JPH03130402A - Glove - Google Patents

Abstract

PURPOSE:To provide working or sports gloves made of a hydrogenated diene block copolymer and a polyolefin at a specific ratio, having excellent elongation, elongation recovery and softness, comfortably fittable to hand and having excellent form stability. CONSTITUTION:The objective gloves are made of a nonwoven cloth having an average fiber diameter of 0.5-30mum and an areal weight of 30-200g/m<2> and produced by compounding (A) 100-65wt.% of a hydrogenated block copolymer obtained by hydrogenating a block copolymer having (i) >=2 block polymers composed mainly of vinyl aromatic compound (e.g. styrene) and (ii) >=2 block polymers composed mainly of conjugated diene compound using titanocene compound, etc., and (B) 0-35wt.% (preferably 5-30wt.%) of a polyolefin (e.g. block copolymer of propylene and ethylene).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to gloves, and particularly to work or sports gloves made of a stretchable nonwoven fabric mainly made of a hydrogenated diene copolymer.

[Conventional technology]

BACKGROUND ART Conventionally, gloves for work or sports have been known to be made of cloth with rubber latex coated on the outside, that is, so-called rubberized gloves. However, such rubberized gloves have low breathability (and are thick),
It is uncomfortable to wear, especially as it inhibits the sensation and touch of the fingers.
They were unsuitable for precision work or sports that relied on them. Waterproof gloves made of synthetic resin films or sheets fused and cut are also known, but because the base fabric has little stretch, these gloves are significantly larger than the size of the hand.
It has the same problems as above because it does not fit the hand and is easy to slip when worn. In addition, in order to improve these shortcomings,
Gloves lined with thin films of elastic synthetic resin or rubber are also well known. Although they fit the hand, such elastic films generally have a relatively high modulus, so the fingers feel tied up, and lack breathability, which causes sweat to accumulate inside the film, impairing the feeling of wearing it.

In order to provide good air permeability, sheet materials made of fibers such as woven/knitted fabrics and non-woven fabrics are optimal, but fiber sheet materials that are thin enough not to significantly impede the tactile sensation of hands and fingers are suitable for dimensional and structural stability. It is unsuitable as a material for gloves for work or sports because it lacks in hardness and tends to cause white streaks due to slight friction.

In addition, in order to impart dimensional and morphological stability to such sheet materials, many proposals have been made in the past to bond the intersection points of the constituent fibers through resin processing, etc., but this leads to rough hardening of the sheet material and causes expansion and contraction. The wearability and tactile sensation of the hands and fingers are further impaired.

Further, Japanese Patent Application Laid-Open No. 61-289102 discloses a glove whose essential constituent material is an elastic polyurethane nonwoven fabric having breathability. This is a stretchable glove with excellent breathability, but since it is made of polyurethane nonwoven fabric, it has poor weather resistance and light resistance (yellowing, etc.) and poor hydrolysis resistance. Furthermore, since the average diameter of the fibers constituting the nonwoven fabric is large, there are also problems in that the bacteria barrier property and water pressure resistance are low.

The present inventors have filed a patent application No. 63-327935
By applying the stretchable non-woven fabric made of a diene copolymer water additive proposed in No. 2003, the above-mentioned problems of existing gloves are solved, and the gloves are suitable for use in work and sports. The present invention was achieved based on the discovery that the following can be obtained.

[Problem to be solved by the invention]

An object of the present invention is to provide a good glove that has excellent elongation and elongation recovery, is soft, fits the hand well, and has excellent shape stability.

A further object of the present invention is to provide gloves that have excellent air permeability and moisture permeability, do not get stuffy, and are comfortable to wear.

Another object is to manufacture such gloves in a simple process and at low cost.

[Means to solve the problem]

The object of the present invention is to obtain a block copolymer obtained by hydrogenating a block copolymer having at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least two polymer blocks B mainly composed of a conjugated diene compound. 100 to 65% by weight of hydrogenated block copolymer and 0 to 65% of polyolefin
This is achieved by a glove made of a stretchable nonwoven fabric of 35% by weight.

Examples of the vinyl aromatic compound forming the block copolymer (hereinafter referred to as precursor polymer) before hydrogenation include styrene, α-methylstyrene, vinyltoluene, p-t
Examples include ert-butylstyrene, and styrene is particularly preferred. These may be used alone or in combination of two or more. Further, examples of the conjugated diene compound forming the precursor polymer include 1.3-butadiene, isoprene, 1.3-pentadiene, 2.3-
Examples include dimethyl-1,3-butadiene, but butadiene and isoprene are particularly preferred.

These may be used alone or in combination of two or more.

These precursor polymers can be produced by performing sequential block copolymerization using a lithium alkyl catalyst, or by performing sequential block copolymerization followed by coupling reaction.

The precursor polymer thus obtained is then selectively hydrogenated. That is, the hydrogenation reaction is carried out using known hydrogenation catalysts, such as supported noble metal catalysts such as platinum and palladium, Raney nickel, organic nickel compounds, organic cobalt compounds, or composite systems of these compounds and other organic metal compounds. This can be done using a catalyst or the like.

In particular, titanocene compounds have extremely high activity as hydrogenation catalysts for block copolymers, and the hydrogenation reaction can be carried out with a small amount of catalyst, and the catalyst residue does not adversely affect the heat resistance stability of the hydrogenated block copolymers. There is no need to remove catalyst residue because it does not give
Preferably (see Japanese Patent Application Laid-Open No. 155446/1983).

Preferably, the hydrogenation is performed selectively. This is because the double bonds of the conjugated diene compound are undesirable for nonwoven fabric products because they lead to a decrease in weather resistance and light resistance. Conversely, when vinyl aromatics are hydrogenated, their fluidity deteriorates;
Unfavorable from spinnability.

That is, at least 80%, preferably 90% or more of the conjugated diene compound is hydrogenated, and 2% of the vinyl aromatic compound is hydrogenated.
Partial hydrogenation is preferred so that 0% or less, preferably 5% or less, of the nonwoven fabric is hydrogenated from the viewpoint of weather resistance, light resistance, and spinnability of the nonwoven fabric.

The number average molecular weight (hereinafter abbreviated as Mn) of the entire precursor polymer is 10.000 to 100,000, and further 15.00.
0-90,000, especially 20,000-go, oo
It is preferably in the range o. When Mn decreases, single fiber strength decreases and nonwoven fabric strength decreases. In particular, Mn is 1
If it is less than 0.000, the strength will be too low to be used as a product. In addition, as Mn increases, the strength increases, but as well as the increase in melt viscosity, the spinnability tends to be poor due to the increase in goo pressure.The average fiber diameter of the resulting nonwoven fabric also increases, and the dispersibility of single fibers also deteriorates. , product texture and appearance deteriorate, and especially when Mn exceeds 100,000, it is difficult to use as a product.

In addition, the content of vinyl aromatic compounds in the precursor polymer is
It is preferably in the range of 10 to 45 weight percent (hereinafter abbreviated as vt%), particularly 15 to 4 Qwt%. In the hydrogenated block copolymer, the so-called hard segment is a vinyl aromatic compound, which increases the strength of the material. The soft segment is a conjugated diene compound and has elasticity.

That is, the content of the vinyl aromatic compound influences the strength of the nonwoven fabric, and if it is less than 1Qwt%, the strength of the nonwoven fabric will be too low to be used as a product. Also 45wt%
If it exceeds , the strength increases, but the elongation rate decreases and the material becomes hard. In addition, the melt viscosity increases, the pressure at the sticky part increases, the spinnability becomes poor, and the resulting nonwoven fabric also begins to contain polymer beads.
The average fiber diameter becomes larger and the dispersibility of single fibers becomes worse.
The product's texture and appearance deteriorate, and it becomes unusable. Therefore, in the range of 10 to 45 wt%, the spinnability becomes good, and the resulting nonwoven fabric is soft and of good quality with excellent strength and elongation rate.

In addition, three types of hydrogenated block copolymers with different structures: ■ A-B-A ■ B-A-B-A ■ B-A-B-A-B (A is mainly a vinyl aromatic compound) Regarding the polymer blocks A and B (meaning polymer B mainly composed of a conjugated diene compound), the above three types are Mn.

When comparing the total weight ratio of A and B with the same total weight ratio and fixed spinning conditions, it was found that only A-B-A had poor fluidity, poor spinnability, was difficult to form into fibers, and produced polymer balls. , m
The fiber dispersion was poor, the average fiber diameter was large, and the texture was slightly hard, resulting in an unsatisfactory product. That is,
The precursor polymer of the hydrogenated block copolymer used in the present invention has at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least two polymer blocks B mainly composed of a conjugated diene compound. As a product nonwoven fabric, it has a good appearance and texture, and has excellent physical properties such as elongation properties (elongation, elongation recovery rate) and flexibility (flexibility), and has good flowability, so it has good spinnability. Yes, it turned out to be favorable.

The structure of the precursor polymer may be linear, branched or radial, and some examples can be represented by the following general formula.

(B-A)nn≧2 (B-A)n-Bn≧2 (B-A)m-X(B-A)n m, n≧l,
m+n=2 to 4 (in the formula, X represents a so-called coupling agent) In addition, stabilizers for the hydrogenated block copolymer used in the present invention include hindered amine compounds, hindered phenol compounds, and phosphorus compounds. , benzophenone compounds, benzotriazole compounds, and mixtures thereof, among which hindered amines are particularly preferred because they have a remarkable effect of improving heat resistance and weather resistance. If the amount of stabilizer used exceeds 5 parts by weight per 100 parts by weight of the hydrogenated block copolymer, adverse effects such as coloring may occur, although no improvement in the effect as a stabilizer is observed. I don't like it because it is.

Furthermore, the stretchable nonwoven fabric made of the hydrogenated block copolymer of the present invention can also have adhesive properties, and this tendency increases as the vinyl aromatic compound content decreases.

When a polyolefin is mixed with the hydrogenated block copolymer of the present invention, the melt viscosity of the mixed polymer is reduced, the spinnability is significantly improved, and ultrafine fibers with an average fiber diameter of 5#1 or less can be easily obtained. was discovered. In addition, the breaking strength of the nonwoven fabric is improved by mixing polyolefin,
The effect of reducing tackiness was also found. Examples of polyolefins include polyethylene, polypropylene,
Examples include copolymers of propylene and ethylene or α-olefins such as 1-butene, but block copolymers of propylene and ethylene and polypropylene are particularly preferred. In addition, the melt flow rate (MFR) is 50~
150 is preferred.

The mixing ratio of polyolefin is 0 based on the total polymer weight.
~35% by weight, preferably 5-30% by weight, more preferably 10-20% by weight. If the mixing ratio of polyolefin exceeds 35% by weight, the elongation and elongation recovery rate will decrease and the fit will be poor. Methods for mixing polyolefins include a method of chip blending during spinning, a method of using chips in which two types of polymers are melt-mixed in advance, and the like. Alternatively, the hydrogenated block copolymer and the polyolefin may be separately spun, and the two types of fibers may be mixed during or after spinning.

The method of mixing these two types of polymers is not particularly limited, but
Particularly preferred is the polymer blend method. These two types of polymers can be mixed in a single fiber, fibers made of each polymer are mixed together, or a mixture of these two types of polymers. You can. Further, without departing from the spirit of the present invention, a third
It may also be a mixture of polymers, etc.

The average fiber diameter of the fibers constituting the nonwoven fabric used for the glove of the present invention is preferably 0.5 to 30 μm, more preferably 0.5 to 10 μm, and particularly preferably 1.0 to 6 μm. If it is less than 0.5μ, it is flexible but not strong, and has poor air permeability and moisture permeability. on the other hand,
If it is 10μ or more, especially 30μ or more, it will have a strong rough feel, hard texture, and poor wearing comfort, as well as poor water pressure resistance.
Poor bacterial barrier properties. Fiber diameter is 1.0 to 6.0
If it is in the - range, not only will breathability, moisture permeability, texture, and wearing comfort be satisfied, but water pressure resistance will be increased, hands will not get wet even when working with water, and bacteria barrier and dust resistance will be improved. This is particularly preferable.

Further, the fibers constituting the stretchable nonwoven fabric used in the present invention may be short fibers or long fibers, but short fibers are generally preferred when the fiber diameter is small.

The date amount of the stretchable nonwoven fabric used in the present invention is 30 to 2
00 g/m' is preferable, more preferably 50-1
50 g/m'. If it is less than 30 g/m', the strength of the elastic nonwoven fabric decreases, making it unsuitable for use in gloves.

Furthermore, the nonwoven fabric used in the present invention has an air permeability of 5cc/
cnf/sec, water pressure resistant 300mm820
In addition to the above, it is further preferable to have 500 mmHzO or more.

Methods for producing the stretchable nonwoven fabric used in the present invention include melt-blowing and spun-pounding, and methods for forming fibers obtained by melt-spinning into sheets using conventional dry or wet methods. From the viewpoint of spinnability, the melt blow method is particularly preferred.

An example of the melt blowing method of the present invention is shown below in Figures 2 and 3.
This will be explained using figures.

The hydrogenated block copolymer is melted by an extruder 1, fed into a die 2, and extruded from a large number of spinning orifices 12 arranged in a row provided in a nozzle. The molten polymer is extruded from orifice 12 through polymer channel 11 . At the same time, the heated high-speed gas supplied through the gas inlet 13 is injected from the slits 15 provided on both sides of the orifice 12 through the gas header 14, and is blown against the flow of the extruded molten polymer. A gas header 14 and an injection slit 15 can be provided between the nozzle 9 and the lip 10. The extruded molten polymer is pulled into the shape of ultrafine fibers 4, thinned, and solidified by the action of the high-speed airflow. The ultrafine fibers formed in this way are
It is deposited on a screen (collector) 7 circulating between a pair of rotating rollers 66 to form a random web 5. Steam, air, etc. are suitable as the gas, and the gas conditions include a temperature of 300 to 400°C, preferably 350 to 400°C, and a pressure of 0.3 kg/cat.
G or more, although it varies depending on the discharge amount, preferably 0.4
~5.0 kg/Cr1G. Extruder temperature is 250
-320°C, preferably 270-300°C, and the Gui temperature is 330-400°C, preferably 350-400°C.

In addition, the distance between the goo and the collector is also important from the viewpoint of improving the dispersibility of single fibers and the strength of the nonwoven fabric due to the bonding between single fibers by self-thermal adhesion, and it is preferable that the distance is short, preferably 70 cm or less. is 50 cm or less, more preferably 40 cm or less.

As a thermal bonding method, the above-mentioned self-thermal adhesiveness is particularly preferable because it not only improves the product quality by improving the dispersibility of single fibers but also is advantageous in terms of cost.

Furthermore, other thermal bonding methods include a hot embossing method, a hot roll method, a hot air method, an ultrasonic bonding method, and the like, which can be used. In particular, the hot roll method (e.g., upper metal roll, lower rubber roll) can apply pressure uniformly to the entire elastic nonwoven fabric, and by using a rubber roll (e.g., silicone rubber hardness 70°) for the lower layer, it is more compatible with the elastic nonwoven fabric. It is preferable because it strengthens the bond between elastic fibers, improves the strength of the nonwoven fabric, and improves the surface smoothness. The temperature is 150
℃ or less, preferably 80 to 130℃, more preferably,
The temperature range is from 100 to 120°C, and the pressure is from 0.5 to 1
00 kg/cm, preferably 1-75 kg/cm
am range.

When exposed to high temperature and pressure, it becomes a molten film and impairs breathability. In addition, at low temperatures and low pressures, thermal bonding becomes insufficient, making it impossible to improve the strength and surface smoothness of the nonwoven fabric.

〔Example〕

EXAMPLES The present invention will be explained in more detail with reference to Examples below.

The definitions and measurement methods of various physical properties shown in Examples and Comparative Examples are shown below.

◎Average fiber diameter (c) Ten arbitrary points on the sample were examined using an electron microscope at a magnification of 2000.
Take 10 photos at double magnification. Measure the diameter of 10 arbitrary fibers for each photograph, and do this for each of the 10 photographs. A total of 100 fiber diameter measurements are obtained and the average value is calculated.

◎Polymer beads: Refers to bead-shaped polymers having a diameter of several times to 500 times the diameter of the fibers constituting the web, or knob-shaped polymers formed at the ends or intermediate portions of fibers. Many of these polymer beads are extremely small and cannot be seen with the naked eye. Detection is facilitated by observation using a microscope or by increasing the fiber density of the web as it is or by pressing, calendering, entangling or other means.

◎ Breaking strength and elongation: JIS L-
According to 1096, grip interval 5cm, pulling speed 10cm
/+y+in, and measure the strength and elongation per lam width at break.

◎100% elongation recovery rate: 100% when a sample with a width of 2 cm is grasped at a spacing of 12 cm and a tensile speed of 10 cm/min.
Stretch and immediately recover to original length at the same speed. Before elongation, the elongation difference (a) before and after elongation of a 10 cm line drawn in the elongation direction was determined and calculated using the following formula.

UU ◎Water pressure resistance (mmLO) Measured by JIS-L-1092B method.

◎Air permeability Measured by JIS-1096 method (Fraziel method).

◎Light resistance: Discoloration and fading after 40 hours of irradiation using a fade meter.
The strength retention rate before and after irradiation was determined.

◎Number average molecular weight (Mn): Determined from styrene equivalent molecular weight by GPC.

◎Vinyl aromatic content (wt%): The vinyl aromatic polymer block content in the total polymer is expressed in weight percent.

It was determined according to the method of Polymer Sci, Vol. 1, p. 429 (1946).

Example 1 Sequential block copolymerization was carried out using a lithium alkyl catalyst, and a butadiene-styrene-butadiene-styrene type block copolymer was used as a precursor polymer. This product has Mn of 50,000 and polystyrene content of 25wt%.
Met. This product was hydrogenated, and 5 wt % of hindered amine stabilizer Q was added to form a pellet to form a sample. (Example 1 of the aforementioned Japanese Patent Application Laid-Open No. 61-155446.
) Separately prepared polypropylene MFR90 (230℃,
(2.16 kg, 10 minutes) pellets were prepared, and the hydrogenated block copolymer resin 80
and polypropylene 20 are mixed, put into an extruder, heated and melted at an extruder temperature of 300°C, and a single hole discharge rate of 0.20
g/min, using a melt blowing nozzle with a sharpened tip of 0.4 mmφ in diameter and having slits for jetting heated fluid at both ends, the fluid was heated to 380°C.
superheated steam is injected from the slit at a pressure of 3.0 kg/cdG to draw and thin the molten polymer,
Moving net conveyor (distance between die and collector 40
This group of fibers was collected on the fibers (cm). Various physical property tests were conducted on the obtained web. The results obtained are shown in Table 1.

Regarding the polymer beads, single fiber dispersibility, and texture in Table 1, visually or to the touch, those that were particularly good were marked ◎, those that were good were marked ○, those that were somewhat poor were marked Δ, and those that were poor were marked ×. It is indicated by a mark.

As shown in FIG. 1, two webs 21 and 22 are used to create a glove by welding the peripheral edge 24 leaving the wrist opening 23.
0 was created. This glove 20 had excellent fit and breathability, and moreover, even when the hand was put in water, the hand did not get wet.

Table 1 Examples 2 and 3 and Comparative Example I A stretchable nonwoven fabric was obtained under the same conditions as in Example 1, except that the amount of PP chip blended was changed, and its physical properties were investigated. The results obtained are shown in Table 2.

Table 2 When gloves were made from these three types of nonwoven fabrics, Example 2
The gloves of Comparative Example 1 and 3 had excellent fit, but the glove of Comparative Example 1 had poor fit, and moreover, the shape deformed after wearing.

Example 4 A butadiene-styrene-butadiene-styrene type block copolymer was synthesized as a precursor polymer by performing sequential block copolymerization using a lithium alkyl catalyst. This material had an Mn of 50,000 and a polystyrene content of 3 Qwt%. This product was hydrogenated, and 5 wt % of hindered amine stabilizer Q was added to form a pellet to form a sample.

The hydrogenated block copolymer resin thus obtained was put into an extruder, heated and melted at an extruder temperature of 300°C, and the single holes were arranged in a row at a discharge rate of 0.22 g/min with a diameter of 0.4 mm.
Using a melt blowing nozzle with a sharpened tip of mmφ and having heated fluid injection slits at both ends, superheated steam at 400°C was used as the fluid at a rate of 0.7 kg/ca.
The molten polymer was sprayed from a slit at a pressure of t G to pull the molten polymer into thinner fibers, and the fibers were collected on a moving net conveyor (die-collector distance: 10 cm). The obtained web was pressed with a hot roller (upper metal, lower rubber) at 110° C. and a pressure of 15 kg/cm to obtain a stretchable nonwoven fabric. Table 3 shows the physical properties of this nonwoven fabric.

table Gloves made from this nonwoven fabric fit sex, General He had a great temperament.

Comparative Example 3 A styrene-butadiene-styrene type block copolymer was synthesized and spun under the same conditions as in Example 1, but the spinnability was poor and polymer balls were generated, and a good quality web could not be obtained.

〔Effect of the invention〕

Since the stretchable glove of the present invention is constructed as described above, it has excellent breathability, is soft, has good fit, and has an excellent wearing feeling. In addition, these gloves have excellent elongation properties (elongation, elongation recovery), weather resistance, and light resistance, as well as good heat resistance, chemical resistance, and electrical insulation properties, as well as water pressure resistance, bacterial barrier properties, and dust resistance. Shows excellent performance.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing an example of the glove of the present invention, in which the wrist opening is left and the peripheral portion is fused. FIG. 2 is a perspective view showing an example of a melt blowing process. FIG. 3 is a sectional view showing an example of a die used in the melt blow process. 1... Extruder, 2... Melt blow die, 3... Gas pipe, 4... Ultrafine fiber group,
5...Random web, 6...Drive roller 7
... Screen, 8 ... Calendar roll, 9 ... Nozzle, 10 ... Lip, 1
1... Molten polymer flow path, 12... Spinning orifice, 13... Gas inlet,
14... Lip gas header, 15... Gas slit, 20... Gloves, 21
, 22...Stretchable nonwoven fabric.

Claims (1)

[Claims] 1. Polymer block A mainly composed of vinyl aromatic compounds
A hydrogenated block copolymer obtained by hydrogenating a block copolymer having at least two polymer blocks B and at least two polymer blocks B mainly composed of a conjugated diene compound is 1
00 to 65% by weight, and 0 to 35% by weight of polyolefin.