JP2008025065A - Fibrous product used for sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an fibrous product used as flame retardant sheet fibrous products, in particular, a sheet for construction, sheet for curing, tent, body cover of automobile, motorcycle, etc., curtain, etc., without giving any drip of raw materials on burning, excellent in flame retardant performance and also excellent in washing durability and dry cleaning durability. <P>SOLUTION: This fibrous product used for the sheet containing a polyester-based fiber contains a silicone-based compound having a constituent unit expressed by RSiO<SB>1.5</SB>(wherein, R is an organic group) and a compound having an imide structure in the polyester-based fiber and having no drip (melt-dripping) in a flame retarding test specified by the D method of the JIS L1091 (1992). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a flame retardant sheet fiber product containing a polyester fiber, and more particularly to a sheet fiber product having no drip (melting dripping) due to melting at the time of combustion and having improved flame retardant performance. is there.

  In recent years, in the fiber sheet products, there is a strong demand for flame retarding in order to prevent fires in construction sheets and tents. In addition, the danger of secondary disasters such as burns due to drip (melting dripping) at the time of combustion of thermoplastic fibers is also sought, and a technique for suppressing drip is strongly demanded.

  Conventionally, as a flame retardant method for polyester fibers, etc., a lot of sheet fiber products containing halogen flame retardants such as chlorine-containing flame retardants, bromine-containing flame retardants, or halogen flame retardants and antimony flame retardants have been proposed. Has been.

  Particularly in recent years, a sheet fiber product containing a phosphorus compound has been proposed in order to suppress the generation of harmful gases during combustion (see Patent Document 1).

  However, although this example is excellent in flame retardancy, it tends to promote drip at the time of combustion, so the problem of secondary disaster caused by drip cannot be solved.

In order to solve these problems, studies using silicone compounds have been conducted. This silicone compound is monofunctional R ₃ SiO _0.5 (M unit), bifunctional R ₂ SiO _1.0 (D unit), trifunctional RSiO _1.5 (T unit), 4 It is composed of any one of units represented by functional SiO _2.0 (Q unit).

  As an example of using a silicone-based compound, a silicone oil having a functional group and an organic phosphorus compound are included in the fiber structure, and the improvement of the drip suppression effect, the suppression of the generation of toxic gas, and the prevention of the deterioration of the mechanical properties are studied. (Refer to Patent Document 2) However, in any case, the flame retardancy performance does not reach that of the halogen-based flame retardant, and problems remain with the current technology.

In addition, there is one in which a silicone resin is contained in a fiber structure and the dispersion state of the silicone resin is defined (see Patent Document 3). Certainly this example has some flame retardancy and drip suppression effects, and is also excellent in environmental and safety, but it is still a challenge to improve further flame retardancy and drip suppression effects. This technology has not yet solved various problems.
JP 2003-013367 A (Claims 1 and 5) JP 09-268423 A (Claim 1) Japanese Patent Laying-Open No. 2005-097819 (Claim 1)

  The present invention has been made in view of the above-described situation, and an object of the present invention is to provide a sheet fiber product in which the flame retardancy of the sheet fiber product and the drip suppression effect during combustion are improved and the weather resistance is excellent.

The present invention adopts the following configuration in order to solve the above problems. That is,
(1) A sheet fiber product containing a polyester fiber, which contains a silicone compound having a structural unit represented by RSiO _1.5 (R is an organic group) and a compound having an imide structure in the polyester fiber. In addition, a sheet fiber product characterized by having no drip (melting dripping) in a flameproof test defined in JIS L1091 (1992) D method.
(2) The organic group R constituting the silicone compound contains a phenyl group, and the content of the phenyl group is 30 mol% or more in terms of a molar ratio with respect to all organic groups constituting the silicone compound. The sheet fiber product according to (1).
(3) The sheet fiber product according to (1) or (2), wherein the silanol group content contained in the silicone compound is 2% or more and 10% or less by weight with respect to the silicone compound.
(4) The sheet fiber product according to any one of (1) to (3), wherein the compound having an imide structure is a polyetherimide.

  According to the present invention, flame retardancy and drip suppression are used in sheet fiber products, specifically, for example, construction seats, curing sheets, tents, body covers for automobiles, motorcycles, and seats for curtains. It is possible to provide a sheet fiber product that is highly effective and has excellent weather resistance.

  Hereinafter, the present invention will be described in detail.

As described above, the silicone compound is monofunctional R ₃ SiO _0.5 (M unit), bifunctional R ₂ SiO _1.0 (D unit), trifunctional RSiO _1.5 (T Unit) is composed of any of the units represented by tetrafunctional SiO _2.0 (Q unit), and the silicone compound referred to in the present invention is trifunctional RSiO _1.5 polyester fiber. It contains at least inside. By including a unit represented by RSiO _1.5 (T unit) in the structure of the silicone compound, the heat resistance of the silicone compound is improved, and a sheet fiber product having high flame retardancy can be obtained.

From the viewpoint of heat resistance and flame retardancy, the content of RSiO _1.5 is preferably 20% or more, more preferably 50% or more, in terms of molar ratio to the silicone compound.

  Further, in the present invention, from the viewpoint of dispersibility and flame retardancy in polyester fibers, the organic group constituting the silicone compound contains a phenyl group, and the content of the phenyl group is the total organic group constituting the silicone compound. The molar ratio is preferably 30% or more, more preferably 60% or more.

  The amount of silanol groups in the silicone compound is preferably 2% or more by weight with respect to the silicone compound in order to have sufficient flame retardancy, and preferably 10% or less from the viewpoint of processability. Preferably they are 3% or more and 8% or less. Here, the amount of silanol groups is the weight of OH groups bonded to Si in the silicone compound. By making the amount of silanol groups within the range of the present invention, it is possible to efficiently form a crosslinked structure with a polyester fiber at the time of combustion, and to improve the flame retardancy and drip suppression effect.

  Further, the amount average molecular weight of the silicone compound is preferably 500 or more, since the melt viscosity is high when the silicone compound is melt-kneaded, and the dispersibility to fibers is good. From the viewpoint of sex. More preferably, it is 1000 or more and 100,000 or less, More preferably, it is 3000 or more and 50000 or less.

  Next, the compound having an imide structure of the present invention is a compound having a structure of -CO-NR-CO- (R is an organic group) in the molecular structure.

  By containing the compound having an imide structure and the silicone compound in the polyester fiber, it is possible for the silicone compound, the compound having the imide structure and the polyester fiber to efficiently form a carbonized layer during combustion, This can remarkably improve the flame retardancy and drip suppression effect as compared with the case where each of the silicone compound and the compound having an imide structure is contained alone.

  Moreover, the compound which has an imide structure has a thermoplastic thing from a point of workability. That is, the glass transition temperature is preferably 130 ° C. or higher and 300 ° C. or lower, more preferably 130 ° C. or higher and 250 ° C. or lower.

  Specific examples of the compound having an imide structure include polyimide, polyamideimide, and polyetherimide. Among them, polyetherimide is preferable from the viewpoint of workability, but the molecular structure has an imide structure. This is not the case.

The content ratio of the silicone compound contained in the polyester fiber and the compound having an imide structure is preferably in the range of 5 (silicone compound): 95 (compound having an imide structure) to 95: 5 by weight ratio, The range of 10:90 to 90:10 is preferable.
The composition ratio of the polyester fiber of the present invention is 94 (polyester fiber): 1 (silicone compound): 5 (compound having an imide structure) to 40 in terms of weight ratio from the viewpoint of flame retardancy and drip suppression effect. : 20: 40 is preferable, and 90: 3: 7 to 70:10:20 is more preferable.

  The polyester fiber of the present invention is a polymer synthesized from a dicarboxylic acid such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate or the like and an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, as well as poly-L-lactic acid, These are non-petroleum polyester compounds of poly-D-lactic acid, and these may be used alone or in combination of two or more, such as mixed spinning and mixed fiber.

  The sheet fiber product obtained by the present invention refers to a sheet fiber product such as a construction sheet, a curing sheet, a body cover sheet for a tent, an automobile, a motorcycle, or a curtain.

  The sheet fiber product of the present invention preferably contains a polyester fiber in a weight ratio of 30% by weight or more from the viewpoint of flame retardancy and drip suppression effect. Synthetic fibers and natural fibers can be mixed.

  The form of the polyester fiber used for the sheet fiber product is, for example, a multifilament in which the single yarn fineness is in the range of 0.1 dtex to several tens of dtex, the total fineness is in the range of 50 to 300 dtex, and the number of filaments is in the range of 10 to 100. Is mentioned.

  However, since the construction sheet is used at the construction site and the strength of the fiber product is necessary from the viewpoint of fall prevention, the single yarn fineness is in the range of 3 dtex to several tens of dtex, and the total fineness is in the range of 800 dtex to 4000 dtex. The number ranges from 10 to 100.

  In addition, the filaments obtained in this way can be obtained as a sheet fiber product by weaving, for example, a woven fabric such as a triple structure, a change structure, a double structure, a double structure, or a double structure, which is a single structure. Can do.

In addition, the basis weight of the sheet fiber product at this time is in the range of 50 g / m ^{2 to} 800 g / m ² .

  In addition to multifilaments, short fibers, woven fabrics composed of short fibers, and non-woven fabrics can be used depending on the application, and the present invention is not limited to the form of fibers or the texture of the fabrics.

  Further, the sheet fiber product of the present invention is characterized in that there is no drip (melting dripping) in a flameproof test specified in JIS L1091 (1992) D method.

  JIS L1091 (1992) The flame-proof test of method D is a method of measuring the number of flame contact when a fiber sample having a length of 10 cm and a mass of 1 g is tilted at 45 ° in a coil and flame contacted from below the sample. As the number of flame contacts increases, flame retardancy increases.

  The present invention is characterized in that there is no drip at the time of this flameproof test, and the drip is a molten drop from a sample.

  In the sheet fiber product of the present invention, since the silicone compound and the imide structure-containing compound contained in the polyester fiber are excellent in weather resistance, the flame retardant performance due to ultraviolet rays and rainwater, and the drip suppression effect decrease in performance are small. Since flame retardant sheet fiber products are used outdoors such as construction sheets, curing sheets, body cover sheets for tents, automobiles, motorcycles, etc., durability of performance against ultraviolet rays and rainwater is important. A sheet fiber product exhausted with a flame retardant of the same type may deteriorate, decompose or drop off the chemical, resulting in reduced performance.

  Next, the manufacturing method of the present invention will be described in detail.

The silicone compound can be produced by general polycondensation. For example, R ₃ SiOCl (triorganochlorosilane), R ₂ SiOCl ₂ (diorganodichlorosilane), RSiOCl ₃ (monoorganotrichlorosilane), and SiOCl ₄ (tetrachlorosilane) are used as monomers and condensed under an acid or alkali catalyst. A silicone compound is synthesized. R ₃ SiOCl (corresponding to M unit), R ₂ SiOCl ₂ (corresponding to D unit), RSiOCl ₃ (corresponding to T unit), R ₃ SiOCl (corresponding to D unit), R ₃ SiOCl ₂ (corresponding to D unit), The molar ratio of SiOCl ₄ (corresponding to the Q unit) is adjusted.

  Further, the content of the organic group R contained in the silicone compound is governed by the content of the organic group R in the monomer. Therefore, the content of the phenyl group contained in the silicone compound can be adjusted by substituting the desired amount of R in the monomer with a phenyl group.

The content of silanol groups contained in the silicone compound can be controlled by the reaction time. It is also possible to control the content of silanol groups by reacting R ₃ SiOCl or R ₃ SiOH with a silanol group as a blocking agent. The content of silanol groups is the peak area (integral value) of SiO _2.0 , RSiO _1.5 , R ₂ SiO _1.0 , and R ₃ SiO _0.5 derived from a structure not containing a silanol group in ²⁹ Si-NMR. ) And a silanol group-containing Si (OH) ₄ , SiO _0.5 (OH) ₃ , SiO _1.0 (OH) ₂ , SiO _1.5 (OH), RSi (OH) ₃ , RSiO _{0 .5} (OH) ₂ , RSiO _1.0 (OH), R ₂ Si (OH) ₂ , R ₂ SiO _0.5 (OH), R ₃ Si (OH) from the ratio of peak areas (integrated values) It is possible to calculate.

For example, if the silicone compound is composed only of _{RSiO 1.5} and _RSiO 1.0 _(OH), the ratio of the integrated value of the _{RSiO 1.5} and _RSiO 1.0 (OH) is 1.5 _{(RSiO 1.5} ): 1.0 (RSiO _1.0 (OH)) can be obtained as in the following formula 1.
(Formula 1)
Silanol group content (wt%)
= {(17 × the ratio of the integrated value of _{RSiO 1.0 (OH)) / (} RSiO 1.0 (OH) of molecular weight × _{RSiO 1.0} (OH) of the integrated value of the ratio + _{RSiO 1.5} molecular weight × RSiO _1.5 integral value ratio)} × 100
= {(17 × 1.0) / (138 × 1.0 + 129 × 1.5)} × 100
= 5.13
Moreover, the weight average molecular weight of a silicone type compound is controllable by the reaction time at the time of manufacture. The molecular weight can be measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.

  As a method for imparting a silicone compound and a compound having an imide structure to a fiber structure, a method of adding at the time of polymerization of a polyester fiber, a polyester fiber and these compounds are dissolved in a solvent, mixed and then dried. Examples thereof include, but are not limited to, a method of melt-mixing polyester fibers and these compounds with a kneader such as a biaxial extruder or a Banbury mixer. From the viewpoint that the compound having a structure can be sufficiently dispersed and stably produced, a method of melt-mixing with a kneader such as a twin screw extruder or a Banbury mixer is preferred.

  Next, the manufacturing method of a polyester fiber is demonstrated.

  As a manufacturing method of a polyester fiber, the method of manufacturing using a melt spinning machine is mentioned, for example.

  For example, after mixing a polyester fiber, a silicone compound, and an imide structure-containing compound by the method described above, and cutting the obtained resin composition into a 3 mm square chip shape, the chip is charged into a hopper of a melt spinning machine. The polyester fiber can be obtained by melting at a temperature equal to or higher than the melting temperature of the polyester fiber and discharging from the base. Moreover, it can use suitably as a fiber used for a sheet fiber product by extending | stretching and thread-processing the polyester fiber obtained at this time.

  Next, the manufacturing method of a sheet fiber product is demonstrated.

  The manufacturing method can be manufactured by a known method, and weaving using the polyester fiber obtained by the above-described method, and manufacturing a sheet fiber product through processes such as scouring, intermediate setting, dyeing and washing. It is possible.

  Here, the process conditions such as scouring, intermediate setting, and dyeing can be processed under the same conditions as those for the polyester fiber alone. For example, in scouring, 1 to 50 g / L of sodium carbonate using a liquid dyeing machine, interface It can be processed under the conditions of 1 to 50 g / L of activator, processing temperature 60 to 100 ° C., processing time 10 minutes to 60 minutes, and the intermediate set is processed at a processing temperature 130 ° C. to 200 ° C. using a tenter, and the processing time 30 seconds to It can be processed under conditions of 5 minutes, and dyeing can be carried out using a flow dyeing machine or the like to dye disperse dyes at a desired concentration under conditions of a processing temperature of 120 ° C to 200 ° C and a processing time of 10 minutes to 2 hours. It is.

  Then, it can manufacture as a sheet fiber product through the process of cutting and sewing.

  Hereinafter, the present invention will be described more specifically with reference to examples.

  First, the silicone compounds in Examples and Comparative Examples were prepared as follows, and silicone compounds 1 to 6 shown in Table 1 were obtained.

<Preparation of proportions of M, D, T, and Q units>
R ₃ SiOCl (corresponding to R ₃ SiO _0.5 ), R ₂ SiOCl ₂ (corresponding to R ₂ SiO _1.0 ), RSiOCl ₃ (corresponding to RSiO _1.5 ), SiOCl ₄ (corresponding to SiO _2.0 ) Were mixed at a molar ratio of each structural unit shown in Table 1, then hydrolyzed with water, and the generated hydrochloric acid was removed with methanol. Then, condensation of potassium hydroxide as a _{catalyst, R 3 SiO 0.5, R 2} SiO 1.0, RSiO 1.5, the proportion of structural units of _{SiO 2.0} was to produce a different silicone compound.

<Adjustment of the ratio of phenyl group and methyl group>
Using raw materials obtained by substituting the above R moiety with a phenyl group and a methyl group, silicone compounds having different molar ratios of phenyl group and methyl group were prepared.

<Adjustment of silanol group content>
The reaction time for condensing the silicone compound was adjusted to obtain a silicone compound. The obtained silicone compound was measured by ²⁹ Si-NMR using CDCl ₃ as a solvent and TMS (tetramethylsilane) as a standard substance at a total number of 256 times. The area (integrated value) of peaks of SiO _2.0 , RSiO _1.5 , R ₂ SiO _1.0 , R ₃ SiO _0.5 derived from a structure not containing a silanol group and Si derived from a structure containing a silanol group ( OH) ₄ , SiO _0.5 (OH) ₃ , SiO _1.0 (OH) ₂ , SiO _1.5 (OH), RSi (OH) ₃ , RSiO _0.5 (OH) ₂ , RSiO _1.0 ( The silanol group amount (wt%) was calculated from the ratio of the peak areas (integrated values) of OH), R ₂ Si (OH) ₂ , R ₂ SiO _0.5 (OH), and R ₃ Si (OH).

<Measurement of weight average molecular weight>
Each of the reaction times for condensing the silicone compound was adjusted, and the obtained silicone compound was measured with a gel permeation chromatography (GPC) using chloroform as a separation solution, a sample concentration of 1 wt%, and a detector RI. The weight average molecular weight was calculated in terms of polystyrene.

  Moreover, about the combustion evaluation in each Example, it performed as follows.

<Combustion evaluation method>
A fiber structure having a length of 100 mm and a mass of 1 g was prepared as a test piece, and the number of times of flame contact, the number of drips, and carbonization when evaluated according to JIS L1091 (1992) D method were evaluated. In addition, it shows that a flame retardance is so high that the number of times of flame contact is large, and it shows that the effect of drip suppression is so high that the number of times of drip is small. In addition, carbonization is evaluated by the shape of the carbide of the sample after completion of the test. X indicates that there is no carbide, △ indicates that the carbide remains in its original form, △ indicates that the carbide is not continuous, and carbide indicates that the original shape is continuous. The carbonization property was evaluated with the circle formed as.

<Exposure test>
The treatment was carried out as follows with reference to JIS B7753 (1993).

  The fiber fabric sample was set in a sunshine weather meter model S80D (manufactured by Suga Test Instruments Co., Ltd.) and subjected to an accelerated exposure test. The test conditions are a black panel temperature of 63 ° C. (± 3 ° C.), spray water spraying of 12 minutes / 60 minutes, and a processing time of 1000 hours.

Examples 1-5
Polyether imide (product name ULTEM (product name) manufactured by GE Plastics Co., Ltd.) having a glass transition temperature (Tg) of 210 ° C. as a compound containing an imide structure is used as the polyester fiber, and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.65 Registered trademark) 1010). Using the silicone compounds 1 to 5 shown in Table 1, the blending ratio is 75 wt% (polyethylene terephthalate): 20 wt% (polyetherimide): 5 wt% (silicone compound), polyethylene terephthalate, polyetherimide and silicone system. The compound was kneaded using a twin screw extruder under the conditions of kneading temperature: 290 ° C., L / D: 30, screw rotation speed: 300 rpm, and the strand was cut into 3 mm square chips to obtain chips.

  Thereafter, the obtained chip was dried at 150 ° C. for 12 hours and 2 Torr with a vacuum dryer, and then the spinning temperature was 295 ° C., the spinning speed was 3000 m / min, the nozzle diameter was 0.35 mm-24H (hole), and the discharge amount was 43 g / min. Spinning was performed under the following conditions to obtain a UY yarn having a composition ratio of 75 wt% (polyethylene terephthalate): 20 wt% (polyetherimide): 5 wt% (silicone compound). Next, the UY yarn was drawn at a draw ratio such that the fineness of the drawn yarn obtained under the conditions of a drawing temperature of 90 ° C., a set temperature of 130 ° C., and a processing speed of 400 m / min was 84 dtex-24 filaments to obtain a drawn yarn. .

  Then, using the obtained drawn yarn, weaving using an air jet loom under the conditions of weaving structure: plain weave, warp density 99 / inch and weft density 90 / inch, followed by scouring and intermediate setting, and a combustion test The fiber fabric used for was obtained.

  As a result of evaluating the number of flame contact and the number of drip according to the above-described combustion evaluation method using the obtained fabric, Examples 1 to 5 are the number of flame contact is 10 times or more, the number of drip is 0 times, The carbonization was ◯, and the results were excellent in flame retardancy and drip suppression.

  Moreover, as a result of evaluating the number of times of flame contact and drip of the fiber fabric sample obtained by the exposure treatment again according to the combustion evaluation method, Examples 1 to 5 exhibited the same performance as that before the exposure treatment as shown in Table 3. And the result which was excellent in a weather resistance was obtained.

Comparative Example 1
A fiber fabric comprising 100 wt% of polyethylene terephthalate with a blending ratio of 100 wt% (polyethylene terephthalate) was produced in the same manner as in Examples 1-5. In addition, since the imide structure containing compound and the silicone compound were not included, kneading was not performed.

  As a result of evaluating the number of flame contact and the number of drip according to the above-described combustion evaluation method using the obtained fabric, Comparative Example 1 has a flame contact number of 1, and the drip number of 10 or more. , Drip suppression effect, and carbonization were both low.

Comparative Example 2
A fiber fabric was produced in the same manner as in Examples 1 to 5 except that the blending ratio was 95 wt% (polyethylene terephthalate): 5 wt% (silicone compound 1 shown in Table 1).

  As a result of evaluating the number of times of flame contact and the number of drip according to the above-described combustion evaluation method using the obtained fabric, Comparative Example 1 has a number of times of flame contact of 5 times, the number of times of drip is 0 times, It was (triangle | delta) and the effect of drip suppression was equivalent to Examples 1-5, but the flame retardance and carbonization were low.

Comparative Example 3
A fiber fabric was produced in the same manner as in Examples 1 to 5, except that the blending ratio was 80 wt% (polyethylene terephthalate): 20 wt% (the same polyetherimide as in Examples 1 to 5).

  As a result of evaluating the number of times of flame contact and the number of drip according to the above-described combustion evaluation method using the obtained fabric, Comparative Example 1 has a number of times of flame contact of 1, and the number of times of drip is 10 times or more. Was x, and both flame retardancy, drip suppression effect and carbonization were low.

Comparative Example 4
A fiber fabric was produced in the same manner as in Examples 1 to 5 except that the silicone compound 6 shown in Table 1 was used as the silicone compound.

  As a result of evaluating the number of flame contact and the number of drip in accordance with the above-described combustion evaluation method using the obtained fabric, Comparative Example 1 has 5 times of flame contact, 2 times of drip, and carbonization is It was (triangle | delta) and the flame retardance, the drip suppression effect, and carbonization were both low.

Claims (4)

A sheet fiber product containing a polyester fiber, which contains a silicone compound having a structural unit represented by RSiO _1.5 (R is an organic group) and a compound having an imide structure in the polyester fiber, and JIS L1091 (1992) A sheet fiber product characterized by having no drip (melting dripping) in the flameproof test specified in the D method.   2. The organic group R constituting the silicone compound contains a phenyl group, and the content of the phenyl group is 30 mol% or more in a molar ratio with respect to all organic groups constituting the silicone compound. The sheet fiber product as described in.   The sheet fiber product according to claim 1 or 2, wherein the silanol group content contained in the silicone compound is 2% or more and 10% or less by weight with respect to the silicone compound.   The sheet fiber product according to any one of claims 1 to 3, wherein the compound having an imide structure is a polyetherimide.