KR102532532B1 - Composition for silicon-based insulating hose and preparation method for insulating hose - Google Patents

Abstract

Disclosed is an insulating hose with improved strength and heat resistance. The insulating hose according to the embodiment is made of silicone rubber as a raw material, and has improved satisfactory heat resistance, strength, and permanent compression set without being harmful to a human body. A method for manufacturing an insulating hose with improved strength and heat resistance comprises: a first step of adding extrusion solid silicone rubber and flame retardant solid silicone rubber to a double roller mixer and mixing the same; a second step of mixing heat-resistant powder containing cerium oxide and zirconium oxide with silicon gum, and mixing the mixture by adding the same to the double roller mixer according to the first step; a third step of preparing an inorganic pigment and mixing the inorganic pigment by adding the same to the double roller mixer according to the second step; a fourth step of mixing an extrusion curing agent and a curing agent containing peroxide, and mixing the mixture by adding the same to the double roller mixer according to the third step; and a fifth step of taking the mixture out of the double roller mixer and then compressing and forming the same.

Description

Composition for silicone-based insulating hose and manufacturing method of insulating hose {COMPOSITION FOR SILICON-BASED INSULATING HOSE AND PREPARATION METHOD FOR INSULATING HOSE}

The following embodiments relate to a composition for a silicone-based insulating hose and a manufacturing method technology for the insulating hose.

Demand for electric wires or hoses for automobiles or gaskets that can satisfy heat resistance, strength, and permanent compression set at the same time continues.

Korean Patent Registration No. 10-0878877 discloses "a rubber gasket composition for a plate type heat exchanger based on EPDM and a method for manufacturing a rubber gasket using the same. Here, 40 to 65% by weight of EPDM and 25 to 50% by weight of carbon black" , Oil 1 to 3% by weight, anti-aging agent 3 to 8% by weight, crosslinking agent 1 to 3% by weight, and crosslinking activator 3 to 8% by weight of the mixture was weighed and mixed with a rubber mixer (Kneader) to 120 to After sufficiently mixing within 20 minutes in the temperature range of 160℃, make it into a ribbon-shaped sheet on an open roll at 40~60℃, cool it in a cooling device, dry it, extrude it in a rubber extruder, and A rubber gasket composition prepared by crosslinking in a rubber compression press at a temperature of 160 to 200 ° C for 3 to 7 minutes, forming into a desired shape, and then packaging through a post-processing process was proposed.

Korean Patent Registration No. 10-1157161 discloses "a resin composition for a gasket, a gasket for sealing the door of a drum type washing machine using the same, and a drum type washing machine equipped with the gasket". 22 to 25% by weight of a thermoplastic elastomer including a styrene block and a diene block; 10 to 15% by weight of ethylene propylene diene (EPDM) vulcanized rubber having a shore A of 40A to 90A prepared by a dynamic crosslinking method of a polypropylene/ethylene propylene diene terpolymer rubber mixture; 5 to 8% by weight of polyphenylene ether resin; 4 to 5% by weight of polypropylene resin; 21 to 25% by weight of an oil component; A resin composition for gaskets containing 28 to 32% by weight of silica as an inorganic additive was proposed.

Such resin compositions are intended to improve heat resistance and compression set, but have not yet been provided at a satisfactory level, may contain many components harmful to the human body, and have unsatisfactory strength.

In this context, the present inventors have tried to provide an insulating hose with improved heat resistance, strength, and permanent compression set while using silicone rubber as a raw material and a component that is not harmful to the human body, and the composition and manufacturing method of the present invention The present invention was completed by confirming that it had an excellent effect.

Embodiments have a problem to solve in providing an insulating hose with improved heat resistance, strength, and permanent compression set, while using a component that is not harmful to the human body using silicone rubber as a raw material.

As one aspect for solving the above problems, the present invention,

A first step of adding and mixing the solid silicone rubber for extrusion and the flame retardant solid silicone rubber in a double roller mixer;

a second step of mixing silicon gum with a heat-resistant powder containing cerium oxide and zirconium oxide, and adding and mixing the mixture to the double roller mixer according to the first step;

a second step of preparing an inorganic pigment and adding and mixing the inorganic pigment to the double roller mixer according to the second step;

A third step of mixing an extrusion vulcanizer and a curing agent including peroxide, and mixing the mixture by adding it to the double roller mixer according to the third step; and

It provides a method for manufacturing an insulating hose with improved strength and heat resistance, including a fourth step of compressing and molding the mixture after taking it out of the double roller mixer.

According to one embodiment, the solid silicone rubber for extrusion has a thickness of 1.17 to 1.21 g/cm ³ , hardness of 66 to 74, plasticity of 230 to 380 mm/100, tensile strength of 6.0 to 10.1 MPa, and 330 to 620% It has an elongation of 55 to 65% of compression set (180 ° C / 22 h),

The flame retardant solid silicone rubber has a thickness of 1.44 to 1.47 g/cm ³ , hardness of 67 to 74, plasticity of 235 to 321 mm/100, tensile strength of 6.4 to 9.3 MPa, elongation of 180 to 280%, and elongation of 9 to 13%. It has a permanent compression set (180 ° C / 22 h) of

Based on 100 parts by weight of the total insulating hose, the solid silicone rubber for extrusion and the flame retardant solid silicone rubber may include 45 to 55 parts by weight and 20 to 30 parts by weight.

According to one embodiment, based on 100 parts by weight of the total insulating hose, the silicon gum, cerium oxide, and zirconium oxide may include 2.5 to 3.5 parts by weight, 1.5 to 2.5 parts by weight, and 0.5 to 1.5 parts by weight.

According to one embodiment, based on 100 parts by weight of the total insulating hose, the inorganic pigment may include 0.5 to 1.5 parts by weight of cadmium yellow, 0.25 to 0.75 parts by weight of cadmium red, and 0.25 to 0.75 parts by weight of titanium white.

According to one embodiment, the curing agent comprises Bis (2, 4-dichlorobenzoyl) peroxide, based on 100 parts by weight of the total insulating hose, the extrusion vulcanization agent and the curing agent include 5 to 9 parts by weight and 8 to 12 parts by weight it could be

An apparatus according to an embodiment may be combined with hardware and controlled by a computer program stored in a medium to execute any one of the methods described above.

The insulating hose according to the embodiment is improved in heat resistance, strength, and permanent compression set that are not harmful to the human body but are satisfactory by using silicone rubber as a raw material.

1 is a diagram showing a double roller mixer used in the manufacture of one embodiment.
2 is a view showing an electric wire coated using a hose according to an embodiment.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes can be made to the embodiments, the scope of the patent application is not limited or limited by these embodiments. It should be understood that all changes, equivalents or substitutes to the embodiments are included within the scope of rights.

Specific structural or functional descriptions of the embodiments are disclosed for illustrative purposes only, and may be modified and implemented in various forms. Therefore, the embodiments are not limited to the specific disclosed form, and the scope of the present specification includes changes, equivalents, or substitutes included in the technical spirit.

Although terms such as first or second may be used to describe various components, such terms should only be construed for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element.

It should be understood that when an element is referred to as being “connected” to another element, it may be directly connected or connected to the other element, but other elements may exist in the middle.

Terms used in the examples are used only for descriptive purposes and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which the embodiment belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

Advantages and features of the present invention, and methods of achieving them, will become clear with reference to the detailed description of the following embodiments taken in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms, only these embodiments make the disclosure of the present invention complete, and common knowledge in the art to which the present invention belongs. It is provided to fully inform the holder of the scope of the invention, and the present invention is only defined by the scope of the claims.

In the embodiments of the present invention, unless otherwise defined, all terms used herein, including technical or scientific terms, are the same as those commonly understood by one of ordinary skill in the art to which the present invention belongs. It has meaning. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the embodiments of the present invention, an ideal or excessively formal meaning not be interpreted as

The shapes, sizes, ratios, angles, numbers, etc. disclosed in the drawings for explaining the embodiments of the present invention are illustrative, so the present invention is not limited to the details shown. In addition, in describing the present invention, if it is determined that a detailed description of related known technologies may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. When 'includes', 'has', 'consists of', etc. mentioned in this specification is used, other parts may be added unless 'only' is used. In the case where a component is expressed in the singular, the case including the plural is included unless otherwise explicitly stated.

In interpreting the components, even if there is no separate explicit description, it is interpreted as including the error range.

The size and thickness of each component shown in the drawings are shown for convenience of description, and the present invention is not necessarily limited to the size and thickness of the illustrated components.

Each feature of the various embodiments of the present invention can be partially or entirely combined or combined with each other, and as those skilled in the art can fully understand, various interlocking and driving operations are possible, and each embodiment can be implemented independently of each other. It may be possible to implement together in an association relationship.

The silicone gum is added to impart functionality to the silicone rubber of the present invention, and a high molecular weight polysiloxane compound having a viscosity of about 1,000 to 5,000,000 cPs as measured by a Brookfield viscometer at 25° C. is used. Silicone gums can be classified by organic groups attached to siloxane side chains, and these organic groups may include methyl groups, vinyl groups, phenyl groups, fluoro groups, acryl groups, urethane groups, and the like. In the present application, when a silicone gum having a vinyl group is used, it is confirmed to have high fire resistance.

ASTM also classifies silicone gum as one with a methyl group, which includes molding, ultra-low temperature, low comprssion set, high tear, high tensile, oil resistance, and food.

As the inorganic pigment of the present invention, not only pigments having colors such as cadmium yellow, cadmium red, and chrome yellow, but also conventional types such as iron oxide, talc, lead oxide, strontium chromate, carbon black, titanium white, or barium sulfate may be used. there is. In the present invention, the content used is good in terms of effectiveness and economy to use 1 to 3 parts by weight based on 100 parts by weight of the total hose composition.

The extrusion vulcanizing agent serves to improve elasticity and stability, and may be included in an amount of 6 to 8 parts by weight based on 100 parts by weight of the total hose composition. If the extrusion vulcanization agent is less than 6 parts by weight, elasticity, stability and flame retardancy may be deteriorated, and if the extrusion vulcanization agent exceeds 8 parts by weight, problems may occur in curing during hose manufacture.

The curing agent is added to perform the curing process of the silicone rubber dough.

In general, silicone rubber is cured by crosslinking siloxane chains by an addition reaction between polysiloxane containing a vinyl group and polysiloxane having a Si-H bond. During the curing reaction, it serves to cross-link the silicone hydrides of the solid silicone rubber, which is the main component of the silicone rubber dough.

Hereinafter, the configuration of the present invention and its effects will be described in more detail through specific examples and comparative examples. However, these examples are for explaining the present invention in more detail, and the scope of the present invention is not limited to these examples.

Example 1. Composition for insulating hose and manufacturing method of insulating hose

As a solid silicone rubber for extrusion, Dow's RBB-2070-70 was prepared. Density (21 to 25°C) is 1.20 (1.17 to 1.21) g/cm ³ , hardness (JIS-TYPE-A) is 70 (66 to 74), plasticity is 290 (230 to 380) mm/100, It satisfies that the tensile strength (JIS Cutter K6251 Pattern 3, DIE 3) is 9.1 (6.0 to 10.1) MPa, the elongation is 480 (330 to 620) %, and the permanent compression set (180 ° C / 22 h) is 60%.

As a flame retardant silicone rubber, Dow's RBB-6300-70 was prepared. Density (21 to 25°C) is 1.45 (1.44 to 1.47) g/cm ³ , hardness (JIS-TYPE-A) is 72 (67 to 74), plasticity is 262 (235 to 321) mm/100, It satisfies that the tensile strength (JIS Cutter K6251 Pattern 3, DIE 3) is 7.9 (6.4 to 9.3) MPa, the elongation is 200 (180 to 280) %, and the permanent compression set (180 ° C / 22 h) is 11%.

A silicone rubber dough was prepared by mixing 50 kg of the solid silicone rubber for extrusion and 25 kg of the flame retardant silicone rubber, and compounding using an 18-inch two-roll mixing facility.

Next, 2 kg of cerium oxide and 1 kg of zirconium oxide were added to 3 kg of silicone gum (AB109409 from ABCR Chemical) containing a vinyl group, followed by stirring. The mixture was added while continuously mixing the silicone rubber dough.

Next, a mixture of 1,000 g of cadmium yellow, 500 g of cadmium red, and 500 g of titanium white was prepared as an inorganic pigment, and then added to the silicone rubber dough in a mixing state.

Next, 7 kg of an extrusion vulcanization agent and 10 kg of a curing agent were added to the silicone rubber dough on a roller and prepared in a sheet form. As the curing agent, 10 kg of PERKADOX PD-50S-PS containing Bis(2,4-dichlorobenzoyl) peroxide and silicone oil from Akzo Noble Polymer Chemical was used.

Finally, a hose was prepared and packaged by compressing to a thickness of 10 mm.

Comparative Examples 1 to 10

A composition for a hose was prepared in the same manner as in Example 1, but the composition was changed so that there were differences as shown in Table 1 below. In the table below, ““ indicates the same conditions as in Example 1.

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Solid silicone rubber for extrusion 50kg 75kg 0kg 40kg - - - - - Flame retardant solid silicone rubber 25kg 0kg 75kg 30kg - - - - - silicon sword Contains 3 kg of vinyl groups - - - 3 kg containing phenyl group - - - - heat resistant powder 2 kg of cerium oxide and 1 kg of zirconium oxide - - - Cerium Oxide 3kg Zirconium Oxide 3kg 1 kg of cerium oxide and 2 kg of zirconium oxide - inorganic pigment 2kg - - - - - - - - extrusion vulcanization agent 7kg - - - - - - - - curing agent Bis(2,4-dichlorobenzoyl) peroxide 50% containing 10kg - - - - - - - 10 kg containing 50% dibenzoyl peroxide

Experimental Example 1. Comparison of physical properties of hoses according to Examples and Comparative Examples

Table 2 below measures the tensile strength, tear strength, heat resistance tensile strength change rate (%), and compression set (%) of hose samples according to Examples and Comparative Examples of the present invention, respectively. The heat resistance test was measured according to KS M ISO 188, and the change in tensile strength was measured after heat treatment at 150 ° C for 70 hours. The compression set test was measured according to KS M6518, and the measurement condition was 25% compression for 22 hours at 150 ℃, and the compression set under these conditions was measured.

tensile strength
(kgf/cm ² ) tear strength
(kgf/cm) Heat resistance tensile strength change rate (%) Permanent compression set (%) Example 1 23.5 9.64 -15 21 Comparative Example 1 18.7 7.47 -53 45 Comparative Example 2 13.5 4.61 -22 32 Comparative Example 3 19.5 7.89 -25 38 Comparative Example 4 18.4 8.31 -17 31 Comparative Example 5 15.2 4.92 -25 35 Comparative Example 6 17.0 7.91 -27 29 Comparative Example 7 17.3 8.02 -29 25 Comparative Example 8 15.2 5.25 -18 43

Comparing Comparative Examples 1 to 3 with Example 1, it was confirmed that the solid silicone rubber for extrusion and the flame retardant solid silicone rubber were used at the same time, and in particular, when the composition of Example 1 was used, the strength increased and particularly the heat resistance significantly increased. .

Comparing Comparative Example 4 and Example 1, it was confirmed that the strength was improved when the vinyl group-containing silicone gum was used.

Comparing Comparative Examples 5 to 7 with Example 1, it was confirmed that when cerium oxide and zirconium oxide were included in the combination, particularly in the composition of the examples, not only the heat resistance was significantly improved, but also the strength was partially improved.

Comparing Comparative Example 8 and Example 1, when using a curing agent containing Bis (2, 4-dichlorobenzoyl) peroxide, it was confirmed that the effect was significantly improved in terms of strength.

Claims (3)

As a first step of adding and mixing the solid silicone rubber for extrusion and the flame retardant solid silicone rubber in a double roller mixer,
The solid silicone rubber for extrusion has a thickness of 1.17 to 1.21 g/cm ³ , hardness of 66 to 74, plasticity of 230 to 380 mm/100, tensile strength of 6.0 to 10.1 MPa, elongation of 330 to 620%, and elongation of 55 to 65 % permanent compression set (having 180 ° C,
The flame retardant solid silicone rubber has a thickness of 1.44 to 1.47 g/cm ³ , hardness of 67 to 74, plasticity of 235 to 321 mm/100, tensile strength of 6.4 to 9.3 MPa, elongation of 180 to 280%, and elongation of 9 to 13%. The permanent compression set (having 180 ℃,
Based on 100 parts by weight of the total insulating hose, the solid silicone rubber for extrusion and the flame retardant solid silicone rubber include 45 to 55 parts by weight and 20 to 30 parts by weight, a first step;
a second step of mixing silicon gum with a heat-resistant powder containing cerium oxide and zirconium oxide, and mixing the mixture by adding it to the double roller mixer according to the first step;
A third step of preparing an inorganic pigment and mixing the inorganic pigment by adding it to the double roller mixer according to the second step;
A fourth step of mixing an extrusion vulcanization agent and a curing agent including peroxide, and adding and mixing the mixture to the double roller mixer according to the third step; and
A method for manufacturing an insulating hose with improved strength and heat resistance, comprising a fifth step of compressing and molding the mixture after taking it out of the double roller mixer.
According to claim 1,
The silicone gum is a silicone gum containing a vinyl group,
Based on 100 parts by weight of the total insulating hose, the silicon gum, cerium oxide and zirconium oxide are 2.5 to 3.5 parts by weight, 1.5 to 2.5 parts by weight, and 0.5 to 1.5 parts by weight of an insulating hose with improved strength and heat resistance, manufacturing method.


delete

Images