JP5978419B2 - Compound yarn - Google Patents

Description

  The present invention relates to a composite yarn suitable for use for reinforcing rubber products. More specifically, it is a composite that is embedded in the base rubber to reinforce rubber products such as various belts such as tires, transmission belts, V belts, timing belts, radiator hoses, heater hoses, power steering hoses, etc. Regarding yarn.

  For reinforcing rubber products, continuous reinforcing fibers such as metal fibers, glass fibers, and aramid fibers alone or composite yarns composed of continuous reinforcing fibers and organic fibers combined with twisted yarns may be used. Reinforcing a rubber product with a continuous reinforcing fiber alone is generally performed, and improvements in properties such as strength and dimensional stability of the rubber product are achieved. However, continuous reinforcing fibers alone may not be able to fully meet the increasing demands of customers. In particular, rubber products for automobile parts need to satisfy conflicting characteristics such as high strength, high dimensional stability, light weight, and low price at a high level, and continuous reinforcing fibers alone may not be sufficient. is there. In order to satisfy the conflicting characteristics at a high level, a composite yarn in which continuous reinforcing fibers and continuous organic fibers are combined may be used. When obtaining a rubber product, it is important that the composite yarn has excellent handleability so that the continuous reinforcing fibers are not easily damaged. In addition, composite yarns generally used for reinforcing rubber products are produced in a process that includes twisted yarn, but the continuous reinforcing fiber is not damaged so that the strength is not significantly reduced by the twisting process. It is very important that the continuous reinforcing fibers and the continuous organic fibers are uniformly dispersed and mixed to suppress the direct contact between the reinforcing fibers.

  As a method for uniformly dispersing and mixing the continuous reinforcing fiber and the continuous organic fiber, the following Patent Document 1 discloses a method in which gas (air) is collided with the mixed yarn, and the following Patent Document 2 discloses an organic fiber bundle ( A method for imparting crimpability to a thermoplastic resin fiber bundle) and a method for specifying a sizing agent application amount in each fiber bundle are disclosed in Patent Document 3 below. Further, Patent Documents 4 and 5 below disclose a method of opening a fiber bundle in a liquid in order to suppress the occurrence of single fiber breakage, and Patent Document 6 below discloses a method of sucking air flow into a bent fiber bundle. A method is disclosed in which the fiber bundles are mixed together after the fiber has been spread by the action of the fiber, and the following patent document 7 discloses a method of mixing fibers by the so-called Taslan method, the electric fiber opening method, the interlace method, or the like. ing.

JP 60-209034 A JP-A-2-308824 JP-A-3-33237 JP-A-2-28219 JP-A-4-73227 Japanese Patent Laid-Open No. 9-324331 JP-A-7-109640

However, in any of the above conventional methods and conditions in which continuous reinforcing fibers and continuous organic fibers are dispersed and mixed, it is difficult to uniformly mix continuous reinforcing fibers and continuous organic fibers. When trying to obtain a fine state, single yarn breakage tends to occur, and there is a problem that it is impossible to obtain the original mechanical properties of the reinforcing fiber. And, when trying to prevent single yarn breakage, a sufficient mixed fiber state cannot be obtained, the handleability is inferior, the twist strength maintenance rate described later is lowered, and the purpose of obtaining a composite yarn having excellent mechanical properties cannot be achieved. There was a problem.
For example, in Patent Document 7, it is important that the matrix fiber and the reinforcing fiber are in a mixed state at a single fiber level, and the matrix fiber is uniformly dispersed in the gap between the reinforcing fibers. Examples of the fiber method include so-called Taslan method, electric fiber opening method, interlace method and the like. However, the properties required for the reinforcing fiber and the matrix fiber to achieve such a mixed state are only described as fineness and single yarn fineness, and other properties and appropriate ranges of the properties are described. Is not described at all, and there is a problem in that it cannot always be guaranteed that a uniformly dispersed mixed state can be achieved even if the fiber mixing method is used.

  In addition, the method of mixing fibers in a liquid has a problem that an extra step of removing the liquid is required. Further, in the method of mixing fibers by combining widely opened fiber bundles, the spread fiber bundles are combined. However, although a uniformly dispersed mixed state can be obtained at the mating portion, there is a problem that a sufficiently uniform mixed state cannot be obtained as a whole.

  The present invention has been made in view of the above problems, and its purpose is to obtain a rubber product by continuously mixing continuous reinforcing fibers and continuous organic fibers uniformly without damaging the continuous reinforcing fibers. An object of the present invention is to provide a composite yarn that is excellent in properties and is suitable for obtaining a rubber product in which a decrease in the twist strength maintenance rate is suppressed and the mechanical properties satisfy a high level.

As a result of intensive studies, the inventors of the present invention have obtained excellent handling properties by uniformly mixing continuous reinforcing fibers having specific characteristics and continuous organic fibers having specific characteristics, and then twisting them, so that both fibers are uniformly distributed. It has been found that a composite yarn suitable for obtaining a rubber product satisfying mechanical properties at a high level can be obtained by suppressing a decrease in the twist strength maintenance ratio.
That is, the present invention is as follows.

[1] A continuous reinforcing fiber and a continuous organic fiber are mixed and twisted, and the product RD of the single reinforcing fiber diameter R (μm) and density D (g / cm ³ ) is 5 to 100 μm. Composite yarn that is g / cm ³ .
[2] The composite yarn according to [1], wherein the twist strength maintenance rate (%) satisfies the following formula (1).
Twist strength maintenance ratio (%) ≧ 100 × exp (−2.5 × K / 10 ⁵ ) (1)
However, K is a twist coefficient of the composite yarn represented by the following formula (2).
K = Y × Dt ^0.5 (2)
Here, Y is the number of twists per 1 m of twisted yarn (times / m), and Dt is the fineness (dtex) of the continuous reinforcing fiber.
[3] The composite yarn according to [1] or [2], wherein the tensile breaking strength of the continuous yarn obtained by connecting continuous reinforcing fibers by an air splicer is 50 to 100% of the tensile breaking strength of the continuous reinforcing fiber yarn. Article.
[4] The composite yarn according to any one of [1] to [3], wherein the continuous reinforcing fiber is substantially untwisted and substantially unentangled.
[5] The continuous reinforcing fiber is at least one selected from glass fiber, carbon fiber, aramid fiber, ultra high strength polyethylene fiber, polybenzazole fiber, liquid crystal polyester fiber, polyketone fiber, metal fiber, and ceramic fiber. The composite yarn according to any one of [1] to [4].
[6] The ratio of the continuous reinforcing fiber product RD to the continuous organic fiber product RD (continuous reinforcing fiber / continuous organic fiber) is 0.3 to 5, according to any one of [1] to [5] above. The composite yarn described.
[7] Any one of [1] to [6] above, wherein the ratio of the single yarn diameter of the continuous reinforcing fiber to the single yarn diameter of the continuous organic fiber (continuous reinforcing fiber / continuous organic fiber) is 0.3 to 2. The composite yarn described in the item.
[8] The composite yarn according to any one of [1] to [7], wherein the total fineness of the continuous reinforcing fiber and the continuous organic fiber is 100 to 20,000 dtex.
[9] The composite yarn according to any one of [1] to [8], wherein the continuous organic fiber is substantially untwisted and substantially unentangled.
[10] The composite yarn according to any one of [1] to [9], wherein the continuous organic fiber is a continuous cellulosic fiber and / or a continuous thermoplastic resin fiber.
[11] The continuous thermoplastic resin fiber is selected from polyolefin resin, polyamide resin, polyester resin, polyether ketone, polyether ether ketone, polyether sulfone, polyphenylene sulfide, thermoplastic polyether imide, and thermoplastic fluorine resin. The composite yarn according to [10] above, which is a continuous fiber obtained by melt spinning the at least one thermoplastic resin.
[12] The composite yarn according to any one of [1] to [11], wherein the blending method is a fluid entanglement method.
[13] The composite yarn according to [12], wherein the continuous reinforcing fiber and the continuous organic fiber are aligned and supplied substantially perpendicularly to the introduction hole surface of the fluid entanglement nozzle.

  According to the present invention, the continuous reinforcing fiber and the continuous organic fiber are continuously and uniformly mixed without damaging the continuous reinforcing fiber, the handling property for obtaining the rubber product is excellent, and the decrease in the twist strength maintenance rate is suppressed. Thus, it is possible to obtain a composite yarn for reinforcing rubber products suitable for obtaining a rubber product satisfying mechanical properties at a high level.

It is a schematic side view which shows an example of the fiber mixing apparatus for implementing this invention. It is the schematic which shows an example (used by Example 1, 2) of the supply state of the alignment thread | yarn to the fluid entanglement nozzle in the apparatus shown in FIG. It is the schematic which shows another example (used in Example 15) of the supply state of the aligning yarn to the fluid entanglement nozzle in the apparatus shown in FIG.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
The present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.

The composite yarn of this embodiment is a product of a continuous reinforcing fiber and a continuous organic fiber mixed and twisted, and a product of a single yarn diameter R (μm) and a density D (g / cm ³ ) of the continuous reinforcing fiber. It is important that the RD is 5 to 100 μm · g / cm ³ . Preferably it is 10-50, More preferably, it is 15-45, Most preferably, it is 20-45 micrometer * g / cm < ³ >.

If the product RD is 5 to 100 μm · g / cm ³ , when both fibers are mixed, the continuous reinforcing fibers are easily damaged without damaging the continuous reinforcing fibers, and both fibers are continuously and uniformly mixed. It is possible. When the product RD is less than 5 μm · g / cm ³ , continuous reinforcing fibers are easily damaged during fiber mixing, and fluff is likely to occur. By receiving, it becomes difficult for the composite yarn to exhibit sufficient mechanical properties.

When the product RD exceeds 100 μm · g / cm ³ , the continuous reinforcing fibers are difficult to open, and the continuous reinforcing fibers and the continuous organic fibers are difficult to be mixed uniformly and continuously. Therefore, a decrease in the twist strength maintenance rate is suppressed, and it is difficult to obtain a composite yarn that satisfies the mechanical characteristics at a high level.

  If the product RD is within the above range, the continuous reinforcing fiber can be easily opened without damaging the continuous reinforcing fiber, and the reason why the two fibers can be mixed uniformly and continuously is not necessarily clear. There is no reason, but the reason is as follows. That is, when an external force is applied to the continuous reinforcing fiber, it is assumed that an external force proportional to the circumferential diameter, that is, the single yarn diameter is applied to one single yarn. On the other hand, the inertial mass per unit length per single yarn is proportional to the product of the square of the single yarn diameter and the density. According to the equation of motion, the acceleration generated in the single yarn is proportional to the value obtained by dividing the external force by the inertial mass, so the acceleration generated in the single yarn of the reinforcing fiber during blending is inversely proportional to the product RD of the single yarn diameter and density. Then it is guessed. Therefore, when the product RD is too small from a certain range, it is assumed that the continuous reinforcing fiber is easily damaged because the acceleration becomes excessive. On the other hand, when the product RD is excessively larger than a certain range, it is estimated that the continuous reinforcing fiber is difficult to open because the acceleration is excessively small.

In this embodiment, the catalog value is used for the density of the continuous reinforcing fiber, and the single yarn diameter R (μm) is the fineness T (dtex), the number of single yarns F (the number), and the density D (g / cm ³ ) of the continuous reinforcing fiber. And is calculated by the following formula (3).
R = 20 × (T / π · F · D) ^0.5 (3)

In order to set the product RD within the predetermined range, it may be appropriately selected from commercially available continuous reinforcing fibers. That is, when the glass fiber described later is used as the continuous reinforcing fiber, since the density is about 2.5 g / cm ³ , a fiber having a single yarn diameter of 2 to 40 μm may be selected. For example, a single yarn diameter of 9 μm, a fineness of 660 dtex and 400 single yarns, a single yarn diameter of 17 μm, a fineness of 11,500 dtex and a single yarn number of 2,000 can be selected. Moreover, when using carbon fiber, since the density is about 1.8 g / cm ^3, it is sufficient to select one having a single yarn diameter of 2.8 to 55 μm. For example, one having a single yarn diameter of 7 μm, a fineness of 2,000 dtex and a number of single yarns of 3,000 can be selected. When an aramid fiber is used, since the density is about 1.45 g / cm ³ , a fiber having a single yarn diameter of 3.4 to 68 μm may be selected. For example, one having a single yarn diameter of 12 μm, a fineness of 1,670 dtex, and 1,000 single yarns can be selected. In order to make the product RD within a particularly preferable range, for example, a glass fiber having a fineness of 660 dtex and 400 single yarns may be used.

  The composite yarn in this embodiment needs to be produced through a twisting process after blending continuous reinforcing fibers and continuous organic fibers. By mixing fibers, continuous reinforcing fibers and continuous organic fibers can be mixed continuously and uniformly, and in order to suppress continuous contact between the continuous reinforcing fibers, in the twisting process, use, purpose It is possible to design an optimum number of twisted yarns according to the above, and it is possible to suppress a significant decrease in the strength of the composite yarn by the twisting process.

The composite yarn in this embodiment preferably has a twist strength maintenance ratio (%), which is a ratio of strength of the composite yarn before and after the twisting step, in the range of the following formula (1).
Twist strength maintenance ratio (%) ≧ 100 × exp (−2.5 × K / 10 ⁵ ) (1)
However, K is a twist coefficient of the composite yarn represented by the following formula (2).
K = Y × Dt ^0.5 (2)
Here, Y is the number of twists per 1 m of twisted yarn (times / m), and Dt is the fineness (dtex) of the continuous reinforcing fiber.
If the twist strength maintenance rate is below the above range, the reinforcing effect of the rubber product will be insufficient, and it will be necessary to increase the amount of composite yarn used in order to obtain the required strength and other characteristics. A composite yarn excellent in properties cannot be obtained. The closer the twist strength maintenance rate is to 100%, the better, and it is desirable that it is in the range of the following formula (4).
Twist strength maintenance ratio (%) ≧ 100 × exp (−2.0 × K / 10 ⁵ ) (4)

[Continuous reinforcing fiber]
<Type>
As the continuous reinforcing fiber in the present embodiment, those normally used for reinforcing rubber products can be used. For example, glass fiber, carbon fiber, aramid fiber, ultra-high strength polyethylene fiber, polybenzazole fiber, liquid crystal polyester fiber Preferably, at least one selected from polyketone fibers, metal fibers, and ceramic fibers. Glass fibers, carbon fibers, and aramid fibers are particularly preferable from the viewpoint of mechanical properties, thermal properties, and versatility, and glass fibers are particularly preferable from the viewpoint of price.

<Form>
The continuous reinforcing fiber used in the present embodiment is substantially untwisted and substantially unentangled, which improves the tensile breaking strength of the connecting yarn by an air splicer described later and the spreadability in the blending process. It is preferable from the viewpoint of improvement. Substantially no twist means a state in which there is no twist other than unintentional twist accompanying unraveling and the like, and the number of twists is 10 times / m or less. Substantially non-entangled means a state in which no intentional entanglement by normal entanglement means such as fluid entanglement is present, and the number of entanglement is 5 times / m or less.
The number of single yarns of continuous reinforcing fibers is preferably 30 to 15,000 from the viewpoints of fiber opening and handling properties in the fiber mixing process.

<Tensile breaking strength of splicing yarn>
In this embodiment, it is preferable that the tensile breaking strength of the connecting yarn in which continuous reinforcing fibers are connected by an air splicer is 50 to 100% of the tensile breaking strength of the continuous reinforcing fiber yarn. More preferably, it is 60 to 100%, and particularly preferably 65 to 100%. An air splicer is a device that connects yarn ends by opening the yarn ends by air injection and tangling single yarns at the yarn ends. Therefore, if the tensile breaking strength of the splicing yarn by the air splicer is in the above range, it is preferable that the continuous reinforcing fiber can be opened and mixed with air and can be judged to be less damaged.

The connecting yarn is produced using a commercially available air splicer. For example, a joint air type 110 manufactured by Machinetex Co., Ltd. can be used. The chamber and chamber cover of the air splicer are appropriately selected and attached according to the fineness of the continuous reinforcing fiber, and the reinforcing fiber is connected by a predetermined procedure of the air splicer under the following conditions.
Supply air pressure 0.7 MPa
Scale 4 of air injection time adjustment knob PT150
Thread length Length Scale 4 of regulator PT40
The tensile breaking strength of the obtained connecting yarn and continuous reinforcing fiber yarn is measured by the method described in JIS L1013.

  In order to set the tensile breaking strength of the continuous reinforcing fiber joining yarn to the above range, the product RD of the single yarn diameter R and the density D is set to an appropriate range, and the sizing agent attached to the bundle surface of the continuous reinforcing fiber is used. Select the type and amount of adhesion as appropriate. The sizing agent prevents the continuous reinforcing fibers from breaking into single yarns, prevents the continuous reinforcing fibers from being damaged in the processing process, and adheres the continuous reinforcing fibers to the rubber after becoming a rubber product. It functions to improve performance. In this embodiment, the bundling effect that prevents the single yarn from breaking is necessary until the continuous fiber is not damaged until the fiber blending process, but if the bundling effect is excessive, the fiber opening process is performed in the fiber blending process. Since it becomes difficult to mix, it is preferable to appropriately select the type of sizing agent and the amount of adhesion.

<Glass fiber sizing agent>
What is necessary is just to select the kind of sizing agent suitably from a well-known sizing agent according to the kind of continuous reinforcement fiber and continuous organic fiber.
For example, when glass fiber is selected as the continuous reinforcing fiber, the sizing agent is preferably composed of a silane coupling agent, a lubricant, and a binding agent.

(Silane coupling agent)
A silane coupling agent is usually used as a surface treatment agent for glass fibers, and contributes to improving the adhesive strength with rubber. Although it does not restrict | limit especially as a silane coupling agent, For example, aminosilanes, such as (gamma) -aminopropyltriethoxysilane, (gamma) -aminopropyltrimethoxysilane, and N- (beta)-(aminoethyl) -gamma-aminopropylmethyldimethoxysilane Mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. It is preferable that it is 1 or more types selected from said enumeration component, Especially, aminosilanes are especially preferable.

(lubricant)
The lubricant contributes to the adjustment of the glass fiber sizing agent and the improvement of the opening property. As the lubricant, any ordinary liquid or solid lubricating material suitable for the purpose can be used. Although not limited to the following, for example, animal and plant or mineral waxes such as carnauba wax and lanolin wax, and surfactants such as fatty acid amides, fatty acid esters or fatty acid ethers, or aromatic esters or aromatic ethers Can be used.

(Binder)
The binding agent contributes to the improvement of the binding property of the glass fiber and the improvement of the adhesive strength with rubber. As the binder, a polymer or a thermoplastic resin suitable for the purpose can be used. Examples of the polymer include, but are not limited to, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary, and tertiary amines. Can be mentioned. In addition, for example, epoxy resins such as bisphenol A type epoxy resins, phenol resins obtained by reacting various phenols with formalin, urea resins obtained by reacting urea and formalin, melamine obtained by reacting melamine and formalin Examples thereof include thermosetting resins such as resins. For example, polyurethane resins obtained from isocyanates such as m-xylylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate and polyester or polyether diols are also preferably used. The
The acrylic acid homopolymer preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.

  The monomer that forms a copolymer with the acrylic acid constituting a copolymer of acrylic acid and other copolymerizable monomer is not limited to the following, but, for example, among monomers having a hydroxyl group and / or a carboxyl group, acrylic acid , Maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid, including at least one type (except for acrylic acid only) ). Of the above monomers, it is preferable to have one or more ester monomers.

  The salt of the acrylic acid homopolymer and / or copolymer with the primary, secondary and tertiary amines is not limited to the following, and examples thereof include triethylamine, triethanolamine and glycine. The neutralization degree is preferably 20 to 90% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor, and is preferably 40 to 60%. It is particularly preferable to do this.

  The weight average molecular weight of the acrylic acid polymer forming the salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. 3,000 or more are preferable from the viewpoint of improving the converging property of the glass fiber, and 50,000 or less are preferable from the viewpoint of improving the characteristics of the rubber product.

  Examples of the thermoplastic resin used as a binder include, but are not limited to, polyolefin resins, polyamide resins, polycarbonate resins, polyester resins, polyacetal resins, polyether ketones, polyether ether ketones, poly Examples include ether sulfone, polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluororesin, and modified thermoplastic resins obtained by modifying these. In the case where the adhesive strength between the glass fiber and the rubber is improved and the sizing agent is attached to the glass fiber as an aqueous dispersion, from the viewpoint of reducing the ratio of the emulsifier component or making the emulsifier unnecessary, as the thermoplastic resin, Modified thermoplastic resins are preferred. Here, the modified thermoplastic resin means that, in addition to the monomer component that can form the main chain of the thermoplastic resin, different monomer components are copolymerized for the purpose of changing the properties of the thermoplastic resin, and hydrophilicity, crystallinity, and the like. Means a modified thermodynamic property.

  Examples of the modified thermoplastic resin include, but are not limited to, modified polyolefin resins, modified polyamide resins, and modified polyester resins.

  The modified polyolefin resin is a copolymer of an olefin monomer such as ethylene or propylene and a monomer copolymerizable with an olefin monomer such as an unsaturated carboxylic acid, and can be produced by a known method. A random copolymer obtained by copolymerizing an olefin monomer and an unsaturated carboxylic acid may be used, or a graft copolymer obtained by grafting an unsaturated carboxylic acid on an olefin may be used.

  Examples of the olefin monomer include ethylene, propylene, 1-butene and the like, and these can be used alone or in combination of two or more. Examples of monomers that can be copolymerized with olefinic monomers include acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Saturated carboxylic acid etc. are mentioned, These can also be used individually or in combination of 2 or more types.

  As a copolymerization ratio of the above olefin monomer and a monomer copolymerizable with the olefin monomer, the total weight of the copolymerization is 100% by weight, and the olefin monomer can be copolymerized with 60 to 95% by weight. It is preferably 5 to 40% by weight of the monomer, more preferably 70 to 85% by weight of the olefin monomer, and more preferably 15 to 30% by weight of the monomer copolymerizable with the olefin monomer. If the weight percentage of the olefin monomer is less than 60 weight%, the affinity with rubber may be reduced. If the weight percentage of the olefin monomer exceeds 95 weight%, the water content of the modified polyolefin resin may be reduced. Dispersibility is lowered, and uniform application to continuous glass fibers may be difficult, which is not preferable.

  In the modified polyolefin resin, a modified group such as a carboxyl group introduced by copolymerization may be neutralized with a basic compound. Examples of the basic compound include metal salts such as sodium hydroxide and potassium hydroxide; ammonia; amines such as monoethanolamine and diethanolamine. The weight average molecular weight of the modified polyolefin resin is not particularly limited, but is preferably 5,000 to 200,000, and more preferably 50,000 to 150,000. 5,000 or more is preferable from the viewpoint of improving the converging property of the glass fiber, and 200,000 or less is preferable from the viewpoint of emulsion stability in the case of water dispersibility.

  The modified polyamide resin is a modified polyamide compound in which a hydrophilic group such as a polyalkylene oxide chain or a tertiary amine component is introduced into a molecular chain, and can be produced by a known method. In the case of introducing a polyalkylene oxide chain into the molecular chain, for example, it is produced by copolymerizing a part or all of polyethylene glycol, polypropylene glycol or the like modified with diamine or dicarboxylic acid. When a tertiary amine component is introduced, for example, aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylaminoε-caprolactam and the like are copolymerized.

  The modified polyester resin is a resin of polycarboxylic acid or anhydride thereof and polyol, and has a hydrophilic group in the molecular skeleton including the terminal, and can be produced by a known method. Examples of the hydrophilic group include polyalkylene oxide groups, sulfonates, carboxyl groups, and neutralized salts thereof.

  Examples of the polycarboxylic acid or its anhydride include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and trifunctional or higher functional polycarboxylic acids.

Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and phthalic anhydride.
Examples of the sulfonate-containing aromatic dicarboxylic acid include sulfoterephthalate, 5-sulfoisophthalate, and 5-sulfoorthophthalate.
Aliphatic or alicyclic dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, succinic anhydride, and anhydrous And maleic acid.
Examples of the tri- or higher functional polycarboxylic acid include trimellitic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride, and the like.

  Among these, from the viewpoint of improving the heat resistance of the modified polyester resin, it is preferable that 40 to 99 mol% of the total polycarboxylic acid component is an aromatic dicarboxylic acid. Moreover, from the viewpoint of emulsion stability when the modified polyester resin is used as an aqueous dispersion, it is preferable that 1 to 10 mol% of the total polycarboxylic acid component is a sulfonate-containing aromatic dicarboxylic acid.

  Examples of the polyol include diols and trifunctional or higher functional polyols. Diols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, polytetramethylene Examples include glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A or an alkylene oxide adduct thereof. Examples of the tri- or higher functional polyol include trimethylolpropane, glycerin, pentaerythritol and the like.

  As the copolymerization ratio of the above polycarboxylic acid or its anhydride and polyol, the total weight of copolymerization is 100% by weight, and the polycarboxylic acid or its anhydride is 40 to 60% by weight, and the polyol is 40 to 60% by weight. Preferably, the polycarboxylic acid or its anhydride is 45 to 55% by weight, and the polyol is 45 to 55% by weight.

  The weight average molecular weight of the modified polyester resin is preferably 3,000 to 100,000, and more preferably 10,000 to 30,000. 3,000 or more is preferable from the viewpoint of improving the converging property of the glass fiber, and 100,000 or less is preferable from the viewpoint of emulsion stability when water dispersibility is achieved.

  The polymer and thermoplastic resin used as the binder may be used alone or in combination of two or more. However, the total amount of the binder is 100% by weight, and the acrylic acid homopolymer, acrylic acid and other co-polymers are used. It is preferable to use 50% by weight or more, particularly 60% by weight or more of at least one polymer selected from a copolymer with a polymerizable monomer and salts of these primary, secondary and tertiary amines.

(composition)
The glass fiber sizing agent preferably contains 0.1 to 2% by weight of a silane coupling agent, 0.01 to 2% by weight of a lubricant, and 1 to 25% by weight of a binder as solids. These ingredients are diluted with water and the total weight is adjusted to 100% by weight.

The blending amount of the silane coupling agent is preferably from 0.1 to 2% by weight, more preferably from 0.1 to 1%, from the viewpoints of improving the converging property of the glass fiber, improving the adhesive strength, and improving the mechanical strength of the rubber product. % By weight, particularly preferably 0.2 to 0.5% by weight.
The blending amount of the lubricant is 0.01% by weight or more, particularly from the viewpoint of providing sufficient lubricity, and from the viewpoint of improving the tensile breaking strength of the binding yarn by the air splicer and improving the opening property in the blending process. The content is preferably 02% by weight or more, and is preferably 2% by weight or less, particularly preferably 1% by weight or less, from the viewpoint of improving the adhesive strength and improving the mechanical strength of the rubber product.
The blending amount of the binding agent is preferably 1 to 25% by weight, more preferably 3 to 15% by weight, from the viewpoints of control of glass fiber bundling and improvement of adhesive strength and mechanical strength of rubber products. Preferably, it is 3 to 10% by weight.

(how to use)
The glass fiber sizing agent may be adjusted to any form, such as an aqueous solution, a colloidal dispersion form, or an emulsion form using an emulsifier, depending on the mode of use. From the viewpoint of improvement, an aqueous solution is preferable.

  The glass fiber used in the present embodiment is obtained by applying the sizing agent described above to a glass fiber using a known method such as a roller-type applicator in a known glass fiber production process, and drying the produced glass fiber. Can be obtained continuously. The sizing agent is preferably added in an amount of 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, particularly preferably 0.2 to 1% by weight, based on 100% by weight of the glass fiber. %. From the viewpoint of controlling the sizing property of the glass fiber and improving the adhesive strength, it is preferable that the amount of sizing agent applied is 0.1% by weight or more as a solid content with respect to 100% by weight of the glass fiber. On the other hand, it is preferably 3% by weight or less from the viewpoint of improving the tensile breaking strength of the connecting yarn by the air splicer and improving the spreadability in the fiber mixing process.

<Carbon fiber sizing agent>
On the other hand, for example, when carbon fiber is selected as the continuous reinforcing fiber, the sizing agent is preferably composed of a lubricant and a binding agent.

(lubricant)
The lubricant contributes to adjustment of the carbon fiber sizing agent, improvement in damage prevention, and improvement in fiber opening. As the lubricant, any ordinary liquid or solid lubricating material suitable for the purpose can be used. Although not limited to the following, for example, animal and plant or mineral waxes such as carnauba wax and lanolin wax, and surfactants such as fatty acid amides, fatty acid esters or fatty acid ethers, or aromatic esters or aromatic ethers Can be used.

(Binder)
The binding agent contributes to the improvement of the binding property and the adhesive strength of the carbon fiber. As the binder, a polymer or a thermoplastic resin suitable for the purpose can be used. Examples of the polymer include, but are not limited to, epoxy resins such as bisphenol A type epoxy resins, phenol resins obtained by reacting various phenols with formalin, urea resins obtained by reacting urea and formalin, and melamine Examples thereof include thermosetting resins such as melamine resins obtained by reacting formalin. For example, polyurethane resins obtained from isocyanates such as m-xylylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate and polyester or polyether diols are also preferably used. The

  Examples of the thermoplastic resin used as a binder include, but are not limited to, polyolefin resins, polyamide resins, polycarbonate resins, polyester resins, polyacetal resins, polyether ketones, polyether ether ketones, poly Examples include ether sulfone, polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluororesin, and modified thermoplastic resins obtained by modifying these. In the case of improving the adhesive strength between carbon fiber and rubber and attaching the sizing agent to the carbon fiber as an aqueous dispersion, the thermoplastic resin is modified from the viewpoint of reducing the ratio of the emulsifier component or eliminating the need for an emulsifier. Thermoplastic resins are preferred. Here, the modified thermoplastic resin means that, in addition to the monomer component that can form the main chain of the thermoplastic resin, different monomer components are copolymerized for the purpose of changing the properties of the thermoplastic resin, and hydrophilicity, crystallinity, and the like. Means a modified thermodynamic property.

  Examples of the modified thermoplastic resin include, but are not limited to, modified polyolefin resins, modified polyamide resins, and modified polyester resins.

  The modified polyolefin resin is a copolymer of an olefin monomer such as ethylene or propylene and a monomer copolymerizable with an olefin monomer such as an unsaturated carboxylic acid, and can be produced by a known method. A random copolymer obtained by copolymerizing an olefin monomer and an unsaturated carboxylic acid may be used, or a graft copolymer obtained by grafting an unsaturated carboxylic acid on an olefin may be used.

  Examples of the olefin monomer include ethylene, propylene, 1-butene and the like, and these can be used alone or in combination of two or more. Examples of the monomer copolymerizable with the olefin monomer include acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like. Saturated carboxylic acid etc. are mentioned, These can also be used individually or in combination of 2 or more types.

  As a copolymerization ratio of the above olefin monomer and a monomer copolymerizable with the olefin monomer, the total weight of the copolymerization is 100% by weight, and the olefin monomer can be copolymerized with 60 to 95% by weight. It is preferably 5 to 40% by weight of the monomer, more preferably 70 to 85% by weight of the olefin monomer, and more preferably 15 to 30% by weight of the monomer copolymerizable with the olefin monomer. If the weight percentage of the olefin monomer is less than 60 weight%, the affinity with rubber may be reduced. If the weight percentage of the olefin monomer exceeds 95 weight%, the water content of the modified polyolefin resin may be reduced. Dispersibility is lowered, and uniform application to continuous reinforcing fibers may be difficult, which is not preferable.

  In the modified polyolefin resin, a modified group such as a carboxyl group introduced by copolymerization may be neutralized with a basic compound. Examples of the basic compound include metal salts such as sodium hydroxide and potassium hydroxide; ammonia; amines such as monoethanolamine and diethanolamine. The weight average molecular weight of the modified polyolefin resin is not particularly limited, but is preferably 5,000 to 200,000, and more preferably 50,000 to 150,000. 5,000 or more is preferable from the viewpoint of improving the sizing property of the carbon fiber, and 200,000 or less is preferable from the viewpoint of emulsion stability in the case of water dispersibility.

  The modified polyamide resin is a modified polyamide compound in which a hydrophilic group such as a polyalkylene oxide chain or a tertiary amine component is introduced into a molecular chain, and can be produced by a known method. In the case of introducing a polyalkylene oxide chain into the molecular chain, for example, it is produced by copolymerizing a part or all of polyethylene glycol, polypropylene glycol or the like modified with diamine or dicarboxylic acid. When a tertiary amine component is introduced, for example, aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylaminoε-caprolactam and the like are copolymerized.

The modified polyester resin is a resin of polycarboxylic acid or anhydride thereof and polyol, and has a hydrophilic group in the molecular skeleton including the terminal, and can be produced by a known method. Examples of the hydrophilic group include polyalkylene oxide groups, sulfonates, carboxyl groups, and neutralized salts thereof.
Examples of the polycarboxylic acid or its anhydride include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and trifunctional or higher functional polycarboxylic acids.

Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and phthalic anhydride.
Examples of the sulfonate-containing aromatic dicarboxylic acid include sulfoterephthalate, 5-sulfoisophthalate, and 5-sulfoorthophthalate.
Aliphatic or alicyclic dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, succinic anhydride, and anhydrous And maleic acid.
Examples of the tri- or higher functional polycarboxylic acid include trimellitic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride, and the like.

  Among these, from the viewpoint of improving the heat resistance of the modified polyester resin, it is preferable that 40 to 99 mol% of the total polycarboxylic acid component is an aromatic dicarboxylic acid. Moreover, from the viewpoint of emulsion stability when the modified polyester resin is used as an aqueous dispersion, it is preferable that 1 to 10 mol% of the total polycarboxylic acid component is a sulfonate-containing aromatic dicarboxylic acid.

  Examples of the polyol include diols and trifunctional or higher functional polyols. Diols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, polytetramethylene Examples include glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A or an alkylene oxide adduct thereof. Examples of the tri- or higher functional polyol include trimethylolpropane, glycerin, pentaerythritol and the like.

  As the copolymerization ratio of the above polycarboxylic acid or its anhydride and polyol, the total weight of copolymerization is 100% by weight, and the polycarboxylic acid or its anhydride is 40 to 60% by weight, and the polyol is 40 to 60% by weight. Preferably, the polycarboxylic acid or its anhydride is 45 to 55% by weight, and the polyol is 45 to 55% by weight.

  The weight average molecular weight of the modified polyester resin is preferably 3,000 to 100,000, and more preferably 10,000 to 30,000. 3,000 or more are preferable from the viewpoint of improving the converging property of the carbon fiber, and 100,000 or less are preferable from the viewpoint of emulsion stability when water dispersibility is achieved.

  The polymer and thermoplastic resin used as a binder may be used alone or in combination of two or more.

(composition)
The carbon fiber sizing agent preferably contains 0.01 to 2% by weight of a lubricant and 1 to 25% by weight of a binder as solids, and these components are diluted with water to give a total weight of 100%. Adjust to%.

The blending amount of the lubricant is 0.01% by weight or more, particularly from the viewpoint of providing sufficient lubricity, and from the viewpoint of improving the tensile breaking strength of the binding yarn by the air splicer and improving the opening property in the blending process. The content is preferably 02% by weight or more, and is preferably 1% by weight or less, particularly preferably 0.5% by weight or less, from the viewpoint of improving the adhesive strength and improving the mechanical strength of the rubber product.
The blending amount of the binder is preferably 1 to 25% by weight, more preferably 3 to 15% by weight, particularly preferably from the viewpoints of control of carbon fiber bundling, improvement of adhesive strength, and improvement of mechanical strength of rubber products. Is 3 to 10% by weight.

(how to use)
The carbon fiber sizing agent may be adjusted to any form, such as an aqueous solution, a colloidal dispersion form, or an emulsion form using an emulsifier, depending on the mode of use. From the viewpoint of improvement, an aqueous solution is preferable.

  The carbon fiber used in the present embodiment is obtained by applying the sizing agent described above to a carbon fiber using a known method such as a roller-type applicator in a known carbon fiber production process, and drying the produced carbon fiber. Can be obtained continuously. The sizing agent is preferably added in an amount of 0.1 to 8% by weight, more preferably 0.2 to 5% by weight, particularly preferably 0.2 to 3% by weight, based on 100% by weight of carbon fiber. It is to be. From the viewpoint of controlling the sizing property of carbon fibers and improving the interfacial adhesive strength, it is preferable that the amount of sizing agent applied is 0.1% by weight or more as a solid content with respect to 100% by weight of carbon fibers. On the other hand, it is preferably 8% by weight or less from the viewpoint of improving the tensile breaking strength of the connecting yarn by the air splicer and improving the spreadability in the fiber mixing process.

<Other sizing agents for continuous reinforcing fibers>
Moreover, when using fibers other than glass fiber and carbon fiber as the continuous reinforcing fiber, it is preferable to set the type and amount of sizing agent according to the sizing agent used for the carbon fiber.

[Continuous organic fiber]
The continuous organic fiber used in this embodiment is a continuous cellulosic fiber and / or a continuous thermoplastic resin fiber, and it is preferable to use at least one fiber selected from the fibers exemplified below.

<Type>
Known continuous cellulose fibers can be used, for example, rayon produced by the viscose method, polynosic which is a rayon with a high degree of crystallinity having an average degree of polymerization of 450 or higher, high strength and high when wet. Examples include modal elastic rayon, lyocell obtained by organic solvent spinning method, cupra obtained by copper ammonia method, cellulose acetate acetate, triacetate, etc., from the viewpoint of strength and adhesiveness to rubber, rayon, Polynosic, modal and lyocell are preferred.
As the continuous thermoplastic resin fibers used in the present embodiment, known ones can be used. For example, polyolefin resins such as polyethylene and polypropylene, polyamide resins such as polyamide 6, polyamide 66, and polyamide 46, polyethylene terephthalate, Polyester resins such as polybutylene terephthalate and polytrimethylene terephthalate, polyacetal resins such as polyoxymethylene, polycarbonate resins, polyether ketone, polyether ether ketone, polyether sulfone, polyphenylene sulfide, thermoplastic polyetherimide, tetra Melt spinning at least one thermoplastic resin selected from thermoplastic fluororesins such as fluoroethylene-ethylene copolymers and modified thermoplastic resins obtained by modifying them. It is preferable obtained a continuous fiber. Among these, polyolefin-based resins, modified polyolefin-based resins, polyamide-based resins, and polyester-based resins are more preferable from the viewpoints of mechanical properties and general versatility, and polyamide-based resins and polyester-based resins are more preferable from the viewpoint of thermal properties. Particularly preferred. Further, from the viewpoint of durability against repeated load application and durability adhesion to rubber, a polyamide-based resin is particularly preferable, and polyamide 66 is most preferable.

<Polyamide resin>
The polyamide-based resin means a polymer compound having a —CO—NH— (amide) bond in the main chain. Examples thereof include polyamides obtained by ring-opening polymerization of lactam, polyamides obtained by self-condensation of ω-aminocarboxylic acid, polyamides obtained by condensing diamine and dicarboxylic acid, and copolymers thereof. It is not limited to. As the polyamide, one kind may be used alone, or two or more kinds may be used as a mixture.

The lactam is not limited to the following, and examples thereof include pyrrolidone, caprolactam, undecane lactam, and dodecalactam.
On the other hand, examples of the ω-aminocarboxylic acid include ω-amino fatty acid which is a ring-opening compound of the above lactam with water. The lactam or the ω-aminocarboxylic acid may be condensed using two or more monomers.

  Examples of the diamine (monomer) include linear aliphatic diamines such as hexamethylene diamine and pentamethylene diamine; branched aliphatic diamines such as 2-methylpentane diamine and 2-ethyl hexamethylene diamine; Aromatic diamines such as p-phenylenediamine and m-phenylenediamine; cycloaliphatic diamines such as cyclohexanediamine, cyclopentanediamine and cyclooctanediamine are listed.

Examples of the dicarboxylic acid (monomer) include aliphatic dicarboxylic acids such as adipic acid, pimelic acid and sebacic acid; aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Is mentioned.
Each of the diamine and dicarboxylic acid as the monomer may be condensed alone or in combination of two or more.

  Examples of the polyamide obtained as described above include polyamide 4 (poly α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), polyamide 12 (polydodecanamide), and polyamide 46 (polytetramethylene azide). Pamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), and polyamide 6I (polyhexamethylene isophthalamide) ), And copolymerized polyamides containing these as constituents.

  Examples of the copolymerized polyamide include a copolymer of hexamethylene adipamide and hexamethylene terephthalamide, a copolymer of hexamethylene adipamide and hexamethylene isophthalamide, and hexamethylene terephthalamide and 2-methylpentanediamine. Examples include terephthalamide copolymers.

<Form>
The continuous organic fibers used in the present embodiment are preferably substantially untwisted and substantially unentangled from the viewpoint of improving the spreadability in the blending process. Substantially no twist means a state in which there is no twist other than unintentional twist accompanying unraveling and the like, and the number of twists is 10 times / m or less. Substantially non-entangled means a state where the intentional entanglement by normal entanglement means such as fluid entanglement is the minimum number of times to maintain the handleability, and the number of entanglement is 5 times / m or less.
The number of single yarns of the continuous organic fibers is preferably 30 to 20,000 from the viewpoints of spreadability and handling properties in the blending process.

[Combination of continuous reinforcing fiber and continuous organic fiber]
In this embodiment, the product RD (reinforcing fiber) of the single yarn diameter R (μm) and the density D (g / cm ³ ) of the continuous reinforcing fiber, the single yarn diameter R (μm) and the density D (g / g) of the continuous organic fiber. cm ³ ) ratio RD (organic fiber), RD (reinforced fiber) / RD (organic fiber) is preferably 0.3 to 5, more preferably 0.5 to 4, particularly preferably 0. 6-2. In the fiber mixing step, it is preferable that the continuous reinforcing fiber and the continuous organic fiber are opened and mixed with each other. For this purpose, it is preferable that the acceleration generated in each fiber is substantially equal due to the external force that acts during fiber mixing. It is guessed. If the ratio of the product RD of both fibers is within the above range, it is presumed that the acceleration generated in each fiber is substantially equal, and the continuous reinforcing fiber and the continuous organic fiber are easily mixed with each other, which is preferable.

  In this embodiment, the ratio of the single yarn diameter of the continuous reinforcing fiber and the single yarn diameter of the continuous organic fiber is preferably 0.3 to 2, more preferably 0.5 to 1.5, and particularly preferably 0.00. 5-1. In the fiber mixing step, it is presumed that the continuous reinforcing fiber and the continuous organic fiber are preferably opened and mixed with each other. For this purpose, it is presumed that the external force acting during the fiber mixing is preferably substantially the same. If the ratio of the single yarn diameter is within the above range, it is presumed that the external forces acting on each fiber are substantially equal, and the continuous reinforcing fiber and the continuous organic fiber are easily mixed with each other, which is preferable. Furthermore, if the ratio of the single yarn diameter is within the above range, the single yarn diameter is substantially the same, and thus the geometric distribution state of both fibers in the composite yarn is likely to be uniform, which is preferable.

  In this embodiment, the total fineness of the continuous reinforcing fiber and the continuous organic fiber is preferably 100 to 20,000 dtex, more preferably 200 to 10,000 dtex, particularly preferably 500 to 5,000 dtex, and most preferably 500. ~ 3,000 dtex. The above range is preferable from the viewpoints of the spreadability and uniform mixing properties of both fibers in the fiber blending process, and the handling properties when obtaining rubber products.

  The content of each of the continuous reinforcing fiber and the continuous organic fiber is preferably 30 to 85% by weight / 70 to 15% by weight, and more preferably 40 to 70% by weight / 60 to 30% by weight. If the content of the continuous reinforcing fiber in the composite yarn is less than 30% by weight, the reinforcing effect of the rubber product is relatively low, the mechanical strength of the rubber product is relatively low, and the content of the continuous reinforcing fiber is If it exceeds 85% by weight, the effect of the continuous organic fiber compensating for the defects of the continuous reinforcing fiber such as insufficient adhesion to rubber, high specific gravity, and high price may be insufficient.

[Production method of composite yarn]
<Mixed fiber>
The 1st process of manufacturing the composite yarn of this embodiment is manufacture of the mixed yarn of a continuous reinforcement fiber and a continuous organic fiber. A known method can be used as a method for producing the mixed yarn. For example, after opening by external force due to electrostatic force, pressure by fluid spraying, pressure applied to rollers, etc., then opening and combining continuous reinforcing fibers and continuous organic fibers with the fibers opened and aligned, Two or more vortex turbulent zones created by fluids such as air, nitrogen gas, and water vapor are made almost parallel to the yarn axis, and fibers are guided to the zone so that they are not bulky under tension that does not cause loops or crimps. The so-called fluid entanglement (interlacing) method, which is used as the yarn, and the fluid entanglement method after opening the fibers after opening only the continuous reinforcing fibers or after opening both the continuous reinforcing fibers and the continuous organic fibers. Fluid entanglement methods such as a fluid entanglement method and a fluid entanglement method that are excellent in spreadability, can be mixed uniformly, and can be uniformly mixed are preferable.

  Supplying to the fluid entanglement nozzle with continuous organic fibers after opening or without opening the continuous reinforcing fibers is performed only on the continuous reinforcing fibers. It is preferable that the continuous reinforcing fiber can be prevented from being damaged without the turbulent turbulent flow caused by the fluid acting on it. Furthermore, supplying the aligned fibers substantially perpendicularly to the thread introduction hole surface of the fluid entanglement nozzle allows continuous reinforcing fibers to be applied without excessive elongation and compression force due to bending acting on the continuous reinforcing fibers. This is preferable because it can suppress damage. In particular, when glass fibers, carbon fibers, and ceramic fibers, which are brittle materials, are used as continuous reinforcing fibers, supplying the aligned fibers substantially perpendicularly to the thread introduction hole surface of the fluid entanglement nozzle has a damage suppressing effect. Is remarkable and preferable. In addition, when using aramid fibers that are susceptible to buckling failure due to compressive force as continuous reinforcing fibers, supplying the aligned fibers substantially vertically to the thread introduction hole surface of the fluid entanglement nozzle will cause buckling failure. It can be suppressed and is preferable. Here, “substantially perpendicular to the yarn introduction hole surface of the fluid entanglement nozzle” means a state where the yarn path can be confirmed to be vertical by visual observation.

Although the specific manufacturing method of the said mixed fiber yarn is not restrict | limited below, For example, the fluid entanglement method using the fluid entanglement apparatus illustrated in FIG. 1 is illustrated.
In FIG. 1, 11 is a wound body of continuous reinforcing fibers 12a, 21 is a wound body of continuous organic fibers 22a, 13 is a drive roll for pulling out the continuous reinforcing fibers 12a and the continuous organic fibers 22a while combining and drawing them together. , 14 is a fluid entanglement nozzle using compressed air, and 16 is a winder for winding the obtained mixed yarn 15b.

  According to this apparatus, the continuous reinforcing fiber 12a is pulled out while rotating the continuous reinforcing fiber wound body 11, and similarly, the continuous organic fiber 22a is pulled out and driven while rotating the continuous organic fiber wound body 21. After combining and drawing just before the roll 13, the drawn yarn 15 a is supplied to the fluid entanglement nozzle 14 through the drive roll 13. As shown in FIG. 2A, it is preferable to supply the aligned yarns 15a so as to be substantially perpendicular (90 degrees) to the yarn introduction hole surface of the fluid entanglement nozzle. The reason why the continuous reinforcing fibers 12a and the continuous organic fibers 22a are pulled out while rotating the respective wound bodies 11 and 21 is to prevent the continuous reinforcing fibers 12a and the continuous organic fibers 22a from being twisted.

The fluid entanglement nozzle 14 can use a well-known thing, for example, KC-AJI-L by Kyocera Corporation, ASM-4522 by Awa Spindle Co., Ltd., etc. are illustrated. For example, compressed air having a pressure of 1 to 3 kg / cm ² is supplied to the fluid entanglement nozzle to create two or more vortex turbulence zones in the nozzle. A non-bulky mixed fiber that does not cause loops or crimps by guiding the yarn 15a aligned in the zone and opening and mixing the continuous reinforcing fiber 12a and the continuous organic fiber 22a by the action of vortex turbulence. The yarn 15b. The obtained mixed fiber yarn 15b is wound up in the direction of arrow A by the winder 16. The processing speed defined by the winding speed may be appropriately determined in consideration of damage suppression to the continuous reinforcing fiber 12a and productivity, and examples thereof include 10 to 500 m / min.

The fluid supplied to the fluid entanglement nozzle is not particularly limited as long as it is a safe gas, and examples thereof include air, nitrogen, water vapor, helium, and argon. Air is preferable from the viewpoint of being inexpensive and easy to use. The pressure of the fluid is preferably 1 to ³ kg / cm ² from the viewpoint that the continuous reinforcing fibers 12a are not damaged and the continuous reinforcing fibers 12a and the continuous organic fibers 22a are continuously and uniformly mixed.

  In the mixed yarn for obtaining the composite yarn of this embodiment, it is preferable that the continuous reinforcing fiber and the continuous organic fiber are uniformly mixed, and the continuous organic fiber is substantially uniformly dispersed in the gap between the continuous reinforcing fibers. . Here, “distributed substantially uniformly” means that the number of continuous reinforcing fibers in contact with the single yarn of continuous organic fibers in any cross section of the mixed yarn is A (main) and continuous. The total number of single yarns of the reinforcing fibers is B (number), and the dispersion ratio of the continuous reinforcing fibers calculated by (A / B) × 100 (%) is 30 to 75%, preferably 40 to 75%. From the viewpoint of uniformly mixing the continuous reinforcing fiber and the continuous organic fiber and setting the twist strength maintenance rate of the mixed yarn to the range of the above formula (1), the dispersion rate is preferably 30% or more. The dispersion rate is preferably 75% or less from the viewpoint of suppressing damage to the continuous reinforcing fibers during blending and preventing the occurrence of fluff.

  In the mixed yarn, it is preferable that the continuous reinforcing fiber is not damaged at the time of mixing. Here, the fact that the continuous reinforcing fiber is not damaged means that the tensile breaking strength maintenance ratio obtained by dividing the tensile breaking strength of the mixed fiber yarn by the tensile breaking strength of the continuous reinforcing fiber yarn is 60% or more. . Since the continuous reinforcing fiber is not damaged and the occurrence of fluff is prevented, the tensile fracture strength maintenance rate is preferably 60% or more from the viewpoint of exerting the reinforcing effect of the rubber product.

<Twisted yarn>
The 2nd process of manufacturing the composite yarn of this embodiment is a process of twisting together the above-mentioned mixed fiber yarn. The twisting method uses a known twisting machine such as a ring twisting machine, double twister twisting machine, aroma twisting machine, etc., once twisting the mixed yarn, winding it, and combining two or more obtained twisted yarns. Even a method of twisting two or more blended yarns separately, and a method of twisting each other without winding the obtained twisted yarn may be used.
There is no restriction | limiting in particular about the kind of twisted yarn, a method, and the number of combined twists, As a kind of composite yarn, for example, a single twisted yarn, a mash twisted yarn, a picco mash twisted yarn, a strong twisted yarn etc. are mentioned. There are no particular restrictions on the number of twisted yarns, and there may be one twist, two twists, three twists, four twists, five twists, or six or more twists.
Moreover, what is necessary is just to select arbitrary twist numbers according to a use and use environment also about the number of twists, and generally the above-mentioned twist coefficient K is twisted in the range of 1000-30000. In order to obtain a composite yarn excellent in strength and dimensional stability, it is preferable to set the twisting tension to an appropriate range, and it is preferable to set both the lower twisting tension / upper twisting tension to 0.01 to 0.2 cN / dtex. . If it is the said range, there is little possibility of producing a sagging and an unreasonable distortion in twisting, and a uniform composite yarn is obtained and it is preferable.

  EXAMPLES Hereinafter, although an Example and a comparative example of this invention are given and demonstrated concretely, this invention is not limited only to these Examples.

〔Evaluation method〕
Hereinafter, evaluation methods performed in Examples and Comparative Examples will be described.
(Single yarn diameter of continuous reinforcing fiber and continuous organic fiber)
The single yarn diameter R (μm) of the continuous reinforcing fiber and the continuous organic fiber is represented by the following formula (1) using the density D (g / cm ³ ), the fineness T (dtex), and the number of single yarns F (the number) of the catalog value. Calculated.
R = 20 × (T / π · F · D) ^0.5 (1)

(Tensile rupture strength of continuous reinforcing fiber connecting yarns)
Select and install the air splicer chamber and chamber cover according to the fineness of the continuous reinforcing fiber using the joint air type 110 manufactured by Machinetex Co., Ltd. Obtained.
Supply air pressure 0.7 MPa
Scale 4 of air injection time adjustment knob PT150
Thread length Length Scale 4 of regulator PT40
The tensile strength at break of the obtained splicing yarn and continuous reinforcing fiber yarn was measured with a Tensilon manufactured by Orientec Co., Ltd. according to JIS L1013 at a gripping interval of 20 cm and a pulling speed of 20 cm / min, and the ratio of the two measured values was calculated. did.

(Dispersion rate of continuous reinforcing fiber)
Three points of 20 cm in length are sampled every 20 m in the longitudinal direction of the mixed fiber yarn, and the cross section (surface perpendicular to the yarn axis) is cut with a sharp blade for each sample collected. Take a photo of the whole area. From the photograph, the number of single yarns of continuous reinforcing fibers that would come into contact with a single yarn of continuous organic fibers or contact a single yarn of continuous organic fibers by shifting the position by 10% of the single yarn diameter was measured. (Book). The number of single yarns of continuous reinforcing fibers existing in the entire cross section of the composite yarn photographed in the photograph is measured, and this is designated as B (book). From the measured A and B, the average value (n = 3) of the dispersion rate% of the continuous reinforcing fibers was calculated by the following formula (5).
Dispersion rate = (A / B) × 100% (5)

(Tensile rupture strength maintenance ratio of mixed yarn)
The tensile breaking strength of the mixed yarn and the continuous reinforcing fiber yarn is measured according to JIS L1013 with a tensilon manufactured by Orientec Co., Ltd., with a grip interval of 20 cm, a pulling speed of 20 cm / min, and n = 10. The average value was obtained, and the ratio of both arithmetic average values was calculated and used as the maintenance rate.

(Twist strength maintenance rate of composite yarn)
The tensile breaking strength of the composite yarn and the mixed yarn is measured according to JIS L1013 with Tensilon manufactured by Orientec Co., Ltd., with a grip interval of 20 cm, a pulling speed of 20 cm / min, and n = 10. The ratio of both arithmetic mean values was calculated and used as the maintenance rate.

Examples 1 and 2
Glass fibers having a fineness of 660 dtex to which the following sizing agent A was attached at a weight of 660 dtex and 400 single yarns were used as continuous reinforcing fibers.
Composition of sizing agent A (solid content conversion):
Silane coupling agent: 0.6% by weight of γ-aminopropyltriethoxysilane [trade name: KBE-903 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
・ Lubricant: 0.1% by weight of wax [Brand name: Carnauba Wax (manufactured by Hiroyuki Kato)]
-Binder: 5% by weight of acrylic acid / maleic acid copolymer salt [trade name: Aqualic TL (manufactured by Nippon Shokubai Co., Ltd.)]
Table 1 shows the results of measuring the tensile breaking strength of the connecting yarns of this glass fiber.
Polyamide 66 fibers (trade name: Leona (registered trademark) 470 / 144BAU (manufactured by Asahi Kasei Fibers Co., Ltd.), fineness 470 dtex, number of single yarns 144) not subjected to entanglement treatment were used as continuous organic fibers.
After the fibers were combined and aligned, as shown in FIG. 2A, the fibers were supplied substantially vertically to the fluid entanglement nozzle and fluid entangled under the following conditions to obtain a mixed yarn.
-Fluid entanglement nozzle: Kyocera KC-AJI-L (1.5 mm diameter, propulsion type)
Air pressure: 2 kg / cm ² (Example 1), 4 kg / cm ² (Example 2)
Processing speed: 30 m / min Table 1 shows the results of measuring the dispersion ratio and tensile breaking strength of the obtained mixed fiber yarn.
Further, the mixed yarn was used, and after twisting in the Z direction using a ring twisting machine manufactured by Kaji Iron Works, two of these were twisted and twisted in the S direction to obtain a composite yarn. Both the lower twist tension and the upper twist tension were 0.05 cN / dtex, and both the lower twist number and the upper twist number were 380 times / m. Table 1 also shows the results of measuring the tensile strength at break of the obtained composite yarn and calculating the twist strength maintenance rate.

[Comparative Examples 1 and 2]
Example except that glass fiber alone (Comparative Example 1) is not subjected to special fiber mixing, and only glass fiber and polyamide 66 fiber are mixed and aligned (Comparative Example 2) and no special fiber mixing is performed. In the same manner as in No. 1, a composite yarn was obtained. In Comparative Example 1, the glass fiber was broken at the time when the lower twist was applied, and a twisted yarn could not be obtained.
The evaluation results are shown in Table 1.

Example 3
A composite yarn was obtained in the same manner as in Example 1 except that the number of single fibers of the glass fiber was 100.
The evaluation results are shown in Table 1.

Example 4
A composite yarn was obtained in the same manner as in Example 1 except that the number of single fibers of the glass fiber was 60.
The evaluation results are shown in Table 1.

Example 5
Other than using the stainless steel fiber [trade name: Naslon (registered trademark) (manufactured by Nippon Seisen Co., Ltd.), fineness 470 dtex, number of single yarns 72] to which the sizing agent A is attached as 1.0% by weight as continuous reinforcing fiber Produced a composite yarn in the same manner as in Example 1.
The evaluation results are shown in Table 1.

[Comparative Example 3]
A composite yarn was obtained in the same manner as in Example 5 except that the number of single yarns of stainless steel fiber was 36.
The evaluation results are shown in Table 1.

From Table 1 above, when Example 1 and Comparative Examples 1 and 2 are compared, not only continuous reinforcing fibers alone and mere splicing / alignment, but also continuous reinforcing fibers and continuous organic fibers are mixed by a fluid entanglement method or the like. When applied, the blended yarn has a high dispersion rate, is uniformly mixed, and the tensile breaking strength maintenance rate is equal to or higher than that. Therefore, it is confirmed that the twist strength maintenance rate is excellent when a composite yarn is used. did.
Further, when Examples 3 to 5 are compared with Comparative Example 3, when the product RD of the single yarn diameter (R) and the density (D) of the continuous reinforcing fiber is in a specific range, the joining yarn breaking strength of the continuous reinforcing fiber is It has been confirmed that it is high, excellent in spreadability and blendability, has a high dispersion rate of blended yarns, is uniformly mixed, and therefore has excellent twist strength maintenance rate when it is made into a composite yarn. .

Example 6
A composite yarn was obtained in the same manner as in Example 1 except that the adhesion amount of the sizing agent A was 2.0% by weight.
The evaluation results are shown in Table 2.

Example 7
A composite yarn was obtained in the same manner as in Example 1 except that the amount of the sizing agent A applied was 4.0% by weight.
The evaluation results are shown in Table 2.

Example 8
A composite yarn was obtained in the same manner as in Example 1 except that the binder was 0.5% by weight in terms of solid content.
The evaluation results are shown in Table 2.

Example 9
A composite yarn was obtained in the same manner as in Example 8 except that the amount of sizing agent deposited was 4.0% by weight.
The evaluation results are shown in Table 2.

Example 10
A composite yarn was obtained in the same manner as in Example 1 except that the continuous reinforcing fiber was twisted 50 times / m.
The evaluation results are shown in Table 2.

Example 11
As continuous organic fibers, polyamide 66 fibers having 72 single yarns (trade name: Leona (registered trademark) 470/72 BAU (manufactured by Asahi Kasei Fibers) fineness of 470 dtex, 72 single yarns) were used as in Example 1. A composite yarn was obtained.
The evaluation results are shown in Table 2.

Example 12
A composite yarn was obtained in the same manner as in Example 1 except that the polyamide 66 fiber used as the continuous organic fiber was entangled 15 times / m by the fluid entanglement method.
The evaluation results are shown in Table 2.

Example 13
A composite yarn was obtained in the same manner as in Example 1 except that polyethylene terephthalate fiber (Type 556 manufactured by Hyousung, fineness 470 dtex, number of single yarns 96) was used as the continuous organic fiber.
The evaluation results are shown in Table 2.

Example 14
Continuous reinforcing fibers and continuous thermoplastic resin fibers are each opened by electrostatic force, then mixed and aligned, and then mixed by the opening and combining yarn method in which the fibers are opened again by electrostatic force (no fluid entanglement) Except for the above, a composite yarn was obtained in the same manner as in Example 1.
The evaluation results are shown in Table 2.

Example 15
As shown in FIG. 2B, a composite yarn was obtained in the same manner as in Example 1 except that the aligned yarn was supplied to the fluid entanglement nozzle at substantially 45 degrees.
The evaluation results are shown in Table 2.

  From the above, the mixed yarn obtained by using continuous reinforcing fibers and continuous organic fibers having specific characteristics has a high dispersion rate and high tensile breaking strength maintenance rate, and therefore a composite yarn excellent in twist strength maintenance rate. Can be manufactured, and can be sufficiently applied to applications that require advanced characteristics such as rubber products for automobile parts.

  The composite yarn of the present invention is useful as a reinforcing material for rubber products such as tires, transmission belts, various belts such as V belts and timing belts, and various hoses such as radiator hoses, heater hoses and power steering hoses.

DESCRIPTION OF SYMBOLS 11 Continuous reinforcement fiber winding body 12a Continuous reinforcement fiber 21 Continuous organic fiber winding body 22a Continuous organic fiber 13 Drive roll 14 Fluid entanglement nozzle 15a Assortment yarn 15b Mixed fiber yarn 16 Winding roll

Claims (12)

Continuous reinforcing fiber and continuous organic fiber are mixed and twisted, and the product RD of single yarn diameter R (μm) and density D (g / cm ³ ) of continuous reinforcing fiber is 5 to 100 μm · g / cm. ³ der is, and twisting strength maintenance rate (%) is represented by the following formula (1):
Twist strength maintenance ratio (%) ≧ 100 × exp (−2.5 × K / 10 ⁵ ) (1)
{Wherein K is the following formula (2):
K = Y × Dt ^0.5 (2)
(Where Y is the number of twists per 1 m of twisted yarn (times / m), and Dt is the fineness (dtex) of the continuous reinforcing fiber). } . A composite yarn characterized by satisfying 2. The composite yarn according to claim 1, wherein a tensile breaking strength of a continuous yarn obtained by connecting the continuous reinforcing fibers by an air splicer is 50 to 100% of a tensile breaking strength of the continuous reinforcing fiber raw yarn. The continuous reinforcing fibers are in substantially non-twisted, and is substantially free entangled composite yarn according to claim 1 or 2. The continuous reinforcing fibers, glass fibers, carbon fibers, aramid fibers, ultra high strength polyethylene fibers, polybenzazole fibers, liquid crystal polyester fibers, at least one selected from the group consisting of polyketone fibers, metal fibers, and ceramic fibers in it, the composite yarn according to any one of claims 1-3. The ratio of product RD of the continuous organic fiber and the product RD of continuous reinforcing fibers (continuous reinforcing fiber / continuous organic fiber) is 0.3 to 5, the composite yarn according to any one of claims 1-4 Article. Wherein the ratio of the single yarn diameter of the continuous organic fiber and a single yarn size of continuous reinforcing fibers (continuous reinforcing fiber / continuous organic fibers) is 0.3 to 2, according to any one of claims 1 to 5 Composite yarn. Wherein the total fineness of the total fineness及 beauty said continuous organic fibers of the continuous reinforcing fibers 100～20,000Dtex, composite yarn according to any one of claims 1-6. The continuous organic fibers, and a substantially non-twisted, and is substantially free entangled composite yarn according to any one of claims 1-7. The continuous organic fibers, continuous cellulosic fibers 及 beauty / or a continuous thermoplastic resin fiber, a composite yarn according to any one of claims 1-8. The continuous thermoplastic resin fibers, polyolefin resins, polyamide resins, polyester resins, polyether ketone, polyether ether ketone, polyether sulfone, polyphenylene sulfide, of a thermoplastic polyetherimide, and thermoplastic fluororesin it is a continuous fiber composed of at least one thermoplastic resin selected from the group, the composite yarn of claim 9. Align pulling continuous reinforcing fibers continuous organic fibers, comprising the step of intermingling the fluid entangling method of producing a composite yarn according to any one of claims 1-10. The mixed fiber is aligned pull the continuous organic fiber and continuous reinforcing fibers, and is more performed in substantial fed perpendicularly to the introducing hole surface of the fluid entangling nozzles, The method according to claim 11.

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