JP3990531B2 - Flame retardant vinyl chloride resin laminate and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a member in which a layer made of a flame retardant polyvinyl chloride resin (also referred to as PVC) is laminated.
[0002]
[Prior art]
Since PVC contains chlorine in the molecule, it is excellent in flame retardancy. Moreover, 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, it is possible to color with a high degree of freedom by using many kinds of pigments.
[0003]
Since PVC has the characteristics as described above, particularly rigid PVC laminates are used for interior / exterior materials for transport aircraft such as aircraft, ships, vehicles, etc .; interior / exterior materials for buildings; daily goods such as furniture and office equipment; Housing materials for equipment, electronic equipment, etc .; have been used as parts of semiconductor devices.
[0004]
For example, in Japanese Utility Model Publication No. 3-1250, a post-chlorinated polyvinyl chloride (also referred to as CPVC) plate is used as a core material as a member for producing a chemical solution tank, and a hard PVC plate is heated on one or both sides. A welded PVC laminate has been disclosed.
[0005]
In addition, in Utility Model Registration No. 2596796, a middle layer having a chlorination rate of 62 to 65% and an average degree of polymerization before chlorination of 500 to 800, a chlorination rate of 58 to 62%, and before chlorination. A PVC laminate comprising a surface layer having an average degree of polymerization of 800 to 1000 has been disclosed.
[0006]
However, when PVC is exposed to a temperature higher than the heat-resistant temperature due to a fire or the like, a large amount of smoke is generated due to chlorine in the molecule, and a toxic gas such as chlorine gas or hydrogen chloride gas is generated.
[0007]
For this reason, it is possible to produce a flame retardant PVC composition in which the generation of toxic gas is suppressed by examining the type and blending amount of the filler, and to produce a flame retardant PVC laminate using this. Has been tried.
[0008]
[Problems to be solved by the invention]
For example, JP 2000-80230 A discloses a molded body in which a surface layer is laminated and integrated on at least one surface of a base layer, and the base layer is based on 100 parts by weight of a vinyl chloride resin having a chlorination degree of 58 to 73%. The surface layer is a layer containing titanium oxide in the range of 4 to 30 parts by weight, and the surface layer has 0 to 20 titanium oxide with respect to 100 parts by weight of vinyl chloride resin having a chlorination degree of 50 to 57%. A flame-retardant vinyl chloride resin molded body, which is a layer contained within the range of parts by weight, has been proposed.
[0009]
That is, the publication discloses that the use of titanium oxide as a flame retardant effectively increases the flame retardancy of PVC. For the reason, when titanium oxide is present in the combustion process of PVC, Titanium oxide does not decompose to a high temperature of 1200 to 1300 ° C., but acts to block heat from the outside due to its high whiteness, and at the stage of thermal decomposition and combustion of PVC after detachment of chlorine, PVC is made faster. It is presumed that flame retardancy is improved because it functions to carbonize.
[0010]
However, as described in the publication, since titanium oxide is a filler with high whiteness, a flame-retardant vinyl chloride resin laminate (also referred to as a flame-retardant PVC laminate) is colored in a favorite color. In some cases, a large amount of pigment is required. In particular, when an organic material is used as the pigment, the organic pigment easily burns, so that it may be difficult to obtain a flame retardant PVC laminate that simultaneously satisfies each standard of the FM standard.
[0011]
Therefore, in order to obtain a flame retardant PVC laminate that satisfies the FM standard with a favorite color, it is necessary to blend more titanium oxide and pigment, and the strength and chemical resistance of the laminate can be improved by blending a large amount of titanium oxide. In some cases, it caused a drop.
[0012]
In view of such a situation, in the gazette, by containing titanium oxide at a specific ratio in PVC having a specific range of chlorine content, not only satisfies the FM standard, but also has sufficient strength, chemical resistance, It is said that a flame-retardant PVC laminate having both bending deformability and the like and easy to be colored in a desired color can be obtained.
[0013]
However, in this publication, no examples relating to flame retardant PVC laminates colored with pigments are described, and as described in the publication, 100 parts by mass of PVC having a chlorine content of 58 to 73%. A flame-retardant vinyl chloride resin molded product (also referred to as a flame-retardant PVC molded product) such as a sheet is produced by simply mixing 4 to 30 parts by mass of titanium oxide, and a flame-retardant PVC laminate is produced using this. In some cases, the colorability and appearance of the flame retardant PVC laminate obtained may be insufficient.
[0014]
That is, even if the method described in the publication is adopted, titanium oxide has a high hiding power, and therefore when the amount necessary for realizing sufficient flame retardancy is used, the obtained flame retardant PVC laminate is obtained. In some cases, it was still difficult to color freely.
[0015]
In particular, flame retardant PVC laminates used in semiconductor device components and the like may be required to be colored in dark colors such as red and blue, and good colorability has been desired. It was.
[0016]
In addition, flame retardant PVC laminates used in transport aircraft interior and exterior materials, building interior and exterior materials, daily goods, housing materials and the like are generally colored light colors such as ivory and light gray. When titanium oxide is used as a flame retardant, coloring may be difficult even in these light colors.
[0017]
Furthermore, when an amount of titanium oxide necessary for realizing sufficient flame retardancy is used, it is necessary to add a large amount of colorant in order to color the obtained flame retardant PVC laminate.
[0018]
For this reason, in a flame-retardant vinyl chloride resin composition (also referred to as a flame-retardant PVC composition), titanium oxide, a colorant, and the like may cause poor dispersion. As a result, unevenness and color unevenness occurred in the obtained flame-retardant PVC laminate, and an appearance defect sometimes occurred.
[0019]
In particular, when mechanical properties and processability are reduced due to the addition of a sufficient amount of titanium oxide, fillers such as resin modifiers and processing aids are further added. Since the viscosity is high, poor dispersion of the colorant may be promoted.
[0020]
In addition, even when fillers such as a resin-based modifier and a processing aid are added, the mechanical properties of the obtained flame-retardant PVC laminate may be insufficient.
[0021]
In view of the situation as described above, in the present invention, sufficient flame retardancy and good colorability are realized, it has a high-quality appearance that is substantially free from irregularities and color unevenness, and also has mechanical characteristics. It aims at providing the outstanding flame-retardant PVC laminated body.
[0022]
According to the present invention for achieving the above object, at least a first layer comprising a first polyvinyl chloride (PVC) matrix and a second layer comprising a second polyvinyl chloride (PVC) matrix; In the flame-retardant vinyl chloride resin laminate comprising the first layer, the first layer comprises 100 parts by mass of a first polyvinyl chloride (PVC) matrix, 1 to 30 parts by mass of a flame retardant containing titanium oxide, and 0 colorant. There is provided a flame retardant vinyl chloride resin laminate comprising 0.01 mass part or more and 5 mass parts or less and a lubricant 0.05 mass part or more and 10 mass parts or less.
In accordance with the present invention, a flame retardant vinyl chloride comprising at least a first layer comprising a first polyvinyl chloride (PVC) matrix and a second layer comprising a second polyvinyl chloride (PVC) matrix. In the resin laminate,
The first layer as the surface layer is a polyvinyl chloride resin selected from vinyl chloride homopolymer, vinyl chloride-vinyl acetate copolymer or vinyl chloride-ethylene copolymer, or has a chlorine content of 60% by mass or more 62% or less rear Chlorination Poly Vinyl chloride (CPVC) Or 100 parts by mass of a first (PVC) matrix made of the composition, 5 to 30 parts by mass of a flame retardant containing titanium oxide, 0.01 to 5 parts by mass of a colorant, and 0 lubricant. .05 parts by mass or more and 10 parts by mass or less
The second layer as the base layer contains 100 parts by mass of a second (PVC) matrix made of a polyvinyl chloride resin having a high chlorine content of 60% by mass or more and 70% by mass or less, and titanium oxide. It comprises 5 parts by weight or more and 30 parts by weight or less of a flame retardant, 0.01 parts by weight or more and 5 parts by weight or less of a colorant, and 0.05 parts by weight or more and 10 parts by weight or less of a lubricant. A flame retardant vinyl chloride resin laminate is provided in which two layers are added by mixing at least a colorant and a lubricant.
[0023]
In the present invention, the second layer is composed of 100 parts by mass of a second polyvinyl chloride (PVC) matrix, 1 part by mass or more and 30 parts by mass or less of a flame retardant containing titanium oxide, and 0.01 part by mass or more of a colorant. A flame-retardant vinyl chloride resin laminate comprising 5 parts by mass or less and a lubricant 0.05 parts by mass or more and 10 parts by mass or less can also be provided.
[0024]
In addition, according to the present invention, the flame retardancy comprising at least a first layer comprising a first polyvinyl chloride (PVC) matrix and a second layer comprising a second polyvinyl chloride (PVC) matrix. A method for producing a vinyl chloride resin laminate, wherein (a) at least 1 part by weight of a colorant and 0.01 parts by weight or more and 2 parts by weight or less of a lubricant are mixed to produce a first masterbatch; (B) At least 1 part by mass to 30 parts by mass of a lead stabilizer, 0.01 part by mass to 10 parts by mass of a lubricant, and 1 part by mass to 10 parts by mass of a resin modifier are mixed. A step of producing a second masterbatch, (c) at least 100 parts by mass of a first or second polyvinyl chloride (PVC) matrix, 1 part by mass to 30 parts by mass of a flame retardant comprising titanium oxide, 1 master bag Powder mixture of 0.01 parts by mass to 5 parts by mass, the second masterbatch 2 parts by mass to 50 parts by mass, and processing aid 0.5 parts by mass to 10 parts by mass to produce a mixture And (e) a step of producing a composition by melt-kneading the mixture, and (e) a step of producing at least one of the first layer and the second layer using the composition. A process for producing a flame retardant vinyl chloride resin laminate is provided.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described.
[0026]
In the present invention, the PVC matrix, titanium oxide, colorant, etc. are not mixed together, but at least the colorant and lubricant are premixed at a predetermined mass ratio to form a first master batch, and other predetermined fillings are made. Part of the agent and lubricant are premixed at a predetermined mass ratio to form a second master batch, and these master batch, PVC matrix and predetermined compound such as titanium oxide are mixed at a predetermined mass ratio and melted. A flame retardant PVC composition is prepared by kneading.
[0027]
And the obtained flame-retardant PVC composition is processed into a flame-retardant PVC molded product having a desired shape, and this is laminated as a first layer and / or a second layer, and a flame-retardant PVC laminate is obtained. To manufacture.
[0028]
As a result, despite the presence of a large amount of titanium oxide, good colorability can be realized with a small amount of colorant, and a high-quality appearance that is substantially free of unevenness and color unevenness can be realized.
[0029]
Also, in addition to titanium oxide, even when high viscosity fillers such as resin modifiers and processing aids are added, good colorability is achieved, and there is substantially no unevenness and color unevenness. A quality appearance can be achieved.
[0030]
Although the above reason is not clear, it is presumed that the lubricant functions as a dispersant for the colorant by previously mixing the colorant and the lubricant in a predetermined mass ratio.
[0031]
In addition, it is presumed that the lubricant functions as a dispersant for the filler by previously mixing other filler and lubricant in a predetermined mass ratio.
[0032]
Furthermore, it is inferred that various fillers are uniformly dispersed in the PVC matrix by adopting a mixing method in which a master batch is prepared in advance. As a result, sufficient mechanical properties are realized.
[0033]
The type of lubricant used in the present invention is not limited as long as it can function as a dispersant for colorants and fillers, but for reasons such as high dispersibility, higher fatty acids such as stearic acid and palmitic acid. Higher fatty acid esters such as stearic acid ester and palmitic acid ester; higher fatty acid ethers such as stearic acid ether and palmitic acid ether; natural waxes such as carnauba wax and candelilla wax; methylene bisstearamide and ethylene bisstear Synthetic waxes such as rhoamide; liquid paraffins such as paraffin wax and white mineral oil can be used.
[0034]
Among these, dibasic lead stearate (also referred to as DSL) is preferable.
[0035]
Regarding the addition amount of the lubricant, when the PVC matrix is mainly made of PVC, in addition to the dispersion effect, in order to improve the melt fluidity of the PVC and suppress the sticking to the mold, to achieve a sufficient lubricant effect, It is 0.05 mass part or more with respect to 100 mass parts of matrices, and 0.1 mass part or more is more preferable. Moreover, in order to suppress that other characteristics deteriorate by addition of a lubricant, it is 10 mass parts or less, and 8 mass parts or less are more preferable.
[0036]
In addition, when the PVC matrix is mainly made of CPVC, in addition to the dispersion effect, in order to improve the melt flowability of PVC, suppress the adhesion to the mold, and realize a sufficient lubricant effect, 100 parts by mass of the PVC matrix is added. On the other hand, it is 1 mass part or more, and 2 mass parts or more is more preferable. Moreover, in order to suppress that other characteristics deteriorate by addition of a lubricant, it is 10 mass parts or less, and 8 mass parts or less are more preferable.
[0037]
The type of the colorant used in the present invention is not particularly limited as long as it has good dispersibility, but is preferably an inorganic pigment because it has high heat resistance and is difficult to discolor and discolor during processing. .
[0038]
And among inorganic pigments, BON Red, Red Lake C, Lithol Rubines Bordeaux R, Cadmium Selenide, Cadmium Lithone, Pigment Scallet, Red Lead, Modden Red, Candum Red Orange pigments such as Orange, Litharge, etc .; Yellow pigments such as Cadmium Yellow, Chrome Yellow, Strontium Chromate, Benzidin Yellow, Titanium Yellow, Zinc Chromate, etc .; Phthalocyanine Green, green pigments such as een, Emerald Green, Guignet's Green; blue pigments such as Phthalocyanine Blue, Indanthrene Blue, Ultramarine Blue, Iron Blue, Cobalt Blue; Black pigments; aluminum; aluminum bronze powder; fish scales; Vermilion and the like are preferable.
[0039]
In addition, an inorganic pigment may be inferior in dispersibility compared with an organic pigment. However, in the present invention, since the colorant and the lubricant are mixed in advance at a predetermined mass ratio to form the first master batch, even when an inorganic pigment is used, poor dispersion is suppressed and good colorability is achieved. Is realized.
[0040]
As a result, sufficient coloring can be performed with a small amount of colorant, and since the colorant is generally expensive, the production cost can also be reduced.
[0041]
The specific amount of the colorant added is 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and 5 parts by mass or less is sufficient with respect to 100 parts by mass of the PVC matrix. Or less.
[0042]
By using the colorant as described above, it is possible to produce a dark flame retardant PVC laminate such as red and blue that can be used in parts of a semiconductor device.
[0043]
It is also possible to produce light-color flame retardant PVC laminates such as ivory and light gray that can be used in transport aircraft interior and exterior materials, building interior and exterior materials, daily goods, housing materials, and the like.
[0044]
In particular, an ivory flame retardant PVC laminate can be produced by using at least one pigment selected from the group consisting of yellow pigments, black pigments and orange pigments.
[0045]
In this case, the addition amount of yellow pigment to 100 parts by mass of PVC matrix is preferably 0.1 parts by mass or more and 4.5 parts by mass or less, and the addition amount of black pigment to 100 parts by mass of PVC matrix is 0.01 parts by mass or more. 1 part by mass or less is preferable, and the addition amount of the orange pigment to 100 parts by mass of the PVC matrix is preferably 0.01 part by mass or more and 1 part by mass or less.
[0046]
The PVC matrix in the present invention is preferably mainly composed of CPVC when particularly high flame retardancy is required. In general, CPVC exhibits better processability as the chlorine content decreases, and exhibits higher flame retardancy as the chlorine content increases. From such a viewpoint, the chlorine content of CPVC is preferably 60% by mass or more and 70% by mass or less.
[0047]
In addition, as CPVC, what carried out the post-chlorination process of the general polyvinyl chloride can be used.
[0048]
The PVC matrix in the present invention is preferably mainly composed of PVC when particularly high mechanical properties and low processing temperature are required. Since PVC is superior in mechanical properties and processability compared to CPVC, the obtained flame-retardant PVC composition is also excellent in processability, and the flame-retardant PVC laminate is excellent in mechanical properties. As the PVC having such characteristics, general polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, and the like can be used.
[0049]
In addition, in order to balance flame retardancy, mechanical properties, workability, etc., 100 parts by mass of the PVC matrix is composed of 60 parts by mass to 99 parts by mass of CPVC, and 1 part by mass to 40 parts by mass of PVC. It may be composed of Thus, by making the PVC matrix a mixture of CPVC and PVC, mechanical properties such as elongation and impact resistance of CPVC can be improved.
[0050]
Similarly, 100 parts by mass of the PVC matrix may be composed of 60 to 99 parts by mass of PVC and 1 to 40 parts by mass of CPVC. Thus, the flame retardance of PVC can be further improved by making the PVC matrix a mixture of PVC and CPVC.
[0051]
In the present invention, titanium oxide is used as a flame retardant. As a flame retardant action of titanium oxide, in addition to the conventional knowledge, when the PVC matrix burns for reasons such as a fire, titanium oxide does not burn, but the knowledge that a film is formed on the surface of the molded product It has gained. It is assumed that this coating exhibits gas barrier properties and suppresses generation of toxic gases such as chlorine gas and hydrogen chloride gas.
[0052]
In order to ensure such a gas barrier property of titanium oxide, the amount of titanium oxide added is 1 part by mass or more with respect to 100 parts by mass of the PVC matrix, and more preferably 5 parts by mass or more. Moreover, in order to suppress the fall of the mechanical characteristics etc. resulting from addition of titanium oxide, it is 30 mass parts or less, and 20 mass parts or less are more preferable.
[0053]
Titanium oxide includes a rutile type and an anatase type, and both of them can be used in the present invention, but the rutile type is preferred for reasons such as high gas barrier properties.
[0054]
Moreover, as titanium oxide, what was coat | covered with the alumina is preferable. Titanium oxide coated with alumina is considered to act synergistically with alumina, promote carbonization of the PVC matrix, and develop a smoke reduction effect. Alumina is thought to adsorb toxic gases. Furthermore, when the PVC matrix is burned, it is surmised that the coating made of titanium oxide becomes dense due to the aggregating action of the alumina component, and the gas barrier property is improved.
[0055]
In addition, the average particle diameter of titanium oxide is preferably 0.1 μm or more and 0.5 μm or less in order to realize sufficient gas barrier properties. If the average particle size is 0.1 μm or more and 0.5 μm or less, the titanium oxide powder can be well kneaded with the PVC matrix, and a uniform dispersion state can be realized.
[0056]
In the present invention, barium sulfate can be used in combination with titanium oxide as a flame retardant. Barium sulfate is a flame retardant having the following characteristics although it is inferior in flame retardant effect to titanium oxide.
[0057]
First, since the hiding power of barium sulfate is lower than that of titanium oxide, the colorability of the resulting flame-retardant PVC laminate can be improved by replacing part of the titanium oxide with barium sulfate. Secondly, since barium sulfate is a fine powder, it has high gas barrier properties and good dispersibility. Thirdly, since barium sulfate is soft, the mechanical properties of the resulting flame retardant PVC laminate can be improved.
[0058]
In order to prevent the flame retardancy of the obtained flame retardant PVC laminate from being lowered by taking advantage of the above barium sulfate, when the PVC matrix is mainly made of PVC, the addition amount of barium sulfate is: 1 mass part or more is preferable with respect to 100 mass parts, 5 mass parts or more are more preferable, 20 mass parts or less are preferable, and 18 mass parts or less are more preferable.
[0059]
When the PVC matrix is mainly composed of CPVC, the addition amount of barium sulfate is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 20 parts by mass or less, with respect to 100 parts by mass of the PVC matrix. 18 parts by mass or less is more preferable.
[0060]
Barium sulfate has sedimentation and barite powder, and both of them can be used in the present invention. However, since precipitated barium sulfate is finer and softer than barite powder, the use of precipitated barium sulfate achieves high gas barrier properties, good dispersibility, good mechanical properties, etc. be able to.
[0061]
From such a viewpoint, the average particle diameter of the barium sulfate used is preferably 0.03 μm or more, preferably 6 μm or less, and more preferably 0.5 μm or less.
[0062]
The type of lead-based stabilizer used in the present invention is not particularly limited, but lead white, tribasic lead sulfate, dibasic lead sulfite, dibasic lead phosphite, dibasic lead phthalate, three Examples include lead salts such as basic maleate, lead silicate, and silica gel coprecipitates of lead silicate; lead soaps such as normal lead stearate and dibasic lead stearate.
[0063]
These lead-based stabilizers are preferable because they have a large stabilizing effect on the PVC matrix, and in order to realize a sufficient stabilizing effect, the amount added to 100 parts by weight of the PVC matrix is preferably 1 part by weight or more. Moreover, in order to suppress that another characteristic deteriorates by addition of a lead-type stabilizer, 30 mass parts or less are preferable.
[0064]
If necessary, stabilizers other than lead-based, for example, metal soaps such as cadmium stearate, cadmium laurate, barium soap, calcium soap, etc .; organotin compound, etc. with respect to 100 parts by mass of the PVC matrix It can be added in the range of 2 parts by mass or more and 20 parts by mass or less.
[0065]
Further, if necessary, ultraviolet absorbers such as benzophenone derivatives, phenyl salicylates, resorcinol esters, benzotriazole derivatives, etc., in a range of 0.1 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the PVC matrix. Can be added.
[0066]
Although the kind in particular of processing aid used in this invention is not restrict | limited, (meth) acrylic-type resin, ethylene vinyl acetate type-resin, etc. can be illustrated.
[0067]
These processing aids improve the processability of the PVC matrix, and the amount added to 100 parts by mass of the PVC matrix is preferably 0.5 parts by mass or more. Moreover, in order to suppress that other characteristics deteriorate by addition of a processing aid, 10 mass parts or less are preferable.
[0068]
The resin modifier used in the present invention is not particularly limited as long as it improves the impact resistance and workability of the PVC matrix, but butadiene styrene methyl methacrylate resin (also referred to as MBS), chlorinated polyethylene. Resins, chlorinated polypropylene resins, chlorinated polystyrene resins, ABS resins and the like can be exemplified. Among them, MBS is preferable because a high improvement effect can be realized in rigid PVC.
[0069]
About the addition amount of these resin-type modifiers, in order to implement | achieve sufficient modification | reformation effect, 1 mass part or more is preferable with respect to 100 mass parts of PVC matrices. Moreover, in order to suppress that other characteristics deteriorate by addition of a resin-type modifier, 10 mass parts or less are preferable.
[0070]
In the present invention, a smoke reducing agent can be used in combination. As the smoke reducing agent for the PVC matrix, many have been proposed so far, and these can be used, and among them, zinc compounds and molybdenum compounds are preferable.
[0071]
Examples of the zinc-based compound include zinc borate, zinc oxide, zinc hydroxystannate, zinc stannate and the like, and these compounds promote carbonization of PVC at the time of combustion and reduce smoke generation.
[0072]
Examples of molybdenum compounds include molybdenum trioxide, ammonium octamolybdate, and zinc molybdate.
[0073]
Moreover, the pulverized smoke control agent which uses talc and / or calcium carbonate as a core material, and contains 1 or more types chosen from the group which consists of molybdenum, zinc, phosphorus, and calcium can also be used.
[0074]
The amount of the smoke reducing agent added to 100 parts by mass of the PVC matrix is preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more for a sufficient smoke reduction effect. Moreover, in order to suppress that another characteristic deteriorates by addition of a smoke reducing agent, 3.0 mass parts or less are preferable and 2.8 mass parts or less are more preferable.
[0075]
Furthermore, in the present invention, a plasticizer can be added. The type of plasticizer is not particularly limited, but phthalates such as dibutyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, butyl lauryl phthalate, dilauryl phthalate, butyl benzyl phthalate; dioctyl adipate, dioctyl azeate Linear dibasic acid esters such as rate, dioctyl sebacate; phosphate esters such as tricresyl phosphate, trixylenyl phosphate, monooctyl diphenyl phosphate, monobutyl-dixylenyl phosphate, trioctyl phosphate; castor oil derivatives Epoxidized vegetable oil; ethylene glycol derivatives such as triethylene glycol ester, tetraethylene glycol ester, butyl phthalyl butyl glycolate; polyester plasticizer; It can be exemplified nitrile synthetic rubber; paraffin, chlorinated, such as five-butyl chloride stearate.
[0076]
In general, the addition amount of the plasticizer as described above is preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the PVC matrix. In particular, in the case of rigid PVC, 5 parts by mass or less is preferable in order to suppress a decrease in flame retardancy due to the addition of a plasticizer.
[0077]
In the present invention, a general filler added to PVC, such as calcium carbonate, calcined clay, talc, mica, silica, etc., is preferably 5 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the PVC matrix. It can also be added in the range of less than or equal to parts by mass.
[0078]
About the total addition amount of the various fillers described above, it is necessary to make the range in which the chlorine content of the obtained flame-retardant PVC laminate decreases and the flame retardancy does not decrease. Specifically, the chlorine content of each layer of the finally obtained flame retardant PVC laminate is preferably 30% by mass or more and more preferably 35% by mass or more when the PVC matrix is mainly composed of PVC.
[0079]
Moreover, when a PVC matrix becomes mainly from CPVC, 35 mass% or more is preferable and 40 mass% or more is more preferable.
[0080]
Next, the manufacturing method of the flame-retardant PVC laminated body of this invention characterized by producing the 1st and 2nd masterbatch which has a lubricant is demonstrated.
[0081]
The mass ratio of the lubricant and the colorant at the time of preparing the first masterbatch is carefully optimized because it affects the colorability and appearance. Specifically, when the PVC matrix is mainly composed of PVC, the lubricant is 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and 2 parts by mass or less with respect to 1 part by mass of the colorant. 1 part by mass or less is more preferable.
[0082]
When the PVC matrix is mainly composed of CPVC, the lubricant is used in an amount of 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and more preferably 2 parts by mass or less with respect to 1 part by mass of the colorant. Less than the mass part is more preferable.
[0083]
Even in the case of the second masterbatch, the mass ratio of the lead-based stabilizer, the lubricant, and the resin-based modifier is carefully optimized because it affects the appearance. Specifically, when the PVC matrix is predominantly PVC, the lead-based stabilizer is 1 part by mass or more and 30 parts by mass or less; the lubricant is 0.01 parts by mass or more, and more preferably 0.05 parts by mass or more. 10 parts by mass or less, more preferably 5 parts by mass or less; and 1 to 10 parts by mass of the resin modifier.
[0084]
Further, when the PVC matrix is mainly composed of CPVC, the lead-based stabilizer is 1 part by mass or more and 30 parts by mass or less; the lubricant is 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, more preferably 10 parts by mass. And 5 parts by mass or less are more preferable; the resin modifier is 1 part by mass or more and 10 parts by mass or less.
[0085]
The first and second master batches described above can be produced using a powder mixer such as a Henschel mixer and a blender.
[0086]
Next, a predetermined amount of the first and second master batches, CPVC, PVC, titanium oxide, processing aid, and the like are powder-mixed using a blender, a Henschel mixer, or the like (mixing step). In addition, other compounds, such as a plasticizer, are also mixed in this compounding process as needed. In addition, the lubricant, the colorant, the lead-based stabilizer, and the resin-based modifier are added to the first and second master batches. However, if necessary, they can be added alone in this blending step. it can.
[0087]
The mixture obtained as described above is melt-kneaded using a roll kneader, a Banbury mixer, a kneader, a planetary roll, a kneading extruder, or the like (melt kneading step) to obtain a flame-retardant PVC composition. .
[0088]
In order to obtain a uniform flame retardant PVC composition, the melt-kneading step is generally performed at 160 ° C. or more and 200 ° C. or less when the PVC matrix is mainly composed of PVC.
[0089]
Further, when the PVC matrix is mainly composed of CPVC, it is generally performed at 180 ° C. or higher and 220 ° C. or lower.
[0090]
The obtained flame retardant PVC composition is formed into a flame retardant PVC molded product such as a film, a sheet, a plate material, a pipe, and an odd-shaped product by a molding method such as a calendar method, an extrusion molding method, and an injection molding method at the same time of manufacture. Processed and laminated to produce a flame retardant PVC laminate.
[0091]
In particular, a case where a flame-retardant PVC molded product is produced by a heat-in rolling process using a calendar method will be described. That is, the flame retardant PVC composition is continuously supplied to the rough kneading roll, and then continuously supplied to the hot roll. Then, it processes into a sheet | seat shape with a reverse L-shaped calendar roll, and cut | disconnects to a desired magnitude | size via a cooling roll and a take-up roll. In general, the thickness of the sheet is in the range of 0.1 mm to 10 mm.
[0092]
The original sheet (flame retardant PVC molded product) obtained as described above is laminated together with other predetermined sheets, and is pressed (pressing process) with a load of about 70 MN in the range of 150 ° C to 220 ° C. And processed into a flame retardant PVC laminate (lamination process).
[0093]
In addition, the above lamination | stacking process can be performed by techniques, such as heat welding and welding, besides press work.
[0094]
Further, if necessary, functional layers such as antibacterial, charging, matting, and scratch resistance can be laminated.
[0095]
Below, the specific example of a flame-retardant PVC laminated body is demonstrated using drawing.
[0096]
FIG. 1 shows a flame retardant PVC laminate having a three-layer structure in which an intermediate layer 11 is sandwiched between a surface layer 12 and a surface layer 13.
[0097]
Here, any one or more of the layers 11 to 13 are the flame-retardant PVC molded product in the present invention. Especially, it is preferable that the surface layer 12 and / or the surface layer 13 are the flame-retardant PVC molded products in this invention from a viewpoint of coloring property, and all the layers 11-13 are flame-retardant in this invention from a flame-resistant viewpoint. It is preferable that it is a property PVC molded article.
[0098]
FIG. 3 shows a flame retardant PVC laminate having a four-layer structure including a surface layer 31, a middle layer 32, a middle layer 33, and a surface layer 34.
[0099]
Here, any one or more of the layers 31 to 34 is the flame-retardant PVC molded product in the present invention. Especially, it is preferable that the surface layer 31 and / or the surface layer 34 are the flame-retardant PVC molded products in this invention from a viewpoint of coloring property, and all the layers 31-34 are flame-retardant in this invention from a flame-resistant viewpoint. It is preferable that it is a property PVC molded article.
[0100]
In addition, a flame-retardant PVC laminated body may be heat-welded using a welding rod etc. In this case, defects such as cracks occurring on the surface of the flame retardant PVC laminate and insufficient weld strength may occur.
[0101]
In order to suppress such problems, it is preferable that the surface layer PVC matrix is made of PVC.
[0102]
For the same reason, 100 parts by mass of the PVC matrix of the surface layer is 60 parts by mass or more and 99 parts by mass or less of PVC, and 1 part by mass or more and 40 parts by mass or less of CPVC having a chlorine content of 60% by mass to 70% by mass. Are preferably included.
[0103]
However, when a particularly high flame retardancy is required for the surface layer, the surface layer PVC matrix is preferably composed of CPVC having a chlorine content of 60% by mass to 62% by mass.
[0104]
For the same reason, 100 parts by mass of the PVC matrix of the surface layer is 60 to 99 parts by mass of CPVC having a chlorine content of 60 to 70% by mass and 1 to 40 parts by mass of PVC. Are preferably included.
[0105]
On the other hand, the middle layer PVC matrix is preferably made of CPVC having a chlorine content of 60% by mass or more and 70% by mass or less in order to ensure sufficient flame retardancy.
[0106]
For the same reason, 100 parts by mass of the middle-layer PVC matrix is 60 to 99 parts by mass of CPVC having a chlorine content of 60 to 70% by mass, and 1 to 40 parts by mass of PVC. Are preferably included.
[0107]
However, when particularly good workability is required for the middle layer, the middle layer PVC matrix is preferably made of PVC.
[0108]
For the same reason, 100 parts by mass of the middle-layer PVC matrix includes 60 to 99 parts by mass of PVC and 1 to 40 parts by mass of CPVC with a chlorine content of 60 to 70% by mass. Are preferably included.
[0109]
In FIG. 2, the flame-retardant PVC laminated body of the 2 layer structure which consists of the lower layer 21 and the upper layer 22 was shown.
[0110]
Here, any one or more of the lower layer 21 and the upper layer 22 is the flame-retardant PVC molded product in the present invention. Especially, it is preferable that both layers are the flame-retardant PVC molded article in this invention from a flame-retardant viewpoint.
[0111]
In addition, a flame-retardant PVC laminated body may be heat-welded using a welding rod etc. In this case, defects such as cracks occurring on the upper surface of the flame retardant PVC laminate and insufficient welding strength may occur.
[0112]
In order to suppress such inconveniences, the upper layer PVC matrix is preferably made of PVC.
[0113]
For the same reason, 100 parts by mass of the upper layer PVC matrix is 60 parts by mass or more and 99 parts by mass or less of PVC, and 1 part by mass or more and 40 parts by mass or less of CPVC having a chlorine content of 60% by mass to 70% by mass. Are preferably included.
[0114]
However, when particularly high flame retardancy is required for the upper layer, the upper layer PVC matrix is preferably composed of CPVC having a chlorine content of 60% by mass to 62% by mass.
[0115]
For the same reason, 100 parts by mass of the upper layer PVC matrix includes 60 to 99 parts by mass of CPVC having a chlorine content of 60 to 70% by mass and 1 to 40 parts by mass of PVC. Are preferably included.
[0116]
On the other hand, the lower layer PVC matrix is preferably made of CPVC having a chlorine content of 60% by mass or more and 70% by mass or less in order to ensure sufficient flame retardancy.
[0117]
For the same reason, 100 parts by mass of the lower layer PVC matrix is 60 to 99 parts by mass of CPVC having a chlorine content of 60 to 70% by mass and 1 to 40 parts by mass of PVC. Are preferably included.
[0118]
However, when particularly good workability is required for the lower layer, the lower layer PVC matrix is preferably composed of PVC.
[0119]
For the same reason, 100 parts by mass of the lower layer PVC matrix is 60 to 99 parts by mass of PVC and 1 to 40 parts by mass of CPVC having a chlorine content of 60 to 70% by mass. Are preferably included.
[0120]
In addition, in the case of FIGS. 1-3, in order to suppress the malfunction at the time of a welding process, it is preferable that the PVC matrix of the layer to which a welding process is performed consists of PVC.
[0121]
Further, 100 parts by mass of the PVC matrix of the layer subjected to the welding process is 60 parts by mass or more and 99 parts by mass or less of PVC and 1 part by mass or more and 40 parts by mass of CPVC having a chlorine content of 60% by mass to 70% by mass. It is preferable that the following is included.
[0122]
On the other hand, in order to ensure sufficient flame retardancy, the PVC matrix of the layer not subjected to welding is preferably made of CPVC having a chlorine content of 60% by mass to 70% by mass.
[0123]
In addition, 100 parts by mass of the PVC matrix of the layer not subjected to the welding process includes 60 to 99 parts by mass of CPVC having a chlorine content of 60 to 70% by mass and 1 to 40 parts by mass of PVC. Are preferably included.
[0124]
Furthermore, it is preferable that the PVC matrix of the layer not subjected to the welding process is made of CPVC having a chlorine content of 62% by mass or more and 70% by mass or less.
[0125]
The flame retardancy of the flame retardant PVC laminate as exemplified above can be evaluated using a cone calorimeter according to ASTM E1354. The flame retardant properties evaluated by a combustion test using a corn calorimeter are the maximum value of the calorific value due to combustion per unit area and unit time (also described as maximum calorific value, PHRR; unit: kW / m) ² ), Average value of calorific value due to combustion per unit area and unit time (also described as average calorific value, AHRR; unit: kW / m) ² ), Total calorific value due to combustion (also described as total calorific value, THR; unit: MJ / m) ² ), Average value of mass reduction rate due to combustion per unit area and unit time (also described as mass reduction rate, AMLR; unit: g / sec · m) ² ), Maximum value of light extinction volume due to combustion per unit area and unit time (maximum light extinction volume, also referred to as PSEA; unit: m ² / G), the average value of the light extinction volume due to combustion per unit area and unit time (also referred to as mean light extinction volume, ASEA; unit: m ² / G) and the like.
[0126]
Conventionally, as one of the flame retardant indicators, evaluation standards defined by the Factory Mutual Insurance System have been used effectively.
[0127]
This evaluation standard was measured based on the flame retardant test (FMRC, Clean Room Materials Flammability Test Protocol) of clean room materials listed as Class Number 4910. An index SDI, a corrosion index CDI indicating the generation of corrosive gas, and the like are used as indexes (also referred to as FM standards).
[0128]
In the present invention, instead of the FM standard, a value evaluated by a combustion test using a cone calorimeter is used as an index of flame retardancy. The FM standard is a standard that is obtained by submitting test specimens to an industry mutual insurance organization and evaluating the industry mutual insurance organization, so it takes time to obtain an evaluation result and is inefficient. The combustion test using a corn calorimeter is efficient because it can be performed by the inventors.
[0129]
In particular, FPI has a strong correlation with indices related to calorific values such as PHRR, AHRR and THR measured by a corn calorimeter. In addition, SDI has a strong correlation with indicators related to dimming volume such as PSEA and ASEA. Furthermore, CDI has a strong correlation with an index related to mass loss such as AMLR.
[0130]
Therefore, by evaluating the flame retardancy using a corn calorimeter, the approximate value of the FM standard can be obtained efficiently.
[0131]
In the FM standard, FPI is 6 or less, SDI is 0.4 or less, and CDI is 1.1 or less. However, in the present invention, one or more layers are configured as equal to or more than this standard. For fire-retardant PVC molded products, PHRR is 130 kW / m ² Hereinafter, AHRR is 82 kW / m ² THR is 100 MJ / m ² Hereinafter, AMLR is 13 g / sec · m. ² Below, PSEA is 1500m ² / G or less, ASEA is 1000m ² / G or less is preferable.
[0132]
The colorability and the like in the present invention are evaluated by observing the surface of the produced flame retardant PVC laminate with visual observation and an optical microscope. That is, whether or not the flame retardant PVC laminate is colored to a necessary level can be confirmed by comparing the flame retardant PVC laminate and a color sample. In addition, when there is no irregularity having a diameter of 100 μm or more on the surface of the flame-retardant PVC laminate, no irregularity is assumed. Further, when the surface of the flame retardant PVC laminate is uniformly colored, no color unevenness is assumed.
[0133]
The flame retardant PVC laminate provided by the present invention is also excellent in mechanical properties such as tensile strength, elongation, and Izod impact strength. Specifically, for a flame-retardant PVC molded product constituting one or more layers, the tensile strength measured according to JIS K 6745 is 45 N / mm. ² As described above, the elongation measured according to JIS K 6745 is 40% or more, and the Izod impact strength (notched) measured according to JIS K 6745 is 5 kJ / m. ² This can be done.
[0134]
The flame retardant PVC laminate in the present invention is excellent in flame retardancy, has a small amount of smoke generation, is excellent in colorability, and is substantially free from unevenness and color unevenness.
[0135]
It also has excellent mechanical properties.
[0136]
Therefore, in particular, laminates of rigid PVC compositions are used for interior / exterior materials for transport aircraft such as aircraft, ships, vehicles, etc .; interior / exterior materials for buildings; furniture for daily use such as office equipment; housing materials for home appliances, electronic devices, etc. It can be suitably used as a component of a semiconductor device.
[0137]
【Example】
The present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention. Unless otherwise specified, commercially available high-purity products were used as reagents.
[0138]
(Evaluation methods)
(A) Evaluation of flame retardancy: PHRR (kW / m) according to ASTM E1354 using a cone calorimeter manufactured by Atlas ² ), AHRR (kW / m ² ), THR (MJ / m ² ), AMLR (g / sec · m ² ), PSEA (m ² / G), ASEA (m ² / G) was measured.
[0139]
(A) Evaluation of coloring property: The surface of the flame-retardant PVC laminate was evaluated by visual observation and observation with an optical microscope. Whether or not the flame retardant PVC laminate was colored to the required level by the colorant was confirmed by comparing the flame retardant PVC laminate with a color sample. In addition, when there was no irregularity having a diameter of 100 μm or more on the surface of the flame retardant PVC laminate, no irregularity was assumed. Furthermore, when the surface of the flame-retardant PVC laminate was uniformly colored, no color unevenness was assumed.
[0140]
(C) Evaluation of mechanical properties: according to JIS K 6745, tensile strength (N / mm ² ), Elongation (%), Izod impact strength (notched) (kJ / m ² ) Was measured.
[0141]
Reference Example 1 Flame-retardant PVC composition 1 and flame-retardant PVC molded product 1
Black pigment P4710 (manufactured by Dainichi Seika) 0.019 parts by mass, yellow pigment P4490 (manufactured by Dainichi Seika) 1.793 parts by mass, and orange pigment P4377 (manufactured by Dainichi Seika) 0.028 A first master batch was prepared by mixing 1 part by weight of DSL (manufactured by Sakai Chemical Co., Ltd.) as a lubricant with a Henschel mixer.
[0142]
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.), and MBS (manufactured by Kureha Co., Ltd.) as a resin modifier BTA3NS) 5 parts by mass was mixed with a Henschel mixer to prepare a second masterbatch.
[0143]
Thereafter, 100 parts by mass of CPVC (Kaneka Chemical Co., Ltd., H-527) having a chlorine content of 65% by mass as a PVC matrix, 12 parts by mass of titanium oxide (RK-1 by Sakai Chemical Co., Ltd.) as a flame retardant, and the first master 2.84 parts by mass of batch, 18 parts by mass of second masterbatch, 1 part by mass of MMA resin (P551A manufactured by Mitsubishi Rayon Co., Ltd.) as a processing aid, and calcium stearate (SC-100 manufactured by Sakai Chemical Co., Ltd.) as a lubricant 5 parts by mass, 0.5 part by mass of stearyl stearate (G-32 made by Henkel) as a lubricant and 0.3 part by mass of fatty acid ester (G-70S made by Henkel) as a lubricant were mixed by a Henschel mixer.
[0144]
The obtained mixture was melt-kneaded at 190 ° C. with a kneading roll to produce flame retardant PVC composition 1. Furthermore, a flame-retardant PVC molded article 1 having a sheet shape of 1 mm in thickness was produced by a calendering method using an inverted L-shaped calender roll at 210 ° C.
[0145]
The obtained flame-retardant PVC molded product 1 had an ivory color equivalent to that of the color sample, and no irregularities and color unevenness were confirmed.
[0146]
Moreover, as a flame retardant property, PHRR is 21 kW / m. ² , AHRR is 17kW / m ² , THR is 45MJ / m ² , AMLR 5.6 g / sec · m ² , PSEA is 150m ² / G, ASEA is 112m ² / G.
[0147]
Furthermore, as a mechanical property, the tensile strength is 61 N / mm. ² Elongation is 50%, Izod impact strength is 8 kJ / m ² Met.
[0148]
Reference Example 2 Flame-retardant PVC composition 2 and flame-retardant PVC molded product 2
Black pigment P4710 (manufactured by Dainichi Seika) 0.0373 parts by mass, yellow pigment P4490 (manufactured by Dainichi Seika) 2.894 parts by mass, orange pigment P4377 (manufactured by Dainichi Seika) 0.0502 A first master batch was prepared by mixing parts by mass with 0.3 parts by mass of DSL (manufactured by Sakai Chemical Co., Ltd.) using a Henschel mixer.
[0149]
Next, 5 parts by mass of tribasic lead sulfate (TL5000 manufactured by Sakai Chemical Co., Ltd.) as a lead-based stabilizer, 0.2 parts by mass of DSL (manufactured by Sakai Chemical Co., Ltd.), and MBS (Kureha) as a resin-based modifier. 3 parts by mass of BTA3NS) were mixed with a Henschel mixer to prepare a second master batch.
[0150]
Thereafter, 100 parts by mass of PVC (S-1008 manufactured by Kaneka Chemical Co., Ltd.) as a PVC matrix, 14 parts by mass of titanium oxide (RK-1 manufactured by Sakai Chemical Co., Ltd.), and 3.2815 parts by mass of the first masterbatch Then, 8.2 parts by mass of the second master batch and 1 part by mass of MMA resin (P551A manufactured by Mitsubishi Rayon Co., Ltd.) as a processing aid were mixed using a Henschel mixer.
[0151]
The obtained mixture was melt-kneaded at 180 ° C. with a kneading roll to produce flame retardant PVC composition 2. Further, a flame-retardant PVC molded product 2 having a sheet shape of 8 mm in thickness was produced by a calendering method using a 200 ° C. inverted L-type calender roll. In addition, the above processing temperature was 10 degreeC lower than the case where CPVC was used, and the workability was favorable.
[0152]
The obtained flame-retardant PVC molded product 2 had an ivory color equivalent to that of the color sample, and no irregularities and color unevenness were confirmed.
[0153]
Moreover, as a flame retardant characteristic, PHRR is 72 kW / m. ² , AHRR is 46kW / m ² , THR is 56MJ / m ² , AMLR 8.3g / sec · m ² , PSEA is 900m ² / G, ASEA is 430m ² / G.
[0154]
Furthermore, as a mechanical property, the tensile strength is 56 N / mm. ² Elongation is 150%, Izod impact strength is 6 kJ / m ² Met.
[0155]
(Example 1) Flame retardant PVC laminate 1
A flame retardant having a three-layer structure is formed by sandwiching one flame retardant PVC molded product 1 as an intermediate layer with two flame retardant PVC molded products 2 as a surface layer and pressing it at 180 ° C. under a load of 70 MN. A PVC laminate 1 was produced. In this case, the layer to be welded is made of a flame-retardant PVC molded product 2.
[0156]
The surface of the obtained flame-retardant PVC laminate 1 had an ivory color equivalent to that of the color sample, and no irregularities and color unevenness were confirmed.
[0157]
Moreover, as a flame retardant property, PHRR is 53 kW / m. ² , AHRR is 25kW / m ² , THR is 60MJ / m ² , AMLR 6.0 g / sec · m ² , PSEA is 800m ² / G, ASEA is 130m ² / G.
[0158]
Furthermore, as a mechanical property, the tensile strength is 51 N / mm. ² Elongation is 150%, Izod impact strength is 8 kJ / m ² Met.
[0159]
In addition, using the flame retardant PVC laminate 1, heat welding was performed using a welding rod, but there was no inconvenience such as cracking on the surface, and sufficient welding strength could be obtained. .
[0160]
(Reference Example 3) Flame-retardant PVC composition 3 and flame-retardant PVC molded product 3
100 parts by mass of CPVC (Kaneka Chemical Co., Ltd. H-527) having a chlorine content of 65% by mass as a PVC matrix, 12 parts by mass of titanium oxide (RK-1 by Sakai Chemical Co., Ltd.), and MMA as a processing aid 1 part by weight of resin (P551A manufactured by Mitsubishi Rayon Co., Ltd.), 0.019 part by weight of black pigment P4710 (manufactured by Dainichi Seika Co., Ltd.), 1.793 parts by weight of yellow pigment P4490 (manufactured by Dainichi Seika Co., Ltd.), orange -Based pigment P4377 (manufactured by Dainichi Seika Co., Ltd.) 0.028 parts by mass, 2 parts by mass of DSL (manufactured by Sakai Chemical Co., Ltd.) as a lubricant, and 12 parts by mass of tribasic lead sulfate (TL5000 manufactured by Sakai Chemical Co., Ltd.) as a lead-based stabilizer Part, 5 parts by mass of MBS (BTA3NS manufactured by Kureha Co., Ltd.) as a resin modifier, 0.5 part by mass of calcium stearate (SC-100 manufactured by Sakai Chemical Co., Ltd.), and stearyl stearate as a lubricant And (Henkel G-32) 0.5 parts by weight, and a fatty acid ester (manufactured by Henkel Co. G-70S) 0.3 parts by weight as the lubricant, were batch mixed by a Henschel mixer.
[0161]
The obtained mixture was melt-kneaded at 190 ° C. with a kneading roll to produce flame retardant PVC composition 3. Furthermore, a flame-retardant PVC molded product 3 having a sheet shape of 1 mm in thickness was produced by a calendering method using an inverted L-shaped calender roll at 210 ° C.
[0162]
The obtained flame-retardant PVC molded product 3 had a light ivory color as compared with the color sample, and was confirmed to have irregularities and color unevenness.
[0163]
In addition, both the flame retardancy characteristics and the mechanical characteristics were lower than those of the flame retardant PVC molded article 1.
[0164]
Reference Example 4 Flame-retardant PVC composition 4 and flame-retardant PVC molded product 4
100 parts by weight of PVC (S-1008 manufactured by Kaneka Chemical Co., Ltd.) as a PVC matrix, 14 parts by weight of titanium oxide (RK-1 manufactured by Sakai Chemical Co., Ltd.) as a flame retardant, and MMA resin (P551A manufactured by Mitsubishi Rayon Co., Ltd.) as a processing aid ) 1 part by mass, black pigment P4710 (manufactured by Dainichi Seika Co., Ltd.), 0.0373 parts by mass, yellow pigment P4490 (manufactured by Dainichi Seika Co., Ltd.), 2.894 parts by mass, and orange pigment P4377 (Dainichi Seika) 0.0502 parts by mass), 0.5 parts by mass of DSL (manufactured by Sakai Chemical Co., Ltd.) as a lubricant, 5 parts by mass of tribasic lead sulfate (TL5000 manufactured by Sakai Chemical Co., Ltd.), and a resin system As a modifier, 3 parts by mass of MBS (Kureha BTA3NS) were mixed together by a Henschel mixer.
[0165]
The obtained mixture was melt-kneaded at 180 ° C. with a kneading roll to produce flame retardant PVC composition 4. Furthermore, a flame-retardant PVC molded product 4 having a sheet shape of 8 mm in thickness was produced by a calendering method using a 200 ° C. inverted L-type calender roll.
[0166]
The obtained flame-retardant PVC molded product 4 had a light ivory color as compared with the color sample, and was confirmed to have irregularities and color unevenness.
[0167]
Moreover, both the flame retardant characteristics and the mechanical characteristics were lower than those of the flame retardant PVC molded product 2.
[0168]
(Comparative Example 1) Flame retardant PVC laminate 2
A flame retardant having a three-layer structure is formed by sandwiching one flame retardant PVC molded product 3 as an intermediate layer between two flame retardant PVC molded products 4 as a surface layer and pressing it at 180 ° C. under a load of 70 MN. A PVC laminate 2 was produced. In this case, the layer to be welded is made of a flame-retardant PVC molded product 4.
[0169]
The surface of the obtained flame-retardant PVC laminate 2 had a light ivory color as compared with the color sample, and was confirmed to be uneven and uneven in color.
[0170]
In addition, both the flame retardant properties and the mechanical properties were lower than those of the flame retardant PVC laminate 1.
[0171]
【The invention's effect】
As is clear from the above description, at least a colorant and a lubricant are premixed at a predetermined mass ratio to form a first master batch, and a part of a predetermined other filler and a lubricant are premixed at a predetermined mass ratio. Then, as a second master batch, these master batches, a PVC matrix and a predetermined compound such as titanium oxide are mixed at a predetermined mass ratio, and 100 parts by mass of the PVC matrix and 1 part by mass of a flame retardant made of titanium oxide. By laminating a flame-retardant PVC molded product comprising 30 parts by mass or less, a colorant 0.01 parts by mass to 5 parts by mass, and a lubricant 0.05 parts by mass to 10 parts by mass, a large amount In spite of the presence of titanium oxide, it is well colored by a small amount of colorant, has a high-grade appearance with substantially no unevenness and color unevenness, and has mechanical properties. It can be produced a good flame retardant PVC laminate.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view for explaining an example of a flame retardant PVC laminate of the present invention.
FIG. 2 is a schematic cross-sectional view for explaining another example of the flame-retardant PVC laminate of the present invention.
FIG. 3 is a schematic cross-sectional view for explaining another example of the flame-retardant PVC laminate of the present invention.
[Explanation of symbols]
11 Middle class
12 Surface
13 Surface
21 Lower layer
22 Upper layer
31 Surface
32 middle class
33 Middle class
34 Surface

Claims (7)

In a flame-retardant vinyl chloride resin laminate comprising at least a first layer comprising a first polyvinyl chloride (PVC) matrix and a second layer comprising a second polyvinyl chloride (PVC) matrix,
The first layer as the surface layer is a polyvinyl chloride resin selected from vinyl chloride homopolymer, vinyl chloride-vinyl acetate copolymer or vinyl chloride-ethylene copolymer, or a chlorine content of 60% by mass to 62% by mass. 100 parts by mass of a first (PVC) matrix made of the following post- chlorinated polyvinyl chloride (CPVC) or a composition thereof, 5 parts by mass to 30 parts by mass of a flame retardant containing titanium oxide, and a colorant of 0.01 The second layer, which is a base layer comprising not less than 5 parts by mass and not more than 5 parts by mass and a lubricant of not less than 0.05 parts by mass and not more than 10 parts by mass, has a chlorine content of 60% by mass to 70% by mass. 100 parts by mass of a second (PVC) matrix made of a polyvinyl chloride-based resin, 5 to 30 parts by mass of a flame retardant containing titanium oxide, and 0.01 to 5 parts by mass of a colorant And flame retardant, characterized in that it comprises 0.05 parts by weight or more and 10 parts by weight or less of a lubricant, and at least a colorant and a lubricant are mixed and added to the first layer and the second layer. Vinyl chloride resin laminate.   100 parts by mass of the second polyvinyl chloride (PVC) matrix is composed of 60 to 99 parts by mass of post-chlorinated polyvinyl chloride (CPVC) with a chlorine content of 60 to 70% by mass and polyvinyl chloride (PVC). The flame retardant vinyl chloride resin laminate according to claim 1, comprising 1 part by weight or more and 40 parts by weight or less.   The flame retardant vinyl chloride resin laminate according to claim 1 or 2, wherein the colorant is an inorganic pigment.   The flame retardant according to any one of claims 1 to 3, 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 laminate.   The flame retardant chloride according to any one of claims 1 to 4, wherein the flame retardant contains 1 to 20 parts by mass of barium sulfate with respect to 100 parts by mass of a polyvinyl chloride (PVC) matrix. Vinyl resin laminate.   A method for producing a flame retardant polyvinyl chloride resin laminate comprising at least a first layer comprising a first polyvinyl chloride (PVC) matrix and a second layer comprising a second polyvinyl chloride (PVC) matrix Wherein (a) at least 1 part by weight of a colorant and 0.01 parts by weight or more and 2 parts by weight or less of a lubricant are mixed to produce a first masterbatch; and (b) at least lead-based stability. A step of preparing a second masterbatch by mixing 1 part by weight or more and 30 parts by weight or less of the agent, 0.01 part by weight or more and 10 parts by weight or less of the lubricant, and 1 part by weight or more and 10 parts by weight or less of the resin modifier. And (c) at least 100 parts by mass of the first or second polyvinyl chloride (PVC) matrix, 5 to 30 parts by mass of a flame retardant made of titanium oxide, and 0.01 parts by mass of the first master batch More than 5 A step of powder-mixing 2 parts by mass or less of the second master batch and 50 parts by mass or less of the second master batch and 0.5 parts by mass or more and 10 parts by mass or less of the processing aid, and (d) And (e) a step of producing at least one of the first layer and the second layer using the composition. A method for producing a flame-retardant vinyl chloride resin laminate. A flame-retardant vinyl chloride resin laminate obtained by the production method according to claim 6.

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