JP3170937B2 - Modified resin and its hydrogenated product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified resin and a hydrogenated product thereof. The present invention relates to a modified resin of a thermoplastic aliphatic cyclic hydrocarbon resin having excellent properties and a hydrogenated product thereof.

[0002]

2. Description of the Related Art A thermoplastic norbornene-based polymer such as a hydrogenated hydrogenated ring-opening polymer of a norbornene-based monomer, a norbornene-based monomer and ethylene as a polymer material having a high heat resistance, a resistance to moisture deformation and an excellent transparency. Are known (Japanese Unexamined Patent Publication No. Sho 60-2602).
No. 4, JP-A-64-24826, JP-A-60-24
-168708, JP-A-61-115912, JP-A-61-120816, etc.).

However, in these prior arts, polycyclic monomers such as tetracyclododecenes are used as norbornene-based monomers, but production of polycyclic monomers is not always easy. In addition, as the demand for polymer materials has increased in recent years, there has been a case where heat resistance is insufficient even when these monomers are used. For imparting further heat resistance, monomers having a larger number of rings are required, but these monomers are more difficult to obtain than tetracyclododecenes.

On the other hand, a method for improving heat resistance by treating a ring-opening (co) polymer of phenylnorbornenes with an acidic compound is known (Japanese Patent Application Laid-Open No. 50-154).
399). In this method, the general formula 1:

Embedded image Structural units derived from phenylnorbornenes represented by
General formula 2:

Embedded image Isomerized into the structural unit represented by

However, it was not known at all whether or not a thermoplastic resin substantially free of the structural unit represented by the general formula 1 was treated with an acidic compound to improve heat resistance.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have discovered that even a thermoplastic aliphatic cyclic hydrocarbon resin substantially free of the structural unit represented by the general formula 1 can be brought into contact with an acidic compound. It has been found that the heat resistance is improved by denaturation, and the present invention has been completed.

[0007]

According to the present invention, there is provided a thermoplastic aliphatic cyclic hydrocarbon system having substantially no ring-opening polymerization structural unit of phenylnorbornenes and having an aliphatic saturated 5-membered ring structure. A modified resin obtained by contacting a resin with an acidic compound to modify the resin, and a hydrogenated product thereof are provided.

(Thermoplastic Aliphatic Hydrocarbon Resin) The thermoplastic aliphatic cyclic hydrocarbon resin used in the present invention does not substantially contain the structural unit represented by the general formula 1, and is a 5-membered aliphatic saturated resin. It has a ring structure. In particular, those having an aliphatic saturated five-membered ring structure in the main chain structure are preferable because the heat resistance is greatly improved by the modification treatment of the present invention. Having an aliphatic saturated 5-membered ring structure in the main chain structure means that a part of the main chain structure has the general formula 3:

Embedded image Alternatively, general formula 4:

Embedded image Or a substituted structure thereof (the aliphatic 5-membered ring structure may be a part of a polycyclic structure). Those having no unsaturated bond in the main chain structure and a part of the main chain structure represented by the general formula 5:

Embedded image Alternatively, general formula 6:

Embedded image Or a structure having a structure substituted with the structure (the aliphatic five-membered ring structure may be a part of a polycyclic structure).

Such thermoplastic aliphatic cyclic hydrocarbon resins are disclosed in JP-A-51-80400 and JP-A-60-80400.
No. 26024, JP-A-1-168725, JP-A-1-190726, JP-A-3-14882, JP-A-3-122137, JP-A-4-63
807 and the like, and specifically, a ring-opening polymer of a norbornene-based monomer, an addition polymer of a norbornene-based monomer, a thermal polymer of a norbornene-based monomer, and an addition-type polymer of a cyclopentene-based monomer And addition-type linear polymers of cyclopentadiene-based monomers. It may be copolymerized with a monomer typified by an olefin monomer, which can be copolymerized with these monomers. Moreover, you may hydrogenate as needed.

The norbornene-based monomers are described in the above publications,
JP-A-2-227424, JP-A-2-27684
It is a monomer known in, for example, JP-A No. 2 (Kokai) Publication Specifically, 2-
Norbornene, 5-methyl-2-norbornene, 5,5
-Dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butylnorbornene, 5-ethylidene-
2-norbornene, 5-isopropenyl-2-norbornene, 5-methoxycarbonyl 2-norbornene, 5-
Norbornene such as cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-octadecyl-2-norbornene, and alkyl and alkylidene thereof; , Alkenyl, aromatic-substituted derivatives, and halogen-, hydroxyl-, ester-, alkoxy-, cyano-, amide-, imide-, silyl- and other polar group-substituted products; 1,4: 5,8-dimetano-1, 4,
4a, 5,6,7,8,8a-octahydronaphthalene, 6-methyl-1,4: 5,8-dimetano-1,4
4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethyl-1,4: 5,8-dimethano-1,4
4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4: 5,8-dimetano-1,
4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-methyl-6-methoxycarbonyl-1,4:
5,8-Dimethano-1,4,4a, 5,6,7,8,8
a-octahydronaphthalene, 6-cyano-1,4:
5,8-Dimethano-1,4,4a, 5,6,7,8,8
a monomer obtained by adding one or more cyclopentadiene to norbornene such as a-octahydronaphthalene, a derivative or a substitute thereof as described above; dicyclopentadiene;
Dicyclopentadiene derivatives such as 2,3-dihydrodicyclopentadiene; and the like.

Examples of the cyclopentene monomer include cyclopentene, cyclopentene derivatives such as 1-methylcyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, tricyclo [4.3.0.1 ^2,5 ] -7-decene, and the like. Substituents are mentioned.

As the cyclopentadiene-based monomer,
In addition to cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene, 5,
Examples thereof include cyclopentadiene derivatives such as 5-dimethylcyclopentadiene and substituted products.

The copolymerizable monomers include ethylene, propylene, isobutene, dipentene, limonene, vinylcyclohexene, 2-methyl-1-butene,
Α-olefins such as 2-methyl-1-pentene, 4-methyl-1-pentene, allyl alcohol, acrylic acid, acrylic acid ester, methacrylic acid and methacrylic acid ester; styrenes such as styrene and α-methylstyrene; Conjugated dienes such as butadiene, isoprene, 1,3-pentadiene, furan and thiophene; cycloolefins such as cyclopentene, cyclohexene, 1-methylcyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, cycloheptene and cyclooctene; Olefins, ethylene oxide, propylene oxide, trimethylene oxide,
Cyclic ethers such as trioxane, dioxane, cyclohexene oxide, styrene oxide, epichlorohydrin and tetrahydrofuran; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl pyridine, N-vinyl carbazole, N-
Heterocycle-containing vinyl compounds such as vinyl-2-pyrrolidone; and the like.

The thermoplastic aliphatic cyclic hydrocarbon resin used in the present invention is disclosed in JP-A-60-26024 and JP-A-6-26024.
JP-A-168708, JP-A-61-115912, JP-A-61-120816, and JP-A-64-108816.
No. 24826 and JP-A-4-63807, a monomer is polymerized using a metathesis polymerization catalyst, an addition polymerization catalyst, a cationic polymerization catalyst, a living cation catalyst, a Ziegler catalyst, a Kaminsky catalyst, or the like. Can be obtained.

Further, when hydrogenation is performed as required, the hydrogenation method is not particularly limited, and examples thereof include a Wilkinson complex, cobalt acetate / triethylaluminum,
For homogeneous catalysts such as nickel acetylacetonate / triisobutylluminium, diatomaceous earth, magnesia, alumina, silica, alumina-magnesia, silica-magnesia, silica-alumina, and synthetic zeolites
A known method using a heterogeneous catalyst supporting a catalyst metal such as nickel, palladium, and platinum may be used. The hydrogenation rate is 90% or more, preferably 95% or more, more preferably 9% or more.
9% or more.

The ring-opening (co) polymer of phenylnorbornenes has a structure represented by the general formula 1, and cannot be used as a thermoplastic aliphatic cyclic hydrocarbon resin in the present invention. When modified by hydrogenation so as to have substantially no structure represented by the general formula 1, in the present invention, it can be used as a thermoplastic aliphatic cyclic hydrocarbon-based resin.

The resin and hydrogenated resin of the present invention can be prepared by a method known in Japanese Patent Application Laid-Open No. 3-95235 and the like.
-It may be modified with unsaturated carboxylic acids and / or derivatives thereof, styrene-based hydrocarbons, organosilicon compounds having olefinically unsaturated bonds and hydrolyzable groups, unsaturated epoxy monomers and the like.

The thermoplastic aliphatic cyclic hydrocarbon resin used in the present invention has an intrinsic viscosity [η] measured in decalin or toluene at 25 ° C. of 0.01 to 20 dl / g, preferably 0.05 to 20 dl / g. 10 dl / g, more preferably 0.1 dl / g.
1 to 5 dl / g. If the intrinsic viscosity is too small, the mechanical strength will be poor, and if it is too large, the moldability will be poor.

The glass transition temperature (hereinafter referred to as Tg) of the thermoplastic aliphatic cyclic hydrocarbon resin is 0 ° C.
The temperature is 200C, preferably 50C to 180C, more preferably 70C to 160C.

(Acid Compound) The acidic compound used in the present invention is a Lewis acid or a Bronsted acid, and specifically, AlCl ₃ , AlBr ₃ , AlI ₃ , BF ₃ , BF
₃ OEt ₂ , BBr ₃ , BBr ₃ OEt ₂ , TiCl ₄ , Ti
Br ₄ , TiI ₄ , FeCl ₃ , FeCl ₂ , SnCl ₂ ,
SnCl ₄ , WCl ₆ , MoCl ₅ , SbCl ₅ , TeCl
Metal halides from Group IIIA to Group VIII of the Periodic Table such as ₂ ; Hydrogen acids such as HCl, HF, HBr;
H ₂ SO ₄ , H ₃ BO ₃ , HClO ₄ , CH ₃ COOH, H ₃
PO ₄ , P ₂ O ₅ , oxo acids such as p-toluenesulfonic acid, and high molecular compounds such as ion exchange resins having these groups; CH ₂ ClCOOH, CHCl ₂ COOH, C
Halogenated acetic acid such as Cl ₃ COOH; heteropolyacid such as phosphomolybdic acid, phosphotungstic acid; SiO ₂ ;
Al ₂ O ₃ , SiO ₂ —Al ₂ O ₃ , MgO—SiO ₂ , B _{2
O 3 -Al 2 O 3, WO} 3 -Al 2 O 3, Zr 2 O 3 -Si
Zeolite exchanged with O ₂ , H ⁺ or a rare earth element, activated clay, acid clay, γ-Al ₂ O ₃ , solid acid such as solid phosphoric acid having P ₂ O ₅ supported on diatomaceous earth; and the like. These may be used in combination, or when the activity of the acidic compound can be improved by adding another compound or the like, such a compound may be added.
For example, compounds that improve the activity of metal halides as acidic compounds include MeLi, EtLi, and B
uLi, Et ₂ Mg, EtMgBr, Et ₃ Al, Et ₂
AlCl, EtAlCl ₂ , Et ₃ Al ₂ Cl ₃ , (i-B
u) ₃ Al, Et ₂ Al (OEt), Me ₄ Sn, Et ₄ S
metal alkyl compounds such as n, Bu ₄ Sn and Bu ₃ SnCl; 2-methoxy-2-phenylpropane, t-butanol, 1,4-bis (2-methoxy-2-propyl) benzene, 2-phenyl-2- A compound used as a polymerization initiator in living cationic polymerization, such as propanol; and the like.

The acidic compound is added in an amount of 0.01 to 100 parts by weight of the thermoplastic aliphatic cyclic hydrocarbon resin used in the present invention.
It is modified using 1000 parts by weight, preferably 0.1 to 100 parts by weight. These oxides may be uniform or non-uniform in the reaction system.

The acidic compound can be separated from the denatured resin by treating with a neutralizing agent after the denaturation reaction. However, if a solid acid such as silica or alumina is used, the catalyst may not be removed depending on the application. It may be left as it is in the modified resin.

(Modification reaction) In the present invention, the modification reaction
It is carried out in an inert organic solvent or in a molten state of the resin. When performing the denaturation reaction in an inert solvent, the reaction temperature is usually
The reaction is performed at a temperature in the range of -70 ° C to 200 ° C, preferably 0 ° C to 150 ° C. If the reaction temperature is too low, the denaturation reaction takes time, and if it is too high, control of the reaction is difficult and reproducibility is hardly obtained. When the modification reaction is performed in a state where the resin is molten, the modification is usually performed at 350 ° C. or lower, preferably 300 ° C. or lower as long as the resin is molten. If the reaction temperature is too low,
It takes a long time for the denaturation reaction, and if it is too high, the control of the reaction is difficult and reproducibility is hardly obtained.

The reaction pressure for carrying out the modification is not particularly limited, and is preferably 0.5 to 50 atm, more preferably 0.1 to 50 atm.
What is necessary is just to carry out in the range of 7-30 atmospheres. Usually, the denaturation reaction is performed at about 1 atm.

The reaction time for the modification is not particularly limited.
The reaction time may be determined in accordance with factors such as the resin used, the amount thereof, the acidic compound, the reaction temperature, the reaction pressure, and the like so as to obtain the required performance of the modified resin. Usually, 0.
It is from 01 hour to 24 hours, preferably from 0.2 hour to 10 hours.

As described above, the resin can be denatured in a molten state. However, when the resin is denatured in an inert organic solvent, examples of the inert organic solvent include aromatic hydrocarbons such as benzene, toluene, and xylene. Hydrogen based solvents; pentane,
Aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane, and decalin; methyl chloride, methylene chloride, 1,
2-dichloroethane, 1,1,1-trichloroethane,
Halogenated hydrocarbon solvents such as 1,1,2-trichloroethane and 1,1,2-trichloroethylene; oxygen-containing solvents such as alcohols, esters and ethers; and the like can be used. In terms of reactivity, aromatic hydrocarbons,
Aliphatic hydrocarbon solvents and halogenated hydrocarbon solvents are preferred. These may be used in combination.

In the present invention, when an inert organic solvent is used in the modification reaction, the inert organic solvent is usually used in an amount of 100 to 100 parts by weight of the thermoplastic aliphatic cyclic hydrocarbon resin.
10,000 parts by weight, preferably 120 to 2000 parts by weight, more preferably 150 to 1000 parts by weight. If the amount of the solvent is insufficient, it is difficult to perform uniform mixing with the acidic compound and the like, so that the reaction becomes non-uniform, so that a uniform modified resin cannot be obtained or the control of the reaction becomes difficult. If the amount of the solvent is excessive, the resin hardly comes into contact with the acidic compound, the progress of the modification reaction is slow, and the efficiency is poor.

In the present invention, when the modification reaction is carried out in a molten state of the resin, the means for mixing the resin and the acidic compound is not particularly limited. A roll, kneader, screw extruder or the like is used. As the acidic compound to be used, a solid acid is preferable because of easy mixing.

(Modified Resin) The modified resin of the present invention and a hydrogenated product thereof have an intrinsic viscosity [η] measured in decalin or toluene at 25 ° C. of 0.01 to 20 dl /.
g, preferably 0.05 to 10 dl / g, more preferably 0.1 to 5 dl / g. If the intrinsic viscosity is too small, the mechanical strength will be poor, and if it is too large, the moldability will be poor.

The modified resin of the present invention has a higher Tg than the resin before the modification. Although the range of increase in Tg varies depending on the reaction time, Tg is preferably increased by 5 ° C. or more, more preferably 10 ° C. or more.

(Hydrogenation) The modified resin of the present invention may be hydrogenated as required. Further, it may be further modified with an α, β-unsaturated carboxylic acid or the like. Hydrogenation reaction,
The method of the further modification reaction is a known method as in the case of reacting the resin before modification described above.

(Additives) Various additives may be added to the modified resin of the present invention or a hydrogenated product thereof, if necessary. Examples of the additives to be used include antioxidants such as phenol-based and phosphorus-based agents; antistatic agents; ultraviolet absorbers; light stabilizers; lubricants;
Dyes; Antiblocking agents; Rubbery polymers such as polybutadiene, polyisoprene, styrene-butadiene-styrene block polymers; Thermoplastic resins such as petroleum resins, polyethylene, and polypropylene; Fibrous fillers such as glass fibers and carbon fibers Fine particle fillers such as silica, alumina and talc; tetrakis [2- (3,5-di-t-butyl-4-hydroxyphenyl) ethylpropionate] methane;
An antioxidant such as di-t-butyl-4-methylphenol; a leveling agent such as a fluorine-based nonionic surfactant, a special acrylic resin-based leveling agent, and a silicone-based leveling agent;

In order to avoid elution from the modified resin of the present invention or its hydrogenated product, these additives are preferably as large as possible in molecular weight and as small as possible.

(Molding) The modified resin of the present invention or a hydrogenated product thereof can be produced by a known method, for example, injection molding, extrusion molding, cast molding, inflation molding, blow molding, vacuum molding, press molding, compression molding, rotation. It can be formed by molding, cutting or the like.

(Molded Article) The modified resin of the present invention or a hydrogenated product thereof is useful in various fields as various molded articles including optical materials. For example, optical materials such as optical disks, optical lenses, prisms, light diffusion plates, optical cards, optical fibers, optical mirrors, liquid crystal display element substrates, light guide plates, polarizing films, retardation films; liquid chemical containers for injection, ampules, and prefilled Liquids or powders such as syringes, infusion bags, solid medicine containers, eye drop containers, eye drop containers, solid drug containers, food containers, sampling tubes for blood tests, caps for drug containers,
Sample containers such as blood collection tubes, specimen containers, medical instruments such as syringes, sterile containers such as medical instruments such as scalpels, forceps, gauze, contact lenses, and experimental and analytical instruments such as beakers, petri dishes, flasks, test tubes, and centrifuge tubes , Medical optical components such as plastic lenses for medical examinations, medical infusion tubes, piping materials such as pipes, joints, valves, artificial organs and parts such as denture bases, artificial hearts, artificial roots, etc. Medical equipment such as medicine bottles, prefilled syringes, sealed medicine bags, press-through packages, ophthalmic containers, ampules, vials, ophthalmic containers for storing liquid medicines; for processing tanks, trays, carriers, cases, etc. And protective materials such as transfer containers, carrier tapes, separation films, pipes, tubes, valves, shippers Equipment for processing electronic components such as piping, flow meters, filters, pumps, and other liquid containers such as sampling containers, bottles, ampules, and bags;
Cable coating materials, consumer / industrial electronic devices, copiers /
General insulating materials such as OA equipment such as computers and printers, and instruments; circuit boards such as rigid printed boards, flexible printed boards, and multilayer printed wiring boards, particularly high-frequency circuit boards for satellite communication equipment requiring high-frequency characteristics; Equipment for transparent conductive films, such as substrates, optical memories, surface heating elements such as automobile and aircraft defrosters, and electricity, such as transistors, ICs, LSIs, and LEDs.
Sealing materials and parts for conductors, sealing materials for electric and electronic parts such as motors, capacitors, switches, and sensors; body materials for TVs and video cameras; and electrical insulating materials for structural members such as parabolic antennas, flat antennas, and radar domes. And the like.

[0036]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The intrinsic viscosity was measured in decalin at 25 ° C., the glass transition temperature was measured by the DSC method, and the retardation value was measured by the double pass method at a wavelength of 830 nm.

Example 1 Five hydrogenated dicyclopentadiene ring-opening polymers (intrinsic viscosity [η] 0.52 dl / g, Tg 95 ° C., hydrogenation rate 9
9.9%) and 900 parts by weight of cyclohexane were added and heated to 50 ° C. While stirring, 5 parts by weight of aluminum chloride was added, and the reaction was allowed to proceed at a reaction temperature of 50 ° C. After reacting for 0.5 hour, 1 hour, 2 hours, 3 hours and 6 hours, the reaction solution was poured into 2000 parts by weight of isopropyl alcohol while stirring, and the precipitated denatured product was collected and subjected to a reduced pressure of 1 torr or less. For about 24 hours to obtain about 95 parts by weight of a colorless resin.

Reaction time 0.5 hour, 1 hour, 2 hours, 3 hours
Time, Tg of the modified resin obtained in 7 hours, respectively,
102 ° C., 111 ° C., 124 ° C., 141 ° C., and 187 ° C., and the intrinsic viscosity [η] was 0.59 dl /
g, 0.57 dl / g, 0.54 dl / g, 0.48 d
1 / g, 0.43 dl / g and 0.30 dl / g.

The resin obtained in a reaction time of 3 hours was heated at 200 ° C.
To form a plate having a thickness of 2 mm and a diameter of 100 mm. This press plate is colorless and transparent, tough,
No deformation was observed even after boiling for 1 hour in hot water at 00 ° C. The light transmittance of the press plate was 90.2%, and the retardation value was 20 nm or less.

Example 2 96 parts by weight of a colorless resin at a reaction temperature of 30 ° C. and 98 parts by weight at a reaction temperature of 30 ° C. and 80 ° C., except that the reaction time was 3 hours. I got a copy.

The modified resin obtained at a reaction temperature of 30 ° C. and 80 ° C. has a Tg of 99 ° C. and 153 ° C., respectively, and an intrinsic viscosity [η] of 0.53 dl /
g, 0.41 dl / g.

The obtained resin was heated at 170 ° C. and 21 ° C., respectively.
A plate having a thickness of 2 mm and a diameter of 100 mm was produced by press molding at 0 ° C. The pressed plate was colorless and transparent and tough, and no deformation was observed even when the pressed plate was boiled in hot water at 100 ° C. for 1 hour.

Example 3 In the same manner as in Example 1 except that 20 parts by weight of tin chloride was used instead of aluminum chloride, 20 parts by weight of BF ₃ .OEt _{2 was} used, and the reaction time was 24 hours. Was obtained in an amount of 97 parts by weight.

The Tg of the modified resin obtained using tin chloride and BF ₃ .OEt ₂ was 121 ° C. and 116 ° C., respectively, and the intrinsic viscosity [η] was 0.49 dl /
g, 0.52 dl / g.

The obtained resin was press-formed at 180 ° C. to produce a plate having a thickness of 2 mm and a diameter of 100 mm.
This press plate was colorless and transparent, tough, and no deformation was observed even after boiling in hot water at 100 ° C. for 1 hour.

Example 4 Instead of hydrogenated dicyclopentadiene ring-opening polymer, hydrogenated methyltetracyclododecene ring-opening polymer (intrinsic viscosity [η] 0.35 dl / g, Tg 150 ° C., hydrogenation rate 99 2.9%), 20 parts by weight of aluminum chloride instead of 5 parts by weight, and a reaction time of 0.5 hour, 1 hour.
The treatment was carried out in the same manner as in Example 1 except that the time was changed to 2 hours, 3 hours, and 4 hours to obtain 95 to 99 parts by weight of a colorless resin for each reaction time.

Reaction time 0.5 hour, 1 hour, 2 hours, 3 hours
Time, Tg of the modified resin obtained in 4 hours,
152 ° C., 156 ° C., 159 ° C., 165 ° C., 171 ° C., and the intrinsic viscosity [η] is 0.35 dl /
g, 0.33 dl / g, 0.33 dl / g, 0.32 d
1 / g and 0.31 dl / g.

The resin obtained in a reaction time of 4 hours was converted to 230
A plate having a thickness of 2 mm and a diameter of 100 mm was produced by press molding at ℃. This press plate was colorless and transparent, tough, and no deformation was observed even after boiling in hot water at 100 ° C. for 1 hour. The light transmittance of the press plate was 90.3.
%, And the retardation value was 20 nm or less.

Example 5 In place of the hydrogenated dicyclopentadiene ring-opening polymer, an addition-type linear polymer hydrogenated cyclopentadiene (intrinsic viscosity [η] 0.60 dl / g, Tg 80 ° C., hydrogenation rate 99.9%, consisting of 1,4 addition type bonds and 1,2 addition type bonds, the ratio of which is about 50:50), and colorless as in Example 1 except that the reaction time is 5 hours. Resin 95
Parts by weight were obtained. The Tg of this resin was 120 ° C., and the intrinsic viscosity [η] was 0.50 dl / g.

The obtained resin was pressed at 180 ° C. to produce a plate having a thickness of 2 mm and a diameter of 100 mm. This press plate was colorless and transparent, tough, and no deformation was observed even after boiling in hot water at 100 ° C. for 1 hour. The light transmittance of the press plate was 90.2%, and the retardation value was 20 nm or less.

Example 6 Dicyclopentadiene Ring-Opening Polymer Instead of hydrogenated product, cyclopentadiene addition type linear polymer (intrinsic viscosity [η] 0.41 dl / g, Tg 70 ° C., 1,4 addition type bonding And 1,2 addition type bonds, the ratio of which is 50: 5
Example 1 except that the reaction time was 10 hours using
In the same manner as in the above, 97 parts by weight of a colorless resin was obtained. T of this resin
g was 79 ° C., and the intrinsic viscosity [η] was 0.37 dl / g.

Example 7 Dicyclopentadiene Ring-opening Polymer Instead of the hydrogenated product, an addition-type polymer of tetracyclododecene and ethylene (intrinsic viscosity [η] 0.54 dl / g, Tg 69 ° C., tetracyclododecene 98% by weight of a colorless resin was obtained in the same manner as in Example 1 except that the molar ratio of ethylene was 1: 3), aluminum chloride was used instead of 5 parts by weight, and the reaction time was changed to 24 hours. . The Tg of this resin was 87 ° C., and the intrinsic viscosity was 0.50 dl / g.

The obtained resin was press-molded at 160 ° C. to produce a plate having a thickness of 2 mm and a diameter of 100 mm. This press plate is colorless and transparent and tough. The light transmittance of the press plate is 90.1% and the retardation value is 20 n.
m or less.

Example 8 Dicyclopentadiene ring-opened polymer Instead of hydrogenated product, 6-methyl-6-methoxycarbonyl-1,4: 5,8
-Hydrogenated ring-opening polymer of dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene (intrinsic viscosity [η] 0.64 dl / g, Tg 162 ° C, hydrogenation rate 9
9.9%), 700 parts of toluene and 200 parts of cyclohexane instead of 900 parts of cyclohexane, methanol instead of isopropyl alcohol, 20 parts by weight of aluminum chloride instead of 5 parts by weight, and a reaction time of 24 hours. A colorless resin 9 was prepared in the same manner as in Example 1 except for
5 parts by weight were obtained. This resin had a Tg of 173 ° C. and an intrinsic viscosity [η] of 0.60 dl / g.

The obtained resin was press-molded at 230 ° C. to produce a plate having a thickness of 2 mm and a diameter of 100 mm. The board was colorless and transparent and tough.

Example 9 The press plates obtained in Examples 1, 4, 5, and 7 were treated with ethanol,
When immersed in acetone, ethyl acetate, and toluene for 6 hours, no change was observed in any of the press plates except for toluene, and in the toluene, some of the press plates obtained in Examples 2 and 3 dissolved, The press plates obtained in Examples 1 and 4 were completely dissolved.

Example 10 The pressed plates obtained in Examples 1, 4, 5, and 7 were treated with 10% hydrochloric acid (10%), concentrated hydrochloric acid, 10% sulfuric acid, concentrated sulfuric acid, 30% acetic acid, 10% formic acid, nitric acid, Phosphoric acid, hydrofluoric acid (7%) / nitric acid (42%) / pure water (51%), 50% caustic soda,
24% for each of 0% ammonia water, 40% formaldehyde, 10% saline, 1% soap water and 30% hydrogen peroxide
A time immersion test was performed. No change was observed in any of the press plates except for concentrated sulfuric acid, and the surface of each press plate was carbonized with concentrated sulfuric acid. Thereby, it turned out that the resin of this invention can be used for the equipment for electronic component processing.

Example 11 The modified resin obtained in Examples 1, 4, 5, and 7 was dissolved again in cyclohexane, filtered through a 1 μm filter, poured into isopropyl alcohol, coagulated again, and purified. The purified modified resin was press-molded in the same manner as in Example 1, and using the prepared press plate, the Japanese Pharmacopoeia Law No. 12
The eluate test was conducted in accordance with the revised "Plastic Test Method for Infusion". All foaming disappears within 3 minutes and the pH difference is-
0.02--0.04, UV absorption is 0.005-0.
007, potassium permanganate reducing substance is 0.09-
0.13 ml. This proved that the resin of the present invention had characteristics suitable for medical use.

Using the modified resin purified in Example 11,
A plate having a thickness of 1.2 mm and a diameter of 12.5 cm was prepared. This
And the respective volume resistivity values and 10^Two
Hz, 10⁶Hz, 10⁹With the permittivity at a frequency of Hz
The dielectric loss tangent was measured. Modified resins of Examples 1, 4, 5, and 7
Were purified, the volume resistivity was 5 × 10
¹⁶Ωcm and dielectric constants are 2.36, 2.41 and 2.
39, 2.47, the dielectric loss tangent at any frequency
4 × 10 each^-Four, 5 × 10^-Four, 5 × 10^-Four , 6 × 1
0^-FourMet. As a result, the resin of the present invention is
It was found that the material had characteristics suitable for use as a material.

Example 13 An average particle size of 1.5 μm was added to 100 parts by weight of the same hydrogenated dicyclopentadiene ring-opening polymer as used in Example 1.
m-silica-alumina powder (acidic compound), 15 parts by weight, and using a twin-screw kneader (manufactured by Toshiba Machine Co., Ltd., TEM-35) under a nitrogen atmosphere at a resin temperature of 290 ° C., a screw rotation speed of 190 rpm, and Under the condition of a feed rate of 0.5 kg / h, the mixture was extruded by kneading to prepare 105 parts by weight of pellets. The Tg of the obtained pellet was 118 ° C. The pellet was press-formed at 200 ° C. to produce a plate having a thickness of 2 mm and a diameter of 100 mm. This press plate was opaque but tough, and no deformation was observed even after boiling for 1 hour in hot water at 100 ° C.

[0061]

The modified resin of the present invention has a higher glass transition temperature and improved heat resistance than the resin before modification.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Io Natsuume 1-2-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Examiner, R & D Center, Zeon Corporation Examiner Satoshi Morikawa (56) References JP 61 −225201 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 61/00-61/08

Claims (5)

(57) [Claims] 1. Modification obtained by contacting a thermoplastic aliphatic cyclic hydrocarbon resin having an aliphatic saturated five-membered ring structure with an acidic compound substantially without containing a ring-opening polymerization structural unit of phenylnorbornenes. resin. 2. The modified resin according to claim 1, wherein the thermoplastic aliphatic cyclic hydrocarbon resin is a thermoplastic norbornene resin. 3. The modified resin according to claim 1, wherein the thermoplastic aliphatic cyclic hydrocarbon resin is an addition type linear polymer of a cyclopentadiene monomer and / or a hydrogenated product thereof. 4. The modified resin according to claim 1, wherein the thermoplastic aliphatic cyclic hydrocarbon resin has an aliphatic saturated 5-membered ring structure in the main chain structure. 5. A modified resin hydrogenated product of the modified resin was hydrogenated as described in claim 1.