JPH05279545A - Thermoplastic saturated norbornene resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition having improved humidity resistance at high temperatures and does not form microcracks even under high- temperature and high-humidity conditions by mixing a thermoplastic saturated norbornene resin with a resin comprising specified structural units each containing a ring structure. CONSTITUTION:A resin comprising structural units of formula I or II (wherein R is H or CH3; (n) is 0-10; and the ring structure may have substituents) is mixed with a thermoplastic saturated norbornene resin (e.g. a hydrogenation product of a ring-opening polymer of 5-methyl-2-norbornene) to produce a resin composition of improved humidity resistance. This composition can be desirably used for a water tank for a steam iron, a component of a microwave oven, an optical or magnetic disc base, a spectacle lens, etc. The resin comprising structural units of formula I or II can be obtained by polymerizing a monomer of formula III, IV or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic saturated norbornene resin composition, and more particularly to a thermoplastic saturated norbornene resin composition having excellent moisture resistance.

[0002]

2. Description of the Related Art Polymethyl methacrylate (PMMA) and polycarbonate (PC) have been conventionally known as resins used for optical materials. However, PMMA is excellent in transparency, but has problems in heat resistance and humidity resistance. In addition, PC is superior in heat resistance and humidity resistance to PMMA, but has a large birefringence. Therefore, a thermoplastic saturated norbornene-based resin excellent in transparency, heat resistance, moisture resistance, low birefringence and the like has been attracting attention as an optical material. However, although there was no problem with moisture resistance under general use environment, micro cracks may occur under severe high temperature and high humidity environment, and higher moisture resistance is required with technological progress. Was there.

Further, a resin composition in which an acrylic resin such as polyacrylate, polymethacrylate, polyacrylamide or polyacrylonitrile is mixed with a thermoplastic saturated norbornene resin is moldable, heat resistant, solvent resistant, rigid,
It was also known that it has excellent impact resistance (Japanese Patent Laid-Open No. 2-276816, etc.). However, even if an acrylic resin is actually blended with a thermoplastic saturated norbornene-based resin, they may not be compatible with each other and may become cloudy, so that they cannot be used as an optical material.

[0004]

DISCLOSURE OF THE INVENTION As a result of earnest research, the present inventors have found that a composition obtained by blending a thermoplastic saturated norbornene resin with a specific resin has higher moisture resistance. The present invention has been completed.

[0005]

Thus, according to the present invention, 90 to 99.9 parts by weight of the thermoplastic saturated norbornene resin and the general formula 1

[Chemical 3] (In the formula, R represents H or CH ₃ , represents an integer of n or more and 10 or less, and the ring structure portion may have a substituent)
Structural unit represented by or general formula 2

[Chemical 4] (In the formula, R represents H or CH ₃ , represents an integer of n or more and 10 or less, and the ring structure portion may have a substituent)
A resin composition comprising 10 to 0.1 parts by weight of a resin having a structural unit represented by

(Thermoplastic Saturated Norbornene Resin) A thermoplastic saturated norbornene resin is disclosed in JP-A-3-14882.
And a resin known in JP-A-3-122137, specifically, a ring-opening polymer hydrogenated product of a norbornene-based monomer, an addition-type polymer of a norbornene-based monomer, a norbornene-based monomer Examples thereof include addition-type polymers of a body and an olefin, and modified products of these polymers and hydrogenated polymers.

The norbornene-based monomer is also a monomer known in the above publications, JP-A-2-227424 and JP-A-2-276842, and examples thereof include norbornene, its alkyl, alkylidene and aromatic substituted derivatives. And halogens, hydroxyl groups of these substituted or unsubstituted olefins,
Polar group substituents such as ester group, alkoxy group, cyano group, amide group, imide group and silyl group, for example, 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5- Ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-
2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5-methyl- 2-norbornene and the like; a monomer in which one or more cyclopentadiene is added to norbornene, a derivative or a substitution product similar to the above, for example, 1,4: 5,8-dimethano-
1,2,3,4,4a, 5,8,8a-2,3-cyclopentadienonaphthalene, 6-methyl-1,4: 5,8
-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4: 5,10: 6,9-trimethano-1,2,3,4,4a, 5,5a , 6, 9,
9a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene, etc .; a polycyclic monomer that is a multimer of cyclopentadiene, a derivative or substituent similar to the above, for example, dicyclopentadiene, 2,3-dihydrodicyclopentadiene and the like; adducts of cyclopentadiene and tetrahydroindene and the like, derivatives and substitution products similar to the above, for example, 1,4-methano-1,4,4
a, 4b, 5,8,8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4a, 5,8,
8a-octahydro-2,3-cyclopentadienonaphthalene and the like; and the like.

The norbornene-based monomer may be polymerized by a known method, and if necessary, it is a thermoplastic saturated norbornene-based resin by copolymerizing with another copolymerizable monomer or by hydrogenation. It can be a thermoplastic norbornene-based polymer hydrogenated product. Further, a polymer or a polymer hydrogenated product is subjected to a method known in JP-A-3-95235 or the like to obtain an α, β-unsaturated carboxylic acid and / or derivative thereof, a styrene-based hydrocarbon, an olefin-based unsaturated bond and a hydrolyzed product. It may be modified by using an organosilicon compound having a decomposable group or an unsaturated epoxy monomer.

The molecular weight is 1 to 200,000 in number average molecular weight and 2 in weight average molecular weight measured by GPC (gel permeation chromatography) analysis using a toluene solvent.
It is suitable that the number average molecular weight is 2 to 600,000.
It has a weight average molecular weight of 100,000 and 30,000 to 300,000. If the molecular weight is smaller than this range, sufficient strength cannot be obtained and cracking easily occurs. If the molecular weight is larger than this range, molding However, the fluidity of the resin deteriorates and molding is difficult, and it is difficult to synthesize the resin with good reproducibility and productivity.

Further, from the viewpoint of light resistance and weather resistance, and resistance to deterioration such as decomposition from various chemicals and coloration, it is preferable not to contain a large amount of olefinic unsaturated bond. In the case where one or more carbon-carbon unsaturated bonds are present, hydrogenation is preferable, and in that case, the hydrogenation rate is usually 90% or more, preferably 95% or more, more preferably 99%. That is all.

(Blended Resin) In the present invention, a resin containing a structural unit represented by the general formula 1 or the general formula 2 as a main component is blended with a thermoplastic saturated norbornene resin.

This compounded resin is represented by the general formula 1 or the general formula 2.
In addition to the monomer for deriving the structural unit represented by, vinyl-based monomers such as styrene and methyl methacrylate may be used for copolymerization.
The structural unit represented by is 50 mol% or more, preferably 70
It is a mol% or more, particularly preferably 80 mol% or more. Molecular weight (Mn) is 5000 or more, usually 8000-2
It is 0000.

If n in the formula is too large, the glass transition temperature of the compounded resin becomes too high, and molding of the fat composition of the present invention becomes difficult. Therefore, n is preferably 0 or 1. Further, although it may have both the structural units of the general formula 1 and the general formula 2, in order to improve the weather resistance of the resin composition of the present invention, a structural unit having a double bond Is preferable, and among the structural units represented by the general formulas 1 and 2, those having a large number of structural units represented by the general formula 1 are preferable.

The glass transition temperature varies depending on the type of monomer, the type and ratio of comonomer, the molecular weight and the like. In general, the larger n in the general formula 1 or the general formula 2, the larger the molecular weight, and the R in the general formula 1 or the general formula 2.
Is higher than CH ₃ , the glass transition temperature is higher. n is 0, R
Is H, and in the case of a resin consisting only of the structural unit represented by the general formula 1, the molecular weight is 8000 to 20000 and the glass transition temperature is about 80 to 110 ° C. Also, n is 0, R
Is H and the resin having a molecular weight of only the structural unit represented by the general formula 1 within the above range has a glass transition temperature of 8
It is about 0 to 110 ° C. n is 0, R is CH ₃ ,
When the molecular weight is composed of only the structural unit represented by the general formula 2 within the above range, the temperature is 140 to 170 ° C. Depending on the type of comonomer, the glass transition temperature may increase as the proportion of copolymerization increases, but general vinyl monomers such as styrene and methylmethacrylate will lower the glass transition temperature as the proportion of copolymerization increases. .. The glass transition temperature of the compounded resin of the present invention is usually 30.
It is about 170 ° C.

Further, the ring structure portion may have a substituent, and the substituent may be a polar substituent. In order to improve the dispersibility of the blended resin in the thermoplastic saturated norbornene-based resin, which is the main component of the resin composition, when the thermoplastic saturated norbornene-based resin does not have a polar substituent, the blended resin also It preferably has no polar substituents.

In order to obtain this compounded resin, generally, a photopolymerization initiator, a thermal polymerization initiator, etc. are added to a solution of a monomer,
It may be polymerized. Suspension polymerization or emulsion polymerization may be carried out, but solution polymerization which is easy to purify is preferred.

(Blending) The resin composition of the present invention is a blend of the above-mentioned blended resin with a thermoplastic saturated norbornene resin. The blending ratio is preferably 10 parts by weight of the above blended resin with respect to 100 parts by weight of the thermoplastic saturated norbornene resin.
~ 0.1 parts by weight, more preferably 8 to 0.15 parts by weight,
Particularly preferably, it is 6 to 0.2 parts by weight.
If the blending amount is too small, the effect of the present invention cannot be obtained, and if the blending amount is too large, the moisture resistance is poor.

The method of blending is not particularly limited, and in addition to a method of pelletizing using a general twin-screw extruder, for example, both are dissolved in a good solvent for both and a poor solvent for both is added in a large amount. A resin composition in a powder form may be obtained by solidifying the resin by the above method, recovering the resin solidified by filtration or the like, and sufficiently drying the resin.

(Additive) In the composition of the present invention, if desired, an antioxidant such as a phenol type or a phosphorus type; a heat deterioration inhibitor such as a phenol type; an ultraviolet stabilizer such as a benzophenone type or a hindered amine type; an amine Various additives such as antistatic agents such as systems; auxiliary agents such as esters of aliphatic alcohols, partial esters of polyhydric alcohols and partial ethers; and the like may be added. Further, other resins and the like can be mixed and used as long as the object of the present invention is not impaired. Furthermore, when used for a member for electronic component production that does not require transparency, various minerals such as talc and titanium white and other fillers for the purpose of improving identification and heat resistance and strength by color coding, It is also possible to use an organic or inorganic pigment.

(Thermoplastic Saturated Norbornene-Based Resin Composition) The thermoplastic saturated norbornene-based resin composition of the present invention has heat resistance, chemical resistance, dielectric properties, rigidity and low hygroscopicity because the amount of the compounded resin added is small. , Is substantially the same as the thermoplastic saturated norbornene-based polymer without addition.

The method for molding the resin composition is not particularly limited. Depending on the purpose, an injection molding method, a blow molding method, an injection blow molding method, a rotational molding method, a vacuum molding method, an extrusion molding method, a calender molding method, a solution casting method and the like are possible.

The molded product of the resin composition of the present invention is superior in adhesiveness to an acrylic resin and the like as compared with a thermoplastic saturated norbornene resin. Thermoplastic saturated norbornene-based resin is used as a material for optical discs and the like, and a hard coat layer may be formed on the surface using an acrylic UV-curable hard coat agent.
The hard coat layer is difficult to peel off from the disk substrate.

Further, the resin composition of the present invention is superior in moisture resistance at high temperature as compared with the thermoplastic saturated norbornene-based polymer. Thermoplastic saturated norbornene-based polymers are excellent in heat resistance and moisture resistance, but, for example, in severe high-temperature and high-humidity treatment such as pressure steam sterilization at 121 ° C in an autoclave, a large number of microcracks occur and transparency deteriorates. There was something to do. On the other hand, in the molded article of the resin composition of the present invention, the transparency is not substantially reduced.

The resin composition of the present invention can be utilized for such properties, for example, a water tank of a steam iron, a microwave oven component or container, a printed wiring board, a high-frequency circuit board, and a transparent conductive material. Electrical or non-transparent sheets, speaker diaphragms, semiconductor manufacturing carriers, lighting fixture covers and decorations, electric wire coatings, insulating films, capacitor films, electronic element sealing materials, etc .; Food packaging films , Denture base materials, various chemical containers, food containers, cosmetics containers, stopcocks, equipment inspection cells for blood, medical tubes, blood and infusion bags, chemical resistant coatings, disposable syringes and containers, etc. Applications: Camera parts, industrial parts such as housings and containers for various instruments and devices; Various seats, helmets, protectors Daily sundries such as nose guards for spectacles; widely applicable to fields such as windshields and window glass substitutes, and more particularly due to their transparency, magneto-optical discs, dye-based discs, music compact discs, image music simultaneously Information disc substrate such as recording / playback type disc; lens or mirror lens of imaging system or projection system used in cameras, VTRs, copiers, OHPs, projection TVs, printers, etc .; to pick up information such as information discs and barcodes Lenses; automotive lamps, glasses and goggles lenses; information transfer parts such as optical fibers and their connectors; information recording substrates other than disks such as optical cards, liquid crystal substrates, retardation films, polarizing films, light guide plates, protection Information recording such as moisture-proof film, films and sheets in the information display field It is suitable as an optical material such as.

Particularly when used as an optical disk substrate, it is preferable to apply an ultraviolet-curable coating agent and irradiate it with ultraviolet rays to form a hard coat layer of acrylic resin, because the hard coat layer has good adhesiveness. .. In this case, in order to have an antistatic effect, it is preferable to add an antistatic agent, an antistatic filler or the like to the ultraviolet curable coating agent.

[0026]

EXAMPLES The present invention will be described more specifically below with reference to reference examples, examples and comparative examples.

Reference Example 1 Cyclohexane 900 g in a 2 l separable flask,
General formula 3

[Chemical 5] 100 g of a monomer having the structure shown in (FA-513A, manufactured by Hitachi Chemical), 1 g of azobisisobutyronitrile
Was charged, the temperature was maintained at the cyclohexane reflux temperature (78 to 85 ° C.), and polymerization was performed for 7 hours under reflux and stirring. After the reaction, the solution was dropped into 10 kg of ethanol to precipitate the polymer, which was separated by filtration and vacuum dried at 2 mmHg and 60 ° C. for 48 hours, and then 95 g of powdered resin (hereinafter referred to as polymer A)
Got Number average molecular weight 11,000 measured by GPC analysis with a THF solvent, weight average molecular weight 27,000,
The glass transition temperature was 87 ° C.

Reference Example 2 Instead of 100 g of FA-513A, a compound of the general formula 4

[Chemical 6] 97 g of a powdery copolymer resin (hereinafter referred to as polymer B) was obtained in the same manner as in Reference Example 1 except that 90 g of the monomer having the structure shown in (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) and 10 g of styrene were used. It was Number average molecular weight is 160
00, the weight average molecular weight was 53,000, and the glass transition temperature was 110 ° C.

Example 1 ZEONEX 280 thermoplastic saturated norbornene resin
100 parts by weight (manufactured by Zeon Corporation) were dissolved in 400 parts by weight of cyclohexane in a separable flask, and a 1% by weight cyclohexane solution of polymer A was added in an amount of 5 parts by weight, 1 part by weight, 0.2 parts by weight of polymer A. It was added so as to be part by weight. The mixture was kept in an oil bath at 250 ° C. for 5 hours under a nitrogen stream to remove the solvent and obtain a lump resin mixture.

Each resin mixture was press-molded into a plate having a thickness of 5 mm, the light transmittance at 500 nm was measured, and the presence or absence of white turbidity was determined. In addition, a square test piece with a side of 1 cm was cut out and placed in an autoclave at 121 ° C. for 30 minutes.
After performing a steam sterilization treatment for 1 minute and observing with an optical microscope, the amount of microcracks generated was examined. The results are shown in Table 1.

Example 2 Example 1 was repeated except that polymer B was used instead of polymer A. The results are shown in Table 1.

Example 3 100 parts by weight of ZEONEX 280 and 5 parts by weight, 1 part by weight, and 0.2 parts by weight of Polymer A were kneaded at 180 ° C. using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM-35). Then
Made into pellets. The obtained pellets were press-molded in the same manner as in Example 1, and the light transmittance and the amount of microcracks generated after the steam sterilization treatment were examined. The results are shown in Table 1.

Comparative Example 1 Using ZEONEX 280, press molding was carried out in the same manner as in Example 1, and the light transmittance and the amount of microcracks generated after steam sterilization treatment were examined. The results are shown in Table 1.

Comparative Example 2 The procedure of Example 3 was repeated except that 1 part by weight of PMMA (Acrypet VH, manufactured by Mitsubishi Rayon) was used instead of the polymer A. The results are shown in Table 1.

Comparative Example 3 The procedure of Example 3 was repeated except that 1 part by weight of polystyrene resin (Styron 666, manufactured by Asahi Kasei) was used instead of polymer A. The results are shown in Table 1.

[0036]

[Table 1] However, in the column of the generation state of microcracks after steam sterilization in the table, ⊚: less than 10 pieces / cm ² , ◯: 1
0 pieces / cm ² or more and less than 50 pieces / cm ² , Δ: 50 pieces / cm
² or more and less than 200 pieces / cm ² , and x: 200 pieces / cm ² or more.

[0037]

INDUSTRIAL APPLICABILITY The thermoplastic saturated norbornene-based resin composition of the present invention is excellent in transparency, has excellent moisture resistance at high temperature, and has microcracks under high temperature and high humidity as compared with thermoplastic saturated norbornene-based resin. It is less likely to occur and the adhesiveness with other resins is improved.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ima Natsume 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Co., Ltd. Research and Development Center

Claims (1)

[Claims] 1. A thermoplastic saturated norbornene resin having the general formula 1 (In the formula, R represents H or CH ₃ , n represents an integer of 0 or more and 10 or less, and the ring structure portion may have a substituent), or a general formula 2 2] (In the formula, R represents H or CH ₃ , n represents an integer of 0 or more and 10 or less, and the ring structure portion may have a substituent). Resin composition.