WO2008038709A1

WO2008038709A1 - Flame-retardant resin composition

Info

Publication number: WO2008038709A1
Application number: PCT/JP2007/068800
Authority: WO
Inventors: Toshiyuki Maeda
Original assignee: Du Pont-Mitsui Polychemicals Co. Ltd.
Priority date: 2006-09-29
Filing date: 2007-09-27
Publication date: 2008-04-03

Abstract

Disclosed is a flame-retardant resin composition which contains a crosslinked product of an ethylene-vinyl acetate copolymer having a high vinyl acetate content and has a good balance between flexibility and flame retardancy. The flame-retardant resin composition comprises: a crosslinked ethylene-vinyl acetate copolymer (A) having a content of a vinyl acetate unit of 26 to 47 mass% and an MFR value of 0.01 to 4 g/10 min.; a polymer (B) selected from an Mg ionomer (b-1) of an ethylene-unsaturated carboxylic acid copolymer having a degree of neutralization of 5 to 60 mol% and an MFR value of 0.1 to 100 g/10 min and a modified alternating copolymer (b-2) which is produced by modifying at least a part of an alternating copolymer of a C4-olefin and an α,β-unsaturated carboxylic acid anhydride or a derivative thereof by a procedure selected from the items (C-1) and (C-2) below; and a flame-retardant agent (D). (C-1) Modification with a compound having a hydroxyl group and/or a compound having an ether group. (C-2) Partial ionomerization with a metal ion.

Description

Specification

Flame retardant resin composition

Technical field

[0001] The present invention relates to a flame retardant resin composition having an excellent balance between flexibility and flame retardancy. More specifically, the present invention relates to a flame retardant resin composition having a good balance between flexibility and flame retardancy, including a cross-linked product of an ethylene acetate butyl copolymer having a high acetate acetate content.

[0002] Olefin-based resins are widely used as electrical insulating materials because they generally have excellent electrical characteristics, mechanical properties, workability, and the like. Particularly in applications such as electric wires and cables, ethylene-unsaturated ester random copolymers are widely used because of a good balance of strength, low-temperature characteristics, scratch resistance, hardness, and the like.

[0003] Since such an ethylene copolymer is flammable, it needs to be flame retardant depending on the application. For this reason, it has long been dealt with by blending a halogen flame retardant. However, there is a problem that such a compound generates a harmful gas during combustion. For this reason, in recent years, a formulation containing a flame retardant of metal hydroxide such as non-halogenated magnesium hydroxide or aluminum hydroxide has been proposed. Has been adopted. However, since metal hydroxide flame retardants cannot exert a sufficient flame retardant effect unless they are added in a considerably large amount, they often sacrifice the processability, scratch resistance, and other mechanical properties of ethylene copolymers. There was something to do. In particular, in applications such as thin-walled electric wires, thin building material sheets, and thin-walled vehicle seats, high flame retardancy and good moldability and mechanical properties are demanded for thin-walled materials. Formula development was not easy.

[0004] For example, a flame retardant resin composition based on an ethylenically unsaturated carboxylic acid ester copolymer represented by an ethylene ethyl acrylate copolymer has the advantage of excellent shell-forming properties during combustion. It is difficult to add a large amount of flame retardant with low flame retardancy and toughness of base polymer. In other words, if the amount of the flame retardant is small, sufficient flame retardant effect cannot be exerted.If the amount of the flame retardant is increased, the workability is deteriorated and the mechanical strength is reduced. Application to was difficult.

[0005] Ethylene acetate butyl copolymer is the most excellent toughness among ethylene copolymers, and can be loaded with a large amount of flame retardants. In addition, it is an inexpensive and attractive material compared to the ethylene unsaturated carboxylic acid ester copolymer, but the flame retardant resin composition based on it is also sufficiently flame retardant. In particular, there is a problem that the shell does not easily form during combustion and drip, and it is also difficult to apply to the above-mentioned use.

[0006] In addition, the ethylene acetate butyl copolymer increases in flexibility and elongation as the content of butyl acetate increases, but the tensile strength decreases. Therefore, in order to improve the tensile strength, crosslinking with an organic oxide or electron beam is performed. The power that has been applied has not improved flame retardancy. A material with a good balance between flexibility and flame retardancy is desired, but no satisfactory material has yet been proposed.

[0007] Patent Document 1: Japanese Patent Laid-Open No. 63-225641

Patent Document 2: JP-A-5 117452

Disclosure of the invention

Problems to be solved by the invention

[0008] The present invention provides a flame retardant resin composition having an excellent balance between flexibility and flame retardancy.

The present invention provides a flame retardant resin composition having a good balance between flexibility and flame retardancy, including a cross-linked product of an ethylene acetate butyl copolymer having a high content of butyl acetate.

Means for solving the problem

[0009] The present invention is acetate Bulle unit content (JIS K7192: 1999 method) 26-47 mass ^_0/0, Merutofu Roreito (JIS K7210: 1999 method, 190 ° C, load 2,160 g) is 0.0 ; ~~ 4g / 10 min cross-linked ethylene acetate acetate copolymer (A), neutralization degree 5 ~ 60mol%, melt flow rate (J IS K7210: 1999 method, 190 ° C, load 2,160g ) Is 0.;! To lOOg / 10 min. Magnesium ionomer (b— 1) of ethylene-unsaturated carboxylic acid copolymer and 4-carbon olefin and α, β unsaturated carboxylic anhydride or derivative thereof At least one selected from a modified copolymer (b-2) obtained by modifying at least a part of the copolymer comprising at least one of the following methods (C-1) and (C-2): A resin composition comprising a seed polymer (B) and a flame retardant (D),

(C 1) Modification by hydroxyl group-containing compound and / or ether group-containing compound

(C2) Partial ionomerization with metal ions (A) is (parts by weight) (8) / [(8)] (parts by mass) = 50 to 99.9 / 50-0.1, (D) is the total amount of (A) and (B) Provided is a flame retardant resin composition that is 20 to 300 parts by mass with respect to 100 parts by mass.

[0010] The above-mentioned flame retardant resin composition having an unsaturated carboxylic acid unit content of 2 to 30% by mass in an ethylene 'unsaturated power rubonic acid copolymer as a base polymer of the magnesium ionomer (b-1) Is a preferred embodiment of the present invention.

[0011] With respect to 100 parts by mass of the total amount of the cross-linked ethylene acetate butyl copolymer (A), magnesium ionomer (b-1) and modified copolymer (b-2), the unsaturated carboxylic acid and / or At least one modified polymer selected from the group consisting of an olefin polymer (E-1) modified with a derivative and a styrene polymer (E-2) modified with an unsaturated carboxylic acid and / or derivative thereof The above-described flame retardant resin composition containing 25 parts by mass or less of (E) is a preferred embodiment of the present invention.

[0012] The viscosity-average molecular weight is 30, 0 00 to 100 parts by mass of the total amount of the crosslinked ethylene-acetate copolymer (A), the magnesium ionomer (b-1) and the modified copolymer (b-2). The above-mentioned flame retardant resin composition comprising 0.01 to 10 parts by mass of an olefin-based wax (F) having a density force of 80 to 980 kg / m ³ and a melting point of 60 to 160 ° C. This is a preferable mode.

In the modified copolymer (b 2), a copolymer comprising a olefin having 4 carbon atoms and an α, β-unsaturated dicarboxylic acid anhydride or a derivative thereof is obtained by combining the olefin having 4 carbon atoms with an α, β-unsaturated product. The flame retardant resin composition described above, which is an alternating copolymer composed of a dicarboxylic acid anhydride or a derivative thereof, is a preferred embodiment of the present invention.

[0014] The present invention provides a molded article comprising the flame retardant resin composition described above.

The invention's effect

[0015] According to the present invention, a flame retardant resin composition having an excellent balance between flexibility and flame retardancy is provided. According to the present invention, a flexible product containing a cross-linked product of an ethylene acetate butyl copolymer having a high content of butyl acetate. Provided is a flame retardant resin composition having an excellent balance between property and flame retardancy.

BEST MODE FOR CARRYING OUT THE INVENTION [0016] Crosslinked ethylene acetate acetate copolymer (A)

The content of butyl acetate in the crosslinked ethylene acetate butyl copolymer (A) used in the present invention is 26 to 47% by mass, preferably 28 to 47% by mass, and more preferably 32 to 47% by mass. Flow rate (MFR) (In accordance with JIS K 7210-1999, 190. Value measured at C, 2,160g load 0.0;! ~ 4g / 10min, preferably 0.05 ~ 3g / 10min, More preferably, 0.;!-3g / 10 min is desirable.

[0017] Further, the Mw / Mn value measured by the gel permeation chromatography (GPC) method of the ethylene acetate butyl copolymer of the present invention is 6 to 12; preferably 6 to 10; I like it.

[0018] In the present invention, the cross-linked ethylene acetate butyl copolymer (A) can be obtained by cross-linking an ethylene vinyl acetate copolymer, but is used to obtain a cross-linked ethylene acetobutyl copolymer (A). Preferred ethylene acetate butyl copolymers prior to crosslinking are those having a melt flow rate of 4 to 150 g / 10 min, preferably 10 to 120 g / 10 min, more preferably 30 to 120 g / 10 min. Can be mentioned.

[0019] The cross-linking of the ethylene acetate butyl copolymer in the present invention may be performed to the extent that meets the purpose of the present invention. As a measure of the degree of cross-linking, it is recommended that the cross-linked condition is such that the descent rate of menore flow rate defined by the following formula is in the range of 70 to 99.9%.

Melt flow rate drop rate = (X-Y) / X X 100

X: Melt flow rate of ethylene acetate butyl copolymer

Y: Melt flow rate after cross-linking of ethylene acetate butyl copolymer

[0020] As a method for obtaining the crosslinked ethylene acetate butyl copolymer (A) of the present invention, the ethylene-butyl acetate butyl copolymer is obtained by using an organic peroxide, electron beam crosslinking (radiation crosslinking), a silane crosslinking agent, or the like. Cross-linking techniques that cross-link can be used. In the case of crosslinking with an organic peroxide, it can be produced by adding a predetermined amount of an organic peroxide to an ethylene acetate butyl copolymer and melt-kneading with a kneading apparatus such as a single-screw or twin-screw extruder. .

[0021] When the ethylene acetate butyl copolymer is crosslinked with an organic peroxide, examples of the organic peroxide include tertiary butyl Tamil peroxide, dicumyl peroxide, 2, 5 dimethyl- 2,5 bis (tertiary butylperoxy) hexane, 2,5 dimethyl-2,5 bis (tertiary butylperoxy) hexyne 3,1,3 bis (2 tert-butylperoxyisopropyl) benzene, di-tertiary butyl Dialkyl peroxides such as peroxides; tertiary butyl peroxyisobutyrate, tertiary butyl peroxymaleic acid, tertiary butyl peroxy isonanoate, tertiary butyl peroxyisopropyl carbonate, tertiary butyl peroxy-2-ethylenohexyl carbonate , Tertiary butinoleperoxyacetate, tertiary butinoleperoxybenzoate, 2,5 dimethyl-2,5 bis (benzoylperoxy) hexane, 2,5 dimethylhexyl 2,5 bisperoxy Alkyl peroxyesters such as benzoate; 1, 1 bis (tertiary butyl peroxy) 3, 3, 5— Limethylcyclohexane, 1,1 bis (tertiary butyroleperoxy) cyclohexane, 1,1 bis (tertiary amylberoxy) cyclohexane, 2,2 bis (tertiary butylperoxy) butane, n-butyl-4 , 4 Peroxyketals such as bis (tertiary butylperoxy) valerate and ethyl-3,3-bis (tertiary butylperoxy) butyrate

Yes

[0022] The amount of the organic oxide added is in the range of 50 to 10,000 ppm depending on the melt rate of the ethylene acetate butyl copolymer used, the type of organic peroxide, and the desired melt flow rate. . The temperature conditions for crosslinking vary depending on the type of organic oxide, but are preferably in the range of 50 to 230 ° C.

[0023] Magnesium ionomer (b— 1)

The magnesium ionomer (b-1) of the ethylene / unsaturated carboxylic acid copolymer used in the present invention is a part of the carboxyl group of the ethylene / unsaturated carboxylic acid copolymer by magnesium (ion). be one neutralized formed by, the neutralization degree of 5 to 60 mole ⁰ / o, preferably from 10 to 60 Monore ^_0/0, and particularly preferably 20 to 60 mole ^{_{0/0, JIS K7210- 1999,}} 190 . C, Menoleto flow rate force at a load of 2160 g 0.;! ~ LOOg / 10 min, preferably 0.;! ~ 50 g / 10 min, more preferably 0 ·;! ~ 25 g / 10 min.

[0024] The ethylene.unsaturation power rubonic acid copolymer used as the base polymer of the magnesium ionomer (b-1) preferably has an unsaturated carboxylic acid unit content of 2 to 30% by mass, more preferably 10 to 30%. % By weight, more preferably 10-25% by weight It is.

[0025] The ethylene / unsaturated carboxylic acid copolymer used as the base polymer includes not only a binary copolymer composed of ethylene and an unsaturated carboxylic acid, but also other polar monomers and styrene monomers. It may be a multi-component copolymer containing as a polymerization component! /. Examples of the unsaturated carboxylic acid constituting the copolymer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, and itaconic anhydride. Among these, acrylic acid or methacrylic acid is particularly preferable.

[0026] Other polar monomers that are optional copolymerization components of the copolymer include vinyl esters such as vinylol acetate and butyl propionate, methyl acrylate, ethyl acrylate, isopropyl acrylate, and isobutyl acrylate. , Unsaturated carboxylic acid esters such as n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, dimethyl maleate, and jetyl maleate be able to. Examples of styrenic monomers include styrene, α-methylstyrene, butyltoluene, and ρ-methylisopropenyltoluene.

[0027] For example, the other polar monomer as described above is effective for imparting flexibility to the copolymer, and the unit content thereof is, for example, about 30% by mass or less, particularly about 20% by mass or less. preferable.

[0028] Such an ethylene.unsaturated carboxylic acid copolymer can be obtained by radical copolymerization under high temperature and high pressure.

[0029] The flame retardant resin composition of the present invention is selected from a cross-linked ethylene-acetic acid butyl copolymer (Α), a magnesium ionomer (b-1), and a modified copolymer (b-2). The proportion of magnesium ionomer (b-l) in at least one polymer (B) is 50 to 0.1% by mass, preferably 35 to 1% by mass, more preferably 25 to 3% by mass. Is desirable.

[0030] Modified copolymer (b-2)

The modified copolymer (b 2) of the present invention is composed of olefins having 4 carbon atoms and α, β unsaturated dialkyls. It is a modified copolymer obtained by modifying at least a part of a copolymer comprising an acid anhydride or a derivative thereof by at least one of the following methods (C 1) and (C 2). (C 1) Modification with hydroxyl group-containing compounds and / or ether group-containing compounds (C 2) Partial ionomerization with metal ions

[0031] In the present invention, it consists of olefins having 4 carbon atoms (before modification) and _α , β unsaturated dicarboxylic acid anhydrides or derivatives thereof that are subjected to modification by (C 1) and / or (C 2). The copolymer may be a random copolymer, but is particularly preferably an alternating copolymer of a olefin having 4 carbon atoms and an α, β unsaturated dicarboxylic acid anhydride or a derivative thereof.

[0032] Examples of olefins having 4 carbon atoms in the copolymer include 1-butene and isobutylene. A, β Examples of unsaturated dicarboxylic acid anhydrides include maleic anhydride, citraconic anhydride, and ethylmaleic anhydride. It is possible to use a force S, particularly maleic anhydride. Β-unsaturated dicarboxylic anhydride derivatives include dicarboxylic acids, metal salts, ammonium salts, amine salts, half esters, diesters, monoamides, diamides, imides, etc. Maleic anhydride is a preferred derivative. is there. When the alternating copolymer has derivative units of these α and β unsaturated dicarboxylic anhydrides, it is necessary that some or all of the α and β unsaturated dicarboxylic anhydride units are derivative units. S and can contain more than one derivative unit.

[0033] In the modified copolymer (b-2), olefins having 4 carbon atoms before modification and (alpha), beta unsaturated dicarboxylic acid anhydrides, which are subjected to modification by (C1) and / or (C2) or An example of such a derivative copolymer is an alternating copolymer of isoptylene and maleic anhydride! This alternating polymer has the structural formula shown below!

[0034] [Chemical 1

[0035] The alternating copolymer of isobutylene and maleic anhydride can be obtained by copolymerizing isobutylene and maleic anhydride in the presence of a radical polymerization catalyst. Further, by reacting a part or all of the maleic anhydride unit of this alternating copolymer with alkali hydroxide, ammonia, ammine, alcohol, etc., an alternating copolymer having a maleic anhydride derivative unit can be obtained. it can.

[0036] In the modified copolymer (b-2) of the present invention, a copolymer comprising a olefin having 4 carbon atoms and an α, β unsaturated dicarboxylic anhydride or a derivative thereof (particularly preferably an alternating copolymer) Is at least partially modified by at least one of the methods (C-1) and (C-2).

[0037] In the method of modifying a copolymer comprising olefins having 4 carbon atoms and α, / 3 unsaturated dicarboxylic acid anhydride or a derivative thereof by at least one of the methods (C 1) and (C 2), In particular, the power that can be carried out by appropriately selecting methods and conditions that can be modified without limitation, specifically, the following methods can be mentioned.

[0038] In the present invention, a specific method of modifying by the method (C1) includes a copolymer (particularly preferably alternating) of a olefin having 4 carbon atoms and an α, β unsaturated dicarboxylic anhydride or a derivative thereof. A method of blending (blending) a hydroxyl group-containing compound and / or an ether group-containing compound with a copolymer), or a copolymer comprising α-, β-unsaturated dicarboxylic anhydride or a derivative thereof (particularly preferred) Is a method of reacting an alternating copolymer) with a hydroxyl group-containing compound and / or an ether group-containing compound.

[0039] Preferable examples of the hydroxyl group-containing compound used for the modification of (C1) include the ability to mention alcohols. A monohydric or polyhydric aliphatic alcohol is particularly preferable. Among alcohols, from the viewpoint of foaming at the time of molding, higher alcohols, for example, an alcoholic alcohol having 4 to 25 carbon atoms, particularly an aliphatic alcohol having 4 to 25 carbon atoms are preferable.

[0040] The ether group-containing compound used for the modification of (C-1) is preferably a polyether.

Yes

[0041] Further, the compound used for the modification of (C 1) may be a compound containing a hydroxyl group and an ether group. Such compounds include polyoxyalkylene glycol monoesters. The ability to raise a tel S Polyoxyalkylene glycol monoether has the formula RO (AO) nH (wherein R is a carbon number;! To 10 alkyl group, A is substituted with a phenyl group! /, An alkylene group having 2 to 4 carbon atoms) , N is a compound represented by 1 to about 100). Examples of the polyoxyalkylene glycol monoether include those described in Japanese Patent No. 2882648. Note that the compounding amount (blend amount) of the compound used for the modification of (b-1) is 100 parts by weight of a copolymer consisting of olefins having 4 carbon atoms and α, β unsaturated dicarboxylic acid anhydrides or derivatives thereof. It is preferably in the range of 25 to 75 parts by weight.

[0042] As a condition for modifying the modified copolymer (C2) in the present invention with polyoxyalkylene glycol monoether, it is described in Japanese Patent No. 2882648! /, A copolymer of isoptylene and maleic anhydride And the conditions for the esterification reaction with polyoxyalkylene glycol monoether.

Further, as the modified copolymer (b-2) in the present invention, a polymer obtained by esterifying a copolymer of isobutylene and maleic anhydride described in the publication with polyoxyalkylene glycol monoether may be used. Yo! /

[0043] With regard to partial ionomerization by metal ions, which is modification by (C-2), monovalent metals such as Na, K and Li, and divalent metals such as Zn, Mg and Ca can be mentioned.

[0044] A method of modifying a copolymer comprising olefins having 4 carbon atoms and α, / 3-unsaturated dicarboxylic anhydride or a derivative thereof by at least one of the methods (C 1) and (C 2). Can be carried out by appropriately selecting methods and conditions that can be modified without particular limitation.

[0045] In the flame-retardant resin composition of the present invention! /, From the crosslinked ethylene-acetic acid copolymer (Α), magnesium ionomer (b-1) and modified copolymer (b-2) The ratio of the modified copolymer (b-2) in at least one polymer (B) selected is 50 to 0.1% by mass, preferably 20 to 0.5% by mass, more preferably 10 to 1%. It is desirable that it is mass%.

[0046] In the flame retardant resin composition of the present invention, the ratio of (A) in the cross-linked ethylene acetate butyl copolymer (A) and the polymer (B) is expressed in parts by mass (A) / (B). (Parts by mass) = 50 to 99 · 9/50 to 0.1, preferably (or 80 to 99.5 / 20—0.5, more preferably (or 90 to 99/10 to; It is desirable to be.

[0047] Examples of the flame retardant (D) used in the present invention include metal hydrates such as magnesium hydroxide, aluminum hydroxide and hydrated talcite, basic magnesium carbonate, calcium carbonate, silica and alumina. , Talc, clay, zeolite, brominated flame retardant, antimony trioxide, polyphosphoric acid flame retardant and the like. Of these, metal hydrates are preferred. When sufficient flame retardancy is required, it is preferable to use magnesium hydroxide or aluminum hydroxide or a mixed inorganic flame retardant containing at least 50% by weight of magnesium hydroxide or aluminum hydroxide.

[0048] Considering the miscibility of the flame retardant (D) and the appearance of the molded product obtained from the flame retardant resin composition, the average particle size is 0 · 05 to 20〃111, especially about 0 · to 5〃m. It is desirable to use the ones. For the same reason, the surface of the inorganic flame retardant is fatty acid, fatty acid amide, fatty acid salt, fatty acid ester, aliphatic alcohol, silane coupling agent, titanium coupling agent, silicon oil, silicon polymer, phosphate ester, etc. A surface-treated product may be used.

[0049] The ratio of the flame retardant (D) in the flame retardant resin composition of the present invention is 20 to 20 parts by mass with respect to 100 parts by mass of the total amount of the crosslinked ethylene acetate acetate copolymer (A) and the polymer (B). It is desired to be 300 parts by mass, preferably 80 to 250 parts by mass, more preferably 100 to 250 parts by mass.

[0050] In addition to the flame retardant (D) of the present invention, known flame retardant aids such as red phosphorus and zinc borate may be blended within the range not impairing the object of the present invention!

[0051] The flame retardant resin composition of the present invention further includes an olefin polymer (E-1) modified with an unsaturated carboxylic acid and / or derivative thereof and an unsaturated carboxylic acid and / or derivative thereof. Or at least one modified polymer (E) selected from the group consisting of a modified styrene polymer (E-2).

[0052] The ratio of (E-1) and / or (E-2) in the flame retardant resin composition of the present invention is:

) And (B) is preferably 25 parts by mass or less with respect to 100 parts by mass.

[0053] The olefin-based polymer (E-1) modified with an unsaturated carboxylic acid or a derivative thereof is a resinous or elastomeric olefin-based polymer converted to an unsaturated carboxylic acid or an derivative thereof. Graft-modified or copolymer-modified with a conductor. Examples of the olefin-based polymer used as the base polymer include olefin-based homopolymers, copolymers of two or more olefins, and copolymers of olefin and polar monomers. Specifically, as the resinous polyolefin polymer, high-, medium-, low-density polyethylene, ethylene-a-olefin copolymer, ethylene-based copolymer such as ethylene 'unsaturated ester copolymer, propylene homopolymer, propylene Examples include a-olefin random copolymers, propylene polymers such as propylene 'α-olefin block copolymers, and poly-1-butene. Elastomer-like olefin polymers include ethylene / α-olefin copolymer rubbers such as ethylene / propylene copolymer rubber, propylene / α / olefin copolymer rubbers, and ethylene / propylene / gen copolymer rubbers. Ethylene such as _α- olefin gen copolymer rubber, block copolymer obtained by copolymerizing ethylene with propylene copolymer on polypropylene with controlled regularity, ethylene 'methyl acrylate copolymer rubber, ethylene' Mention may be made of, for example, methyl acrylate / crosslinked site monomer copolymer rubber. The α-olefins in the above copolymers are preferably those having 2 to 12 carbon atoms. The elastomeric olefin polymer may be crosslinked or non-crosslinked.

Styrenic polymer (Ε-2) modified with unsaturated carboxylic acid or its derivative is a resin- or elastomer-like styrene-based polymer graft-modified or copolymerized with unsaturated carboxylic acid or its derivative. It is. Examples of the styrenic polymer that serves as the base polymer include polystyrene, styrene / gen block copolymer, and hydrogenated products thereof. Specific examples of styrene / gen block copolymer and its hydrogenated product include styrene / butadiene / styrene block copolymer (SBS) and its hydrogenated styrene / ethylene / butene styrene block copolymer ( SEBS), styrene. Isoprene. Styrene block copolymer (SIS) and its hydrogenated styrene. Ethylene / propylene. Styrene block copolymer (SEPS), styrene 'ethylene' ethylene / propylene 'styrene block copolymer. Examples thereof include a polymer (SEEPS). The flame retardant resin composition of the present invention preferably has a total amount of bridged ethylene acetate butyl copolymer (A) and polymer (B) within a range not impairing its processability, physical properties and flame retardancy. You may mix another polymer in the ratio to 100 weight part with respect to weight part. You can mix Other polymers include styrene elastomers such as SEBS and SEPS, olefin elastomers such as EBR, EPR, EPDM, and ethylene acrylic rubber, or acid-modified products obtained by modifying these with maleic anhydride, plants, etc. Examples include plastics derived from cellulose (cellulose, starch, lactic acid, succinic acid, butyric acid, glycol).

[0055] The unsaturated carboxylic acid or derivative thereof used for modifying the olefin polymer or styrene polymer of the base polymer includes acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, and the like. Examples thereof include unsaturated carboxylic acid anhydrides such as unsaturated carboxylic acid, maleic anhydride and itaconic anhydride. The graft monomer unit in the modified olefin polymer (E-1) or styrene polymer (E-2) is! / ヽ, the content of the copolymer monomer unit is preferably 0, based on the modified polymer. 01 to 20% by weight, particularly preferably 0.;! To 5% by weight. As the above-mentioned modified polymer, when the base polymer is an ethylene-based polymer, JIS K7210-1999, 190 ° C, 2160 g load, maleolate flow rate force 0 ·;! ~ 50g / 10min, especially 0 · 2 ~; l Og / 10 min is preferred. JIS K7210-1999, 230 when the base polymer of the modified polymer is a propylene polymer or styrene polymer. C, Menore flow rate force at 2160g load 0 ~ 50g / 10min, especially 0.2 ~ 0g / 10min.

[0056] The flame retardant resin composition of the present invention may further contain an olefin wax (F).

Examples of olefin waxes include those obtained by thermal decomposition of high-molecular-weight polyolefins, those obtained by homopolymerization of olefins or copolymerization with other olefins, and the like, which can be appropriately selected and used. From the viewpoint of solubility, ethylene wax is preferred for the purpose of the present invention.

[0057] Examples of the ethylene wax include polyethylene wax obtained by thermal decomposition of high molecular weight polyethylene, polyethylene wax obtained by free radical polymerization of ethylene in a high pressure method, or homopolymerization of ethylene in the presence of a metal catalyst. For example, polyethylene wax obtained by copolymerizing ethylene and α-olefin in the presence of a metal catalyst. Among them, ethylene'a-olefin copolymer wax is more preferred from the above compatibility point. Preferably used. As α-olefin, those exemplified above can be cited as preferred examples. The content of α- Orefin in the ethylene 'a Orefuin copolymer wax is preferably more preferably it is preferred instrument is 15 mol% or less is under 10 mol ^_0/0 or more.

[0058] Examples of the metal catalyst suitably used for the production of such an ethylene-based wax include a multi-site catalyst such as a Ziegler catalyst and a single-site catalyst such as a meta-locene catalyst. When ethylene wax is used with a meta-octacene catalyst, preferable results are obtained from the viewpoint of improving the mechanical properties. Therefore, a single-site catalyst, particularly an ethylene wax produced with a meta-nuccene catalyst is preferred.

[0059] A meta-octacene catalyst is a catalyst component composed of a meta-cholecene compound having a ligand having at least one cyclopentagenyl skeleton in a transition metal such as titanium, zirconium, or hafnium, and an alumoxane. Catalysts composed of co-catalyst components such as organoaluminum compounds such as alkylaluminum, organoaluminumoxy compounds, and ionized ionic compounds. Because of its characteristics as a catalyst, it is sometimes called a single site catalyst.

[0060] Examples of the ligand having a cyclopentaenyl skeleton include a cyclopentagenyl ring indenyl ring, a fluorenyl ring and the like, and these ligands may have a substituent, In addition, the ligands may be bonded via a hydrocarbon group, a silyl group, etc.

[0061] Specific examples of the meta-octacene catalyst include, for example, JP-A-58-19309, JP-A-59-96292, JP-A-60-35005, JP-A-61-130314, JP-A-3-130314. — Forces S that can include those described in 163088, European Patent Publication 420,436, US Pat. No. 5,055,438, etc., but are not limited thereto.

[0062] Examples of meta-octene compounds include cyclopentachenyltitanium (dimethylamide), dimethylsilyltetramethylcyclopentadienyl t-butylamidezirconium dichloride, indurtitanium (jetylamide), bis (cyclopentagenyl ) Zirconium dichloride, bis (indul) zirconium bis (methylphosphonate), and the like. [0063] Ethylene-based waxes obtained with a meta-orthocene-based catalyst can be produced with reference to, for example, the methods described in JP-A-8-231640 and JP-A-2004-59869. . Moreover, you may select and use from what is marketed as polyethylene wax.

[0064] The viscosity average molecular weight of the olefin wax used in the present invention is 30,000 or less, preferably 8000 or less, more preferably 1,000 to 8,000, and the density is 880 to 980 kg / m ³ . Preferably it is 900 to 980 kg / m ³ and the melting point is 60 to 160; C, preferably 60-; C is desirable.

An ethylene-based wax having a viscosity average molecular weight of 8,000 or less, a density force of 80 to 980 kg / m ³ and a melting point of 60 to 130 ° C. is more preferable than the olefin wax of the present invention. Refin wax.

[0066] The olefin-based wax of the present invention may contain a reactive group such as a hydroxyl group, a carboxylic acid group, or an epoxy group in the molecule. These reactive groups can be introduced by copolymerizing an unsaturated compound containing a reactive group at the time of wax production or by grafting it to olefinic wax. Inclusion of a reactive group in the olefin wax molecule is called modification of the olefin wax. Further, as the modified olefin wax, an olefin oxide wax obtained by an oxidation reaction of the olefin wax can also be used. The modified olefin wax is preferably one obtained by grafting an unsaturated compound to an olefin wax. Unsaturated compounds can include unsaturated carboxylic acids, anhydrides or derivatives thereof, among which maleic anhydride is particularly preferred!

[0067] The amount of the olefin-based wax in the flame-retardant resin composition of the present invention is 10 parts by mass or less with respect to 100 parts by mass of the total amount of the cross-linked ethylene acetate butyl copolymer (A) and the polymer (B). Preferably, it is 0.5 to 5 parts by mass, more preferably 0.5 to 3.

[0068] The flame retardant resin composition of the present invention can be blended with various additives as necessary within a range not impairing the object of the present invention. Examples of such additives include antioxidants; light stabilizers; UV absorbers; flame retardant aids such as zinc borate and aluminum stearate; pigments such as carbon black; dyes; silicone oils and aliphatics. Compounds, trees It is possible to display lubricants such as oil wax, anti-blocking agents, foaming agents, foaming aids, cross-linking agents, and cross-linking aids.

[0069] In order to prepare the flame retardant resin composition of the present invention, a crosslinked ethylene acetate butyl copolymer (Α), a magnesium ionomer (b-1) and / or a modified copolymer (b-2), The flame retardant (D) and other components blended as necessary may be kneaded using a normal kneader such as a single-screw extruder, twin-screw extruder, banner mixer, pressure kneader, or roll. . When an organic peroxide is blended, it may be melt kneaded at a temperature below its melting point. Such blending may be performed collectively or stepwise.

[0070] Further, the flame retardant resin composition of the present invention is composed of an ethylene acetate butyl copolymer, a magnesium ionomer (b-1) and / or a modified copolymer (b-2), and other blended as necessary. The components are kneaded using an ordinary kneader in the presence of an organic peroxide, for example, and a flame retardant (D) is further added to the resulting composition and then kneaded using an ordinary kneader, or Ethylene acetate butyl copolymer, magnesium ionomer (b-1) and / or modified copolymer (b-2), flame retardant (D) and other ingredients blended as required, for example, The force S can also be obtained by a method of kneading using an ordinary kneader in the presence of an oxide.

[0071] Specific examples of the molded product as a use of the flame-retardant resin composition of the present invention include, for example, the field of civil engineering such as toys, artificial turf, mats, waterproof sheets, tunnel sheets, roofing, hoses, Pipes such as tubes, home appliances such as packing and vibration damping sheets, backing materials such as carpets, door panel waterproof sheets, mudguards, automobiles such as malls, and building materials such as wallpaper, furniture, flooring and foam sheets Wiring cables, communication cables, equipment cables, power cords, plugs, fireproof cables, control instrumentation cables, cable applications such as shrinkable tubes, adhesive tapes and other adhesive applications.

Example

[0072] Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.

In addition, the raw material used in the Example and the comparative example is as follows.

[0073] (1) cross-linked EVA (A- 1): ethylene acetate Bulle copolymer (acid Bulle content 45 weight ^_0/0 , MFR110g / 10min) (cross-linked ethylene acetate butyl copolymer of MFR2g / 10min obtained by crosslinking EVA-1)

(2) Cross-linked EVA (A— 2): Ethylene acetate bull copolymer (Butyl acetate content 32% by weight, MFR20g / 10min) ¥ 8-2) Cross-linked ^^! ^ 0. 3g / 10 Crosslinked ethylene acetate butyl copolymer

(3) MglO: Magnesium ionomer of an ethylene-methacrylic acid copolymer with a methacrylic acid unit content of 15% by weight (degree of neutralization 55%, MFRO. 7 g / 10 min)

(4) Modified alternating copolymer: isobutylene maleic anhydride alternating copolymer added with higher alcohol and further ionized with calcium (Lucite 'Japan, product name: 050622A)

(5) Modified EVA: Product name HPR VR101 (Mitsui, manufactured by DuPont Polychemical Co., Ltd., MFR6g / 10min, density: 940kg / m ³ )

(6) Olefin-based wax: Trade name XXELEX HW48070B (Mitsui Chemicals, viscosity average molecular weight: 4600, density: 902kg / m ³ , melting point: 90 ° C)

(7) Magnesium hydroxide: Trade name: Kisuma 5L (Kyowa Chemical Industry Co., Ltd.)

(8) Hindered phenolic antioxidants: Ciba Specialty 'Chemicalo Rezu, product name: Inoreganox 1010

(9) Organic oxide: alkyl peroxy ester, molecular weight = 216.3, active oxygen content = 7. 18%, half-life (1 Ohr) = 77 ° C (measuring solvent: dodecane)

[0074] (a) Melt flow rate (MFR)

JIS K 7210 (1999) Law C, determined with a load of 2,160 g.

[0075] (b) Molecular weight distribution (Mw / Mn)

Using a model PL-GPC220 (manufactured by Polymer Laboratories), measurement was performed under the following conditions. Measurement method: GPC method (polystyrene conversion)

Column: 2 TSKgel GMH_H (S) HT X + 1 TSKgel G2000H (20) HT X

HR HR

Column temperature: 140 ° C

Solvent: ortho-dichroic benzene Injection volume: 400 1

[0076] (c) Tensile strength and elongation

According to the JIS K 6760 method, measurement was performed using a JIS K 6301 No. 3 dumbbell under the conditions of lmm thickness and tensile speed 200mm / min. The tensile strength and elongation were calculated by the following formula (see JIS K7161: 1994).

• Bow I Tensile strength: Convert per unit area according to the following formula.

σ = F ÷ A

σ: Tensile strength (MPa)

F: Maximum tensile load (N)

A: Cross section of specimen (mm ² )

• Elongation: Measure the length between marked lines at the time of cutting and calculate with the following formula.

ε = (L1-LO) ÷ LOX100

ε: Elongation (%)

L1: Length between marked lines when cutting (mm)

L0: Marking distance (mm)

[0077] (d) Flammability

According to UL94 vertical combustion test method (manufactured by Suga Test Instruments Co., Ltd.). The thickness of the sample piece was 0.5 mm and lmm.

(e) Acetyl butyl content

Measured according to JIS K 7192 (1999) method.

[0078] (Preparation Example 1)

100 parts by mass of the above ethylene acetate butyl copolymer (EVA-1) and 0.15 parts by mass of organic peroxide were uniformly blended with a Henschel mixer and then cross-linked using a single screw extruder (resin temperature 180 ° C). EVA (A-1) was prepared. Table 1 shows the physical properties of the resulting crosslinked ethylene-butyl acetate copolymer.

[0079] (Preparation Example 2)

After blending 100 parts by mass of the above ethylene acetate butyl copolymer (EVA-2) and 0.2 parts by mass of organic peroxide with a Henschel mixer, single screw extruder (resin temperature 180 ° C) Cross-linked EVA (A-2) was prepared using Table 1 shows the physical properties of the resulting cross-linked ethylene-butyl acetate copolymer.

[0080] [Table 1]

[0081] (Example 1)

Table 2 shows the crosslinked EVA (A-1) obtained in Preparation Example 1, the ethylene ionomer (MglO) of ethylene 'methacrylic acid copolymer, modified EVA, olefin wax, magnesium hydroxide, and antioxidant. After blending uniformly with a Henschel mixer at the ratio shown in the following, melt blend with a pressure kneader (resin temperature 195 ° C) for 10 minutes, pelletize, and press sheet (160 ° C X preheat 5 minutes X pressure 5 minutes) X cooling 5 minutes). Table 2 shows the physical properties of the obtained flame-retardant resin composition.

[0082] (Example 2)

In the same manner as in Example 1 except that olefinic wax is not blended in Example 1.

A flame retardant resin composition was obtained. Table 2 shows the physical properties of the obtained flame-retardant resin composition.

[0083] (Example 3)

In Example 1, instead of the crosslinked EVA (A-1), the crosslinked EVA (A-2) obtained in Preparation Example 2 was used, and the blending ratio was changed to the amount ratio shown in Table 2, and the same as in Example 1. Thus, a flame retardant resin composition was prepared. Table 2 shows the physical properties of the obtained flame-retardant resin composition.

[0084] (Example 4)

A flame retardant resin composition was obtained in the same manner as in Example 3 except that modified EVA and olefin-based wax were not blended in Example 3. Table 2 shows the physical properties of the obtained flame-retardant resin composition. [0085] (Comparative Example 1)

A flame retardant resin composition was prepared in the same manner as in Example 1 except that the use of an ethylene / methacrylic acid copolymer magnesium ionomer (Mgl 2 O), modified EVA, and olefin wax was omitted. Table 2 shows the physical properties of the obtained flame-retardant resin composition.

[0086] (Comparative Example 2)

A flame retardant resin composition was prepared in the same manner as in Example 2, except that the use of magnesium ionomer (Mgl 2 O), modified EVA and olefin-based wax of ethylene / methacrylic acid copolymer was omitted. Table 2 shows the physical properties of the obtained flame-retardant resin composition.

[0087] [Table 2]

* 1: The sample drips during ignition, starts to burn vigorously, and drops intermittently.

* 2: Sagging and dripping of the sample is not observed, but the fire cannot be extinguished within the prescribed time.

[0088] (Example 5)

The crosslinked EVA (A-1), alternating copolymer, magnesium hydroxide, and antioxidant obtained in Preparation Example 1 were uniformly blended with a Henschel mixer in the proportions shown in Table 3, and then a pressure feeder ( After melt blending for 10 minutes at a resin temperature of 190 ° C and pelletizing, a press sheet (160 ° C X preheating 5 minutes X pressure 5 minutes X cooling 5 minutes) was prepared. Table 3 shows the physical properties of the flame retardant resin composition obtained.

[0089] (Example 6) In Example 5, in place of the crosslinked EVA (A-1), the crosslinked EVA (A 2) obtained in Preparation Example 2 was used, and the flame retardant properties were the same except that the blending ratio was changed to the amount ratio shown in Table 2. A resin assembly was prepared. Table 3 shows the physical properties of the obtained flame-retardant resin composition.

[Table 3]

Industrial applicability

The flame retardant resin composition provided by the present invention is a flame retardant resin composition having an excellent balance between flexibility and flame retardancy.

The flame retardant resin composition provided by the present invention includes a cross-linked product of an ethylene acetate butyl copolymer having a high content of acetic acid but has an excellent balance between flexibility and flame retardancy. It is.

The flame retardant resin composition provided by the present invention is particularly difficult to achieve the V-0 level even under the severe conditions of 0.5 mm of thin wall thickness according to UL flame resistance test standards! Since it is a flammable resin composition and has flexibility, it can be processed into various molded products by various molding methods.

The flame retardant resin composition provided by the present invention can be used by being laminated with various other materials. Specifically, it is effective in fields that require a high degree of flame retardancy, such as thin wire, thin building material sheet, thin vehicle sheet, toy, hose, sheet, tape, wallpaper, other wire coating materials, and other building materials. Used for

Claims

Claims [1] Unit content of butyl acetate (JIS K7192: 1999 method) is 26 to 47 mass 0/0, melt flow rate (JIS Κ7210: 1999 method, 190 ° C, load 2,160 g) is 0.0 ; ~~ 4g / 10min cross-linked ethylene acetate acetate copolymer (A), neutralization degree 5-60 mol 0/0, melt flow rate (JIS 7210: 1999 method, 190 ° C, load 2, 160 g, the same shall apply hereinafter) 0;; to lOOg / 10 min. Magnesium ionomer (b—1) of ethylene 'unsaturated carboxylic acid copolymer, and C 4 olefin and α, β unsaturated carboxylic acid From a modified copolymer (b-2) obtained by modifying at least one part of a copolymer comprising an anhydride or a derivative thereof by at least one of the following methods (C-1) and (C-2): A resin composition comprising at least one selected polymer (B) and a flame retardant (D),

(C2) Partial ionomerization with metal ions

(A) is the mass part ratio (A) / [(B)] (mass part) = 50 to 99 · 9 / 50-0.1, (D) is the total amount of (Α) and (Β) A flame-retardant resin composition that is 20 to 300 parts by mass with respect to 100 parts by mass.

[2] The flame retardant according to claim 1, wherein the content of unsaturated carboxylic acid units in the ethylene'unsaturated rubonic acid copolymer is 2 to 30% by mass as a base polymer of the magnesium ionomer (b-1). Resin composition.

[3] The unsaturated carboxylic acid and / or the cross-linked ethylene acetate acetate copolymer (A), the magnesium ionomer (b-1) and the modified copolymer (b-2) with respect to 100 parts by mass in total. At least one modified polymer selected from the group consisting of an olefin polymer (E-1) modified with a derivative thereof and a styrene polymer (E-2) modified with an unsaturated carboxylic acid and / or a derivative thereof. The flame retardant resin composition according to claim 1 or 2, comprising 25 parts by mass or less of the coalescence (E).

[4] The crosslinked ethylene acetate butyl copolymer (A), the magnesium ionomer (b

1) and the modified copolymer (b-2) with respect to a total amount of 100 parts by mass, the viscosity average molecular weight force ¾0,000 or less, density force 80-980kg / m ³ , melting point 60-; 160 ° C The flame retardant resin composition according to any one of claims 1 to 3, comprising: olefin fin wax (F) in an amount of 0.01 to 10 parts by weight. object.

[5] The resin composition according to any one of claims 1 to 4, wherein the modified copolymer (b-2) is a 4-carbon olefin inker or isopylene.

[6] The resin composition according to any one of claims 1 to 5, wherein the _α , β unsaturated carboxylic acid anhydride or derivative thereof in the modified copolymer (b-2) is maleic anhydride or a derivative thereof. .

[7] The copolymer of the modified copolymer (b-2) consisting of olefins having 4 carbon atoms and _α , β-unsaturated dicarboxylic acid anhydrides or derivatives thereof, The flame retardant resin composition according to any one of claims 1 to 6, which is an alternating copolymer comprising a saturated dicarboxylic acid anhydride or a derivative thereof.

[8] The Mw / Mn of the gel permeation chromatographic (GPC) method of the crosslinked ethylene acetate butyl copolymer (Α) is 6 to 12; Flammable resin composition.

[9] The flame retardant resin composition according to any one of claims 1 to 8, wherein the flame retardant (D) power is aluminum hydroxide and / or magnesium hydroxide.

[10] The flame retardant resin according to any one of claims 1 to 9, wherein in a vertical flame retardant test conforming to UL94 flame resistance test, a 0.5 mm thick test piece exhibits a flame retardant equivalent to V-1 or more. Composition.

[11] A composition comprising the flame retardant resin composition according to any one of claims 1 to 10;

[12] A molded product obtained by using the flame retardant resin composition according to any one of claims 1 to 10;