JPS5823844A - Polyvinyl chloride composition - Google Patents

Abstract

PURPOSE:The titled semirigid or nonrigid composition having extremely improved plasticity, low-temperature impact resistance, and flexibility, obtained by blending chlorinated ethylene.1-butene copolymer rubber, etc. with polyvinyl chloride. CONSTITUTION:100pts.wt. polyvinyl chloride is blended with 30-200pts.wt. chlorinated rubber with a chlorine content of 5-50wt% obtained by chlorinating ethylene.1-butene copolymer rubber having a molar ratio of ethylene to 1-butene of (85/15)-(95/5) or ethylene.1-bitene.5-ethylidene-2-norbornene copolymer rubber having a molar ratio of ethylene to 1-butene of (85/15)-(95/5). The addition of 1-20pts.wt. ethylene.alpha-olefin copolymer rubber having a molar ratio of ethylene to alpha-olefin of (95/5)-(20/80) and/or ethylene.alpha-olefin.polyene (preferably nonconjugate polyene) terpolymer rubber to the polyvinyl chloride improves further low-temperature impact strength.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyvinyl chloride composition, and more particularly,
The present invention relates to a polyvinyl chloride composition which has improved the plasticity of vinyl chloride, and has also improved the low-temperature needle percussion properties and flexibility of vinyl chloride.

Polyvinyl chloride is one of the representative plastics.
It is formed into shapes such as films, sheets, paper products, reso-1 paper products, extrusions, molds, fibers, etc., and is used for a wide variety of table applications.

However, this polyvinyl chloride has poor plasticity, poor properties at low temperatures, and low impact resistance,69 and for this reason, various lubricants are mixed with modifiers and used. The current situation is that DOP (dioctyl phthalate) has traditionally been used as a modifier for tetrachloride such as ζO.
7# acid esthetics such as DBP (dittylphthalate), A/@Nakatcp, X7. Shinshun esters such as -)) are known, but these liquid plasticizers have migration and leaching properties, and also have defects in that they lose weight when heated. Blending with polymers such as nitrile rubber and chlorinated tetraethylene as plasticizers has been practiced.

However, by blending nitrile rubber and chlorinated I-lyethylene, 911! C.L. chloride improved the layering properties, but the impact resistance at low (1) and the flexibility at (medium and low) 11 were improved by %/%t.

The present inventors have found that such conventional chlorinated fxle compositions have no drawbacks! As a result of intensive research to improve -PVC=#
By adding 4 to 4 and 5 to 5], not only is the chlorinated 1fxle O wearability significantly improved, but also the nitrile is reduced to chlorinated/V ethylene. It has been found that the impact resistance and flexibility of PVC can be improved in a suitable manner, leading to the present invention.That is, according to the present invention, the impact resistance and flexibility of polyvinyl chloride can be improved.

(b) (The ratio of 1-2 ethylene to 4 is about 8
5/1! Ethylene and 1-)P ranging from 1 to 95A
Copolymer rubber with ten or op) ethylene and 1-1
Ethylene, 1-1 thene, 5-ethylidene-2-nor, runene and O copolymer rubber in which the molar ratio of ten is in the range of about 85/15 to 95/') [salt content obtained by chlorination] A polyvinyl chloride composition is provided comprising about 5 to 50% by weight of at least 1" 1IiO chlorinated tm.

According to the invention, the molar ratio of (a) -vinyl chloride and (b) (1) ethylene to 1-Latin is about 1.
45-95A (Ethylene, 1-1 tene and O copolymer rubber in the D range or (11) ethylene and 1-1 tene molar ratio of about 85/15 to 9! S15 O copolymer rubber or (11) ethylene and 1-1 tene in the range D At least one chlorinated rubber having a chlorine content of S ~ 50% by weight obtained by chlorinating a copolymer of 1-ten and S-ethylidene-2-nor with runene, tAt, and (.) (1) Ethylene. A copolymer of ethylene, an α-olefin and a olefin, and a copolymer of ethylene, an α-olefin and a 4-ethylene chloride composition comprising 1 to 20 parts by weight is provided. be done.

Chlorination added to vinyl chloride in this book 11mK/
Ethylene/l-1 to be chlorinated as A O raw material
Tene copolymer f or ethylene/1-2 tene/5-ethylidenenor I rune copolymer f with ethylene and 1-1
The molar ratio with ten is approximately 85/15 to 9574. Good'＊
L <HA87/13~94'6 O range must be nina, and even if such a mole ratio Oζ0 copolymer/AQ chlorinated product is blended with vinyl chloride, the OO relative product #i Oka same molar ratio A binary or ternary copolymer containing ethylene, propylene, and t-copolymer component fAO chlorinated w and blended with vinyl chloride. If the above amount is blended, it will be very strong and have excellent flexibility when it is intended to be used as a semi-rigid or soft OSV vinyl chloride composition. In addition, if the molar ratio of ethylene to 1-1 ten in this binary or ternary copolymer rubber is about 154 d4y- or more in 1-1 ten units, molded products of chlorinated rubber T-4 blended with vinyl chloride is inferior in strength, and when compared to chlorinated f5 and 1F, when compared to the chlorination of a known binary or ternary copolymer rubber containing ethylene and propylene as comonomer components. There's nothing to change.

On the other hand, if the ethylene unit exceeds about 95 moles, the molded product will have a disadvantage of poor impact resistance.

1 ethylene/1-1 tenene/nonconjugated diene terpolymer
In place of 5-ethylidene-2-norurunene as a non-conjugated diene comonomer component when used as a material,
Ethylene, l-1 ten, using dicyclopentadiene tube
When zocyclopene/diene copolymer fA is used, the amount of chlorinated compounds is large (it cannot be uniformly blended even when blended with vinyl chloride), so molded products have low impact resistance and #Low h* On the other hand, rs-ethylidene-2-norurunene is a preferable non-conjugated diene in view of its small amount of Ael produced.

Ethylene l-1ten- used as raw material for chlorination
The content of 3-ethylidenenor runene component in the 5-ethylidenenor runene copolymer is approximately 30 in raw material value.
Since it is recommended that the content of ethylene/l-1, which is the raw material for MAR conversion used in the present invention, is A copolymer of ethylene/l-1ten/5-ethylidene-2-nor is a runene copolymer,
Approximately S~100. Approximately 10 to 800 Mooney viscosity [
(ML 100°C) 1+4, is not used, 5-2- If the viscosity is too low, the strength of chlorinated rubber! On the other hand, if it is too high, chlorinated rubber 0Ill! Melt flowability decreases, moldability and processing!
When 1 is blackened and blended with vinyl chloride, it becomes uniform!
1 becomes impaired.
A method of crushing A into fine particles, making the fine particles into aqueous droplets, and contacting them with molecular chlorine at about 70 to 90 C, for chlorine such as carbon tetrachloride and tetrachlorethylene. A method in which the copolymer rubber is dissolved in a stable solvent and brought into contact with molecular chlorine as a homogeneous solution, or
-Chloracetamide, N-chlorsuccinimide, l,
Chlorinated compounds such as 3-ditar-5.5-someterhydantoin are uniformly incorporated into the copolymer rubber using a tube roll or Banbury mixer, and the temperature at which the chlorine enters the tube [K heating method, etc.] O
Chlorination is preferred, since the ethylene and 1-1 tenene in the copolymer rubber (D4 ratio is within the range specified above).
Also, a copolymer f A with an O crystal index of 25 or more can be made into fine particles by mechanical pulverization at room temperature, and molecular chlorine is blown into an aqueous suspension that can be chlorinated with low friction. This is because the method can be adopted. In addition, the crystalline index here is low-density &#lyeethylene Milason M-9 (Mitsui-Rike Kencal low-density polyethylene, A8TM-D-1238
Method of measurement (190℃) 1.5, A8
A dense [9,9!1)0 differential thermal analysis was performed using the TM-D-1505 method, and the endothermic area in the range of 20°C to 120°C was set as 1looo, and the ratio of the endothermic area of the copolymer to this was defined. The fine particles used for this suspension chlorination are preferably 10 mesh, (Tyl@r No.) passing through.If the fine particles are larger than this, the time required for chlorination will be longer and it is not suitable for industrial use. This is not good, and it is difficult to chlorinate uniformly.
If there are disadvantages such as the occurrence of chlorination, and ζOll cloudy chlorination, it is recommended to use a surfactant tube to stabilize the chlorination reaction system.

The li& of chlorination depends on the amount of molecular chlorine or other chlorinating agent used, reaction time, reaction strength, etc. selected as appropriate.
, can be adjusted. Furthermore, when chlorinating using a molecular chlorine tube, it is known that the chlorination reaction rate can be greatly increased (by irradiation).

The chlorination reaction is carried out as follows.

In the case of aqueous chlorination, monomolecular chlorine is removed from the chlorinated rubber by washing with water, and the rubber is dried. #!
In the case of chlorination in a liquid state, the reaction solution is poured into a poor solvent of chlorinated rubber along with an excess of methanol, and the precipitate is washed with this solvent and dried.

The chlorinated rubber thus obtained has approximately 5%
It should have a chlorine content of ~50% by weight, preferably about 5-35% by weight, and a Mooney viscosity Wl (ML1+4.100°C) of about 20-150, preferably about 30-80. If the chlorine content and Mooney viscosity are too high, the melt fluidity of the chlorinated rubber will decrease, the moldability and processability will deteriorate, and the uniformity when blended with polyvinyl chloride resin may be impaired. The impact strength rjl of the molded product is not sufficient.

On the other hand, if the chlorine content is lower than this, the impact resistance of the molded product obtained by mixing it with tetrachloride will not be sufficient.If the viscosity is low, the impact resistance of the molded product will decrease as well. do.

According to the present invention, the method of blending chlorinated rubber with fluorinated vinyl chloride is conventionally performed using nitrile pum or chlorinated polyethylene [-
Any method of blending with vinyl chloride can be employed. In particular, the chlorine rubber used in the present invention is easily granulated and has a particle size of 4H'C10 or less.

~1OO mesh, when the particles are refined to O particle size, the loading time is lower than when conventional chlorinated ethylene-propylene copolymer rubber or chlorinated ethylene-propylene-nonconjugated zoene copolymer/A is refined to a particle size of 9. 10. King-IIX 1k exhibits excellent storage stability, making it extremely advantageous when reacting with 4-vinyl chloride in a Henschelmikiner in an extruder.

The blending ratio of the chlorinated rubber of the present invention to Isu C chloride varies depending on its use (soft or medium hard), but
Generally, it is desirable that the amount of chlorinated rubber is 3 to 2σO parts by weight, preferably about 5 to 1OO parts by weight, per 100 weight parts of vinyl chloride IIK. If it is less, it is not preferable because impact resistance cannot be imparted to 19-vinyl chloride, and conversely, even if it is added in a large amount, the modification effect of 1-g-vinyl chloride will increase [unexpected and wasteful]. So I don't like it.

According to the present invention, in addition to the above chlorinated rubber,
Furthermore, as the %A component, (1) copolymer rubber of ethylene and α-olefin or/and (11) ethylene and α-olefin
Olefin, I diene and O copolymer rubber t.

Preferably 1 to 100 parts by weight of vinyl I9#1
By adding 20 parts by weight of p in a conventional manner, the low-temperature impact strength rjIL of polyvinyl tetrachloride can be greatly improved.

Specific examples of the above α-olefin include propylene, l
Examples include -1-tene, 1--4-tene, 4-methyl-1-pentene, 1-hexene, 1-octene, and l-decene.

In addition, non-conjugated 4-lienes are preferable as the I diene, and specifically, 1,4-hexadiene, l,6-otatadiene,
2-methyl-1,5-hexadiene, 6-methyl-1,
Go to 5-! tadiene, linear non-conjugated dienes such as 7-methyl-1,6-octazoene, diterhexadiene, dicyclointadiene, methyltetrahydroindene, 5-
Vinylnorrunene, 5-ethylidene-2-norrunene, 5-methylene-2-norrunene, 5-isozolobylidene-2-norrunene, 6-rinmethyl-5-iso! (1-cyclic non-conjugated diene such as nyl-2-norurunene, 2,3-diisopropylidene-5-ralupylene, 2-ethylidene-3-iso7''!-pylidene-5-/
Typical examples include lunene, 2-7'' gastric benylene, 2,2-nor#lunadiene, !, 3,7-octatriene, 1,4,9-decatriene, and 41. 1.4-hexadiene, dicyclopentadiene, 6-ethylidene-2-norurunene and the like are preferred.

Therefore, there are various O copolymer rubbers that can be used as the third component, and it goes without saying that a t-mix of these rubbers can be used.

Industrially, ethylene/propylene binary copolymer is used, and ethylene/1-1 tenium binary copolymer is used! ethylene/propylene 1-) cyclointadiene terpolymer rubber, ethylene/propylene/5-ethylidene-2-norurunene rubber copolymer f, ethylene/l-1tene/disic w
-4-ntadiene copolymer im, ethylene, 1-1 ten,
The use of 5-ether-2-nor-I runene terpolymer rA is recommended.

The molar ratio of ethylene to α-olefin in these copolymers is typically in the range of 9515 to 20 AO, and Mooney coagulation (ML, +4.100°C) #I is about 20 to 15
It is recommended that it be 0. Also, if there is a copolymer in which 17 components are copolymerized, the base price is about 3
It is preferable to use a copolymer rubber of 0 or less. When the intention is to provide hard vinyl chloride with excellent impact resistance, this effect is remarkable, and a hard vinyl chloride molded product having excellent impact resistance 1 even at low temperatures can be obtained.

However, when blending into tetravinyl chloride, very good results can be obtained if the third component table is uniformly mixed in advance using the chlorinated foot roll extruder or the like. If the third component has a modulus of force 11p, the impact resistance may actually decrease.

From the composition of the present invention, molded hard/IJ vinyl chloride with excellent shooting properties (about 3 to 50 parts by weight of chlorinated rubber per 100 parts by weight of vinyl chloride, and further about 1 to 20 parts by weight) By blending copolymer rubber made from ethylene, α-olefin, and in some cases 4-recycle components, it is possible to obtain semi-rigid or flexible polyvinyl chloride molding with excellent equipment and flexibility. A product (when 50 parts by weight or more of chlorinated rAl is blended with 100 parts by weight of 11# chloride) is obtained, and can be used satisfactorily for conventional polyvinyl chloride resin applications.

The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples.

Ethylene/l-butene/5-ethylidene-2-norgyrunene copolymer fAl having the properties shown in Table 1
, 20 meshes with targashiru (made by targa industry), ('l
It was mechanically crushed at room temperature to a size that could pass through a wire mesh. 1g2 of copolymer rubber powder obtained by pulverization
009. A mixture of 0.111 of X-NO-FUIN 750 (Nonionic Emulsifier I Daiichi Kogyo Seiyaku Products) and 2J of water was charged into a glass container with an internal volume of 3 mm equipped with a stirrer and a temperature needle, and heated. When the temperature of the system reaches 80°C, chlorine gas t2.
into the suspension of the mixture at a rate of 1'/min,
The chlorination reaction was continued for the time shown in Table 1 at a temperature of 0 to 83°C. After that, we met and had two baths of 60℃ warm water.
Repeat washing for 3 times, then wash once with cold water for 5 hours.
Dry under reduced pressure at 0°C for 20 mesh.

A chlorinated rubber having a particle size that could pass through a wire mesh was obtained. The chlorine content in this chlorinated rubber was measured using the -npe combustion method. ! The glue fraction of these chlorinated rubbers was measured as follows.

Make a screen basket with 100 mesh wire mesh,
In this, about 0.21 chlorinated rubber 0. Precisely weigh it to the nearest 1.5 kg, leave it in boiling p-xylene for 1 hour, dry the insoluble matter remaining in the screen basket at 50°C for 3 hours under reduced pressure, and leave it to cool to 0. ．． Weighed accurately to the nearest 9 units, and expressed the insoluble content as the glue fraction. To determine the properties of unvulcanized chlorinated rubber, the chlorinated rubber was preheated at 150°C for 6 minutes without splinters. , 100
Press for 4 minutes under pressure of kll/al, followed by 25c,
lo Ok$/aF A press sheet with a thickness of 2 cm was produced by cold glazing under 4D pressure, and the stress at break and elongation values of this sheet were measured in accordance with the method of JI8 K-6301. . The results are shown in the 111th K.

Synthesis example 3 1st! Powdered (20 mesh, screen passed) ethylene/1-2 tenene copolymer fJ- with IK and hole properties
ni':) Vh, chlorination using the same method as Synthesis Examples 1 and 2
T59 minutes Yukihana, 20 Messi, wire mesh [Rice passing through,
leO chlorinated fAl was obtained. When the chlorine content in this chlorinated rubber was measured by the combustion method, a weight value of 21 was obtained. The physical properties of this chlorinated fAK were added to 181, and the results were summarized in Table 1. Example 1 (III Vinyl chloride hard application) 20 mesh obtained from synthetic fll, size to pass through the wire mesh of (Tyl@r No-) 10 parts by weight of powdered gym chloride, 100 parts by weight of powdered tetravinyl chloride (product name: Zep103ΣP1 manufactured by Nippon Zeon), and an organic Cd-Ba-Zm stabilizer for vinyl chloride (product name: Ll[1Z- 80 Kasuri Kagaku)
1.5 parts by weight, Cd-Zn stabilizer (trade name LCZ-
101 Chemical) 0. Henschel Z at 50°C in a stoichiometric part and 1.0 part by weight of calcium stearate (manufactured by Wako Junkei)
Mix in a water heater and add the ζO mixture to a boiling temperature of 130~
The mixture was kneaded for 5 minutes using an 8-inch roll at 140°C. This mixed wire was press-molded under the following conditions to produce a press sheet with a thickness of 2 mm (1 sheet for the hammer impact strength test) and used for various measurements. The measurement result tl1211K is shown.

(f-less molding conditions) III. Vinyl chloride mixed material t Preheat at 170°C for 3 minutes,
Next, heat press at 170℃ for 2 minutes under a pressure of 100yen7512%A, then at 20℃ for 5 minutes at 100hya,
io Perform a cold press under pressure.

j! Example 2 In Example I, synthesis f11 yields hazardous chlorinated ethylene 1
-:j'Ten・5-Fsf''No2-Norrunene Rubber Combined Plum P, the chlorinated ethylene obtained in Synthesis Example 2
The vinyl chloride composition I9 was molded in exactly the same manner as in Example 1 except that the l-butene copolymer rubber was used. The measurement results are shown in Table 2.

Comparative Example 1 In IPvI, #i is exactly the same as Example 1 except that the futuristic ethylene 1-2 tenene copolymer before chlorination of Synthesis Example 2 was used instead of the chlorinated rubber obtained in Synthesis Example 1. The fresh vinyl chloride composition tllll L was press laminated. Measurement results [shown in Table 2].

Comparative Example 2 Chlorinated ethylene (trade name Elasrene 301 A) was used in place of the large chlorinated rubber O obtained in Synthesis Example 1.
Molding was carried out in exactly the same manner as in Example 1 except that Showa Denko M) was used, except that the polyvinyl chloride composition was molded. The measurement results are shown in Table 2.

Implementation 9 $3 (1) J Vinyl chloride semi-rigid use) Synthesis f13
100 parts by weight of powdered chlorinated rubber of a size that can pass through a wire mesh of 20 mm (Tyl@r No.) obtained in step 1 and 100 parts by weight of powdered polyvinyl chloride (trade name: Zeon 103EP, manufactured by Nippon Zeon). and organic Cd-IIs-Z
11 series vinyl chloride stabilizer (trade name IJilZ-80J
fp chemical all) 15 parts by weight, Cd-Zn stabilizer (
0.5 parts by weight of calcium stearate (product name LCZ-10 manufactured by Sakai Chemical) and 1.0 parts by weight of calcium stearate (manufactured by Wako Junkei Co., Ltd.)
The mixture was kneaded for 5 minutes using an 8-inch micrometer of 11F at 130-140°C. This mixed wire was press-molded under the following conditions and subjected to various measurements. The measurement results are shown in the third RK.

(Press molding conditions) Quadrivinyl chloride kneaded material [Preheated at 170°C for 3 minutes, then heat pressed at 170°C for 2 minutes, then cooled at 20°C for 5 minutes at 100 kg/am'. conduct.

Comparative Example 3 The pK of the chlorinated rubber obtained in Synthesis Example 3 in Example f13
, chlorinated polyethylene (product name MR104 Osaka Soho 11
) was used in the same manner as in Example 3, except that semi-rigid
Table 3 shows the ELL determination results obtained by making a polyvinyl chloride composition tlI, press layering it, and measuring its properties.

Comparative Example 4 100 parts by weight of chlorinated rubber obtained in Synthesis Example 3 in Example f13 fiK% dioctyl 7 tala ■ Wako Pure JIII
A semi-rigid polyvinyl chloride composition was prepared in exactly the same manner as in Example 36, except that the composition was 40% A for weight Wt, and then press laminated and its physical properties were measured.

The measurement results are shown in Table 1 and 3.

The following margins are Examples 4 to 6 and Comparative Example 5 Various copolymers fAQ mixture shown in Table 4-1O weight l1
The mixture was kneaded using a T8-inch roll at 80°C for 5 minutes. ζO kneading f rubber G weight St.

II* Form 0III Vinyl chloride (Product name: Yaon 103
1P Nippon Zeon) 100 parts by weight, organic C-Ba-
Stabilizer for Z+a-based chloride 11”xle (product name: IJIZ)
-80, Sakai Chemical Co., Ltd.) 1.5 parts by weight, Cd-Km stabilizer (trade name LCD-10, manufactured by Waki Kagaku) O, S parts by weight, and calcium stearate (Wako Cotton I & Co., Ltd.) 1.01 parts by weight. ll! EIIl1gtso~140C01 inch carbon-
Knead for 5 minutes.

The ζO kneading tube was pressed in the same manner as in Example 1, and various -*
**Determined. The results are shown in Table 4.

The following is a blank procedural amendment (spontaneous) dated January 13, 1980 Director General of the Japan Patent Office Shima 1) Haruki-dono 1, Indication of the case 1982 Patent Application No. 138616 2, Title of invention Polyvinyl chloride composition 3, Amendment Relationship with the case of a person who does Column 6, "Detailed explanation of the Sunshine Weather rotor" column 6, contents of correction 1) Table 2, page 21 of the specification, "After 500 hours of irradiation with Sunshine Weather rotor" in the column of physical properties of polyvinyl chloride composition. Corrected to 5'00 hour irradiation 1 (25°C)j.

2) Same page 21 jl! Table 2, "Drop impact strength" in the column of physical properties of polyvinyl chloride compositions r Drop impact strength (-20°C)
”.

that's all

Claims (1)

[Scope of Claims] l (a) vinyl chloride; (b) (i) ethylene and a 1-1 ten-O molar ratio of about 8;
5/1 m~9! Ethylene in the 150 range and 1-7
"Tene and O copolymer fm or (11) ethylene and 1
-5 in terms of chlorine content obtained by chlorinating ethylene, 1-ytene, 5-ethylidene-2-norrunene and O copolymer/A with a tenyl ratio in the range of about 85/15 to 95A. A vinyl chloride composition comprising at least four types of chlorinated rubber having a weight of ~50% by weight. L (a) Vinyl chloride, (b) (1) Ethylene and 1-2O2 O2 ratio is approximately a
s/1S ~ms/ISom range L/7 and 1-
ff and O copolymer f or (11) ethylene and 1
-2f Q4 has a ratio of approximately 86/is to 9615 range 1
Ethylene, 1-1 thene and S-ethylidene-2- in 1
(e) (1) At least one type of chlorination with a cumulative salt content of about 5 to 50% by weight obtained by chlorinating norl-runene and O copolymer fAl; (e) (1) ethylene and α-olefin; A vinyl chloride composition comprising a copolymer f and/or Fi (ii> copolymer f of ethylene, α-olefin, and f-riene).