JP2006249306A - Flame-retardant film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant film by making a film from a non-halogen type polyolefinic resin molding material which is excellent in extruding and calendering properties without plate-out, and excellent in flame resistance, and having good low temperature impact resistance, anti-whitening property, printing suitability, transparency, etc. <P>SOLUTION: This flame-retardant film is prepared by making a film from a polyolefinic resin molding material containing 100 parts by mass random copolymer (A) of propylene and ethylene and/or 4-20C α-olefin having an MFR value of 0.1-20 g/10 minutes and a melting point of 130-150°C, and 0.1-1.5 parts by mass alkoxyimino group type hindered amine compound (B). As for the molding material, there is no plate-out in a roll kneading test at 200°C for 10 minutes, and as for the film, it shows first grade flame proofing in a flame proofing test, its surface average roughness Ra is 0.3-1.2 μm, it passes an impact tester impact test at 0°C, and there is no whitening in a whitening test at 5°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention includes a flame retardant film, more specifically, a random copolymer of propylene and ethylene and / or α-olefin, and an alkoxyimino group-type hindered amine compound, which has no plate-out and has excellent extrudability and calendar processability. The present invention relates to a flame retardant film obtained by forming an excellent non-halogen type polyolefin-based resin molding material and having excellent flame resistance and good low temperature impact resistance, whitening resistance, printability and transparency.

Conventionally, as a decorative material used for a building member such as a flooring material or a wall material, or a surface decorative plate such as a cabinet of furniture, kitchen products, or household appliances, for example, a structure in which a decorative film is bonded onto a base material is used. It is used. A decorative film used for such a decorative material or a decorative sheet is usually (1) lapping workability, that is, when the substrate has an uneven portion or a complicated shape, it can be bonded according to the shape. Processability, (2) V-cut processability, that is, processability when V-cut processing is applied to the decorative material and surface decorative board after being bonded, and bending or assembling into various shapes is required. . Specifically, it is required that inconveniences such as cracking, cutting, and whitening do not occur in the folded portion of the decorative film.
In order to impart V-cut processability and lapping processability to a decorative film, a vinyl chloride resin film has been generally used so far. However, although this vinyl chloride resin film has good V-cut processability and lapping processability, there is concern about the generation of harmful substances from the vinyl chloride resin when the product eventually becomes waste. Attempts have been made to develop decorative films that do not use vinyl chloride resin films.
As one of them, a polyolefin resin film is known (see, for example, Patent Document 1). However, this polyolefin-based resin film has a problem that it is inferior in flame retardancy as compared with conventional vinyl chloride resin films.
High flame retardancy is required for decorative films used in building components, furniture, kitchen products, cabinets for home appliances, etc., but the polyolefin resin film described in the above publication does not satisfy this requirement. Absent.
By the way, in recent years, the use of halogen-based flame retardants has become a problem due to environmental problems, and the development of non-halogen flame retardant technology has been promoted. Addition of a flame retardant. However, in this case, the flame-retardant polyolefin resin film has a problem that it is inferior in low-temperature impact resistance, whitening resistance, transparency, printability, calendar workability, and the like.
On the other hand, alkoxyimino group-type hindered amine compounds have recently been developed as new non-halogen flame retardants (see, for example, Patent Document 2 and Patent Document 3). A self-extinguishing sheet is disclosed as an example of using this alkoxyimino group-type hindered amine compound in a polyolefin resin product (see, for example, Patent Document 4).
This self-extinguishing sheet is a sheet obtained by blending the alkoxyimino group type hindered amine compound with a propylene homopolymer resin. However, since this self-extinguishing sheet uses a propylene homopolymer resin, there are problems that it is inferior in low-temperature impact resistance and whitening resistance, has poor calendar workability, and is difficult to form a calendar.
Japanese Patent Laid-Open No. 9-226071 Japanese Patent Laid-Open No. 11-315067 Japanese translation of PCT publication No. 2002-507238 JP 2004-238482 A

  Under such circumstances, the present invention is excellent in flame resistance and good resistance to resistance, which is formed by forming a non-halogen type polyolefin resin molding material having no plate-out and excellent extrudability and calenderability. The object of the present invention is to provide a flame retardant film having low temperature impact resistance, whitening resistance, printability and transparency.

As a result of intensive studies to achieve the above-mentioned object, the present inventors, as a non-halogen type polyolefin resin molding material, propylene and ethylene having a specific property and / or an α-olefin having 4 to 20 carbon atoms. Based on this finding, it was found that a film having a specific property, which is formed by forming a film containing a random copolymer of the above and an alkoxyimino group type hindered amine compound at a predetermined ratio, can meet the purpose. The present invention has been completed.
That is, the present invention
(1) (A) Propylene and ethylene having an MFR value (load 21.18 N, temperature 230 ° C.) of 0.1 to 20 g / 10 min and a melting point of 130 to 150 ° C. and / or α having 4 to 20 carbon atoms -Forming a polyolefin resin molding material containing 0.1 to 1.5 parts by mass of (B) an alkoxyimino group-type hindered amine compound per 100 parts by mass of a resin component comprising a random copolymer with olefin. A film made of
In the roll kneading test at 200 ° C. for 10 minutes, the polyolefin-based resin molding material has no plate-out, and the film is (a) a flameproof test based on JIS Z 2150 for a film having a thickness of 50 to 200 μm. (B) an arithmetic average roughness Ra of the surface is 0.3 to 1.2 μm; (c) an impact tester impact test at 0 ° C. based on ASTM D 1790; Among the test pieces, all the test pieces are not broken in any length and width, and (d) there is no whitening in the 5 ° C. whitening test,
Flame retardant film, characterized by
(2) (A ′) (a-1) Propylene and ethylene and / or carbon having an MFR value (load 21.18 N, temperature 230 ° C.) of 0.1 to 20 g / 10 min and a melting point of 130 to 150 ° C. (B) alkoxy per 100 parts by mass of a resin component composed of 60 to 95% by mass of a random copolymer with α-olefin of several 4 to 20 and (a-2) 40 to 5% by mass of high-density polyethylene A film formed by forming a polyolefin resin molding material containing 0.1 to 1.5 parts by mass of an imino group type hindered amine compound,
In the roll kneading test at 200 ° C. for 10 minutes, the polyolefin-based resin molding material has no plate-out, and the film is (a) a flameproof test based on JIS Z 2150 for a film having a thickness of 50 to 200 μm. (B) an arithmetic average roughness Ra of the surface is 0.3 to 1.2 μm; (c) an impact tester impact test at 0 ° C. based on ASTM D 1790; Among the test pieces, all the test pieces are not broken in any length and width, and (d) there is no whitening in the 5 ° C. whitening test,
Flame retardant film, characterized by
(3) The high-density polyethylene of component (a-2) was obtained by the low-pressure method, and had an MFR value (load of 21.18 N, temperature of 190 ° C.) of 0.1 to 5 g / 10 min. The flame retardant film according to the above item (2), in which is 0.94 to 0.98 g / cm ³ ,
(4) Items (1) to (3) above, wherein a polyolefin resin molding material further containing (C) 0.2 to 3.0 parts by mass of a lubricant per 100 parts by mass of the resin component is formed by a calendar method. The flame-retardant film according to any one of (1) to (4), and (5) one or both sides subjected to corona discharge treatment or plasma discharge treatment. the film,
Is to provide.

  According to the present invention, a halogen-free polyolefin-based resin that includes a random copolymer of propylene and ethylene and / or an α-olefin and an alkoxyimino group-type hindered amine compound and has excellent plate-out properties and extrudability and calendar processability. It is possible to provide a flame retardant film which is formed by forming a molding material and has excellent flame resistance and has good low temperature impact resistance, whitening resistance, printability and transparency.

The flame-retardant film of the present invention can be obtained by forming a polyolefin resin molding material I or II shown below.
The polyolefin resin molding material I has (A) propylene, ethylene and / or carbon having an MFR value (load 21.18 N, temperature 230 ° C.) of 0.1 to 20 g / 10 min and a melting point of 130 to 150 ° C. It contains 0.1 to 1.5 parts by mass of (B) an alkoxyimino group-type hindered amine compound per 100 parts by mass of a resin component composed of a random copolymer with a 4 to 20 α-olefin. Polyolefin-based resin molding material II is propylene having an (A ′) (a-1) MFR value (load 21.18 N, temperature 230 ° C.) of 0.1 to 20 g / 10 min and a melting point of 130 to 150 ° C. And a resin component consisting of 60 to 95% by mass of a random copolymer of ethylene and / or an α-olefin having 4 to 20 carbon atoms, and (a-2) 40 to 5% by mass of high-density polyethylene, and 100 It contains 0.1 to 1.5 parts by mass of (B) alkoxyimino group-type hindered amine compound per part by mass.
In the present invention, as the component (A) and the component (A ′) (a-1) in the polyolefin resin molding materials I and II, propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms. Random copolymers are used.
Examples of the α-olefin having 4 to 20 carbon atoms as a comonomer include 1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4 -Methyl-1-pentene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 5 -Methyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, etc., among which 4 carbon atoms -10, specifically 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene are preferred.
In the present invention, as the comonomer, one kind may be selected from ethylene and the α-olefin having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, or two or more kinds may be selected and used in combination.
In addition, in the random copolymer of propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms, the content of the comonomer unit is usually in the range of 0.5 to 12% by mass. If the content of the comonomer unit is in the above range, a film having good low temperature impact resistance, whitening resistance, extrusion processability, calendar processability, and the like can be obtained. The preferable content of the comonomer unit is 1 to 6% by mass, and particularly preferably 2 to 4% by mass.

In the present invention, this random copolymer of propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms has a melt flow rate (MFR) value (load 21.18 N, temperature 230 ° C.) of 0.1. It needs to be in the range of ˜20 g / 10 min and the melting point is in the range of 130 to 150 ° C. If the MFR value and the melting point are in the above ranges, the resulting polyolefin resin molding material has good extrudability and calenderability, and a film having desired properties can be obtained. A preferred MFR value is 1.0 to 10 g / 10 min.
The MFR value is a value measured under conditions of a load of 21.18 N and a temperature of 230 ° C. in accordance with JIS K 7210. The melting point refers to the melting peak temperature (Tm) measured with a differential scanning calorimeter (DSC). This Tm is a value obtained by measuring using “DSC8230” manufactured by Rigaku Corporation and obtaining the temperature of the melting peak in accordance with JIS K7121.
In the polyolefin resin molding material II in the present invention, high-density polyethylene is used as the component (a-2). This high-density polyethylene was obtained by a low-pressure method and has an MFR value in the range of 0.1 to 5 g / 10 min and a density in the range of 0.94 to 0.98 g / cm ^3. More preferably, the MFR value is 0.3 to 1.0 g / 10 min and the density is 0.95 to 0.97 g / cm ³ .
The MFR value is a value measured under the conditions of a load of 21.18 N and a temperature of 190 ° C. in accordance with JIS K 7210. The density is a value measured according to JIS K 7112.

In the polyolefin-based resin molding material II in the present invention, (A ′) as a resin component, random copolymerization of propylene as the component (a-1) and ethylene and / or an α-olefin having 4 to 20 carbon atoms. A mixture of 60 to 95% by mass of coalescence and 40 to 5% by mass of high-density polyethylene as the component (a-2) is used. By using such a mixed resin as the resin component, the calenderability of the molding material obtained is higher than that of a random copolymer of propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms alone. Is better. The preferred proportions of the component (a-1) and the component (a-2) are such that the component (a-1) is 70 to 90% by mass and the component (a-2) is 30 to 10% by mass. It is preferable that the component -1) is 75 to 85% by mass and the component (a-2) is 25 to 15% by mass.
In the polyolefin-based resin molding material I in the present invention, the polyolefin-based resin is used with respect to 100 parts by mass of the random copolymer of propylene of component (A) and ethylene and / or α-olefin having 4 to 20 carbon atoms. In the molding material II, (a-1) a random copolymer of propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms as the component (A ′), and (a-2) high-density polyethylene The alkoxyimino group-type hindered amine compound (B) component is used in a proportion of 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the mixture. The alkoxyimino group-type hindered amine compound of component (B) has an effect of imparting excellent flame retardancy to the resulting film, and the amount of the hindered amine compound used is within the above range. For example, the balance between the effect of imparting flame retardancy and economic efficiency is improved without significantly affecting other physical properties. A preferable use amount is 0.15 to 1.0 part by mass, and 0.2 to 0.6 part by mass is particularly preferable.

  Examples of the alkoxyimino group-type hindered amine compound include those represented by the general formula (I) described in JP-T-2002-507238, for example.

（式中、Ｇ¹及びＧ²は、それぞれ独立に炭素数１〜４のアルキル基又は一緒になってペンタメチレン基を示し、Ｚ¹及びＺ²は、それぞれメチル基を示し、また、たがいに結合して環構造を形成してもよく、この環構造は、エステル基、エーテル基、アミド基、アミノ基、カルボキシル基又はウレタン基によって置換されていてもよい。Ｅは炭素数１〜１８のアルコキシ基、炭素数５〜１２のシクロアルコキシ基、炭素数７〜２５のアラルキルオキシ基、炭素数６〜１２のアリールオキシ基を示す。）

(In the formula, G ¹ and G ² each independently represent an alkyl group having 1 to 4 carbon atoms or together represent a pentamethylene group, Z ¹ and Z ² each represent a methyl group, and A ring structure may be bonded to form a ring structure, which may be substituted by an ester group, an ether group, an amide group, an amino group, a carboxyl group, or a urethane group, and E has 1 to 18 carbon atoms. An alkoxy group, a C5-C12 cycloalkoxy group, a C7-C25 aralkyloxy group, and a C6-C12 aryloxy group are shown.)

The hindered amine type compound containing group represented by these, or its reaction product can be used.
In the general formula (I), Z ¹ and Z ² are bonded to each other to form a 6-membered ring, particularly a substituted piperidine ring, specifically substituted 2,2,6,6- Those having a tetramethylpiperidine structure are preferred.
E is preferably a methoxy group, a propoxy group, a cyclohexyloxy group or an octyloxy group, and particularly preferably a propoxy group, a cyclohexyloxy group or an octyloxy group.
Examples of the hindered amine compound containing a group represented by the general formula (I) or a reaction product thereof include (a) 1-cyclohexyloxy-2,2,6,6, -tetramethyl-4-octadecylamino. Piperidine, (b) bis (1-octyloxy-2,2,6,6, -tetramethylpiperidin-4-yl) sebacate, (c) 2,4-bis [(1-cyclohexyloxy-2,2, 6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -s-triazine, (d) bis (1-cyclohexyloxy-2,2,6,6-tetramethyl Piperidin-4-yl) adipate, (e) 4,4′-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino)- Terminal key with s-triazine Oligomers which are condensation products with capped 2,4-dichloro-6-[(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine (F) 4,4′-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine Oligomers which are condensable products with capped 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine (G) 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) -6-chloro-s-triazine, (h) represented by the following formula Compound

などを挙げることができる。これらの化合物は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
前記（ｈ）の化合物は、過酸化処理した４−ブチルアミノ−２,２,６,６−テトラメチルピペリジンと、２,４,６−トリクロロ−ｓ−トリアジンと、シクロヘキサンと、Ｎ,Ｎ'−エタン−１,２−ジイルビス(１,３−プロパンジアミン)との反応生成物であり、「Ｆｌａｍｅｓｔａｂ ＮＯＲ １１６［登録商標名、チバスペシャルティ・ケミカルズ社製］として市販されている。
本発明において用いられるポリオレフィン系樹脂成形材料Ｉ及びII（以下、これらをまとめて、「ポリオレフィン系樹脂成形材料」と称する。）には、所望に応じ、本発明の目的が損なわれない範囲で各種添加剤、例えば酸化防止剤、紫外線吸収剤や光安定剤、滑剤、無機充填剤、他の難燃剤、着色剤、帯電防止剤などを含有させることができる。

And so on. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
The compound (h) includes peroxidized 4-butylamino-2,2,6,6-tetramethylpiperidine, 2,4,6-trichloro-s-triazine, cyclohexane, N, N ′. A reaction product with ethane-1,2-diylbis (1,3-propanediamine), which is commercially available as “Flamestab NOR 116 [registered trademark, manufactured by Ciba Specialty Chemicals]”.
The polyolefin-based resin molding materials I and II (hereinafter collectively referred to as “polyolefin-based resin molding material”) used in the present invention can be variously used as long as the object of the present invention is not impaired. Additives such as antioxidants, ultraviolet absorbers and light stabilizers, lubricants, inorganic fillers, other flame retardants, colorants, antistatic agents and the like can be included.

  As the antioxidant, phenol-based, sulfur-based, phosphorus-based antioxidants and the like can be used. Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, stearyl (3,3-dimethyl-4-hydroxybenzyl) thioglycolate, stearyl-β- (4-hydroxy-3). , 5-di-tert-butylphenol) propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris (3 ′, 5′-di-tert-butyl- 4'-hydroxybenzylthio) -1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butylbenzyl) malonate, 2,2'-methylenebis (4-methyl-6-tert) -Butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -Cresol], bis [3,5-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6-tert-butyl-m-cresol), 1, 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5- Methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butyl) benzyl isocyanurate, 1,3,6-tris (3,5-di-tert) -Butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxy Phenyl) propionyloxyethyl] isocyanurate, 2-octylthio-4,6-di- (4-hydroxy-3,5-di-tert-butyl) phenoxy-1,3,5-triazine, 4,4′-thiobis Polyphenols such as (6-tert-butyl-m-cresol) and polyhydric acids such as 4,4′-butylidenebis (2-tert-butyl-5-methylphenol) carbonic acid oligoester (eg, degree of polymerization 2 to 10) Phenol carbonic acid oligoesters and the like can be mentioned.

Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl-, dimyristyl- and distearyl- and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl- and stearyl- , Esters of trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol tetralauryl thiopropionate).
Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite. , Tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4- hydroxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) -4,4'-butylidene bis (3-methyl -6-tert -Butylphenol) diphosphite, tris (8,5-di-tert- Til-4-hydroxyphenyl) phosphite, tris (mono-dimixed nonylphenyl) phosphite, hydrogenated-4,4′-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4 ′ -Butylidenebis (3-methyl-6-tert-butylphenol)] 1,6-hexanediol diphosphite, phenyl 4,4'-isopropylidenediphenol pentaerythritol diphosphite, bis (2,4 -Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris [4,4'-isopropylidenebis (2- tert-butylphenol)] phosphite, phenyl diisodecyl phosphite, di (nonylphenyl) Pentaerythritol diphosphite, tris (1,3-di-stearoyloxyisopropyl) phosphite, 4,4′-isopropylidenebis (2-tert-butylphenol) di (nonylphenyl) phosphite, 9,10-di -Hydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, and the like.
Further, as other antioxidants, 6-hydroxychroman derivatives, for example, various tocopherols of α, β, γ, δ or mixtures thereof, 2- (4-methyl-pent-3-enyl) -6-hydroxychroman 2 1,5-dimethyl-substituted, 2,5,8-trimethyl-substituted, 2,5,7,8-tetramethyl-substituted, 2,2,7-trimethyl-5-tert-butyl-6-hydroxychroman, 2, , 2,5-Trimethyl-7-tert-butyl-6-hydroxychroman, 2,2,5-trimethyl-6-tert-butyl-6-hydroxychroman, 2,2-dimethyl-5-tert-butyl-6 -Hydroxychroman etc. can also be used.
These antioxidants may be used individually by 1 type, and may be used in combination of 2 or more type, and the addition amount is usually 0.0001-10 mass based on the polyolefin resin molding material whole quantity. % Is selected.

Examples of the ultraviolet absorber and light stabilizer include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Hydroxybenzophenones such as 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di- tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) Benzotriazoles such as benzotriazole, phenyl salicylate, p-tert-butylphenyl salicylate, 2, Benzoates such as 4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,2 ′ -Thiobis (4-tert-octylphenol) Ni salt, [2,2'-thiobis (4-tert-octylphenolate)]-n-butylamine Ni, (3,5-di-tert-butyl-4-hydroxybenzyl) ) Nickel compounds such as phosphonic acid monoethyl ester Ni salt, substituted acrylonitriles such as methyl α-cyano-β-methyl-β- (p-methoxyphenyl) acrylate, and N′-2-ethylphenyl-N-ethoxy -5-tert-butylphenyl oxalic acid diamide, N-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid dia Oxalic acid dianilides such as amide, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, poly [[[[6- (1,1,3,3-tetramethylbutyl) imino] -1 , 3,5-triazine-2,4-diyl [4- (2,2,6,6-tetramethylpiperidyl) imino] hexamethylene], 2- (4-hydroxy-2,2,6,6-tetra And hindered amine compounds such as a condensate of (methyl-1-piperidyl) ethanol and dimethyl succinate.
These ultraviolet absorbers and light stabilizers may be used singly or in combination of two or more, and the amount added is usually 0, based on the total amount of the polyolefin resin molding material. It is selected in the range of 0001 to 10% by mass.

The lubricant effectively exhibits its function particularly in film formation by the calendar method. Examples of the lubricant include aliphatic hydrocarbons such as paraffin wax, polyethylene wax, and polypropylene wax, capric acids, higher fatty acids such as lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, and behenic acid. Or these metal salts (for example, lithium salt, calcium salt, sodium salt, magnesium salt, potassium salt), aliphatic alcohols such as palmityl alcohol, cetyl alcohol, stearyl alcohol, caproic acid amide, caprylic acid amide, capric acid amide Fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, esters of fatty acid and alcohol, fluoroalkylcarboxylic acid or metal salt thereof, fluoroalkylsulfuric acid Fluorine compounds such as phosphate metal salts.
These lubricants may be used alone or in combination of two or more, and the amount added is usually 0.2 to 3.0 based on the total amount of the polyolefin resin molding material. It is selected in the range of mass parts.
Examples of the inorganic filler include natural silicic acid or silicate such as fine powder talc, kaolinite, calcined clay, vilophyllite, sericite, wollastonite, precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, etc. Powders such as hydroxides such as aluminum hydroxide and magnesium hydroxide, oxides such as zinc oxide, zinc white and magnesium oxide, hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid and anhydrous silicic acid, etc. Fibrous filler, flake filler such as mica, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fiber), zonolite, potassium titanate, elestite Agents, glass balloons, such as a balloon-shaped fillers such as fly ash balloons can be used.
Other flame retardants include, for example, aluminum hydroxide, hydrated gypsum, zinc borate, barium borate, borax, kaolin, clay, calcium carbonate, alumite, basic magnesium carbonate, calcium hydroxide, water Examples include magnesium oxide and ammonium polyphosphate.
In addition, when transparency is requested | required of a film, it is desirable to add these fillers so that transparency of a film may not be impaired.

The polyolefin resin molding material used in the present invention comprises, for example, the (B) component alkoxyimino group-type hindered amine compound and, if desired, various additives in the resin component (A) or (A ′) component. , By mixing with a tumbler blender, Henschel mixer, etc., or by mixing and kneading and granulating using a single screw extruder or multi-screw extruder after mixing, or by kneading and granulating with a kneader, Banbury mixer, etc. Can be prepared.
The polyolefin-based resin molding material thus obtained has no plate-out in the roll kneading test at 200 ° C. and 10 minutes shown below, and is excellent in extrusion processability and calendar processability.
<Roll kneading test (plate-out test)>
The resin composition is kneaded for 10 minutes with an 8-inch test roll apparatus having a roll surface temperature of 200 ° C., and the presence or absence of plate-out is confirmed. As a method of confirmation, a movable roller wound with a surface aluminum foil is pressed against the portion around which the resin compound is wound, and after 10 minutes, the roller is removed and the surface of the aluminum foil is visually confirmed to confirm the adhesion of the plate-out material.

The flame-retardant film of the present invention can be obtained by forming the polyolefin-based resin molding material by a known molding method such as melt extrusion molding, calender molding, cast molding, inflation molding or the like. Although the thickness of this film changes with uses, it is 50-200 micrometers normally, Preferably it is 50-100 micrometers.
The flame retardant film of the present invention has the following properties.
(1) In a flameproof test based on JIS Z 2150 for a film having a thickness of 50 to 200 μm, it is a flameproof first grade.
(2) The arithmetic average roughness Ra (JIS B 0601-1994) of the surface is 0.3 to 1.2 μm, and is excellent in printability. If Ra is less than 0.3 μm, printing ink ink is observed, and there is a problem of blocking after printing. On the other hand, if it exceeds 1.2 μm, the printing will be lost and the sharpness will be insufficient.
(3) In the impact tester impact test at 0 ° C. based on ASTM D 1790, all the test pieces in 10 test pieces are not broken in any length and width. That is, it has excellent low temperature impact resistance.
(4) Whitening does not occur in the 5 ° C. whitening test measured by the method described below. That is, it has excellent whitening resistance.
<5 ° C whitening test>
A test sample is prepared by attaching a predetermined resin film to an aluminum plate with an adhesive, double-sided tape, or the like. The aluminum plate is bent 90 ° after being left for 1 hour in a test chamber adjusted to 5 ° C. Visually observe the film at the top of the fold and check for whitening.

The flame retardant film of the present invention can be subjected to surface treatment on one side or both sides by an oxidation method or a concavo-convex method, if desired, for the purpose of improving adhesion to a layer provided thereon. Moreover, primer treatment can also be performed. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. The law is used. Among these surface treatment methods, corona discharge treatment and plasma discharge treatment are preferably used from the viewpoints of effects and operability.
For the corona discharge treatment, for example, the following method can be employed.
An interval of about 0.5 to 0.6 mm is provided between an electrode connected to a high voltage generator and a metal roll covered with polyester film, hyperon, EP rubber, etc., and several thousand to several at a high frequency of several hundred KC / s. When a high voltage of 10,000 V is applied, a high-pressure corona is generated in the gap. When the film is run in this gap at a constant speed, ozone, nitrogen oxide, and the like that generate corona on the surface of the film react to generate carbonyl groups and the like to make them hydrophilic. The degree of treatment depends on the gap, voltage, current consumption, coating thickness, and film passing speed.
This corona discharge treatment can be performed in air, but in an inert gas containing nitrogen, oxygen, hydrogen, carbon dioxide, chlorine, argon, helium, boron trifluoride, butynediol, acrylonitrile, etc. It is advantageous.

On the other hand, as the plasma discharge treatment, for example, the following method can be employed.
As a first method, the film is cut into a size of about A4 size, and the sample is filled with a mixed gas of argon and carbon dioxide. Subsequently, glow discharge is performed for about 1 second under conditions such as a discharge amount of 1.9 A × 265 V, for example. As a second method, a film having a length of about 50 m × width of about 3000 mm is flowed at a speed of about 20 m / min. The film is continuously subjected to glow discharge at a discharge amount of about 700 W while supplying a mixed gas of argon and carbon dioxide at a flow rate of about 80 L / min.
In the present invention, it is particularly desirable to perform the plasma discharge treatment under the conditions of the second method.
By performing the corona discharge treatment or the plasma discharge treatment in this manner, the film surface is polarized, the surface energy is increased, and the adhesive force with the layer provided thereon can be improved.
The flame retardant film of the present invention is excellent in flame resistance and has good low temperature impact resistance, whitening resistance, printability and transparency, etc., and is produced with good extrudability and calendar workability. For example, it can be suitably used as a decorative film on a decorative material used for a building member such as a flooring material or a wall material, or a surface decorative plate such as a cabinet of furniture, kitchen products, or household appliances. .

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the plate-out test (roll kneading test) of the polyolefin resin molding material, the flame resistance test of the film, and the arithmetic average surface roughness Ra, the low temperature impact resistance, and the whitening resistance measurement are described in the specification text. The method was performed.
The criteria for determining each performance are as follows.
(1) Flame resistance (flameproof test)
○: Flameproof grade 1
X: It is worse than a flameproof 1st grade.
(2) Low temperature impact resistance [0 ° C]
○: No cracks or cracks are observed.
X: Cracks and cracks are observed.
(3) Whitening resistance ○: No whitening is observed.
X: Whitening is observed.
(4) Plate-out test ○: No plate-out is observed.
X: Plate-out is seen.
(5) Extrudability ○: A film / sheet with good appearance can be obtained.
X: Film / sheet with good appearance cannot be obtained.
(6) Calendar workability A: A film / sheet with good appearance can be obtained.
○: A film / sheet having a good appearance can be obtained, but there is a problem in stability in terms of production.
X: Film / sheet with good appearance cannot be obtained.
The total light transmittance was measured by the following method.
<Total light transmittance>
According to JIS K 7361-1, a haze computer [manufactured by Suga Test Instruments Co., Ltd., trade name “HZ-1”] is used for measurement.

Examples 1-4 and Comparative Examples 1-7
First, polyolefin resin molding materials having the blending compositions shown in Tables 1 and 2 were prepared according to a conventional method. In addition, as the resin of the master batch (MB), the same resin as the main raw material resin (polypropylene resin) was used. The content of the NOR flame retardant in the master batch (MB) containing the NOR flame retardant is 10% by mass, and the colorant master batch (MB) contains 50% by mass of titanium oxide.
Further, in each polyolefin resin molding material, phenolic antioxidant, trade name “ADK STAB AO-60” (manufactured by Asahi Denka Kogyo Co., Ltd.) is 0.1 mass% and phosphorus antioxidant, product The name “ADK STAB 2112” (manufactured by Asahi Denka Kogyo Co., Ltd.) is contained by 0.2 mass%.
Next, the polyolefin-based resin molding material was formed into a film having a thickness shown in Tables 1 and 2 by extrusion or calendering according to a conventional method. The evaluation results are shown in Tables 1 and 2.

[note]
(A1) Random PP: Random copolymer of propylene and ethylene, manufactured by Idemitsu Petrochemical (currently Idemitsu Kosan), trade name “F-734NP”, MFR value = 6.5 g / 10 min, melting point = 137 ° C., Ethylene unit = 3.4% by mass
(A2) Random PP: random copolymer of propylene and ethylene, manufactured by Sun Allomer, trade name “Sun Allomer PF430B”, MFR value = 1.8 g / 10 min, melting point = 143 ° C., ethylene unit = 3.5 mass%
(A3) HDPE: high density polyethylene, manufactured by Mitsui Chemicals, trade name “Hi-Zex 6200B”, MFR value = 0.4 g / 10 min, density = 0.96 g / cm ³
(A4) Homo PP: propylene homopolymer, manufactured by Idemitsu Petrochemical Co., Ltd. (currently Idemitsu Kosan), trade name “F-700NPT”, MFR value = 9 g / 10 min, melting point = 160 ° C.
(A5) Block PP: propylene-ethylene block copolymer, manufactured by Nippon Polyolefin Co., Ltd., trade name “J630G”, MFR value = 40 g / 10 min, melting point = 163 ° C.
(B) NOR flame retardant: Ciba Specialty Chemicals, trade name “Flamestab NOR116”
(C) Lubricant: manufactured by Henkel Hakusui Co., Ltd., trade name “G-78”, fatty acid ester (E) magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd., trade name “Kisuma 5A”
(F) Phosphate flame retardant: manufactured by Clariant, trade name “AP750”, ammonium polyphosphate system As can be seen from Tables 1 and 2, the films of the present invention (Examples 1 to 4) In the plate-out test, no plate-out was observed, extrudability or calenderability was good, flame resistance, low-temperature impact resistance, and whitening resistance were excellent, and Ra was 0.3 to 1.2 μm. And has good printability. In addition, since Example 4 uses high-density polyethylene as a resin component, calendar workability is particularly good.
On the other hand, since Comparative Examples 1 and 2 are not flame retardant prescriptions, they fail the flameproof test. In Comparative Example 3, the NOR flame retardant is used more than 1.5 parts by mass, plate-out is seen, and calendar workability is poor. In Comparative Example 4, since a propylene homopolymer is used as a resin component, Ra exceeds 1.2 μm, and low temperature impact resistance, whitening resistance, and calendar workability are poor. In Comparative Example 5, a propylene-ethylene block copolymer is used as the resin component, and Ra exceeds 1.2 μm and the calendar workability is poor.
In Comparative Examples 6 and 7, since the NOR flame retardant is not used and the inorganic flame retardant is used, Ra exceeds 1.2 μm, and the low temperature impact resistance, the whitening resistance, and the calendar workability are poor.

Example 5 and Comparative Examples 8 and 9
First, a polyolefin-based resin molding material having the composition shown in Table 3 was prepared according to a conventional method without using a colorant (transparent formulation).
In addition, in the polyolefin resin molding material, 0.1% by mass of the phenolic antioxidant, trade name “Adeka Stub AO-60” (Asahi Denka Kogyo Co., Ltd.) and phosphorus antioxidant, trade name 0.2% by mass of “ADK STAB 2112” (manufactured by Asahi Denka Kogyo Co., Ltd.) is contained.
Next, the polyolefin-based resin molding material was formed by extrusion according to a conventional method to produce a film having a thickness shown in Table 3. The evaluation results are shown in Table 3.

[note]
(A1) Random PP and (B) NOR flame retardant are the same as the footnotes in Tables 1 and 2 above.
As can be seen from Table 3, the film of the present invention (Example 5) showed no plate-out in the plate-out test, good extrudability, and flame resistance, low-temperature impact resistance, and whitening resistance. In addition to being excellent in properties, Ra is in the range of 0.3 to 1.2 μm, has good printability, and has a good total light transmittance.
On the other hand, since the comparative example 8 is not a flame-retardant prescription, it fails a flameproof test. In Comparative Example 9, the amount of the NOR flame retardant is larger than 1.5 parts by mass, plate-out is observed, and the extrusion processability is poor.
In Examples 1 to 5 and Comparative Examples 1 to 9, the flame retardant prescription using the NOR flame retardant is the first grade of flame prevention. The carbonization length was 5 cm or less in the first grade of flameproofing, but was 3 to 3.5 cm, and the afterflame time and the residual dust time were 0 seconds.

  The flame retardant film of the present invention can be formed with high productivity by extrusion processing, calendar processing, etc., and also has excellent flame resistance and good low temperature impact resistance, whitening resistance, printability and transparency. For example, it is suitably used as a decorative film for a decorative material used for a building member such as a flooring material or a wall material, or a surface decorative plate such as a cabinet for furniture, kitchen products, or home appliances.

Claims (5)

(A) Propylene and ethylene having a melt flow rate (MFR) value (load 21.18 N, temperature 230 ° C.) of 0.1 to 20 g / 10 min and a melting point of 130 to 150 ° C. and / or carbon number 4 to 20 A polyolefin resin molding material containing 0.1 to 1.5 parts by mass of (B) an alkoxyimino group-type hindered amine compound per 100 parts by mass of a resin component made of a random copolymer of α-olefin of A film formed by filming,
In the roll kneading test at 200 ° C. for 10 minutes, the polyolefin-based resin molding material has no plate-out, and the film is (a) a flameproof test based on JIS Z 2150 for a film having a thickness of 50 to 200 μm. (B) an arithmetic average roughness Ra of the surface is 0.3 to 1.2 μm; (c) an impact tester impact test at 0 ° C. based on ASTM D 1790; Among the test pieces, all the test pieces are not broken in any length and width, and (d) there is no whitening in the 5 ° C. whitening test,
Flame retardant film characterized by (A ′) (a-1) Propylene and ethylene having a melt flow rate (MFR) value (load 21.18 N, temperature 230 ° C.) of 0.1 to 20 g / 10 min and a melting point of 130 to 150 ° C. Or the resin component which consists of 60-95 mass% of random copolymers with a C4-C20 alpha olefin, and (a-2) high-density polyethylene 40-5 mass%, per 100 mass parts, (B ) A film formed by forming a polyolefin resin molding material containing 0.1 to 1.5 parts by mass of an alkoxyimino group-type hindered amine compound,
In the roll kneading test at 200 ° C. for 10 minutes, the polyolefin-based resin molding material has no plate-out, and the film is (a) a flameproof test based on JIS Z 2150 for a film having a thickness of 50 to 200 μm. (B) an arithmetic average roughness Ra of the surface is 0.3 to 1.2 μm; (c) an impact tester impact test at 0 ° C. based on ASTM D 1790; Among the test pieces, all the test pieces are not broken in any length and width, and (d) there is no whitening in the 5 ° C. whitening test,
Flame retardant film characterized by The (a-2) component high-density polyethylene was obtained by a low-pressure method, and had an MFR value (load 21.18 N, temperature 190 ° C.) of 0.1 to 5 g / 10 min and a density of 0.00. The flame-retardant film according to claim 2, which is 94 to 0.98 g / cm ³ .   The difficulty according to any one of claims 1 to 3, wherein a polyolefin-based resin molding material further containing (C) 0.2 to 3.0 parts by mass of a lubricant per 100 parts by mass of the resin component is formed by a calendar method. Flammable film.   The flame-retardant film according to any one of claims 1 to 4, wherein one side or both sides are subjected to corona discharge treatment or plasma discharge treatment.