JPH04153310A - Flame-retardant fiber having excellent thermal discoloration resistance - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides flame-retardant fibers that exhibit excellent flame retardancy even in a composite with combustible fibers and have excellent heat-resistant coloring properties; This relates to a manufacturing method.

(Prior art) Conventionally, flame-retardant fibers include combustible natural fibers or synthetic fibers that are post-treated with flame retardants, and synthetic fibers that are produced by mixing flame retardants into raw materials and spinning them. It is being Among them, synthetic fibers that are acetalized after wet spinning by mixing stannic acid as a flame retardant into a spinning dope containing a polyvinyl chloride component, which is a halogen-containing polymeric substance, and polyvinyl alcohol, have excellent flame retardancy. In addition, the toxicity of combustion residue is extremely low, so it is used for interior decoration, bedding, etc.

Generally, in order to improve flame retardancy, fiber properties other than flame retardancy often deteriorate when a flame retardant monomer is copolymerized or a flame retardant is added to the spinning dope. In such cases, it is common practice to use a mixture of combustible fibers with excellent general fiber performance and flame-retardant fibers to form composite fibers.

For this purpose, the same applicant has already published JP-A-2
-6611 publication, the weight ratio is 80:20 to 20:
The main components are 80 halogen-containing polymeric substances and polyvinyl alcohol, and for 100 parts by weight of these main components, 0.3 to 10 parts by weight of stannic acid and 1 to 5 parts by weight of 5
We have proposed a flame-retardant fiber containing antimony oxide.

(Problem to be solved by the invention) Due to the recent rise in flame retardant awareness, not only flame retardant products regulated by the Fire Service Act, but also flame retardant products such as bedding and clothing, mainly for commercial use, are becoming more and more popular. Development is recommended. Commercial sheets, yukatas, etc. are usually used repeatedly through about 100 commercial washes, so in order to complete them as a specific product, they must not only be flame retardant, but also have suitability for commercial washing. It must be of the same type. The drying and ironing processes are particularly problematic when it comes to suitability for commercial laundry, and the process between a fixed heated metal plate and a rotating metal roll whose surface is wrapped with felt made of heat-resistant fibers. A method is adopted in which drying and ironing are accomplished simultaneously by passing through the fabric (hereinafter, this passability is abbreviated as "passability" in the present invention).

For products such as bedding and clothing that require moderate moisture absorption, it is convenient to use composite fibers of cellulose fibers and flame-retardant fibers as previously proposed in JP-A No. 2-6611. However, if the proportion of flame-retardant fibers is increased in order to satisfy flame retardancy, not only will the hygroscopicity of composite fibers be sacrificed, but also the thermoplasticity that flame-retardant fibers inherently have , the permeability deteriorates, and it becomes easily wrinkled, resulting in a product with no commercial value. On the other hand, if the proportion of flame retardant fibers is reduced in order to satisfy the permeability, the flame retardance as a composite fiber will be insufficient.

In other words, the flame-retardant fiber previously proposed in JP-A No. 2-6611 cannot satisfy both flame retardancy and permeability as a composite fiber, and cannot be used as a product that requires commercial laundry. It couldn't happen.

(Means for Solving the Problems) The present inventors have developed a formulation for flame-retardant fibers that satisfies both flame retardancy and permeability in composite fibers of cellulose fibers and flame-retardant fibers. I considered it carefully. We have experimentally confirmed that in order to satisfy the permeability, it is necessary to contain at least 65% cellulose fiber, more preferably 70% or more, and we have found that it is necessary to contain at least 65% cellulose fiber, more preferably 70% or more. As a result of examining a flame retardant formulation that provides the desired flame retardancy, preferably at a content of 30% or less, it was found that increasing the amount of flame retardant added considerably improves flame retardancy, but on the other hand, heat resistance to coloring It became clear that the Therefore, by further considering the combination of flame retardant and heat stabilizer,
At least 65% or more, more preferably 70% of the combination of a specific flame retardant and a specific heat stabilizer in a specific addition amount.
In composite fibers with the above cellulose fibers, permeability,
The present invention was completed by discovering that a flame-retardant fiber can be obtained that can solve the problems of flame retardancy and heat-resistant coloring properties at once.

That is, the present invention uses a halogen-containing polymeric substance and polyvinyl alcohol in a weight ratio of 80:20 to 20:80 as main components, and 0 to 100 parts by weight of the main components.
．． A dye with excellent heat coloring resistance characterized by containing 3 to 10 parts by weight of stannic acid, 5 to 25 parts by weight of antimony pentoxide, and 0.13 to 3.75 parts by weight of an octyltin-based heat stabilizer. The gist of this article is a flammable fiber, a method for producing the same, and a fiber composition comprising the flame-retardant fiber and combustible fiber and having excellent flame retardancy and heat coloring resistance.

First, the substances constituting the flame-retardant fiber with excellent heat-resistant coloring properties of the present invention will be explained in detail.

In addition to the substances described here, substances used for purposes other than achieving the purpose of the present invention, such as pigments, antistatic agents, light fastness improvers, dyeability improvers, matting agents, etc., are required. It goes without saying that it may be included depending on the situation.

In the present invention, the halogen-containing polymeric substance used is a polymer of a halogen-containing polymerizable substance such as vinyl chloride, vinylidene chloride, or chlorobrene, or a polymer of two or more of these substances and, if desired, a polymer of other polymerizable substances. Examples include fine particles of copolymers or mixtures thereof, such as suspensions,
Any emulsion is fine. Moreover, polyvinyl alcohol containing 2% or less of vinyl acetate component is preferably used.

In addition, the stannic acid is preferably one in which the molar ratio of Sn, 02 and H20 is 0.5 to 0.7, and the antimony pentoxide is preferably in the form of a colloid, and those with a particle size of 100 μm or less are preferably used. .

As the octyltin-based thermal stabilizer, laurate-based, malate-based, mercaptomalate-based, mercaptan-based, etc. can be used alone or in combination of two or more. Among these, laurate and mercaptan are preferably used because malate and mercaptomalate tend to be hydrolyzed and lose their functionality during repeated washing or during the fiber manufacturing process.

As is well known, the cause of thermal coloring of halogen-containing polymeric substances is
This is the production of conjugated double bonds through a dehydrohalogenation reaction, and it is said that coloration begins when seven to eight double bonds are in series. It has also been recognized that in a hydrogen halide atmosphere, the dehydrohalogenation reaction is further promoted by an autocatalytic reaction.

The mercaptan-based heat stabilizer preferably used in the present invention inhibits double bond formation by substituting a relatively unstable chlorine atom such as allylic chlorine or tertiary chlorine with a mercapto group, and captures hydrochloric acid. They can both contribute to the inactivation of the autocatalytic reaction by functioning as temperature is 200℃
Because of the close proximity to each other, if the ambient temperature during the fiberization process to obtain the fibers of the present invention, particularly during heat setting, is too high, the fibers will become foamed, making it impossible to obtain fibers that are of any practical use. Not only that, but if the ambient temperature is too high, smoke and odor will be noticeable during the fiberization process, resulting in environmental health.
This causes the second problem.

On the other hand, laurate-based heat stabilizers only have a heat-resistant coloring mechanism by primarily functioning as a hydrochloric acid capturer, so they are one step behind mercaptan-based heat stabilizers in terms of heat-resistant coloring, but on the other hand, thermal stabilizers temperature is 23
Since the temperature is around 0°C, problems with the foamed state of the fibers and smoke and odor during the fiberization process are considerably reduced.

For these reasons, in order to obtain the flame-retardant fiber with excellent heat-resistant coloring properties of the present invention, in addition to heat-resistant coloring properties, in addition to comprehensively considering productivity and environmental hygiene issues, it is necessary to use octyltin-based fibers. Among the heat stabilizers, it is most preferable to use a mixture of mercaptan type and laurate type.

Other known heat stabilizers include barium/zinc based, calcium/zinc based metal soap threads, organic phosphite ester based, epoxy resin based, butyltin based, etc.; The effect on the material system of the present invention is insufficient and a large amount must be used in order to obtain the same effect, which is practically undesirable from the viewpoint of stability of the spinning dope and stability of spinning. Furthermore, for uses of the fibers of the present invention that require acetalization as a post-treatment, the acid resistance of the heat stabilizer becomes a problem.

Organic phosphites also have insufficient effects on the material system of the present invention, and have the same problems as above when used in large quantities.

Epoxy resin systems have problems with the dispersion stability of the heat stabilizer composition, and are also not suitable for practical use. Furthermore, use of butyltin-based materials must be avoided due to their toxicity.

In addition, when adding an octyltin-based heat stabilizer, it is mixed as a heat stabilizer composition containing a phthalic acid-based plasticizer and a surfactant, but as a phthalic acid-based plasticizer in the heat stabilizer composition. Dialkyl phthalates such as dioctyl phthalate and dibutyl phthalate are used as surfactants to stably disperse octyltin-based heat stabilizers and phthalic acid-based plasticizers, and to stably maintain the spinning stock solution. Examples include aromatic nonionic activators such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, and are not particularly limited.
Polyoxyethylene alkyl allyl ether and the like are preferably used.

Secondly, the blending ratio of the substances constituting the flame-retardant fiber with excellent heat-resistant coloring properties of the present invention will be explained in detail.

If the ratio of halogen-containing polymeric material and polyvinyl alcohol in the spinning dope is greater than 80:20, spinning may not be possible smoothly, and the strength and elongation of the obtained fibers will be low, resulting in poor practicality; 20: If it is less than 80, the flame retardance will be insufficient and the object of the present invention will not be achieved.

If the amount of the stannic acid added is less than 0.3 parts by weight based on 100 parts by weight of the solid content of the main constituent components, the flame retardance of the resulting fiber will be insufficient, and if it exceeds 10 parts by weight, the flame retardance will be insufficient. Although the flame retardancy of the fiber alone improves depending on the amount added, the flame retardance of the fiber composition of the fiber and combustible fiber does not improve much, and the spinnability of the fiber decreases, which is not preferable.

If the amount of antimony pentoxide added is less than 5 parts by weight per 100 parts by weight of the solid content of the main constituent components, the flame retardance of the composite fiber mixed with combustible fibers such as cellulose fibers will be insufficient. On the other hand, if the amount exceeds 25 parts by weight, the flame retardance will improve considerably, but the heat coloring resistance will decrease.

Regarding the heat stabilizer compositions described above, heat stabilizer composition 10
0 parts by weight, from the viewpoint of dispersion stability, at least 5 parts by weight of surfactant is required, and from the viewpoints of stability and spinnability of the spinning dope, the amount of octyltin-based thermal stabilizer must be 75 parts by weight or less. . If the phthalic acid plasticizer is less than 200 parts by weight, the slipperiness between the fiber and the metal roll will be insufficient during the fiberizing process, which will prevent smooth spinning.On the other hand, if it exceeds 30 parts by weight, octyl Since the proportion of the tin-based heat stabilizer decreases, heat coloring resistance decreases. As a result, in 100 parts by weight of the heat stabilizer composition, the amount of the octyltin heat stabilizer is 65 to 75 parts by weight, the amount of the phthalic acid plasticizer is 20 to 30 parts by weight, and the amount of the surfactant is 5 to 15 parts by weight. The heat stabilizer composition having such a composition contains 0 parts by weight based on 100 parts by weight of the main constituent components of the flame-retardant fiber of the present invention, which is composed of a halogen-containing polymeric substance and polyvinyl alcohol in a weight ratio of 80:20 to 20:80. If it is less than .2 parts by weight, it will be thermally colored during the fiberization process, and when it is made into a product, it will be significantly colored at the temperature of the drying and ironing process in commercial laundry, making it extremely impractical. On the other hand, if it exceeds 5 parts by weight, the stability of the spinning stock solution decreases, leading to the inability to spin.

When using a combination of mercaptans and laurates as octyltin-based heat stabilizers, the more mercaptans are added, the better the heat coloring resistance is, but if the ambient temperature in the fiberizing process is too high, smoke generation and The odor became more intense,
There are environmental health issues. On the other hand, if the amount of mercaptans decreases, the heat coloring resistance decreases accordingly, so a composition ratio of mercaptans/laurates=515 to 3/7 is most preferable.

Thirdly, the method for producing the flame-retardant fiber with excellent heat-resistant coloring properties of the present invention will be described in detail.

The solid content ratio of the emulsion of the halogen-containing polymeric substance and the polyvinyl alcohol aqueous solution is 80:20 to 20:
80 to prepare an aqueous solution with a solid content concentration of 15 to 30%, for example, to which predetermined amounts of aqueous dispersions of stannic acid, antimony pentoxide, and a heat stabilizer composition are added, and the resulting spinning The flame-retardant fiber of the present invention, which has excellent heat-resistant coloring properties, can be obtained by wet-spinning the stock solution and subjecting it to appropriate post-treatment depending on the application. The stannic acid, antimony pentoxide, and the heat stabilizer composition may be added individually or sequentially, or
It may be added after mixing the three components. Post-treatment usually involves wet heat treatment, water washing, drying, hot stretching, and heat fixing, followed by acetalization treatment in an acetalization bath containing an aldehyde compound, followed by water washing, finishing, crimping, cutting, and drying. However, depending on the application, it may be omitted as appropriate, or other processing may be added and performed.

As the aldehyde compound, formalin, acetaldehyde, furfural, glyoxal, benzaldehyde, etc. can be used.

Fourth, the fiber composition of the present invention having excellent flame retardancy and heat coloring resistance will be described in detail.

To achieve flame retardancy of composites of combustible fibers and flame-retardant fibers, the interaction between combustible pyrolysis products derived from combustible fibers and pyrolysis products derived from flame-retardant fibers is essential. It is necessary to make the combustible thermal decomposition products flame retardant or non-combustible by action and to terminate the chain reaction of combustion.

The combustible products differ depending on the chemical structure of the combustible fibers from which they originate, and therefore it is difficult to achieve flame retardation of composites with various combustible fibers using the same flame-retardant fiber.
Although normally not expected, the flame-retardant fibers of the present invention are effective in composites with any combustible fibers such as cellulose, polyester, acrylic, vinylon, nylon, and polypropylene. Among them, it is effective for cellulose-based fibers, especially cotton fibers. In addition, generally when flame retardance is improved, heat coloring resistance is reduced, but the flame retardant fiber of the present invention overcomes this problem as well.

(Operations and Effects of the Invention) The present invention was studied with the aim of providing flame-retardant textile products especially for fields requiring commercial laundry, and the product characteristics include flame retardancy, heat-resistant coloring. The manufacturing conditions for flame-retardant fibers include the stability of the spinning dope, the stability of the spinning process, and the fiber-forming process. The combination of a specific flame retardant and a specific heat stabilizer composition described in the claims provides various barriers that lead to the completion of the invention, such as coloring of fibers, smoke generation, off-odor, and dispersion stability of the heat stabilizer composition. It has been discovered that clearing can be achieved only in a specific blending amount.

If even one of these conditions is missing, the object of the present invention cannot be achieved.

Furthermore, the flame-retardant fiber of the present invention is effective in imparting flame retardancy to composites with wide combustible fibers, and the flame-retardant fiber product field is becoming increasingly diverse. It will be able to meet the increasingly sophisticated demands of consumers and will make a tremendous contribution to this industry.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to only such embodiments.

Example 1 A polyvinyl chloride emulsion containing polyvinyl chloride as a main component and an aqueous polyvinyl alcohol solution were mixed at a solid content weight ratio of 50:50 to obtain a solid content concentration of 22.
The solid content of the mixed liquid is chopped into 100 parts by weight, and SnO
2:H20=1:0.6 (mole ratio) of 1.5 parts by weight of stannic acid as a solid content, and colloidal antimony pentoxide (Nissan Chemical Co., Ltd., aqueous sol A-2550M) as a solid content of 8.5 parts by weight. 2 parts by weight and solid content of the heat stabilizer composition specified separately
The material added in parts by weight was used as a spinning stock solution, kept at 80°C, wet-spun in a 40°C saturated aqueous sodium sulfate solution, then subjected to wet heat treatment in a saturated aqueous sodium sulfate solution at 95°C, and then cooled with cold water. After washing with water, the fibers were made into fibers through drying, stretching, and heat setting. The stability and spinnability of the spinning dope were sufficiently satisfactory.

The fibers were immersed in an acetalization bath at 70°C containing 15 parts by weight of sulfuric acid, 15 parts by weight of sodium sulfate, 5.5 parts by weight of formaldehyde, and 64°C of 5 parts by weight of water for 60 = 18 minutes, and then squeezed to remove the liquid. After washing thoroughly with warm water at 40°C, neutralizing and washing with 30 g/L aqueous sodium carbonate solution at 50°C, and washing again with water at room temperature, finishing oil treatment, drying, crimping, and cutting were performed. I obtained a 2 denier stable.

The above heat stabilizer composition contains Bretsu T-130FM (mercaptan heat stabilizer manufactured by Dainippon Ink and Chemicals Co., Ltd.) as an octyltin heat stabilizer and Bretsu T-704 as an octyltin heat stabilizer.
, 8 (Laurate heat stabilizer manufactured by Dainippon Ink & Chemicals Co., Ltd.) in a weight ratio of 4 = 6. Monocizer W-520 (as a phthalate plasticizer) was added to 70 heavy electric parts.
After mixing 25 parts by weight of DOP) (Dainippon Ink & Chemicals Co., Ltd.), 5 parts by weight of Neugen EA-112 (Dai-ichi Kogyo Seiyaku Co., Ltd.) as an aromatic nonionic surfactant was added, and 30 parts by weight was added at room temperature. Mix and stir in a homomixer for a minute,
Next, this was added to water to a concentration of 15% by weight, and then dispersed again in a homomixer at room temperature for 10 minutes to prepare.

For comparison, a sample in which the heat stabilizer composition of the present invention was not added and the amount of flame retardant added was changed, ie, comparative sample A, was prepared by adding 1.0 parts by weight of stannic acid and 4.0 parts by weight of colloidal antimony pentoxide. A comparative sample B containing 0 parts by weight of stannic acid and 8.5 parts by weight of colloidal antimony pentoxide were prepared in the same manner.

30 parts by weight of each of the flame-retardant stable fiber with excellent heat-resistant coloring properties of the present invention and comparative samples A and B obtained by acetalization and cutting were mixed with 70 parts by weight of cotton fiber. A blended yarn of cotton count No. 20 was produced using this method, and a plain woven fabric with a basis weight of 140 g/m2 was obtained using this blended yarn.

When this plain woven fabric was washed repeatedly under commercial washing conditions, the surface temperature of the hot metal plate during the drying and ironing process was 175°C, and the passing speed was 40 m/min.
There was no problem with the passability.

The flame retardant properties and whiteness of each plain woven fabric were measured after repeated washing 100 times. Fabrics made of fibers showed superior performance compared to comparative samples.

[Hereinafter, blank spaces] Example 2 Example 10 Flame-retardant fibers with excellent heat-resistant coloring properties of the present invention or comparative sample A, and cotton fibers, polyester fibers, acrylic fibers, hinilon fibers, nylon fibers, and polypropylene fibers, respectively. , were mixed at the mixing ratios shown in Tables 2 and 3 to produce a spun yarn with a cotton count of 20. Using the obtained spun yarn, nine knitted fabrics with a basis weight of 165 to 170 g/m2 were produced, and 2 g/m of Score Roll 700 (a high-grade ether type nonionic refining detergent manufactured by Kao Atlas Co., Ltd.) was added.
I,01 (limiting oxygen index) was measured on these samples after refining in a T-containing 45°C treatment bath for 30 minutes and drying at 75°C.

As shown in Tables 2 and 3, the flame-retardant fibers of the present invention having excellent thermal colorability were effective in increasing the LOI of composite fiber compositions with any combustible fibers.

[Below is the margin Procedural amendment November 30, 1990

Claims (6)

[Claims] (1) The main components are a halogen-containing polymeric substance and polyvinyl alcohol in a weight ratio of 80:20 to 20:80,
0.3 to 10 parts by weight of this main component
A flame-retardant fiber with excellent heat-resistant coloring properties, characterized by containing parts by weight of stannic acid, 5 to 25 parts by weight of antimony pentoxide, and 0.13 to 3.75 parts by weight of an octyltin-based heat stabilizer. . (2) Excellent heat-resistant coloring properties as set forth in claim 1, characterized in that the octyltin-based heat stabilizer has a composition ratio of mercaptan/laurate = 5/5 to 3/7. Flame retardant fiber. (3) A fiber composition having excellent flame retardancy and heat coloring resistance, which is mainly composed of the flame-retardant fiber according to claim 1 and combustible fiber. (4) The fiber according to claim 3, wherein the combustible fiber is a single cellulose fiber, polyester, acrylic, vinylon, nylon, or polypropylene fiber, or a mixture of two or more of these fibers. Composition. (5) The fiber composition according to claim 4, characterized in that cotton fiber is used as the cellulose fiber. (6) In a method for producing fibers whose main constituents are a halogen-containing polymeric substance and polyvinyl alcohol in a weight ratio of 80:20 to 20:80, 0.3 0.2 to 5 parts by weight of a heat stabilizer composition containing ~10 parts by weight of stannic acid, 5 to 25 parts by weight of antimony pentoxide, and an octyltin-based heat stabilizer (the heat stabilizer composition is composed of A stock solution containing 65 to 75 parts by weight of an octyltin heat stabilizer, 20 to 30 parts by weight of a phthalic acid plasticizer, and 5 to 15 parts by weight of a surfactant per 100 parts by weight of the product was wet-spun. A method for producing flame-retardant fibers with excellent heat-resistant coloring properties, which comprises further post-treatment if necessary.