JP2001341247A - Flame retardant vinyl chloride resin molding - Google Patents

Abstract

(57) [Problem] To provide a flame-retardant vinyl chloride resin molded article having excellent flame retardancy and excellent chemical resistance and transparency. SOLUTION: This is a molded article in which a surface layer is laminated and integrated on at least one surface of a base layer. Any one of them may be contained as a flame-retardant component at a specific ratio, or a phosphorus-based flame retardant and / or
Alternatively, a flame-retardant vinyl chloride resin molded article is formed by containing chlorinated polyethylene in a specific ratio. Further, a flame retardant component is contained in a specific ratio in one of the base layer and the surface layer, and a phosphorus-based flame retardant and / or chlorinated polyethylene is contained in a specific ratio in the other, and the flame retardant vinyl chloride is contained. Construct a resin molded body.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a molded article of a vinyl chloride resin having excellent flame retardancy.

[0002]

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

Since such a vinyl chloride resin contains chlorine,
Although it has a certain degree of flame retardancy, it is thermally decomposed when a fire occurs and emits a large amount of smoke and corrosive gas. Smoke and corrosive gas may contaminate the air in the manufacturing facility and contaminate or attack manufacturing equipment, equipment, semiconductor components, and the like. Under these circumstances, a need has arisen for a molded article of vinyl chloride resin having even higher flame retardancy, and studies on molded articles of vinyl chloride resin satisfying this requirement have been made.

[0004] In order to enhance the flame retardancy of a vinyl chloride resin molded product, means such as incorporating a large amount of an inorganic filler or a halogen-based flame retardant have been mainly employed. Humans have also proposed a flame-retardant vinyl chloride resin molded article containing titanium oxide as an inorganic filler (Japanese Patent Application No. 10-267360). However, adopting these means has the following problems.

[0005]

That is, when the inorganic filler is contained in a large amount, the molded article of vinyl chloride resin becomes brittle and it becomes difficult to obtain a molded article having practical strength, and a transparent molded article is obtained. In addition to this, there is a problem that the chemical resistance, corrosion resistance, secondary workability, etc. of the molded body are reduced.

On the other hand, when a halogen-based flame retardant is contained, the flame retardancy of the vinyl chloride resin molded article can be improved, but there is a problem that a large amount of corrosive gas containing halogen is generated at the time of fire. In addition, when a halogen-based flame retardant is contained in a transparent molded article, there is a problem that transparency is greatly reduced.

An object of the present invention is to provide an excellent flame-retardant vinyl chloride resin molded article which can solve these problems.

[0008]

To achieve the above object, a flame-retardant vinyl chloride resin molded product according to claim 1 of the present invention contains a titanium compound in which a surface layer is integrally laminated on at least one surface of a base layer. A molded body that does not have a base layer and / or
Alternatively, 0.0005 to 10 parts by weight of at least one of a foaming agent, a decomposition accelerator, a radical generator, and a crosslinking agent is contained with respect to 100 parts by weight of the vinyl chloride resin of the surface layer. is there.

When a foaming agent, a decomposition accelerator, a radical generator, or a crosslinking agent is contained in the base layer and / or the surface layer of the vinyl chloride resin as in the molded article, the flame retardancy is improved by acting as follows. It is thought to be. In general, when excessive heat is applied to the vinyl chloride resin molded body from the outside, chlorine in the vinyl chloride resin is released by heat to exhibit a flame-retardant effect, and the resin from which the chlorine has been released thermally decomposes and burns. . In the process leading to this combustion, if the vinyl chloride resin contains a foaming agent, the foaming agent foams by thermal decomposition and acts to block external heat, and contains a decomposition accelerator. In such a case, the decomposition accelerator acts to accelerate the decomposition of the vinyl chloride resin to accelerate carbonization, and when a radical generator is contained, the generated radicals promote the decomposition of the vinyl chloride resin to promote carbonization. When a cross-linking agent is contained, the cross-linking agent reacts with polymer molecules of the vinyl chloride resin to increase the molecular weight, thereby suppressing gasification. It is considered that the flame retardancy is improved. Thus, the molded article of claim 1 has excellent flame retardancy.

Next, a flame-retardant vinyl chloride resin molded article according to claim 2 of the present invention is a molded article in which a surface layer is laminated and integrated on at least one surface of a base layer, wherein the base layer and / or the surface layer have a chloride. 0.5 to 15 parts per 100 parts by weight of vinyl resin
It is characterized in that it contains a phosphorus-based flame retardant and / or 0.5 to 20 parts by weight of chlorinated polyethylene.

It is considered that when a phosphorus-based flame retardant or chlorinated polyethylene is contained as in this molded article, the following actions are taken to improve the flame retardancy. That is, when a phosphorus-based flame retardant is contained, the phosphorus-based flame retardant is oxidized or thermally decomposed during combustion to generate phosphoric acid, and the phosphoric acid remains on the surface of the vinyl chloride resin and hinders oxygen transfer. At the same time, it has the effect of promoting carbonization of the surface and suppressing combustion, so that flame retardancy is considered to be improved.When chlorinated polyethylene is contained, this chlorinated polyethylene is converted into chlorine by thermal decomposition. It is considered that since it acts to generate gas and delay combustion, flame retardancy is improved. Thus, the molded article of claim 2 also has excellent flame retardancy.

Next, a flame-retardant vinyl chloride resin molded product according to claim 3 of the present invention is a molded product in which a surface layer is laminated and integrated on at least one surface of a base layer, and one of the base layer and the surface layer is provided. To 100 parts by weight of the vinyl chloride resin, 0.0005 to 10 parts by weight of at least one of a foaming agent, a decomposition accelerator, a radical generator, and a crosslinking agent, and 100 parts by weight of the other vinyl chloride resin for,
0.5 to 15 parts by weight of a phosphorus-based flame retardant and / or 0.5 to
It is characterized by containing 20 parts by weight of chlorinated polyethylene.

In such a molded product, the flame retardancy of either the base layer or the surface layer is due to the heat blocking effect of the foaming agent, the carbonization promoting effect of the decomposition accelerator and the radical generator, and the gasification of the crosslinking agent. The flame retardancy of one of the base layer and the surface layer is increased by the suppression effect, and the flame retardancy of the phosphorus-based flame retardant and the combustion retardation effect of the chlorinated polyethylene are increased. Thus, the molded article of claim 3 also has excellent flame retardancy.

Next, the flame-retardant vinyl chloride resin molded product according to claim 4 of the present invention is a molded product in which a surface layer is integrally laminated on at least one surface of a base layer, and the base layer has a chlorination degree of 5%.
The surface layer is a layer comprising 8 to 73% of vinyl chloride resin, and the surface layer has a foaming agent with respect to 100 parts by weight of vinyl chloride resin having a chlorination degree lower than that of the base layer vinyl resin and not more than 60%. , A layer containing 0.0005 to 10 parts by weight of at least one of a decomposition accelerator, a radical generator, and a crosslinking agent.

In general, there is a positive correlation between the degree of chlorination of vinyl chloride resin and flame retardancy, and the higher the degree of chlorination, the better the flame retardancy. Therefore, when the base layer is formed of a vinyl chloride resin having a high degree of chlorination of 58 to 73% as in the molded article of the fourth aspect, the flame retardancy of the base layer can be obtained without containing a component imparting flame retardancy. Improves. On the other hand, the vinyl chloride resin constituting the surface layer is a resin having a degree of chlorination of 60% or less, which is lower than that of the vinyl chloride resin of the base layer, so that the flame retardancy of the resin itself is slightly inferior. Foaming agent in the layer,
Since at least one of a decomposition accelerator, a radical generator and a crosslinking agent is contained, the flame retardancy of the surface layer is also improved. Thus, the molded article of the fourth aspect also has excellent flame retardancy.

The higher the degree of chlorination, the lower the chemical resistance and corrosion resistance of the vinyl chloride resin, and the lower the moldability and secondary workability of the vinyl chloride resin. When the surface layer is formed with 60% or less of vinyl chloride resin, which is lower than that of the base layer vinyl chloride resin, the chemical resistance and corrosion resistance are lower than when the surface layer is formed with vinyl chloride resin having a high degree of chlorination. Is greatly suppressed. Therefore, this molded article has excellent chemical resistance and corrosion resistance which are almost the same as the excellent chemical resistance and corrosion resistance inherent in the vinyl chloride resin.

Next, a flame-retardant vinyl chloride resin molded product according to claim 5 of the present invention is a molded product in which a surface layer is laminated and integrated on at least one surface of a base layer, and the base layer has a chlorination degree of 5%.
A surface layer containing 0.0005 to 10 parts by weight of at least one of a foaming agent, a decomposition accelerator, a radical generator, and a crosslinking agent with respect to 100 parts by weight of an 8-73% vinyl chloride resin; Is a layer made of a vinyl chloride resin having a degree of chlorination lower than that of the vinyl chloride resin of the base layer and 60% or less.

In this molded article, the base layer occupying most of the molded article is formed of a highly flammable vinyl chloride resin having a high chlorination degree of 58 to 73%, and a foaming agent, a decomposition accelerator, Since the flame retardancy is further enhanced by including at least one of a radical generator and a cross-linking agent, even if the surface layer is formed of a vinyl chloride resin having a low chlorination degree, excellent flame resistance as a whole molded article is obtained. Flammable. Moreover,
When the surface layer is formed of a vinyl chloride resin having a degree of chlorination of 60% or less, which is lower than that of the vinyl chloride resin of the base layer, as in this molded article, the excellent chemical resistance inherent in the vinyl chloride resin,
Demonstrates excellent chemical and corrosion resistance, which is almost the same as corrosion resistance.

Next, the flame-retardant vinyl chloride resin molded article according to claim 6 of the present invention is a molded article in which a surface layer is integrally laminated on at least one surface of a base layer, and the base layer has a chlorination degree of 5%.
A surface layer containing 0.0005 to 10 parts by weight of at least one of a foaming agent, a decomposition accelerator, a radical generator, and a crosslinking agent with respect to 100 parts by weight of an 8-73% vinyl chloride resin; Is a layer made of the above vinyl chloride resin.

Since the base layer of this molded article has the same composition as the base layer of the molded article according to claim 5, it has excellent flame retardancy, and the surface layer is formed of a vinyl chloride resin having a high chlorination degree of 58 to 73%. Therefore, the flame retardancy of the surface layer is good. Therefore, this molded article has better flame retardancy than the molded article of claim 5. When the surface layer is formed of a vinyl chloride resin having a high chlorination degree as in this molded article, the chemical resistance and corrosion resistance of the surface layer are lower than when the surface layer is formed of a vinyl chloride resin having a low chlorination degree. Although slightly reduced, the chemical resistance and corrosion resistance are much improved as compared with the conventional case where a titanium compound or other inorganic filler is contained.

Next, a flame-retardant vinyl chloride resin molded article according to claim 7 of the present invention is a molded article in which a surface layer is laminated and integrated on at least one surface of a base layer, and the base layer has a chlorination degree of 6%.
A layer in which at least one of a foaming agent, a decomposition accelerator, a radical generator, and a crosslinking agent is contained in 0.0005 to 10 parts by weight with respect to 100% by weight of a vinyl chloride resin of 0% or less. And a layer made of a vinyl chloride resin having a chlorination degree of 58 to 73% higher than that of the vinyl chloride resin of the base layer.

The vinyl chloride resin constituting the base layer of the molded article has a low chlorination degree of 60% or less, and the flame retardancy of the resin itself is slightly inferior. However, the foaming agent, decomposition accelerator, radical The flame retardancy of the base layer is enhanced by at least one of a generator and a crosslinking agent, and the surface layer has a chlorination degree higher than that of the vinyl chloride resin of the base layer.
Since the molded article is formed of a vinyl chloride resin having excellent flame retardancy of 3%, the molded article has excellent flame retardancy as a whole.

Next, a flame-retardant vinyl chloride resin molded product according to claim 8 of the present invention is a molded product in which a surface layer is integrally laminated on at least one surface of a base layer, and the base layer has a chlorination degree of 6%.
A layer in which at least one of a foaming agent, a decomposition accelerator, a radical generator, and a crosslinking agent is contained in 0.0005 to 10 parts by weight with respect to 100% by weight of a vinyl chloride resin of 0% or less. , At least one of a foaming agent, a decomposition accelerator, a radical generator, and a crosslinking agent with respect to 100 parts by weight of a vinyl chloride resin having a degree of chlorination higher than that of the vinyl chloride resin of the base layer and 58 to 73%. Is 0.00
It is characterized in that the layer contains 0.05 to 10 parts by weight.

The vinyl chloride resin constituting the base layer of the molded article has a low chlorination degree of 60% or less, similarly to the vinyl chloride resin constituting the base layer of the molded article according to claim 7, but has a blowing agent. By incorporating at least one of a decomposition accelerator, a radical generator, and a cross-linking agent, the flame retardancy of the base layer is improved, and the surface layer is made of a vinyl chloride resin having excellent flame retardancy and a high chlorination degree. Since the flame retardancy is further enhanced by including at least one of a foaming agent, a decomposition accelerator, a radical generator, and a crosslinking agent, this molded article has better flame retardancy than the molded article of claim 7 Having.

Next, the flame-retardant vinyl chloride resin molded article according to claim 9 of the present invention is a molded article in which a surface layer is laminated and integrated on at least one surface of a base layer, and the base layer has a chlorination degree of 5%.
For 100 parts by weight of 8-73% vinyl chloride resin,
0.5 to 15 parts by weight of a phosphorus-based flame retardant and / or 0.5 to
A layer containing 20 parts by weight of chlorinated polyethylene, wherein the surface layer is a layer made of a vinyl chloride resin having a degree of chlorination lower than that of the base layer and less than 60%. And

In this molded article, the base layer occupying most of the molded article is formed of a vinyl chloride resin having a high degree of chlorination and excellent flame retardancy, and further contains a phosphorus-based flame retardant and chlorinated polyethylene. Since the flame retardancy is further enhanced, the molded article as a whole has excellent flame retardancy even when the surface layer is formed of a vinyl chloride resin having a low chlorination degree. Moreover, since the vinyl chloride resin forming the surface layer has a chlorination degree of 60% or less, which is lower than that of the base layer, the molded article has almost the same excellent chemical resistance and corrosion resistance inherent in the vinyl chloride resin. Has the same excellent chemical and corrosion resistance.

Next, the flame-retardant vinyl chloride resin molded article according to claim 10 of the present invention is a molded article in which a surface layer is integrally laminated on at least one surface of a base layer, and the base layer has a chlorination degree of 58. To 100 parts by weight of ~ 73% vinyl chloride resin
0.5 to 15 parts by weight of a phosphorus-based flame retardant and / or 0.5 to
This is a layer containing 20 parts by weight of chlorinated polyethylene, and the surface layer is a layer made of the above-mentioned vinyl chloride resin.

The base layer of the molded article has the same composition as the base layer of the molded article according to claim 9 and thus has excellent flame retardancy, and the surface layer has a high chlorination degree of 58 to 73%. , The surface layer also has good flame retardancy. Therefore, this molded article has better flame retardancy than the molded article of claim 9.

Next, a flame-retardant vinyl chloride resin molded article according to claim 11 of the present invention is a molded article in which a surface layer is integrally laminated on at least one surface of a base layer, and the base layer has a chlorination degree of 60%. % Of vinyl chloride resin of 100% by weight or less,
0.5 to 15 parts by weight of a phosphorus-based flame retardant and / or 0.5 to
A layer containing 20 parts by weight of chlorinated polyethylene, and the surface layer is a layer made of vinyl chloride resin having a degree of chlorination higher than that of the base layer vinyl chloride resin and 58 to 73%. Features.

Although the vinyl chloride resin constituting the base layer of the molded article has a low chlorination degree of 60% or less, the flame retardancy of the base layer is improved by including a phosphorus-based flame retardant or chlorinated polyethylene. Moreover, the surface layer has a degree of chlorination of 58 to 73%, which is higher than that of the vinyl chloride resin of the base layer.
Since this is a layer made of vinyl chloride resin having excellent flame retardancy, this molded article has excellent flame retardancy as a whole.

Next, a flame-retardant vinyl chloride resin molded article according to claim 12 of the present invention is a molded article in which a surface layer is laminated and integrated on at least one surface of a base layer, and the base layer has a chlorination degree of 60. % Of a vinyl chloride resin of 100% by weight or less, the layer containing 0.0005 to 10 parts by weight of at least one of a foaming agent, a decomposition accelerator, a radical generator, and a crosslinking agent. For 100 parts by weight of the vinyl chloride resin having a chlorination degree higher than that of the vinyl chloride resin of the base layer and 58 to 73%, 0.5 to 15 parts by weight of the phosphorus-based flame retardant and / or It is characterized in that it is a layer containing 20 parts by weight of chlorinated polyethylene.

The vinyl chloride resin constituting the base layer of the molded article has a low chlorination degree of 60% or less, as in the case of the vinyl chloride resin constituting the base layer of the molded article according to the above-mentioned claims. Flame retardancy is improved by including at least one of a decomposition accelerator, a radical generator, and a cross-linking agent, and the surface layer is made of a highly chlorinated vinyl chloride resin with excellent flame retardancy and a phosphorus-based flame retardant. Since the flame retardancy is further enhanced by including a flame retardant and chlorinated polyethylene, this molded article has excellent flame retardancy as a whole.

In the above-mentioned molded product according to any one of claims 1 to 12,
When the content of each of the blowing agent, the decomposition accelerator, the radical generator, the cross-linking agent, the phosphorus-based flame retardant, and the chlorinated polyethylene falls below the range described in claims 1 to 12, sufficient flame retardancy for the molded article is obtained. However, even if the content exceeds the range described in claims 1 to 12, the flame retardancy corresponding to the content is hardly further improved. It is wasted.

Next, the flame-retardant vinyl chloride resin molded product according to claim 13 of the present invention is the molded product according to any one of claims 1 to 12, wherein the total light transmittance is 40% or more and the haze value is Is 60% or less. The total light transmittance and the haze value are values when the thickness of the molded product is 5 mm.

Each of the molded articles of claims 1 to 12 is essentially a transparent molded article when it does not contain a lead-based stabilizer, a titanium compound, other inorganic fillers, a pigment having a strong hiding power, and the like. Since no halogen-based flame retardant is contained, the transparency is not extremely reduced. Therefore, unless a lead-based stabilizer is used or a pigment or an inorganic filler is added to make the composition transparent, a transparent mold having a total light transmittance of 40% or more and a haze value of 60% or less as described above is used. Be a body.

Further, since all of the transparent molded articles do not contain a titanium compound and other inorganic fillers, they have good chemical resistance and corrosion resistance, are brittle due to the inorganic fillers, have low moldability, and have a high secondary workability. There is no occurrence of a decrease in the value.

[0037]

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

The flame-retardant vinyl chloride resin molded article of the present invention is a molded article obtained by laminating and integrating a surface layer on at least one surface of a base layer, and is based on 100 parts by weight of the vinyl chloride resin of the base layer and / or the surface layer. , At least one of a foaming agent, a decomposition accelerator, a radical generator, and a cross-linking agent (hereinafter collectively referred to as a flame-retardant component).
A molded article A comprising 10 parts by weight of a molded article A and a surface layer laminated and integrated on at least one surface of the base layer, wherein 0.5 to 0.5 parts by weight per 100 parts by weight of the vinyl chloride resin of the base layer and / or the surface layer A molded article B comprising 15 parts by weight of a phosphorus-based flame retardant and / or 0.5 to 20 parts by weight of chlorinated polyethylene; and a molded article obtained by laminating and integrating a surface layer on at least one surface of the base layer. And with respect to 100 parts by weight of the vinyl chloride resin of either one of the surface layer and 0.0005 to 10 parts by weight of at least one of the flame-retardant components, and 100 parts by weight of the other vinyl chloride resin And a molded article C containing 0.5 to 15 parts by weight of a phosphorus-based flame retardant and / or 0.5 to 20 parts by weight of chlorinated polyethylene.

The following five types of molded articles A ₁ , A ₂ , A ₃ , A ₄ and A ₅ are typical examples of the molded article A.

The molded article A ₁ is a transparent molded article which does not contain an inorganic filler such as a titanium compound in which a surface layer is laminated and integrated on at least one surface of the base layer.
8 to 73% of a vinyl chloride resin. The surface layer is flame-retardant with respect to 100 parts by weight of the vinyl chloride resin having a degree of chlorination lower than that of the base layer and less than 60%. 0.0005 at least one of the property imparting components
-10 to 10 parts by weight.

[0041] The base layer and the surface layer of the molded article A _1, tin stabilizer necessary for molding (e.g., dibutyl tin maleate type or dibutyltin laurate-based stabilizer), lubricants (e.g., higher fatty acids and low molecular weight polyethylene Etc.), reinforcing agents (eg M
Various additives such as BS-based reinforcing agents and MBS-based processing modifiers) and processing aids (eg, acrylic processing aids) are added in appropriate amounts. Incidentally, the molded body A ₁ uses a tin-based stabilizer, does not contain an inorganic filler such as titanium compounds, although a transparent molded body may be opaque moldings. That is, or by adding an inorganic filler such as titanium compounds, calcium carbonate, etc. with opaque pigment in the composition of the molded product A _1, or may be used to lead-based stabilizers, and opaque moldings .

[0042] The chlorination degree of forming the base layer of the molded body A ₁ is 58 to 73% of a vinyl chloride resin, chlorinated degree and a chlorinated vinyl chloride resin after the 58 to 73%, chlorinated Thereafter chloride A mixed resin obtained by mixing a vinyl resin and a general vinyl chloride resin having a chlorination degree of about 56% so that the average chlorination degree is in the range of 58 to 73% is used. Vinyl chloride resin with a chlorination degree higher than 73% is difficult to manufacture,
Since it is inferior in moldability, chemical resistance, corrosion resistance, etc., it is unsuitable as a material resin for molded articles. In addition, chlorination degree is 58%
A lower vinyl chloride resin is not suitable for improving the flame retardancy of a base layer without containing a flame retardancy-imparting component, since the flame retardancy is not so different from that of a general vinyl chloride resin.

On the other hand, as the chlorination degree of 60% or less of the vinyl chloride resin forming the surface layer of the molded product A _1, vinyl chloride resin or the general chlorination degree of about 56%, vinyl chloride resins of this general And the above-mentioned post-chlorinated vinyl chloride resin, so that the average chlorination degree is 60% or less (however, approximately 56% or more). Those with a low degree of chlorination are used. A vinyl chloride resin having a chlorination degree of more than 60% has poor chemical resistance, corrosion resistance, moldability, etc.
It is not suitable as a resin for forming a surface layer of a molded article having corrosion resistance.

The chlorination degree for forming the above-mentioned base layer is 58 to 7
For 3% vinyl chloride resin and vinyl chloride resin having a chlorination degree of 60% or less for forming a surface layer, vinyl acetate resin, acrylic An appropriate amount of a resin or a modified resin such as a vinyl chloride-vinyl acetate-ethylene copolymer resin may be mixed.

As a foaming agent which is one of the flame-retardant components to be contained in the surface layer of the molded article A ₁ ,
Those which start foaming at a temperature of 200 ° C. or higher, which is higher than the molding temperature and the secondary processing temperature of ₁ , are suitable, for example, azodicarbonamide, azobisisobutyronitrile, dinitrosopentamethylenetetramine, hydrazide compound ( For example, paratoluenesulfonyl hydrazide, 4,4 '
-Oxybisbenzenesulfonylhydrazide), a mixture of an inorganic carbonate and an organic acid, and the like are preferably used.

The molded body A ₁ which contains vinyl chloride resin of the surface layer such blowing agents without foaming at the time of molding and during secondary processing, when heated above the foaming temperature at the time of fire- agent for exhibiting heat shielding effect and blowing, flame retardancy of the moldings a ₁ is greatly improved. In addition, since smoke and corrosive gas are taken into the bubbles, the amount of generated smoke and the amount of corrosive gas generated also decrease.

[0047] The decomposition accelerator is another fire resistant component to be contained in the surface layer of the molded article A _1, higher than the molding temperature and the secondary processing temperature of the molded body A ₁ 200
Suitable are those which promote the decomposition of vinyl chloride resin at a temperature of not less than ℃, among which zinc compounds (eg, zinc soaps such as zinc laurate, zinc stearate, zinc benzoate), amine compounds (eg, melamine, triethylamine, etc.) ), Iron hydroxide and the like are preferably used.

The molded body A ₁ which contains such a decomposition accelerator vinyl chloride resin in the surface layer, its but vinyl chloride resin during molding or secondary processing when the surface layer is the never degraded, fire In the process leading to combustion at the time, since the decomposition accelerator promotes the decomposition of the vinyl chloride resin in the surface layer and accelerates the carbonization, excellent flame retardancy is exhibited.

[0049] As the radical generator is yet another fire resistant component to be contained in the surface layer of the molded article A _1, 200 ° C. or higher is higher than the molding temperature and the secondary processing temperature of the molded body A ₁ Suitable are those which generate radicals at a temperature of, for example, peroxides such as diamyl peroxide, peroxydicarbonate, dialkyl peroxide, hydroperoxide, and perchlorates.

The molded body A ₁ which contains such a radical generator in the surface layer, because the radicals during molding and during machining does not occur, there is no possibility that the vinyl chloride resin is deteriorated in the surface layer (where the heat Deterioration occurs to some extent), but in the process of burning in the event of fire, radicals generated by the radical generator accelerate the decomposition of vinyl chloride resin on the surface layer to accelerate carbonization, thus exhibiting excellent flame retardancy. You.

[0051] Further Examples of the crosslinking agent is other flame retardancy-imparting component, the molding temperature and the secondary processing temperature of 200 ° C. or higher temperature above the molded body A ₁ to be contained in the surface layer of the molded article A ₁ The one which initiates cross-linking is suitable, and for example, a triazine thiol compound is preferably used.

[0052] moldings A ₁ which contains such a crosslinking agent in the surface layer can be molded or secondary processed into various shapes because the crosslinking reaction during molding or during secondary processing does not occur. In the process leading to combustion in the event of a fire, the polymer molecules of the vinyl chloride resin are increased in molecular weight by a cross-linking reaction, so that heat resistance is increased and gasification is difficult, so that excellent flame retardancy is exhibited.

The content of these flame-retardant components is 0.1 to 100 parts by weight of the vinyl chloride resin constituting the surface layer.
0005 to 10 parts by weight. 0.0005
If the amount is less than part by weight, the heat blocking effect by the foaming agent, the carbonization promoting effect by the decomposition accelerator or the radical generator, the increase in the molecular weight by the cross-linking agent, and the like become insufficient, so that it is difficult to improve the flame retardancy of the surface layer. On the other hand, even if it is contained in an amount of more than 10 parts by weight, the flame retardancy corresponding thereto is hardly further improved, so that the flame retardant component is wasted. More preferred content of the flame retardant component is 0.05 to
5 parts by weight.

[0054] As already mentioned, chlorinated degree flame retardancy of polyvinyl chloride resin has a positive correlation, since the flame retardant as the chlorination degree increases is improved, as the molded body A ₁ When the base layer is composed of a vinyl chloride resin having a high chlorination degree of 58 to 73%, the flame retardancy of the base layer is improved without containing a flame retardant component. In contrast, the vinyl chloride resin constituting the surface layer has a degree of chlorination of 60% or less, which is lower than that of the vinyl chloride resin of the base layer. because the enhanced flame-retardant surface layer, the molded body a ₁ has excellent flame retardancy as a whole.

[0055] Moreover, when the chlorination degree as the molded body A ₁ to form a surface layer with 60% or less and a low vinyl chloride resin, as compared with the case of forming the surface layer with a high vinyl chloride resin with chlorinated degree In the case where the surface layer is formed of a general vinyl chloride resin having a degree of chlorination of about 56% due to improved chemical resistance and corrosion resistance, a molded article having excellent chemical resistance and corrosion resistance inherent to the vinyl chloride resin is required. can get.

The thickness of the molded body A ₁ is not particularly limited, but the surface layer improves surface properties such as chemical resistance and corrosion resistance of the molded body A ₁ . it is sufficient if the order 4～1.5Mm, also, the base layer thickness is preferably set within a range of about 1~15mm considering the compact application and practical strength of a ₁ and the like.

[0057] Flame retardant vinyl chloride resin molded product A ₁ as described above, the resin for base layer formation chlorination degree is blended with stabilizer and other additives required for forming the 58 to 73% of a vinyl chloride resin Along with preparing the composition, at least one flame-retardant component and a stabilizer and other additives required for molding are added to a 60% or less vinyl chloride resin having a chlorination degree lower than that of the vinyl chloride resin of the base layer. Preparing a resin composition for forming a surface layer, and multilayer extrusion molding these resin compositions,
It is manufactured by laminating into a desired shape by a calender press, laminating or other known means. Thus the molded body A ₁ produced is directly, or secondary processing to be used in various applications where flame retardancy is required.

Next, the molded body A ₂ is a transparent molded body which does not contain an inorganic filler such as titanium compounds and the surface layer integrally laminated on at least one side of the base layer, the base layer, the chlorination degree of 58 to At least one kind of the above-described flame-retardant component is added to 100 parts by weight of a 73% vinyl chloride resin.
The surface layer is a layer of a vinyl chloride resin having a degree of chlorination of 60% or less, which is lower than that of the vinyl chloride resin of the base layer.

[0059] Then, the molded body A ₃ is a transparent molded body which does not contain an inorganic filler such as titanium compounds and the surface layer integrally laminated on at least one side of the base layer, the base layer, the base layer of the shaped body A ₂ Similarly to the above, the chlorination degree is a layer in which at least one kind of the flame retardancy-imparting component is contained in an amount of 0.0005 to 10 parts by weight with respect to 100 parts by weight of a vinyl chloride resin having a chlorination degree of 58 to 73%. The chlorination degree is 5
It consists of a layer of 8-73% vinyl chloride resin.

Also in the case of these molded articles A ₂ and A ₃ , various additives such as tin-based stabilizers, lubricants, reinforcing agents and processing aids described above are added to the base layer and the surface layer in appropriate amounts. the thickness of the base layer and the surface layer is also the same as the thickness of the base layer and the surface layer of the molded article a ₁ of the foregoing. The molded articles A ₂ and A ₃ are transparent molded articles, but a lead-based stabilizer may be used instead of the tin-based stabilizer, or a tin-based or lead-based stabilizer may be used together with an inorganic compound such as a titanium compound or calcium carbonate. If a filler or an opaque pigment is added, an opaque molded body can be obtained.

The foaming agent, decomposition accelerator, radical generator and cross-linking agent, which are flame-retardant components contained in the base layers of these molded articles A ₂ and A ₃ , are the same as those used for the aforementioned molded article A _1. Since they are the same and have the same content, the description is omitted. These moldings A _2, A ₃ of the base layer or surface layer chlorination degree from 58 to 73% of a vinyl resin and chlorinated degree of 60% or less of a vinyl chloride resin chloride constituting the well, the aforementioned molded product A _Since they are the same as those used in ₁ , description is omitted.

In such molded articles A ₂ and A ₃ , the base layer occupying most of them is formed of a highly flammable vinyl chloride resin having a high chlorination degree of 58 to 73%.
Because the enhanced further flame retardant by the inclusion of fire resistant component has excellent flame retardancy, moreover, the molded body A _2, the surface layer is 60% or less of the low chlorination degree Because it is made of vinyl chloride resin, it has good chemical resistance,
Has corrosion resistance. Further, the molded body _3, the surface layer also chlorination degree is formed with excellent vinyl chloride resin to 58 to 73% and high flame retardancy, although chemical resistance and corrosion resistance is inferior moldings A _2, whole has an excellent flame retardancy than the molded body a ₂ as.

These flame-retardant vinyl chloride resin molded articles A
_2, A ₃ is prepared chlorinated degree resin composition for base layer formation formulated with stabilizers and other additives necessary for forming with at least one fire resistant component in 58 to 73% of a vinyl chloride resin In addition, a resin composition for forming a surface layer in which a stabilizer and other additives necessary for molding are added to a vinyl chloride resin having a chlorination degree of 58 to 73%, or a chlorination degree is higher than that of this vinyl chloride resin. A resin composition for forming a surface layer is prepared by blending a stabilizer and other additives necessary for molding into a vinyl chloride resin having a low viscosity of 60% or less, and these resin compositions are subjected to multilayer extrusion molding, calender pressing, laminating, etc. And lamination molding into a desired shape by a known means. The molded bodies A ₂ and A ₃ thus produced can be used as they are or
Secondary processing is used for various applications that require flame retardancy.

Next, the molded body A ₄ is a transparent molded body which does not contain an inorganic filler such as titanium compounds and the surface layer integrally laminated on at least one side of the base layer, the base layer, the chlorination degree of 60% To 100 parts by weight of the following vinyl chloride resin, at least one of the above-described flame retardancy-imparting components was added in an amount of 0.0
005 to 10 parts by weight, and the surface layer has a chlorination degree higher than that of the vinyl chloride resin of the base layer.
It consists of a layer of 73% vinyl chloride resin.

[0065] In the case of the molded body A _4, the base layer and surface layer stabilizer tin described above, a lubricant, a reinforcing agent, various additives such as processing aids is an adequate amount, also the base layer and the surface layer The thickness of the base layer is 1 to 1 in the same manner as in the above-described molded articles A _{1 to} A ₃ .
The thickness is about 15 mm, and the surface layer is about 0.4 to 1.5 mm. Although the molded body A ₄ is a transparent molded body, or using lead-based stabilizers instead of the tin-based stabilizer, an inorganic filler or opaque, such as tin or lead-based stabilizer and the titanium compound, calcium carbonate By adding a pigment, an opaque molded body can be obtained.

[0066] foaming agent is a fire resistant component to be contained in the base layer of the molded body A _4, decomposition accelerators, radical generator,
Crosslinking agent is the same as that used in the molded body A ₁ described above, since the content is the same, the description thereof is omitted.
Further, the chlorination degree of forming the base layer of the molded body A ₄ 60
% Or less of the above-mentioned molded product A ₁
The description is omitted because it is the same as that used.

[0067] Vinyl chloride resin forming the base layer of the molded body A ₄ is those chlorination degree of 60 percent or less lower than the vinyl chloride resin forming the surface layer, at least one element contained in the base layer The flame retardancy is enhanced by the flame retardancy imparting component, and the surface layer is formed of a 58-73% vinyl chloride resin having excellent flammability, which has a higher chlorination degree than the vinyl chloride resin of the base layer. Therefore, this molded article has excellent flame retardancy as a whole. In addition, chlorination degree is 58-
The surface layer formed of 73% vinyl chloride resin is inferior in chemical resistance and corrosion resistance as compared with the surface layer formed of general vinyl chloride resin having a chlorination degree of about 56%. It has much better chemical and corrosion resistance than the surface layer containing it.

Next, the molded body A _5, a transparent molded body which does not contain an inorganic filler such as titanium compounds and the surface layer integrally laminated on at least one side of the base layer, the base layer, the chlorination degree of 60% To 100 parts by weight of the following vinyl chloride resin, at least one of the above-described flame retardancy-imparting components was added in an amount of 0.0
005 to 10 parts by weight containing a surface layer,
The degree of chlorination is higher than that of the base vinyl chloride resin.
0.0005 to 73% by weight of at least one of the above-mentioned components for imparting flame retardancy to 100 parts by weight of a vinyl chloride resin.
It is composed of a layer containing 10 parts by weight.

[0069] In the case of the molded body A _5, the base layer and surface layer stabilizer tin described above, a lubricant, a reinforcing agent, various additives such as processing aids is an adequate amount, also the base layer and the surface layer the thickness of the is the same as the thickness of the base layer and the surface layer of the molded article a ₁ of the foregoing. Although the molded body A ₅ is a transparent molded body, or using lead-based stabilizers instead of the tin-based stabilizer, an inorganic filler or opaque, such as tin or lead-based stabilizer and the titanium compound, calcium carbonate By adding a pigment, an opaque molded body can be obtained.

[0070] foaming agent is a fire resistant component to be contained in the base layer and the surface layer of the molded article A _5, the decomposition accelerating agent, a radical generating agent, crosslinking agent, the same as that used in the molded body A ₁ of the aforementioned And the content thereof is also the same, so that the description is omitted. Further, the chlorination degree of forming the base layer of the molded body A ₅ is or 60% or less of a vinyl chloride resin, chlorinated degree from 58 to 73% of a vinyl chloride resin forming the surface layer is also formed body A ₁ of the aforementioned The description is omitted because it is the same as that used.

[0071] The base layer of the molded body A ₅ are have flame retardancy is enhanced with the same composition as the base layer of the shaped body A _4, moreover, the surface layer is chlorination degree in 58 to 73% and high flame retardancy for excellent vinyl chloride resin in which further enhance the flame retardancy by incorporating the flame retardancy-imparting component, the molded body a ₅ are having an excellent flame retardancy than the shaped body a _4.

The flame-retardant vinyl chloride resin molded product A ₄ ,
A ₅ represents, together with the preparation of a chlorinated degree of at least one resin composition for base layer formation formulated with stabilizers and other additives necessary for forming a fire resistant component to less than 60% of the vinyl chloride resin, A resin composition for forming a surface layer comprising a vinyl chloride resin having a degree of chlorination of 58 to 73% higher than that of the base layer and a stabilizer and other additives required for molding, or a chlorination degree of 58- higher than the vinyl chloride resin of the base layer
A resin composition for forming a surface layer is prepared by blending 73% of a vinyl chloride resin with at least one kind of flame retardancy-imparting component and a stabilizer and other additives necessary for molding, and these resin compositions are subjected to multilayer extrusion molding. It is manufactured by laminating into a desired shape by a calender press, lamination or other known means. The molded bodies A ₄ and A ₅ thus produced are used as they are or after being subjected to secondary processing, for various uses requiring flame retardancy.

Next, as typical examples of the molded article B obtained by adding a phosphorus-based flame retardant and / or chlorinated polyethylene to the vinyl chloride resin of the base layer and / or the surface layer, the following B ₁ , B ₂ ,
B _3, and the like.

The molded article B ₁ is a transparent molded article obtained by laminating and integrating a surface layer on at least one surface of a base layer.
Layer containing 0.5 to 15 parts by weight of phosphorus-based flame retardant and / or 0.5 to 20 parts by weight of chlorinated polyethylene based on 100 parts by weight of vinyl chloride resin having a chlorination degree of 58 to 73% The surface layer is formed of a vinyl chloride resin layer having a degree of chlorination of 60% or less, which is lower than the vinyl chloride resin of the base layer.

[0075] In the case of the molded body B _1, the base layer and surface layer stabilizer tin described above, a lubricant, a reinforcing agent, various additives such as processing aids is an adequate amount, also the base layer and the surface layer the thickness of the is the same as the thickness of the molded body a ₁ of the base layer and surface layer. Although the molded body B ₁ represents a transparent molded body, or using lead-based stabilizers instead of the tin-based stabilizer, an inorganic filler or opaque, such as tin or lead-based stabilizer and the titanium compound, calcium carbonate By adding a pigment, an opaque molded body can be obtained.

[0076] As the phosphorus-based flame retardant to be contained in the base layer of the molded body B _1, halogen-containing phosphoric acid esters, halogen-containing condensed phosphoric acid esters, halogen-phosphoric acid esters, halogen-condensed phosphoric acid ester, orthophosphoric acid esters Suitable are organic phosphorus compounds such as tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, and the like.
Trimethyl phosphate, triphenyl phosphate,
Tricresyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate and the like are preferably used.

Such an organic phosphorus-based flame retardant is more excellent in transparency than a flame retardant such as a halogen-based flame retardant or antimony oxide, so that it is advantageous for obtaining a transparent molded article. The organic phosphorus-based flame retardant is thermally decomposed to generate phosphoric acid, and the phosphoric acid remains on the surface of the vinyl chloride resin to prevent oxygen transfer, and promote carbonization of the surface to suppress combustion. flame retardancy of the base layer of the molded body B ₁ can be improved. In addition, since this organic phosphate ester also functions as an internal lubricant or an external lubricant, there is an advantage that a lubricant which does not impart flame retardancy, such as another higher fatty acid, need not be used. In addition, inorganic phosphorus-based flame retardants such as red phosphorus can be used as long as the transparency is not impaired.

[0078] On the other hand, chlorinated polyethylene to be contained in the base layer of the molded body B ₁ represents a preferred those having 25 to 45% of the chlorination degree, the inclusion of such chlorinated polyethylene, produced by pyrolysis Since the chlorine gas delays the burning of the resin, the flame retardancy of the base layer can be improved. The chlorinated polyethylene also functions as a reinforcing agent and can improve the mechanical strength of the base layer. Chlorinated polyethylene having a chlorination degree of less than 25% is disadvantageous for improving flame retardancy because the amount of generated chlorine gas is small, and chlorinated polyethylene having a chlorination degree of 45% or more has a sufficient reinforcing effect. It is not preferable because there is a disadvantage that it cannot be obtained.

The above-mentioned phosphorus-based flame retardant is used in an amount of 0.5 to 1 based on 100 parts by weight of the post-chlorinated vinyl chloride resin constituting the base layer.
It is necessary to contain 5 parts by weight, and 0.5 to 20 parts by weight of chlorinated polyethylene. When the content of the phosphorus-based flame retardant and chlorinated polyethylene is less than either 0.5 part by weight, it is difficult to sufficiently improve the flame retardancy of the base layer of the molded body B _1, also phosphorus-based flame retardant If the content of is more than 20 parts by weight the content of the case or the chlorinated polyethylene is more than 15 parts by weight, transparency of the molded body B ₁ is reduced. The preferred content of the phosphorus-based flame retardant is 2 to 10
Parts by weight, and the preferred content of chlorinated polyethylene is 3 to 15 parts by weight.

[0080] Incidentally, the chlorination degree of forming the base layer of the molded body B ₁ is and 58-73% of a vinyl chloride resin, chlorinated degree of 60% or less of the vinyl chloride resin forming the surface layer, forming the aforementioned since the same as those used in the body a _1, the description thereof is omitted.

[0081] The molded body B ₁ represents, on the base layer is formed with excellent vinyl chloride resin flame retardant with 58-73% high chlorination degree, the above phosphorus-based flame retardants and chlorinated polyethylene , The flame retardancy of the base layer is greatly enhanced, and the surface layer is formed of a 60% or less vinyl chloride resin having a lower chlorination degree than that of the base layer, Good chemical and corrosion resistance is exhibited. Chlorination degree was formed in 60% or less of the vinyl chloride resin surface layer, although flame retardancy compared to the high chlorination degree vinyl chloride resin is slightly inferior, the proportion of the surface layer in the molded body B ₁ represents slight , and the majority of the molded body B ₁ represents because occupied by excellent substrate of the above flame retardant, having excellent flame retardancy as a whole compact.

Next, the molded article B ₂ is a transparent molded article in which a surface layer is laminated and integrated on at least one surface of the base layer, and the base layer has a chlorination degree of 58%, similarly to the base layer of the molded article B _1. ~
0.5 parts per 100 parts by weight of 73% vinyl chloride resin
A chlorinated polyethylene containing 0.5 to 20 parts by weight of a phosphorus-based flame retardant and / or 0.5 to 20 parts by weight of a chlorinated polyethylene, and the surface layer is made of a vinyl chloride resin having a chlorination degree of 58 to 73%. It consists of layers.

[0083] In the case of the molded body B _2, the base layer and surface layer stabilizer tin described above, a lubricant, a reinforcing agent, various additives such as processing aids is an adequate amount, also the base layer and the surface layer the thickness of the is the same as the thickness of the base layer and the surface layer of the molded article a ₁ mentioned above. The molded body B ₂ is a transparent molded body,
An opaque molded product can be obtained by using a lead-based stabilizer instead of a tin-based stabilizer, or by adding a tin-based or lead-based stabilizer and an inorganic filler or an opaque pigment such as a titanium compound or calcium carbonate. .

[0084] The molded body phosphorus-based flame retardant or chlorinated polyethylene to be contained in the base layer of B ₂ are the same as those used in the molded body B ₁ described above, since the content is the same, the description Omitted. Further, the chlorination degree of from 58 to 73% of a vinyl chloride resin forming the base layer and the surface of the molded body B _2, since the same as those used in the molded body A ₁ of the foregoing, the description thereof is omitted.

[0085] Such molded body B _2, the base layer has excellent flame retardancy because the same composition as the base layer of the molded body B ₁ described above, the surface layer also chlorination degree and a high 58 to 73% Since it is formed of a vinyl chloride resin, the surface layer has good flame retardancy. Accordingly, the molded body B ₂ is
Has better flame retardancy than ₁ . In addition, chlorination degree is 58-
The surface layer made of vinyl chloride resin as high as 73% has a slightly lower chemical resistance and corrosion resistance than the surface layer made of general vinyl chloride resin having a low chlorination degree. Is much better in chemical resistance and corrosion resistance than the surface layer containing.

The flame-retardant vinyl chloride resin molded products B ₁ and B ₂ described above are required to be molded with a vinyl chloride resin having a chlorination degree of 58 to 73% and a phosphorus-based flame retardant and / or chlorinated polyethylene. For preparing a base layer-forming resin composition containing a stabilizer and other additives, and for forming a surface layer containing a stabilizer and other additives necessary for molding in a vinyl chloride resin having a chlorination degree of 60% or less. Or a vinyl chloride resin having a chlorination degree of 58 to 73%, and a resin composition for forming a surface layer prepared by blending a stabilizer and other additives necessary for molding with the resin composition. It is manufactured by laminating the product into a desired shape by multi-layer extrusion, calendar press, lamination or other known means. The molded bodies B ₁ and B ₂ thus produced are used as they are or after secondary processing, and are used for various applications requiring flame retardancy.

Next, the molded article B ₃ is a transparent molded article obtained by laminating and integrating a surface layer on at least one surface of the base layer. The base layer is formed by coating 100 parts by weight of a vinyl chloride resin having a chlorination degree of 60% or less. On the other hand, it is a layer containing 0.5 to 15 parts by weight of a phosphorus-based flame retardant and / or 0.5 to 20 parts by weight of chlorinated polyethylene, and the surface layer is a vinyl chloride resin having a chlorination degree of a base layer. A higher layer of 58-73% vinyl chloride resin.

[0088] In the case of the molded body B _3, the base layer and surface layer stabilizer tin described above, a lubricant, a reinforcing agent, various additives such as processing aids is an adequate amount, also the base layer and the surface layer the thickness of the is the same as the thickness of the base layer and the surface layer of the molded article a ₁ of the foregoing. Although the molded body B ₃ is a transparent molded body, or using lead-based stabilizers instead of the tin-based stabilizer, an inorganic filler or opaque, such as tin or lead-based stabilizer and the titanium compound, calcium carbonate By adding a pigment, an opaque molded body can be obtained.

[0089] phosphorus-based flame retardants and chlorinated polyethylene to be contained in the base layer of the molded body B ₃ are the same as those used in the molded body B ₁ described above, since the content is the same, the description Omitted. Further, the chlorination degree and less than 60% of the vinyl chloride resin forming the base layer of the molded body B _3, chlorination degree of from 58 to 73% of a vinyl chloride resin forming the surface layer, the molded body A ₁ of the aforementioned Is the same as that used for
Description is omitted.

[0090] Vinyl chloride resin forming the base layer of the molded body B _3, although the chlorination degree or less and a low 60%, and increased flame retardancy by the inclusion of phosphorus-based flame retardants and chlorinated polyethylene, moreover since the surface layer is a layer of vinyl chloride resin chlorination degree is excellent in 58-73% of flame retardant above vinyl chloride resin of the base layer, the molded body B ₃ has excellent flame retardancy.

Such a flame-retardant vinyl chloride resin molded article B
₃ prepares a resin composition for forming a base layer in which a vinyl chloride resin having a chlorination degree of 60% or less is blended with a phosphorus-based flame retardant and / or a chlorinated polyethylene and a stabilizer and other additives necessary for molding. A resin composition for forming a surface layer is prepared by blending a stabilizer and other additives necessary for molding into a vinyl chloride resin having a chlorine angle of 58 to 73%, and these compositions are subjected to multilayer extrusion molding, calender pressing, It is manufactured by laminating into a desired shape by laminating or other known means. Moldings B ₃ produced thus is directly, or secondary processing to be used in various applications where flame retardancy is required.

Next, as a representative example of a molded article C in which at least one of the flame-retardant-imparting component is contained in one of the base layer and the surface layer and the other contains a phosphorus-based flame retardant and / or chlorinated polyethylene. include the following moldings C _1.

The molded product C ₁ is a transparent molded product in which a surface layer is laminated and integrated on at least one surface of a base layer. The base layer is based on 100 parts by weight of a vinyl chloride resin having a chlorination degree of 60% or less. A layer containing 0.0005 to 10 parts by weight of at least one of the above-mentioned components for imparting flame retardancy, wherein the surface layer has a chlorination degree of 58 to 73% higher than that of the vinyl chloride resin of the base layer. With respect to 100 parts by weight of the vinyl resin, 0.5 to 15 parts by weight of the phosphorus-based flame retardant and / or 0.
It is composed of a layer containing 5 to 20 parts by weight of chlorinated polyethylene.

[0094] In the case of the molded body C _1, the base layer and surface layer stabilizer tin described above, a lubricant, a reinforcing agent, various additives such as processing aids is an adequate amount, also the base layer and the surface layer the thickness of the is the same as the thickness of the base layer and the surface layer of the molded article a ₁ of the foregoing. Although the molded body C ₁ is a transparent molded body, or using lead-based stabilizers instead of the tin-based stabilizer, an inorganic filler or opaque, such as tin or lead-based stabilizer and the titanium compound, calcium carbonate By adding a pigment, an opaque molded body can be obtained.

A foaming agent, a decomposition accelerator, a radical generator, which are flame retardancy-imparting components contained in the base layer of the molded product C ₁ ,
Crosslinking agent is the same as that used in the molded body A ₁ described above, since the content is the same, the description thereof is omitted.
Also, phosphorus-based flame retardant or chlorinated polyethylene to be contained in the surface layer is the same as that used in the molded body B ₁ described above, since the content is the same, the description thereof is omitted.
Furthermore, chlorinated degree to form a base layer of the molded body C ₁ 60
% Or less, or a vinyl chloride resin having a chlorination degree of 58 to 73% for forming a surface layer is formed of the above-mentioned molded article A ₁
The description is omitted because it is the same as that used in the above.

[0096] The base layer of the molded body C ₁ is the compact A _4,
And enhanced flame retardancy at the same composition as the base layer of A _5, moreover, the surface layer of the phosphorus-based flame retardants and chlorinated polyethylene chlorination degree excellent vinyl chloride resin to 58 to 73% and high flame retardancy for the further contain those further enhanced flame retardancy, the moldings C ₁ has excellent flame retardancy.

Such a flame-retardant vinyl chloride resin molded article C
₁ is to prepare a resin composition for forming a base layer comprising a vinyl chloride resin having a chlorination degree of 60% or less and at least one kind of flame retardant-imparting component and a stabilizer and other additives necessary for molding. A resin composition for forming a surface layer is prepared by blending a vinyl chloride resin having a degree of conversion of 58 to 73% with a phosphorus-based flame retardant and / or chlorinated polyethylene and a stabilizer and other additives necessary for molding. It is manufactured by laminating the composition into a desired shape by multi-layer extrusion, calendar press, lamination or other known means. Thus moldings C ₁ produced is directly, or secondary processing to be used in various applications where flame retardancy is required.

[0098] Incidentally, contrary to the molded body C ₁ described above, at least one fire resistant component with respect to 100 parts by weight of the vinyl chloride resin of the surface layer is contained 0.0005 parts by weight,
0.5 to 1 with respect to 100 parts by weight of the vinyl chloride resin of the base layer
5 parts by weight of a phosphorus-based flame retardant and / or 0.5 to 20 parts by weight of chlorinated polyethylene may be contained.

The molded articles A ₁ , A ₂ , A ₃ , A described above
₄ , A ₅ , B ₁ , B ₂ , B ₃ , and C ₁ are essentially transparent molded products because they do not contain a titanium compound or other inorganic filler, and do not contain a halogen-based flame retardant. Therefore, the total light transmittance at a thickness of 5 mm is 40% unless a lead-based stabilizer is used or a pigment or an inorganic filler is added to make the film opaque because transparency is not extremely reduced. As described above, a transparent molded body having a haze value of 60% or less when the thickness is 5 mm is obtained.

Each of the molded bodies containing neither the base layer nor the surface layer containing an inorganic filler has good chemical resistance and corrosion resistance, and is weakened by the inorganic filler, deteriorated in moldability.
There is no risk of lowering the secondary workability.

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

Examples 1 to 8 4 parts by weight of a dibutyltin malate-based heat stabilizer and 1 part by weight of stearic acid as a lubricant were added to 100 parts by weight of a post-chlorinated vinyl chloride resin having a degree of chlorination of about 64%. Parts, 2 parts by weight of a processing aid and 5 parts by weight of an MBS-based reinforcing agent, and then mixed with a basic composition (chlorination degree: about 6).
4%) was prepared.

Further, based on 100 parts by weight of a general vinyl chloride resin having a degree of chlorination of about 56%, 4 parts by weight of a dibutyltin maleate-based heat stabilizer, 1 part by weight of stearic acid, and 2 parts by weight of a processing aid Parts and 5 parts by weight of an MBS-based reinforcing agent were mixed to prepare a basic composition (chlorination degree: about 56%).

Further, the average chlorination degree obtained by mixing a post-chlorinated vinyl chloride resin having a chlorination degree of about 64% and a general vinyl chloride resin having a chlorination degree of about 56% at a weight ratio of 3: 7 is substantially the same. 58
% Of the mixed resin, 4 parts by weight of a dibutyltin malate-based heat stabilizer, 1 part by weight of stearic acid, 2 parts by weight of a processing aid, and 5 parts by weight of an MBS-based reinforcing agent were mixed. A basic blend composition (average chlorination degree: approximately 58%) was prepared.

Next, a hydrazide compound as a foaming agent, zinc stearate as a decomposition accelerator, diamyl peroxide as a radical generator, triazine thiol as a crosslinking agent were added to 112 parts by weight of the above-mentioned basic composition. The composition for base layer formation and the composition for surface layer formation were prepared by selective mixing at the ratios shown in Table 1 below. Then, a calendar sheet for forming a base layer and a calendar sheet for forming a surface layer are respectively prepared using these compositions,
The transparent flame-retardant vinyl chloride resin plates of Examples 1 to 8 having a three-layer structure having a surface layer of 0.5 mm thickness on both sides of a base layer of 4 mm thickness (overall thickness) 5 mm).

These resin plates (50 × 50 × 5 mm) were placed in an electric furnace heated to 800 ° C., and the presence / absence of ignition and the time until ignition were examined to conduct a flame retardancy test. The results are shown in Table 1 below.

The chemical resistance of these resin plates was examined, and the results are shown in Table 1. This chemical resistance is 97
2% for each chemical solution of 35% sulfuric acid, 35% sulfuric acid and 28% ammonia water
The discoloration of the appearance after immersion at 3 ° C. for 7 days was observed, ◎ indicates no discoloration, and ○ indicates slight discoloration.

Further, these resin plates are described in JIS.
The total light transmittance and the haze value were measured based on K-7105, and the results are shown in Table 1.

[Comparative Examples 1 and 2] A calendar sheet for forming a base layer was prepared using the basic composition (chlorination degree: about 56%) prepared in Examples 1 to 8, and Examples 1 to 8 were prepared.
A calender sheet for forming a surface layer is prepared using the basic blending composition (degree of chlorination: approximately 64%) prepared in the above, and the laminate is pressed together to form a 0.5 mm thick layer on both sides of a 4 mm thick base layer. Thus, a transparent flame-retardant vinyl chloride resin plate (total thickness: 5 mm) of Comparative Example 1 having a three-layer structure having the above surface layer was obtained.

Conversely, a calendar sheet for forming a surface layer was prepared using the basic blended compositions (degree of chlorination: approximately 56%) prepared in Examples 1 to 8. 8 (chlorination degree: about 64)
%) To form a base layer-forming calender sheet, and by pressing the sheets together, the transparent sheet of Comparative Example 2 having a three-layer structure having a 0.5 mm thick surface layer on both sides of a 4 mm thick base layer is pressed. Flame-retardant vinyl chloride resin plate (total thickness 5m
m).

For these resin plates, a flame resistance test was performed in the same manner as in Examples 1 to 8, and the chemical resistance, the total light transmittance, and the haze value were measured. The results are shown in Table 1 below.

[0112]

[Table 1] Note 1: The resin plate of Example 2 ignited after 90 seconds, but fired spontaneously after the surface layer burned for 6 seconds and did not reignite thereafter, so it was judged that there was substantially no ignition. Note 2: The resin plate of Comparative Example 1 ignited after 40 seconds, burned for 97 seconds and most of it disappeared, so it was judged that ignition was present. Note 3: The resin plate of Comparative Example 2 ignited after 16 seconds, burned for 48 seconds and most of it disappeared, so it was judged that ignition was present.

From Table 1 above, it can be seen that all of the vinyl chloride resin plates of Examples 1 to 8 have excellent flame retardancy and good chemical resistance and transparency. On the other hand, the vinyl chloride resin plates of Comparative Examples 1 and 2 containing no flame retardancy-imparting component have excellent chemical resistance and transparency inherent to the vinyl chloride resin, but have the flame retardancy of Examples 1 to 8. It can be seen that it is inferior to the vinyl chloride resin plate. Further, when Examples 1, 2, and 3 are compared, the vinyl chloride resin plate of Example 2 in which the surface layer was formed only with the basic blending composition having a low chlorination degree of about 56% naturally ignited once immediately after ignition. Although the fire was extinguished, the resin plate of Example 3 in which the surface layer was formed only with the basic composition having a high chlorination degree of 64%, and the basic composition having a low chlorination degree of about 56% were flame-retardant. Since the resin plate of Example 1 in which the surface layer was formed by adding the imparting component did not ignite at all, it is not often that the surface layer is formed only with the basic blending composition of the vinyl chloride resin having a low chlorination degree. Unfavorably, a flame retardant component is blended as in Example 1, or a surface layer is formed with a basic blend composition of a vinyl chloride resin having a chlorination degree of more than 60% as in Example 3. It turns out that it is more preferable.

[Examples 9 to 13] Phosphorus based on 112 parts by weight of the three basic blending compositions having chlorination degrees of about 64%, about 58% and about 56% prepared in Examples 1 to 8 The base layer forming composition is prepared by selectively mixing tricresyl phosphate as a flame retardant, chlorinated polyethylene having a degree of chlorination of about 35%, and triazine thiol as a cross-linking agent in proportions shown in Table 2 below. And a composition for forming a surface layer were prepared. Then, a calender sheet for forming a base layer and a calender sheet for forming a surface layer are respectively prepared using these compositions, and the calender sheets are stacked and pressed to have a thickness of 4 mm.
The transparent flame-retardant vinyl chloride resin plates (total thickness 5 mm) of Examples 9 to 13 having a three-layer structure having a surface layer of 0.5 mm thickness on both sides of a base layer of 5 mm were obtained.

For these resin plates, a flame retardancy test was performed in the same manner as in Examples 1 to 8, and the chemical resistance, total light transmittance, and haze value were measured. The results are shown in Table 2 below.

[0116]

[Table 2] Note 4: The resin plate of Example 9 ignited after 32 seconds, but fired spontaneously after the surface layer burned for 9 seconds and did not reignite thereafter, so it was judged that there was substantially no ignition.

From the above Table 2, it can be seen that the vinyl chloride resin plates of Examples 9 to 13 have excellent flame retardancy, and in particular, Examples 9 to 1 containing a phosphorus-based flame retardant and chlorinated polyethylene in the base layer.
It can be seen that the vinyl chloride resin plate 1 is also excellent in chemical resistance and transparency. Also, comparing Examples 9, 10, and 11, the vinyl chloride resin plate of Example 9 in which the surface layer was formed only with the basic blending composition having a low chlorination degree of about 56% was naturally ignited once immediately after ignition. Fire extinguishing, chlorination degree 6
Since the vinyl chloride resin plates of Examples 10 and 11 in which the surface layer was formed only with the basic composition of as high as 4% did not ignite at all, the surface was formed only with the basic composition of the vinyl chloride resin having a low chlorination degree. It is found that it is not so preferable to form a layer, and it is more preferable to form a surface layer with a basic composition of a vinyl chloride resin having a chlorination degree higher than 60%.

[0118]

As is apparent from the above description, the flame-retardant vinyl chloride resin molded article of the present invention has excellent flame retardancy,
The chemical resistance and the corrosion resistance of the surface are good, and the effect is that the transparency is good as long as it is not opaque.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 27/06 C08L 27/06 // (C08L 27/06 (C08L 27/06 23:28) 23:28) F-term (reference) 4F071 AA24 AA78 AA79 AC15 AE01 AE02 AE07 AF30 AH12 BB04 BB06 BC01 4F100 AK10A AK10B AK15A AK15B AT00A AT00B BA02 BA16 CA01A CA01B CA02A CA02B CA08A CA08B CA30A CA30B EJ20 JB01 JB02 JJ07 JJ07A JJ07B JK01 JN01 YY00A YY00B 4J002 BB242 BD041 BD181 EG047 EG077 EK037 EK087 EQ017 EQ027 ES007 ET007 EV267 EW046 EW056 FD136 FD147 FD197 FD207 FD327 GF00

Claims (13)

[Claims] 1. A molded article which does not contain a titanium compound wherein a surface layer is laminated and integrated on at least one surface of a base layer, wherein a foaming agent and a decomposition accelerator are added to 100 parts by weight of a vinyl chloride resin of the base layer and / or the surface layer. A flame-retardant vinyl chloride resin molded product characterized by containing 0.0005 to 10 parts by weight of at least one of an agent, a radical generator and a crosslinking agent. 2. A molded article in which a surface layer is laminated and integrated on at least one side of a base layer, wherein 0.5 to 15 parts by weight of a phosphorus-based compound is used with respect to 100 parts by weight of vinyl chloride resin of the base layer and / or the surface layer. A flame-retardant vinyl chloride resin molded product containing a flame retardant and / or 0.5 to 20 parts by weight of chlorinated polyethylene. 3. A molded article in which a surface layer is laminated and integrated on at least one surface of a base layer, wherein a foaming agent, a decomposition accelerator, and a radical are added to 100 parts by weight of either one of the base layer and the surface layer. A generator and at least one of a crosslinking agent are contained at 0.0005 to 10 parts by weight,
0.5 to 100 parts by weight of the other vinyl chloride resin
A flame-retardant vinyl chloride resin molded article containing 15 parts by weight of a phosphorus-based flame retardant and / or 0.5 to 20 parts by weight of chlorinated polyethylene. 4. A molded article in which a surface layer is laminated and integrated on at least one surface of a base layer, wherein the base layer has a chlorination degree of 58 to 73.
% Of the vinyl chloride resin, and the surface layer has a degree of chlorination lower than that of the vinyl chloride resin of the base layer and is 60%.
% To 100 parts by weight of vinyl chloride resin, which is 0.0005 to 10 parts by weight of at least one of a foaming agent, a decomposition accelerator, a radical generator, and a crosslinking agent. Flame-retardant vinyl chloride resin molding. 5. A molded article in which a surface layer is laminated and integrated on at least one surface of a base layer, wherein the base layer has a chlorination degree of 58 to 73.
% Of a vinyl chloride resin in an amount of 0.0005 to 10 parts by weight with respect to 100 parts by weight of a blowing agent, a decomposition accelerator, a radical generator, and a crosslinking agent. A flame-retardant vinyl chloride resin molded product, which is a layer made of a vinyl chloride resin having a degree of conversion lower than that of the base layer and less than 60%. 6. A molded article in which a surface layer is laminated and integrated on at least one surface of a base layer, wherein the base layer has a chlorination degree of 58 to 73.
% Of a vinyl chloride resin, and 0.0005 to 10 parts by weight of at least one of a foaming agent, a decomposition accelerator, a radical generator, and a crosslinking agent. A flame-retardant vinyl chloride resin molded article characterized in that it is a layer made of a vinyl chloride resin. 7. A molded article in which a surface layer is laminated and integrated on at least one surface of a base layer, wherein the base layer is a foaming agent and a decomposition accelerator based on 100 parts by weight of a vinyl chloride resin having a chlorination degree of 60% or less. A layer containing at least one of a radical generator and a crosslinking agent in an amount of 0.0005 to 10 parts by weight, and the surface layer has a chlorination degree higher than that of the vinyl chloride resin of the base layer and 58 to 73%. A flame-retardant vinyl chloride resin molded article characterized in that it is a layer made of vinyl chloride resin. 8. A molded article in which a surface layer is laminated and integrated on at least one surface of a base layer, wherein the base layer is a foaming agent and a decomposition accelerator based on 100 parts by weight of a vinyl chloride resin having a chlorination degree of 60% or less. A layer containing at least one of a radical generator and a crosslinking agent in an amount of 0.0005 to 10 parts by weight, and the surface layer has a chlorination degree higher than that of the vinyl chloride resin of the base layer and 58 to 73%. Vinyl chloride resin 10
0.0005 parts by weight of at least one of a foaming agent, a decomposition accelerator, a radical generator, and a crosslinking agent.
A flame-retardant vinyl chloride resin molded product, which is a layer containing 10 parts by weight. 9. A molded article in which a surface layer is laminated and integrated on at least one side of a base layer, wherein the base layer has a chlorination degree of 58 to 73
% Based on 100 parts by weight of vinyl chloride resin.
A layer containing 5 parts by weight of a phosphorus-based flame retardant and / or 0.5 to 20 parts by weight of chlorinated polyethylene, wherein the surface layer has a chlorination degree lower than that of the base layer vinyl chloride resin and is 60 % Of a flame-retardant vinyl chloride resin molded product, which is a layer made of a vinyl chloride resin having a concentration of not more than 10%. 10. A molded article in which a surface layer is laminated and integrated on at least one surface of a base layer, wherein the base layer has a chlorination degree of 58 to 7%.
0.5 to 100 parts by weight of 3% vinyl chloride resin
It is a layer containing 15 parts by weight of a phosphorus-based flame retardant and / or 0.5 to 20 parts by weight of chlorinated polyethylene, and the surface layer is a layer made of the above vinyl chloride resin. Flammable vinyl chloride resin molded product. 11. A molded article in which a surface layer is laminated and integrated on at least one surface of a base layer.
A layer containing 5 parts by weight of a phosphorus-based flame retardant and / or 0.5 to 20 parts by weight of chlorinated polyethylene. A flame-retardant vinyl chloride resin molded product, which is a layer made of a vinyl chloride resin of about 73%. 12. A molded article in which a surface layer is laminated and integrated on at least one surface of a base layer. , A radical generator or a crosslinking agent containing at least one of 0.0005 to 10 parts by weight, and the surface layer has a chlorination degree higher than that of the vinyl chloride resin of the base layer and 58 to 73%. Vinyl chloride resin 10
Flame-retardant vinyl chloride, characterized in that it is a layer containing 0.5 to 15 parts by weight of a phosphorus-based flame retardant and / or 0.5 to 20 parts by weight of chlorinated polyethylene with respect to 0 parts by weight. Resin molding. 13. The flame-retardant vinyl chloride resin molded product according to claim 1, wherein the total light transmittance is 40% or more and the haze value is 60% or less.