JP2002053726A - Flame-retardant vinyl chloride resin composition, flame- retardant vinyl chloride resin molding, and production method for flame-retardant vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant PVC composition which is colored well with a colorant, has a high-quality appearance, substantially having neither acne nor color shading, and is excellent in mechanical characteristics. SOLUTION: This composition is prepared by mixing a colorant and a lubricant in a specified mass ratio to give a first master batch, mixing a part of a specific other filler and a lubricant in a specified mass ratio to give a second master batch, and mixing these master batches, a PVC matrix, and titanium oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame retardant polyvinyl chloride resin (also referred to as PVC) composition.

[0002]

2. Description of the Related Art PVC contains chlorine in its molecule.
Excellent flame retardancy. Further, since various fillers can be added in a wide content, a wide range of mechanical properties, heat resistance, moldability, and weather resistance can be realized. In particular, coloring can be performed with a high degree of freedom by using various kinds of pigments and the like.

[0003] Because PVC has the above properties, molded articles of rigid PVC compositions are particularly suitable for aircraft, ships,
They have been used as interior and exterior materials for vehicles such as vehicles; interior and exterior materials for buildings; daily goods such as furniture and office tools; housing materials for home appliances and electronic devices; and parts of semiconductor devices.

However, when PVC is exposed to a high temperature higher than the heat resistance temperature due to fire or the like, a large amount of smoke is generated due to chlorine in the molecule, and toxic gases such as chlorine gas and hydrogen chloride gas are generated. I do. For this reason, it has been attempted to suppress the generation of toxic gas by examining the type and amount of the filler.

[0005] For example, in Japanese Patent Application Laid-Open No. Hei 10-139967, one kind of molybdenum oxide or ammonium molybdate or 100 parts by weight of a vinyl chloride-based resin composition is used for the purpose of suppressing the emission of PVC. 2 or more molybdenum compounds are 2 parts by weight or more, magnesium hydroxide is 4 parts by weight or more, and the total amount thereof is 25 parts by weight or less, and 1 to 5 parts by weight of silicone powder is blended. A vinyl chloride-based resin composition has been disclosed.

In Japanese Patent Application Laid-Open No. 10-298380, for the purpose of PVC having excellent mechanical properties and reduced smoke generation, 20 to 80 parts by weight of a metal hydroxide, 100 parts by weight of polyvinyl chloride, A flame-retardant vinyl chloride resin composition comprising 2 to 25 parts by weight of at least one selected from molybdate compounds and phosphoric acid compounds and 1 to 5 parts by weight of red phosphorus has been disclosed.

Further, Japanese Patent Application Laid-Open No. H11-181204 discloses that, for the purpose of PVC satisfying the FM standard, it is difficult to form a desired shape by adding calcium carbonate, talc and a chlorine trapping compound to a vinyl chloride resin. A flammable vinyl chloride resin molding has been disclosed.

However, in the flame-retardant vinyl chloride resin composition as described above (also referred to as a flame-retardant PVC composition), the effect of suppressing the generation of toxic gas is not sufficient, When an amount of the filler necessary for sufficiently suppressing the addition is added, other characteristics such as mechanical characteristics may be impaired.

[0009]

In order to avoid the above-mentioned problems, JP-A-2000-80230 discloses that 4 parts of titanium oxide are added to 100 parts by weight of a vinyl chloride resin having a chlorination degree of 58 to 73%. A flame-retardant vinyl chloride resin molded article contained in the range of up to 30 parts by weight has been proposed.

[0010] That is, this publication discloses that the use of titanium oxide as a flame retardant effectively enhances the flame retardancy of PVC because titanium oxide is used in the process of burning PVC. When present, the titanium oxide does not decompose to a high temperature of 1200 to 1300 ° C., and serves to block heat from the outside due to its high whiteness, and at the stage of thermal decomposition and combustion of PVC after dechlorination, PVC It is presumed that it acts to carbonize swiftly, thereby improving the flame retardancy.

However, as described in this publication, titanium oxide is a filler having a high whiteness, so that a large amount of pigment may be required in order to color a molded product to a desired color. Was. In particular, when an organic pigment is used as the pigment, the organic pigment easily burns.
In some cases, it was difficult to obtain a molded body that simultaneously satisfied the respective standards.

[0012] Therefore, in order to obtain a molded product satisfying the FM standard with a desired color, it is necessary to mix more titanium oxide and pigment, and a large amount of titanium oxide reduces the strength and chemical resistance of the molded product. In some cases.

In view of such a situation, the publication discloses that by adding titanium oxide to PVC having a chlorine content in a specific range at a specific ratio, not only the FM standard is satisfied, but also sufficient strength and resistance to FM are satisfied. Flame retardant P that has both chemical properties and bending deformability, and can be easily colored to the desired color
It is said that a VC composition is obtained.

However, this publication does not describe any examples relating to flame-retardant PVC molded articles colored with a pigment, and as described in this publication, describes PVC 100 having a chlorine content of 58 to 73%. When a flame-retardant PVC molded article such as a sheet is manufactured by only uniformly mixing 4 to 30 parts by mass of titanium oxide to parts by mass, the obtained flame-retardant PV is obtained.
In some cases, the colorability and appearance of the C molded product were insufficient.

That is, even if the method described in this publication is adopted, since titanium oxide has a high hiding power, when the amount necessary to realize sufficient flame retardancy is used, the obtained flame retardant PVC can be obtained. It was sometimes difficult to color the composition freely.

In particular, a flame-retardant vinyl chloride resin molded product (also referred to as a flame-retardant PVC molded product) used in a part of a semiconductor device or the like should be colored in a dark color such as red or blue. May be required, and good coloring properties have been desired.

[0017] Further, a transport interior / exterior material, a building interior / exterior material,
Flame retardant P used in daily goods, housing materials, etc.
VC molded articles are generally colored in a light color such as ivory and light gray. However, when titanium oxide is used as a flame retardant, coloring may be difficult even in these light colors. .

Furthermore, when titanium oxide is used in an amount necessary to realize sufficient flame retardancy, it is necessary to add a large amount of a coloring agent in order to color the obtained flame retardant PVC composition. Was.

Therefore, in the flame-retardant PVC composition,
Titanium oxide, coloring agents, and the like sometimes caused poor dispersion. As a result, the obtained flame-retardant PVC molded product may have irregularities and color unevenness, resulting in poor appearance.

In particular, when the mechanical properties, workability and the like are reduced due to the addition of a sufficient amount of titanium oxide,
Fillers such as resin-based modifiers and processing aids are added, and since these fillers have a high viscosity, poor dispersion of the colorant may be promoted.

Even when fillers such as resin-based modifiers and processing aids are added, the mechanical properties of the resulting flame-retardant PVC molded product are poor because the mechanical properties of CPVC are insufficient. In some cases, it was not enough.

In view of the above situation, in the present invention, sufficient flame retardancy and good coloring properties are realized, and a high-quality appearance substantially free from bumps and color unevenness is provided.
An object of the present invention is to provide a flame-retardant PVC composition capable of producing a flame-retardant PVC molded article having excellent mechanical properties and a method for producing the same.

[0023]

According to the present invention for achieving the above object, according to the present invention, a polyvinyl chloride which is mainly composed of a post-chlorinated polyvinyl chloride (CPVC) having a chlorine content of 60% by mass or more and 70% by mass or less. (PVC) 100 parts by mass of a matrix, 1 part by mass to 30 parts by mass of a flame retardant composed of titanium oxide, 0.01 part by mass to 5 parts by mass of a colorant,
A flame-retardant vinyl chloride resin composition comprising 1 part by mass or more and 10 parts by mass or less of a lubricant.

According to the present invention, (a) a step of preparing at least 1 part by mass of a coloring agent and 0.1 to 2 parts by mass of a lubricant to prepare a first master batch; B) at least 1 part by weight or more and 30 parts by weight or less of a lead-based stabilizer, and 0.1 part by weight or more and 10 parts by weight or less of a lubricant;
A step of preparing a second masterbatch by mixing 1 part by weight or more and 10 parts by weight or less of a resin-based modifier; and (c) at least a chlorine content of 60% by weight or more and 70% by weight or less of post-chlorinated polychlorinated 100 parts by mass of a polyvinyl chloride (PVC) matrix mainly composed of vinyl (CPVC), 1 to 30 parts by mass of a flame retardant composed of titanium oxide, and 0.01 to 5 parts by mass of the first masterbatch And
2 to 50 parts by mass of the second master batch,
A flame retardant process comprising: powder mixing 0.5 to 10 parts by mass of a processing aid to produce a mixture; and (d) melt kneading the mixture. A method for producing a water-soluble vinyl chloride resin composition is provided.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a preferred embodiment of the present invention will be described.

In the present invention, a PVC matrix,
Rather than mixing titanium oxide and colorant at once,
At least a colorant and a lubricant are premixed at a predetermined mass ratio to form a first masterbatch, and a part of a predetermined other filler and a lubricant are premixed at a predetermined mass ratio to form a second masterbatch, These masterbatches, P
A VC matrix and a predetermined compound such as titanium oxide are mixed at a predetermined mass ratio.

As a result, despite the presence of a large amount of titanium oxide, a good coloring property can be realized with a small amount of coloring agent, and a high-quality appearance substantially free of bumps and color unevenness can be realized. .

Further, even when high-viscosity fillers such as resin-based modifiers and processing aids are added in addition to titanium oxide, good coloring properties are realized and spots and color unevenness are substantially reduced. A high-quality appearance that does not exist can be realized.

Although the above reasons are not clear, it is presumed that the lubricant functions as a dispersant for the colorant by previously mixing the colorant and the lubricant at a predetermined mass ratio.

It is presumed that by preliminarily mixing other fillers and lubricants at a predetermined mass ratio, the lubricant functions as a filler dispersant.

Further, it is presumed that various fillers are uniformly dispersed in the PVC matrix by adopting a mixing method of preparing a master batch in advance. As a result, sufficient mechanical properties are realized.

The types of the lubricant used in the present invention include:
It is not limited as long as it can function as a dispersant for a colorant and a filler. However, higher fatty acids such as stearic acid and palmitic acid; and higher fatty acids such as stearic acid ester and palmitic acid ester because of their high dispersibility. Fatty acid esters; higher fatty acid ethers such as stearic acid ether and palmitic acid ether; natural waxes such as carnauba wax and candelilla wax; synthetic waxes such as methylene bis-stearamide and ethylene bis-stearamide; paraffin wax; Liquid paraffins such as oil can be used.

Of these, dibasic lead stearate (also referred to as DSL) is preferred.

With respect to the amount of the lubricant to be added, in addition to the dispersing effect, in order to improve the melt fluidity of PVC, suppress adhesion to the mold, and realize a sufficient lubricant effect, the amount of the lubricant is based on 100 parts by mass of the PVC matrix. 1 part by mass or more, more preferably 2 parts by mass or more. Further, in order to suppress the deterioration of other properties due to the addition of the lubricant, the amount is set to 10 parts by mass or less, more preferably 8 parts by mass or less.

The type of the colorant used in the present invention is not particularly limited as long as it has good dispersibility. However, inorganic colorants are preferred because of their high heat resistance and difficulty in discoloring and fading during processing. Pigments are preferred.

Among the inorganic pigments, BON R
ed, Red Lake C, Lithol Rubi
nes Bordeaux R, Cadmium S
elenide, Cadmium Lithopon
e, Pigment Scarlet, Red Lea
d, Molybdenum Red, CadmiumR
red pigments such as ed; Chrome Orange, M
olybdate Orange, Benzidine
Orange pigments such as Orange and Lithage; Ca
dmium Yellow, Chrome Yellow
w, Strontium Chromate, Benz
Idine Yellow, Titanium Yel
yellow pigments such as low and Zinc Chromate;
Phthalocyanine Green, Chromo
me Green, Emerald Green, Gu
green-based pigments such as Ignet's Green; Phth
alocyanine Blue, Indianre
ne Blue, Ultramarine Blue,
Blue pigments such as Iron Blue and Cobalt Blue; brown pigments such as red petals; black pigments such as carbon black and iron black; aluminum; aluminum bronze powder; fish scales;

In some cases, inorganic pigments are inferior in dispersibility to organic pigments. However, in the present invention, since the colorant and the lubricant are preliminarily mixed at a predetermined mass ratio to form the first masterbatch, even when an inorganic pigment is used, poor dispersion is suppressed, and good coloring properties are obtained. Is realized.

As a result, sufficient coloring can be performed with a small amount of coloring agent, and since coloring agents are generally expensive,
Production costs can also be reduced.

The specific amount of the colorant added is PVC.
The amount is 0.01 part by mass or more, preferably 0.1 part by mass or more, more preferably 5 parts by mass or less, and may be 3 parts by mass or less based on 100 parts by mass of the matrix.

By using the above-mentioned coloring agents, it is possible to produce a red-colored and blue-colored flame-retardant PVC molded product of a red color or a blue color, which can be used in parts of a semiconductor device.

In addition, the interior and exterior materials for transport, the interior and exterior materials for buildings,
It is also possible to produce thin-color flame-retardant PVC molded articles such as ivory and light gray, which can be used in articles for daily use, housing materials and the like.

In particular, by using at least one pigment selected from the group consisting of a yellow pigment, a black pigment and an orange pigment, an ivory flame-retardant PVC molded article can be produced.

In this case, the amount of the yellow pigment added is 0.1 part by mass or more based on 100 parts by mass of the PVC matrix.
5 parts by mass or less is preferable, the addition amount of the black pigment to 100 parts by mass of the PVC matrix is preferably from 0.01 part by mass to 1 part by mass, and the addition amount of the orange pigment to 100 parts by mass of the PVC matrix is 0.01 part by mass. Not less than 1 part by mass and not more than 1 part by mass.

The PVC matrix of the present invention is mainly composed of CPVC. In general, CPVC shows better workability as the chlorine content is lower, and shows higher flame retardancy as the chlorine content is higher. From such a viewpoint, C
The chlorine content of PVC is 60% by mass or more and 70% by mass or less.

As the CPVC, general polyvinyl chloride obtained by post-chlorination treatment can be used.

In particular, flame-retardant PVC having a low processing temperature
If a composition is required, a PVC matrix 100
A mass part is a CPVC of 60 mass parts or more and 99 mass parts or less.
And 1 to 40 parts by mass of polyvinyl chloride (P
VC). As described above, by using the PVC matrix as a mixture of CPVC and PVC, mechanical properties such as elongation and impact resistance of CPVC can be improved.

As PVC, general polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-
Ethylene copolymers and the like can be used.

In the present invention, titanium oxide is used as a flame retardant. Regarding the flame-retardant action of titanium oxide, besides the conventionally known, it is considered that when the PVC matrix burns due to fire or the like, the titanium oxide does not burn and forms a film on the surface of the molded article. It has gained. It is presumed that this coating shows gas barrier properties and suppresses the generation of toxic gases such as chlorine gas and hydrogen chloride gas.

To ensure such gas barrier properties of titanium oxide, the amount of titanium oxide added must be PVC.
The amount is 1 part by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the matrix. Further, in order to suppress a decrease in mechanical properties and the like due to the addition of titanium oxide,
It is 30 parts by mass or less, and more preferably 20 parts by mass or less.

The titanium oxide includes a rutile type and an anatase type, and both types can be used in the present invention, but the rutile type is preferable because of its high gas barrier property.

The titanium oxide is preferably coated with alumina. It is considered that the titanium oxide coated with alumina acts synergistically with alumina, promotes carbonization of the PVC matrix, and exhibits a smoke reducing effect. Alumina is considered to adsorb toxic gas. Further, it is presumed that the coating made of titanium oxide becomes dense due to the cohesive action of the alumina component during combustion of the PVC matrix, and the gas barrier properties are improved.

In addition, the average particle size of the titanium oxide is 0.1 μm or more and 0.5 μm or more in order to realize a sufficient gas barrier property.
μm or less is preferred. If the average particle size is 0.1 μm or more and 0.5 μm or less, the titanium oxide powder is made of PVC.
It can be satisfactorily kneaded with the matrix, and a uniform dispersion state can be realized.

In the present invention, barium sulfate can be used in combination with titanium oxide as a flame retardant. Barium sulfate is less flame-retardant than titanium oxide,
It is a flame retardant having the following properties.

First, since the hiding power of barium sulfate is lower than that of titanium oxide, it is possible to improve the colorability of the resulting flame-retardant PVC composition by replacing part of titanium oxide with barium sulfate. it can. Second, since barium sulfate is a fine powder, it has high gas barrier properties and good dispersibility. Third, since barium sulfate is soft, the mechanical properties of the resulting flame-retardant PVC molded article can be improved.

In order to take advantage of the above-mentioned barium sulfate and suppress the flame retardancy of the obtained flame-retardant PVC composition from decreasing, the amount of barium sulfate added is set to 100 parts by mass of the PVC matrix. It is preferably at least 1 part by mass,
It is more preferably at least 2 parts by mass, preferably at most 20 parts by mass, more preferably at most 18 parts by mass.

It should be noted that barium sulfate has sedimentation properties and barite powder, and both of them can be used in the present invention. However, precipitated barium sulfate is finer and softer than barite powder,
By using the sedimentable barium sulfate, high gas barrier properties, good dispersibility, good mechanical properties, and the like can be realized.

From such a viewpoint, the average particle size of the barium sulfate used is preferably 0.03 μm or more, and 6 μm
Or less, more preferably 0.5 μm or less.

The type of the lead-based stabilizer used in the present invention is not particularly limited, but may be lead white, tribasic lead sulfate, dibasic lead sulfite, dibasic lead phosphite, dibasic phthalic acid. Lead salts such as lead, tribasic lead maleate, lead silicate and silica gel coprecipitates of lead silicate; lead soaps such as lead stearate and dibasic lead stearate can be exemplified.

These lead-based stabilizers are preferred because they have a large stabilizing effect on the PVC matrix, and in order to achieve a sufficient stabilizing effect, the amount added is preferably 1 part by mass or more based on 100 parts by mass of the PVC matrix. Further, in order to suppress the deterioration of other characteristics due to the addition of the lead-based stabilizer, the amount is preferably 30 parts by mass or less.

In addition, if necessary, a stabilizer other than lead-based
For example, metal soaps such as cadmium stearate, cadmium laurate, barium soap, and calcium soap; organotin compounds and the like are added in a range of 2 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the PVC matrix. be able to.

If necessary, a benzophenone derivative, phenyl salicylate, resorcinol ester,
UV absorbers such as benzotriazole derivatives
It can be added in a range of 0.1 part by mass or more and 2 parts by mass or less based on 100 parts by mass of the C matrix.

The type of the processing aid used in the present invention is not particularly limited, and examples thereof include (meth) acrylic resins and ethylene vinyl acetate resins.

These processing aids improve the processability of the PVC matrix.
The amount added to parts by mass is preferably 0.5 parts by mass or more. Further, in order to suppress the deterioration of other characteristics due to the addition of the processing aid, the amount is preferably 10 parts by mass or less.

The resin-based modifier used in the present invention is not particularly limited as long as it improves the impact resistance and processability of the PVC matrix. Butadiene styrene methyl methacrylate resin (also described as MBS), Chlorinated polyethylene resins, chlorinated polypropylene resins, chlorinated polystyrene resins, ABS resins and the like can be exemplified. Above all, MBS is preferable because a high improvement effect can be realized in hard PVC.

The amount of addition of these resin-based modifiers is preferably at least 1 part by mass with respect to 100 parts by mass of the PVC matrix in order to realize a sufficient modifying effect. Further, in order to suppress deterioration of other characteristics due to the addition of the resin-based modifier, the amount is preferably 10 parts by mass or less.

In the present invention, a smoke reducing agent can be used in combination. As the smoke reducer for the PVC matrix, many have been proposed so far, and these can be used. Among them, zinc compounds and molybdenum compounds are preferable.

Examples of the zinc compound include zinc borate, zinc oxide, zinc hydroxystannate, zinc stannate, and the like. These compounds promote the carbonization of PVC during combustion and reduce the amount of smoke. .

Examples of the molybdenum-based compound include molybdenum trioxide, ammonium octamolybdate, zinc molybdate and the like.

It is also possible to use a fine powdery smoke suppressant containing talc and / or calcium carbonate as a core material and containing at least one selected from the group consisting of molybdenum, zinc, phosphorus and calcium.

The PVC matrix 1 of the smoke reducing agent as described above
The amount added to 00 parts by mass is preferably at least 0.05 part by mass, more preferably at least 0.1 part by mass, for a sufficient smoke reduction effect. Further, in order to suppress deterioration of other properties due to the addition of the smoke reducing agent, the amount is preferably 3.0 parts by mass or less, more preferably 2.8 parts by mass or less.

Further, in the present invention, a plasticizer may be added. The type of plasticizer is not particularly limited,
Phthalates such as dibutyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, butyl lauryl phthalate, dilauryl phthalate, and butyl benzyl phthalate; dioctyl adipate;
Linear dibasic acid esters such as dioctyl azelate and dioctyl sebacate; phosphate esters such as tricresyl phosphate, trixylenyl phosphate, monooctyl diphenyl phosphate, monobutyl-dixylenyl phosphate, and trioctyl phosphate; Oil derivatives; Epoxidized vegetable oils; Ethylene glycol derivatives such as triethylene glycol ester, tetraethylene glycol ester, and butylphthalylbutyl glycolate; Polyester plasticizers; Chlorinated products such as paraffin chloride and butyl pentastearate; Nitrile synthesis Rubber and the like can be exemplified.

The amount of the plasticizer added as described above is generally
0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the VC matrix. In particular, in the case of hard PVC, the amount is preferably 5 parts by mass or less in order to suppress a decrease in flame retardancy due to addition of a plasticizer.

In the present invention, a general filler added to PVC, for example, calcium carbonate, calcined clay, talc, mica, silica, etc., is preferably added in an amount of 5 parts by mass based on 100 parts by mass of the PVC matrix. More than 20
It can be added in a range of not more than part by mass.

The total amount of the various fillers described above must be within a range where the chlorine content of the obtained flame-retardant PVC composition decreases and the flame retardancy does not decrease.
Specifically, the chlorine content of the finally obtained flame retardant PVC composition is preferably 35% by mass or more, more preferably 40% by mass or more.

Next, a method for producing a flame-retardant PVC composition and a molded article of the present invention, which is characterized by producing first and second masterbatches having a lubricant, will be described.

The mass ratio of the lubricant and the colorant during the preparation of the first masterbatch is carefully optimized because it affects the colorability and appearance. Specifically, with respect to 1 part by mass of the colorant, the lubricant is 0.1 parts by mass or more,
0.3 parts by mass or more is more preferable, and 2 parts by mass or less, and 1 part by mass or less is more preferable.

Also in the case of the second masterbatch, the mass ratio of the lead-based stabilizer, the lubricant and the resin-based modifier affects the appearance and is therefore carefully optimized. Specifically, the amount of the lead-based stabilizer is not less than 1 part by mass and not more than 30 parts by mass;
The lubricant is used in an amount of 0.1 part by mass or more, preferably 0.5 part by mass or more, more preferably 10 parts by mass or less and more preferably 5 parts by mass or less; and 1 to 10 parts by mass or less of a resin-based modifier. .

The production of the first and second master batches can be performed by using a powder mixer such as a Henschel mixer and a blender.

Next, a predetermined amount of the first and second masterbatches, CPVC, titanium oxide, processing aids and the like are powder-mixed using a blender, a Henschel mixer or the like (blending step). In addition, if necessary, other compounds such as PVC and a plasticizer are also mixed in this blending step. Further, the lubricant, the colorant, the lead-based stabilizer, and the resin-based modifier are added to the first and second master batches, and if necessary, may be further added alone in this compounding step. it can.

The mixture obtained as described above was mixed with a roll kneader, a Banbury mixer, a conida, a planetary roll,
It is melt-kneaded using a kneading extruder or the like (melt kneading step),
A flame retardant PVC composition can be obtained. In addition, in order to obtain a uniform flame-retardant PVC composition, the melt-kneading step is 18
It is performed at a temperature of 0 ° C or more and 220 ° C or less.

The obtained flame-retardant PVC composition can be used at the same time as the production thereof, by using a molding method such as a calendering method, an extrusion molding method or an injection molding method. Processed into molded products.

In particular, a production example of the hot-rolling process by the calender method will be described. That is, the prepared flame retardant P
The VC composition is continuously supplied to a milling roll, and subsequently,
It is continuously supplied to a heating roll. Thereafter, the sheet is processed into a sheet shape by an inverted L-type calender roll, and cut into a desired size via a cooling roll and a take-up roll.

The original sheet (flame-retardant PVC molded product) obtained as described above is sandwiched and supported by a decorative plate which has been subjected to a mirror surface treatment or the like, and is pressed at a temperature of 160 ° C. or more and 190 ° C. or less by a load of about 70 MN. (Pressing process). As a result, a flame-retardant PVC molded article having a desired surface condition is manufactured. In addition, if necessary, a functional film such as antibacterial, electrification, matting, and scratch resistance may be laminated in the pressing step.

The flame retardancy of the flame-retardant PVC molded article produced as described above can be evaluated using a cone calorimeter according to ASTM E1354. The flame-retardant properties evaluated by a combustion test using a cone calorimeter include the maximum value of the calorific value due to combustion per unit area and unit time (also described as the maximum calorific value, PHRR;
Unit: kW / m ² ), average value of calorific value by combustion per unit area and unit time (average calorific value, also described as AHRR; unit: kW / m ² ), total calorific value by combustion (total calorific value, Also described as THR; unit: MJ /
m ² ), average value of mass reduction rate due to combustion per unit area and unit time (mass reduction rate, also referred to as AMLR; unit: g / sec · m ² ), dimming due to combustion per unit area and unit time The maximum value of the volume (maximum dimming volume, also described as PSEA; unit: m ² / g), the average value of the dimming volume due to combustion per unit area and unit time (average dimming volume, also described as ASEA; unit) : M ² /
g) and the like.

Conventionally, one of the indicators of flame retardancy is an industrial mutual insurance organization (Factory Mutual Sys.).
tem) has been effectively used.

This evaluation criterion is as follows: Class Number
r 4910, the flame retardancy test of clean room materials (FMRC, Clean Room M)
materials Flammability Tes
t Protocol), and a fire spread index FPI indicating flame retardancy, a smoke index SDI indicating smoke generation, a corrosion index CDI indicating corrosive gas generation, and the like are used as indices (also described as FM standards).

In the present invention, a value evaluated by a combustion test using a cone calorimeter was used as an index of flame retardancy instead of the FM standard. The FM standard is a standard obtained by submitting test specimens to the mutual insurance organization and evaluated by the mutual insurance organization. Therefore, it takes time to obtain the evaluation result and is inefficient. A combustion test using a cone calorimeter is efficient because it can be performed by the inventors.

In particular, FPI has a strong correlation with indices related to the calorific value such as PHRR, AHRR, and THR measured by a cone calorimeter. SDI also
It has a strong correlation with indices related to the dim volume such as PSEA and ASEA. Furthermore, CDI has a strong correlation with an index relating to mass loss such as AMLR.

Therefore, an approximate value of the FM standard can be efficiently obtained by evaluating the flame retardancy using a cone calorimeter.

In the FM standard, if the FPI is 6 or less,
The DI is required to be 0.4 or less and the CDI is required to be 1.1 or less.
PHRR is 130kW / m ² or less, AHRR is 82kW
/ M ² or less, THR is 100MJ / m ² or less, AMLR is 13g / sec · m ² or less, PSEA is 1500m ² / g
Hereinafter, it is preferable that ASEA is 1000 m ² / g or less.

The coloring property and the like in the present invention are evaluated by visually observing the surface of the manufactured flame-retardant PVC molded article and observing it with an optical microscope. That is, the flame-retardant PV
The degree to which the molded product is colored to the required degree depends on the flame-retardant P
It can be confirmed by comparing the VC molded product with a color sample. The surface of the flame-retardant PVC molded product has a diameter of 100 μm.
The case where there is no such thing is regarded as no thing. Further, the case where the surface of the flame-retardant PVC molded article is uniformly colored is regarded as having no color unevenness.

The flame-retardant PVC molded article provided by the present invention also has excellent mechanical properties such as tensile strength, elongation and Izod impact strength. Specifically, the tensile strength measured according to JIS K 6745 is 45 N / mm ² or more,
An elongation measured according to K 6745 of at least 40%,
The Izod impact strength (notched) measured according to JIS K 6745 can be 5 kJ / m ² or more.

The flame-retardant PVC molded article of the present invention has excellent flame retardancy, has a small amount of smoke, is excellent in coloring properties, and has substantially no spots and color unevenness.

Further, it has excellent mechanical properties.

Accordingly, molded articles made of the rigid PVC composition are particularly suitable for interior and exterior materials of transport aircraft such as aircraft, ships, and vehicles; interior and exterior materials of buildings; household articles such as furniture and office tools; It can be suitably used as a housing material of a semiconductor device.

[0096]

The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention in any way. Unless otherwise specified below, commercially available high-purity reagents were used.

(Evaluation Method) (a) Evaluation of Flame Retardancy: Using a cone calorimeter manufactured by Atlas Co., Ltd., according to ASTME 1354, PHRR (kW
/ M ² ), AHRR (kW / m ² ), THR (MJ /
m ² ), AMLR (g / sec · m ² ), PSEA (m ²
/ G) and ASEA (m ² / g).

(A) Evaluation of coloring property: The surface of the flame-retardant PVC molded article was evaluated by visual observation and observation with an optical microscope. Whether the flame-retardant PVC molded article was colored to a necessary degree by the colorant was confirmed by comparing the flame-retardant PVC molded article with a color sample. In addition, flame-retardant PV
When there were no lumps having a diameter of 100 μm or more on the surface of the C molded product, no lumps were determined. Further, when the surface of the flame-retardant PVC molded product was uniformly colored, it was determined that there was no color unevenness.

(C) Evaluation of mechanical properties: JIS K6
745, tensile strength (N / mm ² ), elongation (%), Izod impact strength (with notch) (kJ / m
² ) was measured.

(Example 1) Flame retardant PVC composition 1 and flame retardant PVC molded article 1 0.019 parts by mass of black pigment P4710 (manufactured by Dainichi Seika) and yellow pigment P4490 (Dainichi Seika) 1.79)
3 parts by mass and orange pigment P4377 (manufactured by Dainichi Seika)
0.028 parts by mass and DSL as a lubricant (manufactured by Sakai Chemical Co., Ltd.)
One part by mass was mixed with a Hensiel mixer to prepare a first master batch.

Next, 12 parts by mass of tribasic lead sulfate (TL5000, manufactured by Sakai Chemical Co., Ltd.) as a lead stabilizer, 1 part by mass of DSL (manufactured by Sakai Chemical Co., Ltd.) as a lubricant, and MBS ( 5 parts by mass of Kureha BTA3NS) were mixed with a Henschel mixer to prepare a second master batch.

Thereafter, CPVC having a chlorine content of 65% by mass (H-527 manufactured by Kanegafuchi Chemical Co., Ltd.) was used as a PVC matrix.
100 parts by mass, 12 parts by mass of titanium oxide (RK-1 manufactured by Sakai Chemical Co., Ltd.) as a flame retardant, and 2.84 of the first master batch
Parts by mass, 18 parts by mass of the second master batch, 1 part by mass of MMA resin (P551A manufactured by Mitsubishi Rayon Co., Ltd.) as a processing aid, and 0.5 parts by mass of calcium stearate (SC-100 manufactured by Sakai Chemical Co.) as a lubricant. 0.5 parts by mass of stearyl stearate (G-32 manufactured by Henkel) as a lubricant, and a fatty acid ester (G-70 manufactured by Henkel) as a lubricant.
S) 0.3 parts by mass were mixed with a Henschel mixer.

The obtained mixture was mixed with a kneading roll for 190 minutes.
The mixture was melted and kneaded at ℃ to produce a flame-retardant PVC composition 1.
Furthermore, a sheet-shaped flame-retardant PVC molded article 1 having a thickness of 0.5 mm was produced by a calendering method using an inverted L-shaped calender roll at 210 ° C.

The obtained flame-retardant PVC molded article 1 had an ivory color equivalent to that of a color sample, and no bumps and uneven color were observed.

Further, the flame retardant properties are such that PHRR is 21%.
kW / m ^2, AHRR there is 17kW / m ^2, THR 45M
J / m ² , AMLR 5.6 g / sec · m ² , PSEA
Was 150 m ² / g and ASEA was 112 m ² / g.

Further, as for the mechanical properties, the tensile strength is 6
1N / mm ² , elongation 50%, Izod impact strength 8
kJ / m ² .

(Comparative Example 1) Flame-retardant PVC composition 2 and flame-retardant PVC molded article 2 CP having a chlorine content of 65% by mass as a PVC matrix
100 parts by mass of VC (H-527 manufactured by Kanegafuchi Chemical Co., Ltd.), 12 parts by mass of titanium oxide (RK-1 manufactured by Sakai Chemical Co., Ltd.) as a flame retardant, and MMA resin (P5 manufactured by Mitsubishi Rayon Co., Ltd.) as a processing aid.
51A) 1 part by mass, 0.019 parts by mass of black pigment P4710 (manufactured by Dainichi Seika), 1.793 parts by mass of yellow pigment P4490 (manufactured by Dainichi Seika), and orange pigment P437
7 (manufactured by Dainichi Seika) 0.028 parts by mass and D as a lubricant
2 parts by mass of SL (manufactured by Sakai Chemical Co., Ltd.), 12 parts by mass of tribasic lead sulfate (TL5000, manufactured by Sakai Chemical Co., Ltd.) as a lead-based stabilizer,
MBS (BTA3NS manufactured by Kureha) as a resin-based modifier
5 parts by mass, 0.5 parts by mass of calcium stearate (SC-100, manufactured by Sakai Chemical Co.) as a lubricant, 0.5 parts by mass of stearyl stearate (G-32, manufactured by Henkel) as a lubricant, and a fatty acid ester ( Henkel G-
70S) and 0.3 parts by mass were mixed at once with a Henschel mixer.

The obtained mixture was mixed with a kneading roll for 190 minutes.
The mixture was melted and kneaded at ℃ to produce a flame-retardant PVC composition 2.
Further, a sheet-shaped flame-retardant PVC molded article 2 having a thickness of 0.5 mm was produced by a calendering method using an inverted L-shaped calender roll at 210 ° C.

The obtained flame-retardant PVC molded product 2 had a light ivory color as compared with the color sample, and irregularities and color unevenness were confirmed.

Further, both the flame-retardant properties and the mechanical properties were lower than those of the flame-retardant PVC molded article 1.

(Example 2) Flame retardant PVC composition 3 and flame retardant PVC molded article 3 9 parts by mass of titanium oxide (RK-1 manufactured by Sakai Chemical Co.) and barium sulfate (B manufactured by Sakai Chemical Co., Ltd.) -30) Except for using 3 parts by mass, the flame-retardant PVC composition 3 and the flame-retardant PVC molded article 3 were prepared in the same manner as in the case of the flame-retardant PVC composition 1 and the flame-retardant PVC molded article 1. Manufactured.

The obtained flame-retardant PVC molded article 3 had an ivory color equivalent to that of a color sample, and no bumps and color unevenness were observed.

Further, both the flame-retardant properties and the mechanical properties were as good as those of the flame-retardant PVC molded article 1.

[0114]

As is apparent from the above description, at least a colorant and a lubricant are mixed in advance in a predetermined mass ratio to form a first masterbatch, and a part of a predetermined other filler and a predetermined amount of a lubricant are mixed. A second masterbatch is preliminarily mixed at a mass ratio, and these masterbatches, a PVC matrix, and a predetermined compound such as titanium oxide are mixed at a predetermined mass ratio to obtain a chlorine content of 60% by mass or more and 70% by mass.
100 parts by mass of a polyvinyl chloride (PVC) matrix comprising the following post-chlorinated polyvinyl chloride (CPVC):
1 part by weight or more and 30 parts by weight or less of a flame retardant composed of titanium oxide, 0.01 part by weight or more and 5 parts by weight or less of a colorant;
Flame retardant PVC comprising not less than 10 parts by mass and not more than 10 parts by mass
By using the composition, despite the presence of a large amount of titanium oxide, it is well colored by a small amount of a coloring agent, and has a high-quality appearance substantially free of bumps and color unevenness. A flame-retardant PVC molded article having good mechanical properties can be produced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08K 3/26 C08K 3/26 3/30 3/30 3/32 3/32 3/34 3/34 5 / 06 5/06 5/09 5/09 5/098 5/098 5/101 5/101 // (C08L 27/24 (C08L 27/24 91:00) 91:00) (C08L 27/24 (C08L 27/24 27:06) 27:06) (C08L 27/24 (C08L 27/24 33:00 33:00 23:08) 23:08) (C08L 27/24 (C08L 27/24 51:04 51: 04 23:28) 23:28) F-term (Reference) 4F070 AA20 AB11 AC15 AC16 AC20 AC22 AC40 AC42 AC73 AC76 AC83 AC94 AE03 AE07 AE09 AE30 FA01 FA17 FB03 FB06 FC05 4F071 AA12X AA22X AA24 AA31X AA77 AB18 AB18 AB24 AF34 AF47 AH19 BA01 BB04 BB05 BB06 BB13 BC01 BC07 4J002 AE033 AE053 BB074 BB245 BD032 BD181 BG004 BN165 DE136 DE258 DG048 DG056 EG108 FD038 FD097 FD136 FD203 FD204 FD20 Five

Claims (9)

[Claims] 1. A flame retardant composed of 100 parts by mass of a polyvinyl chloride (PVC) matrix mainly composed of a post-chlorinated polyvinyl chloride (CPVC) and a titanium oxide having a chlorine content of 60% by mass or more and 70% by mass or less. A flame-retardant vinyl chloride resin composition comprising at least 30 parts by mass and at most 30 parts by mass, at least 0.01 part by mass and at most 5 parts by mass of a coloring agent, and at least 1 part by mass and at most 10 parts by mass of a lubricant. 2. The flame-retardant vinyl chloride resin composition according to claim 1, wherein the colorant is an inorganic pigment. 3. The flame retardant according to claim 1, wherein the colorant is at least one pigment selected from the group consisting of a yellow pigment, a black pigment, and an orange pigment. Vinyl chloride resin composition. 4. The flame-retardant vinyl chloride resin composition according to claim 1, comprising 1 to 20 parts by mass of a flame retardant made of barium sulfate. 5. 100 parts by weight of the polyvinyl chloride (PVC) matrix is a post-chlorinated polyvinyl chloride (CPV).
C) The flame-retardant chloride according to any one of claims 1 to 4, comprising 60 parts by mass to 99 parts by mass and 1 part by mass to 40 parts by mass of polyvinyl chloride (PVC). Vinyl resin composition. 6. A composition comprising 1 to 30 parts by mass of a lead stabilizer, 0.5 to 10 parts by mass of a processing aid, and 1 to 10 parts by mass of a resin modifier. The flame-retardant vinyl chloride resin composition according to any one of claims 1 to 5, wherein 7. The maximum heating value (PHRR), the total heating value (THR) and the average extinction volume (ASEA) measured according to ASTM E1354 are each 130 kW / m.
The flame-retardant vinyl chloride resin composition according to any one of claims 1 to 6, wherein the composition is ² or less, 100 MJ / m ² or less, and 1000 m ² / g or less. 8. A flame-retardant vinyl chloride resin molded article produced from the flame-retardant vinyl chloride resin composition according to any one of claims 1 to 7, which is substantially free from spots and color unevenness. . 9. (a) at least 1 part by mass of a colorant;
A step of preparing a first master batch by mixing 0.1 part by mass or more and 2 parts by mass or less of a lubricant; (b) at least 1 part by mass or more and 30 parts by mass or less of a lead-based stabilizer and 0.1 part by mass of a lubricant To prepare a second masterbatch by mixing at least 10 parts by mass and at most 10 parts by mass of the resin-based modifier with at least 10 parts by mass of the resin-based modifier, and (c) at least a chlorine content of 60% by mass.
Not less than 70% by mass of post-chlorinated polyvinyl chloride (CPV)
C) 100 parts by mass of a polyvinyl chloride (PVC) matrix which is mainly composed of 1 part by mass or more and 30 parts by mass or less of a flame retardant composed of titanium oxide;
A step of preparing a mixture by mixing powders of not less than 5 parts by mass, not more than 5 parts by mass, not less than 2 parts by mass and not more than 50 parts by mass of the second master batch, and not less than 0.5 parts by mass and not more than 10 parts by mass of a processing aid; (D) a step of melt-kneading the mixture; and a method of producing a flame-retardant vinyl chloride resin composition.