KR20230164792A - Brake hose for hydrogen electric vehicles - Google Patents

Abstract

The present invention relates to a brake hose for a hydrogen electric vehicle. To be described in more detail, the center layer 10, the first fiber layer 20, the middle layer 30, the second fiber layer 40, and the outer layer 50 are interconnected. It exhibits excellent adhesion properties, does not cause rupture or separation between layers even under the pressure of brake fluid, has excellent heat resistance, and is effective in maintaining adhesion between layers despite temperature changes.
The brake hose according to the present invention has two fiber layers, such as a first fiber layer 20 and a second fiber layer 40, and thus has the effect of improving pressure resistance characteristics.

Description

Brake hose for hydrogen electric vehicles}

The present invention relates to a brake hose for a hydrogen electric vehicle. To be described in more detail, it includes a central layer through which brake fluid flows, a first fiber layer formed on the outer peripheral surface of the central layer, an intermediate layer formed on the outer peripheral surface of the first fiber layer, and the A brake hose for hydrogen electric vehicles that does not rupture or separate layers due to the pressure of brake fluid for hydrogen electric vehicles and has excellent heat resistance, including a second fiber layer formed on the outer peripheral surface of the middle layer and an outer layer formed on the outer peripheral surface of the second fiber layer. It's about.

In general, a brake hose is a hose that transmits the hydraulic pressure of brake oil (fluid) and is composed of flexible pipes to be used in relatively moving parts such as the car body and suspension.

That is, a brake hose composed of a commonly known flexible pipe can transmit the hydraulic pressure of brake oil by connecting the master cylinder operated by the brake pedal and the wheel cylinder provided in the wheel portion.

The brake hose is a very important part for ensuring the safety of automobiles, and generally consists of an inner layer filled with brake fluid, a fiber layer sequentially formed on the outer peripheral surface of the inner layer, a middle layer, and an outer layer.

In addition, because the brake hose is used in harsh environments for long periods of time, the required characteristics are diverse and are strictly regulated. In particular, expansion resistance to sensitively transmit the hydraulic pressure of brake fluid, fatigue resistance to vibration or bending, and corrosion resistance to brake fluid can be said to be particularly important characteristics. These properties depend on the adhesion between the fiber layer and the inner, middle, and outer layers surrounding them.

Generally, the fiber layer is formed by weaving or braiding mainly using polyvinyl alcohol fibers and polyethylene terephthalate fibers. Polyvinyl alcohol fiber is known as a material that provides excellent expansion resistance, and polyethylene terephthalate fiber is known as a material that has excellent expansion resistance at high temperatures, fatigue resistance, and corrosion resistance to brake fluid compared to polyvinyl alcohol fiber.

However, brake hoses using these fibers as a reinforcing fiber layer do not show satisfactory performance in terms of expansion resistance and liquid resistance. For example, even when using polyvinyl alcohol fibers, which are known to exhibit excellent expansion resistance, bending fatigue resistance, pressure resistance, and high adhesion between each layer are required due to the high hydraulic pressure of brake fluid, but unlike the excellent performance at room temperature, they are not When the number of braking increases due to long-term driving, the expansion resistance at high temperatures decreases due to an increase in the temperature of the brake fluid, which has the disadvantage of lowering braking performance.

Publication Patent No. 10-2019-0131228 (published on November 26, 2019)

The present invention is a technology developed to solve the problems caused by the prior art described above, and includes a central layer (10), a first fiber layer (20), a middle layer (30), a second fiber layer (40), and an outer layer (50). The purpose is to provide a brake hose for a hydrogen electric vehicle that can improve heat resistance and fatigue resistance by further mixing a resorcinol-formaldehyde-latex (RFL) mixed resin and an adhesive additive to the mixed resin.

The present invention, in order to realize the above-mentioned object, includes a central layer 10 through which brake fluid flows; A first fibrous layer (20) formed on the outer peripheral surface of the central layer; An intermediate layer (30) formed on the outer peripheral surface of the first fiber layer (20); A second fiber layer 40 formed on the outer peripheral surface of the intermediate layer 30; And an outer layer 50 formed on the outer peripheral surface of the second fiber layer 40.

In addition, the yarn constituting the center layer 10, middle layer 30, and outer layer 50 of the present invention is selected from ethylene propylene diene rubber, natural rubber, chloroprene rubber, styrene butadiene rubber, and isobutylene rubber. It includes one or more yarns, and the yarn constituting the first fiber layer 20 and the second fiber layer 40 is selected from polyester, polyvinyl alcohol, polyacrylic, polyamide, polyurethane, and polyimide. It is characterized in that it is composed of one or more pieces.

In addition, the first fiber layer 20 and the second fiber layer 40 of the present invention are characterized by a tensile strength of 12.0 kgf or more and an intermediate elongation of 3.7% or less at 4.5 kgf, as measured according to ASTM D 885.

In addition, the first fiber layer 20 and the second fiber layer 40 of the present invention include a plying step (S10) of plying a plurality of fiber filaments; A twist applying step (S20) of applying a twist to the braided filament; It is characterized in that it is manufactured including a step (S30) of immersing the filament of the twist imparting step (S20) in an adhesive composition containing a phenolic resin, a carbonyl compound, and a latex resin.

In addition, the carbonyl compound of the present invention is characterized in that it contains one or more compounds selected from formaldehyde, acetaldehyde, propionaldehyde, ketone, and furfural.

In addition, the latex resin of the present invention is characterized by comprising one or more selected from natural rubber, styrene-butadiene rubber, neoprene rubber, ethylene-propylene rubber, and hydrogenated nitrile butadiene rubber.

In addition, the adhesive composition of the present invention is characterized by further comprising an adhesion aid.

In addition, the adhesion aid of the present invention is characterized by comprising one or more selected from polyurethane prepolymer, ethylene glycol, 1,3-propylene glycol, 1.4-butadiol, and 1,6-hexanediol. Do it as

The brake hose for a hydrogen electric vehicle according to the present invention presented as described above exhibits excellent adhesion characteristics between the central layer, first fiber layer, middle layer, second fiber layer, and outer layer, and does not cause rupture or separation between layers even under the pressure of brake fluid. It has excellent heat resistance and is effective in maintaining interlayer adhesion even when temperature changes.

The brake hose according to the present invention has the effect of improving pressure resistance characteristics by having two fiber layers, such as a first fiber layer and a second fiber layer.

1 is a perspective view showing a brake hose for a hydrogen electric vehicle manufactured according to a preferred embodiment of the present invention.
Figure 2 is a flowchart showing a method of manufacturing the first fiber layer 10 and the second fiber layer 20 according to a preferred embodiment of the present invention.

Hereinafter, the brake hose for a hydrogen electric vehicle according to the present invention will be described in more detail through examples and comparative examples. However, the specific examples introduced below are provided as examples so that the idea of the present invention can be sufficiently conveyed to those skilled in the art.

Accordingly, the present invention is not limited to the specific examples presented below and may be embodied in other forms. The specific examples presented below are only described to clarify the spirit of the present invention, and the present invention is not limited thereto.

At this time, if there is no other definition in the technical and scientific terms used, they have meanings commonly understood by those skilled in the art to which this invention pertains, and the following description will not unnecessarily obscure the gist of the present invention. Descriptions of possible notification functions and configurations are omitted.

Additionally, as used in the specification and appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly dictates otherwise.

In addition, in the present invention, the term "twisted yarn" refers to a yarn that is twisted by adding more twist to a continuous fiber yarn or spun yarn, or by combining two or more yarns.

In addition, general twisting methods for the above-mentioned yarn include ordinary twisting or flat twisting, and special twisting or decorative twisting to produce special effects. By distinguishing the direction of twist, the left twist is called a left twist or Z twist, and the right twist is called a coincidence or S twist.

Machines used for the above twisting machine include a ring twister and a flyer twister. In Korea, the Italian-style flyer twister is often used for twisting yarns for long fibers, and like a two one twister, it rotates one turn. There is also a twist that is given twice. When creating various unusual shapes and effects, such as decorative twisters, special twisters or fancy twisters are used.

Hereinafter, a brake hose for a hydrogen electric vehicle according to a preferred embodiment of the present invention will be described in detail as follows.

First, in the present invention, the brake hose for a hydrogen electric vehicle is

A central layer (10) into which brake fluid flows; A first fibrous layer (20) (20) formed on the outer peripheral surface of the central layer (10); An intermediate layer (30) formed on the outer peripheral surface of the first fiber layer (20) (20); A second fiber layer (40) (40) formed on the outer peripheral surface of the intermediate layer (30); And an outer layer (50) formed on the outer peripheral surface of the second fiber layer (40) (40); It may be composed of a sequentially laminated structure.

In addition, the brake hose for a hydrogen electric vehicle is provided with a double fiber reinforcement layer and a polymer resin layer on the outer surface of the pipe through which the fluid directly passes in order to transport high-pressure fluid or transmit pressure, so as to improve the adhesion characteristics between each layer. At the same time, mechanical properties such as heat resistance and pressure resistance can be strengthened.

The central layer (10), middle layer (30), and outer layer (50) yarns, which are components of the present invention, are

It can be composed of a polymer resin that basically has the properties of rubber and has various physical properties depending on the characteristics required for a brake hose for hydrogen electric vehicles.

The central layer 10 is a layer through which brake fluid directly passes, and may be configured to have resistance to deformation due to high temperature of brake fluid and corrosion due to components of brake fluid.

In addition, the center layer 10, middle layer 30, and outer layer 50 yarns may include one or more yarns selected from ethylene propylene diene rubber, natural rubber, chloroprene rubber, and styrene butadiene rubber. You can.

The ethylene propylene diene rubber (EPDM) is a rubber with excellent weather resistance, ozone resistance, and heat aging resistance. Although its dynamic fatigue resistance is lower than that of other rubbers, heat aging resistance and weather resistance can be improved when mixed with other rubbers. .

The ethylene propylene diene rubber is a terpolymer of ethylene, propylene, and non-conjugated diene,

Specific examples of the non-conjugated diene include chain non-conjugated dienes such as 1,4-hexadiene, ethylidene norbornene (ENB), norbornadiene, methylene norbornene, dicyclopentadiene, and 2-methylnorbornene. Cyclic non-conjugated dienes such as bornadiene and 5-vinyl-2-norbornene can be used.

At this time, it is preferable to use ethylidene norbornene (ENB), which can match the vulcanization speed or degree of vulcanization with other rubbers.

The ethylene propylene diene rubber has an oxo number that determines the diene content of 15 to 35, preferably 18 to 25. If the non-conjugated diene amount of the ethylene propylene diene rubber is outside the above range, especially if it is kept above the above range, the crack growth resistance is extremely poor, so dynamic deformation may occur significantly and the mechanical strength may decrease.

In addition, the ethylene propylene diene rubber preferably has a Mooney viscosity of 10 to 100, more preferably 20 to 80, as measured at ML ¹⁺⁴ and 125°C according to ASTM D1646. Within the above range, processability of the inner layer, etc. can be secured, and at the same time, mechanical properties can also be satisfied.

In addition, when using the ethylene propylene diene rubber, it is preferable to mix it with one or more elastomer compositions to increase mechanical strength.

Examples of the elastomer composition include natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, and chloroprene rubber, which are mixed in an amount of 5 to 50 parts by weight based on 100 parts by weight of the ethylene propylene diene rubber. This is desirable because it can secure the heat resistance of the inner layer, etc. and at the same time greatly increase the mechanical properties.

The natural rubber (abbreviated as NR) is a rubber material obtained from natural plants, and refers to isoprene rubber whose main component is cis-1, 4-polyisoprene, mainly Hevea-brazili, which is native to the Amazon basin in South America. It can be used from the Heavea Brasiliensis rubber tree.

The chloroprene rubber (CR) can be manufactured by polymerizing 2-chromium-1, 3-butazene (chloroprene) with styrene, isoprene, and acrylonitrile, and has excellent oil resistance, wear resistance, and flame retardancy, making it suitable for electrical wires. , can be used as cable covering material, rubber belt, rubber lining, and adhesive.

The styrene butadiene rubber (abbreviated as SBR) is made by mixing and polymerizing styrene and butadiene at a weight ratio of 25:75, accounts for 80% of all synthetic rubber, and has cold resistance and elasticity compared to natural rubber. However, it has excellent heat resistance, abrasion resistance, aging resistance, durability, and gas permeability, so it can be used in lightweight tires, belts, and hoses.

Additionally, the central layer may be composed of various additives in addition to the rubbers described above.

In further explanation, the additive may further include one or more selected from fillers, softeners, vulcanizing agents, vulcanization accelerators, antioxidants, and co-vulcanizers.

The filler may be carbon black, graphite, Ketjen black, finely divided silicic acid, calcium carbonate, calcium carbonate, talc, and clay.

At this time, it is preferable to add 10 to 200 parts by weight of the filler based on 100 parts by weight of the ethylene propylene diene rubber because it can improve mechanical properties such as wear resistance, fatigue resistance, and dynamic fatigue resistance.

The softeners include petroleum-based softeners such as process oil, lubricant, paraffin, liquid paraffin, petroleum asphalt, and vaseline; Coltal-based softeners such as coaltal and coalpitch; Fatty oil-based softeners such as castor oil, linseed oil, fluid oil, and palm oil; tallyu; serve; Leads such as beeswax, powdered nauba wax, and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, and zinc laurate; Synthetic polymer materials such as petroleum resin, atactic polypropylene, and coumalin indene resin can be used.

The vulcanizing agent includes sulfur-based compounds such as sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and dimethyldithiocarbamic acid serene; Dicumyl peroxide, 2,5-dimethyl-2,5-di(tertiary butylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl- Organic substances such as 2,5-di(tertiary butylperoxy)hexyne-3, ditertiary butylperoxide, ditertiary butylperoxy-3,3,5-trimethylcyclohexane, and tertiary butylhydroperoxide. Peroxide can be used.

The vulcanization accelerator is N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N,N-diisopropyl-2-benzothiazole-sulfenamide, 2-Mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole, dibenzothiadyl -Thiazole-based compounds such as disulfides; Guanidine-based compounds such as diphenylguanidine, triphenylguanidine, diolsotriguanidine, orsotril-biguanide, and diphenylguanidine-phthalate; Aldehyde-amine or aldehyde-ammonia-based compounds such as acetoaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, and acetoaldehyde-ammonia reactant; Imidazoline-based compounds such as 2-mercaptoimidazoline; Thiourea-based compounds such as thiocarbaniride, diethylthiourea, dibutylthiourea, trimethylthiourea, and diolsotrithiourea; thiuram-based compounds such as tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, and pentamethylene thiuram tentrasulfide; Zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, sodium dimethyldithiocarbamate Dithioate-based compounds such as serine obacamic acid and terium diethyldithiocarbamate, and xanthate-based compounds such as zinc dibutyl xanthogenate can be used.

The antioxidant is added to increase heat resistance, and is 2-mercaptobenzimidazole or 4-(1-methyl-1-phenylethyl)-N-[4-(1-methyl-1-phenylethyl)phenyl. ]Aniline, etc. can be used.

The co-vulcanizers are used to promote vulcanization and increase mechanical properties, such as dicumyl peroxide, di(tetra-butylperoxyisopropyl)benzene, butyl 4,4-di(tetra-butylperoxy)valerate, etc. General peroxide, triallyl cyanurate, triallyl isocyanurate, zinc diacrylate, zinc dimethacrylate, N,N`-m-phenylene dimaleimide, and trimethoxypropane trimethacrylate. You can use it.

The first fiber layer 20 and the second fiber layer 40, which are components of the present invention, are

It is provided to prevent rupture of the brake hose due to brake fluid by controlling the expansion amount of the brake hose for hydrogen electric vehicles, and can be configured to satisfy a specific range of physical properties such as tensile strength and intermediate elongation.

In addition, the yarns of the first fiber layer 20 and the second fiber layer 40 are configured to satisfy the range of tensile strength of 12.0 kgf or more and intermediate elongation of 3.7% or less at 4.5 kgf as measured according to ASTM D 885. desirable.

When the tensile strength of the first fiber layer 20 and the second fiber layer 40 measured according to ASTM D 885 is less than 12.0 kgf, the yarns are vulnerable to friction, bending, and weathering, so the dimensional stability is reduced and easily deformed. This may occur, and if the intermediate elongation exceeds 3.7% at 4.5 kgf, a problem may occur in which the fatigue resistance of the yarns of the first fiber layer 20 and the second fiber layer 40 is reduced, so that the fibers composed of physical properties within the above range may occur. It is desirable.

In addition, the yarns of the first fiber layer 20 and the second fiber layer 40 may be configured to satisfy specific ranges in physical properties of elongation at break, shrinkage, rigidity, and adhesion.

The yarns of the first fiber layer 20 and the second fiber layer 40 have an elongation at break of 14.2% or less, a shrinkage rate of 3.7% or less, a stiffness of 1.5 g or less, and an adhesive force of 5.3 kgf or more, as measured according to ASTM D 885. It is desirable to configure it to be satisfactory.

If the yarns of the first fiber layer (20) and the second fiber layer (40) have an elongation at break measured in accordance with ASTM D 885 exceeding 14.2%, the shape of the yarn of the first fiber layer (20) and the second fiber layer (40) There may be a problem of temporary deformation, and if the shrinkage rate exceeds 3.7%, the yarn of the first fiber layer 20 and the second fiber layer 40 may break easily, and the rigidity is less than 1.5g. If it exceeds this, a problem may occur in which the amount of wear due to friction increases, and if the adhesive force is less than 5.3 kgf, a problem may occur in which the yarns of the first fiber layer 20 and the second fiber layer 40 are separated from other layers. It is desirable to configure it to satisfy physical properties within the range.

Meanwhile, the first fiber layer 20 and the second fiber layer 40 are

A plying step (S10) of plying a plurality of fiber filaments and a twisting step (S20) of applying a twist to the twisted filaments, and the filaments of the twisting step (S20) are mixed with a phenol-based resin, a carbonyl compound, and a latex resin. As the product is manufactured through a immersion step (S30) of immersing in an adhesive composition containing the immersion material and a drying step (S40) of drying the impregnated untwisted yarn of the plying step (S10), the adhesion of each layer is maintained at a constant level by using brake fluid. Braking force can be generated by directly transmitting hydraulic pressure to the wheels.

In addition, the plying step (S10) is a step of plying dozens of filament yarns, and strength, elongation, and mechanical properties can be secured.

The filament yarn can be used by mixing one or more materials selected from polyester, polyvinyl alcohol, polyacrylic, polyamide, polyurethane, and polyimide.

As an example of the polyester, polyethylene terephthalate yarn can be used. Compared to polyvinyl alcohol yarn, which is currently used as a reinforcing yarn for brake hoses, it has excellent heat resistance and, in particular, a small decrease in modulus at high temperatures, and has excellent mechanical properties. It is much easier to supply and cheaper than polyvinyl alcohol, and has excellent heat resistance, preventing deterioration of modulus at high temperatures.

However, in the case of polyethylene terephthalate yarn, the moisture content is low due to a lack of functional groups such as hydroxy groups (-OH), and the bonding property with the adhesive composition (RFL resin) described later is greatly reduced, so to compensate for this, yarns with functional groups are used. It is desirable.

That is, since the yarn constituting the first fiber layer 20 and the second fiber layer 40 is a filament bundle and includes several filaments, if necessary, a certain number of filaments of other components are braided to the polyethylene terephthalate filament. It can compensate for the insufficient physical properties of Additionally, by making the filament have a non-circular cross-section, the surface area of the filament can be expanded and strength and elongation can be maintained.

The polyvinyl alcohol (PVA) is a polymer compound obtained by saponifying polyvinyl acetate in alkali, acid, aqueous ammonia, etc., has good affinity for water, and has good tensile strength, impact resistance, and friction resistance.

The polyacrylic is a polymer compound manufactured by polymerizing acrylonitrile, has little discoloration by sunlight, and has good heat resistance and chemical resistance.

The polyamide can be made of nylon (for example, nylon 6 and nylon 6,6), which has an amide group in the main chain and has high affinity for moisture. The polyamide has a chemical bond between the amide groups or a covalent bond with the hydroxy group of the adhesive composition. It can be formed to further increase heat resistance and mechanical properties.

The polyurethane is a polymer compound made by combining alcohol groups and isocyanic acid groups with urethane bonds, and has good elasticity, durability, heat resistance, abrasion resistance, and chemical resistance.

The polyimide is a polymer of imide monomers, and is flexible and has good heat resistance, wear resistance, and chemical resistance.

The twist applying step (S20) is a step of applying twist to the braided filaments, and can improve the strength of the first fiber layer 20 and the second fiber layer 40.

In addition, the twist imparting step (S20) is performed by plying 10 to 2,000 monofilaments with a fineness of 1 to 10 denier to ensure the stability and pressure resistance of the working process, so that the final fiber fineness is 100. It is better to form it to 2,000 denier. If the final fiber fineness is less than the above range, pressure resistance may be reduced, and if it exceeds the above range, it is not easy to adjust the size of the brake hose.

When less than 10 monofilaments are twisted, the filament is likely to be cut during weaving or the contact area between the filament and the adhesive composition is reduced, which reduces durability, so it is preferable to adjust it to the above range.

At this time, the twist imparting step (S20) can be performed in the form of air textured yarn (ATY) using air pressure using a direct twisting machine or an interlace nozzle in which false twisting and twisting are carried out simultaneously. At this time, it is preferable to manufacture plied yarn with the same number of filament twists by simultaneously performing the lower twisting process and the upper twisting process, if necessary.

The immersion step (S30) involves immersing the filament of the twisting step (S20) in an adhesive composition containing a phenolic resin, a carbonyl compound, and a latex resin, and the center layer 10, the middle layer 30, and the outer layer (50) This is the step of providing adhesion to the adhesive.

In addition, the twist imparting step (S20) may include a heat treatment step (S21) of heat treatment to fix the twist of the filament.

The heat treatment step (S21) is preferably performed at a temperature of 100 to 200°C for 10 to 200 seconds, and it is desirable to provide tension to the fiber during the heating process so that the intermediate elongation can be controlled while providing temperature for each section.

In addition, the phenol-based resin is an addition condensate of phenol and formaldehyde, and phenol, cresol, xylenol, and resorcinol can be used, and has characteristics such as excellent heat resistance, heat resistance, electrical insulation, and chemical resistance. It can be used in electronics, aviation, space, insulators, automobile parts, and electrical products.

In addition, it is preferable to use resorcinol (m-dihydrobenzene) as the phenolic resin. Since it is a small molecule, it is uniformly distributed in the rubber during the compounding process to provide excellent physical and mechanical properties of the cured rubber product. It can provide steel cord adhesion, and has superior adhesion to rubber than phenol, cresol, and xylenol.

The resorcinol is an isomer of catechol and hydroquinone, and is a dihydric phenol with a hydroxy group bonded to the meta position of the benzene ring. It has a high heat resistance temperature and is used as a main ingredient in adhesives and paints.

In addition, the carbonyl compound is a general term for organic compounds having a carbonyl group, and is also called an oxo compound, and may be composed of one or more compounds selected from formaldehyde, acetaldehyde, ketone, and furfural.

In addition, formaldehyde is preferably used as the carbonyl compound, which is cheaper than acetaldehyde, ketone, and furfural and easily undergoes a condensation reaction with resorcinol.

The formaldehyde reacts with phenol (C ₆ H ₅ OH), melamine (C ₃ H ₆ N ₆ ), urea ((NH ₂ ) ₂ CO), etc. and is used as a raw material to make various thermosetting resins. The polymer produced by the reaction between the above urea and formaldehyde can be used in various adhesives.

Acetaldehyde is a highly volatile, colorless liquid and a compound with various reactivity, and can be used as a starting material for organic synthesis of resins, dyes, and chemicals.

In addition, the acetaldehyde can undergo a condensation reaction with resorcinol to obtain a liquefied resorcinol-type biomass resin, and after cooling to room temperature, it can be used as a resorcinol-type biomass resin adhesive.

The propionaldehyde is a structural isomer of acetone and is mainly used as a precursor for trimethyl ethane through condensation reaction with formaldehyde. It has a pungent rotting odor and is used in the manufacture of propionic acid, polyvinyl and other plastics, and rubber chemicals. It can be used as a synthesis agent, disinfectant, preservative, and flavoring agent.

In addition, the propionaldehyde can undergo a condensation reaction with resorcinol to obtain a liquefied resorcinol-type biomass resin, and after cooling to room temperature, it can be used as a resorcinol-type biomass resin adhesive.

The ketone is an organic compound having a carbonyl group bonded to two alkyl groups (or aryl groups). It can be obtained by oxidizing a secondary alcohol, and those with a small carbon chain are highly soluble in water.

In addition, the ketone may include acetone, acetophenone, and benzophenone, and the acetone is used to make paper coating, adhesives, and heat-sealing coatings.

The furfural is an aldehyde group attached to a furan ring, and is also called furan-2-carbaldehyde or α-furanaldehyde. It is an oil-like liquid with a special odor and can be left in the air. It becomes a yellow-brown resinous compound due to oxidation. It is soluble in water and easily soluble in ethanol, ether, etc. Its chemical properties are similar to benzaldehyde and it reacts with cannichar.

In addition, furfural is used as a raw material for adipic acid to synthesize nylon and is also used as a solvent, and can be condensed with resorcinol to obtain liquefied resorcinol-type biomass resin, and cooled at room temperature. It can later be used as a resorcinol type biomass resin adhesive.

In addition, the carbonyl compounds can be used individually, but it is better to mix two or more. When using a mixture of two or more as described above, it is most preferable to mix formaldehyde and acetaldehyde.

When formaldehyde and acetaldehyde are mixed with the phenolic resin resorcinol as described above, the curing speed is fast, making it suitable for use in adhesives, plywood, laminated materials, and surface coatings, and has excellent adhesion to rubber and fiber. .

In addition, when the resin is made using only the phenolic resin and the carbonyl compound, the adhesion to rubber is excellent, but the rigidity is high and it is easy to break, so the adhesive part is easily damaged when the structure is bent. Therefore, additional latex resin is added to make the adhesive composition. manufacture.

The latex resin may include one or more selected from natural rubber, styrene-butadiene rubber, neoprene rubber, ethylene-propylene rubber, and hydrogenated nitrile butadiene rubber.

The natural rubber (abbreviated as NR) is a rubber material obtained from natural plants, and refers to isoprene rubber whose main component is cis-1, 4-polyisoprene, mainly Hevea-brazili, which is native to the Amazon basin in South America. It is collected from the Heavea Brasiliensis rubber tree. Raw rubber is manufactured by collecting latex, which contains about 30 to 40 wt% of rubber powder, from rubber trees and drying the latex. Even in natural rubber, there are few examples of use of raw rubber, and the use of vulcanized rubber is common.

In addition, when the natural rubber is mixed with the phenolic resin and the carbonyl compound to produce an adhesive composition, it can prevent breakage by increasing flexibility.

The styrene-butadiene rubber (abbreviated as SBR) is made by mixing and polymerizing styrene and butadiene at a weight ratio of 25:75, accounts for 80% of all synthetic rubber, and has cold resistance, elasticity, etc. compared to natural rubber. Although it is low in heat resistance, wear resistance, aging resistance, durability, and gas permeability resistance, it is mainly used to make lightweight tires, belts, hoses, molded products, rubber plates, soles, etc. In latex form, it is used as an adhesive and sizing agent for paper.

In addition, the styrene-butadiene rubber can prevent breakage by increasing flexibility when manufacturing an adhesive by mixing it with the phenolic resin and carbonyl compound.

The neoprene rubber (abbreviated as NR), also called polychloroprene, is an oil-resistant synthetic rubber produced by radical polymerization of chloroprene. It has excellent weather resistance, ozone resistance, bending resistance, and chemical stability, and maintains flexibility over a wide temperature range.

In addition, the neoprene rubber can prevent breakage by increasing flexibility when manufacturing an adhesive by mixing it with the phenolic resin and carbonyl compound.

The ethylene-propylene rubber (abbreviated as EPR) is a rubber-like elastomer made by polymerizing ethylene and propylene. It has excellent durability, heat resistance, weather resistance, and electrical properties, and is used as an insulator for wire coverings, hoses, etc. It is used.

In addition, the ethylene-propylene rubber can be mixed with the phenolic resin and carbonyl compound to increase flexibility and prevent breakage when manufacturing an adhesive.

In addition, the ethylene-propylene rubber may be an ethylene-propylene-diene monomer (ethylene-propylene rubber, abbreviated as EPDM) copolymerized with a small amount of dienes such as ethylidene norbolene.

The hydrogenated nitrile butadiene rubber (abbreviated as HNBR) is a double bond portion of the nitrile-butadiene rubber polymer molecular structure that is hydrogenated, and has good wear resistance, hydrocarbon and diesel fuel, antioxidants, hydraulic oil, oil additives, ozone, It has excellent resistance to dilute acids and bases, and has high tensile strength.

In addition, the hydrogenated nitrile butadiene rubber can prevent breakage by increasing flexibility when manufacturing an adhesive by mixing it with the phenolic resin and carbonyl compound.

In addition, the latex resins can be used individually, but it is better to mix two or more. When using a mixture of two or more as described above, it is best to mix styrene-butadiene rubber and hydrogenated nitrile butadiene rubber. desirable.

That is, when mixing styrene-butadiene rubber, hydrogenated nitrile butadiene rubber, resorcinol, and formaldehyde, it has excellent heat resistance, weather resistance, bending resistance, ozone resistance, flexibility, tensile strength, and chemical stability, and has excellent adhesion to rubber or fiber. do.

Additionally, the adhesive composition of the present invention may further include additional additives in an amount that does not impair the properties of the present invention.

The additives include basic catalysts such as sodium hydroxide, potassium hydroxide, and ammonia, acid catalysts such as hydrochloric acid and sulfuric acid, paraffinic oils, naphthenic oils, aromatic oils, vegetable oils such as soybean oil and rapeseed oil, and dibutylphthalic acid ester or dioctyl. Phthalic acid esters such as phthalic acid esters, plasticizers such as liquid rubber such as liquid butadiene rubber, vulcanizing agents such as sulfur and benzoyl peroxide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and morpholinodithiobenzothia. Vulcanization accelerators such as sol, diphenyl thiourea, diphenyl guanidine, mercaptobenzothiazole, N-sulfenamide, zinc dimethyl dicarbamate, and metal oxides such as magnesium oxide and vulcanization accelerator. , anti-scorch agents such as phthalic anhydride and nitrosodiphenylamine, aging with N-isopropyl N'-phenyl-p-phenylenediamine, 2,6-di-t-butylcatechol, mercaptobenzimidazole, etc. Anti-oxidants, loosening agents such as thioxylenol and dizyle disulfide, lubricants such as wax and stearic acid, tackifiers such as terpene phenol, gum rosin, tall oil rosin, sodium bicarbonate, azodicarbonamide, p ,p'-oxybis(benzenesulfonylhydrazide) and other foaming agents, and there are no particular restrictions on their use.

In addition, the adhesive composition may be formed by adding an adhesion aid to provide reactivity to the fibrous layers of the first fibrous layer 20 and the second fibrous layer 40, improve fatigue resistance and pressure resistance, and maintain dimensional stability.

The adhesion aid is based on blocked isocyanate, and it is especially preferable to use lactam-blocked isocyanate. Examples of such isocyanates include s-caprolactam or d -4-4-diisocyanate diphenylmethane (MDI), toluene diisocyanate (TDI) and/or naphthyl isocyanate blocked with d-valerolactam ; NDI), etc. are preferably used, but are not limited thereto, and US 2002/0122938 A1 and the diisocyanate described therein can be used.

In addition, the adhesion aid may further include known blocking agents in addition to the above-mentioned isocyanate, examples of which include methyl ethyl ketoxime (butanone oxime, methyl amyl ketoxime) oximes such as amyl ketoxime and cyclohexanone oxime; phenol, resorcinol, cresol, trim ethyl phenol, tert. butyl phenol Monophenols such as (tert. butyl phenol); primary alcohols, secondary alcohols and tertiary alcohols, glycol ethers such as acetylacetone, malonic acid derivatives, secondary aromatic amines, etc. glycol ether), imides, mercaptans, and triazoles, but are not limited to these.

In addition, the adhesion aid can increase the reaction rate when a catalyst is added in the form of a metal compound. Examples of these catalysts include sodium, potassium, cesium, strontium, silver, cadmium, barium, cerium, uranium, titanium, chromium, tin, antimony, manganese, iron, cobalt, nickel, copper, zinc, lead, and calcium. and zirconium, among which zinc acetate, zinc sulfate, zinc carbonate, zinc oxide, zinc acetylacetonate, and zinc chloride are preferably used.

Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the following examples and comparative examples are only examples to explain the present invention in more detail, and the present invention is not limited to the following examples.

The physical properties of the specimens prepared through the following examples and comparative examples were measured as follows.

(Example 1)

It is composed of a central layer 10, a first fiber layer 20, a middle layer 30, a second fiber layer 40, and an outer layer 50, wherein the first fiber layer 20 and the second fiber layer 40 are The brake hose for a hydrogen electric vehicle manufactured by immersing it in an adhesive composition containing a phenolic resin, a carbonyl compound, and a latex resin was subjected to temperature changes and repeated stress (bending) to observe the presence or absence of defects in the brake hose.

(Comparative Example 1)

It is composed of a central layer 10, a first fiber layer 20, a middle layer 30, and an outer layer 50, wherein the first fiber layer 20 is an adhesive containing a phenolic resin, a carbonyl compound, and a latex resin. The brake hose for a hydrogen electric vehicle manufactured by immersing it in the composition was subjected to temperature changes and repeated stress (bending) to observe the presence or absence of defects in the brake hose.

(Comparative Example 2)

Temperature changes and repetitive stress (bending) are applied to the brake hose for a hydrogen electric vehicle, which is formed including the center layer 10, the first fiber layer 20, the middle layer 30, the second fiber layer 40, and the outer layer 50. The presence or absence of defects in the brake hose was observed.

(Adhesion measurement)

The specimens of Example 1 and Comparative Examples 1 to 2 were cut into lengths of 150 mm, widths of 10 mm, and heights of 10 mm, mounted on a tensile tester, and peeled at a speed of 200 m/min. Force at the moment of peeling was measured.

(Chemical resistance measurement)

Example 1 and Comparative Examples 1 to 2 The specimens were sequentially immersed in a 5N aqueous solution of sodium hydroxide and a 5N aqueous sulfuric acid solution for 24 hours in a constant temperature and constant humidity room at 200 degrees Celsius and 65% humidity, and then the tensile strength retention rate was measured. It was evaluated according to the following criteria. Unit is expressed as %.

100 to 95%: 10 points

94 to 90%: 9.0 points

89 to 85%: 8.0 points

84 to 80%: 7.0 points

Less than 79%: 6.0 points

(Heat resistance measurement)

The specimens of Example 1 and Comparative Examples 1 to 2 were left at 400 to 1000 degrees for 30 minutes in 200 degree increments, and then their tensile strength was measured and evaluated according to the following criteria. The unit is expressed as g (weight)/d (fineness, denier).

1100 to 1000g/d: 10 points

999 to 900g/d: 9.0 points

899 to 800g/d: 8.0 points

799 to 600 g/d: 7.0 points

Less than 500g/d: 6.0 points

(Measurement of defects and fatigue resistance during rotation)

When the brake hose is rotated while filled with fluid at a certain pressure, if the pressure inside the brake hose is reduced during rotation, harmful defects such as cracks, water leaks, and local expansion in the brake hose are measured.

The defect can be determined by determining whether the brake hose is decompressed through a pressure gauge, and the fatigue resistance of the brake hose can be measured by measuring the number of revolutions at the time of decompression.

150,000 to 141,000 rotations: 10.0 points

140,000 to 131,000 rotations: 9.0 points

130,000 to 121,000 rotations: 8.0 points

120,000 to 111,000 rotations: 7.0 points

Less than 110,000 rotations: 6.0 points

(Measurement of defects during repeated pressurization)

With one end of the brake hose fixed and the other end left free, repeatedly pressurize the inside of the brake hose through the fixed end. At this time, DOT4 brake fluid was filled internally through one fixed end and a pressure test was performed 150,000 times repeatedly at a pressure of 10 MPa or less, a pressure cycle of 2,500 cycles/hr, and a temperature of 100 degrees to prevent harmful effects such as cracks, water leaks, and local expansion of the brake hose. The presence or absence of defects was observed.

Cracks, water leaks, and local expansion all occur: O

When 1 or 2 of cracks, water leaks, or local expansion occur: △

No cracks, water leaks, or local expansion:

Example 1 Comparative Example 1 Comparative Example 2 adhesion 5.3kgf 4.8kgf 2.6kgf Chemical resistance 9.0 6.0 8.0 heat resistance 9.0 6.0 8.0 Fatigue resistance 10.0 7.0 8.0 presence or absence of defects X O O

As shown in Table 1, it is composed of a central layer 10, a first fiber layer 20, a middle layer 30, a second fiber layer 40, and an outer layer 50, with the first fiber layer 20 and the second fiber layer Example 1, where the fiber layer 40 was manufactured by immersing in an adhesive composition, consists of a center layer 10, a first fiber layer 20, a middle layer 30, and an outer layer 50, and the first fiber layer 20 is adhesive. Comparative Example 1 prepared by immersing in the composition or a comparison consisting of a center layer (10), a first fiber layer (20), a middle layer (30), a second fiber layer (40), and an outer layer (50), but without using an adhesive composition. It can be seen that the adhesion is better than Example 2, the chemical resistance, heat resistance, and fatigue resistance are high, and defects such as cracks, water leaks, and expansion do not occur.

Specifically, brake hoses for hydrogen electric vehicles must have high fatigue resistance due to high temperature and high pressure and corrosion due to brake fluid, that is, high chemical resistance. In the case of Comparative Example 1, which consists of only one fiber layer, the chemical resistance was that of Example 1. Significantly lower, heat resistance and fatigue resistance are low, defects occur,

In the case of Comparative Example 2, which did not contain an adhesive composition, it can be seen that the adhesive strength was significantly lower than that of Example 1, chemical resistance, heat resistance, and fatigue resistance were low, and defects occurred.

That is, the brake hose for a hydrogen electric vehicle includes a central layer 10, a first fiber layer 20, a middle layer 30, a second fiber layer 40, and an outer layer 50, and the first fiber layer 20 And it can be seen that it is preferable to manufacture the second fiber layer 40 by immersing it in an adhesive composition containing a phenol-based resin, a carbonyl compound, and a latex resin.

The above has been described with reference to preferred embodiments of the present invention, and is not limited to the above embodiments, and the scope of the present invention to those skilled in the art through the above embodiments without departing from the gist of the present invention. It can be implemented with various changes.

Center layer: 10 First fiber layer (20): 20
Middle layer: 30 Second fiber layer (40): 40
Outer layer: 50

Claims (8)

A central layer (10) into which brake fluid flows;
A first fiber layer (20) formed on the outer peripheral surface of the central layer (10);
An intermediate layer (30) formed on the outer peripheral surface of the first fiber layer (20);
A second fiber layer 40 formed on the outer peripheral surface of the intermediate layer 30; and
An outer layer 50 formed on the outer peripheral surface of the second fiber layer 40;
A brake hose for a hydrogen electric vehicle comprising:
According to paragraph 1,
The yarns constituting the center layer 10, middle layer 30, and outer layer 50 are,
Contains one or more selected from ethylene propylene diene rubber, natural rubber, chloroprene rubber, styrene butadiene rubber, and isobutylene rubber,
The yarns constituting the first fiber layer 20 and the second fiber layer 40 are,
A brake hose for a hydrogen electric vehicle, comprising one or more materials selected from polyester, polyvinyl alcohol, polyacrylic, polyamide, polyurethane, and polyimide.
According to paragraph 1,
The first fiber layer 20 and the second fiber layer 40,
A brake hose for a hydrogen electric vehicle, characterized in that it has a tensile strength of 12.0 kgf or more and an intermediate elongation of 3.7% or less at 4.5 kgf, as measured according to ASTM D 885.
According to paragraph 1,
The first fiber layer 20 and the second fiber layer 40,
A plying step (S10) of plying a plurality of filament yarns;
A twist imparting step (S20) of applying a twist to the braided filament yarn;
An immersion step (S30) of immersing the filament of the twist imparting step (S20) in an adhesive composition containing a phenolic resin, a carbonyl compound, and a latex resin; and
A brake hose for a hydrogen electric vehicle, characterized in that it is manufactured including.
According to paragraph 4,
The carbonyl compound is,
A brake hose for a hydrogen electric vehicle, comprising one or more of formaldehyde, acetaldehyde, propionaldehyde, ketone, and furfural.
According to paragraph 4,
The latex resin is,
A brake hose for a hydrogen electric vehicle, comprising one or more selected from natural rubber, styrene-butadiene rubber, neoprene rubber, ethylene-propylene rubber, and hydrogenated nitrile butadiene rubber.
According to paragraph 4,
The adhesive composition is,
A brake hose for a hydrogen electric vehicle, characterized in that it further includes an adhesive aid.
In clause 7,
The adhesion aid is,
A brake hose for a hydrogen electric vehicle, comprising one or more selected from polyurethane prepolymer, ethylene glycol, 1,3-propylene glycol, 1.4-butadiol, and 1,6-hexanediol.