JP2003261765A - Processing agent for improving abrasion resistance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing agent for improving abrasion resistance, capable of processing a fiber structure at a low temperature, capable of decreasing an amount of adhered materials gummed up on rolls when the structure is subjected to in-line processing, capable of making a formed film of the agent have low frictional force, and therefore capable of giving extremely good smoothness, abrasion resistance, and resistance to flexural fatigue to the processed fiber structure. <P>SOLUTION: This processing agent for improving the abrasion resistance contains a polyamide-based resin and an organopolysiloxane as main components, wherein the polyamide-based resin and the organopolysiloxane are contained in weight ratios of 0.40-0.60 and 0.30-0.50 based on the total weight of the processing agent, respectively. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a rope, a cord,
The present invention relates to a wear resistance improving agent capable of improving wear resistance and flex fatigue resistance of a fiber structure such as a woven fabric. More specifically, it relates to a belt-shaped structure, a cord-shaped structure, a woven structure, and a net. Twisted, braided, and braided structures and ropes
Alternatively, the present invention relates to a wear resistance improving agent capable of improving the wear resistance and flex fatigue resistance of a woven fiber structure or a felt-like (nonwoven fabric) fiber structure.

[0002]

2. Description of the Related Art Usually, belts, cords, ropes, woven fabrics,
Fiber materials used for fiber structures such as felts and nets include polyester, nylon, vinylon, wholly aromatic polyamide (aramid), wholly aromatic polyester, and glass used for special purposes. There are fibers and carbon fibers.

These fibers are usually used alone and often without treatment. However, depending on the application, abrasion resistance and bending fatigue resistance may be insufficient, so that the excellent properties originally possessed by the fiber material may not be sufficiently expressed, and such a problem occurs particularly in applications involving water. Often.

In order to solve such a problem, fiber surface coating and impregnation processing with various treatment agents have been conventionally used, and as such treatment agents, polyurethane-based and silicone-based resins are widely used. .

For example, JP-B-62-60511 discloses a wear resistance improver containing polyurethane, polyethylene oxide and an ethylene urea compound as main components.
No. 173174, a wear resistance improving resin containing a urethane prepolymer blocked product as a main component, JP-B-1-2
No. 9909 discloses a wear-resistant material which is treated with a first treatment agent containing a silane coupling agent as a main component and then treated with a second treatment agent containing polyurethane, polyethylene oxide, and an ethylene urea compound as a main component. Improvement method, JP-A-3-
No. 249280 discloses a polyurethane, polyethylene oxide, a fluororesin, an abrasion resistance improver containing an ethyleneurea compound as a main component, and JP-A No. 7-157978 discloses a polyurethane, a polyethylene oxide, a fluororesin,
A wear resistance improver containing an ethylene urea compound and an organopolysiloxane as main components is disclosed (hereinafter referred to as prior art).

However, the treatment agents disclosed in the above prior art are not only difficult to control the amount of adhesion to the fiber structure due to foaming in the treatment step, but also lack smoothness and easily generate fluff. However, there is a problem in that the formed treatment agent film absorbs water and swells due to the presence of water to deteriorate the film strength, and the effect of improving wear resistance and bending fatigue resistance is not sufficiently exhibited.

Further, in the above-mentioned prior art, it is premised that a strong coating film of the treating agent is formed on the fiber surface in order to fully exhibit the characteristics of the treating agent. For that purpose, the treating liquid is applied to the fiber structure. After impregnation, it is indispensable to keep the fiber at a high temperature to cause the treating agent to carry out a crosslinking reaction, but this high temperature treatment causes the fiber structure to be thermally deteriorated to increase its rigidity, and to increase its strength and durability. Not only the problem that the fatigue property decreases, heat treatment equipment for high temperature treatment is required, and there is a problem that the production cost increases, but when impregnating a large amount of fiber structure, the impregnating roll or the squeezing roll surface, Alternatively, there is a problem that a so-called "gum-up" phenomenon occurs in which a coating film of a treatment agent is formed on a yarn guide or the like, which induces fluff during processing or a product.

Particularly, the para-aramid fiber is 17.6c.
Since it has a high strength of N / dtex or more, it has recently been widely used for belts, cords, ropes, etc., but it is easily fibrillated due to friction between fibers / fibers or fibers / objects. The generation of fluff due to this "gum-up" is a fatal defect and hinders the expansion of applications.

On the other hand, in order to improve the abrasion resistance of the above-mentioned fiber structure, a method of arranging polyamide fibers on the surface layer portion of a belt, a cord, a rope or the like made of aramid fibers to form a composite is also known. However, even in these composites, it is not possible to completely prevent the fibrillation of aramid fibers, and since the elongation of the fibers to be composited is different, the degree of development of strength with respect to the thickness of the product is reduced. In addition to the above, there is a drawback in that the fibers are partially fibrillated due to mutual friction between the fibers during the use of the product.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art, to enable processing at low temperature, and to reduce the amount of gum up adhered to the roll during in-line processing. And to provide a wear resistance improving treatment agent capable of imparting extremely good smoothness, wear resistance, and bending fatigue resistance to a treated fiber structure by reducing the friction force of the treatment agent coating. is there.

[0011]

Means for Solving the Problems As a result of various studies conducted by the present inventors in order to achieve such an object, as a result of blending a polyamide resin and an organopolysiloxane in an appropriate ratio, desired resistance The present invention has been completed by finding that an agent for improving abrasion resistance can be obtained.

That is, the present invention comprises a polyamide resin,
A wear resistance improving agent mainly comprising an organopolysiloxane, wherein the content ratio of the polyamide resin and the organopolysiloxane to the wear resistance improving agent is 0.40 to 0.60, respectively. 0.30-
It is a wear resistance improving treatment agent characterized by being 0.50.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The wear resistance improving agent of the present invention is
The main components are a polyamide resin and an organopolysiloxane. Here, the polyamide resin is a conventionally known polyamide resin called a so-called nylon resin,
For example, "nylon 6", "nylon 66", "nylon 610", "nylon 612", "nylon 12" and copolymers or modified resins thereof, among which an aqueous solution of a polyamide resin modified with ethylene oxide is preferably used. it can.

Organopolysiloxane is 25
A dimethylpolysiloxane usually referred to as silicone oil and / or a modified polysiloxane represented by the following general formula (1) having a viscosity of 5 to 200,000 centipoise at ° C.

[0015]

[Chemical 3]

Here, R ₁ , R ₂ , R ₃ and R ₄ in the above formula are —CH ₃ , —OH, —COOH, —NH ₂ and (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b H is a kind of group selected from the group consisting of at least one group other than -CH ₃ . Further, a + b is an integer of 1 to 60, m and n are integers of 1 or more.

Among these organopolysiloxanes,
When the other components are water-based compositions, those which have been imparted with water dispersibility by modification can be used as they are. However, when ordinary silicone oil is used, it is desirable to mix the emulsion with an emulsifier or the like.

The content ratios of the above-mentioned polyamide resin and organopolysiloxane to the total weight of the antiwear agent are 0.40 to 0.60 and 0.30 to 0.5, respectively.
It is essential that it is 0.

When the content ratio of the polyamide resin to the total weight of the wear resistance improving treatment agent is less than 0.40, the strength of the treatment agent coating formed on the surface of the fiber or the fiber structure is not sufficient, and The interfacial adhesion between the coating and the fiber is also insufficient. On the other hand, when the content ratio exceeds 0.60,
The surface frictional resistance of the coating becomes too large and the smoothness becomes insufficient.

When the content ratio of the organopolysiloxane with respect to the total weight of the antiwear agent is less than 0.30, foaming of the antioxidizing agent cannot be sufficiently prevented and the amount of the agent adhering to the fiber structure cannot be sufficiently prevented. Not only is it difficult to control, but the smoothness of the treatment agent coating is insufficient and the occurrence of fluff is reduced, water repellency is imparted to the fiber structure after treatment, and the amount of gum up adhesion on each roll is reduced. It will not appear. On the other hand, when the content ratio exceeds 0.50, the strength of the treatment agent coating formed on the surface of the fiber or the fiber structure becomes insufficient, and the ascending adhesion between the coating and the fiber also decreases. According to our study, when the content ratio of the organopolysiloxane to the total amount of the wear resistance improving agent is in the range of 0.30 to 0.40, the gum up adhesion amount on the roll during in-line processing, It has been confirmed that it exhibits the best improvement effect on various properties such as fluff generation, surface friction resistance of fiber structure, abrasion resistance, and bending fatigue resistance.

The wear resistance improving agent of the present invention contains, in addition to the above polyamide resin and organopolysiloxane, polyethylene oxide and an ethylene urea compound in an amount of 0.20 based on the total weight of the wear resistance improving agent. It is preferable that the content is less than or equal to 0.05 and less than or equal to 0.05.

If the content ratio of the oxidized polyethylene to the total weight of the antiwear agent is more than 0.20, not only the strength of the coating becomes insufficient, but also the interfacial adhesion between the coating and the fiber may deteriorate. Not preferable.

Further, when the content ratio of the ethylene urea compound to the total weight of the antiwear agent is more than 0.05,
The flexibility of the coating may be insufficient and the flexural fatigue resistance of the treated fiber or fiber structure may be reduced.

The term "oxidized polyethylene" as used herein refers to polyethylene that has been oxidized to have a low molecular weight, and has a hydroxyl group and / or
Alternatively, those having a carboxyl terminal group are preferable, and more preferable are high density polyethylene oxides having a molecular weight of 1,000 to 7,000.

As the ethylene urea compound, compounds represented by the following general formula (2) are preferably exemplified.

[0026]

[Chemical 4]

Here, R in the above formula represents an aromatic or aliphatic hydrocarbon residue. Further, n is 0, 1 or 2, and when n = 0, the terminal of R is a hydrogen group.

Specifically, aromatic or aliphatic isocyanates such as octadecyl isocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate and triphenylmethane triisocyanate, and ethyleneimine. Reaction products with
It is usually used in the form of an aqueous dispersion.

The wear resistance improving agent thus obtained is
Since a clean film is formed on the fiber surface by drying at a low temperature of 180 ° C or lower, the amount of gum up adhered to the roll during in-line processing is small, and fluff is not generated in the processing step. The treated fibrous structure has significantly improved wear resistance and flex fatigue resistance, and since the deterioration of wear resistance and flex fatigue resistance especially in the presence of water is small, it is used especially in the field of marine products. It can be preferably applied to a fiber structure.

The reason why the above treatment agent is excellent in abrasion resistance and flex fatigue resistance is not clear, but a polyamide resin having both light resistance and water resistance and good adhesion to fibers has a low friction coefficient. By using polyethylene oxide and organopolysiloxane in combination, a flexible and highly smooth film is formed on the fiber surface with excellent water resistance and low water absorption, and by further using an ethylene urea compound, It is considered that this is because a crosslinking reaction occurs and the cohesive force of the coating is further improved.

As a treatment method when the above-mentioned abrasion resistance improving agent is applied to the fiber structure, any conventionally known method such as a spray method and a coating method may be used, but a polyamide resin, an organopolysiloxane, A thread-like, cord-like, rope-like, belt-like, woven cloth-like, or felt-like fiber structure is dipped and impregnated in a liquid mixture of aqueous dispersions of polyethylene oxide and ethylene urea compound, then dried and heat treated. The method is the simplest and preferred. Of course, the fiber structure may be formed after the treatment agent is applied to the fiber by the above method.

At this time, the solid concentration of the treating agent in the aqueous dispersion is appropriately 1 to 10% by weight, preferably 2 to
It is 4% by weight. The drying temperature is 100 to 180 ° C, more preferably 110 ° C to 150 ° C, and the drying time is 0.1 to 2
It is 0 minutes, more preferably 0.2 to 10 minutes. When the drying temperature is lower than 100 ° C, the coating film is not sufficiently formed by the treating agent, and when the drying temperature is higher than 180 ° C, the moisture in the treating agent evaporates rapidly to form a good coating film. It may disappear.

The amount of the treatment agent adhering to the treated fiber or fiber structure (weight of the solid content of the treatment agent film) is suitably 0.1 to 5.0% by weight, preferably 0.1. 5
~ 2.5% by weight. If the adhered amount is less than 0.1% by weight, abrasion resistance and bending fatigue resistance are not sufficiently improved and no practical effect is exhibited, and if the adhered amount exceeds 5% by weight, after treatment, The fiber or fiber structure becomes extremely coarse and hard,
Flex fatigue resistance may be reduced.

[0034]

The agent for improving wear resistance of the present invention has the following effects. 1) Since a strong coating can be formed on the fiber surface only by low-temperature drying, processing (in-line processing) can be performed even in the line during the spinning process, and processing costs are much higher than post-processing (post-processing), which is completely separate from the spinning process. Can be significantly reduced. 2) The amount of gum up on rolls during in-line processing is small, so it is possible to suppress the generation of fluff in the treatment process, and as a result, prevent fibrillation of fibers during actual use and improve durability. . 3) The treated fiber structure has extremely excellent wear resistance in the air and in the presence of water.

[0035]

EXAMPLES The present invention will be specifically described below with reference to examples. The abrasion resistance and the amount of gum up adhesion on the roll in the in-line processing step were evaluated according to the following methods.

(1) Abrasion resistance (method A) An evaluation apparatus is shown in FIG. In FIG. 1, 1 is 0.8 mm
φ is a piano wire with tension, 2 is a load, and 3 is a chord-shaped evaluation sample. In FIG. 1, 0.
After attaching a load of 177 cN / dtex, the other end of 3 is reciprocated, and the number of reciprocations until cutting by friction with the piano wire 1 is made wear resistant.

(2) Abrasion resistance (method B) An evaluation device is shown in FIG. In FIG. 2, 5 is a freely rotating roll having an outer diameter of 20 mmφ, 4 is also a freely rotating roll having an outer diameter of 10 mmφ, 3 is a cord-shaped evaluation sample, and 6 is for interposing water in the evaluation sample 3. The container, 7 is water.

In FIG. 2, the sample 3 was twisted 1.5 times, and a part of the sample 3 was immersed in water, and then the sample 3 was twisted 3 times.
Attach a load of 0.177cN / dtex to one end of 3
Reciprocate the other end of. The abrasion resistance is defined as the number of reciprocations until the cord-shaped samples 3 wear each other and cut each other.

(3) Amount of gum up on roll The amount of gum up on a drying roll was measured when 600 g of a long fiber yarn of 1667 dtex / 1000 filament was treated, and its weight was measured. Is 0.2g
The following cases were evaluated in three grades: ◯, more than 0.02 g, less than 0.1 g, Δ, and more than 0.1 g, x.

Example 1 An aqueous dispersion of nylon resin modified with ethylene oxide (active ingredient: 20% by weight),
Aqueous dispersion of polyethylene oxide having a molecular weight of about 4500 (active ingredient: 25% by weight), aqueous dispersion of ethyleneurea compound consisting of reaction product of diphenylmethane diisocyanate and ethyleneimine (active ingredient: 33% by weight), and amino An aqueous dispersion of the modified silicone (active ingredient: 15% by weight) was mixed in the content ratio shown in Table 1 to obtain a wear resistance improving treatment agent. The solid content concentration in this treating agent was 2.7% by weight.

1667 dtex / 100 was added to the above treatment agent.
0 filament para-aramid filament yarn (Teijin Ltd.)
(Technola Co., Ltd.) was continuously dipped while running, lightly squeezed with a nip roll, and then in-line processing of drying at 120 ° C. for 1.0 minute was performed. At this time, the solid content of the treating agent attached to the yarn was 1.0% by weight. Table 1 shows the amount of gum up adhered onto the roll in the in-line processing.

Next, three para-type aramid filament fiber yarns to which the abrasion resistance improving treatment agent is attached are aligned, and the two are arranged in the Z direction.
Twist the yarn so that the number of twists is 0 times / 10 cm, and then combine the two twisted cords 20 times / 1 in the S direction.
Combined with 0 cm twist, total layer fineness is 10000 dtex
The cord-like fiber structure of was obtained. Table 1 also shows the results of evaluating the abrasion resistance of this cord-shaped fiber structure by the A method and the B method.

Comparative Example 1 Example 1 is the same as Example 1 except that the treatment with the wear resistance improving agent is not performed.
It carried out similarly to. The abrasion resistance of the obtained cord-shaped fiber structure is shown in Table 1.

[Examples 2-3, Comparative Examples 2-4] Example 1
In Example 1, the same procedure as in Example 1 was performed except that the content ratio of the components constituting the treating agent was changed as shown in Table 1. Table 1 shows the amount of gum-up adhered to the roll and the abrasion resistance of the cord-like fiber structure in the in-line processing.

[Examples 4 to 8 and Comparative Example 5] In Example 1, an aqueous dispersion of dimethyl silicone (active ingredient: 75% by weight) was used in place of the amino-modified silicone. Example 1 was repeated except that the content ratio was changed as shown in Table 1. Table 1 shows the amount of gum-up adhered to the roll and the abrasion resistance of the cord-like fiber structure in the in-line processing.

[0046]

[Table 1]

[Brief description of drawings]

FIG. 1 is a side view showing a wear resistance evaluation apparatus by method A.

FIG. 2 is a side view showing a wear resistance evaluation device by a B method.

[Explanation of symbols]

1 piano wire 2 load 3 Evaluation sample in code form 4, 5 Rolls that can rotate freely 6 containers 7 water

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) D06M 15/53 D06M 15/53 15/59 15/59 15/647 15/647 F term (reference) 4J002 BB25Y CL01W CL03W CP02X CP03X CP06X CP09X CP18X EU016 GK02 HA06 4L033 AA05 AA07 AA08 AA09 AB03 AB05 AB07 AC08 AC15 BA91 CA48 CA55 CA56 CA60

Claims (4)

[Claims] 1. A wear resistance improving agent containing a polyamide resin and an organopolysiloxane as main components, wherein the content ratio of the polyamide resin and the organopolysiloxane to the total weight of the wear resistance improving agent is 1. Is 0.40 to 0.60 and 0.30 to 0.50, respectively. 2. The wear resistance according to claim 1, wherein the polyamide resin is an ethylene oxide-modified polyamide resin, and the organopolysiloxane is dimethylpolysiloxane and / or a modified polysiloxane represented by the following general formula (1). A property improving treatment agent. [Chemical 1] Here, R ₁ , R ₂ , R ₃ and R ₄ in the above formula are -C.
_{H 3, -OH, -COOH, -NH} 2, and (C ₂ H
₄ O) _a (C ₃ H ₆ O) _b H, which is a group selected from the group consisting of at least one group other than —CH ₃ .
Further, a + b is an integer of 1 to 60, m and n are integers of 1 or more. 3. The wear resistance improving treatment agent further contains an oxidized polyethylene and an ethylene urea compound, and the content ratio of the polyethylene oxide and the ethylene urea compound to the total weight of the wear resistance improving treatment agent is 0.20 or less, respectively. And 0.05 or less, the abrasion resistance improving treatment agent according to claim 1 or 2. 4. The molecular weight of the oxidized polyethylene is from 1000 to 1000.
The abrasion resistance improving agent according to claim 3, wherein the treating agent is 7,000, and the ethylene urea compound is a compound represented by the following general formula (2). [Chemical 2] Here, R in the above formula represents an aromatic or aliphatic hydrocarbon residue. Further, n is 0, 1 or 2, and when n = 0, the terminal of R is a hydrogen group.