasticizer, an antioxidant, a light stabilizer, a flame retardant, a dye, a crosslinking agent, a foaming agent, an antistatic agent, and other polymer materials may be added to the hydrogenated cyclohexadiene-based polymer. , Etc., or an inorganic compound can be added and mixed. As an example of this, as a plasticizer,
For example, phthalic acid esters, aliphatic dibasic acid esters, halogenated paraffins, polyester-based plasticizers, epoxy-based plasticizers, phosphate-based plasticizers, trimellitate-based plasticizers, and antioxidants such as phenol-based As sulfur-based, phosphorus-based antioxidants and light stabilizers, for example, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, hindered amine-based light stabilizers, and as flame retardants, for example, halogen-based flame retardants, phosphorus-based flame retardants Examples of the flame retardant, inorganic flame retardant, and lubricant include hydrocarbon lubricant, fatty acid / higher alcohol lubricant, aliphatic amide lubricant, metal soap lubricant, and ester lubricant.

Other polymer materials include, for example, nylon 4, nylon 6, nylon 8, nylon 9, nylon 10, nylon 11, nylon 46, nylon 66, nylon 610, nylon 612, nylon 636, nylon 1212 and the like. Aliphatic polyamide, nylon 4T
(T: terephthalic acid), nylon 4I (I: isophthalic acid), nylon 6T, nylon 6I, nylon 12T,
Aromatic polyamides such as nylon 12I and nylon MXD6 (MXD: meta-xylene diamine) and polyamide polymers such as copolymers thereof, polybutylene terephthalate (PBT), polyethylene terephthalate (PE
T), polycarbonate (PC), polyarylate (P
AR), olefin polymers such as polypropylene (PP), polyethylene (PE), ethylene propylene rubber (EPR), polystyrene, polybutadiene (PBd), polyisoprene (PI
p), conjugated diene polymers such as styrene-butadiene copolymer (SBR) or hydrides thereof, thiol polymers such as polyphenylene sulfide, ether polymers such as polyethylene oxide, polyacetal and polyphenylene ether, or acrylic resins , AB
S resin, AS resin, polysulfone, polyether ketone, polyamide imide, polyvinylidene chloride, polyvinylidene fluoride and the like can be exemplified. The kind and amount of other polymer materials to be mixed are the same as those of the above-mentioned hydrogenated cyclohexadiene system. There is no particular limitation as long as the polymer is contained in an amount of 50% by weight or more, and it is determined as needed.

In the resin material of the present invention, the hydrogenated cyclohexadiene-based polymer is contained in an amount of 50% by weight or more, and the content of the organic compound or the inorganic compound is less than 50% by weight. Further, the resin material of the present invention can also be used as a composite material containing ceramics, metal and / or semiconductor material. The content of the ceramics, metal, and semiconductor to be composited can be adjusted according to the intended use, and there is no limitation on the content of the ceramics, metal, and semiconductor in the composited material. Therefore, these composite materials can be included in the resin material, and the surface of a ceramic, metal, or semiconductor can be coated with the resin material.

Examples of the ceramic to be composited include glass fiber, glass wool, talc, mica, kaolin, silica, alumina, magnesium oxide, iron oxide, titanium oxide, nickel oxide, cobalt oxide, ceria, rock wool, and silicon nitride. Carbon such as silicon carbide, diamond, carbon cluster, carbon nanotube, fluoride such as calcium fluoride, magnesium fluoride, rare earth fluoride, oxyfluoride, calcium phosphate, potassium phosphoborate, phosphorus such as indium phosphorus, gallium phosphorus Compounds, nitrides such as silicon nitride, iron nitride, iron nitride alloys, and lithium nitride are exemplified. Further, as the metal to be composited, for example, aluminum, copper, silver, iron, cobalt,
Examples thereof include simple metals such as stainless steel, lead, tin, indium, gold, platinum, palladium, and rhodium, and alloys such as aluminum-magnesium alloys, aluminum-silicon alloys, rare-earth cobalt alloys, and rare-earth iron alloys, and graphite and coke. Further, as the composite semiconductor material,
For example, silicon, germanium, gallium arsenide, indium gallium arsenide, gallium nitride, indium nitride,
Simple oxides such as titanium oxide, tin oxide, lead oxide, indium oxide, and cobalt oxide, and composite oxides such as indium tin oxide and lithium titanate based on these compounds, lead oxide, zinc oxide, zinc sulfide, and organic compounds Semiconductors and the like.

In the composite resin material of the present invention, the above-mentioned materials to be contained can be used alone or in a mixture, and the shapes of the contained materials are fibrous, chopped strand,
Cloths, non-woven fabrics, flakes, powders, fine particles, sheets, and films can be used. As the manufacturing method, a composite can be formed by a method in which the resin is uniformly dispersed in a resin material in advance and a method in which the above-described ceramic, metal, and semiconductor are joined to the surface of the resin material. This composite is preferable because not only the optical and electronic functions of the materials to be mixed are exhibited as a resin material, but also the low linear expansion coefficient and high elastic modulus of the composite material are reflected in the composite material.
In addition, since the refractive index of the cyclic conjugated diene-based polymer resin used in the present invention is close to that of a general-purpose glass material, a composite material with a general-purpose glass exhibits excellent transparency and is preferable as an optical material.

The resin material of the present invention may be in the form of a fiber, and may have a cross-sectional shape such as a circle, an ellipse, a rectangle, a polygon, and a concentric circle. This fiber diameter is expressed as the average diameter of the major axis and the minor axis of the cross section. The average diameter of the fibrous resin material of the present invention is in the range of 0.02 μm to 1 mm, and preferably in the range of 0.05 μm to 500 μm. When the diameter is less than 0.02 μm, not only is production difficult, but handling is complicated, and the melting point decreases with an increase in surface energy. Further, a diameter exceeding 1 mm is not preferable because the range of surface modification or use as a filler is limited, and bendability and the like are reduced. Since the diameter and the diameter distribution are different depending on the application to be used, they cannot be specified. However, when they are used for woven fabrics, meshes, and the like, it is preferable that the diameter distribution of the fibers is narrow.

The method for producing the fibrous resin material is as follows.
For example, a method in which a polymer solution is spun into a poor solvent and coagulated, a method in which a polymer solution is spun and dried, a method in which a polymer is spun in a heat-melted state, and a mixture of a polymer, a plasticizer, and additives are heat-melted. After spinning and coagulating in a state, a method of removing at least a part of a plasticizer and an additive may be mentioned. For example, when producing by a method of spinning and coagulating a polymer solution in a poor solvent, after preparing a polymer solution of a solvent that dissolves the polymer (good solvent), the polymer is not dissolved,
A fibrous resin material can be prepared by spinning out a solvent (poor solvent) that can be uniformly mixed with the good solvent. The fiber shape can be adjusted by the solvent type of this polymer solution, polymer concentration, poor solvent type, poor solvent amount, discharge condition of polymer solution, and nozzle shape.
Thereafter, centrifugation and pressing can be additionally performed. For example, in the case of polycyclohexane, simple or mixed solvents such as decalin, cyclohexane, dimethylcyclohexane and toluene are used as good solvents, and simple or mixed solvents such as acetone, MEK, ethyl acetate, diethyl ether, ethanol and methanol are used as poor solvents. Mixed solvents can be used.

In the case where the solvent is evaporated and dried after discharging the polymer solution, the polymer solution of the above-mentioned good solvent is discharged from a nozzle into a space to form a thread-like polymer solution. Can be solidified. The diameter and cross-sectional shape can be adjusted by the solvent type, polymer concentration, viscosity, nozzle shape, discharge speed, temperature and flow rate of the solvent evaporation space of the polymer solution. Centrifugation, pressing and cutting steps can be added after the polymer solidification step.

In the method of producing a fibrous resin material by discharging and cooling a polymer in a molten state from a nozzle, a fibrous resin material is discharged from the molten state similarly to the above-described method. The winding speed and the like affect the fiber shape and physical properties. Also, after fiber formation, stretching,
Pressing, cutting, etc. can be added. When producing a fibrous resin material by these methods, a plasticizer, an additive, a stabilizer, and the like can be mixed with the polymer solution or polymer. Also, if necessary, the resin material in a fibrous form obtained here may be subjected to plating, oxidation, reduction, surface modification such as coating, internal stabilizer, plasticizer, ultraviolet absorber, etc. Can be modified or mixed with other particles.

The resin material of the present invention may be in the form of particles, and may be in the form of a sphere, ellipsoid, rod, needle, plate or the like. The cross-sectional shape may be circular, elliptical, rectangular, or the like. This particle size is expressed as an average of the major axis and minor axis of the particle. The average particle size of the particles of the present invention is in the range of 0.05 μm to 1 mm, preferably 0.1 μm.
The range is from μm to 500 μm. This particle size is 0.05μ
If it is less than m, an aggregate is likely to be formed, and the surface energy increases, so that the melting point may be lowered, which is not preferable. Further, if the particle size exceeds 1 mm, the range of surface modification or use as a filler is limited, and the characteristics of the bulk molded article are unclear. Although the particle size and particle size distribution cannot be specified because they differ depending on the use,
When used as a lubricant, a release material, a paint additive, and the like, it is preferable that the particle size distribution is narrow.

This particulate resin material is prepared by a method of reprecipitating a polymer solution with a poor solvent, a method of spray drying a polymer solution, a method of atomizing a polymer in a molten state, and a method of pulverizing at a temperature below the glass transition point. can do. For example, in the case of preparing by a reprecipitation method, after preparing a polymer solution of a solvent that dissolves the polymer (good solvent), the polymer is not dissolved, and mixed with a solvent (poor solvent) that can be uniformly mixed with the good solvent to obtain particles. A resin material in the shape of a letter can be produced. The particle shape can be adjusted by the solvent type, polymer concentration, poor solvent type, poor solvent amount, and mixing conditions of the polymer solution. Generally, this reprecipitation method can produce a spherical or spherical aggregate-shaped resin material. For example, in the case of polycyclohexane, simple or mixed solvents such as decalin, cyclohexane, dimethylcyclohexane and toluene are used as good solvents, and simple or mixed solvents such as acetone, MEK, ethyl acetate, diethyl ether, ethanol and methanol are used as poor solvents. Mixed solvents can be used.

When manufacturing by the spray drying method,
The polymer solution of the good solvent is discharged from a nozzle into a space to form a particulate polymer solution, and the polymer can be solidified into particles by solvent evaporation. The particle size and shape can be adjusted by the solvent type, polymer concentration, viscosity, nozzle shape, discharge speed, temperature and flow rate of the solvent evaporation space of the polymer solution. When the viscosity of the polymer solution is high in this preparation, the resin material is in a spinning state and an ellipsoidal or fibrous resin material is formed. In this case, an interparticle agglomerate is likely to be generated, so that a pulverization or cutting step can be added to this polymer solidification step.

The atomizing method is a method in which a molten polymer is discharged from a nozzle and cooled to produce a particulate resin material. The viscosity of the molten polymer, that is, the heating temperature affects the particle shape. Usually, in the case of a molten state at a high temperature and a low viscosity, the particle shape is fine and spherical particles are easily generated. Also in this method, a particle aggregate or a string structure may be generated in the production step, and in this case, a step of pulverizing or cutting the particles can be added.

Next, a method for producing a particulate resin material by a pulverization method will be described. For example, the polymer can be pulverized by a ball mill, a crusher, or the like at a temperature equal to or lower than the glass transition point of the polymer by a wet or dry method. In this method, the particle size distribution may be widened depending on the pulverization conditions. Therefore, after the pulverization, a classification step using a sieve, a cyclone or the like can be added to control the particle size distribution or recycle.

By these methods, a particulate resin material can be produced. Modification of the particulate resin material obtained here, such as plating, oxidation, reduction, surface modification such as coating, internal stabilizers, plasticizers, UV absorbers, etc. Can also be mixed with the particles. Further, depending on the application to be used, a slurry dispersed in a liquid such as a solution, a solvent, or water can be used. Further, the resin material of the present invention may be in the form of a sheet or a film, and may be in the form of a long or strip-shaped plate. The thickness is preferably 0.05 μm or more and 5 mm or less. The thickness varies depending on the application, and can be obtained as a sheet or film having a thickness suitable for the application. Also,
Depending on the application, the surface may have an uneven shape or a locally changed thickness, or may be used by being laminated with another material.

The method for producing the resin material in the form of a sheet or film will be described. Examples of the production method include melt molding, solution cast molding, and powder fusion molding. In the case of melt molding, after the resin is heated and melted, it can be molded by press molding, extrusion molding, or injection molding. The molding conditions vary depending on the structure and the molecular weight of the resin material. For example, in the case of polycyclohexane having a molecular weight of 40,000, the molding conditions include melting at a temperature of 300 ° C., followed by press molding or extrusion molding. In addition, it is preferable that the molding be performed in an inert gas environment or a reduced pressure environment in order to suppress the oxidative deterioration of the resin material. As an additive to the resin material, an antioxidant, a stabilizer, an ultraviolet absorber,
Pigments, dyes, and the like. If necessary, a stretching process, a calendering process, a pressing process, a blasting process, or the like can be added during or after the molding.

In a method for producing a resin material in the form of a film or sheet by a solution casting method, a resin solution is spread on a base material with a predetermined thickness, and the solvent is evaporated to form the resin material. As the solvent, for example, when the polymer is polycyclohexane, a simple substance or a mixed solvent such as decalin, cyclohexane, dimethylcyclohexane, and toluene is used. As a base material on which the polymer solution is developed, a material that does not deform or swell due to a solvent is preferable, and a sheet or belt of metal, resin, ceramic, or the like can be used. Then, drying is performed to remove the solvent, and a film or a sheet can be formed. In this drying step, the resin molded body is stretched,
It is possible to apply tension, calendering, and press.

As a method for producing a resin material in the form of a sheet or film by powder melt molding, for example, a slurry in which powder is uniformly dispersed in a liquid is prepared, and then the slurry is cast onto a substrate, followed by solvent removal. The molded body can be produced by heating to melt the powder. Further, after the powder is filled in a mold having a predetermined shape, the mold is heated and the powder is melted and solidified to produce a molded body. When the resin material in the form of a sheet or film prepared here is used for low birefringence, it is preferable to maintain isotropy without applying stress in molding, and it is preferable to use solution cast molding or powder melt molding as a production method.

The surface of the resin material of the present invention described above is
Oxidation treatment is possible. The surface-oxidized resin material will be described. This oxidation treatment can be applied to the entire surface or a part of the surface of the resin material, depending on the intended use. By subjecting the resin material of the present invention to a surface oxidation treatment, it is possible to improve the adhesion to other materials and the interfacial bonding. Examples of the surface oxidation treatment method include a discharge treatment, a flame treatment, an ozone treatment, an ionizing actinic radiation treatment, a plasma treatment, a high-temperature heating treatment, and an oxidizing agent treatment. You may. By this surface oxidation treatment, the surface of the resin material of the present invention is oxidized, so that the resin material of the present invention can have excellent adhesion and interface bonding properties with metals, ceramics, and other polymer materials.

Further, specific methods include corona discharge and glow discharge as discharge treatment, ultraviolet irradiation, electron beam irradiation, radiation treatment, high-temperature hot air treatment as ionization active ray treatment.
Includes infrared and far infrared processing. As the oxidizing agent used in the oxidizing agent treatment, organic peroxides such as peracetic acid, trifluoroperacetic acid, and benzoyl peroxide; inorganic peroxides such as sodium peroxide and lithium peroxide; inorganic such as cerium oxide compounds and chromium oxide compounds Oxides. The degree of the surface treatment can be adjusted and used by performing these surface treatments at a predetermined temperature, a predetermined atmosphere, and a predetermined time. Further, it is also possible to perform a surface masking or a processing operation only on a predetermined portion to perform a surface treatment on only a part of the surface of the molded body. These surface oxidation treatments are industrially preferable because they are simpler and cheaper than surface coating treatments of other materials that are usually used.

Although the principle is not clear, it is considered that a polar functional group such as a ketone group, a hydroxyl group, or an epoxy group is introduced on the surface, and that the adhesion is improved by the polarization action of the polar group. This means that the improvement in wettability by the polar functional group can be expressed using the surface tension as an index. Measurement of surface tension is JI
SK6768. The surface tension of the molded article of the present invention is preferably 0.030 N / m or more, more preferably 0.033 N / m or more, and further preferably 0.035 N / m or more.

Examples of materials having excellent bonding properties with the surface-oxidized resin material of the present invention include metals, ceramics, and resins. The resin material subjected to the surface oxidation treatment of the present invention,
Since the oxidation treatment is performed only on the surface, it has a feature that physical properties inside the resin material are maintained. For this reason, for example, when the resin material of the present invention is used as a transparent material, it can be used as a resin material having excellent surface adhesion and interface bonding without impairing optical properties. For example, a transparent conductive material in which indium tin oxide is coated on the surface of a resin material, a reflective material in which a metal layer such as aluminum or silver is formed on the surface and the metal layer is used as a reflective layer, and It is suitably used for a wiring material used as a conductive layer, a magneto-optical recording medium having a magnetic material formed on the surface, and the like. Also, in applications where a functional material is coated on the surface of a material that has been surface-treated as a functional material other than optical applications, the functional resin material can be used without impairing the properties such as mechanical and electrical properties inside the material. Is preferred.

Further, the resin material of the present invention is characterized by having excellent heat resistance.
The temperature is preferably 90 ° C. or higher, more preferably 2 ° C.
It is at least 00 ° C, most preferably at least 210 ° C. This heat resistance is due to the fact that the cyclohexadiene-based polymer mainly contained in the resin material of the present invention has excellent heat resistance. It is considered that the cyclohexadiene-based polymer has a structure in which cyclohexane rings are linked, and the cyclohexane ring has better thermal stability than a cyclopentane ring or a methylene group. In order to improve the heat resistance temperature of the resin material of the present invention, the content of cyclohexane structural units in the cyclohexadiene-based polymer contained in the resin material of the present invention is preferably high, and the cyclohexadiene contained in the resin material is preferably high. It is preferable that the content of the system polymer is high. Further, in order to increase the heat resistance of the cyclohexadiene-based polymer, it is preferable that the 1,2-bond content is high as a polymerization mode of the cyclohexane ring of the cyclohexadiene-based polymer because a high thermal deformation temperature results.

The resin material of the present invention is characterized by a low dielectric constant. This evaluation can be performed by the method of ASTM (D-150) in the present invention. The relative permittivity of the insulating material of the present invention is preferably 2.5 or less, more preferably 2.4 or less. For example, the dielectric constant of cyclohexane alone is 2.31. This relative permittivity can be adjusted by the kind of polymer and resin composition used for the insulating material and the structure of the molded body. Examples of this include the copolymer composition of a cyclohexadiene-based polymer, other material types in a mixture of a cyclohexadiene polymer and another material, and the blend composition. Can also be adjusted.

Polyolefins such as polyethylene and polypropylene, which are general-purpose materials, have a dielectric constant of 2.2 to 2.6, which is a relatively low value as a polymer material, and are used as insulating materials but have poor heat resistance. A material having both dielectric constants has been desired. Due to the above properties, the resin material of the present invention has a wire covering material, a power supply component, a signal transfer cable covering material, a coaxial cable covering material, a wiring board material, a wiring board interlayer insulating film, a semiconductor element sealing material, a battery, and a high frequency communication component. ,
Optical fiber, photodiode, light emitting diode, semiconductor laser, transistor, IC, LSI, HEM
It can be used for devices such as T, MMIC, recording media, communication parts, and devices using these.

Further, transparency is a feature of the resin material of the present invention. When the resin material of the present invention is used as a transparent material, the total light transmittance (JIS K7105) is preferably 85% or more, and more preferably 88% or more. Therefore, taking advantage of transparency, lenses, liquid crystal substrates, liquid crystal polarizers, plasma display protection plates, FED protection plates, display materials such as touch panel substrates, optical fibers, optical computing elements, LEDs, laser diodes, optical disk substrates, solar cells It can be applied to substrates, protective layers for solar cells, transparent containers, transparent containers, window materials, and the like. The resin material of the present invention can be used in various fields, and has high industrial value due to excellent heat resistance.

[0046]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to embodiments.

[0047]

EXAMPLE 1 A 10% by weight decalin solution was prepared using 3-cyclohexadiene (CHD) as a monomer, and mixed with n-butyllithium (n-BuLi) and tetramethylethylenediamine (TMEDA) as catalysts (CH).
D / n-BuLi / TMEDA = 200/1/1) After 4
Polymerization was carried out at a temperature of 0 ° C. for 6 hours. The synthesized polycyclohexadiene solution was charged into an autoclave, and hydrogenation was performed using a Raney nickel catalyst (three times the weight of the polymer) under hydrogen pressure (held at 150 ° C. for 3 hours, initial hydrogen pressure 5.23).
MPa) to synthesize polycyclohexane (infrared absorption spectrum confirmed that 98% of the cyclohexene units had been hydrogenated). The solution after hydrogenation was reprecipitated with acetone and dried to obtain a powdery polymer.

Next, a decalin solution of the polymer (10
% By weight) on a glass plate and dried to prepare a film (300 mm × 100 mm). The obtained film had a thickness of 80 μm. The film was loaded into an autoclave, immersed in Freon (HFC-134a), and sealed and heated (80 ° C, 2 hours) to impregnate the film with Freon. Then, the film was taken out and brought into contact with a roll heated to 300 ° C. to cause foaming, whereby a foamed sheet having a thickness of 140 μm was obtained. The porosity determined from the specific gravity of the obtained foam was 80% (expansion ratio 4 times). Further, as a result of heating the sheet-like foam at 200 ° C., no change in film thickness was observed, and it was found that the sheet-like foam had excellent high-temperature stability.

[0049]

Example 2 Using the polymerization catalyst of Example 1, styrene (St) was charged into this decalin solution and polymerized (40 ° C., 2 hours)
Thereafter, cyclohexadiene (CHD) is charged (St / CH
D = 2/8) to synthesize a diblock polymer of styrene-cyclohexadiene. Raney nickel was added to this polymer solution (the amount added was 3 times the weight of the polymer), and then a heating reaction (150 ° C., 4 hours) was performed in a hydrogen pressurized environment. The hydrogenation rate of the obtained hydrogenated polymer was evaluated by infrared absorption spectrum and proton NMR.
It was found that 0% and 99% of the styrene aromatic rings were hydrogenated. Next, the polymer solution was reprecipitated in an acetone solution having a weight four times the weight of the polymer solution, and dried to obtain a copolymer powder.

After the polymer was heat-melted into chips having a diameter of 1 mm, it was impregnated with Freon in the same manner as in Example 1.
A bead-shaped resin foam foamed on a hot plate heated to an average temperature of 2.1 mm was prepared. The specific gravity of the beads was determined using an air pycnometer, and the porosity was determined. As a result, the porosity of the foam was 73% (expansion ratio: 3). The beaded foam was loaded into a cylindrical mold (internal volume: diameter 10 mm, length 10 mm), and the mold was heated at 250 ° C.
To produce a cylindrical foam molded article. The molded body was heated to 200 ° C., but no deformation was observed.

[0051]

Example 3 The polymer produced in Example 2 was melt-molded with a single screw (screw diameter 25 mm, nozzle 1 mm) and carbon dioxide gas was supplied to the screw vent at 10 k.
The mixture was filled at a pressure of g / cm, and heated and extruded at a molding machine temperature of 290 ° C., whereby a white wire-like foam (2 mm in diameter) was obtained. The specific gravity of the foam is evaluated with an air pycnometer,
As a result of determining the porosity, the porosity was 50%. After heating the wire-shaped resin foam at a temperature of 200 ° C. for 1 hour, the porosity was evaluated. As a result, the porosity was 49%, and almost no structural change was observed.

[0052]

Example 4 A solution of the polymer prepared in Example 1 in decalin (5% by weight of polymer) was prepared, reprecipitated in acetone having a weight ratio of 5 times, filtered and dried to obtain a powdery polymer. . The obtained polymer was dissolved in decalin to prepare a polymer solution (5% by weight). Then, the solution was
The fibrous material was discharged from a nozzle having 100 holes with a diameter of m, immersed in an acetone solution, and solidified to produce a fiber. The obtained fiber had a diameter of 11 μm and had a structure having a slight unevenness on the surface. 200 ° C
After heat treatment in an oven for 1 hour, microscopic observation showed no deformation or melting of the fiber.

[0053]

Example 5 The polymer solution obtained in Example 2 was reprecipitated in acetone and dried to prepare a polymer powder. A decalin solution of the polymer (polymer concentration of 5% by weight) was discharged from a nozzle into the air, and dried to produce fibers. As a result of microscopic observation, it was found that the average diameter was about 12 μm. When this fiber was heated to a temperature of 200 ° C. using a differential thermal analyzer, no heat absorption or heat radiation was observed. The fibers cooled after heating were observed under a microscope, and as a result, no aggregation or fusion of particles was observed.

[0054]

Example 6 The polymer obtained by polymerization and hydrogenation in Example 2 was introduced into a melt molding machine having a cylinder having a diameter of 25 mm.
Heat extrusion molding at a temperature of 00 ° C (discharge nozzle diameter 25μ)
m was arranged in 20 holes) to draw out a molten polymer to produce a fibrous polymer. The resulting fiber has an average diameter of 1
It was found by microscopic observation to be 8 μm. After heating the fiber at a temperature of 200 ° C. in the atmosphere for 1 hour, the shape was examined by microscopic observation. As a result, no morphological change such as melting or deformation was observed.

[0055]

Example 7 A decalin solution (5% by weight of polymer) of the polymer prepared in Example 1 was reprecipitated in 5 times by weight of acetone, filtered and dried to obtain a powdery polymer. As a result of microscopic observation of the obtained powdery resin, the average particle size was 8 μm.
m spherical body. As a result of heating the powder to a temperature of 200 ° C. using a differential thermal analyzer, no heat absorption or heat radiation was observed. Further, as a result of microscopic observation of the powder sample cooled after heating, aggregation and fusion of particles were not observed.

[0056]

Example 8 The polymer decalin solution (polymer 3% by weight) obtained in Example 2 was reprecipitated in acetone having a weight ratio of 5 times.
After filtration and drying, a copolymer powder was obtained. As a result of microscopic observation of the obtained powdery resin, it was found to be a spherical body having an average particle size of 15 μm. As a result of heating the powder to a temperature of 200 ° C. using a differential thermal analyzer, no heat absorption or heat radiation was observed. Further, as a result of microscopic observation of the powder sample cooled after heating, aggregation and fusion of particles were not observed.

[0057]

Example 9 Using the polymer prepared in Example 1, a 1% by weight solution of a mixed solvent of decalin / cyclohexane (volume ratio of decalin / cyclohexane = 1/1) was prepared. The solution was formed into droplets of the solution by an atomizer and dropped on a hot plate to obtain a powdery polymer. Next, it was dried by heating at a temperature of 100 ° C. with a vacuum dryer. Microscopic observation of the obtained powder revealed that it was a particulate resin having an average particle size of 3 μm. Heating was performed to a temperature of 200 ° C. with a differential thermal analyzer in the same manner as in Example 1, but no heat generation or endotherm was observed. Microscopic observation of the powder after heating showed no aggregation or melting of the particles.

[0058]

Example 10 The polymerized and hydrogenated polymer in Example 2 was
Introduced to a melt molding machine with a 25 mm diameter cylinder,
Heat extrusion molding at a temperature of 300 ° C (discharge nozzle diameter 50
Then, the molten polymer was drawn out to form a thread-like polymer. The winding speed of the filament was adjusted to produce a thread having an average diameter of 18 μm. Next, the yarn was cut and then ball milled to produce cylindrical rod-shaped particles having an average length of about 50 μm. After heating the particles at a temperature of 200 ° C. for 1 hour in the atmosphere, the shape was examined by microscopic observation. As a result, no morphological change such as melting or deformation was observed.

[0059]

Example 11 The heat resistance of the polymer prepared in Example 1 was evaluated by a differential thermal analyzer in a nitrogen atmosphere, and it was found that the glass transition point was 255 ° C. In addition, hot press molding of polymer powder to form a 1 mm thick plate,
As a result of evaluating the heat deformation temperature (ASTMD-648), the heat deformation temperature was 230 ° C. A film obtained by casting a decalin solution (10% by weight) of the polymer on a glass plate was dried to obtain a film having a thickness of 30 μm. As a result of cutting the film to a diameter of 12 cm, sandwiching the film with a disk-shaped electrode having a diameter of 10 cm, and evaluating the electric resistance by a DC two-terminal method,
It was found that the volume resistivity was> 10 ¹⁶ ohm · cm. After aluminum was vapor-deposited on the surface of the film through a mask, impedance analysis between the electrodes was performed to determine the dielectric constant. As a result, it was found to be 2.31.

[0060]

Example 12 The polymer prepared in Example 2 was replaced with Example 1
As a result of evaluation in the same manner as in Example 1, the glass transition point was 205 ° C,
Thermal deformation temperature 203 ° C, volume resistivity> 10 ¹⁸ ohm · c
m and the dielectric constant were 2.35.

[0061]

EXAMPLE 13 The polymer obtained in Example 2 was extruded into pellets having a diameter of 3 mm and a length of 3 mm.
A plate of polycyclohexane was formed by press molding at a temperature of 5 ° C. in a reduced pressure atmosphere. The surface tension of the molded body is 0.02
It was 9 N / m. Next, the surface of the molded body was subjected to corona discharge treatment using a quartz electrode manufactured by Kasuga Electric Co., Ltd. The surface tension after this discharge treatment was 0.041 N / m, indicating that the wettability was improved. Aluminum was vacuum-deposited to a thickness of 2 μm on the surface of the obtained polycyclohexane plate, and a Scotch (registered trademark) tape was adhered and peeled off. As a result, peeling of the aluminum layer was not recognized.

[0062]

Example 14 The polymer decalin solution (polymer concentration of 5% by weight) prepared in Example 2 was cast on a glass plate and dried to prepare a film having a thickness of 65 μm. Next, the surface of the film was subjected to ozone treatment with a UV ozone cleaner (NL-UV type device manufactured by Takeda Rika Kogyo Co., Ltd.). The surface tension of the obtained film was 0.036 N / m, and it was found that the wettability was improved as compared to before the treatment (0.030 N / m). In addition, the light transmittance at 600 nm was 92%, and it was found that good transparency was exhibited even after the surface treatment.

Further, an oxygen / argon mixed gas (oxygen 3) was applied to the surface of the surface-treated film at a pressure of 10 ⁻⁴ Pa by magnetron sputtering (a target composed of 90% by weight of indium oxide and 10% by weight of indium oxide).
0%) in a flow atmosphere to form an indium / tin oxide thin film with a thickness of 2 μm. The scotch tape was adhered to and peeled off from the resin plate having the transparent conductive film formed on the surface. As a result, no peeling of the transparent conductive film on the surface was observed.

[0064]

Example 15 The cast film produced in Example 14 was loaded into the substrate holder of the sputtering apparatus used in Example 14, and subjected to reverse sputtering (ion milling) under a flow of a mixed gas of oxygen and argon (50% by volume of oxygen). For 10 minutes to perform oxygen plasma treatment. Then, as a result of evaluating the surface tension of the surface-treated film, 0.036 N
/ M. Barium titanate is sputter-deposited on the surface of this film (barium titanate target, 10 ⁻⁴ Pa, thin film growth to a thickness of 5 μm using a quartz oscillator under a flow of a mixed gas of argon and oxygen (mixing ratio: 1/1)). I did.) Scotch tape was peeled off in the same manner as in Example 13, but no thin film was peeled off.

[0065]

Example 16 A decalin solution (resin 10% by weight solution) of the resin prepared in Example 1 was prepared, impregnated into a glass fiber nonwoven fabric (Surface mat 3600, manufactured by Asahi Fiberglass Co., Ltd.), and the solvent was evaporated. Then, pressing was performed with a mirror twin roll heated at 250 ° C. to produce a composite material having a thickness of 80 μm. As a result of evaluating the linear expansion coefficient of the sheet, it was found to be 0.8 × 10 ⁻⁵ / deg. The total light transmittance was 90% and the flexural modulus was 12 GPa.

[0066]

Example 17 A decalin solution (resin 10% by weight solution) of the resin prepared in Example 1 was prepared, and glass flake (Glaslon flake GF, manufactured by Asahi Fiberglass Co., Ltd.) was prepared.
-C325A) was added in an equal amount to the weight of the resin to prepare a uniformly mixed slurry. The slurry was cast on a glass plate and dried to prepare a sheet having a dry film thickness of 50 μm. The linear expansion coefficient of the sheet was 1.6 × 10 ⁻⁵ / deg, and the total light transmittance was 91%.

[0067]

According to the present invention, it has become possible to provide a composite of a particulate resin, a fibrous resin, a sheet, a film, and a ceramic, metal, or semiconductor having excellent heat resistance and environmental safety. In addition, transparency, insulation, heat resistance,
The present invention provides a material having a low dielectric constant, is applicable to various uses, and is industrially useful.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 45/00 C08L 45/00 5G305 // C08J 9/04 C08J 9/04 H01B 3/44 H01B 3/44 Z F term (for reference) 4F071 AA12X AA22X AA39X AA75 AA86 AB06 AB29 AE15 AF30 AF62 AH05 BB02 BC01 4F074 AA08B AA16 AA16B AA32B BA53 CA29 CC04X CC04Y CC10X DA02 4J002 AA002 BP011 DE0 BP011 BP011 BP011 DJ005 BA23 BA24 BA25 CA08

Claims (5)

[Claims] 1. The cyclohexadiene-based polymer represented by the following formula (1) has a hydrogenation rate (molar fraction) of 80% or more of a molecular structural unit (A), and the molecular structural units (B) and (C) A resin material comprising a hydrogenated cyclohexadiene-based polymer having a hydrogenation rate (molar fraction) of 80% or more, respectively, in an amount of 50% by weight or more. Embedded image [Formula (1) represents a composition formula of a polymer. (A)-(C)
Represents each molecular structural unit constituting the polymer main chain. i ~ n
Represents wt% of each molecular structural unit contained in the polymer main chain. (A): selected from cyclohexadiene-based monomers,
A molecular structural unit derived from one or more monomers. (B): a molecular structural unit derived from one or more monomers selected from linear conjugated diene monomers. (C): a molecular structural unit derived from one or more monomers selected from vinyl aromatic monomers. However, i + m + n = 100, 50 ≦ i ≦ 100, and the number average molecular weight of the polymer is 10,000 or more and 200,000 or less. ] 2. The resin material according to claim 1, which is in a fibrous form. 3. The resin material according to claim 1, which is in a particulate form. 4. The resin material according to claim 1, which is in the form of a sheet or a film. 5. A composite resin material according to claim 1, wherein the resin material contains a ceramic, a metal and / or a semiconductor material.