JP2005097751A - Mesh sheet for roll curtain - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mesh sheet for a high-strength roll curtain having flexibility and flame retardance without emitting toxic gases and without emitting corrosive gases during incineration. <P>SOLUTION: This mesh sheet for the roll curtain is a mesh-like woven or knitted fabric composed of two or more kinds of polypropylenes having different melting points and using a conjugated monofilament yarn containing the polypropylene having a high melting point as a core layer and the polypropylene having a low melting point as a sheath layer in a warp yarn and a weft yarn. The mesh sheet is obtained as follows. A composition prepared by compounding 100 pts.wt. of the polypropylene having the high melting point with 10-40 pts.wt. of a thermoplastic elastomer and 0.1-5 pts.wt. of a flame retardant composed of a nitrogen-containing compound represented by the formula (1) H(R1)N-(CH2)a-N(R2)-(CH2)b-N(R2')-(CH2)c-N(R1)H is used as the core layer and, on the other hand, a composition obtained by compounding the polypropylene having the low melting point with 0.1-5 pts.wt. of the flame retardant composed of the nitrogen-containing compound represented by the formula (1) is used as the sheath layer, respectively. Thereby, the resultant high-stength mesh sheet has the flexibility and flame retardance without emitting the toxic gases or corrosive gases during the incineration. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a mesh sheet for a roll curtain for light shielding. More specifically, it is a mesh sheet for a light-shielding roll curtain used for a window for a vehicle, and has a flame retardancy that does not generate toxic gas during incineration after use and has a combustion ash content of less than 0.1%. The present invention relates to a curtain mesh sheet.

Conventionally, woven and knitted fabrics of filament yarns such as polyvinyl chloride and flame retardant polyester have been used as a light shielding roll curtain mesh sheet in windows of railway vehicles, automobile vehicles, ships and the like.
However, when polyvinyl chloride is burned at the time of disposal, toxic gases, especially dioxins, are generated, causing environmental pollution problems, and corrosive gases such as hydrogen chloride are generated, causing problems such as damage to incinerators. is there.
Moreover, as a flame retardant polyester, a method of flame retardant treatment using a phosphorous flame retardant as a flame retardant for polyester has been proposed (for example, Patent Document 1).
However, the above-mentioned phosphorus flame retardants have problems such as generating toxic gas during incineration and not only causing environmental pollution.

JP 2002-294554 A (2 pages)

  The present invention has been made by paying attention to the above-mentioned problems, and has a high strength and flexibility, does not generate a toxic gas during incineration, and has a flame retardance that does not generate a corrosive gas. It aims at providing the mesh sheet | seat for curtains.

（式中、R₃は炭素原子数１〜１０のアルキル基または水素原子を表し、R₄は炭素原子数５〜１０のシクロアルキル基または炭素原子数１〜４のアルキル基で置換された炭素原子数５〜１０のシクロアルキル基を表す。） The mesh sheet for roll curtain of the present invention is made of a composite monofilament yarn made of two or more types of polypropylene having different melting points, having a high melting point polypropylene as a core layer and a low melting point polypropylene as a sheath layer as warp and weft yarns. A flame retardant made of a nitrogen-containing compound represented by 10 to 40 parts by weight of a thermoplastic elastomer and the following general formula (1) is added to 100 parts by weight of polypropylene having a high melting point as a core layer. On the other hand, what mix | blended weight is used as a sheath layer, what blended 0.1-5 weight part of the flame retardant which consists of a nitrogen containing compound shown by following General formula (1) in the low melting point polypropylene, respectively. It exists in the mesh sheet | seat for roll curtains characterized by the above-mentioned.
H (R ₁ ) N- (CH ₂ ) _a -N (R ₂ )-(CH ₂ ) _b -N (R _{2 '} )-(CH ₂ ) _c -N (R ₁ ) H (1)
(In the formula, R ₁ is a triazine derivative group containing a piperidyl group represented by the following general formula (2), R _{2 and} R _{2 ′} represent R ₁ or a hydrogen atom, and a, b and c are respectively Represents a positive number from 2 to 5.)

(In the formula, R ₃ represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and R ₄ is a carbon substituted with a cycloalkyl group having 5 to 10 carbon atoms or an alkyl group having 1 to 4 carbon atoms. Represents a cycloalkyl group having 5 to 10 atoms.)

  The mesh sheet for roll curtains of the present invention is made of a composite monofilament yarn made of two or more types of polypropylenes having different melting points, having a high melting point polypropylene as a core layer and a low melting point polypropylene as a sheath layer as warp and weft yarns. A flame retardant made of a nitrogen-containing compound represented by 10 to 40 parts by weight of a thermoplastic elastomer and 100 parts by weight of a polypropylene having a high melting point as a core layer and 0.1 to 5 parts of a nitrogen-containing compound represented by the above general formula (1). On the other hand, what mix | blended weight is used as a sheath layer, what blended 0.1-5 weight part of the flame retardant which consists of a nitrogen containing compound shown by the said General formula (1) in the low melting point polypropylene, respectively. Therefore, the mesh sheet for roll curtains has high strength and flexibility, and has excellent flame retardancy that does not cause the generation of toxic gases during incineration. It is.

In the present invention, a composite monofilament yarn made of two or more types of polypropylene resins having different melting points and having a high melting point polypropylene as a core layer and a low melting point polypropylene as a sheath layer is used.
As the polypropylene resin having a high melting point (hereinafter referred to as a high melting point polypropylene) as the core layer, the polypropylene resin may be a known propylene polymer, ethylene-propylene block copolymer, ethylene-propylene random copolymer, or the like. These polypropylene copolymers or a mixture thereof are preferable, and among these, a propylene homopolymer capable of obtaining high strength is desirable. The melt flow rate (hereinafter abbreviated as MFR) of the polypropylene resin is usually selected from the range of 0.1 to 10 g / 10 minutes, preferably 0.5 to 8.0 g / 10 minutes.

  On the other hand, the low melting point polypropylene (hereinafter referred to as low melting point polypropylene) serving as the sheath layer is determined by the combination with the above high melting point polypropylene, but is at least 10 ° C., preferably 15 to 15 ° C. higher than this high melting point polypropylene. Polypropylene with a low melting point of 50 ° C. For example, when a propylene homopolymer is used as a high melting point polypropylene, an ethylene-propylene block copolymer, an ethylene-propylene random copolymer, a metallocene catalyst method polypropylene (which is obtained using a metallocene catalyst method) can be used as the low melting point polypropylene. And polypropylene). The MFR of the polypropylene is selected from the range of 0.1 to 30 g / 10 minutes, preferably 0.5 to 20 g / 10 minutes.

As the thermoplastic elastomer used by blending with the high melting point polypropylene of the core layer, a polystyrene-based thermoplastic elastomer or an ethylene-propylene-diene monomer elastomer is used.
A polystyrene-based thermoplastic elastomer (hereinafter abbreviated as PSB) is a block copolymer containing a polymer of at least one vinyl aromatic monomer and a polymer of at least one conjugated diene. It may be a mold or a radial mold. Further, the polymer containing a conjugated diene may be a random copolymer with a small amount of vinyl aromatic monomer, or a so-called taper type block copolymer in which the amount of vinyl aromatic monomer increases temporarily. It may be a polymer.

  The structure of the block copolymer is not particularly limited, and any of (AB) n type, (AB) n-A type and (AB) n-C type can be used. In the formula, A is a polymer of a vinyl aromatic monomer, B is a polymer of a conjugated diene, C is a coupling agent residue, and n is an integer of 1 or more. In addition, in the said block copolymer, it is also possible to use the block copolymer by which the conjugated diene part was hydrogenated.

  As the vinyl aromatic monomer constituting the block copolymer, styrene, α-styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl naphthalene, or the like is used. preferable. As the conjugated diene, 1,3-butadiene, isoprene, piperylene and the like are used, and among them, 1,3-butadiene and isoprene are particularly preferable.

 Examples of the block copolymer include styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene / butylene-styrene block copolymer (SEBS) obtained by hydrogenating the butadiene portion of SBS, and styrene-isoprene. Styrene block copolymer (SIS), styrene-isoprene / butadiene-styrene block copolymer (SIBS), styrene-ethylene / propylene-styrene block copolymer (SEPS) obtained by hydrogenating the isoprene portion of SIS, and the like. SIBS and SEBS are preferred. The block copolymer preferably has a weight average molecular weight of 10,000 to 800,000, more preferably 50,000 to 500,000. Further, the content of the vinyl aromatic monomer in the block copolymer is preferably 5 to 60% by weight, more preferably 10 to 50% by weight.

  The ethylene-propylene-diene monomer elastomer (hereinafter referred to as EPDM) is a ternary polymer (terpolymer) of ethylene, propylene and diene monomer. The diene monomer is a non-conjugated linear or cyclic diene hydrocarbon containing a carbon atom having 5 to 20 carbon atoms. For example, the diene monomer includes ethylidene norbornene, methylene norbornene, 1,4-pentadiene. 1,4-hexadiene, dicyclopentadiene, tricyclopentadiene, isoprene and the like, and ethylidene norbornene is particularly preferable.

The number average molecular weight of the EPDM is usually 5000 or more, preferably 10,000 to 200,000. As EPDM, the respective contents are in the range of 35 to 80% by weight of ethylene, 18 to 55% by weight of propylene and 2 to 10% by weight of diene monomer, preferably 48 to 77% by weight of ethylene, 23 to 52% by weight of propylene and ethylene. And a terpolymer consisting of 2.5 to 9.8% by weight of diene monomer based on the total content of propylene and propylene.

  The compounding quantity of a thermoplastic elastomer is 10-40 weight part of thermoplastic elastomer with respect to 100 weight part of polypropylene, Preferably it is the range of 20-40 weight part. If the blending amount of the thermoplastic elastomer is less than 20 parts by weight, the effect of improving the flexibility is insufficient, and the mechanical strength and heat resistance are lowered, which is not preferable.

（式中、R₃は炭素原子数１〜１０のアルキル基または水素原子を表し、R₄は炭素原子数５〜１０のシクロアルキル基または炭素原子数１〜４のアルキル基で置換された炭素原子数５〜１０のシクロアルキル基を表す。） As the flame retardant used in the present invention, a nitrogen-containing compound represented by the following general formula (1) is used.
H (R ₁ ) N- (CH ₂ ) _a -N (R ₂ )-(CH ₂ ) _b -N (R _{2 '} )-(CH ₂ ) _c -N (R ₁ ) H (1)
(In the formula, R ₁ is a triazine derivative group containing a piperidyl group represented by the following general formula (2), R _{2 and} R _{2 ′} represent R ₁ or a hydrogen atom, and a, b and c are respectively Represents a positive number from 2 to 5.)

(In the formula, R ₃ represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and R ₄ is a carbon substituted with a cycloalkyl group having 5 to 10 carbon atoms or an alkyl group having 1 to 4 carbon atoms. Represents a cycloalkyl group having 5 to 10 atoms.)

また、上記一般式(４)で示されるものは、上記一般式(１)または(３)のR₁を示すものであり、上記一般式(２)のR₃が炭素原子数４のブチル基であり、R₄が炭素原子数６のシクロヘキシル基であるピペリジル基を含有するトリアジン誘導体基である。 As the nitrogen-containing compound represented by the general formula (1), a nitrogen-containing compound represented by the following general formula (3) is preferable, and a combination of the following general formula (3) and the following general formula (4) is particularly preferable.
H (R ₁ ) N- (CH ₂ ) ₃ -N (R ₁ )-(CH ₂ ) ₂ -NH- (CH ₂ ) ₃ -N (R ₁ ) H (3)
That is, in the nitrogen-containing compound represented by the general formula (3), in the general formula (1), R ₁ is a triazine derivative group containing a piperidyl group represented by the general formula (2), and R ₂ is A nitrogen-containing compound in which R ₁ , R _{2 ′} is a hydrogen atom, and a, b, and c are positive numbers 3, 2, and 3, respectively.

Moreover, those represented by the general formula (4) shows the R ₁ in the general formula (1) or (3), R ₃ is a butyl group having 4 carbon atoms in the general formula (2) And R ₄ is a triazine derivative group containing a piperidyl group which is a cyclohexyl group having 6 carbon atoms.

   In the present invention, a desired amount of the flame retardant is blended with the respective resins of the core layer and the sheath layer, and used after being melt-kneaded. The blending ratio of the flame retardant is in the range of 0.1 to 5% by weight, preferably 0.5 to 4% by weight, based on the total weight of the resin of the core layer and the sheath layer. If the blending amount is less than the above range, the flame retardancy is insufficient, and if it exceeds the above range, the flame retardancy effect is not further improved, and conversely, the cost is increased, which is not preferable.

The core-sheath composite monofilament has a structure in which a high melting point polypropylene is used as a base layer and a low melting point polypropylene is coated on the sheath layer. The composition ratio of the core layer / sheath layer in the composite monofilament is preferably 50/50 to 90/10, and more preferably 60/40 to 80/20.
Examples of the combination of the core / sheath composite monofilament core / sheath layer include propylene homopolymer layer / ethylene-propylene block copolymer layer, propylene homopolymer layer / ethylene-propylene random copolymer layer, propylene The combination of a homopolymer layer / metallocene catalyst method polypropylene layer, etc. are mentioned.

  The method for producing the composite monofilament is not particularly limited, and the polypropylene of each layer of the combination resin described above, for example, polypropylene is melt-kneaded with an extruder, and the two-layer discharge holes are substantially concentric at a melting temperature of 170 to 240 ° C. A core layer made of high melting point polypropylene is supplied from the central discharge hole of the die provided above, and a sheath layer made of low melting point polypropylene is extruded and coated on the outer surface to form a composite monofilament, which is then subjected to stretching treatment, etc. Is what you get. As the stretching treatment, a thermal stretching method, that is, this thermal stretching is carried out at a temperature below the melting point of the high melting point polypropylene of the core layer and above the softening point. Usually, the stretching temperature is 110 to 150 ° C., and the stretching ratio is usually 3 -15 times, preferably 5-12 times.

  The fineness of the drawn yarn is preferably 100 to 3000 dtex (hereinafter abbreviated as dt), more preferably 500 to 2000 dt. If the fineness is less than 100 dt, the strength is insufficient, and if it exceeds 3000 dt, the flexibility is inferior and the handleability is lowered.

As the woven structure of the woven or knitted fabric, various structures such as plain weave, twill weave, tangle weave and imitation weave are used. On the other hand, as the knitted structure, warp knitting, weft knitting and the like are appropriately used.
The driving density of the warp and the weft is preferably 20 to 80 yarns / 2.54 cm, and it is particularly preferable to adjust the driving density of the weft so that the light shielding rate is 80% or more.

  Moreover, since the said mesh sheet | seat for roll curtains is exposed to sunlight for a long period of time, high weather resistance is required. The flame retardant used in the present invention is a triazine derivative having a piperidyl group, and itself has a very high weather resistance because it functions as a hindered amine light stabilizer. Furthermore, as a method for improving the weather resistance, a method of adding a weather resistance agent such as an ultraviolet absorber or a light stabilizer may be employed.

  Specific examples of the ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-diphenyl acrylate, and octyl-2-cyano-3. Cyanoacrylate UV absorbers such as 3,3'-diphenyl acrylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, benzophenone UV absorbers such as 2-hydroxy-4-octoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, benzotriazole UV absorbers such as 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, resorcinol monobenzoate, 2,4- Benzoate UV such as di-t-butylphenyl-3'-5'-di-t-butyl-4'-hydroxybenzoate Such as absorption agent and the like. The blending ratio of the ultraviolet absorber is in the range of 0.05 to 5% by weight, preferably in the range of 0.1 to 1% by weight with respect to the thermoplastic resin.

  Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3. , 4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, 1- (2- (Hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol and polycondensate of diethyl succinate. The blending ratio of the light stabilizer is 0.05 to 5% by weight, more preferably 0.1 to 1% by weight, based on the thermoplastic resin.

  To the polypropylene of the present invention, additives that are usually used such as an antioxidant, a dispersant, a lubricant, an antistatic agent, a pigment, an inorganic filler, a cross-linking agent, a foaming agent, a nucleating agent and the like are within the scope of the present invention. An agent may be blended.

Example 1:
As a core layer, polypropylene (MFR = 2.0 g / 10 min, density = 0.90 g / cm ³ , Tm = 164 ° C.) 100 parts by weight, ethylene-propylene-diene monomer elastomer 30 parts by weight and the above general formula (3) And a composition obtained by blending 3.1 parts by weight of a flame retardant composed of a nitrogen-containing compound in combination with the compound represented by the general formula (4) and melt-kneading at 200 ° C. A composition obtained by blending 2.4 parts by weight of a flame retardant composed of a nitrogen-containing compound obtained by combining those represented by the above general formula (3) and general formula (4) with 100 parts by weight of polypropylene, and melt-kneading at 200 ° C. Each was melt-extruded with a composite monofilament molding die, then cooled and solidified, and then stretched to form a composite monofilament having a fineness of 670 dt. Using this composite monofilament for warp and weft, a mesh sheet was formed by plain weaving at a driving density of 24 × 60 / 2.54 cm. The obtained mesh sheet had a basis weight of 250 g / m ² and a light shielding rate of 85%.
The obtained mesh sheet had flexibility that could be folded in the warp direction, and was easy to handle. The mesh sheet passed both during and after alcohol combustion in the flame retardant test of the vehicle material.

Comparative Example 1
In Example 1, the flame retardant was changed to melamine cyanurate (trade name: MC-610, manufactured by Nissan Chemical Co., Ltd.), and 10 parts by weight of the above melamine cyanurate was blended with 100 parts by weight of polypropylene. Was done in the same way.
As a result, the obtained mesh sheet failed in both the alcohol combustion and after the combustion in the flame retardant test of the vehicle material.

Claims (4)

A mesh woven or knitted fabric made of two or more types of polypropylenes having different melting points, wherein a composite monofilament yarn having a high melting point polypropylene as a core layer and a low melting point polypropylene as a sheath layer is used for warp and weft. As a mixture of 100 parts by weight of a polypropylene having a high melting point and 10 to 40 parts by weight of a thermoplastic elastomer and 0.1 to 5 parts of a flame retardant composed of a nitrogen-containing compound represented by the following general formula (1), A roll curtain mesh sheet characterized by using 0.1 to 5 parts by weight of a flame retardant composed of a nitrogen-containing compound represented by the following general formula (1) in polypropylene having a low melting point as a layer. .
H (R ₁ ) N- (CH ₂ ) _a -N (R ₂ )-(CH ₂ ) _b -N (R _{2 '} )-(CH ₂ ) _c -N (R ₁ ) H (1)
(In the formula, R ₁ is a triazine derivative group containing a piperidyl group represented by the following general formula (2), R _{2 and} R _{2 ′} represent R ₁ or a hydrogen atom, and a, b and c are respectively Represents a positive number from 2 to 5.)

(In the formula, R ₃ represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and R ₄ is a carbon substituted with a cycloalkyl group having 5 to 10 carbon atoms or an alkyl group having 1 to 4 carbon atoms. Represents a cycloalkyl group having 5 to 10 atoms.)   The mesh sheet for a roll curtain according to claim 1, wherein the thermoplastic elastomer is a styrene thermoplastic elastomer.   The roll curtain mesh sheet according to claim 1, wherein the thermoplastic elastomer is an ethylene-propylene-diene monomer elastomer. The mesh sheet for roll curtain according to claim 1, wherein the flame retardant is a nitrogen-containing compound represented by the following general formula (3).
H (R ₁ ) N- (CH ₂ ) ₃ -N (R ₁ )-(CH ₂ ) ₂ -NH- (CH ₂ ) ₃ -N (R ₁ ) H (3)
(In the formula, R ₁ is a triazine derivative group containing a piperidyl group represented by the following general formula (4).)