JPH04352810A - Synthetic fiber, excellent in whiteness and stable to light - 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]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic fiber made of a halogen-containing polymer composition that has excellent whiteness and is stabilized against light.

0002

[Prior Art/Problems to be Solved by the Invention] Fibers made from halogen-containing polymers (halogen-containing fibers) are known as flame-retardant fibers, and are used in the production of wigs, children's clothing, work clothes, curtains, carpets, etc. suitable for Recently, it has also been used in fields that require a high degree of light resistance, such as artificial turf and automobile interior parts.

However, general halogen-containing fibers,
For example, vinyl chloride fibers and modacrylic fibers turn brown due to heat during drying, stretching, and heat treatment processes during production, which hinders the development of products in fields where whiteness is required. In addition, long-term exposure to ultraviolet rays also causes browning and deterioration, significantly reducing commercial value.

[0004] Generally, optical brighteners are used to improve the whiteness of various polymer compositions, but this action absorbs ultraviolet rays and emits blue fluorescence, which makes the base material brown. It cancels out.

[0005] Furthermore, in order to eliminate deterioration caused by ultraviolet rays, ultraviolet absorbers have conventionally been widely used as light stabilizers in various polymer compositions.

[0006] Therefore, it is possible to create a halogen-containing fiber with excellent whiteness and light resistance by using the effects of both an optical brightener and an ultraviolet absorber, but in reality, no such product has been found. .

[0007] This is because when a small amount of ultraviolet absorber is added, a slight stabilizing effect is observed, but because the molecular weight is small, it may elute during the coagulation process of fiber production by wet spinning.
Problems such as thermal decomposition and sublimation occur during drying, stretching, and heat treatment steps, making it impossible to obtain sufficient light resistance. On the other hand, even if a large amount of ultraviolet absorber is added to obtain a sufficient stabilizing effect, the expected effect may not be obtained, and instead, too much ultraviolet rays will be absorbed, and the blue fluorescence of the optical brightener will no longer be emitted. , the whiteness may be reduced and the product may become yellowish. Moreover, adding a large amount causes a disadvantage that the cost increases significantly.

[0008]Furthermore, when a large amount of fluorescent brightener is added, there is a problem in that the product becomes yellow due to its own discoloration due to ultraviolet rays.

[0009] In order to eliminate deterioration caused by ultraviolet rays, there is also a method of adding stabilizers against light such as organotin maleate stabilizers and antioxidants. However, there is hardly anything that shows a remarkable stabilizing effect when added in small amounts.

As mentioned above, the actual situation is that there are no halogen-containing fibers used for wigs, curtains, artificial turf, automobile interiors, etc. that have excellent whiteness and highly improved light resistance.

[0011]

[Means for Solving the Problems] The present inventors have made extensive studies in view of the above-mentioned circumstances, and have found that halogen-containing polymers,
It was discovered that a synthetic fiber made of a composition containing a fluorescent brightener and a polymer-type ultraviolet absorber has excellent whiteness and highly improved light resistance, and the present invention was achieved based on this discovery.

[0012] That is, in the present invention, 100 parts (by weight, the same shall apply hereinafter) of a halogen-containing polymer, 0.00 parts of a fluorescent whitening agent,
5 to 0.08 parts and 0.1 part of polymer type ultraviolet absorber
The present invention relates to a synthetic fiber having excellent whiteness and being stable to light, comprising a composition of ~4 parts.

[0013]

[Example] The halogen-containing polymer used in the present invention is
At least one vinyl halide monomer 70-3
0% (weight %, same below), acrylonitrile 30-7
0% and vinyl monomer copolymerizable with these 0-10
% of the polymer is preferred. In the above polymer, if the acrylonitrile unit content is less than 30%, it will be difficult to express the properties as a fiber, and if the halogenated vinyl monomer content is less than 30%, it will provide a high degree of flame retardancy, which is a characteristic of halogen-containing fibers. things become difficult. Furthermore, if the copolymerizable vinyl monomer exceeds 10%, the strength and physical properties of the resulting fibers tend to decrease.

Specific examples of the vinyl halide monomer include vinyl chloride, vinylidene chloride, and vinyl bromide.

The copolymerizable vinyl monomers include acrylic acid and its esters, methacrylic acid and its esters, acrylamide, methacrylamide, vinyl acetate, vinylsulfonic acid and its salts, methallylsulfonic acid and its salts. Examples include salts, styrene sulfonic acid and its salts.

Specific examples of the halogen-containing polymer include vinyl chloride-acrylonitrile copolymer,
Vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinylidene chloride-acrylonitrile copolymer, vinyl bromide-acrylonitrile copolymer, vinyl bromide-vinylidene chloride-acrylonitrile copolymer,
Examples include vinyl chloride-vinyl bromide-acrylonitrile copolymer.

[0017] The fluorescent brightener used in the present invention is not particularly limited, and specific examples thereof include, for example, 2,5-
Oxazole compounds such as bis[5'-tert-butylbenzoxazolyl(2)]thiophene, N-(
Examples include coumarin compounds such as γ-dimethylaminopropyl)-N'-(3-phenylcoumarinyl-7)urea.

The blending amount of the optical brightener is 0.005 to 0.08 parts per 100 parts of the halogen-containing polymer.
Preferably it is 0.01 to 0.05 part. If the amount is less than this range, the fluorescent effect of the optical brightener will be reduced and the whiteness of the fibers made from the polymer will be reduced. Moreover, if the blending amount exceeds this range, the fluorescent whitening agent itself will be colored by ultraviolet rays, and the fibers made from the polymer will be colored. Furthermore, excessive addition of optical brighteners leads to an increase in cost.

The polymer type ultraviolet absorber used in the present invention is a polymer containing a benzophenone derivative having ultraviolet absorbing ability as a monomer component, and is a homopolymer of a benzophenone monomer. However, 20 to 90% of benzophenone monomer, preferably 30 to 8%
A polymer consisting of 0%, and 10 to 80%, preferably 20 to 70%, of at least one vinyl monomer copolymerizable with the same is preferable because of its solubility in solvents and compatibility with the fiber base material. Preferable from the viewpoint of affinity.

[0020] The benzophenone monomer is a benzophenone derivative containing an unsaturated group. Examples of benzophenone monomers include 2-hydroxy-4-(methacryloyloxybutoxy)benzophenone, 2-hydroxy-4-(methacryloyloxyoctoxy)benzophenone, and 2-hydroxy-4-(methacryloyloxyoctoxy)benzophenone.
(methacryloyloxyethoxy)benzophenone,
Examples include 2,2'-dihydroxy-4-(methacryloyloxyethoxy)benzophenone, but 2-hydroxy-4-(
Preferred is methacryloyloxyethoxy)benzophenone.

Examples of the copolymerizable vinyl monomer include methyl methacrylate, vinyl chloride, acrylonitrile, and styrene.

Specific examples of the polymer-type ultraviolet absorber include a homopolymer of 2-hydroxy-4-(methacryloyloxyethoxy)benzophenone,
-hydroxy-4- (methacryloyloxyethoxy)benzophenone- methyl methacrylate copolymer,
2-Hydroxy-4-(methacryloyloxyethoxy)benzophenone-vinyl chloride copolymer, 2-hydroxy-4-(methacryloyloxyethoxy)benzophenone-acrylonitrile copolymer, and other benzophenone monomers as one of the monomers. Examples include copolymers used as components.

[0023] The molecular weight of the polymer type ultraviolet absorber is:
It is preferably 10,000 or more, and 20,000 or more, from the viewpoint of preventing elution into the coagulation bath in the wet method fiber manufacturing process, thermal decomposition and sublimation in the drying, stretching, and heat treatment steps.
More preferably, it is from 00 to 200,000.

[0024] The blending amount of the polymer type ultraviolet absorber is as follows:
The amount is 0.1 to 4 parts, preferably 0.3 to 3 parts, per 100 parts of the halogen-containing polymer. When the blending amount is less than this range, the stabilizing effect against ultraviolet rays becomes small and it becomes difficult to suppress browning and deterioration of the polymer fiber. Also,
If the blending amount exceeds this range, the fibers made from the polymer will instead be colored yellow, and excessive addition of the ultraviolet absorber will lead to an increase in cost.

Furthermore, the ratio of the fluorescent brightener to the polymer-type ultraviolet absorber used is (fluorescent brightener)/(
Units derived from benzophenone monomers in polymer-type ultraviolet absorbers) = 1/5 to 1/100, and even 1/6
A range of 1/90 to 1/90 is preferable, and if the proportion of the optical brightener is greater than this range, the optical brightener will be more likely to be colored by ultraviolet rays, and the polymer fibers will tend to be colored. Furthermore, when the proportion of the optical brightener becomes smaller than this range, the proportion of the ultraviolet absorber becomes large, absorbing too much ultraviolet rays, and the blue fluorescence of the optical brightener is no longer emitted, reducing the whiteness of the polymer fiber. There is a tendency to decrease.

The synthetic fiber of the present invention may also contain a glycidyl methacrylate polymer, which is a component for maintaining the gloss and transparency of the fiber after dyeing. Further, in order to thermally stabilize the halogen-containing polymer, various metal soaps, organic tin compounds, phosphite compounds, antioxidants, etc. can be added.

[0027] The composition used in the present invention contains 2,
If 6-ditertiarybutyl-4-hydroxytoluene or certain organic tin compounds are used together, the effect of improving light resistance may not be achieved sufficiently, so it is preferable to use an appropriate one.

Next, the synthetic fiber of the present invention will be explained based on examples.

Example 1 Vinyl chloride-vinylidene chloride-acrylonitrile copolymer (24% vinyl chloride, 25% vinylidene chloride,
Acrylonitrile 50%, 2-acrylamide-2-
100 parts of methylpropanesulfonic acid (1% copolymer of each monomer component) was dissolved in 300 parts of acetone, and an oxazole optical brightener (2,5-bis[5
'- tert-butylbenzoxazolyl (2)]
Thiophene) (hereinafter referred to as OXF) 0.01 part, 2-
Hydroxy-4- (methacryloyloxyethoxy)
Added 1 part of benzophenone-methyl methacrylate copolymer ultraviolet absorber (units derived from benzophenone monomer/units derived from methyl methacrylate = 30/70 (weight ratio), molecular weight: 3 x 104) (hereinafter referred to as PBM30) The mixture was mixed to obtain a transparent spinning stock solution. Next, this stock solution was extruded into a 40% acetone aqueous solution through a nozzle with a nozzle diameter of 0.08 mm and 500 holes, and after washing with water,
It was dried at 120°C, further hot-stretched 3 times, and heat treated at 140°C for 3 minutes to obtain a sample fiber.

The light resistance and whiteness of the obtained fibers were examined as shown below. The results are shown in Table 1 along with the blending amounts of the fluorescence enhancer and ultraviolet absorber.

(Light resistance) The sample fibers were irradiated for 20 hours using a carbon fade meter at a black panel temperature in the range of 60 to 65°C, and compared with the blue scale, which is an indicator of light resistance, and the fibers before and after irradiation were measured. Measure the color with a color difference meter,
Evaluation was made using the ΔE value (color difference) as an index. The smaller the ΔE value, the smaller the color difference before and after irradiation, and therefore the better the light resistance. It can be said that the light resistance is good, with a blue scale comparison of grade 4 or higher and a ΔE value of 2 or less.

(Whiteness) Similarly, evaluation was made using the Hunter whiteness (W value) and b value (yellowness index) of the fibers before irradiation using a colorimetric colorimeter as indicators. The closer the W value is to 100, the better the whiteness of the fiber is, and the closer the b value is to 0, the less yellow the fiber is. Therefore, the larger the W value and the smaller the b value, the higher the commercial value. For halogen-containing polymer fibers, it can be said that whiteness is good if the W value is 90 or more. Regarding the b value, if it is 3 or less, it can be said that yellowness is small.

Comparative Examples 1 to 2 OXF and PBM30 not added, and OXF
and ordinary low-molecular-weight ultraviolet absorbers (Kyodo Yakuhin, Vio
sorb-550) was added in the amount shown in Table 1 and spun in the same manner as in Example 1 to obtain sample fibers, and the light resistance and whiteness were examined. The results are shown in Table 1 along with the amount of optical brightener and UV absorber added.
Shown below.

[0034]

[Table 1]

From Table 1, it can be seen that Example 1 has excellent light resistance and whiteness. Comparative Example 1, which did not contain a fluorescent brightener and a polymer-type ultraviolet absorber, had low light resistance and low whiteness. Comparative Example 2, in which an ordinary low molecular weight ultraviolet absorber and OXF were blended, had good whiteness but insufficient light resistance. This is because the molecular weight of the UV absorber is small, so it may elute into the bath during the fiber coagulation process, or it may sublimate or decompose during the drying to heat treatment process, causing the amount of UV absorber remaining in the fiber to decrease. This is probably due to the decrease.

Examples 2-3 and Comparative Examples 3-4 Example 1
Sample fibers were prepared in the same manner as in Example 1, except that the amount of OXF was changed as shown in Table 2, and the light resistance and whiteness were examined. The results are shown in Table 2 along with the blending amounts of the optical brightener and ultraviolet absorber.

[0037]

[Table 2]

From Table 2, it can be seen that as the amount of OXF added increases, the whiteness increases, but at the same time the light resistance decreases. It can be seen that fibers with excellent light resistance and whiteness can be obtained when the OXF content is 0.02 part or 0.05 part (Examples 2 and 3). Comparative Example 3, in which only PBM30 was blended, had excellent light resistance but insufficient whiteness. In addition, in Comparative Example 4 in which 0.1 part of OXF was blended, O
The coloring of XF due to ultraviolet rays was significant and the light resistance decreased.

Examples 4-5 and Comparative Examples 5-6 Example 1
Samples were prepared in the same manner as in Example 1, except that the blending amount of PBM30 was changed as shown in Table 3, and the light resistance and whiteness were examined. The results are shown in Table 3 along with the blending amounts of the optical brightener and ultraviolet absorber.

[0040]

[Table 3]

From Table 3, it can be seen that as the amount of PBM30 added increases, the light resistance increases, but at the same time, the whiteness decreases. It can be seen that fibers with excellent light resistance and whiteness can be obtained when the PBM30 content is 0.3 parts or 3 parts (Examples 4 and 5). Comparative Example 5, in which only OXF was blended, had excellent whiteness but insufficient light resistance. In addition, in Comparative Example 6 containing 5.0 parts of PBM30, PBM30 was added in an amount of 5.0 parts.
Yellowness due to BM30 increased and whiteness decreased.

Examples 6-7 Vinyl bromide-vinylidene chloride-acrylonitrile copolymer (vinyl bromide 33%, vinylidene chloride 15%,
100 parts of a copolymer of each monomer component (51% acrylonitrile, 1% sodium methallylsulfonate) was dissolved in 300 parts of dimethyl sulfoxide, and the amount of coumarin-based optical brightener (N -(γ-dimethylaminopropyl)-N'-(3-phenylcoumarinyl-
7) Urea) (hereinafter referred to as CMF) and PBM30
1 part was added and mixed to obtain a transparent spinning stock solution. Next, this stock solution was extruded into a 50% dimethyl sulfoxide aqueous solution through a nozzle with a nozzle diameter of 0.08 mm and a number of holes of 500, washed with water, dried at 120 °C, further hot stretched 3 times, and heat treated at 140 °C for 3 times. The test was carried out for several minutes to obtain sample fibers, and the light resistance and whiteness of the obtained fibers were examined. The results are shown in Table 4 along with the blending amounts of the optical brightener and ultraviolet absorber.

[0043]

[Table 4]

Table 4 shows that fibers with excellent light resistance and whiteness can be obtained even when a coumarin-based optical brightener is used.

Examples 8 to 9 100 parts of a vinylidene chloride-acrylonitrile copolymer (a copolymer of the following monomer components: 43% vinylidene chloride, 56% acrylonitrile, and 1% sodium styrene sulfonate) was added to 300 parts of dimethylformamide. 0.01 part of OXF, 2-hydroxy-4-(methacryloyloxyethoxy)benzophenone-methyl methacrylate copolymer UV absorber (benzophenone monomer) with different copolymerization ratio and molecular weight with PBM30. Unit derived from / Unit derived from methyl methacrylate =
80/20 (weight ratio), molecular weight: 5 x 105) (hereinafter referred to as PBM80) was added and mixed in the amount shown in Table 5 to obtain a transparent spinning dope. Next, apply this stock solution to a nozzle with a hole diameter of 0.0.
It was extruded into a 60% dimethylformamide aqueous solution through a nozzle with a diameter of 8 mm and 500 holes, and after washing with water,
Dry at ℃, further heat stretch 3 times, and heat treatment at 140℃.
C. for 3 minutes to obtain sample fibers, and the light resistance and whiteness of the obtained fibers were examined. The results are shown in Table 5 along with the blending amounts of the optical brightener and ultraviolet absorber.

[0046]

[Table 5]

Table 5 shows that fibers with excellent light resistance and whiteness can be obtained even when benzophenone-based polymer ultraviolet absorbers having different copolymerization ratios and different molecular weights are used.

[0048]

[Effects of the Invention] The synthetic fiber of the present invention has excellent whiteness and is stable against light.

Claims (5)

[Claims] Claim 1: 100 parts by weight of a halogen-containing polymer,
A synthetic fiber having excellent whiteness and being stable against light, comprising a composition containing 0.005 to 0.08 parts by weight of an optical brightener and 0.1 to 4 parts by weight of a polymer type ultraviolet absorber. 2. The halogen-containing polymer comprises 70 to 30% by weight of vinyl halide monomer and 30 to 30% by weight of acrylonitrile.
70% by weight and 0 vinyl monomers copolymerizable with these
Synthetic fiber according to claim 1, which is a polymer consisting of ~10% by weight. 3. The polymer-type ultraviolet absorber has a molecular weight of 10 and is composed of 30 to 80% by weight of a benzophenone monomer and 20 to 70% by weight of a vinyl monomer copolymerizable therewith.
. 4. The synthetic fiber according to claim 3, wherein the benzophenone monomer is 2-hydroxy-4-(methacryloyloxyethoxy)benzophenone. 5. The weight ratio of the optical brightener to the unit derived from the benzophenone monomer in the polymeric ultraviolet absorber is (fluorescent brightener)/(benzophenone monomer component)=
The synthetic fiber according to claim 1, which has a particle size of 1/5 to 1/100.