JP2000007844A - Flame-retardant olefin resin molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant olefin resin molded product satisfying all the evaluation criteria of the FM specifications and further prevent chemical and corrosion resistances from deteriorating. SOLUTION: This flame-retardant olefin resin molded product is composed by including (1) titanium oxide in an amount within the range of 50-150 pts.wt. based on 100 pts.wt. of an olefin resin or (2) including the titanium oxide in an amount within the range of 30-100 pts.wt. based on 100 pts.wt. of the olefin resin and a halogen-based or a phosphorus-based flame retardant in an amount within the range of 5-30 pts.wt. based on 100 pts.wt. of the olefin resin or (3) including the titanium oxide in an amount within the range of 20-80 pts.wt. based on 100 pts.wt. of the olefin resin and other inorganic materials in an amount within the range of 30-100 pts.wt. based on 100 pts.wt. of the olefin resin. The resultant molded product satisfies all the evaluation criteria of the FM specifications. Furthermore, the flame retardant olefin resin molded product is composed by forming a base layer of the same composition as that described above and forming a surface layer of the olefin resin containing 20-80 pts.wt. of the titanium oxide on at least one surface of the base layer. The obtained molded product scarcely causes the deterioration of chemical and corrosion resistances.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant olefin resin molded article improved so as to suppress the generation of smoke accompanying thermal decomposition in a fire.

[0002]

2. Description of the Related Art Olefin resins, especially polypropylene, are resins having good thermoformability and high mechanical strength.
In recent years, it is widely available as a material for industrial use, especially for liquid tanks, vessels, piping members and other materials for semiconductor manufacturing equipment, because it is available at low cost, has good chemical resistance, and does not generate corrosive halogen gas during decomposition. It is used.

[0003] However, polypropylene is easily flammable, and pyrolyzes during combustion to generate smoke and gas. Therefore, if a polypropylene molded article is used in a semiconductor manufacturing apparatus, in the event of a fire, the cleanliness of the air is reduced by the smoke generated. Therefore, there is a problem that various devices, devices, semiconductor parts and the like are contaminated. Therefore, it is desired to impart flame retardancy to the polypropylene molded article to make it less likely to burn even in the event of a fire and to reduce the amount of smoke generated.

The evaluation of the flame retardancy is based on the fact that Factory Mutual Research Corporation (Factory Mutual Research Corporation), which is part of the Factory Mutual System, which is an industrial mutual insurance organization based in North America, is used.
The evaluation criteria defined by Tual Research Corporation) are effectively used. This evaluation criterion is based on the flame retardancy test (FMRC) of a clean room material listed as Class Number 4910.
Clean Room MaterialFlamm
FPI showing the flame retardancy based on the Ability Test Protocol (hereinafter referred to as FM standard)
Is 6 or less, the smoke index SDI indicating smoke emission is 0.4 or less,
It is required that a corrosion index CDI indicating corrosive gas generation be 1.1 or less.

For reference, the flame retardancy index FPI and the smoke index S
Formulas for determining DI and corrosion index CDI are shown below.

FPI = (0.4QCH) ^1/3 / TRP (1) where QCH = △ HCO ₂ · GCO ₂ + △ HCO · GCO (Chemical release rate) TRP = △ Tig · (κ · ρ · CP) ^1/2 (Thermal response parameter) where ΔTig; ignition temperature, κ; heat transfer coefficient, ρ; specific gravity,
And CP; specific heat, and △ HCO ₂ and △ HCO are the heats generated during complete combustion of CO _{2 and} complete combustion of CO, respectively.
GCO ₂ and GCO represent the proportions of the generated gases of CO ₂ and CO, respectively.

SDI = FPI · ys (2) where ys = G / m (smoke generation amount) G = (1.1 · V · D · χ) / (7 / A) (smoke generation ratio) V: smoke flow ratio, D: optical specific gravity, Δ: light source wavelength, A: combustion area, m: mass reduction ratio.

CDI = FPI · CI (3) where CI = (δ / △ te) / (W / VT △ tTEST) (corrosion index) where δ; copper thickness, Δte; test time; W Gas passing velocity, VT; gas generation flow ratio to air, ΔtTES
T: gas generation time.

[0009]

Since the olefin resin molded article does not contain halogen in the polymer itself and rarely generates corrosive gas such as chlorine gas by combustion, among the requirements based on the FM standard, It is easy to make the corrosion index CDI 1.1 or less of the evaluation standard.

However, since the molded product of the olefin resin easily burns and generates a large amount of smoke and gas during combustion, the flame retardancy index FPI is 6 or less of the evaluation standard and the smoke generation index SDI is 0.4 or less of the evaluation standard. It was difficult.

The present invention has been made in view of the above problems,
It is a first object of the present invention to provide an excellent flame-retardant olefin resin molded product that satisfies all FPI, SDI, and CDI evaluation standards based on FM standards. A second object of the present invention is to provide a flame-retardant molded article which hardly deteriorates the inherent good chemical resistance and corrosion resistance of the olefin resin.

As a result of various studies, the present inventors have found that titanium oxide is extremely effective in improving the flame retardancy of an olefin resin molded article, and have completed the present invention.

[0013]

In order to achieve the first object, a flame-retardant olefin resin molded article according to the first aspect of the present invention comprises 50 to 150 parts of titanium oxide per 100 parts by weight of olefin resin. It is contained by weight.

It is not clear why the inclusion of titanium oxide enhances the flame retardancy and reduces the amount of smoke generated. However, it is not clear why titanium oxide, which is a nonflammable inorganic material, is used in a large amount to mix organic substances. , The amount of olefin resin is significantly reduced, that titanium oxide has a higher thermal conductivity than other inorganic materials, and that titanium oxide is 1200
It is presumed that the main reasons are that the particles remain as inorganic particles without being decomposed up to a high temperature range of 〜1300 ° C., and that titanium oxide has an action of promoting carbonization of the olefin resin.

If the content of titanium oxide is less than 50 parts by weight, it is difficult to reduce the burning rate to provide sufficient flame retardancy, the burning index FPI is 6 or less, and the smoke index S
It becomes difficult to obtain a flame-retardant olefin resin molded article having a DI of 0.4 or less and a corrosion index CDI of 1.1 or less.
On the other hand, when the content of titanium oxide is more than 150 parts by weight, the moldability is deteriorated, and the mechanical strength, particularly the elongation is reduced due to the brittleness of the molded body. Further, since the density of titanium oxide exposed on the surface of the molded body increases, chemical resistance and corrosion resistance also decrease.

As the titanium oxide, a titanium oxide coated with alumina as contained in the flame-retardant olefin resin molded article of claim 8 is preferable. When such a titanium oxide is contained in the molded article, the carbonization promoting action of the olefin resin is synergistically enhanced by the titanium oxide and the alumina during combustion, and smoke and gas are adsorbed by the alumina. A compact having a low smoke index SDI is obtained.

The flame-retardant olefin resin molded article according to the second aspect of the present invention is characterized in that 30 to 100 parts by weight of titanium oxide and 5 to 5 parts by weight of a halogen-based or phosphorus-based flame retardant per 100 parts by weight of the olefin resin. -30 parts by weight.

When the halogen-based or phosphorus-based flame retardant is contained in an amount of 5 to 30 parts by weight, even if the content of titanium oxide is reduced to 30 to 100 parts by weight, the synergistic action of the titanium oxide and the flame retardant is sufficient. FP
A flame-retardant olefin resin molded product that satisfies all the evaluation criteria of I, SDI, and CDI is obtained. In addition, a decrease in the mechanical strength of the molded article due to the decrease in titanium oxide is suppressed, and a decrease in chemical resistance and corrosion resistance is also suppressed.

When the content of titanium oxide is less than 30 parts by weight and the content of flame retardant is less than 5 parts by weight, FPI, SDI, CD
It is difficult to obtain a flame-retardant olefin resin molded article that simultaneously satisfies the evaluation criteria of I. In addition, when titanium oxide is 10
When the amount is more than 0 parts by weight and the amount of the flame retardant is more than 30 parts by weight, the flame retardancy is remarkably improved, but the mechanical strength, chemical resistance, corrosion resistance and the like of the molded article are unpreferably reduced.

Further, in the flame-retardant olefin resin molded product according to the third aspect of the present invention, 20 to 80 parts by weight of titanium oxide and 3 parts of another inorganic material are used for 100 parts by weight of the olefin resin.
0 to 100 parts by weight. As the other inorganic material, any one or more of metal hydrates, metal oxides, metal carbonates, talc, barium sulfate, and potassium titanate as contained in the molded article of claim 7 may be used. Combinations are preferred.

Although the other inorganic materials have a lower thermal conductivity and lower thermal decomposition temperature than titanium oxide, they release bound water and promote the carbonization of the olefin resin. When titanium oxide and a flame-retardant inorganic material are used in combination as described above, sufficient flame retardancy can be imparted to the molded article.
Less than 20 parts by weight of titanium oxide and 30 other inorganic materials
When the amount is less than 10 parts by weight, it is difficult to obtain a flame-retardant olefin resin molded article which simultaneously satisfies the evaluation criteria of FPI, SDI, and CDI. On the other hand, the amount of titanium oxide is more than 80 parts by weight, and other inorganic materials are used. If the amount is more than 100 parts by weight, there arises a disadvantage that the mechanical strength, chemical resistance, corrosion resistance and the like of the molded article are significantly reduced.

Next, in order to achieve the second object, the flame-retardant olefin resin molded article according to claim 4 of the present invention contains 50 to 1 part by weight of titanium oxide per 100 parts by weight of the olefin resin.
On at least one surface of the base layer containing 50 parts by weight, titanium oxide was added so that the content of titanium oxide was less than the content of titanium oxide in the base layer with respect to 100 parts by weight of the olefin resin.
It is formed by forming a surface layer containing in the range of 0 to 80 parts by weight.

This molded article contains titanium oxide in the range of 20 to 80 parts by weight so that the content ratio of titanium oxide in the surface layer is smaller than that of the base layer, so that it is exposed on the surface of the molded article. The density of the titanium oxide is low, and the surface (surface layer) of the molded article has chemical resistance and corrosion resistance which are almost the same as the excellent chemical resistance and corrosion resistance inherent in the olefin resin. In addition, the base layer is a layer having the same composition as that of the above-mentioned molded article and having excellent flame retardancy, and the surface layer is made of titanium oxide.
Since it is contained in an amount of 0 to 80 parts by weight, this molded article has good flame retardancy as a whole, and has a combustion index FPI and a smoke index S
The evaluation criteria of DI and corrosion index CDI are simultaneously satisfied.

Further, the flame-retardant olefin resin molded article according to claims 5 and 6 of the present invention also achieves the second object, and the molded article according to claim 5 is based on 100 parts by weight of the olefin resin. The base layer containing 30 to 100 parts by weight of titanium oxide and 5 to 30 parts by weight of a halogen-based or phosphorus-based flame retardant, at least on one side, contained 20 to 80 parts by weight of titanium oxide with respect to 100 parts by weight of the olefin resin. The molded article according to claim 6, wherein the surface layer is formed, and the titanium oxide is 20 to 80 parts by weight based on 100 parts by weight of the olefin resin.
A surface layer containing 20 to 80 parts by weight of titanium oxide based on 100 parts by weight of an olefin resin is formed on at least one surface of a base layer containing 30 to 100 parts by weight of another inorganic material.

The molded articles according to claim 5 and claim 6 also include:
Since the content of titanium oxide in the surface layer is in the range of 20 to 80 parts by weight, a decrease in the chemical resistance and corrosion resistance of the surface of the molded body (surface layer) is suppressed, and the olefin resin is formed. It has chemical resistance and corrosion resistance that are not so different from the original good chemical resistance and corrosion resistance. And the base layer of these molded articles is a layer excellent in flame retardancy of the same composition as the molded articles of claims 2 and 3 described above,
Since the surface layer also contains titanium oxide, these molded articles have good flame retardancy as a whole, and have FPI, SDI,
The CDI evaluation criteria are simultaneously satisfied.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described.

The flame-retardant olefin resin molded article of the present invention is roughly classified into two embodiments. One embodiment is a molded article having a single layer structure having the same composition as a whole, and another embodiment is a molded article having a multilayer structure having a base layer and a surface layer having different compositions from each other.

The former single-layered flame-retardant olefin resin molded article has four types of molded articles A, B, C,
D.

The molded article A is a molded article having a single layer structure containing 50 to 150 parts by weight of titanium oxide with respect to 100 parts by weight of the olefin resin. The molded article A includes a pigment, a dye,
Additives such as an ultraviolet absorber and an antioxidant are appropriately added.

As the olefin resin, polypropylene, polyethylene and the like are used. Among them, polypropylene is preferably used because it has a high heat distortion temperature, good chemical resistance, and high mechanical strength.

As titanium oxide, 0.1 to 0.1.
A powder having an average particle size of about 5 μm is preferably used. This is because the titanium oxide powder having such a particle size has good kneading properties with the olefin resin and can be contained in a uniform dispersed state. In particular, titanium oxide powder whose surface is coated with alumina is preferable, and when such a coated powder is contained, the carbonization promoting action of the olefin resin is synergistically enhanced by titanium oxide and alumina during combustion, Since smoke and gas are adsorbed by alumina, it is extremely effective in improving flame retardancy.

When a large amount of titanium oxide is contained as in the above-mentioned molded article A, the amount of the organic olefin resin is greatly reduced, and the carbonization promoting effect of the olefin resin is enhanced by the titanium oxide. That is, titanium oxide has a thermal conductivity of 100 compared to other inorganic materials such as calcium carbonate.
Twice as high, has the effect of quickly transmitting heat and accelerating the carbonization action, and since titanium oxide remains as inorganic particles without being decomposed up to a high temperature range of 1200 to 1300 ° C., the flame retardancy of the molded article A is remarkable. Increases and reduces smoke production.

The content of titanium oxide must be within the range of 50 to 150 parts by weight based on 100 parts by weight of the olefin resin as described above. If the content is less than 50 parts by weight, the combustion index FPI is 6 or less, Smoke index SDI is 0.4
Hereinafter, it becomes difficult to obtain a flame-retardant olefin resin molded article A having a corrosion index CDI of 1.1 or less. On the other hand, when the content of titanium oxide is more than 150 parts by weight, the moldability and mechanical strength, particularly the elongation are reduced, and it becomes difficult to obtain a molded body A having practical strength as an industrial material, In addition, the density of titanium oxide exposed on the surface of the molded product increases, and the excellent chemical resistance and corrosion resistance inherent in the olefin resin are significantly reduced. A more preferred content of titanium oxide is in the range of 60 to 100 parts by weight.

The molded product A may be 2 to 30 depending on the use or the like.
It is preferably formed to a thickness of about mm, and if it is thinner than 2 mm, the strength of the molded article as an industrial material becomes insufficient. Further, since a molded product having a thickness of more than 30 mm has few uses, it is not necessary to mass-produce the molded product. In addition, the shape of the molded body A can be a desired planar shape or three-dimensional shape depending on the application.

Next, the molded body B is made of an olefin resin 100
The molded article has a single-layer structure containing 30 to 100 parts by weight of titanium oxide and 5 to 30 parts by weight of a halogen-based or phosphorus-based flame retardant with respect to parts by weight. Like the molded body A, the molded body B has a thickness of about 2 to 30 mm and is molded into a desired planar shape or three-dimensional shape. Then, additives such as pigments, dyes, ultraviolet absorbers, antioxidants and the like are also appropriately added.

As the halogen-based flame retardant to be contained together with the titanium oxide, brominated flame retardants such as decabromodiphenylene ether and brominated epoxy compounds, and chlorine-based flame retardants such as chlorinated polyethylene are used. The halogen-based flame retardant has a function of generating a flame-retardant halogen gas by thermal decomposition to delay combustion.

As the phosphorus-based flame retardant, compounds such as red phosphorus, organic phosphate esters, halogen-containing esters, and polyphosphates are used. Phosphorus-based flame retardants generate phosphoric acid by oxidation or thermal decomposition during combustion and remain on the surface of the olefin resin to suppress oxygen transfer, and promote carbonization of the surface to suppress combustion. In particular, red phosphorus is preferably used because it has a higher phosphorus content than other phosphorus-based flame retardants, and exhibits flame retardancy when added in a small amount. Further, among the organic phosphorus-based flame retardants, organic phosphate esters such as triphenyl phosphate, tricresyl phosphate, tris (chloroethyl) phosphate, and tris (chloropropyl) phosphate are preferably used.

The halogen-based or phosphorus-based flame retardants include:
It is necessary to contain the olefin resin in an amount of 5 to 30 parts by weight based on 100 parts by weight of the olefin resin. On the other hand, when the content exceeds 30 parts by weight, in the case of the halogen-based flame retardant, a relatively large amount of corrosive gas is generated at the time of combustion, so that the corrosion index CD
It is difficult to obtain a molded product satisfying the formula (I). In the case of a phosphorus-based flame retardant, adverse effects such as red coloring and poor compatibility with an olefin resin are caused. In the case of red phosphorus, the content is preferably reduced to 5 to 20 parts by weight to prevent the molded body B from being colored red by white titanium oxide used in combination.

When a halogen-based or phosphorus-based flame retardant is used in combination with titanium oxide, the olefin resin 100
Even if the content of titanium oxide is reduced to 30 to 100 parts by weight with respect to parts by weight, sufficient flame retardancy is imparted by the flame retardant, so that the flame retardancy that satisfies all the FPI, SDI, and CDI evaluation standards An olefin resin molded body B is obtained. When the content of titanium oxide decreases as described above, a decrease in mechanical strength of the molded body B is suppressed, and
Due to the decrease in the density of titanium oxide exposed on the surface of the steel, a decrease in chemical resistance and corrosion resistance is also suppressed.

If the amount of titanium oxide is less than 30 parts by weight, it becomes difficult to obtain a flame-retardant olefin resin molded article which simultaneously satisfies the evaluation criteria of FPI, SDI and CDI, even if a flame retardant is used in combination. When the amount of titanium exceeds 100 parts by weight, the flame retardancy is remarkably improved,
It is not preferable because the mechanical strength, chemical resistance, corrosion resistance, and the like of the molded body are considerably reduced.

When a halogen-based flame retardant is contained together with titanium oxide, a scavenger for capturing corrosive gas such as chlorine, bromine, hydrogen chloride, and hydrogen bromide generated from the halogen-based flame retardant is added at the same time. It is preferable to reduce the corrosion index CDI of the molded body B. Halogen scavengers include metal hydroxides (eg, magnesium hydroxide,
Reacts with halogens such as aluminum hydroxide), metal carbonates (eg, magnesium carbonate, lithium carbonate, calcium carbonate), metal oxides (eg, calcium oxide, magnesium oxide), zeolites, etc. to capture halogen. Inorganic substances that adsorb and capture halogen are used. The preferred content of the halogen scavenger is, when it is a metal hydroxide, a metal carbonate, or a metal oxide,
It is 20 to 70 parts by weight based on 100 parts by weight of polyolefin, and 0.5 to 5 parts by weight in the case of zeolite.

Further, the molded article B may contain a flame retardant aid together with the halogen-based or phosphorus-based flame retardant. Flame retardant aids are synergistic with the above flame retardants,
It acts to improve flame retardancy, suppress smoke emission, and suppress corrosive gas.For example, antimony trioxide, which exhibits excellent combustion suppression effect when used in combination with a halogen-based flame retardant, and excellent smoke reduction Zinc stannate, zinc hydroxystannate, zinc borate, zinc hydroxyborate, powdered silicone polymers, and the like, which exert an effect are preferably used.
The preferred content of these flame retardant aids varies slightly depending on the type thereof, but is preferably in the range of 1 to 20 parts by weight based on 100 parts by weight of the polyolefin.

Next, the molded article C is made of olefin resin 100
The molded article has a single-layer structure containing 20 to 80 parts by weight of titanium oxide and 30 to 100 parts by weight of another inorganic material based on parts by weight. The molded body C has a thickness of about 2 to 30 mm similarly to the molded bodies A and B, and is molded into a desired planar shape or three-dimensional shape. Then, additives such as pigments, dyes, ultraviolet absorbers, antioxidants and the like are also appropriately added.

As other inorganic materials to be contained together with titanium oxide, alkaline earth metal hydrates, metal carbonates, metal oxides, talc, barium sulfate, potassium titanate and the like are suitable. Alternatively, two or more kinds are used in combination. Preferred metal hydrates include aluminum hydroxide (including hydrated alumina) and magnesium hydroxide, preferred metal carbonates include calcium carbonate and magnesium carbonate, and preferred metal oxides include calcium oxide and magnesium oxide. No.

Powders of metal hydrates such as aluminum hydroxide (including hydrated alumina) and magnesium hydroxide reduce the amount of olefin resin in the molded product C to lower the burning rate, and reduce the bound water by thermal decomposition. It is effective in reducing the flame-retardant index FPI and the smoke index SDI, since it has the effect of delaying the thermal decomposition of the olefin resin and suppressing the generation of smoke.

Powders of metal carbonates such as calcium carbonate and magnesium carbonate, or powders of metal oxides such as calcium oxide and magnesium oxide can only reduce the amount of olefin resin in the molded article C and lower the burning rate. Rather, as described above, it works as a halogen scavenger, so that when a halogen-based flame retardant is used in combination, it is effective in suppressing the generation of corrosive gas and lowering the corrosion index CDI.

The talc powder not only reduces the burning rate by reducing the amount of the olefin resin of the molded product C, but also has a high whiteness of about 95 and a softness of about 1 and the workability of the molded article is soft. It is suitably used because it has a property of not impairing.

The powder of barium sulfate or potassium titanate is suitable because it not only reduces the amount of olefin resin in the molded product C to lower the burning rate but also does not significantly reduce the chemical resistance and corrosion resistance. Used for

Since each of the inorganic materials other than titanium oxide has the above-described functions and properties, the inorganic material is used in combination with titanium oxide at a ratio of 30 to 100 parts by weight with respect to 100 parts by weight of the olefin resin. By doing so, sufficient flame retardancy can be imparted to the molded article C.

As described above, when an inorganic material other than titanium oxide is used in combination, even if the content of titanium oxide is reduced to 20 to 80 parts by weight with respect to 100 parts by weight of the olefin resin, sufficient flame retardancy is obtained by the inorganic material. To be granted, FPI, SD
It is possible to obtain a flame-retardant olefin resin molded article C that satisfies all the evaluation criteria of I and CDI.

When titanium oxide is less than 20 parts by weight and other inorganic materials are less than 30 parts by weight, FPI, SD
It is difficult to obtain a flame-retardant olefin resin molded article that simultaneously satisfies the evaluation criteria of I and CDI. On the other hand, when the titanium oxide is more than 80 parts by weight and the other inorganic material is more than 100 parts by weight, the molded article is Mechanical strength, chemical resistance, corrosion resistance, etc. of the molded article are greatly reduced, and the molded article is difficult to be put to practical use. The total content of titanium oxide and other inorganic materials is 70 to 150.
It is particularly preferred that the compound is contained so as to be in parts by weight, and when such a compound is contained, a molded article C which sufficiently satisfies FPI, SDI and CDI is obtained.

As other molded articles D, based on 100 parts by weight of the olefin resin, 30 to 100 parts by weight of titanium oxide, 5 to 30 parts by weight of a halogen-based or phosphorus-based flame retardant, and 30 to 30 parts by weight of another inorganic agent. There is a flame-retardant olefin resin molded article having a thickness of 2 to 30 mm, which is a molded article containing 100 parts by weight and whose total content is in the range of 60 to 150 parts by weight.

The titanium oxide, flame retardant, and other inorganic materials used for the compact D are the same as those used for the compacts A, B, and C. When the total content is less than 60 parts by weight, it is difficult to obtain a flame-retardant olefin resin molded article that simultaneously satisfies the evaluation criteria of FPI, SDI, and CDI. Is a molded article that is difficult to be practically used because its mechanical strength, chemical resistance, and corrosion resistance are significantly reduced.

The flame-retardant olefin resin molded articles A, B, C, and D having the single-layer structure described above are obtained by adding titanium oxide, a halogen-based or phosphorus-based flame retardant, other inorganic materials,
An olefin resin composition is prepared by blending a halogen scavenger, other additives, and the like, and is subjected to extrusion molding, press molding, injection molding, or other known molding techniques to obtain a desired flat surface such as a flat plate, pipe, or deformed product. It is obtained by molding into a shape or a three-dimensional shape, is flame-retardant, has a small amount of smoke and a small amount of corrosive gas, and sufficiently satisfies the evaluation standards required by the FM standard. Such a molded body is used as it is or after being subjected to secondary processing, and is suitably used for various purposes, particularly for a liquid tank, a container, a piping member and the like of a semiconductor manufacturing apparatus.

Next, the flame-retardant olefin resin molded article having a multilayer structure according to the present invention has a surface layer formed on at least one surface of the base layer, and has a two-layer structure in which the surface layer is formed only on one surface of the base layer. A molded body having a three-layer structure in which a surface layer is formed on both sides of a base layer and a three-layer structure in which a surface layer is formed on one surface of the base layer and various functional layers (for example, an antistatic layer) are formed on the other surface. There is a body. And the molded body of these ~
Depending on the composition of the base layer and the surface layer, the following four types of molded articles E, F,
G and H, respectively.

First, the molded article E is a layer whose base layer contains 50 to 150 parts by weight of titanium oxide with respect to 100 parts by weight of the olefin resin. It is composed of a layer containing titanium oxide in a range of 20 to 80 parts by weight such that the content of titanium oxide is less than the content of titanium oxide in the base layer.

The base layer of the molded article E is formed by the molding A described above.
This is a layer having the same composition and excellent in flame retardancy, and in order to secure practical strength as an industrial material, 2 to 2
It is formed to a thickness of about 30 mm.

On the other hand, the surface layer is formed in order to improve the physical properties of the surface of the base layer, and in particular, to suppress a decrease in chemical resistance and corrosion resistance due to a large amount of titanium oxide added thereto. Titanium oxide is added to olefin resin 100 so that the content of titanium oxide is smaller.
It must be contained in the range of 20 to 80 parts by weight with respect to parts by weight, and if the content of titanium oxide in the surface layer is larger than the content of titanium oxide in the base layer, there is no point in forming the surface layer.

Even when the content of titanium oxide in the surface layer is smaller than the content of titanium oxide in the base layer, if the content of titanium oxide exceeds 80 parts by weight, the density of titanium oxide exposed on the surface increases, and the olefin resin It becomes difficult to suppress the original good chemical resistance and corrosion resistance so as not to be significantly reduced. On the other hand, if the amount of titanium oxide in the surface layer is less than 20 parts by weight, the decrease in chemical resistance and corrosion resistance can be sufficiently suppressed, but the inconvenience such that the amount of olefin resin in the surface layer increases, resulting in a decrease in flame retardancy occurs. The more preferable content of titanium oxide in the surface layer is 100 olefin resin.
It is in the range of 30 to 70 parts by weight based on parts by weight.

It is desirable that such a surface layer is formed to have a thickness of about 0.3 to 2 mm, and a molded article having a surface layer formed thinner than 0.3 mm may be attacked by a chemical or the like. A thicker formed body has a large amount of olefin resin in the surface layer, and thus may cause a decrease in flame retardancy and an increase in the amount of smoke. The more preferable thickness of the surface layer is 0.4
0.8 mm.

The surface layer is preferably formed of the same olefin resin as the olefin resin of the base layer. Needless to say, additives such as pigments, dyes, ultraviolet absorbers, and antioxidants are appropriately added to this surface layer.

The molded body E having the surface layer formed on at least one side of the base layer has a low density of titanium oxide exposed on the surface, and the surface (surface layer) of the molded body has excellent chemical resistance and corrosion resistance inherent to the olefin resin. Since it has chemical resistance and corrosion resistance almost the same as those of the present invention, there is no fear of being affected by chemicals and the like. Moreover, the base layer is a layer having the same composition as the above-mentioned molded article A and having excellent flame retardancy, and the surface layer also contains 20 to 80 parts by weight of titanium oxide which imparts flame retardancy. Has good flame retardancy as a whole, generates a small amount of smoke and generates a small amount of corrosive gas, and simultaneously satisfies the evaluation criteria of the combustion index FPI, the smoke index SDI, and the corrosion index CDI.

Next, the molded article F is a layer in which the base layer contains 30 to 100 parts by weight of titanium oxide and 5 to 30 parts by weight of a halogen-based or phosphorus-based flame retardant based on 100 parts by weight of the olefin resin. The surface layer formed on at least one side is composed of a layer containing 20 to 80 parts by weight of titanium oxide with respect to 100 parts by weight of the olefin resin.

The base layer of the molded product F is formed by the molding B described above.
This is a layer having the same composition and excellent flame retardancy, and contains the above-mentioned halogen scavenger and flame retardant auxiliary agent as appropriate in addition to titanium oxide and flame retardant. This base layer is also formed to a thickness of about 2 to 30 mm in order to secure practical strength as an industrial material.

The surface layer of the molded body F is a layer having the same composition as the surface layer of the molded body E and having a small decrease in chemical resistance and corrosion resistance.
mm.

In the molded article F having such a multilayer structure, since the surface layer has the same composition as the surface layer of the molded article E, the deterioration of the chemical resistance and corrosion resistance of the molded article surface (surface layer) is suppressed, It has chemical resistance and corrosion resistance that are not so different from the original good chemical resistance and corrosion resistance of olefin resins. Moreover, since the base layer is a layer having the same composition as the above-mentioned molded article B and having excellent flame retardancy, and the surface layer also contains titanium oxide which imparts flame retardancy, the molded article F is generally good. It exhibits excellent flame retardancy and reduces the amount of smoke and corrosive gas generated,
FPI, SDI, and CDI are simultaneously satisfied.

Next, in the molded article G, the base layer contains 20 to 80 parts by weight of titanium oxide with respect to 100 parts by weight of the olefin resin.
It is a layer containing 30 to 100 parts by weight of another inorganic material, and a surface layer formed on at least one surface thereof is a layer containing 20 to 80 parts by weight of titanium oxide with respect to 100 parts by weight of the olefin resin. .

The base layer of the molded product G is the same as that of the aforementioned molded product C
This layer is excellent in flame retardancy and has the same composition as that described above, and is formed to a thickness of about 2 to 30 mm in order to secure practical strength as an industrial material.

The surface layer of the molded body G is a layer having the same composition as the surface layers of the molded bodies E and F and having a small decrease in chemical resistance and corrosion resistance.
It is formed in the thickness of.

Since the surface layer of the molded body G having such a multilayer structure has the same composition as the surface layers of the molded bodies E and F, a decrease in the chemical resistance and corrosion resistance of the surface (surface layer) of the molded body is suppressed. The olefin resin has chemical resistance and corrosion resistance that are not so different from the original good chemical resistance and corrosion resistance. Since the base layer is a layer having the same composition as the above-mentioned molded article C and having excellent flame retardancy, and the surface layer also contains titanium oxide for imparting flame retardancy, the molded article G is generally good. It exhibits excellent flame retardancy and simultaneously satisfies the FPI, SDI, and CDI evaluation criteria.

As another molded article H having a multilayer structure, the base layer is composed of 30 to 100 parts by weight of titanium oxide, 5 to 30 parts by weight of a halogen-based or phosphorus-based flame retardant, based on 100 parts by weight of the olefin resin. A layer having a thickness of about 2 to 30 mm containing 30 to 100 parts by weight of another inorganic agent and having a total content of 60 to 150 parts by weight, and formed on at least one surface thereof. The surface layer is made of titanium oxide in an amount of 20 to 100 parts by weight of the olefin resin.
There is a flame-retardant olefin resin molded article composed of a layer having a thickness of about 0.3 to 2.0 mm containing 80 parts by weight.

The molded body H having such a multilayer structure also has a surface layer having the same composition as the surface layers of the molded bodies E, F, and G, and therefore, the surface of the molded body (surface layer) has reduced chemical resistance and corrosion resistance. It is suppressed and has chemical resistance and corrosion resistance that are not so different from the original good chemical resistance and corrosion resistance of the olefin resin. Since the base layer is a layer having the same composition as the above-mentioned molded article D and having excellent flame retardancy, and the surface layer also contains titanium oxide which imparts flame retardancy, the molded article H is generally good. It exhibits excellent flame retardancy and simultaneously satisfies the FPI, SDI, and CDI evaluation criteria.

The flame-retardant olefin resin molded products E, F, G, and H having a multilayer structure as described above contain titanium oxide, a halogen-based or phosphorus-based flame retardant, other inorganic materials, and other additives. An olefin resin composition for forming a base layer, and an olefin resin composition for forming a surface layer mixed with titanium oxide are prepared, and these resin compositions are formed into a desired shape by multi-layer extrusion molding, calendar press, lamination or other means. It is manufactured by laminating on FPI, SD
Applications that not only simultaneously satisfy the respective standards of I and CDI, but also have good surface chemical resistance and corrosion resistance, so that surface chemical resistance is required, such as a cleaning tank that is part of a semiconductor manufacturing apparatus. It is suitably used as such a material.

The flame-retardant olefin resin molded articles E, F, G, and H having a multilayer structure according to the above-described embodiments all contain titanium oxide in the surface layer. An embodiment in which a surface layer of an olefin resin alone containing no titanium is provided, or a surface layer containing titanium oxide and a halogen-based or phosphorus-based flame retardant (provided that the content ratio of titanium oxide is smaller than that of the base layer) The embodiment or a surface layer containing titanium oxide and another filler (other inorganic material used in the molded body C) (however, the total content ratio of titanium oxide and the filler is smaller than that of the base layer) Embodiments may be provided.

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

Example 1 Commercially available polypropylene 100
To the parts by weight, 50 parts by weight of titanium oxide, 45 parts by weight of magnesium hydroxide, 45 parts by weight of aluminum hydroxide, and 5 parts by weight of red phosphorus were added and uniformly kneaded to obtain a 0.5 mm sheet. Then, 20 sheets were stacked and hot-pressed to obtain a flame-retardant propylene resin plate having a thickness of 10 mm.

With respect to this flame-retardant propylene resin plate, F
When a flame retardancy test according to the M standard was performed, the FPI was 5.7, the CDI was 0.2, and the SDI was 0.4, and all of the evaluation criteria were satisfied.

Example 2 The same polypropylene as in Example 1 was used, and 60 parts by weight of titanium oxide, 70 parts by weight of magnesium hydroxide, and 10 parts by weight of red phosphorus were added to 100 parts by weight of this polypropylene. In the same manner as in Example 1, a flame-retardant propylene resin plate having a thickness of 10 mm was obtained.

The flame-retardant propylene resin plate was subjected to a flame-retardant test according to the FM standard in the same manner as in Example 1. As a result, the FPI was 4.0, the CDI was 0.4, and the SDI was 0.3. This resin plate also satisfied all of the evaluation criteria.

[Comparative Example 1] For comparison, Examples 1 and 2 were used.
A sheet having a thickness of 0.5 mm was prepared using the same commercially available polypropylene as above, and 20 sheets of the sheet were stacked and hot-pressed to obtain a propylene resin plate having a thickness of 10 mm.

The propylene resin plate was subjected to a flame retardancy test according to the FM standard in the same manner as in Examples 1 and 2, and the FPI was 58, the CDI was 0.8, and the SDI was 3.
4, which did not satisfy the FPI and SDI evaluation criteria.

[0082]

As is apparent from the above description, the flame-retardant olefin resin molded article of the present invention, whether it has a single-layer structure or a multi-layer structure, has greatly improved flame retardancy, and has an increased smoke emission and corrosion. Flame retardant index F based on FM standard
It satisfies all the evaluation criteria of PI, smoke index SDI, and corrosion index CDI, has sufficient practical strength as an industrial material, and has no significant decrease in chemical resistance and corrosion resistance. The molded article has many remarkable effects such as a reduction in chemical resistance and corrosion resistance caused by the surface layer.

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Claims (8)

[Claims] 1. A flame-retardant polyolefin molded article containing 50 to 150 parts by weight of titanium oxide based on 100 parts by weight of an olefin resin. 2. A flame-retardant olefin resin article comprising 30 to 100 parts by weight of titanium oxide and 5 to 30 parts by weight of a halogen-based or phosphorus-based flame retardant based on 100 parts by weight of the olefin resin. 3. An amount of titanium oxide of 20 to 80 parts by weight and other inorganic material of 30 to 10 parts by weight per 100 parts by weight of the olefin resin.
A flame-retardant olefin resin molded article containing 0 parts by weight. 4. The method according to claim 1, wherein the base layer contains 50 to 150 parts by weight of titanium oxide with respect to 100 parts by weight of the olefin resin. A flame-retardant olefin resin molded article having a surface layer formed so as to have a small content in the range of 20 to 80 parts by weight. 5. A base layer containing 30 to 100 parts by weight of titanium oxide and 5 to 30 parts by weight of a halogen-based or phosphorus-based flame retardant with respect to 100 parts by weight of an olefin resin. A flame-retardant olefin resin molded article having a surface layer containing 20 to 80 parts by weight of titanium oxide. 6. Titanium oxide is 20 to 80 parts by weight and other inorganic material is 30 to 100 parts by weight based on 100 parts by weight of the olefin resin.
A flame-retardant olefin resin molded article comprising a surface layer containing 20 to 80 parts by weight of titanium oxide with respect to 100 parts by weight of olefin resin on at least one surface of a base layer containing parts by weight. 7. The method according to claim 3, wherein the other inorganic material is one or a combination of two or more of metal hydrate, metal oxide, metal carbonate, talc, barium sulfate, and potassium titanate. The flame-retardant olefin resin molded product according to claim 6. 8. The flame-retardant olefin resin molded article according to claim 1, wherein the titanium oxide is coated with alumina.