JPH01210449A - Heat-resistant vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in initial coloration and gelling property, by adding a stabilizer, a lubricant and/or an impact resistance improver to a specified graft polymer. CONSTITUTION:99-40wt.% PVC as a branch polymer component is graft- polymerized in the presence of 1-60wt.% trunk copolymer of an MW of 500-2000000, obtained by copolymerizing 1-70wt.% N-cyclohexylmaleimide with 99-20wt.% methyl methacrylate and 0-20wt.% other copolymerizable monomers (e.g., styrene) to obtain a graft polymer of an unreacted N- cyclohexylmaleimide content of 0-0.5wt.% and a glass transition temperature >=95 deg.C. 100-5 pts.wt. this polymer is mixed with 0-95 pts.wt. PVC or vinyl chloride polymer, 0.1-10 pts.wt. stabilizer (e.g., zinc stearate), and a 0.05-5 pts.wt. lubricant (e.g., calcium stearate) and/or 0-30 pts.wt. impact resistance improver (e.g., ethylene/vinyl acetate copolymer).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention has excellent initial coloring properties, heat-resistant layer color properties, heat deformation resistance, and gelation properties, and is suitable for use in pipes, valves, hoses, floppy disk jackets, automobile parts, and electrical equipment. The present invention relates to a heat-resistant vinyl chloride resin composition useful for manufacturing molded products for a wide range of uses, including building materials such as parts, sheets, roofing materials, and exterior wall materials.

[Conventional technology]

Vinyl chloride resin has excellent physical and chemical properties and is used in a wide range of fields. However, vinyl chloride resin has the disadvantage of a low heat distortion temperature, and its use is currently limited depending on the application.

Heat deformation resistance of vinyl chloride resin! Several methods have been proposed for the improvement stage, but none have yet been found to be satisfactory.

The methods that have been proposed so far include a method in which the heat distortion resistance is improved by blending the resin with a vinyl chloride side fat that has a high heat distortion temperature, and a method in which the homopolymer is a monomer that exhibits a high heat distortion temperature. There is a method of copolymerizing δ resin with vinyl chloride to improve the heat deformation resistance of vinyl chloride resin.

Several methods have been proposed for blending resins with high heat distortion temperatures into vinyl chloride resins, but one of the most popular methods is to blend chlorinated vinyl chloride resins (hereinafter abbreviated as C-PVC). . However, for products containing C-PVC, the c-PVC will completely melt unless the processing temperature is raised (
However, when the particles are melted in a bath and turned into a moldable state (gelling), the viscosity of the melt during gelling is high, so it has the disadvantage of increasing the load on the machine. There is.

Historically, C-PVC had poor coloring in the first 1iJ3 layer (coloring without much heat history is called initial coloring), and it was difficult to put it to practical use because it was easily discolored due to dehydrochloric acid generation during shipbuilding. However, it has disadvantages such as requiring a large amount of stabilizer.

In order to improve this drawback of c-PVC, a method has been proposed in which a resin with a high heat distortion temperature, which is a combination of a methacrylic acid ester and an N-substituted maleimide compound, is blended with vinyl chloride resin (% JP-A-61-162545, JP-A-61-264037).

However, glass transfer of the N-substituted maleimide compound-methacrylic acid ester copolymer obtained by such a method is S! N-substituted maleimide compound-methacrylic modified ester copolymer must be processed at a temperature equal to or higher than that during C-PVC processing, since the particle size is higher than that of vinyl chloride resin and the particles are dense. There are many problems in practical use, such as ungelled particles that melt in the bath, resulting in a molded product with many so-called fish eyes, and the copolymer hardly gelling.

On the other hand, there is a method in which the heat deformation resistance of a vinyl chloride resin is improved by using monomeric vinyl dichloride whose homopolymer exhibits a high heat deformation temperature. Copolymers of maleimide compounds and vinyl chloride are known as examples of these (Japanese Patent Publication No. 41-9551, Japanese Patent Publication No. 44-12433, Japanese Patent Publication No. 61-255914).

These copolymers of maleimide compounds and vinyl chloride have the effect of increasing the heat distortion temperature of vinyl chloride resin depending on the copolymerization ratio of the maleimide compound, but exposure to high temperatures during processing can cause desalination enemies and ) 1b' has the disadvantage that it turns brown in a short time, so-called heat-resistant coloring property is scary.
To! do. As a result, the resin burns out during the molding process, resulting in poor long-run performance, which is a major practical problem.

[Problem to be solved by the invention]

The present invention is a vinyl chloride resin that maintains the original properties of vinyl chloride resin, has particularly excellent initial coloring properties, heat-resistant layer color properties, heat deformation resistance, and gelation properties, and is resistant to burning in practical use and has excellent long-run properties. A resin composition is provided.

[Issues] + steps to solve]

Unexploded Ff4 C, N-cyclohexylmaleimide 1-7
03 quantity ratio, methyl methacrylate 99-30i4. ft and other monomers that can act together with these 0 to 20Xt (
However, the total of these components is 100N (100N), a trunk copolymer of 1 to 60'' 5Xt graft polymer,
A heat-resistant vinyl chloride resin composition comprising a stabilizer, a lubricant, and/or an impact modifier.

N-cyclohexylmaleimide in the trunk copolymer used in the present invention is 1 to 70 m-t%, preferably 6 to 60 ikt%.
It is. The amount of N-cyclohexylmaleimide used is L]
If it is less than 70]L1%', the resulting graft polymer will not have sufficient optical heat deformation resistance, and if it exceeds 70]L1%', the gelling properties of the resulting graft polymer will deteriorate, both of which are not preferred.

Methyl methacrylate is a material that improves properties such as heat coloring resistance, gelling property, and weather resistance, and its usage rate is 99 to 30 nJt%, preferably 97 to 40 nJt%. If the amount of methyl methacrylate exceeds 99 mol ts, the effect of improving heat deformation resistance will be insufficient, and if it is less than 30 it %, the effect of improving heat resistant layer color property and gelling property will be reduced, which is not preferable.

The content of unreacted N-cyclohexylmaleimide in the obtained backbone copolymer is 101% or less, preferably 5%.
3kj1% or less. 10:&! %'a? If more unreacted N-cyclohexylmaleimide is contained, the heat coloring resistance of the resulting graft polymer will deteriorate, which is undesirable.

In obtaining the trunk copolymer, other monomers capable of co-compounding with N-cyclohexylmaleimide and methyl methacrylate can be used in combination without impairing the characteristics of the present invention.

Other base compounds capable of co-merging include acrylic acid esters such as acrylic acid ether, acrylic ether, and acrylic modified denal; methacrylic quasi esters such as ethyl methacrylate, methacrylic acid flovir, and butyl methacrylate. ;
Polyvalent (meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate;Olefins such as ethylene, propylene, and isobutylene;Styrene, α-methylstyrene, Vinyl aromatics such as vinyltoluene; Unsaturated nitriles such as acrylonitrile, methacrylonitrile, and ethacrylonitrile; Vinyl halides such as vinylidene chloride, vinyl bromide, and vinyl fluoride; Vinyl ethers such as methyl vinyl ether and butyl vinyl ether Examples include saturated monocarboxylic acid esters such as vinyl acetate and vinyl propionate.

The molecular weight of the trunk copolymer suitable for the present invention is not limited to the old man, but if it is too high, the molding processability will be poor, and if it is too low, there will be disadvantages such as poor mechanical properties and heat coloring resistance. ,
Usually 5,000 to 2,000,000°, preferably 10
．． The range is from 000 to 1,500,000. Molecular weight can be adjusted by using commonly used chain transfer agents such as t-dodecylmercaptan, mercaptoethanol, trichlorethylene and the like.

Methods for manufacturing the trunk-type electric combination include the hanging tNg method,
Known polymerization methods such as emulsion method, bath solution method, and bulk polymerization method can be applied, but suspension method and emulsion method are economically advantageous.

As a method for preparing the graft polymer, suspension 1 method, emulsion 1 method, solution 1 method, etc. can be applied, but the suspension polymerization method is economically advantageous.

A method for obtaining the graft polymer is a method in which the stem copolymer YX is synthesized according to the above-mentioned Idai method, and then the stem copolymer is synthesized with vinyl chloride in the presence of the stem copolymer taken out as a dry polymer. There is a method of grafting by adding vinyl chloride to the polymer without removing it after polymerization.

The graft polymer used in the present invention is obtained by polymerizing vinyl chloride in the presence of the above-mentioned stem copolymer, and the proportion of the stem copolymer in the graft polymer is 1 to 60]L, it%,
The proportion of vinyl chloride resin in the branch polymer component is 99 to 40% by weight, preferably the proportion of the trunk polymer is 5 to 5% by weight, and the proportion of vinyl chloride resin in the branch polymer component is 95 to 5% by weight.
I'm so disgusted that I received 0.

If the ratio of the trunk co-merged aggregates in the graft 3 coalescence is less than 1% by weight, the effect of improving P8 deformation resistance will not be obtained, and if it exceeds 60%, the gelation temperature will become high, and the gelation temperature will increase. This is not desirable as it tends to cause fish eyes.

The content of unreacted N-cyclohexylmaleimide in the graft polymer is 0 to 0.5 im%, preferably 0 to 0.
．． 1iif quantity 1-'l. Since N-cyclohexylmaleimide has sublimation property, unreacted N-
If cyclohexylmaleimide is contained in an amount exceeding 0,000 sit, it causes foaming during molding, which is undesirable.

.

The glass transition temperature ('I'g) of the graft polymer can be measured from the tan δ value of the dynamic viscoelastic spectrum, but the Tg of the graft polymer of the present invention does not indicate a value exceeding ';'s'cx. be. TE at 95° C. or lower does not have sufficient heat deformation resistance.

As a 1st polymer initiator used for graft polymer suspension obtained by 1st method, is it generally used for 1st polymer of vinyl chloride? dianruburoxides such as isobutyl peroxide and lauroyl peroxide; peroxydicarbonates such as di(isopropyl) peroxydicarbonate and di(2-ethelhexyl) peroxydicarbonate) 6, t-bunalburoxypyl Peroxides of peroxy esters such as barrate, t-butylperoxyneodecanate, etc.; compound, persulfated potassium, persulfated potassium
Water bath peroxides such as AtXl ammonium are used; It can be used alone or in combination with two or more types.

] Polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyvinyl pyrrolidone, maleic anhydride, commonly used for binding or turbidity of vinyl chloride. Synthetic polymers such as acid-vinyl acetate co-polymer, starch,
Gelatin Temple's natural polymer 921% 1 is available, and these can be used alone or in combinations of two or more rods.

The reaction temperature during the m-combination reaction is preferably 20 to 70°C. 9N, the decomposition rate of the 1st initiator is slow below 20°C.
The integration time becomes longer, the productivity decreases, and there is no good IL. 70'
If it exceeds C'r, the pressure inside the polymerization reactor will increase, which is undesirable in terms of equipment.

In order to maintain the initial colorability and heat-resistant layer colorability of the Mi bottom of the present invention, it is essential to use a stabilizer in combination. Since there are few chains of N-cyclohexylmaleimide and vinyl chloride in the grafted body, which is a component of the present invention, even heat stabilizers commonly used for vinyl chloride trees can be used in the initial layer. The same effects as above in color properties and heat-bleeding resistance can be fully obtained. cI
Examples of stabilizers include calcium, barium,
Gold bullion salts such as stearin #1 or elauryl such as zinc, cadmium, and lead; lead-based stabilizers such as tribasic lead sulfate, dibasic lead phthalate, and dibasic lead phosphite; dibutyltin laurate; diptyltin dilaurate, diptyltin malate, diptyltin simalate, dibutyltin distearate, dibutyltin laurate, diptyltin mercaptide,
Dibutyltin lauryl mercaptide, dioctyltin-8.
S-bis-(isooctyl-mercaptoacetate),
Tin-based stabilizers such as diptyltin bis-isooctylthioglycolate, dioctyltin malate polymer, diptyltin mercaptoprotionate; antimony-based stabilizers such as antimony mercaptocarboxylate ester salts; diethyl phosphite, dibutyl phosphite, tricresyl phosphite; epoxy compounds; and balaram-zinc, calcium! - Combination fc* stabilizers such as sub-ffi, cadmium-barium-zinc, and the like. These stabilizers kXj\L may be used alone or in combination of two or more. The amount of stabilizer to be used is preferably 0.1 to 10'N parts, especially 0.5 to 71f parts, per graft 3 coalescence.

The lubricant used in the present invention is added for various purposes such as preventing burning of the resin during processing, improving the finished state, and reducing power during processing. These lubricants include hydrocarbon waxes such as paraffin wax and polyethylene wax;
Fatty acids such as stearic acid and oleic acid; Kinpo soaps such as calcium stearate and magnesium stearate Fatty acid amides such as nistearamide and oleylamide; Fatty acid esters such as butyl stearate and methyl hydroxystearate Nilauryl alcohol and stearyl Higher alcohols such as alcohol; partial esters of fatty acids and polyhydric alcohols such as stearic acid heptanoglyceride and oleic acid monoglyceride; for example, Mitsubishi Rayon Co., Ltd.'s Metablen P-700, L-1000, L-10
Can be used with acrylic polymer resins such as No. 10. These Wei Zheng 1 may be used alone or in combination. The lubricant is 0.05 to 5ix for the graft polymer.
S is preferable, and 0.1 to 3 km part is particularly good.

Next, the impact modifiers used in the present invention include ethylene-vinyl acetate copolymer, ethylene-acrylic ether copolymer, chlorinated polyethylene, and phthalate polymerized with styrene and methyl methacrylate.
c, '4b (, MB8), polybutadiene with acrylonitrile and sterene grafted (AB
S), a graft polymerization of sterene, methyl methacrylate and acrylonitrile to polybutadiene (
MBAS), methyl methacrylate or methyl methacrylate and styrene graft polymerized to polyacrylate such as polybutyl acrylate,
EPDM.

Examples include EPDM grafted with ethylene and acrylonitrile, EPDM grafted with vinyl chloride, ethylene-butadiene rubber, crosslinked acrylic rubber, and the like.

These 48 improving agents may be used alone or in combination at 28°C or higher. The amount of impact modifier is 0 to 6ON relative to the graft polymer.
Violet is preferable, and 0 to 20 violet is particularly good.

The composition of the present invention can also be blended with a vinyl chloride homopolymer or a vinyl chloride copolymer and used for the purpose of improving the heat deformation resistance of these conventional resins. In other words,
100 to 5 parts by weight of graft polymer, vinyl chloride homopolymer, fc is vinyl chloride co-N+ body 0 to 95 m tray, stabilizer [1,1 to 1 [] weight s, 0.05 to 531 parts by weight
ImJt part and impact modifier part 0 to 30 ujt part of the composition, it is possible to improve heat deformation resistance.

In this case, the heat distortion temperature is lower than when using the graft polymer alone, but as mentioned above, it has excellent initial coloring properties, heat warping resistance, gelation properties, etc., and is similar to conventional vinyl chloride resin. It is possible to obtain molded products with excellent transparency and heat deformation resistance. Examples of vinyl chloride copolymers that can be blended include vinyl chloride-vinyl acetate, vinyl chloride-ethylene, vinyl chloride-acrylic acid ester, vinyl chloride-methacrylic acid ester, vinyl chloride-alkyl vinyl ether, vinyl chloride-propylene, etc. .

In addition to manufacturing the various products described below such as pipes, slopes, and sheets using the composition of the present invention, processing aids, pigments, fillers, flame retardants, antioxidants, ultraviolet absorbers, and antistatic agents may be used as needed. It is possible to use additives that are generally added to vinyl chloride resins, such as agents.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 In a 101 autoclave with a stirrer, deionized water 6.0
Icg, Poval solution (Denka Poval W-24'*Kikagaku Kogyo Co., Ltd.) pre-dissolved in 4-fold II* 0.15 phantom, 6 pre-Methyl methacrylate 1.2 to 9 N-cyclohexyl The total amount of the solution dissolved in a 0.8 cm bath was added with 10J1"Y of di(2-ethylhexyl)peroxydicarbonate, stirred at 500 rpm under nitrogen gas atmosphere, and heated to 55°C. Warm 1 cup Y
After the onset of vomiting, the temperature was maintained at 55°C for 6 hours, and the vomiting was completed. The resulting suspension was passed through a 100-mesh filter cloth, thoroughly washed with deionized water, and then dried in a hot air circulation dryer at 100°C to obtain a granular stem copolymer that had passed through 42 meshes. 91 Cg was obtained. The molecular size of this stem copolymer is 95
39.73kft% of N-cyclohexylmaleimide
, 60.3 ml % of methyl methacrylate, and 4.0 ml of unreacted N-cyclohexylmaleimide.

Then add 6 liters of deionized water to a 10 J autoclave with a stirrer.
．． 0 to 9, Poval solution (Denka Poval W-24/B-05Y85/15!J) previously dissolved in 4N amount
im) Q, 151c9, stem copolymer 0.
51cy, t-butylperoxy t-valley) 1.0
After evacuating the inside of the autoclave, vinyl chloride 1.51)Y was charged, and the temperature was raised to 55° C. while stirring at 500 rpm, and 1 go was started.

The pressure inside one cup is 8.4 kg/cat'! -G, the pressure decreases as the reaction progresses, and the pressure doubles by 6.5 k.
g 7 cm2 Unreacted vinyl chloride at the time of G Natsutomo! The IE aggregates were separated using a centrifuge, and after being optically washed with deionized water, they were dried at 60°C in a hot air circulation dryer to form a white powder that had passed through 42 meshes. I gained about 1.6 kg. The molecular hammer of this graft polymer is 550,000 branches, X? The content rate of vinyl chloride resin in the body component is 68.8mJi, and the content rate in the main body composition is 61.0xi.
ics, and the content of unreacted N-cyclohexylmaleimide was 0.231 LJl.

Graph thus obtained) ] 4 coalescence - the formulation described in section 2k 9, heated to a blush temperature of 170"C and 7'
The mixture was kneaded for 10 minutes using a hot roll with a diameter of 8 inches to obtain a sheet-like product. The deltability was advantageous when obtaining this sheet-like processed product. Obtained Geton 190°C1) 00IG
A test piece was prepared by molding for 5 minutes under the pressure of 9/c'IrL2, and according to the trial method described later, heat coloring resistance, heat distortion temperature,
Charpy impact strength and glass transition degree were measured.

The measurement results are listed in Table 6, and the graft polymer obtained according to the present invention shows excellent performance in initial nine color property, heat color resistance, heat deformation resistance, and scalability. δ was lost.

Examples 2 to 7 In accordance with the same method as in Example 1, each of the grafted composites shown in the first coating was prepared, and test pieces were prepared according to the formulation in Table 2 under the same conditions as in Example 1, and the same evaluation was carried out. went. However, in order to remove unreacted N-cyclohexylmaleimide in the trunk polymer, it was dried under reduced pressure at 85° C. for 12 hours. In Example 6.4, the stem polymer of Example 2 was used to form a graft polymer. As shown in Section 3, the characteristics of the present invention are superior to the comparative example.

Example 8 Graft polymer made in Example 1 and MikK1040
Vinyl chloride polymer (Denka Vinyl 8S-1) 0
Denki Kagaku Kogyo Co., Ltd. 60/70! ffi% ratio, and the physical properties were sub-determined by the second coating formulation, as shown in Table 6, and it was confirmed that it exhibited excellent overall properties 7.

Example 9 A recipe according to Example 1 was combined in a 3001 Jt can, the content of the main fiber polymer was 29.9 km%, the branch polymerization component was vinyl chloride resin, the M car was 70.01 short, unreacted. Contains N-silohexylmaleimide (1) 10.1 in. graph)
Tripolymer 75 has a yield of 9. This resin was compounded according to the second coating, and a pipe extrusion test was performed using one 20#EI press machine and six cylinder cylinders set at 165°C, 170°C, and 175°C, and a die temperature of 180°C.
Even after conducting an 8-hour test, no foaming or burning phenomena were observed, and a pipe with a good surface condition was obtained, and it was confirmed that the pipe had excellent long-run performance.

Comparative Example 1 Stem yarn voluminous material X1 produced in Example 6 1040
Vinyl chloride homopolymer (Denka Vinyl 8B-1) (
1 Denki Kagaku Kogyo Co., Ltd.) and 30/701 weight ratio, according to the formulation of the second coating, the surface temperature was 170℃, and
1 roll each with a diameter of 8 inches heated to 00℃
Even after kneading for 0 minutes, gelation progressed even at both temperatures of 170°C and 200°C, and only an opaque sheet with a rough surface was obtained.

Furthermore, it was confirmed that it was softer and had a lower degree of thermal deformation than Example 6, and was inferior to the present invention.

Comparative Example 2 Stem polymer and graft polymer '1' were produced in the same manner as in Example 1 except that N-cyclohexylmaleimidone was changed to N-phenylmaleimide.

The stem polymer has an N-phenylmaleimide content of 40.6
It was a reddish-brown powder of Shigekura, which was softer than that of Example 1, and had a dull and inferior appearance. The amount of 1fc unreacted N-phenylmaleimide was as high as 831Ejt%, and the monomerization property was also poor.

In order to obtain a graft polymer in the same manner as in Example 1, fc was carried out for 1 time using 0 trunk fiber polymer. 30
In addition, the graft polymer obtained had a reddish-brown color and was extremely poor in initial coloring properties.

Comparative Example 6 N-cyclohexylmaleimide was further added to the trunk polymer 460y of Example 1 so that the content of unreacted N-cyclohexylmaleimide was 15 to 4.
-Cyclohexylmaleimidone 40,? In addition, a grafted ivy composite was prepared according to the method of Example 1 with vinyl chloride 1.5-. The obtained graph) IC coalescence was a white powder and had the composition of the first coating.

The resulting grafted vines were mixed into a second coating to obtain a sheet-like product in the same manner as in Example 1. This product has gelling properties,
Although the initial colorability was good, the heat colorability was poor and the color increased to reddish brown in 25 minutes.

Comparative Example 4 14 hours of deionized water was added to a 3001 autoclave with a stirrer.
4 to 9, 43 to 43 to 85/15i of Bobal solution (Denka Poval W-24/B-LLS)
Mixed with Ji%] 4.8 tons, N-cyclohexylmaleimide 14 tons, t-butyl peroxybivalate 7 tons
6.8,? The inside of the autoclave was replaced with nitrogen, the autoclave was evacuated, and vinyl chloride was added to the autoclave, and N-cyclohexylmaleimidone was dissolved in vinyl chloride at 400 rpm for 1 hour. then 55
The temperature was raised to ℃ and the process was started. The pressure inside the can at the start of 1 cup is 8.4klj/c! At n2G, the pressure necessarily decreases as the first go progresses, but it is 6.5 kg / cm2G.
At the time when the reaction temperature reached 1, unreacted vinyl chloride (9) was collected, and after light and water washing, the copolymer was separated using a centrifugal separator. Thereafter, it was dried in a hot air circulating dryer at 60° C. to obtain a white powdery copolymer 7 that passed through 42 meshes. The composition of the copolymer is vinyl chloride resin 8 [Jmm%, N-cyclohexylmaleimide 19.9mk%, unreacted N-cyclohexylmaleimide included, and the weight of the copolymer is 0.1'.

Kōtō'l! As in Example 1, a sample 1c was prepared by combining the second red, and the initial colorability and gelling properties were good. However, when heat resistance coloring was measured, it turned reddish-brown in 25 minutes, showing poor thermal stability.

Comparative Example 5 Using the copolymer prepared in Comparative Example 4, a pipe extrusion test was conducted under the same conditions as in Example 9 using the second formulation. After about 60 minutes of appearance, many dark brown burnt parts were seen inside the pipe, and the test was stopped after 40 minutes because it was no longer possible to obtain a clean pipe.

Physical property evaluation method (1) Dellability According to the formulation of the second coating, the surface roughness is 170°C or 200°
The mixture was kneaded for 10 minutes using two rolls with a diameter of 8 inches heated to C. The condition of the resulting sheet-like workpiece was visually determined.

0: There are no particles due to fa melting.

Δ: Slight particles due to poor melting are observed.

×: There are many unbathed melted particles.

(2) Initial coloring property Geeton 190°C obtained by kneading at 170°C as in (1)
Using a flat plate press, press molding for 10 minutes at a pressure of 100 cm/cm to explode the roots with a thickness of 1 uI 7.1,
Round as determined by visual inspection.

o: rr No color Δ: Slightly colored ×: Significant one color (3) Heat-resistant layer color property Press sheet obtained in (2) 'Pr: SCM The time it took for the sheet to become colored was measured. Coloring evaluation is the same as (2).

(4) Heat deformation @ degree Pressed under the same conditions as (2), and measured heat deformation temperature according to JIS K 7207.

(Pressed under the same conditions as 51 Charpy impact strength (21), measured Charpy@'s strength according to JISK71) 1, 90 (6) Pressed under the same conditions as Glass turning ye@degree (2), 45 4.5 X
2 (am) test pieces were made and dynamic viscoelastic spectra were measured under the following conditions.

Model: Manufactured by Oiki Seisakusho, V8-FlII type Frequency 0H2 vibration! : 0.020 akm Temperature range = 40°C to 200°G The glass transition temperature was determined from the tan δ peak S degree and pattern of the dynamic viscoelastic spectrum.

Incidentally, the formulations of the samples for measuring viscoelastic spectra were all the same as in Example 1. Roll kneading temperature is 1
70℃.

(7) Composition analysis Vinyl chloride content: Measured according to JIS K 6588 using the plow combustion method.

N-cyclohexylmaleimide content: Measured by nitrogen elemental analysis.

Unreacted N-cyclohexylmaleimide s;'is: Measured by liquid chromatography.

(81 molecular weight Measured by GPC and expressed as polystyrene equivalent molecular weight.

〔Effect of the invention〕

The resin composition of the present invention has excellent initial chromaticity, color resistance, and heat deformation resistance, and has good deltability, and has a temperature range that is almost the same as that of general-purpose vinyl chloride resin. A moldable composition with excellent processability. In addition, the color property of the heat-resistant layer is extremely excellent, making it possible to operate continuously for long periods of time, making it suitable for pipes, valves, hoses, Floragiichi disk jackets, automobile parts, electrical equipment parts, sheets, roofing materials, and exterior wall materials. This is a heat-resistant vinyl chloride resin composition that is useful for manufacturing molded products for a wide range of uses, such as for example.

Patent applicant: 1m Kikagaku Kogyo Co., Ltd.

Claims (3)

[Claims] (1) 1 to 70% by weight of N-cyclohexylmaleimide,
Stem copolymers 1 to 99% to 30% by weight of methyl methacrylate and 0 to 20% by weight of other monomers copolymerizable with these (however, the total of these components is 100% by weight)
60% by weight, branch polymer component vinyl chloride resin 99-10
Weight %, unreacted N-cyclohexylmaleimide 0-0
．． 5% by weight of graft polymer and stabilizers, lubricants, and/or
or a heat-resistant vinyl chloride resin composition comprising an impact modifier. (2) A heat-resistant vinyl chloride resin composition obtained by blending the heat-resistant vinyl chloride resin composition according to claim (1) with a vinyl chloride homopolymer or a vinyl chloride copolymer. (3) Claims (1) or (2) in which the glass transition temperature of the graft polymer is greater than 95°C.
The heat-resistant vinyl chloride resin composition described in 1.