JPH03207739A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in heat resistance, scuffing resistance, water resistance, having a low mold shrinkage factor and a low linear expansion coefficient and capable of imparting surface gloss to moldings by blending a glass fiber with a cyclic olefin-based random copolymer in a specified ratio. CONSTITUTION:An objective composition containing (A) a glass fiber and (B) a random copolymer composed of (i) ethylene and (ii) a cyclic olefin of formula I (1 is 0 or integer; R<1>-R<18> are H, halogen or hydrocarbon; R<15>-R<18> may together form monocyclic or polycyclic structure which may have double bond; R<15> and R<16> or R<17> and R<18> may together form alkylidene), formula II (m is 0 or integer; R<1>-R<10> are H, halogen or hydrocarbon; R<9> and R<10> may together form alkylidene), etc., at least in an amount of (100/1)-(100/100) and having 0.05-10dl/g intrinsic viscosity [eta] in decalin at 135 deg.C and >=70 deg.C softening temperature (TMA).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition containing glass fiber and a cyclic olefin resin. The present invention relates to a fiber-reinforced thermoplastic resin composition suitable for obtaining a molded article having a low coefficient of linear expansion and a glossy surface.

i skin side 55 momme 11 Thermoplastic resin is easy to mold, so it is already used in daily goods,
It is used in large quantities in all fields, including packaging materials, industrial parts, and electrical appliance parts. However, such thermoplastic resins are not without disadvantages; for example, thermoplastic resins have a large difference in specific volume between melting and solidification, so it is difficult to avoid shrinkage of the resulting molded product to a greater or lesser extent. do not have. Therefore, before designing a molded product, molds are manufactured with the shrinkage rate in mind.

On the other hand, in recent years there has been a remarkable development in precision equipment such as communication equipment BOA equipment and optical equipment. Parts for such precision equipment have strict requirements for dimensional accuracy (dimensional stability over a long period of time under various usage conditions), and it is difficult to use thermoplastic resins that have a high shrinkage rate during molding. Non-grade thermoplastic resins have a relatively low mold shrinkage rate, making them suitable for such applications.Such precision equipment parts require long-term dimensional stability under various conditions of use, especially in hot and humid environments. Dimensional changes due to moisture absorption may be a problem. Therefore, such precision equipment parts are usually manufactured by die-casting or metal cutting.

By the way, cyclic olefins having ethylenic double bonds in the ring have polymerizability, and can react with a-olefins such as ethylene to yield cyclic olefin/a-olefin random copolymers. It is known (Japanese Unexamined Patent Publication No. 168708/1983, published in Japanese Unexamined Patent Publication No. 243/1983)
Publication No. 111, JP 63-305111, Public and Private JP 63-223013, JP 1-185307).

Such cyclic olefin resins have the transparency, water resistance, chemical resistance, and thermal properties necessary for optical materials. *One of the resins suitable as a molding material for 8g parts. However, such a cyclic olefin/α-olefin random copolymer still has low heat resistance and rigidity when used alone, and has a large east linear expansion coefficient due to molding shrinkage, so it cannot be used as it is for precision equipment parts such as those mentioned above. Sometimes there isn't.

Therefore, the present inventor, Tun, conducted various studies to improve the molding shrinkage east linear expansion coefficient, etc. of the cyclic olefin/α-olefin random copolymer. It was discovered that the properties such as heat resistance, rigidity, mold shrinkage east linear expansion coefficient, etc. were improved by The object of the present invention is to provide a fiber-reinforced thermoplastic resin composition suitable for obtaining molded articles that are convenient for use and have a low coefficient of linear expansion.

The thermoplastic resin composition according to the present invention comprises [A] glass fiber, [B] ethylene, and at least the following formulas [I] to [W].
It is a copolymer with a cyclic olefin represented by one of the structural formulas selected from The composition ratio of glass fiber [A] and cyclic olefin random copolymer [B] containing a cyclic olefin random copolymer having a temperature of 70°C or higher is [A]/[B] (weight ratio) of 1
It is characterized by being 00/1 to 100/100.

R1 to RIe may be the same or different, and each is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and RIS to R1@ are bonded to each other to form a monocyclic ring. Alternatively, a polycyclic ring may be formed, and the monocyclic ring or polycyclic ring may have a double bond, and R15 and RI6 or R1te and R1@ may form an alkylidene group. ).

... [I] (In the formula [r], 1 is O or a positive integer, and...
・[■Co(In the formula [n], m is 0 or a positive integer, and R1 to
RI @ 14 They may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, even if R11 and R1- form an alkylidene group. good).

... [m] (In formula [m], n is 0 or a positive integer, and R1 to
R12 may be the same or different, and each is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R11 and Re2 may form an alkylidene group. ).

...[ul (in the formula [rvl, p is an integer of 0 or 1 or more, and q
and r is 0, 1, or 2, and R1-R1% each independently represents an atom or group from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group. or R11) and Re
(or R〒) and hawk may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group. ) Thermoplastic resin composition ζdai according to the present invention Glass fiber [A
] and a specific cyclic olefin random copolymer [B]
It is a thermoplastic resin composition suitable for obtaining molded articles having excellent heat resistance, rigidity, scratch resistance, water resistance, and a small linear expansion coefficient.

Next, the thermoplastic resin composition according to the present invention will be specifically explained.

A copolymer of glass fiber [A] for thermoplastic resin composition according to the present invention, ethylene, and a specific cyclic olefin represented by one of the structural formulas selected from formulas [1] to [■] above. It is characterized by containing a cyclic olefin random copolymer [B].

Glass fiber [A
] IL is used as a reinforcing material for thermoplastic resin, and usually has a fiber diameter of 1 to 20 μm, preferably 6 to 12 μm, and a fiber length of 1 to 10 mm, preferably 3 to 12 μm.
It is in the range of 6 mm. Further, the surface of the glass fiber [A] may be treated with a silane compound such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, etc.

The cyclic olefin random copolymer [B] constituting the thermoplastic resin composition of the present invention is a cyclic olefin-based random copolymer composed of a structural unit (a) derived from ethylene and a structural unit (b) derived from a specific cyclic olefin. It is an olefin random copolymer.

The above cyclic olefin has at least the above formulas [r] to [r
It is a cyclic olefin represented by one of the structural formulas selected from vl.

However, in the above formula [11], l is 0 or a positive integer, preferably O to 3. In the above formula [i, m is O or a positive integer, preferably O-3. In the above formula [m], n is O or a positive integer, preferably O-3. In the above formula [■], p is 0 or an integer of 1 or more, preferably 0
It is an integer of ~3.

And R1, RI* (formula [I]), R1 to R11
(Formula [■]), Rt~R+z (Formula [m]) or R1-
RIB (formula [■]) may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups. Here, examples of the halogen atom include If, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of hydrocarbon groups include independent stains, alkyl groups having 1 to 10 carbon atoms, and cycloalkyl groups having 5 to 15 carbon atoms. Specific examples of alkyl groups include methyl groups. ethyl group
Examples of the cycloalkyl group include isopropyl group, isobutyl & n-amyl group, neopentyl & n-hexyl in-octyl Ln-decyl group, 2-ethylhexyl group, etc. Specific examples of cycloalkyl group include cyclopentyl group
Examples include cyclohexyl group, methylcyclohexyl group, and ethylcyclohexyl group.

Furthermore, in the above formula [E], R1' and R1. or RIT and RIIB may form an alkylidene group, and in the above formula ['ri], R9 and RI@ may form an alkylidene group. The above formula [ml
In, R11 and RI2 may form an alkylidene group. Such alkylidene groups 1 Usually include alkylidene groups having 3 to 10 carbon atoms, and specific examples thereof include IL ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, and the like.

Also, in the above formula [■], R8 (or R6) and Re
(or R'') and (dai) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.

Furthermore, in the above formula [xl, R1' to R11 may be bonded to each other (together) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond. You can.

It can be easily produced by condensing the cyclic olefin cyclopentadiene represented by the formula [xcol[rv] with a corresponding olefin or cyclic olefin by a Diels-Alder reaction.

Specifically, the cyclic olefins represented by the above formulas [I] to [■] include, for example, 11° (the following margin), 12.1, 1+1]-3-1'f-1=n112 ,s,l? , 11]-3-tothycene-dodecene, 12.5,1-dodecene, 12.5,1-dodecene, 17.1.]-3-dodecene, and diene compounds such as 8-isopropylidene; 8-isopropylidene-dodecene・Pentacyclo[4,7,0,12・S, Q@13.19 +2]-3-pentadecene derivatives such as 1e-co-3-dodecene; Tetracyclo[4,4,0,12・5.17 such as 1-dodecene・l
1l-3-dodecene derivative.

Cosene and also hebutacyclo[7,8,O,it auto, 02 7.11@ +f, Q 111.112 1] -4-eicosene derivatives such as 11S] -4-eicosene; ! +, 113111. Qlj, l#, l15.1] -5-pentacocene, 2.g+a, +s, 1roL1.] -5-pentacocene, etc. nonacyclo[9,10,1,1'? ,Ql・,Qllll,Q10. 21. l13.21. Qla 1., 11S] -5-bentacocene derivatives and the like can be mentioned.

can be mentioned.

Cyclic olefin-based random copolymer [B] that constitutes the resin composition according to the present invention IL A car whose essential constituent units are the constituent unit (a) derived from ethylene and the constituent unit (b) derived from the cyclic olefin. In addition to the two essential structural units, as long as the object of the present invention is not impaired,
If necessary, it may contain other copolymerizable structural units derived from unsaturated monomers. Examples of unsaturated monomers that may be added as necessary include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1
-dodecene, 1-tetradecene, 1-hexadecene, 1
-C3 to 20, such as octadecene and 1-eicosene
Examples include a-olefins. The structural unit derived from these unsaturated monomers may be contained in an amount less than equimolar to the structural unit (a) derived from ethylene in the generated random copolymer.

In the cyclic olefin random copolymer CB constituting the resin composition according to the present invention, the content of the structural unit (a) derived from ethylene is 40 to 85 mol%, preferably 5
It is desirable that the content is in the range of 0 to 75 mol%.

Furthermore, the structural unit (b) derived from a cyclic olefin is 15
It is desirable that the content is in the range of ~60 mol%, preferably 25-50 mol%. In the present invention, the structural units (a) derived from ethylene and the structural units (b) derived from cyclic olefins are randomly arranged to form a substantially linear cyclic olefin random copolymer.

The intrinsic viscosity [7] of the cyclic olefin random copolymer [B] constituting the resin composition of the present invention measured in decalin at 135°C is 0.05 to 10 dl/g, preferably 0.08 to It is in the range of 5 dl/H.

Further, as the cyclic olefin random copolymer [B] constituting the resin composition according to the present invention, the softening temperature (TMA) measured with a thermomechanical analyzer is 0°C or less, preferably 90 to 250t:, more preferably It is desirable that the temperature is in the range of 100 to 200°C.

Further, it is desirable that the glass transition temperature (Tg) of the cyclic olefin random copolymer [B] constituting the resin composition according to the present invention is usually in the range of 50 to 230°C, preferably 70 to 210°C.

Further, the crystallinity of the cyclic olefin random copolymer [B] constituting the resin composition of the present invention determined by X-ray diffraction analysis is 0 to 10%, preferably 0 to 7%, particularly preferably It is desirable that it be in the range of 0 to 5%.

As the cyclic olefin random copolymer [B] constituting the resin composition according to the present invention, only a copolymer having physical properties within the above range may be used. Some copolymers outside the above range may be used. In this case, the physical property values of the cyclic olefin random copolymer CB as a whole may be within the above range.

The cyclic olefin random copolymer [B] constituting the resin composition according to the present invention is disclosed in Japanese Patent Application Laid-Open No. 60-16870.
8 revolution JP-A-61-120816 revolution JP-A-6
1-115912 revolves JP-A-61-115916 revolves JP-A-61-271308 revolves JP-A-61-
272216 revolution JP 62-252406 revolution
It can be manufactured by a method similar to the method proposed by the present applicant in JP-A-62-252407 and the like.

In the present invention, a part of the cyclic olefin random copolymer as described above may be modified with an unsaturated carboxylic acid such as maleic anhydride. Such modified products can be produced by reacting the above-mentioned cyclic olefin resin with unsaturated carboxylic acids, their anhydrides, and derivatives such as alkyl esters of unsaturated carboxylic acids. In this case, the content of structural units derived from the modifier in the modified cyclic olefin resin is usually 0.001 to 5% by weight or less. Such a cyclic olefin resin modification cutting area can also be produced by blending a modifier with a cyclic olefin resin and carrying out graft polymerization to obtain a desired modification rate.
It can also be produced by preparing a modified product with a high modification rate in advance and then mixing this modified product with an unmodified cyclic olefin resin.

In the thermoplastic resin composition of the present invention, glass fiber [A
] and the cyclic olefin random copolymer component [B] + & [A] component/[B] acid component weight ratio) is 1
00/1~100/Zoo, preferably 10015~
It is 100150.

In the present invention, when producing a cyclic olefin random copolymer as described above, formulas [I] to
[Cyclic olefins other than the cyclic olefin represented by rvl can also be polymerized. Such cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, 2,
3.3a,7a-tetrahyto-o-4,7-methano-I
Besides H-indene, 3a, 5.6.7a-tetrahuman O-4,7-methano-IH-indene, etc.

CHs CH.

Bicyclo[I]-[IV,2,1]hept-2-ene derivatives such as methylbicyclo[I]-[IV, etc., 5.10-dimethyltetraCH.

9-isobutyl 2.7 11,12- ) dimethyl9-inbutyl-11J2 -dodecene 5.8.9 10-tetramethy8-methyltetrasif 8-ethyltetrasif i・co3 dodecene 8-hexyltetrasif C*H+s "J-5-r7c/Ie coco-dodecene 1.17.11] dodecene 1] -3-dodecene-3-dodecene and other tetracyclo[4,4,0,1'5.17.11
]-3-dodecene derivative; (blank space below) 8) (1? @]-3-dodecene+ 1 ]-]3-dodecene-methyl-9-ethylthi 3-dodecene-3-dodecene1.]-]3- dodecene+4] 4-hebutadecene desendecene heptadecene 15-ethyl octashif 13.Q2.7.QII4]-4-hen 2.171-5
- Octacyclo[8,8,0,1'114 7.1st, 1st, I+ such as tococentadecene, hexacyclo[6,6,1,13ts 1ζQ2 , 7 , Q9 @ , Q3 , Lu, O12 +y ]-5-tococene derivative; + 4 ]-]4-heptadecene derivative: IIBαL, O12 + 7 ]-5- tococene, +s, IIt, +s, (ls e, 0+ 7]-5-tocosenbutacyclo- 5-heneicosene derivatives; tricyclo[4,3,0,1, etc., pentacyclo[6,6,1,1”・s, g2?,
tricyclo[4,3,0 12・S]-3-decene derivatives such as Qll, +4]-4-heneicosene derivatives; hebutacyclo-5-icosene derivatives such as to 1
．． pentacyclo[6,5,1,1'',8,0 such as tricyclo[4,4,0,12S]-3-undecene derivatives such as 6-dimethylbenta10-methyl-tricif-14,15-dimethylben
2.1.09.+ 3 ]-]4-pentadecene derivatives can be mentioned.

(Left below) Such other cyclic olefins can be used alone or in combination, and are usually 0 to 20 mol%
used in amounts of

Furthermore, the resin composition of the present invention has the above-mentioned [A] and [
B] Acid component part number: Contains a rubber component to improve impact strength, heat-resistant stable ship, weather-resistant stable ship, anti-static ship, slip longevity, anti-blocking ship, anti-fogging agent, lubricant,
Dyes, pigments, natural oils, synthetic oils, waxes, etc. can be blended, and the blending ratios are appropriate. Specifically, 4 stabilizers are added as optional ingredients.
1 Tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane, β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2,2°-oxamidobis[ethyl-3(3,5-di-t-butyl-
Phenolic antioxidants such as 4-hydroxyphenyl) cobrobionate, stearite, fatty acid metal salts such as calcium stearate and calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol mono Examples include fatty acid esters of polyhydric alcohols such as stearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be used alone or in combination. ,
Tetrakis methylene-3 (3,5-di-t-butyl-
Examples include a combination of 4-hydroxyphenyl)propionate comethane, zinc stearate, and glycerin monostearate.

In the present invention, it is particularly preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol. Polyhydric alcohol fatty acid esters are preferred.

As a fatty acid ester of such polyhydric alcohol, L
Specifically, IL glycerin monostearate, glycerin monolaurate, glycerin monomyristate,
Glycerin fatty acid esters such as glycerin monopalmitate, glycerin distearate, glycerin dilaurate, pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate,
Fatty acid esters of pentaerythritol such as pentaerythritol tristearate are used.

Such phenolic antioxidant ill +k is 0.01 to 10 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.
．． The fatty acid ester of polyhydric alcohol may be used in an amount of 1 to 1 part by weight.
It is used in an amount of 1 to 10 parts by weight, preferably 0.05 to 3 parts by weight.

Fillers other than glass fiber [A] may be added to the thermoplastic resin composition of the present invention within a range that does not impair the object of the present invention. Such fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, Barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, potassium titanate fiber, carbon woven rim, boron woven rim, silicon carbide woven rim polyethylene woven edging
Polypropylene woven edge Polyester fiber Fillers such as polyamide fibers are used.These fillers can be used alone,
Or they can be used in combination. The amount of fillers other than glass fiber [A] to be added varies depending on the type of filler added.
] and the cyclic olefin random copolymer [B] in an amount of usually 5 to 50 parts by weight based on 100 parts by weight of the total amount.

For example, in the above filler, potassium titanate fiber 1
- It is a fibrous crystal represented by the formula 20.(TiO2)n, and the fiber diameter is usually 0.1 to 3 μm, preferably 0.2 to 1 μm, and the fiber length is 5 to 100 μm, preferably 10 It is preferable to use one having a diameter of 50 μm. One such potassium titanate fiber is used in an amount of 5 to 50 parts by weight, preferably 8 to 30 parts by weight, per 100 parts by weight of the total amount of glass fiber [A] and cyclic olefin random copolymer [B]. It is preferable. By adding potassium titanate fibers in such an amount to the resin composition according to the present invention, the appearance of a molded article using the resin composition according to the present invention may be improved.

For example, in the above filler, the carbon fiber diameter is usually 3 to 20 μm, preferably 7 to 18 μm, and the fiber length is 0.1 to 10 mm, preferably 0.3 to 3 mm.
It is preferable to use one in the range of .

Such carbon fiber melon is preferably used in an amount of 5 to 50 parts by weight, preferably 8 to 30 parts by weight, based on 100 parts by weight of the total amount of glass fiber [A] and cyclic olefin random copolymer [B]. . Carbon fiber in such an amount,
By adding it to the resin composition according to the present invention, the linear expansion relationship, sliding properties, etc. of a molded article using the resin composition according to the present invention may be improved.

In addition to the above-mentioned components, the thermoplastic resin composition of the present invention includes various fillers and a cyclic olefin random copolymer [B
] In order to increase affinity and adhesion with maleic anhydride, modified polyolefins are graft-modified with unsaturated carboxylic acids such as maleic anhydride. An unsaturated carboxylic acid-containing cyclic olefin random copolymer obtained by graft-modifying a graft-modified unsaturated carboxylic acid-containing polyolefin group-based copolymer and a cyclic olefin-based random copolymer with maleic anhydride may be added. . 1 piece of such unsaturated carboxylic acid-containing polyolefin copolymer or unsaturated carboxylic acid-containing cyclic olefin random copolymer to 100 parts by weight of the total amount of glass fiber [A] and cyclic olefin random copolymer [B] On the other hand, it is desirable that it is added in an amount of 100 parts by weight or less, preferably 5 to 80 parts by weight.

As a method for producing the thermoplastic resin composition according to the present invention, a known method can be applied, and glass fibers [A and cyclic olefin random copolymers] and other components added as desired are mixed in an extruder, kneader, etc. - Mechanical blending methods, such as mechanical blending, or dissolving each component simultaneously in a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, xylene, etc., or dissolving each component separately and then mixing. Examples include a method for removing the solvent, and a method that combines these two methods.

Since the thermoplastic resin composition obtained by the above manufacturing method is composed of glass fiber [A] and a specific cyclic olefin random copolymer [B], it has excellent heat resistance, rigidity, scratch resistance, and water resistance. It is a thermoplastic resin composition suitable for obtaining molded products with a small linear expansion coefficient.

Examples of applications include electrician J%, OA equipment, cameras,
Housing for pumps etc. Chassis for precision equipment department &
Examples include automobile interior and exterior materials such as instrument panels, radiator grills, cluster grills, console boxes, garnishes, and foil covers, as well as cases and covers for seats, connectors, coil bobbins, switches, etc.

As described above, according to the present invention, glass fiber [A] is blended into the cyclic olefin random copolymer component [B], so it has excellent heat resistance, rigidity, scratch resistance, and water resistance, and is moldable. A thermoplastic resin composition suitable for obtaining a molded article having a small linear expansion coefficient can be obtained.

[Examples] The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.

In addition, the measuring method and evaluation method of various physical property values in this invention are shown next.

(1) Melt flow index (MFRy) According to ASTM D1238, at a predetermined temperature T°C and a load of 2.
(2) Preparation of test piece The test piece was molded under the following molding conditions using an injection molding machine 1S-50EPN manufactured by Toshiba Machine ■ and a specified mold for the test piece. After molding, the island test piece was molded at room temperature for 48 hours. Molding conditions measured after standing: Cylinder temperature 270°C, mold temperature 90°C, Sayaro pressure Car secondary/secondary = 1000/800kg/cm2 Injection speed (-next) 30mm/sg - Screw rotation speed 1
5Orpm (3) Bending test Performed according to ASTM D790.9 Test piece shape: 5X 1/2X 1/8t inches, distance between spans 1mm Test speed: 20mm/min Test temperature: 23℃, 80℃, 100℃ (4) Heat Deformation Temperature (HDT) Test specimen shape according to ASTM D628: 5X 1/4X 1/2t inch load
Weight: 264psi (5) Softening temperature (TMA) Thermo Mechanical A manufactured by DuPont
The thermal deformation behavior of a 1 mm thick sheet was measured using a nalyzer. That is, a quartz needle was placed on the sheet, a load of 49 g was applied, and the temperature was raised at a rate of 5°C/min, until the needle became 0.635 mm. (6) Glass transition temperature (Tg) and melting point (Tm) (D
SC method) Measured at a heating rate of 10°C/min using DSC-20 manufactured by SEIKO Electronics Co., Ltd. (7) Rockwell hardness Measured at 23°C according to ASTM D785 (R scale) (8) Izot impact Test Test conducted in accordance with ASTM D256 Test piece shape: 5/2 x 1/8 /min Test temperature: 23°C 10 [A
]Acid component is Asahi Fiber glass fiber C8486A
[B] The acid component has an ethylene content of 63 molXMFR2, @e, measured by 13 cm NMR, is 32 g
/10m] A135℃ Intrinsic viscosity measured in decalin [
V] is 0.48 dl/a TMA is 150°C, Tg is 140°C (Tm not observed) and 1.4.5
．． 8-dimethano-1,2,3,4゜4a, 4b, 5
．． 8.8a, 9a-decahydrofluorene (hereinafter referred to as DM
Random copolymer (ethylene/DMD) with DF (abbreviated as DF)
Table 1 shows the results of blending 8 kg of pellets of F random copolymer) while the resins are melted.

The cylinder temperature was 240°C, and the glass fiber was fed from the resin melting zone to a part of the cylinder after the resin melting zone. DMDF random copolymer) 7.7 kg of maleic anhydride-modified ethylene produced by the method below.
DMDF random copolymer (hereinafter [C] acid component abbreviated) 0
．． The same operation as in Example 1 was carried out except that a mixture of 3 kg was used, and the results are shown in Table 1.

(Method for producing maleic anhydride-modified ethylene/DMDF random copolymer) Ethylene and DMDF used as the [B] acid component in Example 1
5kg of pellets of random copolymer with E.

5 units of maleic anhydride dissolved in 25 g of acetone Organic peroxide (manufactured by NOF Corporation, Perhexine 2 trademark)
After adding 3 g and thoroughly mixing, a twin-screw extruder (manufactured by Ikegai Iron Works ■, PCM 45) was used to carry out a reaction under melting conditions at a cylinder temperature of 250°C, and the resultant maleic anhydride-modified resin was pelletized using a pelletizer. The acid content was 0.8% by weight. Ethylene D used as the [B] acid component in Example 1
Ethylene/propylene random copolymer (ethylene content: 80 mo) was added to 85 parts by weight of MDF random copolymer.
L% MFR2z e”c: 0.7g/10m]A
Intrinsic viscosity [v] measured in decalin at 135°C: 2°2
dl/g.

% knee 54°C) was melt-blended using a twin-screw extruder (manufactured by Ikegai Iron Works, PCM 45), and further this resin 1
1g of Perhexine 25B manufactured by NOF ■ per kg,
Divinylbenzene was added at a rate of 3 g.The mixture was thoroughly mixed and then passed through a twin-screw extruder at a cylinder temperature of 23°C.
The reaction was carried out in the melt at 0°C and pelletized using a pelletizer. Table 1 shows the results of carrying out the same operation as in Example 2 except that the obtained resin was used in place of the [B] acid component in Example 2. .

Table 1 shows the results of carrying out the same operation as in Example 3 by changing the proportions of the [A], [B], and [C] acid components used in Example 3.

1.1: Instead of the ethylene/DMDF copolymer used as the [B] acid component used in Example 3, a copolymer of ethylene and another cyclic olefin was used as the [B] acid component. The physical properties of the [B] acid component used are shown in Table 2.
Shown below.

The results are shown in Table 1.

Claims (1)

[Claims] (1) [A] Glass fiber, [B] ethylene, and at least the following formulas [I] to [IV]
] It is a copolymer with a cyclic olefin represented by one of the structural formulas selected from a cyclic olefin random copolymer having a temperature of 70°C or higher, and the composition ratio of the glass fiber [A] and the cyclic olefin random copolymer [B] is [A]/[B] (weight ratio). 10
A thermoplastic resin composition characterized in that the ratio is 0/1 to 100/100. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [I] (In the formula [I], 1 is 0 or a positive integer, and R^
1 to R^1^8 may be the same or different, and each is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R^1^5 to R^ 1^8 may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R^1^5 and R With ^1^6 or R^1^7
and R^1^8 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [II] (In formula [II], m is 0 or a positive integer, and R^1
~R^1^8 may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, and R^9 and R^1^0 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [III] (In formula [III], n is 0 or a positive integer, and R^
1 to R^1^2 may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, and R^1^1 and R^ 1^2 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ...[IV] (In formula [IV], p is 0 or an integer of 1 or more, q and r are 0, 1 or 2, and R^1 ~R^1^8
each independently represents an atom or group from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and R^5 (or R^6
) and R^9 (or R^7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group. )