JP2009083270A - Antistatic vinyl chloride resin laminated body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic vinyl chloride resin laminated body having excellent heat stability and sliding property required for ensuring transparency, flame resistance, and high productivity and antistatic property. <P>SOLUTION: This antistatic vinyl chloride laminated body is a laminated body having at least one antistatic layer on a basic material. The basic material is composed of a vinyl chloride resin composition containing chlorine containing resin having high temperature decomposition promoting function of 1-50 pts.wt., organic compound having high temperature decomposition inhibiting function of 0.1-7 pts.wt., and heat stabilizer having low temperature decomposition suppressing function of 1-10 pts.wt. for vinyl chloride resin of 100 pts.wt. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antistatic vinyl chloride resin laminate having transparency, flame retardancy, and antistatic properties.

Vinyl chloride resin contains chlorine in the molecule and is not only excellent in flame retardancy, but also various additives can be added in a wide content, so mechanical properties, heat resistance, moldability, weather resistance Etc. can be adjusted over a wide range and has been used in various applications. For example, molded products of rigid vinyl chloride resin compositions include: interior / exterior materials for transport aircraft such as aircraft, ships, vehicles, etc .; interior / exterior materials for buildings; daily necessaries such as furniture and office equipment; housing materials for home appliances and electronic devices; It has been used as a part of equipment.

  However, when the vinyl chloride resin 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. For this reason, attempts have been made to suppress the generation of toxic gases by examining the types and amounts of additives.

For example, in Patent Document 1, for the purpose of a transparent vinyl chloride resin that satisfies the FM standard, 0.005 to 5 parts by weight of a zinc compound in terms of a metal zinc amount with respect to 100 parts by weight of a vinyl chloride resin, A transparent flame retardant vinyl chloride resin molded article containing 0.5 to 7 parts by weight of a tin stabilizer and molded into a desired shape is disclosed.
However, with this disclosed technology, sufficient flame retardancy cannot be secured, and depending on the processing conditions, there is a possibility of poor appearance such as poorly dispersed burn derived from the zinc compound of the powder, and inferior lubricity and thermal stability. Since the moldability was poor, an improvement was desired.

Patent Document 2 discloses that a transparent vinyl chloride resin molded body having flame retardancy is laminated with a vinyl chloride layer having a low chlorination degree and a vinyl chloride layer having a high chlorination degree. A transparent flame-retardant vinyl chloride resin molded product having a degree of conversion of 60% or more and formed into a desired shape is disclosed.
However, in this disclosed technique, since resins having different compositions are laminated, a difference in refractive index is generated at the resin interface, and it is difficult to obtain high transparency, and the process becomes complicated and productivity does not increase. When a single layer is used to increase productivity, not only the flame retardancy becomes insufficient, but also it is difficult to ensure sufficient transparency.

Furthermore, Patent Document 3 discloses that in a vinyl chloride resin composition containing an organotin stabilizer, 0.01 to 1 part by mass of an organic zinc compound as a high-temperature decomposition accelerator is used for 100 parts by mass of a vinyl chloride resin. A vinyl chloride resin composition characterized by having 0.001 to 1 part by mass of a metal hydroxide as an inhibitor and a molded product obtained therefrom are disclosed.
In this disclosure, excellent transparency and flame retardancy can be secured, but in addition to further improvement in transparency and flame retardancy, improvement in workability is expected.

As described above, it has been difficult for conventional vinyl chloride resin moldings to satisfy high productivity as well as high transparency and flame retardancy.

On the other hand, Patent Document 4 discloses an antistatic synthetic resin plate in which a conductive layer made of a conductive agent and a binder resin is provided on the surface of a plastic film.
However, it has been difficult to provide an antistatic synthetic resin plate that satisfies the transparency, flame retardancy, and high productivity and has antistatic properties in the plastic film of the base material of this disclosure.

JP 2001-192520 A JP 2005-15620 A JP 2004-3000299 A JP-A-8-311217

  The present invention provides an antistatic vinyl chloride resin laminate that has excellent transparency, flame retardancy, thermal stability and lubricity necessary to ensure high productivity, and has antistatic properties. The purpose is to do.

  For this purpose, the present inventor is a laminate having at least one antistatic layer on a base material, wherein the base material has a high-temperature decomposition promoting function with respect to 100 parts by weight of the vinyl chloride resin. 1 to 50 parts by mass of a resin, 0.1 to 7 parts by mass of an organic compound having a high-temperature decomposition inhibiting function, and 1 to 10 parts by mass of a thermal stabilizer having a low-temperature decomposition inhibiting function Invented an antistatic vinyl chloride resin laminate characterized by being a material.

  According to the antistatic vinyl chloride resin laminate of the present invention, the synergistic effect of the decomposition promoting function of the chlorine-containing resin having the high temperature decomposition promoting function and the decomposition inhibiting function of the organic compound having the high temperature decomposition inhibiting function is difficult. In addition to being excellent in flammability, the high transparency inherent in vinyl chloride resins can be maintained at the same level, and in terms of thermal stability and lubricity necessary to ensure high productivity. And has antistatic properties by providing an antistatic layer.

Further, the present inventor, together with a specific high-temperature decomposition accelerator and a low-temperature decomposition inhibitor, is a specific organic compound, particularly an organic compound having an excellent function as a lubricant or a processing aid, and the specific ratio. When blended into a vinyl chloride resin as described above, the following knowledge was obtained and the present invention was conceived based on such knowledge.
(1) Such an organic compound functions as a high-temperature decomposition inhibitor in a system in which the specific high-temperature decomposition accelerator and the low-temperature decomposition inhibitor coexist.
(2) The function as a high-temperature decomposition inhibitor (decomposition-inhibiting function), combined with the decomposition-accelerating function of the high-temperature decomposition accelerator, improves the decomposition of the base material resin (vinyl chloride resin) at high temperatures. Control and give even better flame retardancy to vinyl chloride resin.
(3) Since the function as a lubricant or processing aid, which is the other characteristic of the organic compound, eliminates the use of ordinary lubricants or processing aids generally used for vinyl chloride resins, The high transparency inherent to the vinyl chloride resin that is impaired by the blending of these auxiliaries can be maintained at the same level.

  Hereinafter, an antistatic vinyl chloride resin laminate (hereinafter referred to as “the laminate”) as an example of an embodiment of the present invention will be described. However, the scope of the present invention is not limited to the embodiments described below.

  The laminate is a laminate having a substrate and at least one antistatic layer on the substrate. Here, “on the substrate” as used in the present invention refers to the case where an antistatic layer is provided directly on the surface of the substrate, and another layer which is directly a single layer or a multilayer on the surface of the substrate, This means that an antistatic layer is provided on the other layer.

  In addition, in the present invention, when “X to Y” (X and Y are arbitrary numbers) is described, it is “greater than X and smaller than Y” with the intention of “X to Y” unless otherwise specified. The intention of “preferably” is also included.

(Base material)
The base material of the laminate is composed of a vinyl chloride resin composition. Moreover, the vinyl chloride resin composition constituting the base material of the laminate contains a high temperature decomposition accelerator, a low temperature decomposition inhibitor, and a high temperature decomposition inhibitor in addition to the vinyl chloride resin as a base resin. .

Here, the high temperature decomposition accelerator is a substance having a function of promoting the decomposition of the laminate in a high temperature region, and the high temperature decomposition inhibitor is a substance having a function of inhibiting the decomposition of the laminate in a high temperature region. The low-temperature decomposition inhibitor is a substance having a function of suppressing decomposition of the laminate in a low-temperature region.
Regarding the decomposition behavior of this laminate, the dehydrochlorination behavior starts at the processing temperature range of 220 ° C., and the temperature range from 220 ° C. to 370 ° C. is where the dehydrochlorination behavior occurs actively. . In a temperature range higher than that, for example, 450 ° C. or higher, the main chain of the present laminate is decomposed or carbon of the present laminate is burned or carbonized. Therefore, in the present invention, the decomposition in the low temperature region refers to the decomposition behavior in the temperature region up to 220 ° C. which is the molding processing temperature region, and the decomposition in the high temperature region means that the main chain is broken and carbon combustion occurs 450. The decomposition behavior in the temperature range above ℃.
Further, the high temperature decomposition promoting function in the present invention means that the vinyl chloride resin is decomposed by breaking the main chain of the vinyl chloride resin at 450 ° C. or higher, or carbonized by the combustion of carbon in the vinyl chloride resin. It can be said that it is a function that promotes being done. Moreover, it can be said that the high temperature decomposition inhibiting function in the present invention is a function of inhibiting the decomposition and carbonization of the vinyl chloride resin at 450 ° C. or higher. Furthermore, it can be said that the low-temperature decomposition suppressing function in the present invention is a function of suppressing the start of dehydrochlorination behavior from a vinyl chloride resin at less than 220 ° C.

The lower limit value of the thickness of the substrate is 0.5 mm or more, preferably 1 mm or more, more preferably 3 mm or more, and the upper limit value is 40 mm or less, preferably 30 mm or less, more preferably 15 mm or less. If the thickness of the base material is 0.5 mm or more, the thickness of the base material is sufficient, so that the problem that the entire laminate is bent does not occur. Moreover, if the thickness of the base material is 40 mm or less, visible light can be easily transmitted, and it is possible to obtain desired values for the total light transmittance and haze.

(Vinyl chloride resin)
As the base material of the laminate, a vinyl chloride homopolymer or a copolymer of vinyl chloride and another vinyl compound, which is a vinyl chloride resin, can be used. Moreover, these can be used individually or as these 2 types of mixed resin.

  In the above copolymer, other vinyl compounds that can be copolymerized with the vinyl chloride component are not particularly limited. For example, fatty acid vinyl esters such as vinyl acetate and vinyl propionate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; ethylene And α-olefins such as propylene and styrene; alkyl vinyl ethers such as vinyl methyl ether and vinyl butyl ether; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride, or acid anhydrides thereof. Can be used alone or in combination of two or more.

  In the above copolymer, if the copolymerization amount of the other vinyl compound does not exceed 30% by mass, the inherent flame retardancy and high transparency of the vinyl chloride resin are not impaired. It is preferable to contain in the range which does not exceed 30 mass%. The amount of copolymerization is preferably 20% by mass and more preferably 10% by mass from the viewpoints of transparency and flame retardancy.

  The average degree of polymerization of the vinyl chloride resin is preferably 300 to 2,000, and more preferably 500 to 1,500. If the average degree of polymerization is too small, the molded product may not have sufficient strength, and if it is too large, it is difficult to knead sufficiently during molding and the processability may be reduced.

  The polymerization method of the vinyl chloride resin is not particularly limited, and a polymer obtained by polymerization using various methods such as an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method can be used.

(High temperature decomposition accelerator)
The high-temperature decomposition accelerator plays a role of reducing the amount of smoke generated by promoting the cutting and carbonization of the main chain of the vinyl chloride resin at the time of burning the molded body in a high temperature region (for example, 450 ° C. or more).

As the high-temperature decomposition accelerator, a chlorine-containing resin capable of generating hydrogen chloride, which has an action of promoting the cleavage behavior of the main chain of the vinyl chloride resin, is preferable.
As the chlorine-containing resin having a function of promoting high-temperature decomposition, chlorinated polyethylene resin, post-chlorinated vinyl chloride resin, vinylidene chloride resin and the like can be mentioned as particularly preferable ones.

  The chlorinated polyethylene is a resin obtained by chlorinating polyethylene having a mass average molecular weight of 50,000 to 350,000, and has a chlorine content of 28 to 43% by mass and a heat of crystal melting by DSC method of 25 cal / g or less. A certain chlorinated polyethylene etc. can be illustrated. Among them, from the viewpoint of transparency, a resin obtained by chlorinating polyethylene having a mass average molecular weight of 50,000 to 150,000, having a chlorine content of 28 to 35% by mass and a crystal melting heat by DSC method of 10 to 25 cal / g. A chlorinated polyethylene is preferred.

As the post-chlorinated vinyl chloride resin, those having an average degree of polymerization of the vinyl chloride resin before chlorination of 500 to 1400 are preferable. If the average degree of polymerization is less than 500, impact resistance may be lowered, and if it exceeds 1400, melt fluidity may be lowered and molding may be difficult.
The average chlorine content of the post-chlorinated vinyl chloride resin is 58 to 70% by mass, preferably 60 to 70% by mass. If the average chlorine content is too low, the heat resistance is lowered and deformation tends to occur. If the average chlorine content is too high, especially when it exceeds 70% by mass, the fluidity is greatly reduced and molding becomes difficult.

Examples of the vinylidene chloride resin include homopolymers and copolymers of vinylidene chloride. It is preferable to use a copolymer having a difference between the thermal decomposition temperature and the melting point, that is, a copolymer.
As the copolymer of vinylidene chloride, a copolymer obtained by copolymerizing vinylidene chloride and a known radical polymerizable monomer alone or in combination of two or more thereof can be used.
Examples of the radical polymerizable monomer include unsaturated fatty acids such as vinyl chloride, acrylonitrile, acrylic acid or methacrylic acid and esters thereof, vinyl esters such as vinyl acetate, vinyl ketones, olefins such as ethylene and propylene, n -Monomers containing special functional groups such as methylacrylamide and cyclohexylmaleimide.
The composition of the copolymer of vinylidene chloride and the monomer is not particularly limited, but in order to satisfy the flame retardancy, the content of vinylidene chloride is 65 to 99 mass%, preferably 80 to 97 mass%. Is preferably selected.
The molecular weight of the vinylidene chloride copolymer is not particularly limited, but a mass average molecular weight of 30,000 to 150,000, preferably 50,000 to 120,000 is preferable in terms of processability and physical properties of the molded article.
Examples of the polymerization method of the vinylidene chloride polymer include suspension polymerization, emulsion polymerization, bulk polymerization, gas phase polymerization, and the like. From the viewpoint of obtaining a good powder at low cost, suspension polymerization is particularly preferable.

  If the addition amount of the high-temperature decomposition accelerator is small, the flame retardancy is not improved because carbonization is not promoted at the time of combustion. On the other hand, if the addition amount is too large, the transparency is deteriorated or the hot water whitening resistance is deteriorated. Become. Therefore, the content of the high-temperature decomposition accelerator is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, and particularly preferably 10 to 20 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

(Low-temperature decomposition inhibitor)
As the low-temperature decomposition inhibitor, it is preferable to select and use one having good transparency from those conventionally known as a heat stabilizer for vinyl chloride and a heat stabilization aid. For example, butyl tin malate, octyl tin malate, di-n alkyl tin mercaptide, di-n-alkyl tin dilaurate, dibutyl tin dimaleate, dibutyl tin lauryl mercaptide, dioctyl tin S, S'-bis- (isooctyl-mercaptoacetate) Tin stabilizers such as dibutyltin bis-isooctylthioglycolate, di- (n-octyl) tin malate polymer, dibutyltin mercaptopropionate, lead stabilizer, potassium, magnesium, barium, zinc, cadmium Metal soap stabilizers derived from metals such as lead and fatty acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, behenic acid, Ba-Zn series, Ca-Zn series, Ba-Ca-Sn series, Composite metal soap stabilizers such as a-Mg-Sn, Ca-Zn-Sn, Pb-Ba and Pb-Ba-Ca, metal groups such as barium and zinc, 2-ethylhexanoic acid and isodecane Acids, branched fatty acids such as trialkylacetic acid, unsaturated fatty acids such as oleic acid, ricinoleic acid and linoleic acid, alicyclic acids such as naphthenic acid, aromatic acids such as carboxylic acid, benzoic acid, salicylic acid and substituted derivatives thereof. Metal salt stabilizers derived from usually two or more organic acids selected from the above, these stabilizers are dissolved in organic solvents such as petroleum hydrocarbons, alcohols, glycerin derivatives, and phosphites, epoxy Metal stabilizers such as compounds, color stabilizers, transparency improvers, light stabilizers, antioxidants, plate-out inhibitors, metal salt liquid stabilizers containing stabilizers such as lubricants, epoxy resins, Epoxy compounds such as epoxidized vegetable oils, epoxidized fatty acid alkyl esters, and epoxidized aromatic alkyl esters, phosphorus is substituted with alkyl groups, aryl groups, cycloacryl groups, alkoxyl groups, etc., and dihydric alcohols such as propylene glycol, hydroquinone , Organic phosphites having aromatic compounds such as bisphenol A, hindered amine or nickel complex light stabilizers, polymethyl alcohols such as trimethylolpropane, pentaerythritol, sorbitol, mannitol, β-aminocrotonates, 2- Nitrogen-containing compounds such as phenylindole, diphenylthiourea, dicyandiamide, sulfur-containing compounds such as dialkylthiodibropionate, keto compounds such as ethyl acetoacetate, dehydroacetic acid, β-diketone, organosilicon Preferred examples include non-metallic stabilizers such as compounds and borate esters. Those selected from these may be used alone or in combination of two or more.
Of these, organotin stabilizers, metal soap stabilizers, zeolite stabilizers, hydrotalcites, aluminum-based and magnesium-based hydroxides are preferred. From the viewpoint of superiority, tin stabilizers and metal soap stabilizers are particularly suitable.

  Examples of the tin stabilizer include a malate tin stabilizer, a laurate tin stabilizer, a mercapto tin stabilizer, and the like. Among these, a mercapto tin stabilizer advantageous in transparency is particularly preferable.

Examples of the metal soap stabilizer include metal soaps of saturated to unsaturated fatty acids having 10 to 22 carbon atoms, particularly 14 to 18 carbons, such as alkali metal salts such as sodium salts and potassium salts; calcium salts, magnesium salts and barium salts. Alkaline earth metal salts, zinc salts and the like can be mentioned, and among these, calcium salts, magnesium salts, barium salts and zinc salts are particularly suitable. These can be used alone or in combination of two or more.
Examples of fatty acids of metal soaps include saturated fatty acids such as capric acid, undecanoic acid, 2-ethylhexoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, and arachidic acid, Mention may be made of unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and arachidonic acid, and aromatic fatty acids such as benzoic acid and t-butyl-benzoic acid.
Above all, from the viewpoint of transparency, aromatic fatty acid zinc is preferable to fatty acid zinc if the number of carbon atoms is the same, and a shorter carbon number is more compatible with vinyl chloride resin and has higher transparency. It is preferable because it is easy to obtain. Therefore, t-butyl-benzoic acid and calcium, zinc salt of 2-ethylhexoic acid are particularly suitable.

  As a heat stabilization aid, as a zeolite stabilizer, synthetic zeolite such as zeolite A, zeolite X and zeolite Y, partially or completely acid-treated products thereof, or metal ions thereof (for example, calcium, magnesium, zinc ions) The aluminosilicate of the exchange treatment product can be mentioned. Among these, sodium ion-exchanged A-type zeolite that has good thermal stability is particularly suitable.

Examples of hydrotalcites include those represented by the following formulas (1) to (4).
That is, Equation _{(1): Mg x Al y} (OH) 2x + 3y-2 CO 3 · aH 2 O ( wherein, x, y is a positive number that satisfies 1/4 ≦ x / y ≦ 8, a is Is a positive number satisfying 0.01 ≦ a / (x + y) ≦ 1.0),
Equation _{(2): Mg x Al y} (OH) 2x + 3y-2 · (Y n -) b · aH 2 O ( wherein, x, y is a positive number that satisfies 1/4 ≦ x / y ≦ 8 , N is an integer of 1 or more, b is a positive number satisfying O <b ≦ 2, b · n = 2, a is a positive number satisfying 0.01 ≦ a / (x + y) ≦ 1.0, Y is At least one integer molar unit selected from the group consisting of phosphorus oxyacid, sulfur oxyacid, nitrogen oxyacid, boron oxyacid, carbonic acid, halogen hydroacid, halogen oxygen acid, perhalogen oxygen acid, carboxylic acid Can be combined with a single or complex anion),
Equation _{(3): M x Al y} (OH) 2x + 3y-2z (Y) z · aH in ₂ O (wherein, x, y, z are 1/4 ≦ x / y ≦ 8 and z / x + y> 1 / 20 is a positive number, M is a divalent metal ion such as Mg, Ca, Zn, Y is a divalent anion such as CO ₃ ²⁻ , SO ₄ ²⁻ , a is 0 or a positive number) What is represented by
Equation _{(4): Mg x Al y} (OH) 2x + 3y-z (A 2-) P (A -) q · aZ · bH in ₂ O (wherein, A ^2-divalent CO ₃ ^2-, etc. Anion, A ⁻ is a halogen oxyacid ion, Z is a polyhydric alcohol or a partial ester thereof, x, y and z are z = 2p + q, 8 ≧ (x / y) ≧ ¼ and z / (x + y)> 1 / 20 is a positive number satisfying p and q satisfying 1 ≧ q / (2p + q) ≧ 1/10, and a and b are 0.01 ≦ a / (x + y) ≦ 1.0 and Examples thereof include a composite hydroxide described in JP-B-3-36839, which has a chemical composition of 0 ≦ b / (x + y) ≦ 1.0).

  Examples of the aluminum hydroxide and the magnesium hydroxide include aluminum hydroxide and magnesium hydroxide. Moreover, the hydroxide which surface-treated to these hydroxide powders may be sufficient. As this surface treating agent, it is preferable in terms of dispersibility and flame retardancy to use one containing a fatty acid or a molybdenum compound.

  The inorganic low-temperature decomposition inhibitor has a lower limit of the average particle size of 0.01 μm or more, preferably 0.05 μm or more, and an upper limit of less than 0.6 μm, preferably less than 0.3 μm. If the average particle size is 0.01 μm or more, the heat stabilizer itself does not aggregate and is easy to handle. On the other hand, if it is less than 0.6 μm, it is smaller than the wavelength of visible light, so that transparency is good.

  In view of the above, the low-temperature decomposition inhibitor is particularly preferably an organic tin mercapto stabilizer, hydrotalcite, or magnesium hydroxide compound having a refractive index close to that of a vinyl chloride resin in consideration of transparency.

  If the low-temperature decomposition inhibitor is not added, the dynamic thermal stability is too low to be molded, and if the addition amount is too large, the transparency and physical properties are lowered, and a satisfactory molded product cannot be obtained. Therefore, the blending amount of the low-temperature decomposition inhibitor is, when the vinyl chloride resin is 100 parts by mass, the lower limit is 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, The upper limit is 10 parts by mass or less, preferably 8 parts by mass or less, and more preferably 6 parts by mass or less. If the blending amount of the low-temperature decomposition inhibitor is 1 part by mass or more, the low-temperature decomposition is not promoted and the moldability is good, and if it is 10 parts by mass or less, the flame retardancy is good.

(High temperature decomposition inhibitor)
In the present vinyl chloride resin composition, it is important to blend an organic compound having a high-temperature decomposition inhibiting function as a high-temperature decomposition inhibitor in addition to the above-described blending components.

  As this high-temperature decomposition inhibitor, lubricants, processing aids, impact modifiers, plasticizers, antistatic agents, ultraviolet absorbers, antioxidants, etc. are included because they have functions such as physical properties and molding processability. It can mention as a preferable example, It is preferable to use combining 1 type, or 2 or more types chosen from these.

Examples of the lubricant include pure hydrocarbons such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, and low molecular weight polyethylene; halogenated hydrocarbons; fatty acids such as higher fatty acids and oxy fatty acids; fatty acid amides and bis fatty acids. Fatty acid amides such as amides; fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters such as glycerides, fatty acid polyglycol esters, fatty acid fatty alcohol esters (ester waxes) and other ester systems; metal soaps, fatty alcohols, Examples thereof include polyhydric alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, fatty acids and polyglycols, partial esters of polyglycerol, and the like. Of these, lower alcohol esters of fatty acids having excellent high-temperature decomposition inhibiting function, polyhydric alcohol esters of fatty acids such as glycerides and partial esters thereof are particularly preferable.
These can also be used individually by 1 type chosen from these, and can also be used together in combination of 2 or more type.

Examples of the processing aid include homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; and copolymers of the above alkyl methacrylates with alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate. Polymer; Copolymer of the above alkyl methacrylate with an aromatic vinyl compound such as styrene, α-methylstyrene, vinyl toluene; Copolymer of the above alkyl methacrylate with a vinyl cyan compound such as acrylonitrile or methacrylonitrile Etc. Among these, a copolymer of methyl methacrylate, butyl acrylate and ethyl methacrylate having an excellent high-temperature decomposition inhibiting function is particularly preferable. These can also be used individually by 1 type chosen from these, and can also be used together in combination of 2 or more type.
By making such an acrylic processing aid into an appropriate addition amount, an effect of improving flame retardancy can be obtained, and the load on the molding machine drive unit during molding is increased, and molding does not become difficult.

Examples of the impact modifier include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene graft copolymer. Polymer, acrylonitrile-styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene graft copolymer, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene copolymer rubber, styrene-ethylene- Butylene-styrene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPDM), silicone-containing acrylic rubber, silicone / acrylic composite rubber graft copolymer, silica It can be given over emissions-based rubber and the like. Of these, acrylonitrile-styrene-butadiene copolymer rubber and acrylonitrile-styrene-butadiene graft copolymer having a low high-temperature decomposition inhibiting function are particularly preferable. These impact modifiers can be used alone or in combination of two or more.
Examples of the diene of the ethylene-propylene-diene copolymer rubber (EPDM) include 1,4-hexanediene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, and propenyl norbornene.
These impact modifiers can be used alone or in combination of two or more.

Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dinormal octyl phthalate, 2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl. Phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl phthalate, butyl octyl phthalate, octyl benzyl phthalate, normal hexyl normal decyl phthalate, normal octyl normal decyl phthalate, etc. Phthalate ester plasticizer; tricresyl phosphate Phosphate ester plasticizers such as tri-2-ethylhexyl phosphate, triphenyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate; di-2-ethylhexyl adipate, diisodecyl adipate, normal octyl-normal decyl adipate, normal heptyl -Adipate plasticizers such as normal nonyl adipate, diisooctyl adipate, diisonormal octyl adipate, dinormal octyl adipate, didecyl adipate; dibutyl sebacate, di-2-ethylhexyl sebacate, diisooctyl sebacate Sebacic acid ester plasticizers such as butylbenzyl sebacate; di-2-ethylhexyl azelate, dihexyl azelate, diisooctyl azele Azelaic acid plasticizers such as triethyl citrate, triethyl acetylcitrate, tributyl citrate, tributyl citrate citrate, tri-2-ethylhexyl citrate; methylphthalylethylglyco Glycolate ester plasticizers such as rate, ethylphthalylethyl glycolate, butylphthalylbutyl glycolate; tributyl trimellitate, tri-normal hexyl trimellitate, tri-2-ethylhexyl trimellitate, tri-normal octyl Trimellitic acid ester plasticizers such as trimellitate, tri-isoctyl trimellitate, tri-isodecyl trimellitate; phthalic acid isomers such as di-2-ethylhexyl isophthalate and di-2-ethylhexyl terephthalate Ester plasticizers; ricinoleic acid ester plasticizers such as methyl acetyl ricinolate and butyl acetyl ricinolate; polyester plasticizers such as polypropylene adipate, polypropylene sebacate and their modified polyesters; epoxidized soybean oil, epoxy butyl stearate Examples thereof include epoxy plasticizers such as rate, epoxy (2-ethylhexyl) stearate, epoxidized linseed oil, and 2-ethylhexyl epoxy torate. Among these, a phosphate ester plasticizer having a low high-temperature decomposition inhibiting function is particularly preferable.
These can also be used individually by 1 type chosen from these, and can also be used together in combination of 2 or more type.

As the antistatic agent, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used.
Anionic surfactants include fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, aliphatic amines, amide sulfates, dibasic fatty acid ester sulfonates, fatty acid amide sulfonates, alkylaryls Examples thereof include sulfonates, formalin-condensed naphthalenesulfonates, and mixtures thereof.
Examples of the cationic surfactant include aliphatic amine salts, quaternary ammonium salts, alkyl pyridium salts, and mixtures thereof.
Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol esters, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters and mixtures thereof. Can do.
A mixture of a nonionic surfactant and an anionic surfactant or a cationic surfactant may be used.
Examples of amphoteric surfactants include imidazoline type, higher alkylamino type (betaine type), sulfate ester, phosphate ester type, and sulfonic acid type.
Among these, nonionic surfactants having a low high-temperature decomposition inhibiting function are preferable, and sorbitan alkyl esters are more preferable among them.

  Examples of the ultraviolet absorber include hindered phenol, salicylic acid ester, benzophenone, and benzotriazole. Among these, a benzotriazole-based ultraviolet absorber having a low high-temperature decomposition inhibiting function is particularly preferable.

  Examples of the antioxidant include phenolic antioxidants such as 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol), tris (mixed mono and di-nonylphenyl) phosphite, and the like. Examples thereof include phosphite antioxidants and thioether antioxidants such as distearyl thiodipropionate. Among these, phenolic antioxidants such as 4,4'-butylidenebis- (6-tert-butyl-3-methylphenol) having a low high temperature decomposition inhibiting function are particularly preferable.

  If the amount of the high-temperature decomposition inhibitor is too large, the flame retardancy is deteriorated. If the amount is too small, the effect of improving the flame retardancy cannot be obtained. Therefore, the content of the high-temperature decomposition inhibitor is 100 parts by mass of the vinyl chloride resin. On the other hand, the lower limit is 0.1 parts by mass or more, preferably 0.8 parts by mass or more, more preferably 1.6 parts by mass or more, and the upper limit is 7 parts by mass or less, preferably 5 parts by mass or less, more preferably, 4 parts by mass or less.

(Antistatic layer)
The laminate has at least one antistatic layer on the substrate. The main components constituting the antistatic layer are a binder resin and a conductive agent. Here, the above-mentioned “main component” means that the total mass of the binder resin and the conductive agent is 50 mass% or more, preferably 65 mass% or more, more preferably 80 mass% with respect to the total mass of the antistatic layer. That's it. In addition, the antistatic vinyl chloride resin laminate of the present invention can be provided with a plurality of antistatic layers. For example, when two or more layers are provided, it is possible to provide antistatic layers on both the front surface and the back surface.

The lower limit value of the thickness of the antistatic layer is 0.05 μm or more, preferably 0.06 μm or more, more preferably 0.07 μm or more, and the upper limit value is 0.30 μm or less, preferably 0.20 μm or less, more preferably 0 The range is 15 μm or less. If the thickness of the antistatic layer is 0.05 μm or more, the antistatic layer is thick, so that pinholes can be prevented and film formation is easy. Further, if the thickness of the antistatic layer is 0.30 μm or less, visible light can be easily transmitted, and the total light transmittance and haze can also obtain desired values. .

(Conductive agent)
As the conductive agent used in the antistatic layer of the laminate, a known conductive agent can be used. For example, graphite powder such as natural graphite, pyrolytic graphite, quiche graphite, etc., expanded graphite that has been immersed in an acidic solution and then expanded by heating, ketjen black, acetylene black, furnace method, etc. Carbon fiber such as carbon black, PAN, pitch, etc., carbon fiber made by arc discharge method, laser deposition method, vapor phase growth method, tungsten carbide, silicon carbide, zirconium carbide, tantalum carbide, titanium carbide, Metal carbides such as niobium carbide, molybdenum carbide, vanadium carbide, metal oxides such as conductive titanium oxide, ruthenium oxide, indium oxide, tin oxide, chromium nitride, aluminum nitride, molybdenum nitride, zirconium nitride, tantalum nitride, titanium nitride, Gallium nitride, niobium nitride, vanadium nitride, boron nitride, etc. Metal fibers such as metal nitride, iron fiber, copper fiber, stainless steel fiber, metal powder such as titanium powder, nickel powder, tin powder, tantalum powder, niobium powder, π-electron conjugated polymers such as polyaniline, polypyrrole, polythiophene, etc. Is mentioned.

  The carbon fiber includes so-called carbon nanotubes (CNT) and carbon nanofibers. Carbon nanotubes include single-walled carbon nanotubes whose carbon tube structure is a single tube, and multi-walled carbon nanotubes whose tube structure is double or more. In addition, carbon nanotubes are stacked with a nanohorn type with one end closed and the other end open, and a carbon network layer with a bottomless cup shape, and the annular end surface of the carbon network layer is exposed. It also includes forms such as cup shapes.

Among the above conductive agents, tin oxide, carbon fiber, and conductive titanium oxide are preferably used. Among these, tin oxide and carbon fiber can maintain good transparency of the laminate without significantly impairing the transparency of the antistatic layer unlike carbon powder. In addition, when carbon fiber is contained in the antistatic layer, variation in the surface resistivity of the antistatic layer is reduced, and excellent antistatic properties can be exhibited by adding a small amount of carbon fiber. Even if it does not get entangled, the antistatic property is maintained. Moreover, since the antistatic layer containing conductive titanium oxide tends to become opaque, it is preferable to use it in a small amount.

  As tin oxide used in the conductive agent, the lower limit of the average particle diameter is 0.01 μm or more, preferably 0.03 μm or more, more preferably 0.05 μm or more, and the upper limit is 0.4 μm or less, preferably 0. .3 μm or less, more preferably 0.2 μm or less. If the average particle size is 0.1 μm or more, the tin oxide powder has good kneading properties with the binder resin and can be uniformly kneaded. Moreover, if the average particle diameter is 0.6 μm or less, it is possible to obtain an antistatic vinyl chloride resin laminate having good transparency. Further, tin oxide containing antimony can be used for the antistatic layer of the present invention.

  Further, tin oxide or the like doped with antimony oxide can be used. The tin oxide may be a single tin oxide or a mixture with other oxides (for example, antimony oxide, titanium oxide, yttrium oxide, cerium oxide, etc.). In particular, a material doped with antimony or the like is preferable because of excellent antistatic properties.

  The carbon fiber used as the conductive agent is a fiber having a large aspect ratio and a small wire diameter, and may be an amorphous carbonaceous fiber or a graphitic fiber. Further, carbon fiber in which amorphous carbon and graphite coexist in the fiber may be used. A particularly preferred long carbon fiber is a graphite-like fiber having a circular cross section in which a graphite layer is structurally formed and a graphite layer is coaxially formed on the fiber axis. The lower limit of the wire diameter of the carbon fiber is 0.7 nm or more, preferably 10 nm or more, more preferably 20 nm or more, and the upper limit is 80 nm or less, preferably 70 nm or less, more preferably 60 nm or less. The aspect ratio is 100 or more, preferably 200 or more, and more preferably 300 or more. The upper limit of the aspect ratio is not particularly limited, but 3000 or less can be preferably used. If the carbon fiber has a wire diameter of 3.5 nm or more, the carbon fiber is easy to handle, and if it is 100 nm or less, the antistatic property is well expressed. Moreover, if the aspect ratio is 5 or more, the linear characteristics of the carbon fiber can be utilized.

  The conductive titanium oxide used as the conductive agent is formed by coating the surface of titanium oxide having a spherical shape, flake shape, needle shape, etc. with tin oxide or antimony-doped tin oxide. Titanium is preferably used because of its frequent contact with each other.

The antistatic vinyl chloride resin-based laminate is characterized by having antistatic properties. In the present invention, having antistatic property means that the surface resistivity of the antistatic layer is 10 ¹⁰ Ω / □ or less, preferably 10 ⁸ Ω / □ or less, more preferably 10 ⁶ Ω / □ or less. If the surface resistivity of the antistatic layer is 10 ¹⁰ Ω / □ or less, sufficiently prevent dust and the like from adhering to the surface of the antistatic layer of the antistatic vinyl chloride resin-based laminate. Can do. Further, the lower the surface resistivity of the antistatic layer, the better. However, if it is 10 ³ Ω / □ or more, it is possible to sufficiently prevent adhesion of dust and the like due to static electricity.

  The lower limit of the mass% of tin oxide used in the present invention is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass with respect to the total mass of all components constituting the antistatic layer. The upper limit is 95% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. If the amount of tin oxide added is 60% by mass or more, the antistatic property can be expressed in the antistatic layer. On the other hand, when the amount of tin oxide added is 95% by mass or less, the antistatic layer has good transparency.

  The lower limit of the mass% of the carbon fiber used in the present invention is 2 mass% or more, preferably 3 mass% or more, more preferably 4 mass% or more, and the upper limit is 9 mass% or less, 8 mass% or less. More preferably, it is in the range of 7% by mass. If the mass ratio of the carbon fibers in the antistatic layer is 2% by mass or more, since the amount of carbon fibers is sufficient, fine carbon fibers are easy to contact and the antistatic property is well expressed. Furthermore, since a π-electron jumps between the carbon fibers having a certain distance and a tunneling current due to a tunneling effect exhibiting antistatic properties is likely to occur, the surface resistivity is reduced and dust is difficult to adhere. Moreover, if the mass ratio of the fine carbon fibers in the antistatic layer is 9% by mass or less, visible light is easily transmitted, the total light transmittance is increased, and the haze is easily decreased. In addition, the mass ratio of the carbon fiber of this invention is a mass ratio with respect to the total mass ratio of all the components which comprise an antistatic layer.

(Binder resin)
The transparent binder resin contained in the antistatic layer may be appropriately selected in consideration of the adhesion of the thermoplastic resin to the substrate. For example, polyolefin (PO) resins such as homopolymers or copolymers containing ethylene or polyolefin elastomers, amorphous polyolefin resins (APO) such as cyclic polyolefins, polystyrene (PS), acrylonitrile-butadiene-styrene copolymers (ABS) ), Polystyrene resins such as styrene-butadiene-styrene (SBS) or hydrogenated styrene elastomers such as styrene-ethylene-butadiene-styrene (SEBS), polyvinyl chloride (PVC) resins, polyvinylidene chloride (PVDC) Resin, vinyl chloride-vinyl acetate copolymer, polymethyl methacrylate (PMMA), acrylic resin such as copolymerized acrylic, glycol-modified polyethylene terephthalate (PET-G), amorphous polyethylene phthalate (A-PET) polyester resin such, polycarbonate (PC) resins, and polyurethane resins.

Among the above binder resins, it is excellent in transparency, durability, and adhesion to the base material. Polyvinyl chloride (PVC) resin, vinyl chloride-vinyl acetate copolymer, polycarbonate (PC) resin, glycol modification The use of polyester resins such as polyethylene terephthalate (PET-G) and amorphous polyethylene phthalate (A-PET), acrylic resins such as polymethyl methacrylate (PMMA) and copolymerized acrylic, and urethane resins is preferred. In the vinyl chloride-vinyl acetate copolymer, the proportion of vinyl acetate resin in the vinyl chloride-vinyl acetate copolymer is 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less. is there.

In addition, you may contain another additive in the range which does not inhibit antistatic property. For example, if necessary, lubricants, colorants, pigments, antistatic agents, flame retardants, antibacterial agents, antifungal agents, UV absorbers, light stabilizers, heat stabilizers, antioxidants, plasticizers, flow control agents Additives such as may be added.

As the dispersant, for example, a silane coupling agent, a titanate coupling agent, a surfactant, an organic acid such as oleic acid, a hydroxyl group-containing polymer compound such as an acetal resin, a carboxyl group-containing polymer compound, or the like may be used. Is possible.

The antistatic layer can be provided on the base material by a known method. For example, when adopting a method of applying the antistatic layer to the base material, the antistatic layer is formed. It is necessary to manufacture the coating liquid. The main components of the coating liquid are the binder resin, the conductive agent, and a solvent. The solvent used in the coating solution for constituting the antistatic layer of the present invention is selected in consideration of the compatibility between the binder resin and the conductive agent. For example, as the solvent, tetrahydrofuran (THF), cyclohexane, cyclohexanone, a mixed solution of isopropyl alcohol and water, ethanol, a mixed solution of cyclohexanenone and ethyl acetate, or the like can be used. The amount of the solvent is determined by adjusting so as to develop a general viscosity necessary for coating.

(Manufacturing method of this laminate)
The laminate can be produced by forming a substrate and then providing at least one antistatic layer.
A base material manufactures a vinyl chloride resin composition by the following method. That is, it can be obtained by mixing a predetermined amount of a vinyl chloride resin, a high temperature decomposition accelerator, a low temperature decomposition inhibitor, and a high temperature decomposition inhibitor using a blender or a Henschel mixer. At this time, you may mix | blend other compounding agents, such as a heat resistance improver and a pigment, in the range which does not inhibit the effect of this invention.

The laminate can be formed into various forms depending on the application. For example, it can be formed into a shape such as a film, a sheet, a plate material, a pipe, and an odd-shaped product.
Moreover, the base material of this laminated body can be shape | molded by the well-known method of shape | molding resin. For example, it is possible to mold by extrusion molding, calendar molding, press molding method or continuous press molding.

Of the above molding methods, the calendar press molding method is a molding method under mild conditions, so there is a wide range of selection of stabilizers having a low-temperature decomposition inhibiting function, such as organotin stabilizers, metal soap systems. A stabilizer, zeolite, hydrotalcite, aluminum-based or magnesium-based hydroxide can be used alone or in combination of two or more.
In the calendar press molding method, a thin plate can be preferably molded at the calendar molding stage. In order to obtain a plate body having a desired thickness, a plurality of plates are laminated at a press molding stage to obtain a desired thickness. Therefore, the calendar press molding method does not require a large change in the molding machine when changing the thickness of the molded body, and can change the thickness of the molded body.

  Furthermore, in the calendar press molding method, a plurality of plate bodies obtained in the calendar molding stage are laminated in the press molding stage to obtain a plate body having a desired thickness. There is a certain amount of thickness fluctuation due to molding conditions, etc., and this thickness fluctuation is synergistic with the thickness fluctuation caused by the conditions in the press molding stage, resulting in poor thickness accuracy.

On the other hand, the extrusion molding method is a molding method under harsh conditions of high temperature and high pressure compared to the calendar press molding method, so the range of selection of stabilizers having a low-temperature decomposition inhibiting function is narrow, and organic tin-based stability Agent, metal soap stabilizer, zeolite, hydrotalcite, aluminum and magnesium hydroxide are required in combination. A suitable combination includes a combination of an organotin stabilizer and at least one of zeolite, hydrotalcite, and magnesium hydroxide.
In the extrusion molding method, there is no problem that a so-called glossing phenomenon occurs, and a plate having a desired thickness can be obtained by one-time extrusion, so that there is no problem of delamination (solvent resistance).
The extrusion molding method has problems such as the occurrence of undulations in the plate and uneven thickness by adjusting subtle variations in the extrusion conditions and subtle variations in the drawn plate. It is possible to prevent.

In addition, the extrusion continuous press molding method does not have a problem of delustering or delamination (solvent resistance), and the extruded plate body is pressed subsequent to the extrusion, so there is no waviness phenomenon. This is a particularly preferable molding method in that a plate having a thickness of 5 mm can be obtained with high thickness accuracy.
Examples of the low-temperature decomposition inhibitor suitably used in the continuous extrusion press molding method include organotin stabilizers, hydrotalcites, and magnesium hydroxide.

  The antistatic layer of the laminate can be provided by a known method. For example, a method of providing an antistatic layer by pressing a film provided with an antistatic layer on a base material, a method of directly applying a coating material for forming the antistatic layer to a base material, and a transfer of the antistatic layer There is a method of providing on the surface of the substrate.

The flame retardancy of a flame retardant vinyl chloride resin molded article can be generally evaluated using a cone calorimeter according to ASTM 1354.
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 (maximum calorific value, also referred to as PHRR; unit: kW / m ² ), unit Average value of calorific value due to combustion per area and unit time (average heat rate, also described as AHRR; unit: kW / m ² ), total heat value due to combustion (also described as total heat 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 ), light attenuation due to combustion per unit area and unit time maximum value of the volume (maximum dimming volume, also referred to as PSEA; unit: m ² / g), average (average ratio dimming area dimming volume by combustion per unit area and unit time, and ASEA Described; unit: m ² / kg), and the like.

Conventionally, as one of the flame retardant indicators, evaluation standards defined by the Factory Mutual Insurance System have been used effectively. 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, and the flame spread index FPI indicating flame retardancy and fuming indicating smoke. 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).
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.
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.
Therefore, by evaluating the flame retardancy using a corn calorimeter, the approximate value of the FM standard can be obtained efficiently.

According to the FM standard, FPI is 6 or less and SDI is 0.4 or less. However, in the present invention, PHRR is 130 kW / m ² or less and AHRR is 65 kW / m ² or less as equivalent to or more than this standard. THR is preferably 100 MJ / m ² or less, AMLR is 13 g / sec · m ² or less, PSEA is 1500 m ² / g or less, and ASEA is 800 m ² / kg or less.

The upper limit of the average heat release rate (AHRR) measured according to ASTM E1354 of the molded product when molded into a thickness of 5 μm using the vinyl chloride resin composition constituting the substrate of this laminate is 65 kW / m ² or less, preferably 50 kW / m ² or less, more preferably 30 kW / m ² or less. Further, when the vinyl chloride resin composition constituting the base material of the laminate of the present invention is used and molded to a thickness of 5 μm, the average specific light-reduction area (ASEA) measured according to ASTM E1354 of the molded product Is not more than 800 m ² / kg, preferably not more than 600 m ² / kg, more preferably not more than 500 m ² / kg.
If the average heat generation rate (AHRR) is 65 kW / m ² or less and the upper limit of the average specific attenuation area (ASEA) is 800 m ² / kg or less, the FM standard can be satisfied.

  In addition, the average of the molded object at the time of shape | molding to measure according to ASTM E1354 of the molded object at the time of shape | molding to 5 micrometers in thickness using the vinyl chloride-type resin composition which comprises the base material of this laminated body When adjusting the heat generation rate (AHRR) and the average specific attenuation area (ASEA) to a certain range, put a chlorine-containing resin having a high-temperature decomposition promoting function and a smaller number of parts containing an organic compound having a high-temperature decomposition inhibiting function. It is preferable to do this.

The molded body made of the vinyl chloride resin composition constituting the substrate of the present laminate has a total light transmittance of 55 to 100%, preferably 65 to 100%, and more preferably 70 to 100%. It is desirable that the haze value is 20% or less, preferably 10% or less, more preferably 5% or less, and a transparent or transparent molded body, and it is desirable to have such characteristics particularly when the thickness is 5 mm. .
In order to adjust the total light transmittance and haze of the molded body by the vinyl chloride resin composition constituting the base material of this laminate to a preferable range, a chlorine-containing resin having a high-temperature decomposition promoting function and a low-temperature decomposition suppressing function It is preferable to adjust by adding as little heat stabilizer as possible.

  The base material of the laminate has not only excellent flame retardancy but also excellent transparency. Therefore, by using a hard vinyl chloride resin molded body, in particular, interior and exterior materials for airplanes, ships, vehicles, and other transportation equipment; interior and exterior materials for buildings; daily goods such as furniture and office equipment; housings for home appliances and electronic devices Material: It can be suitably used as a component of a semiconductor device. Moreover, this laminated body which provided the antistatic layer on the said base material can be used suitably as partitions etc. of a clean room etc. by having a flame retardance, transparency, and antistatic property.

  Hereinafter, although an Example and a comparative example demonstrate in more detail, this invention does not receive a restriction | limiting at all in the following Example.

[Examples 1 to 16]
Chlorine-containing resin (high temperature decomposition accelerator in the table) that has a high temperature decomposition promoting function against vinyl chloride resin having a polymerization degree of 800 (vinyl chloride homopolymer), an organic compound that has a high temperature decomposition inhibiting function (in the table) ), A thermal stabilizer having a low-temperature decomposition promoting function (“low-temperature decomposition inhibitor” in the table) is blended in the proportions shown in Tables 1 and 2, and a vinyl chloride resin composition is prepared. Obtained.
Next, the obtained resin composition was molded into a base material of the laminate by the molding methods shown in Tables 1 and 2, and the properties of the molded body were evaluated by methods according to the molding methods (details). See below). Moreover, the antistatic layer was provided on the base material of the said laminated body, and the surface resistivity of this laminated body was measured.

In addition, Examples 1-8 of Table 1 provided the antistatic layer which used the tin oxide (Mitsubishi Materials Corporation make, T-1) for the electrically conductive agent. Moreover, Examples 9-16 of Table 2 provided the antistatic layer which used the multi-walled carbon nanotube (Nanocy company make, NC-7000) for the electrically conductive agent. The amounts of the conductive agent and binder resin and the thickness of the antistatic layer were adjusted as described in Tables 1 and 2. In Tables 1 and 2, PVC described as a binder resin is a polyvinyl chloride resin (TK-800, manufactured by Shin-Etsu Chemical Co., Ltd.), and a vinyl chloride-vinyl acetate copolymer is vinyl chloride and acetic acid. It is a copolymer resin of vinyl (manufactured by Kaneka Corporation, MA-1008). Moreover, the dispersing agent currently used in Examples 1-8, Comparative Examples 1-5, and Comparative Example 13 uses Rapisol A-90 (made by NOF Corporation), and in Example 9 and Comparative Example 6. As the dispersant used, sodium laurylbenzene sulfonate (manufactured by Nacalai Tex Co., Ltd.) was used. The antistatic layer was provided on the base material layer by adjusting the wire bar count to a desired layer thickness.

[Comparative Examples 1 to 13]
For the same vinyl chloride resin used in the examples, a chlorine-containing resin having a high-temperature decomposition promoting function (high-temperature decomposition accelerator in the table), an organic compound having a high-temperature decomposition-inhibiting function (high-temperature decomposition inhibitor in the table) ), A thermal stabilizer having a low-temperature decomposition promoting function (low-temperature decomposition inhibitor in the table) was blended in the ratios shown in Tables 3 and 4, and a comparative vinyl chloride resin composition was obtained.
Moreover, the obtained resin composition was shape | molded by each shaping | molding method shown in Table 3 and 4, and the characteristic of the molded object was evaluated by the method according to each shaping | molding method (refer below for details).

In addition, in Table 1-4, the numerical value of a compounding ratio is a mass part of each compound with respect to 100 mass parts of vinyl chloride resins.
As the vinyl chloride resin, a vinyl chloride resin having a polymerization degree of 800 (trade name “TH-800” manufactured by Taiyo PVC Co., Ltd.) was used.

The following resins were used as chlorine-containing resins having a high-temperature decomposition accelerating function (see Table 1-4).
Chlorinated polyethylene resin: Trade name “404B” manufactured by Showa Denko
Post-chlorinated vinyl chloride resin: Kaneka product name “H527”
Vinylidene chloride resin: Trade name “Saran168” manufactured by Dow Chemical
Zinc compound: Zinc laurate (trade name “ZS-3” manufactured by Kosho)

The following compounds were used as organic compounds having a high-temperature decomposition inhibiting function (see Table 1-4).
Lubricant: Cognis product name “Roxyol G60”
Processing aid: Rohm & Haas product name "K-120N"
Impact modifier: Product name "BTA712" manufactured by Rohm & Haas
Plasticizer: Product name “DINA” manufactured by J-Plus
Antistatic agent: Trade name “Electro Stripper TS-5” manufactured by Kao Corporation
UV absorber: Product name “Chinubin P” manufactured by Ciba Specialty
Antioxidant: Product name “Irganox 1076” manufactured by Ciba Specialty

The following compounds were used as organic compounds having a high-temperature decomposition inhibiting function (see Table 1-4).
Organotin stabilizer: Product name “N-2000E” manufactured by Nitto Kasei Co., Ltd.
Metal soap stabilizer: Product name “NMZ43” manufactured by Shinagawa Chemical
Zeolite: Tosoh product name “GSL-1000”
Hydrotalcite: Kyowa Chemical Co., Ltd. trade name “Alkamizer 1”
Aluminum hydroxide: Trade name “ALH” manufactured by Kawai Lime Industry Co., Ltd.
Magnesium-based hydroxide: Kyowa Chemical Co., Ltd. trade name “Magsarat F”

[Calendar press molding and evaluation method of the obtained molded body]
The result evaluated by the following evaluation method was combined with Tables 1-4, and was shown.

(1) Moldability:
Molding workability when molded as in the following (2) to (4) was evaluated according to the following criteria.
○: Adhesiveness and local decomposition do not occur on the roll, and it is possible to peel from the press plate with a press, and a molded product having a smooth surface, no color unevenness and streaks can be obtained.
Δ: Some sticking and local decomposition occur on the roll, but it can be peeled off from the press plate with a press, and the surface is smooth, and there are some uneven color streaks, but there are obtained practically no molded products.
X: Adhesion and local decomposition occur on the roll, and a calendar sheet cannot be obtained.

(2) Flame retardancy:
The vinyl chloride compositions of Examples and Comparative Examples were kneaded with a 180 ° C. calender roll and sheeted to a thickness of 1 mm, and the obtained six sheets were stacked to form a 200 ° C. hot plate (10 cm × 10 cm, thickness 5 mm). ) After 15 minutes of press molding, AHRR (Kw / m ² ) and ASEA (m ² / kg) were measured according to ASTM E1354 using a cone calorimeter manufactured by Atlas.

(3) Thermal stability:
The compositions of Examples and Comparative Examples were kneaded with a 180 ° C. calender roll, sheeted to a thickness of 0.5 mm, six sheets obtained were stacked, and press molded to a thickness of 2 mm with a 200 ° C. hot plate for 10 minutes. The change in yellowness (ΔYI) between the compact and the compact that was press-molded for 20 minutes was measured with a color difference meter.

(4) Transparency:
The total light transmittance (%) and haze value (%) were measured in accordance with JIS K 7105 for the transparency of the calendar press molded body obtained by molding in the same manner as in the above flame retardant evaluation.

[Method for evaluating extrusion molding and obtained molded article]
The result evaluated by the following evaluation method was combined with Tables 1-4, and was shown.

(1) Moldability:
Molding workability when molded as in the following (2) to (4) was evaluated according to the following criteria.
○: Local decomposition does not occur, the resin temperature and the resin pressure can be controlled, color unevenness and streaks do not occur, and a good molded product can be obtained.
(Triangle | delta): Although local decomposition | disassembly, color unevenness, and a part of streaks generate | occur | produce, the molded object which can be adjusted with resin temperature and resin pressure and is practically satisfactory is obtained.
X: Local decomposition occurs, and a molded product cannot be obtained because it is difficult to control the resin temperature and the resin pressure.

(2) Flame retardancy:
The vinyl chloride resin compositions of Examples and Comparative Examples were extruded into a 5 mm-thick plate, and this molded product was subjected to AHRR (Kw / m ² ) and ASEA (m ² / kg) in the same manner as the calendar press molded product. ) Was measured.

(3) Thermal stability:
The compositions of Examples and Comparative Examples were extruded using a twin screw extruder into a 4 mm thick plate at 200 ° C., and the yellowing change (ΔYI) of the resulting molded product was measured with a color difference meter.

(4) Transparency:
Extrusion-molded into a 1 mm-thick plate with a twin-screw extruder, and the transparency of the resulting molded product was evaluated in the same manner as the calendar press-molded product.

[Continuous press molding and evaluation method of the obtained molded body]
The result evaluated by the following evaluation method was combined with Tables 1-4, and was shown.

(1) Moldability:
Molding workability when molded as in the following (2) to (4) was evaluated according to the following criteria.
○: Local decomposition does not occur, the resin temperature and the resin pressure can be controlled, and peeling can be performed without sticking to the continuous press plate, so that a good molded body can be obtained. In addition, streaks and color irregularities cannot be found visually.
Δ: Partial decomposition occurs, but a molded article that can be adjusted by the resin temperature and the resin pressure and has no practical problem within the range of condition adjustment of the continuous press plate is obtained. Although there are streaks and uneven color, there is no practical problem.
X: Local decomposition occurs, it is difficult to control with the resin temperature and the resin pressure, and the molded product cannot be obtained by sticking with a continuous press plate.

(2) Flame retardancy:
The vinyl chloride resin compositions of Examples and Comparative Examples were extruded into a 10 mm thick plate with a twin screw extruder, and this was continuously press molded into a 5 mm thickness with a 200 ° C. hot plate. for, was measured AHRR as in the calender pressed bodies (Kw / m ²⁾ and ASEA (m ² / kg).

(3) Thermal stability:
The compositions of Examples and Comparative Examples were extruded into a 4 mm thick plate with a twin-screw extruder, pressed into a 2 mm thickness with a hot plate at 200 ° C. for 10 minutes, and molded for 20 minutes. The yellowing change (ΔYI) with the body was measured with a color difference meter.

(4) Transparency:
Transparency in an extrusion press-molded product obtained by molding in the same manner as in the above flame retardancy evaluation was evaluated in the same manner as the calendar press-formed product.

Antistatic:
The surface resistivity of the antistatic vinyl chloride resin laminates of Examples and Comparative Examples was performed as follows according to JIS K6911.
Measuring device: Hitester UP MCP-HT450 type (manufactured by Mitsubishi Chemical Corporation), measuring method: constant voltage applying method, applied voltage: 1000V

  In Examples 1 to 16, since a high temperature decomposition accelerator, a high temperature decomposition inhibitor, and a low temperature decomposition inhibitor were added within a certain range, when processed into a molded product, transparency, flame retardancy, heat A vinyl chloride resin composition having good stability and lubricity was obtained. Further, the vinyl chloride resin composition was molded on the base material of the laminate, and an antistatic layer was provided on the surface of the base material to obtain a laminate having good antistatic properties.

  In Comparative Example 1, since the high-temperature decomposition accelerator was excessively added, the thermal stability was poor, and the molding processability in continuous press molding was not good. In Comparative Examples 2 and 3, since the high temperature decomposition accelerator, the high temperature decomposition inhibitor, and the low temperature decomposition inhibitor were respectively added excessively, the thermal stability was poor. Moreover, regarding the comparative example 3, transparency was also bad. In Comparative Example 4, since no high temperature decomposition accelerator was added, the moldability by the calender press method was poor. In Comparative Example 5, the flame retardancy was poor because the high-temperature decomposition accelerator was small and the high-temperature decomposition inhibitor was excessive. In Comparative Example 6, since the high-temperature decomposition accelerator was a small amount, the flame retardancy was poor, and the moldability by the calendar press molding method was poor. In Comparative Example 7, the high-temperature decomposition accelerator was excessively added, and the high-temperature decomposition inhibitor was also excessively added, so that the thermal stability was poor. In Comparative Examples 8 and 9, since the amount of the high-temperature decomposition accelerator was small, molding processability was poor in calendar press molding and continuous press molding. In Comparative Example 10, since the high temperature decomposition accelerator and the low temperature decomposition accelerator were excessively added and the high temperature decomposition inhibitor was not added, a molded product could not be obtained by continuous pressing. In Comparative Example 11, the high-temperature decomposition accelerator and the high-temperature decomposition inhibitor were excessively added, and the low-temperature decomposition inhibitor was not converted, so that a molded product could not be obtained in the continuous press molding. In Comparative Example 12, the antistatic property was poor because there was no antistatic layer. In Comparative Example 13, since the high temperature decomposition accelerator was not added, the flame retardancy was poor when molded by a continuous press.

This laminate is excellent in flame retardancy and transparency, has a small amount of smoke generation, has a high softening temperature, has a good appearance, and has antistatic properties. In particular, this laminate using a hard vinyl chloride resin as the base material resin of the base material is used for transport equipment such as aircraft, ships, vehicles, etc .; interior / exterior materials for buildings; daily necessaries such as furniture and office equipment; Suitable as housing materials for equipment, electronic equipment, etc .; semiconductor device parts, clean room partitions, etc.
In particular, this laminate formed by the extrusion continuous press molding method has no gloss return during heat processing, has excellent solvent resistance, and has high thickness accuracy. It can be used well as a body.

Claims (8)

  A laminate having at least one antistatic layer on a base material, wherein the base material is 1 to 50 parts by weight of a chlorine-containing resin having a high-temperature decomposition promoting function with respect to 100 parts by weight of a vinyl chloride resin; A base material comprising a vinyl chloride resin composition containing 0.1 to 7 parts by mass of an organic compound having an inhibiting function and 1 to 10 parts by mass of a thermal stabilizer having a low-temperature decomposition inhibiting function. -Based vinyl chloride resin laminate. When the vinyl chloride resin composition is molded to a thickness of 5 μm, the average heat release rate (AHRR) measured according to ASTM E1354 is 65 kW / m ² or less, and the average measured according to ASTM E1354 ^{2. The} antistatic device according to claim 1, wherein the specific light reduction area (ASEA) is 800 m ² / kg or less, the light transmittance is 55 to 100%, and the haze value is 20% or less. -Based vinyl chloride resin laminate.   The chlorine-containing resin having a high-temperature decomposition promoting function is one or a mixture of two or more selected from the group consisting of a chlorinated polyethylene resin, a post-chlorinated vinyl chloride resin, and a vinylidene chloride resin. The antistatic vinyl chloride resin laminate according to claim 1 or 2.   The organic compound having the high-temperature decomposition inhibiting function is one or more selected from the group consisting of a lubricant, a processing aid, an impact modifier, a plasticizer, an antistatic agent, an ultraviolet absorber and an antioxidant. The antistatic vinyl chloride resin laminate according to any one of claims 1 to 3, which is a mixture.   The heat stabilizer having the low-temperature decomposition inhibiting function is one selected from the group consisting of organotin stabilizers, metal soap stabilizers, zeolites, hydrotalcites, aluminum-based and magnesium-based hydroxides or The antistatic vinyl chloride resin laminate according to any one of claims 1 to 4, which is a mixture of two or more kinds. The antistatic vinyl chloride resin laminate according to any one of claims 1 to 7, wherein the main components of the antistatic layer are a binder resin of thermoplastic resin and a conductive agent. The antistatic vinyl chloride resin according to any one of claims 1 to 7, wherein the antistatic layer is a layer mainly containing a binder resin of a thermosetting resin and a conductive agent. Laminated body. The antistatic vinyl chloride resin laminate according to any one of claims 1 to 7, wherein the conductive agent is one or more selected from tin oxide, conductive titanium oxide, and carbon fiber. body.