JPS58179253A - Chlorine-containing synthetic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled novel composition giving a crosslinked resin molded article having excellent thermal stability and flame retardancy, by compounding potassium orthotitanate to a chlorine-containing resin composition. CONSTITUTION:100pts.wt. of a chlorine-containing synthetic resin (e.g. polyvinyl chloride, a resin containing >=70mol% of vinyl chloride unit, etc.) is compounded with 1-100pts.wt. of potassium orthotitanate and if necessary with conventional heat stabilizer and crosslinking agent such as organic peroxide, amine, sulfur- containing compound, etc. to obtain the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) The invention relates to a chlorine-containing synthetic resin composition, and further notes: Reinforced flame retardant r1:
This invention relates to a base material synthetic resin composition.

R chlorine-containing side 1111, especially its representative polyvinyl chloride V1 superior 7, and also has various properties and low chemical properties A
A'+1 and 1. 7F is used in a wide range of fields.However, plastic vinyl vinyl generally has low impact strength and is a resin with poor thermal stability, so it is easily exposed to flames during a fire if kept at high temperatures for a long time. It decomposes into toxic hydrogen chloride gas and a large amount of organic gas, and forms smoke, which is a problem when used as a building material.

By the way, potassium titanate was originally developed as a reinforcing filler for engineering plastinox, but it is chemically unstable with potassium hexatitanate (K2O 6Ti02), which is chemically stable and has excellent heat resistance. Potassium tetratitanate (K2O4Tj02) is known as potassium tetratitanate (K2O4Tj02), which is chemically unstable as mentioned above, and is intended to be used in fields such as catalysts, rather than as a filler. There is. On the other hand, potassium hexatitanate is a white powder that has a needle-like or fibrous shape with a length of 20 to 30 μm and an aspect ratio of about 100, and has excellent chemical and thermal stability. Therefore, it is extremely suitable as a plastic reinforcing filler.
It is used as a reinforcing filler for various plastics.

The present inventors have conducted various studies on the filling effect of potassium titanate in plastics, and have found that not only does potassium tetratitanate have the same filler reinforcing effect as potassium hexatitanate for chlorine-containing synthetic resins, but also We have discovered that its chemically stable properties act favorably to exhibit a thermal stabilizing effect, and that it also has excellent additive effects such as promoting crosslinking and improving 1 heat control properties and 111 II flammability. The present invention was made based on this knowledge.

That is, the present invention provides a chlorine-containing synthetic resin composition comprising 100 parts by weight of a chlorinated synthetic resin and 1 to 100 parts by weight of potassium tetratitanate.

In the present invention, chlorine synthetic resin and resin are synthetic resins containing chlorine atoms in the molecule, and a typical example is vinyl chloride thread resin. In addition, this vinyl chloride resin is a polymer of polyvinyl chloride, vinyl chloride, and other copolymerized resins. It includes resin bullets containing 50 mol% or more, preferably 70 mol% or more of vinyl chloride units.

Additionally, potassium tetratitanate (K
2O・4T10□) is added to the chlorine-containing synthetic resin.
It is added in an amount of 1 to 100 parts by weight per 0 parts by weight. When potassium tetratitanate is added in a small amount of 1 to 5 parts by weight per 100 parts by weight of the synthetic resin, and preferably when used in combination with a commonly used heat stabilizer, its thermal stability improving effect is noticeable. However, if one or more acids are added, an even higher thermal stabilization effect can be obtained, and
Excellent resin reinforcing effect as a reinforcing filler can be obtained.

Furthermore, the chlorine-containing synthetic resin composition of the present invention containing potassium tetratitanate not only suppresses the cutting and decomposition of the chlorine-containing resin under heating and melting conditions of, for example, 170 to 2N)°C, but also
Cross-linking between polymers in the resin progresses, further improving mechanical strength such as tensile strength at break, bending strength, and impact strength, as well as suppressing flammability, which greatly reduces the amount of smoke produced, especially when burned with flame. This is extremely desirable from a practical standpoint. This preferred potassium tetratitanate has a heat stabilizing effect of 1.1% when less than 1 part by weight is added to 100 parts by weight of the chlorine-containing synthetic resin, and even if it exceeds 100 parts by weight, it binds to additive 11. Since the effect of ivy addition may not be obtained and the mechanical strength may be lowered,
A portion of 0 tons will be advantageously adopted.

The mechanism of action of potassium tetratitanate on chlorine-containing synthetic resins is due to its chemical instability.

That is, in potassium tetratitanate, potassium ions in its crystals are exposed to the oven-banked tlA direct q' L, -, which is due to the fact that potassium activated by heat etc. can easily move and react. So, potassium tetraftanate, which has such a crystal structure, is in contact with a chlorine-containing synthetic resin! When 7L is heated in the river,
Chlorine and potassium easily react to form potassium chloride, and titanium oxide is amorphous! Used and released. On the other hand, it is thought that crosslinking progresses by binding to the dechlorinated ^'jJ molecules r1 phase lI. When discharged, the dechlorination reaction of chlorine molecules causes undesirable phenomena such as molecular chain scission and the formation of conjugated double bonds, resulting in coloration, but the potassium tetratitanate-containing composition of the present invention In this case, such undesirable phenomena are practically not observed, and the parts excited by the dechlorination reaction undergo a cross-linking reaction between molecules.
A crosslinked resin is effectively formed, and a molded article with better physical properties is formed. The chlorine-trapping effect and cross-linking effect of potassium tetratitanate are extremely specific and previously unknown, and their specific functions suppress the formation of conjugated double bond chains and the scission of molecular chains. It is thought that the effect of suppressing thermal stability and combustion (11I 1141, especially smoke generation) appears.

- Also, like potassium hexatitanate, potassium tetratitanate is a needle-shaped crystal with a length of about 20 μm and an aspect ratio of about 100, and like potassium hexatitanate, it contains a relatively large amount of filler and i-. When added to a resin, its tensile strength and elastic modulus are significantly increased, but while potassium hexatitanate has a significantly lower impact strength, potassium tetratitanate has the advantage of increasing impact strength as well. It was completely unexpected that the material had such reinforcing performance. Although the reason for this is completely unknown, this unexpected effect can be confirmed by the Examples described later. Normally, when blending the resin with the same weight of 1-IJXO, the impact strength is 1, IJXO, and 4. The impact strength of the material is substantially the same as that of the tree 11iTL'J body, and it is extremely high compared to the filler of the song. By subjecting potassium tetranathanate to a surface treatment that increases the
J-(Is it possible to further increase the impact strength-(
-1 Western hrium titanate has 11 filler characteristics with 11
do.

Potassium tetratitanate is a filler of chlorine-containing synthetic resin and 1
7, when the above-mentioned young fruits are obtained, or the tomashio-based resin molding composition of the present invention (J is the stabilizer, lubricant, cross-linking agent used in the formulation) Nawa shaving, plasticizer,
Other additives can be added as desired.

Potassium tetratitanate used in the present invention, which is added to the chlorine synthetic resin, has a heat stabilizing effect and a crosslinking effect as described above. Crosslinking agents used in resin crosslinking for the purpose of preventing plasticizer bleed, such as organic peroxides,
When used in combination with a crosslinking agent such as an amine or a sulfur-containing compound, even higher crosslinking effects can be obtained. The degree of crosslinking of the composition of the present invention can be easily determined by changing the heat treatment temperature and time.
This can be controlled, and by selecting an appropriate temperature and time depending on the type and amount of other crosslinking agents used in addition to the acid added to potassium tetratitanate, it is possible to obtain molded products with the desired crosslinking properties.・Crosslinking treatment temperature is usually 170-21
The temperature is approximately 0°C, but when considering its control and processing time, a range of 180 to 200°C is preferable. If it is too low, it will take a long time; if it is too high, the crosslinking will be too high to the extent that it will not dissolve in the solvent in a short time. It turns into molecules.

- Furthermore, as mentioned above, the composition of the present invention has the desirable properties of having an extremely slow combustion rate and an extremely low amount of smoke when subjected to forced combustion, as is clear from the examples below. Since the generation of hydrogen chloride gas, incomplete combustion gas, or decomposed organic scum smoke, which is sometimes the most feared, is extremely suppressed, it is also suitable for use as building materials or interior materials. a Chlorine synthetic resin is generally a self-extinguishing substance that is difficult to burn itself, and becomes even more flame-retardant when combined with non-flammable fillers, but when forcibly heated to high temperatures or burned by flame, (1411i)
Component i decomposes, and a large amount of agarwood-based scum is generated as toxic scum smoke along with hydrogen chloride. However, the chlorine-containing synthetic resin composition of the present invention containing potassium tetratitanoate is different from such conventional products.
There were fewer fuming rats, and this is presumed to be due to the special fluorine extraction and crosslinking abilities of potassium tetratitanate.

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

Example 1 25 to 100 parts of potassium tetraditanoate were placed on 41 parts of 100 tons of polyvinyl chloride (Nippon Ceon 103EP), and polyethylene wax and T" were added thereto as a d'f agent.
Add 1 to 2 parts by weight of a mixture of 1:1 of phosphorylated glycerol and 2 to 3 parts by weight of a mixture of dibutyl tin maleate and dibutyl tin malate as a stabilizer. Prepare various compositions,
Each composition was roll-kneaded at a temperature of 165°C +1 to obtain each roll sheet. The obtained roll notebook was cut into a predetermined size, and four cut pieces were stacked to press-form a plate with a thickness of 3.
Each test piece for the Yalpee impact test is cut and made.
Each test was measured in an air-conditioned room with a room temperature of 23° C. and a humidity of 50%. The test results for each sample are shown in Table 1.

Table 1 From this table, it can be seen that the tensile strength and elastic modulus increase with the filling compoundability of potassium tetratitanate. -Also,
The impact strength increases when the filler content is approximately 25 yen (R-, 4), and its peak strength is approximately three times that of the vinyl chloride resin itself (filling amount 0)71, and its reinforcing effect is 1 There are four things that make him unique and special.

Example 2 Polychlorinated Hino L (11 bottles, 103EP manufactured by Zeono) 10
In the 0 ton hanging part, 1 part of potassium 4,000 tannate 2 parts, 1 part of potassium stearate, 1 part of potassium stearate (1.5 parts of paper part and 0.5 parts of zinc stearate)
The heavy paper portion was added and mixed, and roll kneaded at 165° C. and 7 crystallinity to produce a sheet. The obtained rolled sheet is shredded,
The sample was placed in an oven at 185° C. and heated for 60 minutes, and the change in color was checked every 10 minutes. Note that the roll notebook subjected to the heat coloring test was slightly pinkish due to the coloring caused by carunium stearate. The results of the heating test showed that after 10 minutes of heating, the color became slightly reddish, and at 20, 30, and 40 minutes, a slight yellowish tinge was added to this, and after 60 minutes, a light brown color change was observed. .

Generally, when zinc is added to polyvinyl chloride, the thermal stabilizing effect of the zinc stabilizer is weak, and under heating conditions of 185°C,
It turns black (zinc burn) in about 0 to 20 minutes, and if a polyhydric alcohol is added as a co-stabilizer, the stabilizing effect is improved, but the color still turns dark brown after 1 hour.

However, when potassium tetratitanate is used in combination with the zinc stearate stabilizer, as is clear from the above results, the discoloration from light brown to pale yellow-red occurs after 1 hour of heating. , it can be seen that the thermal performance of Ir1l 1'l is significantly improved.

Examples, Example 1 Compact combustion test device 1
1” is used, the stone fire time, the burning rate (1
fI-h (the value obtained by reducing the decrease by the combustion time) and the amount of smoke produced (the value at the time of maximum smoke production = 1, which is small by a common factor) were measured. Their binding is shown together in the second garment. Note that the combustion temperature is approximately 650°C.

Table 2: Potassium tetratitanate 4
The flammability was suppressed to a large degree by the light -C of..., and a remarkable effect was observed on the light frame control. , its filling amount is 1
0 to 30 parts by weight is preferred in practical use.

Patent applicant Makoto Ishizaka, Director of the Agency of Industrial Science and Technology - Designated agent] Fuji Nai, Director of the Osaka Institute of Technology
-man

Claims (1)

[Claims] A chlorine-containing synthetic resin composition consisting of I i' + 100 parts of chlorine synthetic fat resistance and 1 to 1 ()0 parts of potassium tetratitanate.