JP2000313748A - Flame retardant vinyl chloride-based resin molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant vinyl chloride-based resin molded product capable of satisfying all the respective standards of fire propagation index(FPI), smoke development index (SDI) and corrosion development index(CDI) according to the factory Mutual Research Corporation(FM) standards and having a practical strength and chemical and corrosion resistances. SOLUTION: This flame retardant vinyl chloride-based resin molded product is a vinyl chloride-based resin molded product prepared by including 5-50 pts.wt. of titanium oxide in 100 pts.wt. of a vinyl chloride-based resin and adding a lead-based stabilizer so as to provide 2-15 pts.wt. amount thereof expressed in terms of the amount of metal lead. The molded product has 60-95 degree of whiteness, 60-99 glossiness (JIS K-7105) and 0.90-1.15 J/g.K specific heat.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant vinyl chloride resin molded product, and more particularly, to a flame-retardant flame-retardant resin which satisfies the FM standard (evaluation standard of flame retardancy determined by Factory Mutual Research Corporation). The present invention relates to a vinyl chloride resin molded article.

[0002]

2. Description of the Related Art Vinyl chloride resin has good moldability, high mechanical strength, is inexpensive, and has good chemical resistance. Widely used in all fields.

[0003] However, since vinyl chloride resin contains a large amount of chlorine, it has flame retardancy, but has poor heat resistance.
When contacted for a long time as described above, thermal decomposition occurs, and smoke is generated by organic substances, and at the same time, corrosive gases such as chlorine gas and hydrogen chloride gas are generated. Therefore, when a fire occurs in an apparatus using the molded body of the vinyl chloride resin, smoke and gas are generated due to decomposition of the resin.

[0004] To prevent this, conventionally, phosphorus-based flame retardants, halogen-based flame retardants, or hydrated compounds such as magnesium hydroxide have been added to vinyl chloride resins to improve their flame retardancy. However, even if a molded article made of vinyl chloride resin with improved flame retardancy is used in semiconductor manufacturing equipment, the cleanliness of the air in the manufacturing facility will decrease due to smoke and corrosive gas generated during a fire. As a result, there is a possibility that manufacturing equipment, equipment, semiconductor components, and the like may be contaminated or attacked.

[0005] Under such circumstances, even in the case of vinyl chloride resin which is generally said to have flame retardancy, in recent years, flame retardancy and suppression of smoke generation in fire and suppression of corrosive gas generation have been required. This requirement is particularly strong in insurance organizations, especially for factory mutuals, which are North American-based industrial mutual insurance organizations.
The factories that make up the Mutual System
Mutual Research Corporation (Factory
Mutual Research Corporation) has been used effectively.

[0006] This evaluation criterion is based on the FMRC Clean Room Materials Flammability Test, which is listed as Class Number 4910.
t, hereinafter referred to as FM standard), a flame retardancy index FPI indicating a flame retardancy of 6 or less, and a smoke index SDI indicating a smoke generation of 0.
4 or less, and more preferably the corrosion index CDI indicating the generation of corrosive gas is 1.1 or less, and it is required to satisfy these simultaneously.

[0007] In response to the above requirements, it is relatively easy to achieve a flame retardancy index FPI of 6 or less by adding a flame retardant, but the smoke index SDI, preferably the corrosion index CDI, can be achieved. However, it is not easy to obtain a vinyl chloride resin molded product satisfying at the same time. For example, only a small part of the flame-retardant vinyl chloride resin molded product according to Japanese Patent Application No. 9-365319 filed by the present applicant. Molded body is FP
It only satisfies the I, SDI, and CDI criteria simultaneously. However, there is a problem that such a molded article is not very good in strength, chemical resistance, corrosion resistance and the like.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been developed in consideration of the FPI, SDI, C
It is an object of the present invention to develop a flame-retardant vinyl chloride resin molded product that satisfies all of the DI standards and has practical strength, chemical resistance, and corrosion resistance.

[0009]

As a result of intensive studies conducted by the present inventors, it has been found that titanium oxide conventionally compounded in a small amount as a pigment or the like is difficult to contain in a specific proportion in a vinyl chloride resin. In addition to finding the unexpected fact that it acts very effectively as a flame retardant, we also found that the whiteness, glossiness, specific heat, metal lead content, etc. of the vinyl chloride resin molded product had a large effect on flame retardancy. Thus, the present invention has been completed.

That is, the flame-retardant vinyl chloride resin molded article according to claim 1 of the present invention contains 5 to 50 parts by weight of titanium oxide and 100 parts by weight of a vinyl chloride resin, and has a lead-based stability. A vinyl chloride resin molded product in which the agent is added in an amount of 2 to 15 parts by weight in terms of the amount of metallic lead, the whiteness of which is 60 to 95, and the gloss (JISK
-7105) is from 60 to 99, and the specific heat is from 0.90 to
1.15 J / g · K.

The flame-retardant vinyl chloride resin molded article according to the second aspect of the present invention is the molded article according to the first aspect, wherein titanium oxide and a compounding agent are added to 100 parts by weight of the vinyl chloride resin. At least one or more of a chlorine-trapping compound, an inorganic auxiliary agent, and a flame-retardant auxiliary agent are further contained as a compounding agent so that the total content is 60 parts by weight or less.

[0012] These flame-retardant vinyl chloride resin molded products have a combustion index FPI of 6 or less and a smoke index SDI of 0.4 according to the FM standard, as shown in the data of Examples described later.
Hereinafter, the corrosion index CDI is 1.1 or less, which satisfies all the criteria, and also has good strength and chemical resistance.
The reason why the molded article of the present invention has excellent flame retardancy, good strength, chemical resistance and the like as described above will be described in detail later.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant vinyl chloride resin molded article of the present invention is a molded article in a basic mode in which titanium chloride and a lead-based stabilizer (metal lead) are contained as essential components in a vinyl chloride resin. A and a molded article B containing a specific type of compounding agent as an optional component.

The basic molded product A is a vinyl chloride resin 1
With respect to 00 parts by weight, titanium oxide is contained in an amount of 5 to 50 parts by weight, and the lead-based stabilizer is converted to the amount of metallic lead to 2 to
It has a whiteness of 60 to 95, a glossiness according to JIS K-7105 (measuring angle 20 °) of 60 to 99, and a specific heat of 0.90 to 90 parts by weight.
1.15 J / g · K. The molded article A is blended with an appropriate amount of a heat stabilizer, a lubricant, a processing aid, a colorant, and the like necessary for molding.

In the molded article A, the amount of the organic vinyl chloride resin is reduced by the amount of the titanium oxide and the lead stabilizer, and the titanium oxide and the lead stabilizer (metal lead) are reduced. Acts extremely effectively on improving the flame retardancy, so that the flame retardancy is remarkably improved, and the amount of smoke and the amount of gas generated are reduced.

Titanium oxide has high whiteness and thermal conductivity.
It is an inorganic particle that does not decompose up to 200 to 1300 ° C. If such a titanium oxide is contained in a vinyl chloride resin, the reason why the flame retardancy is improved and the amount of smoke and gas generated is reduced is as follows. ) Is not clear,
It is considered as follows.

In general, when excessive heat is applied to the vinyl chloride resin molded product from the outside, the chlorine in the vinyl chloride resin is released by heat to exert a flame-retardant effect, and the resin from which chlorine is released is thermally decomposed. And then burn. When titanium oxide is present in this process, the titanium oxide becomes 1200 to 13
It does not decompose to a high temperature of 00 ° C, but acts to block external heat (heat blocking action) due to its high whiteness, and has a high thermal conductivity in the stage of thermal decomposition and combustion of the resin after chlorine release. It is believed that the resin acts to carbonize the resin faster (carbonization promoting action), so that the flame retardancy of the vinyl chloride resin molded article is improved, and the amount of smoke and gas generated is reduced. In addition, the decrease in the amount of the organic vinyl chloride resin due to the inclusion of titanium oxide also contributes to the improvement in flame retardancy.

It is necessary that such titanium oxide be contained in a proportion of 5 to 50 parts by weight based on 100 parts by weight of the vinyl chloride resin. When the content is less than 5 parts by weight,
As can be seen from the experimental data described below, it becomes difficult to obtain a flame-retardant vinyl chloride resin molded product A having a combustion index FPI of 6 or less, a smoke index SDI of 0.4 or less, and a corrosion index CDI of 1.1 or less. On the other hand, if the content of titanium oxide is more than 50 parts by weight, the mechanical strength and moldability of the molded body A are deteriorated, and the chemical resistance and corrosion resistance are reduced, making it difficult to practically use as an industrial material. The more preferable content of titanium oxide is in the range of 8 to 30 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, and thus the molded article A having a relatively low content of titanium oxide has high chemical resistance. Good mechanical strength, bending workability, coloring property, etc.

As titanium oxide, 0.1 to 0.5 μm
Powders having an average particle size of the order are preferably used. This is because such a titanium oxide powder has a good kneading property with a vinyl chloride resin and can be contained in a uniformly dispersed state. In particular, titanium oxide powder whose surface is coated with alumina is preferable. When such a coated powder is contained, carbonization of the vinyl chloride resin is further promoted by the synergistic action of titanium oxide and alumina during combustion. At the same time, smoke, gas, and the like are adsorbed by the alumina, so that it is possible to obtain a compact A having all small values of the combustion index FPI, the smoke index SDI, and the corrosion index CDI.

On the other hand, the lead-based stabilizer acts as a heat stabilizer at the time of molding the vinyl chloride-based resin. And, even if the vinyl chloride resin is thermally decomposed, it remains as metallic lead, and the metallic lead has good thermal conductivity to promote carbonization, thereby reducing the amount of smoke and the amount of gas generated. In addition, since it remains as metallic lead, the amount of the organic vinyl chloride resin is reduced to improve the flame retardancy. When the amount of the lead-based stabilizer is small, the thermal stability during molding of the molded body A is insufficient, and the carbonization promoting effect is reduced, so that improvement in flame retardancy cannot be expected. On the other hand, if the amount of the lead-based stabilizer is too large, kneading becomes difficult at the time of molding, and the chemical resistance of the obtained molded body A also becomes poor.

The lead stabilizer is a vinyl chloride resin 10
It is necessary to add the metal lead to the metal lead in an amount of 2 to 15 parts by weight based on 0 part by weight. When a lead-based stabilizer is added so that the amount of metallic lead is less than 2 parts by weight, thermal decomposition occurs during molding of the molded article A, and the molded article A cannot be molded. Even when the molded article A is molded in combination, the combustion index FPI increases and exceeds 6. When the lead-based stabilizer is added so that the amount of metallic lead is more than 15 parts by weight, it is difficult to sufficiently knead the molded product A during molding, and the resulting molded product A also has poor chemical resistance and the like. The preferred amount of the lead-based stabilizer is 2 in terms of the amount of metallic lead.
-8 parts by weight.

Examples of the lead stabilizer include tribasic lead sulfate, dibasic lead sulfite, lead stearate, dibasic lead stearate, dibasic lead phthalate, and tribasic lead maleate. However, among these, tribasic lead sulfate (Pb: 79%) and dibasic lead sulfite (Pb:
b: 80%) is preferably used.

The vinyl chloride resin constituting the molded article A includes (a) a general vinyl chloride resin having a chlorination degree of about 56%, and (b) a vinyl chloride resin having a chlorination degree of 58% or more and 73% or less. Chlorinated vinyl chloride resin, (c) a resin in which these vinyl chloride resins are mixed, (d) a resin in which these vinyl chloride resins are mixed with vinyl acetate resin or acrylic resin, (e) vinyl chloride and vinyl acetate or ethylene. And the like. The resins (c), (d) and (e) are mixed or copolymerized so that the average chlorination degree is 50% or more and 73% or less.

The general vinyl chloride resin (a) is particularly effective for obtaining a molded article A having excellent chemical resistance.
The post-chlorinated vinyl chloride resin (b) is particularly effective in obtaining a molded article A having excellent flame retardancy because the carbonization promoting action of titanium oxide is large, and the mixed resin (c) is chemically resistant. This is particularly effective in obtaining a molded article A having a good balance of flame retardancy with the resin composition. The mixed resin (d) and the copolymer resin (e) improve the physical properties such as moldability and bending workability (elongation). This is particularly effective in obtaining a compact A.

There is a correlation between the degree of chlorination of the vinyl chloride resin and the carbonization promoting action of titanium oxide, and the higher the degree of chlorination of the vinyl chloride resin, the stronger the carbonization promoting action of titanium oxide. Therefore, in order to obtain a molded article A having excellent flame retardancy containing titanium oxide, it is desirable to use a vinyl chloride resin having a chlorination degree of 58% or more and 73% or less. The vinyl chloride resin having a degree of chlorination lower than 58% has a less prominent carbonization promoting action by titanium oxide, and therefore, it is necessary to increase the content of titanium oxide in order to impart excellent flame retardancy. A vinyl chloride resin having a degree of chlorination higher than 73% is not suitable as a raw material resin for the molded article A because it is difficult to produce a molded article and has poor thermal stability, moldability, bending workability, and the like. The more preferable chlorination degree of the vinyl chloride resin is 62 to 66%.

Examples of the vinyl chloride resin having a degree of chlorination of 58% or more and 73% or less include the above-mentioned (b) post-chlorinated vinyl chloride resin, and the vinyl chloride resin generally used for the chlorinated vinyl chloride resin. A resin obtained by mixing one or more of vinyl resin, acrylic resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-ethylene copolymer resin and the like so that the average chlorination degree is 58% or more and 73% or less. used.

The degree of chlorination is 58% or more, 73%
When the following vinyl chloride resin is used, the carbonization promoting action of titanium oxide is large. Therefore, the lower limit of the content of titanium oxide is further reduced, and the content of 4 to 30 parts by weight per 100 parts by weight of vinyl chloride resin is reduced. FPI, SD
It is possible to obtain a flame-retardant vinyl chloride resin molded article A that simultaneously satisfies the respective criteria of I and CDI. In this case, the more preferable content of the titanium oxide is a vinyl chloride resin 1
It is 8 to 20 parts by weight with respect to 00 parts by weight.

The whiteness of the molded product A represents the whiteness of the CIE1931 standard table pigment established by the CIE (International Commission on Illumination), and specifically, a color difference meter Z-manufactured by Nippon Denshoku Industries Co., Ltd. It is a value obtained by $ 90. This whiteness needs to be in the range of 60 to 95 as described above. When the whiteness is less than 60, the heat index at the time of fire is small, so that the combustion index FPI increases to exceed 6. Conversely, if the whiteness is to be made higher than 95, the amount of the white pigment (titanium oxide) must be extremely increased, and the mechanical strength and moldability of the molded article A deteriorate. More preferable whiteness is 75 to 90.

Further, JIS K-710 of the molded article A
The glossiness according to No. 5 (measuring angle 20 °) needs to be in the range of 60 to 99 as described above. Gloss 6
If it is less than 0, the heat reflection at the time of fire is small, so that the combustion index F
In many cases, the PI rises and exceeds 6. More preferable glossiness is 70-99.

Further, the specific heat of the molded product A is 0.90 to 0.90.
It must be in the range of 1.15 J / g · K. If the specific heat of the compact A is less than 0.90 J / g · K, the titanium oxide or the lead-based stabilizer is contained in a large amount, and the chemical resistance, corrosion resistance, moldability, bending workability, etc. of the compact A are reduced. Conversely, when the specific heat is higher than 1.15 J / g · K,
Since heat transfer becomes too slow and carbonization is difficult to promote,
In many cases, the combustion index FPI increases and exceeds 6.
More preferable specific heat is 1.00 to 1.12 J / g · K.

The heat loss of the titanium oxide used for the molded body A must be in the range of 0.1 to 5% as described above. When such titanium oxide is blended and uniformly dispersed in the molded body A, the adsorbed water is released during combustion, and the molded body A foams or temporarily assumes a wet state. When the weight loss of titanium oxide is less than 0.1%, the amount of adsorbed water is small, the foaming during combustion is small, and the retention of chlorine gas during decomposition is poor, so that the chlorine gas is adsorbed in the carbonized vinyl chloride resin. If the heating loss exceeds 5%, on the other hand, the humidity of chlorine gas during combustion increases and the corrosive action becomes strong, so that the corrosion index CDI increases and exceeds 1.1. Increase. A more preferable range of the heating loss is 0.5 to 2.5%.

The thickness of the molded body A is not limited, and may be appropriately determined in consideration of the use and the like.
When the thickness is about 3 to 15 mm, sufficient practical strength can be provided.

The flame-retardant vinyl chloride-based resin molded product A described above comprises titanium oxide, a lead-based stabilizer and other additives (tin-based heat stabilizer, organic-based heat stabilizer, lubricant, processing aid, Coloring agent, etc.)
Is prepared by melt extrusion molding, calender press, injection molding, and other known molding means, such as flat plates, pipes, round bars, welding rods, deformed products such as angles, It is obtained by molding into a desired shape, as it is, or by secondary processing,
It is suitably used for various applications, especially for semiconductor manufacturing equipment.

Next, the molded article B containing a specific type of compounding agent as an optional component contains 5 to 50 parts by weight of titanium oxide and 100 parts by weight of a vinyl chloride resin, and contains a lead-based stabilizer in a metal. It is added so as to be 2 to 15 parts by weight in terms of the amount of lead, and furthermore, a chlorine trapping compound and an inorganic assistant are added as a compounding agent so that the total content of titanium oxide and the compounding agent is 60 parts by weight or less. Containing at least one or two or more flame retardant assistants, the whiteness of which is 60
~ 95, glossiness according to JIS K-7105 (measuring angle 20 °) is 60 ~ 99, specific heat is 0.90 ~ 1.15J /
g · K. In addition, a suitable amount of a heat stabilizer, a lubricant, a processing aid, a colorant, etc., other than the lead-based compound, is also blended in the molded body B.

The flame-retardant vinyl chloride resin molded article B is
7 types of molded products depending on the combination of compounding agents to be contained,
That is, a molded article B ₁ containing a chlorine-trapping compound as a compounding agent, and a molded article B containing an inorganic auxiliary as a compounding agent
_2. Molded product B ₃ containing chlorine capture compound and inorganic auxiliary as compounding agent, molded product B ₄ containing flame retardant auxiliary as compounding agent, containing chlorine trapping compound and flame retardant auxiliary as compounding agent Molded article B ₅ , molded article B ₆ containing an inorganic auxiliary and a flame retardant as a compounding agent, and molded article B ₇ containing a chlorine trapping compound, an inorganic auxiliary and a flame retardant as a compounding agent. . Among them, the main ones are molded articles B ₁ , B ₂ , B ₃ , B
Since these are ₄ , these will be described below.

First, the molded body B ₁ is made of a vinyl chloride resin 1
The chlorine-trapping compound is used as a compounding agent so that the total content of titanium oxide and the compounding agent is 60 parts by weight or less, while the titanium oxide and the lead-based stabilizer are contained in the above ratio with respect to 00 parts by weight. Is to be included.

When a chlorine trapping compound is further contained as a compounding agent as described above, chlorine released from the vinyl chloride resin at the time of combustion is trapped by the chlorine trapping compound, so that a corrosive gas such as chlorine gas or hydrogen chloride gas is removed. and the amount of generation is further reduced, the smaller the molded body B ₁ of the corrosion index CDI.

As the chlorine capturing compound, a carbonate is preferable, and any one of calcium carbonate, lithium carbonate and magnesium carbonate alone or a mixture thereof is preferably used. Among them, calcium carbonate has better chemical resistance than others, and is particularly preferably used. These carbonates react with chlorine released from the vinyl chloride resin during combustion, and can capture most of chlorine as chlorides such as calcium chloride and reduce the amount of corrosive gas generated. In particular, carbonate powder having an average particle size of 0.5 μm or less, preferably 0.1 μm or less is very suitably used because it has a large specific surface area and easily reacts with chlorine. In addition to the above carbonates, tin compounds, zeolites, barium sulfate, potassium titanate, sodium compounds, magnesium compounds, aluminum compounds, lithium compounds and the like can also be used.

As described above, the chlorine-trapping compound must be contained so that the total content with titanium oxide is 60 parts by weight or less based on 100 parts by weight of the vinyl chloride resin. It is preferable that the chlorine trapping compound is contained in the range of 5 to 30 parts by weight so that the amount is 60 parts by weight or less. If the total content exceeds 60 parts by weight, not only the moldability is deteriorated, it is difficult to obtain a molded product B ₁ having a practical strength weakened, also, the content of chlorine capture compounds are If the amount is less than 5 parts by weight, the trapping of chlorine becomes insufficient and it becomes difficult to significantly reduce the corrosion index CDI. The more preferable content of the chlorine capturing compound is 7 to 20 parts by weight, the more preferable content of the titanium oxide is 5 to 25 parts by weight, and the more preferable total content of both is 12 to 40 parts by weight.

Next, the molded body B ₂ is made of a vinyl chloride resin 1
With respect to 00 parts by weight, the titanium oxide and the lead-based stabilizer are contained in the above-mentioned ratio, and an inorganic auxiliary is used as a compounding agent so that the total content of the titanium oxide and the compounding agent is 60 parts by weight or less. Is to be included.

As the inorganic auxiliary agent, one or more of silica, alumina, aluminum silicate and talc, which can enhance the carbonization promoting effect synergistically with titanium oxide and remarkably improve flame retardancy, are preferably used. Is done. Of these, alumina and aluminum silicate can also exhibit a chlorine trapping action.

As described above, when the inorganic auxiliary is further contained as a compounding agent, the ratio of the vinyl chloride resin, which is an organic substance, is considerably reduced, and in addition, the titanium oxide and the inorganic auxiliary synergistically promote carbonization. to improve is enhanced flame retardancy remarkably, a small molded body B ₂ especially flammability index FPI and smoke index SDI.

As described above, the inorganic auxiliary must be contained so that the total content with titanium oxide is 60 parts by weight or less based on 100 parts by weight of the vinyl chloride resin.
Specifically, it is preferable that the inorganic auxiliary agent be contained in the range of 2 to 30 parts by weight so that the total content is 60 parts by weight or less. If the total content exceeds 60 parts by weight, not only the moldability is deteriorated, it is difficult to obtain a molded product B ₂ having a practical strength weakened, also inorganic aid 2 parts by weight If the amount becomes smaller, the synergistic carbonization promoting action of titanium oxide and the inorganic auxiliary agent becomes insignificant, so that it becomes difficult to significantly reduce the combustion index FPI and the smoke index SDI. The more preferable content of the inorganic auxiliary agent is 2 to 15 parts by weight, the more preferable content of the titanium oxide is 5 to 25 parts by weight, and the more preferable total content thereof is 7 to 40 parts by weight.

Next, the molded body B ₃ is made of a vinyl chloride resin 1
With respect to 00 parts by weight, the titanium oxide and the lead-based stabilizer are contained in the above-mentioned ratio, and the total content of the titanium oxide and the compounding agent is 60 parts by weight or less. It further contains an inorganic auxiliary,
Specifically, it is preferable to contain 5 to 30 parts by weight of a chlorine trapping compound and 2 to 30 parts by weight of an inorganic auxiliary. The same chlorine trapping compounds and inorganic auxiliaries as those used for the above-mentioned molded bodies B ₁ and B ₂ are used.

As described above, when the chlorine trapping compound and the inorganic auxiliary are further contained as a compounding agent, chlorine released from the vinyl chloride resin at the time of combustion is captured by the chlorine capturing compound, and titanium oxide and the inorganic auxiliary are used. Since the carbonization promoting action is synergistically enhanced and the flame retardancy is significantly improved, the combustion index FPI, the smoke index SDI, and the corrosion index CDI
Moldings B ₃ which satisfies with a margin all criteria are obtained. Moreover, since the total content of the titanium oxide and the chlorine capture compounds and inorganic aids is not more than 60 parts by weight, it can be suppressed within the required limits the reduction in the mechanical strength of the degradation of the moldability and the molded body B ₃ . The preferred content of the chlorine trapping compound is 7 to 20 parts by weight, and the preferred content of the inorganic auxiliary is 2 parts by weight.
~ 15 parts by weight, the preferred content of titanium oxide is 5 ~ 25
Parts by weight, and their preferable total content is 15 to 4 parts by weight.
0 parts by weight.

Next, the molded body B ₄ is made of a vinyl chloride resin 1
The flame-retardant auxiliary is used as a compounding agent so that the titanium oxide and the lead-based stabilizer are contained in the above-mentioned ratio with respect to 00 parts by weight, and the total content of the titanium oxide and the compounding agent is 60 parts by weight or less. Is contained.

As the flame-retardant auxiliary, zinc compounds, molybdenum compounds and phosphorus compounds capable of synergistically enhancing the carbonization promoting action with titanium oxide are selectively used, and these may be used alone or in combination of two or more kinds. It is contained in the system resin. As the zinc compound, zinc stannate, zinc borate, organic zinc which is a zinc soap such as zinc stearate and zinc laurate, and the like are used. As the molybdenum compound, molybdenum oxide, calcium molybdate, zinc molybdate, calcium zinc molybdate, ammonium octamolybdate, and the like are used. As the phosphorus compound, a phosphoric acid ester, a halogen-containing phosphoric acid ester, and a polyphosphate are used. , Red phosphorus and the like are used. Among these compounds, zinc stannate is more excellent in heat resistance and chemical resistance, and calcium zinc molybdate and zinc molybdate are more useful in chemical resistance and handleability than others. Also,
Phosphoric acid esters are effective in reducing the corrosion index CDI of the molded body B _4.

When one or more of the above-mentioned zinc compounds, molybdenum compounds and phosphoric acid compounds are further contained as a flame retardant aid, the flame retardant aid synergistically enhances the carbonization promoting action of titanium oxide during combustion. to the composed FPI, SDI, and the molded body B ₄ which is excellent in all values is less flame retardancy of CDI markedly improved flame retardancy.

The content of titanium oxide is in the range of 5 to 50 parts by weight per 100 parts by weight of the vinyl chloride resin as described above, a combination of a flame retardant aid as the forming body B ₄ In such a case, since the flame retardancy is remarkably improved, a molded product satisfying each standard of the FM standard can be often obtained even if the lower limit of the content of titanium oxide is reduced to 4 parts by weight. Further, the flame retardant auxiliary has a total content of 6 with titanium oxide.
Specifically, it is preferable that the content be in the range of 1 to 10 parts by weight so as to be 0 part by weight or less, and even if the content is so small, the flame retardant aid synergistically works with titanium oxide. Flammability can be sufficiently increased. The preferred content of titanium oxide is 5 to 100 parts by weight of the vinyl chloride resin.
25 parts by weight, a preferable content of the flame retardant aid is 3 to 7 parts by weight, and a preferable total content thereof is 8 to 30 parts by weight. The total content less molded article having weight B ₄ as is
Good moldability, chemical resistance and corrosion resistance, and high mechanical strength.

Incidentally, the vinyl chloride resin is the same as that of the molded article B described above.
_{As in the case of 1} , B ₂ and B ₃ , the degree of chlorination is 58% or more,
Those 73% or less but is preferably used, since the the molded body B ₄ contain a flame retardant agent to improve the flame retardancy, the chlorination degree of 50% or more, less than 58% vinyl chloride system be used resins it is possible to obtain a molded product B ₄ to sufficiently satisfy each criteria FM standard, thus those using not high resin chlorinated degree has good chemical resistance, The cost is also low.

Each of the compacts B ₁ , B ₂ , B ₃ , and B ₄ described above is composed of one of titanium oxide, a lead-based stabilizer, and a chlorine trapping compound, an inorganic auxiliary agent, or a flame retardant auxiliary agent. Two kinds,
A vinyl chloride resin composition containing other additives (other than a lead-based heat stabilizer, a lubricant, a processing aid, a colorant, etc.) is prepared, and melt-extruded in the same manner as in the case of the molded article A described above. Molding,
It is manufactured by molding into a desired single-layer shape by a calendar press, injection molding, or other known molding means. It is suitably used for applications, especially for semiconductor manufacturing equipment.

The main embodiments of the present invention include the molded articles A, B ₁ , B ₂ , B ₃ , and B ₄ described above, but the present invention is not limited to these embodiments. For example, on one or both sides of these molded articles A, B ₁ , B ₂ , B ₃ , B ₄ , vinyl chloride containing little or no titanium oxide, lead-based stabilizer, compounding agent, etc. The surface layer of the system resin may be laminated and integrated. However, when the surface layers are laminated and integrated, the vinyl chloride resin 10
The total amount of titanium oxide and the compounding agent such that the lead-based stabilizer is 2 to 15 parts by weight in terms of the amount of metallic lead so that titanium oxide is 5 to 50 parts by weight with respect to 0 part by weight. It is necessary to adjust each content so that the content is 60 parts by weight or less, and the whiteness is 60 to 95%.
So that the gloss (JIS K-7105) is 60
0.90 to 1.15 J / g, so that
-Needless to say, it is necessary to configure so as to be K.

Next, more specific examples and comparative examples of the present invention will be described.

Example 1 8 parts by weight of a lead-based stabilizer (content of lead metal: 79% by weight) and 2 parts by weight of a lubricant based on 100 parts by weight of a post-chlorinated vinyl chloride resin having a degree of chlorination of 65%. Department,
5 parts by weight of processing aid, titanium oxide whose surface is coated with alumina (average particle size: about 0.2 μm or less, weight loss on heating: 1.
10% by weight) and uniformly kneaded to a thickness of 0.5%.
mm calender sheet was produced. Then, ten calender sheets were stacked and pressed to obtain a flame-retardant vinyl chloride resin plate having a thickness of 5 mm.

With respect to this flame-retardant vinyl chloride resin plate, whiteness and glossiness according to JIS K-7105 (measuring angle:
20 °), amount of metallic lead (parts by weight), specific heat (J / g
K) and loss on heating (%) were measured and were as shown in Table 1 below.

The whiteness was measured using a color difference meter Z- # 90 manufactured by Nippon Denshoku Industries Co., Ltd. The amount of metallic lead was determined based on the content of metallic lead in the lead-based stabilizer and the amount of lead-based stabilizer. The specific heat was calculated from the blending amount of the stabilizer.
It was measured by a laser flash method using a CM-FA8510B type apparatus in a reduced pressure atmosphere at a temperature of 16 ° C. and a pressure of 10 ⁻² torr.
It is determined based on SK-5116.

Further, the flame-retardant vinyl chloride resin plate was subjected to a flame-retardant test listed in Class Number 4910 to determine a flame-retardant index FPI, a smoke index SDI, and a corrosion index CDI, and its mechanical strength (Izod impact). The strength, tensile strength and elongation) and chemical resistance (97% sulfuric acid, 35% sulfuric acid, 28% aqueous ammonia) were examined. The results are shown in Table 1 below. The mechanical strength was measured in accordance with JIS K
The chemical resistance was measured based on −6745, and the chemical resistance was evaluated by observing discoloration after immersion in each chemical solution at 23 ° C. for 7 days.
Indicates no discoloration, ○ indicates slight discoloration, Δ indicates discoloration, and X indicates remarkable discoloration.

Example 2 4 parts by weight of a lead-based stabilizer (content of metallic lead: 79% by weight) per 100 parts by weight of a commercially available vinyl chloride resin (chlorination degree: 56.8%), lubricant 2 parts by weight and 4 parts by weight of a processing aid were added and uniformly mixed to prepare a basic composition. To 110 parts by weight of this basic composition, 15 parts by weight of titanium oxide (average particle size: about 0.2 μm or less) whose surface was coated with alumina used in Example 1 was used,
20 parts by weight of calcium carbonate was blended as a chlorine-trapping compound as a compounding agent, and the mixture was uniformly kneaded to prepare a calender sheet having a thickness of 0.5 mm. Then, ten calender sheets were stacked and pressed to obtain a flame-retardant vinyl chloride resin plate having a thickness of 5 mm.

About this resin plate, as in Example 1,
Whiteness, gloss, amount of metallic lead (parts by weight), specific heat (J / g
-K), FPI, SDI, CDI, mechanical strength, and chemical resistance were examined, and the results are shown in Table 1 below.

Example 3 Titanium oxide whose surface was coated with alumina used in Example 1 (average particle size: about 0.2 μm) was used with respect to 110 parts by weight of the basic composition prepared in Example 2.
15) and 20 parts by weight of talc as an inorganic auxiliary of the compounding agent, and uniformly kneaded to prepare a calender sheet having a thickness of 0.5 mm. Then, 10 calender sheets are stacked and pressed to obtain a thickness of 5 m.
m was obtained.

For this resin plate, as in Example 1,
Whiteness, gloss, amount of metallic lead (parts by weight), specific heat (J / g
-K), FPI, SDI, CDI, mechanical strength, and chemical resistance were examined, and the results are shown in Table 1 below.

Example 4 8 parts by weight of a lead-based stabilizer (content of lead metal: 79% by weight) and 2 parts by weight of a lubricant based on 100 parts by weight of a post-chlorinated vinyl chloride resin having a degree of chlorination of 65%. Department,
5 parts by weight of a processing aid, 15 parts by weight of titanium oxide whose surface was coated with alumina (average particle size: about 0.2 μm or less) used in Example 1, and zinc stannate as a flame retardant auxiliary of a compounding agent Was blended in an amount of 5 parts by weight and uniformly kneaded to prepare a calender sheet having a thickness of 0.5 mm. Then, ten calender sheets were stacked and pressed to obtain a flame-retardant vinyl chloride resin plate having a thickness of 5 mm.

For this resin plate, as in Example 1,
Whiteness, gloss, amount of metallic lead (parts by weight), specific heat (J / g
-K), FPI, SDI, CDI, mechanical strength, and chemical resistance were examined, and the results are shown in Table 1 below.

Example 5 4 parts by weight of a lead stabilizer (content of metallic lead: 79% by weight) and 2 parts by weight of a lubricant based on 100 parts by weight of a vinyl chloride resin having a chlorination degree of 56.8% 5 parts by weight of a processing aid, 10 parts by weight of titanium oxide whose surface was coated with alumina (average particle size: about 0.2 μm or less) used in Example 1, and stannic acid as a flame retardant aid of a compounding agent. 5 parts by weight of zinc and 5 parts by weight of a phosphate ester are blended and uniformly kneaded,
A 0.5 mm thick calender sheet was prepared. Then, ten calender sheets were stacked and pressed to obtain a flame-retardant vinyl chloride resin plate having a thickness of 5 mm.

With respect to this resin plate, as in Example 1,
Whiteness, gloss, amount of metallic lead (parts by weight), specific heat (J / g
-K), FPI, SDI, CDI, mechanical strength, and chemical resistance were examined, and the results are shown in Table 1 below.

Comparative Example 1 Titanium oxide whose surface was coated with alumina used in Example 1 (average particle size: about 0.2 μm) was used in an amount of 110 parts by weight of the basic composition prepared in Example 2.
4 parts by weight) and uniformly kneaded to a thickness of 0.5 m
m was prepared. Then, 10 calender sheets were stacked and pressed to obtain a 5 mm thick vinyl chloride resin plate.

About this resin plate, as in Example 1,
Whiteness, gloss, amount of metallic lead (parts by weight), specific heat (J / g
-K), FPI, SDI, CDI, mechanical strength, and chemical resistance were examined, and the results are shown in Table 1 below.

[Comparative Example 2] A thickness of 5 m was obtained in the same manner as in Comparative Example 1 except that the amount of titanium oxide was changed to 55 parts by weight.
m vinyl chloride resin plate was obtained. Then, in the same manner as in Example 1, whiteness, glossiness, amount of metal lead (parts by weight), specific heat (J / g · K), FPI, SDI, C
DI, mechanical strength, and chemical resistance were examined, and the results are shown in Table 1 below.

Comparative Example 3 4 parts by weight of a tin-based stabilizer was added to 100 parts by weight of a vinyl chloride resin having a chlorination degree of 56.8%.
1 part by weight of a lubricant, 6 parts by weight of a processing aid, titanium oxide whose surface was coated with alumina used in Example 1 (average particle size:
(About 0.2 μm or less) were blended and uniformly kneaded to prepare a calender sheet having a thickness of 0.5 mm. Then, 10 calender sheets were stacked and pressed to obtain a 5 mm thick vinyl chloride resin plate.

About this resin plate, as in Example 1,
Whiteness, gloss, specific heat (J / gK), FPI, SD
I, CDI, mechanical strength and chemical resistance were examined, and the results are shown in Table 1 below. The amount of metallic tin in this resin plate was 1.2 parts by weight.

[0071]

[Table 1]

As shown in Table 1, the flame-retardant vinyl chloride resin plates of Examples 1 to 5 had a combustion index FPI of 1.9 or less, a smoke index SDI of 0.09 or less, and a corrosion index CDI of 0.8.
It is as follows, and it turns out that it has the excellent flame retardancy which fully satisfies the standard of FM standard. In particular, the resin plates of Examples 1 and 4 using a post-chlorinated vinyl chloride resin having a high degree of chlorination and having a large amount of metallic lead have low combustion index FPI and low smoke index SDI, and promote carbonization by titanium oxide and metallic lead. Is remarkable. The flame-retardant vinyl chloride resin plates of Examples 1 to 5 also have good strength and chemical resistance.

On the other hand, the vinyl chloride resin plate of Comparative Example 1 containing too little titanium oxide had good strength and chemical resistance, but had a specific heat of 1.16 (J / g · K). Since the conductivity is poor and carbonization is not easily promoted, the FPI and CDI exceed the reference values, and the flame retardancy is insufficient. The vinyl chloride resin plate of Comparative Example 2 containing too much titanium oxide has flame retardancy that satisfies the FM standard, but is inferior in strength (particularly impact resistance) and chemical resistance. It is also bad and it is difficult to use. Further, in the vinyl chloride resin plate of Comparative Example 3 containing a tin-based stabilizer instead of a lead-based stabilizer, the metal tin in the tin-based stabilizer volatilized during the flame retardancy test and did not remain in the resin plate. The effect of metal tin on promoting carbonization is not exhibited, and the flame retardancy becomes insufficient.
All of SDI and CDI cannot be satisfied.

[0074]

As is clear from the above description, the flame-retardant vinyl chloride resin molded article of the present invention has a significantly improved flame retardancy and a reduced amount of smoke and corrosive gas. F
It can satisfy combustion index FPI, smoke index SDI, and even corrosion index CDI based on M standard, and has sufficient practical strength, formability, bending workability, etc. without weakening, and chemical resistance It has a remarkable effect that the properties and corrosion resistance can be maintained.

Continued on the front page F term (reference) 4F071 AA24 AB05 AB17 AB20 AB21 AB23 AB25 AB26 AB27 AC09 AE07 AF32 AF47 BA01 BB04 BC01 4J002 BD031 DA050 DE090 DE136 DE149 DE180 DE228 DE238 DG047 DJ009 DJ019 DJ049 DK000 EG040 EG037 EG040 EG040 EG040

Claims (7)

[Claims] (1) 100 parts by weight of a vinyl chloride resin,
A vinyl chloride resin molded product containing 5 to 50 parts by weight of titanium oxide and a lead stabilizer added in an amount of 2 to 15 parts by weight in terms of the amount of metallic lead. 60 to 95, and gloss (JIS K-710)
5) is 60 to 99 and the specific heat is 0.90 to 1.15 J
/ G · K, a flame-retardant vinyl chloride resin molded product. 2. 100 parts by weight of vinyl chloride resin,
Characterized in that at least one or more of a chlorine-trapping compound, an inorganic auxiliary, and a flame-retardant auxiliary are further contained as a compounding agent so that the total content of titanium oxide and the compounding agent is 60 parts by weight or less. The flame-retardant vinyl chloride resin molded product according to claim 1. 3. A vinyl chloride resin having a content of 58% or more and 73% or more.
The flame-retardant vinyl chloride resin molded product according to claim 1 or 2, wherein the molded product has the following degree of chlorination. 4. The titanium oxide has a heating loss of 0.1 to 5.0%.
The flame-retardant vinyl chloride resin molded product according to claim 1 or 2, wherein: 5. The flame-retardant vinyl chloride resin molded product according to claim 2, wherein the chlorine-trapping compound is any one of calcium carbonate, lithium carbonate and magnesium carbonate, or a mixture thereof. 6. The flame-retardant vinyl chloride resin molded product according to claim 2, wherein the inorganic auxiliary is any one of silica, alumina, aluminum silicate and talc, or a mixture thereof. 7. The method of claim 1, wherein the flame retardant aid is a zinc compound selected from the group consisting of zinc stannate, zinc borate, zinc stearate and zinc laurate, or molybdenum oxide, calcium molybdate, zinc molybdate, calcium molybdate Zinc, a molybdenum compound selected from the group of ammonium octamolybdate, or a phosphoric acid ester, a halogen-containing phosphoric acid ester, a polyphosphate, a phosphorus compound selected from the group of red phosphorus, alone or a mixture thereof The flame-retardant vinyl chloride-based resin molded product according to claim 2, characterized in that: