JPH026550A - Chlorinated vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in processability, heat expansion resistance, deflection resistance of pipe, high-temperature rigidity, hammering impact resistance, appearance, etc., by mixing a chlorinated vinyl chloride resin with a flaky filler. CONSTITUTION:100 pts.wt. chlorinated vinyl chloride resin (specific viscosity >=0.24, desirably, >=0.40 and a chlorine content of 62-72%, desirably, 65-68%) is mixed with 0.5-50 pts.wt., desirably, 15-30 pts.wt. flaky filler to obtain a chlorinated vinyl chloride resin composition suitable for use in pipes, underground cables, ducts and tanks, domestic articles, electrical components, automobile parts, sprinklers, etc. As said flaky filler, quartz, metal foil, especially, natural and artificial mica of a mean particle diameter >=5mum desirably, 15-100mum, an average thickness <=100mum, desirably, 0.5-5mum and an aspect ratio >=10, desirably, 30-60 can be suitably used.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel chlorinated vinyl chloride resin composition,
In more detail, various physical properties such as processability, heat expansion and contraction resistance, pipe deflection resistance, high temperature rigidity, hammer impact resistance, appearance, etc. are changed.General pipes, hot water pipes, special pipes such as underground cables, ducts, tanks, household supplies, mechanical parts, electrical parts,
Automatic fire extinguishing systems for automobile parts, sprinklers, etc. [Conventional technology and its problems] Chlorinated vinyl chloride resin takes advantage of the excellent properties of vinyl chloride resin, such as chemical resistance, weather resistance, and electrical insulation. Post-chlorination of vinyl chloride resin greatly improves heat resistance, but while impact resistance and processability are reduced, the coefficient of thermal expansion against temperature changes is large, and dimensional stability is poor. It has the disadvantage of being large in deflection under load.

Therefore, unless these drawbacks are improved, the advantages of chlorinated vinyl chloride will not be fully utilized. For this reason, attempts have been made to incorporate various modifiers and fillers as components to improve these drawbacks without reducing heat resistance.

For example, to improve impact resistance and processability, blends of chlorinated vinyl chloride resin and chlorinated polyolefin (Japanese Patent Publication No. 38-12175), blends of chlorinated vinyl chloride resin and polybutadiene-styrene-acrylonitrile copolymer are used. (Special Publication No. 42-13257), Blend of Chlorinated Vinyl Chloride Resin and MBS-EVC (Special Publication No. 47-6)
848), Blend of chlorinated vinyl chloride resin and polyolefin rubber or epichlorohydrin rubber (% Publication No. 47-45420), (Special Publication No. 51-17952)
etc. are known. In addition, in order to improve heat resistance and physical strength, composites of chlorinated vinyl chloride resin with inorganic and/or organic fibers (Japanese Patent Application Laid-Open No. 55-12139), combinations of chlorinated vinyl chloride resin and thermosetting resin, etc. Mixing or crosslinking (Unexamined Japanese Patent Publication No. 1983
-329415, JP-A-48-34238), etc. are known.

However, although these methods are apparently effective in improving impact resistance, processability, and preventing deterioration of heat resistance, they also reduce the thermal expansion coefficient of the composition and reduce the flexibility resistance at high temperatures of around 100°C. No such effect was observed. In addition, for example, compositions with fibers have the drawback of significantly worsening extrusion processability.In other words, when constructing hot liquid piping using chlorinated chlorinated vinyl resin, the thermal expansion coefficient due to temperature changes is large. These methods could not solve problems such as problems with joints coming apart due to expansion and contraction of the pipes, large pipe deflections due to low rigidity at high temperatures, and the need to install supports over short distances.

Therefore, the composition of the present invention improves the above-mentioned drawbacks, has excellent workability, is less likely to cause 11 troubles in hot liquid piping construction (heat expansion and contraction resistance), and has a small 1-pipe deflection rate (pipe deflection resistance). The purpose of the present invention is to provide a chlorinated vinyl chloride resin composition with excellent processability.

[Means for solving problems]

The non-inventor is characterized by workability, heat expansion and contraction resistance, pipe deflection resistance,
As a result of various studies on chlorinated vinyl chloride bond thread compositions with excellent high-temperature rigidity, hammer impact resistance, and appearance, we have discovered a chlorinated vinyl chloride resin composition containing chlorinated vinyl chloride resin and a scaly filler. The inventors have discovered that the above-mentioned physical properties can be improved, and have arrived at the present invention.

The present invention provides a chlorinated vinyl chloride resin composition characterized in that the pre-scaly filler has an average particle size of 5 μm or more, an average thickness of 100 μm or less, and an aspect ratio of 10 or more. A chlorinated vinyl chloride resin composition characterized in that the filler is a cleavage agent; a chlorinated vinyl chloride resin composition characterized in that the flaky filler is mica; Vinyl chloride resin has a specific viscosity of 0.
．． 24 or more and the chlorine content is 62-72%t-
This is a characteristic chlorinated vinyl chloride resin composition.

The term "scaly" as used in the present invention refers to a scale-like strip shape, and refers to a flat plate-like shape having an excessively large surface area with respect to the thickness cross section. In addition, cleavage refers to the property of being more easily cracked along certain parallel planes than other planes, and therefore, materials with cleavage generally take on a scale-like shape as the valves open. be.

The chlorinated vinyl chloride fat used in the present invention includes:
Usually chlorine content is about 59-72% by weight, specific viscosity (JISK
6721 compliant) approximately 0120 or higher is used, but
Preferably, the chlorine content is about 64 to 70% by weight and the specific viscosity is about 0.26 or more, and more preferably about 65% by weight.
Chlorinated vinyl chloride having a specific viscosity of 68% by weight or more and a specific viscosity of about 0.40 or more is preferable because it has excellent heat expansion and contraction resistance and resistance to deflection at high temperatures.

Aspect ratio is the value obtained by dividing the average grain size by the average thickness.

As a method for producing chlorinated vinyl chloride resin, for example, vinyl chloride resin powder is suspended in a gas phase or in water,
Alternatively, it is produced by chlorination in a state dissolved in a solvent, for example, by the method described in Japanese Patent Publication No. 35-888 and Japanese Patent Publication No. 45-30833.

Further, in the composition of the present invention, a blend of 100 parts by weight or less of vinyl chloride resin with 100 parts by weight of chlorinated vinyl chloride resin can also be used.

In addition, the vinyl chloride resin that is the raw material for chlorinated vinyl chloride resin includes not only a homopolymer of vinyl chloride, but also a copolymer of a dominant amount of vinyl chloride and a minor amount of other monomers that can be copolymerized with it. can also be used. Examples of monomers copolymerizable with vinyl chloride include monomers such as vinylidene chloride, acrylic esters, methacrylic esters, fatty acid vinyl esters, acrylonitrile, and monoolefins.

The scale-like filler used in the present invention preferably has an average particle size (measured by an air jet sieve method) of 5 μ or more,
Particularly preferably 1 to 200μ, more preferably 1
5 to 100μ, the average thickness (measured by air jet sieve method) is preferably 100μ or less, particularly preferably 0.1 to 10μ, even more preferably 0.5 to 5μ, and the aspect ratio is preferably 10 or more. Particularly preferably, inorganic fillers such as mica, quartz, and metal foil pieces having an angle of 20 to 100°, more preferably 30 to 6° are used, and natural mica and artificial mica are particularly preferably used. According to the above, if the average particle size is less than 5μ, pipe flexibility and high temperature rigidity tend to deteriorate, and if the average thickness exceeds 100μ, impact resistance and appearance tend to deteriorate, and if the aspect ratio is less than 10. Otherwise, the pipe's deflection resistance and high-temperature resistance tend to deteriorate.

Furthermore, in the composition of the present invention, the scaly filler is generally added to 100 parts by weight of the chlorinated vinyl chloride resin from 0.5 to 50 parts by weight, preferably from 5 to 40 parts by weight, particularly preferably from 10 to 40 parts by weight, and even more preferably from 10 to 40 parts by weight. It is preferable to contain 15 to 30 parts by weight.

The composition of the present invention can be used as a molded article, such as a plate-shaped molded article, a corrugated sheet-shaped molded article, a curved molded article, a tubular molded article, an irregularly shaped molded article, a film-shaped molded article, etc. This is a general term for compounds, and the molding method may be selected from commonly used molding methods as appropriate depending on the shape. Methods such as injection molding, compression molding, extrusion molding, and calender molding may be used, although there are no particular restrictions. It will be done. For example, the composite material of the present invention can be obtained by blending a) a chlorinated vinyl chloride resin with a conventionally known compounding agent and b) a scaly filler to obtain a molding compound, or further rolling it.
What is gelled and kneaded using an extruder or the like or roughly pelletized using a pelletizer can be molded into a desired molded product using various molding machines.

At this time, it is also possible to obtain a molded product by unevenly distributing the resin composition of the present invention in a specific part of the molded product, and compounding other parts with a different resin, metal, or the like.

Next, the known compounding agents include lead, tin-based stabilizers, epoxy-based stabilizers, chelator-1 metal soaps, lubricants such as higher fatty acids and their esters, surfactants, antioxidants, ultraviolet absorbers, plasticizers, etc. agent, MBS, EVA, chlorinated polyethylene L/
7. Polymer modifiers such as MMA, human BS, and Ass; flame retardants such as antimony trioxide and phosphoric acid ester; and others can be used. These can also be made into compounds or pellets using a known mixer, such as a pump blender-Henschel mixer grinder, a Banbury mixer-roll mixer, and an extrusion mixer.

Examples and comparative examples will be specifically described below, and each physical property was measured as follows.

(11 Heating elasticity (heating elasticity resistance) Thickness 5 mm from press plate, side x width 150 x 150 m
Take a test piece, put a marked line in the center vertically and horizontally, and measure 10
Thermal strain was removed for about 3° in hot air at 0°C, and then conditioned at room temperature for 24 hours. This g test piece was immersed in a hot water bath as follows: 25°C → 85°C → 25°C → 85°C...3
The dimensions of the vertical and horizontal marked lines at 25°C and 85°C + l were measured after being conditioned for 10 minutes at each temperature. The expansion/contraction ratio of the dimensions was determined and the average value was calculated.

(2) Pipe Flexibility (Pipe Flexibility) When manufacturing a test pipe with a length of 3.5 m from a molded nominal diameter 25 ml Cl pipe, it was filled with 75°C hot water and supported with a distance of 3 m between supports. The hanging distance due to the deflection l of the central part of the nine pipes was measured and determined as flexibility.

(3) High-temperature rigidity In accordance with JIS K6745, a test piece of predetermined dimensions was punched out from a press plate with a thickness of 1 m, the relationship between temperature and rigidity was measured, and the rigidity at 75°C was determined.

(4) Hammer impact resistance A test pipe with a length of 15α was taken from a molded pipe with a nominal diameter of 25, and after being conditioned for 10 minutes in hot water at 75°C, it was then given an impact with a hammer and destroyed. - Evaluate the degree of deformation with the naked eye.

(5) Processability 65jII + Nominal diameter 251 m (J
I8 K6741 compliant) Pipe molding processability test was conducted 〇 In other words, 40 myda single screw extrusion m, cylinder temperature 1
60~180℃, die temperature 190~200℃, 15~
Molding was performed at 2 Or/m, and the load, discharge rate, and appearance of the molded pipe were evaluated.

Appearance judgment: O Good Δ Slightly poor 4.0 parts by weight of ternary basic lead sulfate, 1.5 parts by weight of dibasic lead stearate, 1.0 parts by weight of lead stearate as a heat stabilizer and b) mica powder mica as a scaly filler. S-200 (average particle size 60 μm, average thickness 1.7 μm, average aspect ratio 50, Canadian mica
A compound was obtained by adding 20 parts by weight of the resin and mixing with a Henschel mixer for about 7 minutes until the resin temperature reached 120°C. One part of this compound was kneaded in a 6" roll at 190°C for 10 minutes to obtain a roll sheet with a thickness of 0.55 m.

Next, stack the required number of each layer and heat at 200℃, 50K.
It was pressed under conditions of y/d for 5 minutes, and the heat stretchability, high temperature rigidity, and workability were measured.

The compound was also used to produce pellets using a 65-type twin-screw extruder in different directions.

A pipe having a nominal diameter of 25 mm as specified in JIS K6741 was formed from the pellets obtained above using a 4oreal single-screw extruder, and the pipe flexibility, hammer impact resistance, and roughness of workability were evaluated. The extrusion processing conditions during pellet production and pipe production are cylinder temperature 160-190'.
C, die temperature 200-210℃, screw rotation speed 1
The speed was 5 to 25 r/m.

The results of these physical property tests are shown in Table-3 and Table-4.

[Examples 2 to 8] Example 1 except that instead of using 20 parts by weight of mica powder mica S-200 in Example 1, the mica powder shown in Table 1 was used. In the same manner, pressed plates and pipes were formed and their % characteristics were evaluated.

The results are shown in Table-3 and Table-4.

[Comparative Examples-1 to 4] A press plate and a A pipe was formed and its characteristics were evaluated.

The results are shown in Tables 3 and 4.

[Reference example]

Instead of using 20 parts by weight of back powder mica S-200 in Example 1, glass fiber (approximately 13μ da, length 6+u
A pipe was formed in the same manner as in Example 1, except that Nittobo ■#RIO was used, and extrusion processability was evaluated. Table the results.
41 notes.

Table * Judgment ◎: Good Δ: Slightly problematic ×: Unsatisfactory Table 4 (Workability) [Effects of the invention] The composition of the present invention has excellent workability, heat expansion and contraction resistance, pipe deflection resistance, high temperature rigidity, General pipes with excellent physical properties such as hammer impact resistance and appearance, hot water pipes, special pipes such as underground cables, ducts, tanks, household goods, mechanical parts, electrical parts, automobile parts, automatic fire extinguishing systems such as sprinklers, etc. This is a chlorinated vinyl chloride resin composition suitable for hard molded products.

Procedural amendment examination 1999 Ushiku month 7th

Claims (1)

[Scope of Claims] (1) A chlorinated vinyl chloride resin composition containing a chlorinated vinyl chloride resin and a scaly filler. (2) The scale-like filler has an average particle size of 5μ or more and an average thickness of 100μ or less,
The chlorinated vinyl chloride resin composition according to claim 1, which has an aspect ratio of 10 or more. (3) The chlorinated vinyl chloride resin composition according to claim 2, wherein the scaly filler is a cleavable filler. (4) The chlorinated vinyl chloride resin composition according to claim 2, wherein the scaly filler is mica. (5) The chlorinated vinyl chloride resin composition according to claim 1, wherein the chlorinated vinyl chloride resin has a specific viscosity of 0.24 or more and a chlorine content of 62 to 72%.