JP3421093B2 - Flame retardant fiber composite - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant acrylic fiber.
The present invention relates to a flame-retardant fiber composite containing fibers . 2. Description of the Related Art As a method for imparting flame retardancy to an acrylic fiber, a flame-retardant monomer such as vinyl chloride, vinylidene chloride, vinyl bromide or vinylidene bromide is copolymerized with acrylonitrile to form an acrylic fiber substrate. Various methods for making the polymer itself flame-retardant are known and commercialized. Further, when high flame retardancy is required, a method of adding a flame retardant such as antimony trioxide or antimony pentoxide to a base polymer is also known. [0003] For example, a method of copolymerizing a flame-retardant monomer and adding a flame retardant is disclosed in JP-A-63-126913, JP-A-61-89339, and JP-A-5-78.
No. 936, etc., it is difficult to add a large amount of antimony pentoxide to obtain high flame retardancy. A large addition of antimony trioxide satisfies both high flame retardancy and mechanical properties. There is a problem that acrylic fiber cannot be obtained. SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant fiber composite having high flame retardancy and good mechanical properties such as good spinnability and workability. It is in. SUMMARY OF THE INVENTION The present invention provides an acrylonitrile polymer (A), an antimony compound (B) copolymerized with 30 to 50% by weight of vinyl chloride and / or vinylidene chloride, and a halogen atom in the polymer. The polymer (C) having a content of 50% by weight or more has a ratio of 40 to 90 parts by weight of (A), 30 to 5 parts by weight of (B), and 30 to 5 parts by weight of (C) in total. 60-75% by weight of flame-retardant acrylic fiber composed of the composition, and 40-25% by weight of cotton
And a flame-retardant fiber composite . In the present invention, an acrylonitrile-based polymer (A) to be used as a component of the composition of the acrylic fiber substrate
Is a polymer obtained by copolymerizing acrylonitrile with 30 to 50% by weight of vinyl chloride and / or vinylidene chloride. If the copolymerization amount of vinyl chloride and / or vinylidene chloride is less than 30% by weight, satisfactory flame retardancy is obtained. On the other hand, when the content exceeds 50% by weight, the heat resistance and the sharpness of dyeing of the obtained fiber are reduced, and the stiffness of the fiber is also reduced. In the present invention, the acrylonitrile-based polymer (A) may contain, in addition to vinyl chloride and / or vinylidene chloride, other copolymer components for improving dyeing properties and fiber properties. Examples of such a copolymer component include vinyl monomers containing a sulfone group such as methallyl sulfonic acid, acrylic sulfonic acid, styrene sulfonic acid and vinyl benzene sulfonic acid; unsaturated carboxylic acids such as (meth) acrylic acid; Acrylic acid esters,
Vinyl monomers such as vinyl esters such as (meth) acrylic amide and vinyl acetate can be mentioned, and can be copolymerized within a range not exceeding 5% by weight. The antimony compound (B) as a component of the composition according to the present invention includes antimony trioxide, antimony pentoxide and the like, and antimony pentoxide is particularly preferably used. The antimony compound (B) used is
The particle size in the fiber is important, and the particle size as an additive component is not particularly limited.
It is preferably 0 nm or less. The polymer (C) in which the content of a halogen atom in the polymer as a component of the composition is 50% by weight or more includes polyvinyl chloride, polyvinylidene chloride, polyvinyl bromide, polyvinylidene bromide. And the like. In particular, polyvinyl chloride and polyvinylidene chloride are preferably used, and the molecular weight is not particularly limited. The ratio of each component in the composition of the present invention is such that the acrylonitrile polymer (A) is 40 to 90 parts by weight, the antimony compound (B) is 30 to 5 parts by weight, and the halogen atom content is 100 parts by weight of the composition. When the amount of the polymer (C) is 30 to 5 parts by weight, and when the amount of the antimony compound (B) is less than 5 parts by weight, sufficient flame retardancy cannot be obtained. The properties are reduced and the mechanical properties of the fibers are also reduced. If the amount of the halogen atom-containing polymer (C) is less than 5 parts by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 30 parts by weight, the mechanical properties of the fiber,
Dye sharpness is reduced. The flame-retardant acrylic fiber of the present invention can be obtained by shaping the above composition into a fiber by a known spinning method. The antimony compound (B) can maintain the mechanical properties of the fiber, From the viewpoint of the performance, it is necessary that the fine particles are uniformly and finely dispersed in the fiber, and the average particle diameter of the antimony compound (B) in the fiber is desirably 200 nm or less. The fine dispersion of the antimony compound (B) uniformly in the fiber is achieved by preparing a spinning dope by the following method during fiber shaping. The flame-retardant acrylic fiber of the present invention is prepared by dissolving the above composition in a solvent to form a spinning solution, and spinning using any spinning method such as wet spinning, dry-wet spinning, and dry spinning.
It can be obtained by spinning by a known method. The solvent used in the preparation of the spinning solution may be any solvent that can dissolve the acrylonitrile-based polymer (A) and the halogen atom-containing polymer (C) in the composition. Examples thereof include dimethylformamide, dimethylacetamide, and dimethylsulfoxide. And the like. In obtaining the flame-retardant acrylic fiber of the present invention,
Preferred methods for preparing a spinning dope include the following methods (1) and (2) from the viewpoint of preventing an increase in the particle diameter due to aggregation of the antimony compound in the spinning dope or the fiber. (1) A colloidal dispersion of antimony pentoxide having an average particle diameter of 80 nm or less is prepared as the antimony compound (B) using the same solvent as used for the spinning solution, and the colloidal dispersion is diluted with a required amount of a solvent. Adjust the pH of the solution to 5-6. Next, predetermined amounts of an acrylonitrile-based polymer (A) and a polyhalogen atom-containing polymer (C) are added together with a solvent, if necessary, to the adjusted solution, and then heated and dissolved to prepare a spinning stock solution. The solvents are (A), (B) and (C)
The amount of 250 to 500 parts by weight per 100 parts by weight of the total amount is appropriately divided and used when preparing each liquid. (2) An antimony compound (B) having an average particle diameter of 80 n
m or less of a colloidal dispersion of antimony pentoxide,
A halogen atom-containing polymer (C) and a solvent are added to the colloidal dispersion adjusted to pH 5 to 6, and the mixture is heated and dissolved to prepare an antimony pentoxide dispersion polymer (C). Separately, a mixture of the acrylonitrile-based polymer (A) and the solvent is dissolved by heating to prepare an acrylonitrile-based polymer (A) solution. Next, the antimony pentoxide dispersion polymer (C) solution and the acrylonitrile-based polymer (A) solution are mixed with a static mixer or the like to prepare a spinning stock solution. The solvent is 100% in total of (A), (B) and (C).
The amount of 250 to 500 parts by weight per part by weight is appropriately divided and used when preparing each liquid. In preparing the spinning solution, including the methods (1) and (2), the pH of the dispersion of the antimony compound is 5 to 5.
The pH is preferably adjusted to 6. When the pH is less than 5, the antimony compound is easily aggregated. pH
The adjustment of is not particularly limited, and the adjustment is performed with a normal buffer or the like. Further, the heating and dissolving of the acrylonitrile-based polymer is preferably performed at a temperature of 60 ° C. or lower. The flame-retardant acrylic fiber of the present invention has a high level of flame retardancy due to containing a large amount of an antimony compound as a flame retardant. Strength 2.5 g / d or more, single fiber elongation 25
% Or more. The flame-retardant acrylic fiber of the present invention is capable of exhibiting the flame-retarding effect remarkably even when it is compounded with other fibers.
Natural fibers such as cotton, hemp, wool, silk, and acetate fibers
Chemical fiber such as fiber, rayon, polyester fiber, Niro
And synthetic fibers such as acrylic fibers. [0019] The flame-retardant fiber composite of the present invention is characterized in that
Combined with fire-resistant acrylic fiber, especially cotton as another fiber
In the fiber composite , the flame retardant
When cotton is compounded with krill fiber, a flame-retardant fiber composite having high flame retardancy can be obtained. In particular , the flame-retardant acrylic fiber of the present invention has 60 to 75% by weight and cotton has 40 to 25% by weight. When made into a composite, surprisingly, compared to the case of the flame-retardant acrylic fiber alone, the flame retardancy is significantly improved,
A flame-retardant fiber composite having excellent cotton feel, moisture absorption and water absorption can be obtained. As a means of compounding, mixed
Any method such as spinning, combusting, weaving, and knitting may be used.
Form of union is yarn, woven, knitted, felt, non-woven, paper, etc.
Any of the above may be used. The reason for the high flame retardancy in the composite of the flame retardant acrylic fiber and cotton of the present invention is considered as follows. Generally, in the burning process of a polymer, OH radicals generated by the reaction between oxygen and polymer in the air cause a chain reaction, and the burning of the polymer continues. But,
When chlorine atoms are present in the polymer, the polymer itself generates hydrochloric acid by thermal decomposition, and the hydrochloric acid traps OH radicals and exhibits a flame retardant effect. If antimony pentoxide is present, antimony pentoxide forms a cycle consisting of antimony oxychloride and antimony trioxide at a high temperature and contributes to the improvement of flame retardancy. In addition, if cotton is present, antimony trichloride reacts with the cotton to provide the driving force for this cycle. Accordingly, the effects of the products in the combustion process are as follows. The effect of diluting oxygen by the generated water and carbon dioxide. Oxygen blocking effect by antimony trichloride staying around combustibles. Oxygen blocking effect by carbon film formed by carbonization of organic matter. The effect of suppressing the chain reaction of combustion by trapping OH radicals of hydrochloric acid and antimony trichloride. The flame retardant effect of cotton by chlorination of cotton with antimony trichloride. In this flame-retardant mechanism, it is necessary to efficiently convert the antimony compound into antimony oxychloride and antimony trichloride in order to improve the flame retardancy. The use of a chlorine atom-containing monomer and a halogen-containing polymer and the fine dispersion of an antimony compound in the polymer in order to accelerate the conversion to antimony trichloride have increased the expression of a flame retardant mechanism. The present invention will be described below in more detail with reference to examples. In the examples, parts and% mean parts by weight and% by weight, respectively. For evaluation of flame retardancy, a knitted fabric having a basis weight of 400 g / m ² was formed using a spun yarn of a fiber to be evaluated, and an LOI value was measured according to JIS K7201A-1. The reduced viscosity of the polymer was measured with a 0.5% dimethylformamide solution at 25 ° C. using a Canon Fenceke viscometer manufactured by Canon Inc., and the average particle diameter of antimony pentoxide in the fiber was measured by using a transmission electron It was observed and measured with a microscope. (Examples 1 to 3) pH5 containing 40% of antimony pentoxide (Sb ₂ O ₅ ) having an average particle diameter of 60 nm.
To 50 parts of antimony pentoxide colloid-dispersed dimethylacetamide (DMAc) solution of No. 2 was added 30 parts of DMAc,
The mixture was stirred and mixed for 1 hour to obtain a diluted colloidal dispersion having a pH of 5.6. To this diluted colloidal dispersion, add polyvinyl chloride (P
VC) was added, mixed with stirring, and heated and dissolved at 60 ° C. to obtain a PVC solution of antimony pentoxide dispersion. next,
25 parts of an AN polymer having a reduced viscosity of 1.98 composed of 57.5% of acrylonitrile (AN), 40% of vinylidene chloride and 2.5% of sodium methallylsulfonate was added to DMAc7.
Add to 5 parts, stir and mix.
A system polymer solution was obtained. This AN-based polymer solution 280
And 75 parts of the antimony pentoxide-dispersed PVC solution were mixed using a static mixer, and DMA was obtained by wet spinning using a nozzle having a hole diameter of 0.06 mm and a number of holes of 3000.
c40% / water 60%, spun into a coagulation bath at 30 ° C., desolventized in hot water, stretched 6 times in boiling water, oiled, dried, moist heat relaxed, and single fiber fineness 2 A denier acrylic fiber was obtained. Hereinafter, similarly, as shown in Table 1,
Acrylic fibers were obtained in which the amounts of the system polymer, antimony pentoxide and PVC were changed. Next, a knitted fabric was prepared using the obtained spun yarn of each acrylic fiber, and the flame retardancy was evaluated. The results are shown in Table 1. In addition, each acrylic fiber 70% and cotton 30
% To form a spun yarn to prepare a knitted fabric, and the flame retardancy of the composite was evaluated. The results are shown in Table 1. [Table 1] (Examples 4 to 5, Comparative Examples 1 and 2) Colloidal dispersion of antimony pentoxide pentoxide (pH 5.2) containing 40% of antimony pentoxide (Sb ₂ O ₅ ) having an average particle diameter of 60 nm
To 25 parts of the Ac solution, 385 parts of DMAc was added and mixed by stirring for 1 hour to obtain a diluted colloidal dispersion having a pH of 5.6. To this diluted colloidal dispersion, 60 parts of an AN-based polymer having a reduced viscosity of 1.98 composed of 57.5% of AN, 40% of vinylidene chloride and 2.5% of sodium methallylsulfonate, and PV
30 parts of C were added, mixed by stirring, and each polymer was heated and dissolved at 60 ° C. This solution was subjected to DMAc by wet spinning using a nozzle having a pore size of 0.06 mm and the number of holes of 3000.
After spinning out into a coagulation bath of 40% / water 60%, 30 ° C., desolvation treatment in hot water, stretching 6 times in boiling water, applying oil agent,
Drying and moist heat relaxation treatment were performed to obtain an acrylic fiber having a single fiber fineness of 2 denier. Hereinafter, similarly, as shown in Table 2, AN
Acrylic fibers were obtained in which the amounts of the system polymer, antimony pentoxide and PVC were changed. Next, a knitted fabric was prepared using the obtained spun yarn of each acrylic fiber, and the flame retardancy was evaluated. The results are shown in Table 2. In addition, each acrylic fiber 70% and cotton 30
% To form a spun yarn to prepare a knitted fabric, and the flame retardancy of the composite was evaluated. The results are shown in Table 2. [Table 2] Comparative Example 3 An acrylic fiber was obtained in the same manner as in Example 1 except that antimony trioxide (Sb ₂ O ₃ ) having an average particle diameter of 300 nm was used instead of antimony pentoxide in Example 1. A knitted fabric was prepared using the obtained spun yarn of acrylic fiber, and the flame retardancy was evaluated. The results are shown in Table 3. [Table 3] Example 6 An acrylic fiber was obtained in the same manner as in Example 1 except that polyvinylidene chloride was used instead of polyvinyl chloride. A knitted fabric was prepared using the obtained spun yarn of acrylic fiber, and the flame retardancy was evaluated. The results are shown in Table 4. [Table 4] ( Comparative Examples 4 to 6 ) 70% of the acrylic fiber obtained in Example 2 and 30% of each fiber of ordinary acrylic fiber from a copolymer of wool, diacetate fiber, 93% AN and 7% vinyl acetate were blended. A knitted fabric was prepared using the spun yarn thus obtained, and the flame retardancy was evaluated. The results are shown in Table 5. [Table 5] ( Examples 7 to 9, Comparative Examples 7 to 8 ) A knitted fabric was prepared using a spun yarn obtained by blending the acrylic fiber and cotton obtained in Example 2 at the ratio shown in Table 6. The flammability was evaluated, and the results are shown in Table 6. [Table 6] [0039] [Effect of the Invention The flame retardant fiber composite of the present invention has a high flame retardancy, and spinning properties, have good mechanical properties of processability, a flame according to the present invention The fuel fiber composite can be suitably used for a wide range of uses such as interior decoration, bedding, and clothing.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Tadao Kobayashi               Mitsubishi Ray, 20-1, Miyukicho, Otake City, Hiroshima Prefecture               Yeon Co., Ltd. Otake Office                (56) References JP-A-60-134014 (JP, A)                 JP-A-3-294515 (JP, A)                 JP-A-5-78936 (JP, A)                 JP-A-61-89339 (JP, A)

Claims (1)

(57) [Claims] [Claim 1] Vinyl chloride and / or vinylidene chloride 3
The acrylonitrile-based polymer (A), the antimony compound (B) and the polymer (C) having a halogen atom content of 50% by weight or more in the copolymer are 0 to 50% by weight, and (A) 40 to 90 parts by weight. , (B) 30 to 5 parts by weight, and (C) 30 to 5 comprising the composition ratio as a total of 100 parts by weight parts by weight flame-retardant acrylic fiber 60-75 fold
Flame-retardant fiber composite consisting of 40% to 25% by weight of cotton
Body .