JP3109766B2 - Composite fiber containing inorganic fine particles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is directed to a method for producing an ultraviolet light-shielding fiber or a white conductive fiber, which contains a large amount of inorganic fine particles and a large amount of inorganic fine particles.
Good spinnability, and fineness of the fiber is 8
For fibers that are denier or less.

[0002]

2. Description of the Related Art In recent years, in order to impart various properties to fibers, a method of selecting inorganic fine particles according to the performance to be imparted, kneading the inorganic fine particles into a fiber constituent polymer, and spinning has been used. For example, a white conductive metal oxide is selected as the inorganic fine particles, and this is kneaded into a fiber-constituting polymer, and then spun to obtain white conductive fibers. When kneaded and spun therein, an ultraviolet shielding fiber is obtained. Further, a specific pigment is selected as the inorganic fine particles, kneaded into a fiber constituting polymer, and spun to obtain a soaked fiber having a specific color tone.

However, in such an inorganic fine particle-containing fiber, it is necessary to increase the amount of the inorganic fine particles in order to sufficiently exert the effect of adding the inorganic fine particles. For example, in the case of a white conductive fiber, if the added amount of the white conductive metal oxide is less than a predetermined amount, the added metal oxide will not be linked and no conductive performance will be obtained. Similarly, in the case of the ultraviolet shielding fiber, when the amount of the ultraviolet shielding inorganic fine particles added is small, a satisfactory ultraviolet shielding effect cannot be obtained. For these reasons, a technique for adding a large amount of inorganic fine particles to fibers has been demanded.

In general, when a large amount of inorganic fine particles are added to a polymer constituting a fiber, the spinnability of the polymer rapidly deteriorates.
Furthermore, if a large amount of inorganic fine particles are present on the fiber surface, the surfaces of guides, rollers, drawing plates and travelers during the fiber manufacturing process will be shaved by the inorganic fine particles exposed on the fiber surface, making these devices unusable. It becomes possible, and if the production of the fiber is continued using such a device whose surface is worn, thread breakage and fluff will frequently occur. Therefore, when adding a large amount of inorganic fine particles to the fiber, it is necessary to prevent the inorganic fine particles from being present on the fiber surface. As a specific method for this, the fiber is formed into a core-sheath type composite fiber. A method of adding the inorganic fine particles to the polymer constituting the core can be considered. However,
In order to obtain a sufficient effect by simply adding the inorganic fine particles to the polymer constituting the core, a larger amount of the inorganic fine particles must be added to the core component polymer. The spinning and spinning properties of the core component polymer are required.

In order to enhance the spinnability of a core component polymer containing a large amount of inorganic fine particles in a core-sheath type composite fiber,
A technique using a thermoplastic elastomer as such a polymer has been proposed (JP-A-2-289118). That is, using conductive metal oxide particles as inorganic fine particles, as a core component polymer, polystyrene-polyisoprene-polystyrene block copolymer, polystyrene-polybutadiene-polystyrene block copolymer, polystyrene-polyisoprene block copolymer,
In addition, the use of these hydrogenated products provides a good spinnability of the core component polymer even when a large amount of inorganic fine particles are added. Certainly, if the technology described in this publication is used, a thick fiber of 10 denier or more can be produced without any problem, but for a fiber of 8 denier or less generally used for clothing, Higher spinnability is required, and it is difficult to stably produce such fine fibers with high yield by the technology described in the above publication, and the quality of the obtained fibers is not satisfactory. If a large amount of inorganic fine particles are further contained in the fiber, even if such a fiber is dyed, a product having a deep color tone, lack of clarity, and a high-grade color tone cannot be obtained.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a fiber having a fineness of 8 denier or less, which is suitably used for general clothing, and which is spun in spite of containing a large amount of inorganic fine particles. An object of the present invention is to provide a fiber having excellent properties and excellent fiber performance. Another object of the present invention is to provide a fiber which can give a product having a clear color tone by dyeing.

[0007]

An important problem when inorganic fine particles are contained in a fiber having a fineness of 8 deniers or less at a high concentration is an important problem due to clogging of a filter medium or yarn breakage in a spinning process. The spinnability is reduced. Further, even if the yarn can be spun, there is frequent occurrence of yarn breakage in the drawing process. Furthermore, there is also a problem in post-processability when fabricating a fabric such as a woven fabric or a knitted fabric, and in particular, there is a problem that a guide or the like is worn. Even if fibers are obtained, there is a problem in fiber performance such as homogeneity. In the present invention, these problems have been solved by using a specific block copolymer containing a specific compound as a base polymer containing a high concentration of inorganic fine particles.

That is, the present invention relates to a protective polymer layer component (A) comprising a fiber-forming thermoplastic polymer and a polymer layer component (B) containing inorganic fine particles, wherein the single-filament fineness is 8 deniers or less; A fiber whose component (A) accounts for at least 60% of the perimeter of the fiber cross section;
The amount of the inorganic fine particles in the component (B) is from 5 to 85% by weight, and (II) In the component (B), the hydroxyl group in which the hydroxyl group is located ortho to the butyl group.
A tertiary butylphenyl compound is added in an amount of 0.1% by weight or more based on the polymer constituting component (B);
I) The polymer constituting the component (B) is a polyaromatic vinyl block in which one block has a number average molecular weight of 4000 to 50,000, and a block in which the number average molecular weight is 1
A block copolymer comprising 0000 to 150,000 polyconjugated diene blocks, wherein 30% or more of the double bonds based on the conjugated diene of the polyconjugated diene block are hydrogenated, and have a number average molecular weight of 30,000 to 2500.
00 is a conjugate fiber.

As the compound forming the polyaromatic vinyl block, which is the first component of the block copolymer used in the present invention, an anionically polymerizable aromatic vinyl monomer such as styrene, 1-vinylnaphthalene, 2-vinyl Examples include naphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, and the like. The above is used.

Compounds forming the polyconjugated diene block as the second component include isoprene, butadiene, piperine and the like, and one or more of these are used.

The block copolymer used in the present invention is mainly composed of a polyaromatic vinyl block and a polyconjugated diene block, and has a functional group such as a carboxyl group, a hydroxyl group, or an acid anhydride in a molecular chain or a molecular terminal. It may have a group. Specific examples of the block copolymer used in the present invention include, for example, a hydrogenated product of a polystyrene-polybutadiene-polystyrene block copolymer (hereinafter abbreviated as SBS) and a polystyrene-polyisoprene-polystyrene block copolymer. (Hereinafter abbreviated as SIS), hydrogenated polystyrene-polyisoprene block copolymer (hereinafter abbreviated as SI), poly α-methylstyrene-polyisoprene-poly α
Hydrogenated product of a block copolymer of methylstyrene, hydrogenated product of a block copolymer of poly α-methylstyrene-polybutadiene-polyα-methylstyrene, poly α-
Examples include hydrogenated products of a block copolymer of methylstyrene-polyisoprene, and particularly preferred are hydrogenated products of a triblock copolymer having a polyaromatic vinyl block at both terminal blocks. Additives are preferred.

The block copolymer used in the present invention comprises:
It is necessary that 30% or more of the double bonds based on the conjugated diene of the polyconjugated diene block are hydrogenated. When the hydrogenation ratio is less than 30%, there is a disadvantage that the block copolymer is thermally decomposed during melt spinning.
Note that the hydrogenation rate referred to herein is a value of carbon-carbon which is a double bond based on a conjugated diene contained in the block copolymer.
Means the percentage of hydrogenated carbon unsaturated double bonds,
Find the iodine value before hydrogenation and the iodine value after hydrogenation,
It is determined by calculating the percentage of the latter with respect to the former. More preferably, the hydrogenation rate is 50% or more.

The number average molecular weight of the block copolymer used in the present invention must be in the range of 30,000 to 250,000. When the number average molecular weight is less than 30,000, the melt viscosity of the polymer at the time of spinning becomes too low, so that single yarn breakage and breakage at the time of spinning frequently occur, and the uniformity of the fiber deteriorates. In particular, when a high-melting-point polymer such as polyester is used as a protective polymer component, it is a serious problem to obtain a conjugate fiber. On the other hand, when the number average molecular weight exceeds 250,000, on the contrary, the melt fluidity of the polymer becomes insufficient and the spinnability deteriorates. From this viewpoint, the number average molecular weight of the block copolymer is preferably in the range of 40,000 to 200,000.

The number average molecular weight of one block of the polyaromatic vinyl block constituting the block copolymer is 400.
The number average molecular weight is 4000
If the amount is less than the above, the cohesive force of the polymer is reduced, the rubber-like elasticity becomes insufficient, and it is difficult to produce a desired fiber. On the other hand, if the number average molecular weight exceeds 50,000, the melt viscosity of the block copolymer becomes too high, the thermoplasticity is impaired,
Melt fluidity is reduced, making spinning difficult. Further, the number average molecular weight of one block of the polyconjugated diene block constituting the block copolymer is in the range of 10,000 to 150,000, and when the number average molecular weight is less than 10,000, the elasticity of the polymer becomes insufficient, and It becomes difficult to form fibers. On the other hand, when the number average molecular weight exceeds 150,000, the melt fluidity of the polymer decreases, and spinning becomes difficult. From these points, the number average molecular weight of one block of the polyaromatic vinyl block is preferably in the range of 5,000 to 40,000, and the number average molecular weight of one block of the polyconjugated diene block is preferably in the range of 15,000 to 130,000.
The number average molecular weight is determined by a conventional GPC method (Gel Parmea).
Tion Chromatography).

The proportion in the polyaromatic vinyl block copolymer is preferably in the range of 5 to 80% by weight. When the proportion of the polyaromatic vinyl block in the block copolymer is less than 5% by weight, the cohesiveness of the polymer is reduced, and the stretchability of the polymer is deteriorated. . On the other hand, if it exceeds 80% by weight, the spinning becomes difficult because the viscosity of the polymer becomes extremely high.

The block copolymer used in the present invention has an MFR (Melt FlowRate) value of 5 g / g.
It preferably has a melt flow property of 10 minutes or more. If the MFR value is less than 5 g / 10 minutes, the melt fluidity will deteriorate when inorganic fine particles are added at a high concentration, and it tends to be difficult to obtain a conjugate fiber having a denier of 8 denier or less. The upper limit of the MFR value is not particularly limited, but is preferably 100 g / 10 min or less, particularly preferably 5 to 80 g / 10 min, in view of spinning processability, productivity and the like. The MFR value referred to here is ASTM D-
It is a value measured under the conditions of 200 ° C. and a load of 10 kg by the measurement method of 1238. The MFR value specified in the present invention is the value of the block copolymer in the fiber after spinning. Therefore, even if the MFR value before the spinning is lower than the above value, it can be said that if the MFR value satisfies the above value during the spinning step, it is suitable for the present invention. The MFR value of the block copolymer is
It is determined by the molecular weight of the block copolymer, the weight ratio of polyaromatic vinyl block / polyconjugated diene block, the molecular chain length of each block, and the like. Therefore, the block copolymer used in the present invention, such a molecular weight, the weight ratio of the block, by selecting the molecular chain length of each block, etc.
Those having an MFR value within the above range are preferred.

The block copolymer used in the present invention can be obtained by the following various known methods. A compound forming a polyaromatic vinyl block using an alkyllithium compound as an initiator, a method of sequentially polymerizing a compound forming a polyconjugated diene block, a compound forming a polyaromatic vinyl block, a compound forming a polyconjugated diene block A method of polymerizing and coupling with a coupling agent, using a dilithium compound as an initiator,
Examples include a method of sequentially polymerizing a compound forming a polyaromatic vinyl block and a compound forming a polyconjugated diene block.

Further, in the present invention, the block copolymer includes a hydroxy-tert-butylphenyl compound, wherein the hydroxy group is located at the ortho-position to the butyl group (hereinafter referred to as a phenol compound). Must be added to the block copolymer in an amount of 0.1% by weight or more. The phenolic compound is generally used as an antioxidant, and many types of antioxidants are known in addition to the phenolic compound, but the phenolic compound is used when the block copolymer is spun. It has a remarkable effect in terms of stability. In general, the addition of inorganic fine particles promotes the thermal decomposability of the block copolymer, but the phenolic compound also has an unexpected effect of greatly suppressing this promoting effect. It is considered that the action of the phenolic compound provides excellent spinnability despite the large amount of inorganic fine particles. When the added amount of the phenolic compound is less than 0.1% by weight, the above-mentioned excellent effects cannot be obtained. The upper limit is not particularly limited, but is preferably 10% by weight or less, and particularly preferably in the range of 0.2 to 5% by weight.

The phenolic compound suitably used in the present invention is a compound represented by the following chemical formula 1.

Embedded image In the above formula, M represents an organic group, R represents an alkyl group, and n represents an integer of 1 to 3. However, when n is 2 or more, R may be the same or different. Specific examples thereof include the following compounds.

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Embedded image Among them, the compound suitable in the present invention is a compound represented by the above formula (2).

The timing of adding the phenolic compound to the block copolymer is arbitrary.
It can be added and kneaded after the production or simultaneously with the inorganic fine particles. When the conjugate fiber of the present invention is spun, the block copolymer, the phenolic compound and the inorganic fine particles may be uniformly kneaded, and the timing of addition is not particularly limited.

In the composite fiber of the present invention, as described above, inorganic fine particles are added to the block copolymer. The amount of the added inorganic fine particles varies depending on the intended fiber, but the present invention contains the inorganic fine particles because the object is to solve the problem of adding a large amount of the inorganic fine particles to the fiber. 5% by weight or more must be added to the block copolymer composition. 5
When the amount is less than% by weight, the problem to be solved by the present invention itself does not exist. The upper limit of the amount is not particularly limited, but is preferably about 85% by weight or less from the viewpoint of spinnability. More preferably, it is in the range of 10 to 70% by weight.

The type of the inorganic fine particles to be added varies depending on the target fiber. For example, when the purpose is to obtain an ultraviolet shielding fiber, the fine particles reflect or absorb ultraviolet rays, ie, do not substantially transmit ultraviolet rays. Fine particles are used. Representative examples thereof include inorganic compounds such as titanium dioxide, zinc oxide, magnesium oxide, alumina, silicon dioxide, barium sulfate, calcium carbonate, sodium carbonate, talc, and kaolin, and various kinds of treated fine particles of inorganic compounds. Or a mixture of two or more. More preferably,
Titanium dioxide, zinc oxide and alumina. Particularly preferred is titanium dioxide. The addition amount is preferably in the above-mentioned range from the viewpoint of ultraviolet shielding properties. In addition, when the purpose is to obtain, for example, brightly colored fibers, an inorganic pigment is used as inorganic fine particles. Further, when the purpose is to obtain conductive fibers, conductive metal oxides or metal powders are used as inorganic fine particles, and when the purpose is to obtain magnetic fibers, iron, cobalt,
Metals such as nickel and magnetic powders such as oxides or ferrites thereof are used as inorganic fine particles.

The average particle diameter of the inorganic fine particles is preferably 5 μm or less, particularly preferably 1 μm or less. If the particle size is too large, problems such as clogging in a filter during spinning and yarn breakage occur, and further, yarn breakage occurs during stretching. The average particle diameter referred to here is a particle size distribution analyzer (CAPA-50 manufactured by Horiba, Ltd.)
0). Further, in the present invention, the inorganic fine particle-containing block copolymer is preferably added with a metal stearate or a titanium-based coupling agent in order to enhance the spinnability. Particularly, a magnesium salt or calcium stearate is preferably used. Salts, zinc salts, and the like are preferable, and in particular, when the inorganic fine particles are titanium oxide or those containing the same, magnesium stearate is preferable. The addition amount of these compounds is preferably in the range of 1 to 10% by weight based on the weight of the inorganic fine particles.

Various methods can be used for incorporating the inorganic fine particles into the block copolymer. For example, the block copolymer polymer and the inorganic fine particles are kneaded and molded by a twin-screw kneading extruder or the like. A method of producing a high-concentration masterbatch, diluting the masterbatch with the block copolymer so as to have a predetermined concentration at the time of spinning, and then spinning. Further, when kneading the block copolymer and the inorganic fine particles, it is preferable to add various dispersing aids because the dispersibility becomes good.

The conjugate fiber of the present invention comprises a block copolymer containing the above-mentioned inorganic fine particles and a phenolic compound (hereinafter referred to as component B) as one component and a fiber-forming thermoplastic polymer (hereinafter referred to as component A). ) As another component. In this case, the composite cross-sectional shape is preferably such that the component A occupies 60% or more of the fiber surface circumference. When the content is less than 60%, the proportion of the component B exposed to the fiber surface increases, and the component B contains a large amount of inorganic fine particles. This is not preferable because friction such as friction becomes severe and troubles such as thread breakage occur.

Various examples of the composite form of the component A and the component B include various ones, and typical ones are shown in FIGS. Figure 1 is a single core,
2 is a three-core fiber, FIG. 3 is a four-core core-sheath structure fiber, FIG. 4 is a three-layer concentric circle, FIGS. 5 and 6 are partially exposed core-sheath structures, and FIGS. 7 and 8 are split-type composite structures. It is. Depending on the combination of component A and component B, the structure of FIGS.
Peeling may occur at the interface between the components, and the structures of FIGS. 5 and 6 cannot sufficiently eliminate friction of the guides and rollers. A core in which the core polymer as shown in FIGS. 1 to 4 is completely covered by the sheath polymer, since friction and yarn breakage of guides and rollers can be further prevented and separation between the polymers can be prevented. A sheath structure is preferred. In these figures, the hatched portion is the component B, and the non-hatched portion is the component A.

The composite weight ratio of component A to component B is preferably from 20:80 to 80:20, more preferably 30: 7.
0 to 76:24. If the ratio of component A is too small,
It is not preferable because the fiber strength decreases. Component A
Is too large, the component B containing inorganic fine particles
Is not preferable because the effect of the above cannot be sufficiently exhibited.

Component A which is the other composite component of the present invention
Nylon 6, Nylon 66, Nylon 61
Polyamides such as 0, nylon 12, nylon 11, nylon 4, and nylon 46; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyhexamethylene terephthalate; polyethylene;
It is selected from polyolefins such as polypropylene and the like, but from the viewpoint of practical performance as a fiber, a polyester polymer containing polyethylene terephthalate or polybutylene terephthalate as a main component or a polyamide polymer containing nylon 6 or nylon 66 as a main component is particularly preferable. Also,
Those obtained by copolymerizing a small amount of the third component with these polymers can also be used. For example, polyesters include terephthalic acid, isophthalic acid, naphthalene-2,5-dicarboxylic acid, α, β- (4-carboxyphenoxy) ethane, 4,4′-dicarboxydiphenyl, alkylene oxide adduct of bisphenol A, adipic acid , Azelaic acid, sebacic acid, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, polyethylene glycol,
A fiber-forming polyester-based polymer synthesized from aromatic, aliphatic, or alicyclic dicarboxylic acids such as polytetramethylene glycol; diols; oxycarboxylic acids such as hydroxybenzoic acid; In particular, a polyester polymer in which 90 mol% or more is an ethylene terephthalate unit or a butylene terephthalate unit is preferable. Further, these polymers may contain additives such as an optical brightener and a stabilizer.

In order to improve the dyeability of a fiber product composed of fibers containing a large amount of inorganic fine particles and to impart sharpness to the color tone to obtain a high-grade color tone, component A is an aromatic group. It is preferable to use a polyester obtained by copolymerizing a bifunctional monomer having a —SO ↓ 3M group (where M is any one of a hydrogen atom, a metal atom, and an alkylphosphonium group) bonded to the polymer. Even if the difunctional monomer is a dicarboxylic acid (or a derivative thereof) compound,
It may be a diol compound or an oxycarboxylic acid compound.

The aromatic group to which the -SO ↓ 3M group is bonded includes a benzenetriyl group, a naphthalenetriyl group, an anthracentriyl group, a diphenyltriyl group, an oxydiphenyltriyl group, a sulfodiphenyltriyl group,
And methylenediphenyltriyl groups. When M is a metal atom, specific metal atoms include sodium, potassium, magnesium, calcium, copper, iron and the like. Specific examples of the case where M is an alkylphosphonium group include a tetrabutylphosphonium group, an ethyltributylphosphonium group, a benzyltributylphosphonium group, a tetraphenylphosphonium group, a phenyltributylphosphonium group, and a benzyltriphenylphosphonium group. Can be

When the bifunctional monomer having a —SO ↓ 3M group is copolymerized with a dicarboxylic acid (or a derivative thereof) compound, the amount of copolymerization of the bifunctional monomer having the It is preferably at least 1.0 mol%, especially at least 1.5 mol%, based on the carboxylic acid compound. Similarly, when the bifunctional monomer is a diol compound, the amount is preferably based on all diol compounds constituting the polyester. When the bifunctional monomer is an oxycarboxylic acid compound, it is 1.0 mol% or more, especially 1.5 mol%, based on either one of the total dicarboxylic acid compound and the total diol compound constituting the polyester. % Or more is preferable. When the amount is less than 1.0 mol%, a sharp color tone cannot be sufficiently obtained.

By using a polyester obtained by copolymerizing a bifunctional monomer having a -SO ↓ 3M group as the component A, a vivid and high-grade color tone can be obtained when dyed with a kaotin dye. However, -S ↓ 3M
If the copolymerization amount of the monomer having a group exceeds 5.5 mol%, the fiber properties, particularly the fiber strength, will be reduced.
5.5 mol% or less is preferable. Of course, in the present invention, a method of mixing a polyester having a high copolymerization amount and a polyester having a low copolymerization amount to obtain a predetermined copolymerization amount may be used.

As a method for obtaining the conjugate fiber of the present invention, component A and component B are heated and melted in separate melting systems, respectively, fed to a spinneret by an ordinary extrusion spinning apparatus, and both are immediately before the spinneret. The components are combined according to the composite shape as described above, and are obtained by winding the extruded yarn or temporarily storing it in a can, followed by stretching and heat treatment. In addition, a method in which the product is extruded from the spinneret and then immediately stretched without winding or storing in a can, or a method in which the product is extruded from the spinneret and wound at a high speed to produce a product as it is, can also be used.
Of course, post-processing such as crimping and false twisting can also be applied.

The present invention is intended to solve a problem which occurs when obtaining a fiber having a fineness of 8 denier or less from a polymer containing a large amount of inorganic fine particles, that is, a problem of deterioration of spinnability. Therefore, there is no problem to be solved by the present invention when attempting to obtain a fiber having a fineness exceeding 8 denier. The present invention exerts an extremely remarkable effect particularly when trying to obtain a fiber having a fineness of 5 denier or less.

The effect of the present invention is exhibited not only in the case of long fibers but also in the case of short fibers.
Further, the composite fiber obtained by the present invention has a fiber cross-section having a shape similar to a polygon such as a pentagon or a hexagon by a higher-order processing such as false twist crimping, or a nozzle having a modified cross-section during spinning. It may have a polygonal shape such as a three-lobe shape, a T-shape, a four-leaf shape, or an eight-leaf shape, or other irregular cross-sectional shapes. In addition, the component B may have an irregular cross-sectional shape other than the round cross-section in the core-sheath structure fiber in FIGS. In short, the object of the present invention can be achieved if the fiber satisfies the requirements described above. The present invention exerts a particularly excellent effect when fine particles that absorb or reflect ultraviolet light are used as the inorganic fine particles. Because, in order to obtain a fiber having a sufficient ultraviolet shielding effect, it is necessary to add a large amount of the fine particles, and in order to use this fiber for clothing,
It is preferable that the thickness is the same as that of ordinary clothing fibers, for example, 3 deniers or less. As such fibers, the fibers of the present invention are very suitable.

The conjugate fiber of the present invention can be used for a wide variety of applications as a fabric such as a woven fabric, a knitted fabric or a nonwoven fabric, alone or in combination with other fibers. When mixed with other fibers, mixed fibers, plying, ply twisting, interweaving, interlacing, and any other means can be used, and the obtained fabric is further subjected to dyeing, resin processing, etc., if necessary. After being processed, it can be used for various purposes. Of course, it is also possible to dye in the form of fibers, yarns or textiles.

When the conjugate fiber obtained in the present invention is a fiber that blocks ultraviolet rays, its preferable use is, for short fibers, staples for clothing, dry nonwoven fabrics, wet nonwoven fabrics, and the like. , Knitting and the like. More specifically, outdoor ball wear such as soccer and golf, T-shirts, polo shirts, and even marathons, beach wear, swimwear and other outdoor sports wear, hats, blouses, veils, stockings, gloves, hoods, curtain,
Blind slats, parasols, tents, agricultural light-shielding materials, and the like, or those used as dyed materials thereof, may be used.

[0038]

The present invention will be described below with reference to examples. In the examples, with respect to the ultraviolet shielding property, the samples were evaluated by the following evaluation methods. First, 75 of the obtained fiber
A denier multifilament was prepared, and a plain weave was prepared from the multifilament at a weave density of 95 warp / inch and weft density of 60 wefts / inch. The measurement was evaluated by measuring the ultraviolet transmittance of the woven fabric using an ultraviolet intensity integrator manufactured by Toray Techno Co., Ltd. That is, a measurement sample is installed at the center of the ultraviolet intensity integrator, and at the same time, an ultraviolet intensity integrator in which no sample is installed is prepared, each is irradiated with ultraviolet light, and the amount is measured. The transmittance was calculated. UV transmittance (%) = 100 X (U / Uo) U = Sample-side UV amount Uo = No-sample-side UV amount The lower the UV transmittance, the better the shielding performance.

In the examples, the fiberization processability was determined by spinning
It was indicated by the A rating in the stretching step. The A rating was calculated by the following equation. A rating = 100 × (number of bobbins without fluff and breakage) / (total number of bobbins) Therefore, a higher value of A rating means better processability. However, in the above formula, the total number of bobbins is the number of bobbins obtained after two hours of full operation in a continuous operation for one week, and during the winding (ie, less than two hours from the beginning of winding)
When the thread breakage occurred at the time, the bobbin was switched to a new one at that point and winding was started.

REFERENCE EXAMPLE A styrene monomer, isoprene was added to a dried and nitrogen-substituted autograve using cyclohexane as a solvent, n-butyllithium as a polymerization catalyst, N, N, N'N'-tetramethylethylenediamine as a vinylating agent. A monomer or a butadiene monomer and a styrene monomer were added in this order and polymerized. The obtained triblock copolymer was subjected to a hydrogenation reaction in cyclohexane using Pd-C as a hydrogenation catalyst at a hydrogen pressure of 20 kg / cm @ 2 to obtain a block copolymer having the molecular characteristics shown in Table 1. Obtained.

EXAMPLE 1 38 parts by weight of a block copolymer (a) containing 0.3% by weight of a hydroxy-tert-butylphenyl compound represented by the following formula 13 was added to a carbon dioxide having an average particle diameter of 0.4 μm. 60 parts by weight of titanium (manufactured by Titanium Industry Co., Ltd .: ultraviolet ray performance: ultraviolet ray transmittance is almost 0) and 2 parts by weight of magnesium stearate are added, and the mixture is kneaded with a twin-screw kneader at a temperature of 230 ° C. and extruded strand. Was cut to obtain a pellet.

[0042]

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The obtained titanium dioxide-containing block copolymer (a) pellets and the block copolymer (a) pellets containing no titanium dioxide were melt-mixed at a weight ratio of 1: 1 as component B. As supplied to the extruder. On the other hand, as component A, polyethylene terephthalate containing 0.05% by weight of titanium dioxide (intrinsic viscosity [η] = 0.65) was melt-extruded with another extruder,
At a spinning temperature of 295 ° C., the component A is joined at the nozzle so as to become a sheath component and the component B is a core component, and the composite weight ratio A: B is adjusted to 2:
1, the cross section is shaped as shown in FIG.
Winding was performed at 00 m / min. The obtained spun yarn is hot rolled at 75 ° C. The plate was stretched under the conditions of 140 ° C. and a draw ratio of 3.4 times to obtain a multifilament of 75 denier / 24 filaments. The core polymer constituting the multifilament fiber was extracted with toluene and its molecular weight distribution was checked. The molecular weight distribution was almost the same as that of the raw material. From this, it was confirmed that the MFR value did not change. When the cross-sectional shape of this multifilament yarn was observed with a microscope, the core-sheath ratio was almost constant in any fiber and also in the length direction, and the core component was completely covered by the sheath component. Excellent in homogeneity and free of fluff.

Using the obtained drawn yarn, a plain woven fabric was prepared at a woven density of 95 warp / inch and weft density of 60 warp / inch, and was refined and finished to obtain a sample for measurement. In the above manufacturing steps, the A rating in the spinning step was 98%, and the A rating in the drawing step was 93%, which was extremely good. Further, both the processability in fabricating the fabric and the processability thereafter were good. When the ultraviolet shielding property was measured, it was found that the ultraviolet shielding property was very good.

Comparative Example 1 Fiberization was carried out under the same polymer and the same conditions as in Example 1 except that no hydroxy-tert-butylphenyl compound was contained in Component B at all. However, the component B polymer is thermally decomposed in the spin pack, and bubbles are generated in the fiber by the decomposed gas.
Single yarn breakage occurred during spinning, and a good spun yarn could not be obtained with good yield.

Examples 2 to 8 were carried out in the same manner as in Example 1 except that the conditions shown in Table 2 were changed. The processability was good, the cross-sectional shape and homogeneity of the fiber were both good, and the ultraviolet light shielding properties were also at a good level.

Examples 9 to 13 Example 9 used polybutylene terephthalate as component A, Example 10 used nylon 6 as component A, and Example 11 used hydroxy-tert-butylphenyl-based compound as Example 12 uses a compound represented by the following formula 15 as a hydroxy-tert-butylphenyl-based compound, and Example 13 uses a compound represented by the following formula 16 as a hydroxy-tert-butylphenyl-based compound. This was carried out in the same manner as in Example 1 except that a drawn yarn of 75 denier / 24 filaments was obtained by a method of continuous drawing without winding. When the cross-sectional shape of the obtained multi-filament yarn was observed with a microscope, the core-sheath ratio of each yarn was almost the same as in Example 1, and all fibers in the multi-filament yarn were extremely uniform. There was no fluff.

[0048]

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Comparative Example 2 Fiberization was carried out under the same conditions as in Example 1 except that no titanium dioxide was added to Component B.
A denier / 24 filament multifilament was obtained. Then, a plain fabric was prepared in the same manner as in Example 1, and the ultraviolet transmittance was examined. The ultraviolet shielding property was at a considerably lower level than in Example 1. Subsequently, a long-sleeved shirt using the woven fabric of Example 1 and the woven fabric of Comparative Example 2 for each of the right and left halves was prepared, and only the long-sleeved shirt was actually worn by five people on the upper body under sunlight. A 50 hour wear test was performed. Table 3 shows the results.

Using the woven fabric of Example 1 and the woven fabric of Comparative Example 2, parasols were produced as umbrellas. When the transmittance of ultraviolet rays was examined for the obtained parasol, a value substantially equal to the value shown in Table 2 was obtained. Furthermore, using the woven fabric of Example 1 and the woven fabric of Comparative Example 2, hats having the same specifications were produced for each. The device of Example 1 had less stuffiness on the head and was more comfortable than the device of Comparative Example 2 even when worn under direct sunlight for a long time.

Examples 14 to 18 The same procedures as in Example 1 were carried out except that the inorganic fine particles in Component B shown in Table 2 were used. In Example 14, 15% by weight of titanium dioxide having an average particle diameter of 0.4 μm (ultraviolet ray performance: not transmitting at all) and 15% by weight of zinc oxide having an average particle diameter of 0.5 μm (ultraviolet ray performance: not transmitting at all) This is an example of addition. Example 15 uses 20% by weight of the above zinc oxide, and Example 16 uses 15% by weight of the above titanium dioxide and 15% by weight of barium sulfate having an average particle size of 0.5 μm (ultraviolet ray performance: hardly transmits). In Example 17, 15% by weight of the above titanium dioxide and 15% by weight of silicon dioxide having an average particle size of 0.1 μm (ultraviolet ray performance: hardly transmitting) were used. This is an example in which alumina of 0.5 μm (ultraviolet ray performance: hardly transmits) was used at 15% by weight and the above-mentioned titanium oxide at 15% by weight. Table 2 shows the results.

Examples 19 to 20 Example 19 used the block copolymer (b) as the component B polymer, and Example 20 used the example except that the block copolymer (c) was used as the component B polymer. The fiber was spun and drawn in the same manner as in Example 1 to obtain a multifilament of 75 denier / 24 filaments. When the cross-sectional shape of the obtained multifilament yarn was observed with a microscope, the core-sheath ratio of each yarn was almost the same as in Example 1, and all fibers in the multifilament yarn were extremely uniform. There was no.

Comparative Examples 3 and 4 Comparative Example 3 used Example 1 except that the block copolymer (d) was used as the component B polymer, and Comparative Example 4 used Example 1 except that the block copolymer (e) was used as the component B polymer. Spinning was performed in the same manner. In all cases, the decomposition of the component B polymer was severe during spinning, and fiberization was impossible.

Example 21 Example 1 was repeated except that polyethylene terephthalate obtained by copolymerizing 1.7 mol% of 5-sodium sulfoisophthalic acid containing 0.05% by weight of titanium dioxide with respect to all acid components was used as Component A. 75 denier / 24
A multifilament of the filament was obtained. The core polymer constituting the multifilament fiber was extracted with toluene and its molecular weight distribution was checked. The molecular weight distribution was almost the same as that of the raw material. From this, it was confirmed that the MFR value did not change. When the cross-sectional shape of this multifilament yarn was observed with a microscope, the core-sheath ratio was almost constant in any fiber and also in the length direction, and the core component was completely covered by the sheath component. Excellent homogeneity and no fluff.

Using the obtained drawn yarn, a plain woven fabric was prepared at a woven density of 95 warp / inch and weft density of 60 warp / inch, refined and finished to obtain a measurement sample. In the above manufacturing process, spinnability, stretchability, processability in fabric production, and processability thereafter were all good. When the ultraviolet shielding property was measured, it was found that the ultraviolet shielding property was very good. In addition, the obtained plain fabric was dyed with a kaolin dye under the following conditions. Cathilon Brill Red 4GH 2% owf Na ↓ 2SO ↓ 4 2 g / l Acetic acid (glacial acetic acid) 1% owf Sodium acetate 0.5% owf Bath ratio 50: 1 120 ° C. × 1 hour Dyeing with disperse dye in Comparative Example 5 described later Compared to the dyed woven fabric, Comparative Example 5 was inferior in sharpness, but Example 19 had clear and very good coloring.

Comparative Example 5 A fiber was produced under the same conditions as in Example 21 except that polyethylene terephthalate containing 0.05% by weight of titanium dioxide was used as Component A. The obtained plain fabric was dyed with a disperse dye under the following conditions. Sumikaron Red SE-RPD 2% owf Dispersant Nikka San Salt # 7000 0.5% / l pH adjuster Ammonium sulfate 1 g / l acetic acid (48%) 1 cc / l Bath ratio 50: 1 130 ° C. × 1 hour Example 21 and In comparison, the color development represented by sharpness was poor.

Comparative Example 6 Fiberization was carried out under the same polymer and the same conditions as in Example 21 except that no hydroxy-tert-butylphenyl compound was contained in Component B at all.
However, the component B polymer is thermally decomposed in the spinning pack, and bubbles are generated in the fiber by the decomposed gas. As a result, a single yarn break occurs at the time of spinning, and a good spun yarn can be obtained with high yield. I could not do it.

Examples 22 to 28 The same procedures as in Example 21 were carried out except that the conditions shown in Table 5 were used. The processability was good, the cross-sectional shape and homogeneity of the fiber were both good, and the ultraviolet light shielding properties were also at a good level. Moreover, the dyed product was extremely excellent in sharpness.

Examples 29 to 33 Example 29 used polyethylene terephthalate obtained by copolymerizing 2.5 mol% of 5-sodium sulfoisophthalic acid as the component A polymer, and Example 30 used 5-sodium sulfoisophthalic acid as the component A polymer. To 4.5 mol%
Example 31 used a compound of the following formula 14 as a hydroxy-tert-butylphenyl-based compound using polyethylene terephthalate copolymerized.
The following 15 compounds are used as the tertiary butyl phenyl compound, and Example 33 uses the following 16 compounds as the hydroxy-tertiary butyl phenyl compound, and is spun and then continuously stretched without winding. Example 21 was carried out in the same manner as in Example 21 except that a drawn yarn of 75 denier / 24 filaments was obtained. When the cross-sectional shape of the obtained multifilament yarn was observed with a microscope, the core-sheath ratio of all the yarns was almost the same as in Example 21, and all the fibers in the multifilament yarn were extremely uniform. There was no fluff. Furthermore, the color clarity after dyeing was also extremely excellent.

Comparative Example 7 Fiberization was carried out under the same conditions as in Example 21 except that titanium dioxide was not added to Component B.
A multifilament of 75 denier / 24 filament was obtained. Then, a plain fabric was prepared in the same manner as in Example 21, and the ultraviolet transmittance was examined. The ultraviolet shielding property was at a considerably lower level than that of Example 21. When dyeing was carried out in the same manner as in Example 21, the sharpness was excellent.

Examples 34 to 38 The same procedures as in Example 21 were carried out except that the inorganic fine particles in Component B shown in Table 5 were used. In Example 34, 15% by weight of titanium dioxide having an average particle diameter of 0.4 μm (ultraviolet ray performance: not transmitting at all) and 15% by weight of zinc oxide having an average particle diameter of 0.5 μm (ultraviolet ray performance: not transmitting at all) This is an example of addition. Example 35 is an example using 20% by weight of the above zinc oxide, and Example 36 is an example using 15% by weight of the above titanium dioxide and 15% by weight of barium sulfate having an average particle size of 0.5 μm (ultraviolet ray performance: not transmitting at all). Example 37 used 15% by weight of the above-mentioned titanium dioxide and 15% by weight of silicon dioxide having an average particle diameter of 0.1 μm (ultraviolet ray performance: hardly transmitted), and Example 38 used 0.5 μm In this example, 15% by weight of alumina (ultraviolet ray performance: hardly permeating) and 15% by weight of the above titanium oxide were used. Table 5 shows the results.

Comparative Example 8 The same procedure as in Example 21 was carried out except that the block copolymer (e) was used as the component B polymer, but the component B polymer was severely decomposed at the time of spinning and fiberization was impossible. .

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

[Table 5]

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a cross-sectional shape of a conjugate fiber of the present invention.

FIG. 2 is a view showing another example of the cross-sectional shape of the conjugate fiber of the present invention.

FIG. 3 is a diagram showing another example of the cross-sectional shape of the conjugate fiber of the present invention.

FIG. 4 is a diagram showing another example of the cross-sectional shape of the conjugate fiber of the present invention.

FIG. 5 is a diagram showing another example of the cross-sectional shape of the conjugate fiber of the present invention.

FIG. 6 is a view showing another example of the cross-sectional shape of the conjugate fiber of the present invention.

FIG. 7 is a view showing another example of the cross-sectional shape of the conjugate fiber of the present invention.

FIG. 8 is a diagram showing another example of the cross-sectional shape of the conjugate fiber of the present invention.

[Explanation of symbols]

A Protective polymer layer component composed of fiber-forming thermoplastic polymer B Block copolymer layer component

────────────────────────────────────────────────── (5) References JP-A-2-289118 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D01F 8/00-8/18

Claims (3)

(57) [Claims] 1. A single fiber fineness of 8 comprising a protective polymer layer component (A) comprising a fiber-forming thermoplastic polymer and a polymer layer component (B) containing inorganic fine particles.
A fiber whose component (A) is not more than denier and 60% or more of the perimeter of the fiber cross-section;
In the component (B), a hydroxy-tert-butylphenyl compound in which a hydroxyl group is located ortho to the butyl group is added in an amount of 0.1% by weight or more with respect to the polymer constituting the component (B). (III) The polymer constituting the component (B) is a polyaromatic vinyl block having a block having a number average molecular weight of 4000 to 50,000 and a block having a number average molecular weight of 10,000 to 1
A block copolymer comprising 50,000 polyconjugated diene blocks, wherein 30% or more of the conjugated diene-based double bonds of the conjugated diene block are hydrogenated;
A conjugate fiber having a number average molecular weight of 30,000 to 250,000. 2. A bifunctional monomer wherein the protective polymer layer component (A) has an aromatically bonded —SO ↓ 3M group (where M is any one of a hydrogen atom, a metal atom and an alkylphosphonium group). The conjugate fiber according to claim 1, wherein the body is a copolymerized polyester. 3. The conjugate fiber according to claim 1, wherein the conjugate fiber is a core-sheath conjugate fiber having the protective polymer layer component (A) as a sheath and the polymer layer component (B) containing inorganic fine particles as a core. .