KR20050012595A - A complex materials having temperature maintenance and shock absorbing function - Google Patents

Abstract

PURPOSE: Provided is an impact-absorbing composite functional material which can maintain temperature and is applied to the inner sole of shoes or an electrical, electronic, industrial or construction material. CONSTITUTION: The impact-absorbing composite functional material comprises an impact-absorbing polymer material as a base; a crosslinking agent; an additive for rubber; and a phase transfer material. Preferably the impact-absorbing polymer material is at least one selected from the group consisting of a styrene-based block copolymer, a styrene-butadiene rubber, 1,2-polybutadiene, an acryl rubber, an epoxylated natural rubber, a poly(vinyl chloride) resin, a poly(vinyl chloride)-nitrile rubber composite and a butyl rubber; and the phase transfer material has a phase transfer temperature of -5.5 to 40 deg.C and is prepared into a microcapsule shape.

Description

A complex materials having temperature maintenance and shock absorbing function}

The present invention relates to a shock absorbing composite functional material having a temperature holding function, and more particularly, having a high heat storage and heat dissipation due to the phase transition characteristics by combining a material exhibiting phase transition characteristics to a polymer material capable of expressing shock absorption At the same time, a polymer material used as a substrate relates to a composite functional material exhibiting shock absorption characteristics.

As one method for improving energy efficiency, currently, thermal storage methods using phase change materials have been actively studied. Phase change material means a material capable of absorbing or dissipating a lot of heat while changing phase from solid to liquid, liquid to gas, or vice versa without changing the temperature at a specific temperature. As such, the heat absorbed or released while the phase change material maintains the same temperature during phase transition is called latent heat. Heat associated with phase transition between the solid and liquid is called heat of fusion or heat of fusion, and heat associated with phase change between liquid or solid and gas. Is called the heat of vaporization. Water is a phase-change material between solid and liquid at 0 ° C, and has a latent heat of fusion of 80 cal / g when ice melts at 0 ° C. That is, when ice turns into water, it is kept at 0 ° C until it absorbs 80 calories of heat per gram of ice from the surroundings. There are a myriad of materials that cause phase transitions at various temperatures, and in recent years, the ultrafine encapsulation of these phase transition materials has been attempted to apply them to various fields that require thermal efficiency enhancement, temperature control, energy saving effect, and application.

Shock-absorbing materials are widely used as functional parts in areas requiring shock absorption as living materials or industrial materials based on various polymers.

Such shock absorbers can be broadly classified into non-foamed foams and foams. Polynorbornene rubber and silicone gels or polyurethane gels are used as non-foamed foams, which are relatively good in absorbing shocks, but have a high price due to high unit cost of rubber itself. It is expensive and has a high specific gravity compared to foam. As foams, shock absorbers are manufactured using ethylene-propylene-diene rubber, ethylene vinyl acetate, or chloroprene rubber, but these foams have the advantage of being lighter than non-foamed foams, but they have poor impact absorption and poor physical properties. Have

The present invention has been made to solve the above problems, by providing a shock-absorbing polymer material based on the phase-transfer material to provide a multi-functional material at the same time to express the temperature holding function including the shock absorber and heat storage and heat dissipation. Is in.

In particular, the present invention overcomes the limitation of the material having only one existing function each by giving two products maximized in one product through the shock-absorbing composite functional material having a temperature holding function manufactured as described above Its purpose is to provide new composite functional materials.

Another object of the present invention is a shock absorber having a temperature holding function, characterized in that it can be applied to various applications such as electrical and electronics, industrial and building materials as well as parts that require both the temperature holding function and shock absorbing properties at the same time, such as a shoe insole To provide a multifunctional material.

1 is a differential scanning calorimeter (DSC) graph of a shock absorbing composite functional material having a temperature maintaining function of Example 1 according to the present invention;

Figure 2 is a differential scanning calorimeter (DSC) graph of the shock absorbing composite functional material having a temperature holding function of Example 2 according to the present invention

Hereinafter, a preferred embodiment according to the present invention will be described in detail. It should be noted that in the following description, only parts necessary for understanding the manufacturing method of the present invention will be described, and descriptions of other parts will be omitted so as not to distract from the gist of the present invention.

The present invention uses a shock absorbing polymer material as a base material, in which a crosslinking agent, a conventional rubber additive, and a phase change material are mixed to express a temperature retention function and a shock absorbency simultaneously,

As the shock absorbing polymer material used as the substrate, styrene block copolymer, styrene / butadiene rubber, 1,2-polybutadiene, acrylic rubber, epoxidized natural rubber, polyvinyl chloride resin, polyvinyl chloride / nitrile rubber composite, Use one or more of butyl rubber. In this case, one or more of various materials, such as thermoplastic elastomers, rubbers, and polyolefins, may be selected and added to 30% by weight.

In the shock-absorbing polymer material, the styrene-based block copolymer is a hard block, and polystyrene forms a freeze-constrained phase, and its mechanical properties are expressed by the hard block. The soft block is composed of 3,4-linked polyisoprene, and the glass transition point (Tg) of the soft phase is determined according to the content of 3,4-bond. Particularly, in the present invention, as the block copolymer, not only the content of 3,4-bonds but also hydrogenated structures can be used, and there are no limitations on saturated or unsaturated structures, but the glass transition point of the soft block is -20. If it is a range of -20 degreeC, it can be used.

In addition, the styrene / butadiene rubber is a solution-polymerized, and can be used if the glass transition point of the rubber is in the range of -40 to -10 ° C, and the butadiene-hydrogenated structure may be used. The 1,2-polybutadiene preferably has a syndiotactic conformation, and the acrylic rubber is preferably a copolymer (ACM) of an alkyl ester of acrylic acid and a crosslinkable monomer containing a small amount of chlorine.

Generally, polymer blends made of such substrates can be crosslinked for physical properties, performance and durability, and these properties are directly related to the number and type of crosslinks formed during the crosslinking reaction.

As a crosslinking form that can be used in the present invention, a sulfur crosslinking mechanism and an organic peroxide crosslinking mechanism may be used.

In the sulfur crosslinking mechanism, it is preferable to add sulfur to 0.1 to 10 parts by weight based on 100 parts by weight of the base material and 0.01 to 8 parts by weight of a vulcanization accelerator based on 100 parts by weight of the base material.

The vulcanization accelerator used may be selected from one or more of aldehydes, ammonia, aldehydes, amines, guanidines, thioureas, thiazoles, sulfenamides, thiurams and dithiocarbamate salts. Can be.

In addition, in order to activate the vulcanization accelerator, the vulcanization accelerator may be used in an amount of 0.01 to 8 parts by weight based on 100 parts by weight of the substrate, and the vulcanization accelerator may be selected from metal oxides such as zinc oxide and fatty acids such as stearic acid.

In the organic peroxide crosslinking mechanism, 0.05 to 10 parts by weight of the organic peroxide can be used with respect to 100 parts by weight of the base material, and if it is less than 0.05 parts by weight, the crosslinking is insufficient.

Examples of the crosslinking agent usable in the present invention include cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxylaurylate, t-butylperoxyacetate, and di-t-butyl as organic peroxides. Diperoxyphthalate, t-dibutyl peroxymaleic acid, t-butyl cumyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, dibenzoyl peroxide, dicumyl peroxide, 1,3-bis (t- Butylperoxyisopropyl) benzene, methylethylketone peroxide, di- (2,4-dichlorobenzoyl) peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, 2,5- Dimethyl-2,5- (t-butylperoxy) -3-hexyne, n-butyl-4,4-bis (t-butylperoxy) valerate, α, α'-bis (t-butylperoxy) One from diisopropylbenzene or the like or It can be used to select at least.

In addition, in the present invention, in order to shorten the molding time during peroxide crosslinking and to obtain an appropriate crosslinking structure, the crosslinking aid may be used in an amount of 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the substrate.

The crosslinking aids are, for example, sulfur, p-quinonedioxime, p, p-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine and trimethylolpropane- Peroxy crosslinking aids such as N, N'-m-phenylenedimaleimide; Divinylbenzene, triarylcyanurate (TAC) and triarylisocyanurate (TAIC); Polyfunctional methacrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and aryl methacrylate; One or more polyfunctional vinyl monomers, such as vinyl butyrate and vinyl stearate, can be selected and used.

The phase change material used in the present invention uses a microcapsule type microencapsulated using a phase change material having a phase transition temperature of -5.5 to 40 ° C. The microcapsules have a structure of a core and a shell. The core is composed of a phase change material, and the cell is mainly made of a polymer material. The amount of the microcapsules may be used in an amount of 2 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the substrate.

In addition, in the present invention, various pigments may be used in consideration of a tackifier, an extended oil, a filler, an antioxidant, an ozonation inhibitor, and a color as a conventional rubber additive.

The tackifier is used to reduce the hardness change according to the temperature change and is selected from one or more of rosin derivative, terpene resin, petroleum resin, coumarone resin, styrene resin, and phenol resin to 100 parts by weight of the substrate. 3 to 40 parts by weight can be used.

The extension oil may be used in an amount of 3 to 45 parts by weight based on 100 parts by weight of one or more selected from hydrocarbon-based processed oils such as naphthenic, aromatic and paraffin-based oils, and natural oils such as rapeseed oil and castor oil.

The filler may include mineral fillers such as carbon black, silica, calcium carbonate, and talc, and may be used in an amount of 3 to 60 parts by weight based on 100 parts by weight of the substrate.

Referring to the manufacturing process of the shock absorbing composite functional material having a temperature maintaining function consisting of the above components as follows.

First, one or more of styrene-based block copolymer, styrene / butadiene rubber, 1,2-polybutadiene, acrylic rubber, epoxidized natural rubber, polyvinyl chloride resin, and polyvinyl chloride / nitrile rubber composite After mixing the additives, a compound containing a cross-linking agent and a microcapsule containing a phase change material was prepared in a sheet form, put into a closed mold, and then pressed at 130 to 170 ° C. and 100 to 150 kg / cm ² using a compression molding machine. By molding under high pressure for 3 to 20 minutes, a shock absorbing composite functional material having a desired temperature holding function can be produced.

The manufacturing process described a cross-linked manufacturing process using a compression molding machine, when the base material is composed of only a thermoplastic material (styrene-based block copolymer, 1,2-polybutadiene, polyvinyl chloride resin) crosslinking agent is not added and usually It can be molded into various forms using the thermoplastic material molding process. (E.g. sheet manufacturing using calendar)

Hereinafter, the present invention will be described in more detail based on the examples produced in the configuration of [Table 1], but the present invention is not limited to the examples.

Example 1

5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 30 parts by weight of tackifier, 2 parts by weight of antioxidant, and an extension oil based on 100 parts by weight of a substrate composed of 40% by weight of styrene / butadiene rubber and 60% by weight of styrene block copolymer. 2 parts by weight of sulfur, 2.5 parts by weight of accelerator and 10 weights of phase-transfer microcapsules with respect to 100 parts by weight of the substrate in a roll mill having a surface temperature of 70 to 80 ° C. after kneading 25 parts by weight in a closed mixer at 100 to 120 ° C. for about 15 minutes. After the addition, the mixture was sufficiently kneaded to prepare a kneaded sheet of 2 to 6 mm, and then aged at room temperature (23 ° C.) for at least 24 hours. The kneaded sheet thus prepared was cut into a cavity of the mold and introduced into the mold, followed by compression molding for an optimal vulcanization time (t ₉₀ ) measured by a vulcanization time measuring instrument under conditions of 155 ° C. and 150 kg / ㎠. A shock absorbing composite functional material having a temperature keeping function was prepared.

Example 2

2 parts by weight of sulfur, 3 parts by weight of crosslinking agent, 1 part by weight of crosslinking aid and phase transition microparticles with respect to 100 parts by weight of the substrate in a roll mill having a surface temperature of 70 to 80 ° C with respect to the kneaded product obtained in the closed mixer according to the process of Example 1. After mixing 20 parts by weight of the capsules sufficiently kneaded, a shock absorbing composite functional material having a temperature keeping function was prepared in the same manner as in Example 1.

Comparative Example 1

5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 40 parts by weight of silica, and 2 parts by weight of activator based on 100 parts by weight of the substrate consisting of 60% by weight of styrene block copolymer, 20% by weight of natural rubber, and 20% by weight of butadiene rubber Parts, 2 parts by weight of antioxidant and 5 parts by weight of extension oil were kneaded in a closed mixer at 100 to 120 ° C. for about 15 minutes, and then 1.5 parts by weight of sulfur to 100 parts by weight of the substrate in a roll mill having a surface temperature of 70 to 80 ° C., 2.5 parts by weight of the accelerator was added and sufficiently kneaded to prepare a shock absorbing composite functional material having a temperature maintaining function in the same manner as in Example 1.

Table 1

[Unit: parts by weight]

division Example Comparative example One 2 One Styrene / butadiene rubber ¹⁾ 40 40 - Styrenic block copolymer ²⁾ 60 60 60 Natural rubber ³⁾ - - 20 Butadiene rubber ⁴⁾ - - 20 Zinc oxide 5 5 5 Stearic acid 2 2 2 Silica ⁵⁾ - - 40 Activator ⁶⁾ - - 2 Tackifier ⁷⁾ 30 30 - Antioxidant ⁸⁾ 2 2 2 Extension oil ⁹⁾ 25 25 5 sulfur 2.0 2.0 1.5 Promoter 1 ¹⁰⁾ 1.0 - 1.0 Accelerator2 ¹¹⁾ 1.5 - 1.5 Crosslinking agent ¹²⁾ - 3.0 - Crosslinking Aid ¹³⁾ - 1.0 - Microcapsules ¹⁴⁾ 10 20 - Optimal crosslinking time (t ₉₀ ) 350 seconds 470 seconds 720 seconds 1) Kumho Petrochemical, SOL5990 2) Kuraray, VS-33) SMR 3L 4) Kumho Petrochemical, KBR015) Rhodia, Zeosil155 6) Dongnam Synthesis, PEG40007) Kohlong Petrochemical, Hi-korez 8) Uniroyal Chemical, BHT9) Michang Petrochemical, Paraffin Oil 10) Dongyang Steel Chemical, Oricel-M11) Dongyang Steel Chemical, Oricel-DM 12) NOF Co., DCP13) Degussa, TAC50 14) 3M, Thermasorb T083 PMU capsule

The properties of the shock-absorbing composite functional material having a temperature holding function prepared in 3 mm sheets according to Examples 1 and 2 and Comparative Example 1 were tested in the following manner, and the results are shown in [Table 2].

TABLE 2

division Hardness A importance Tensile Strength (㎏ / ㎠) Elongation (%) Shock Absorption Rate (%) Endothermic amount (J / g) Example 1 34 0.97 18 470 91 12.7 Example 2 35 0.95 14 400 89 26.5 Comparative Example 1 65 1.16 85 300 65 -

1) Specific gravity

In accordance with KS M6519, the measurement was performed 5 times using a model DMA-3, an automatic specific gravity measurement apparatus of Ueshima Corporation, and the average value was taken.

2) hardness

It measured using the Asker A hardness tester based on KS M6518.

3) tensile strength, elongation

It was measured using a Zwick universal testing machine according to KS M6518.

4) Shock Absorption Rate

Shock absorption was calculated by measuring the resilience, and was measured using a rebound resilience tester of Wallace (UK) as a test piece of 10mm thickness.

5) endothermic amount

The endothermic amount was measured using a differential scanning calorimeter (DSC) manufactured by TA Instruments, USA.

As shown in Table 2, Examples 1 to 2 show excellent shock absorption, whereas Comparative Example 1 shows that the shock absorption is relatively poor. In addition, it can be seen that Examples 1 and 2 show the corresponding heat storage function as the endothermic amounts of 12.7 and 26.5 J / g near 30 ° C., respectively, as shown in FIGS. .

In other words, it can be seen that the embodiment is suitable to simultaneously satisfy the heat absorbing function for shock absorption and temperature maintenance.

As described above, the shock absorbing composite functional material having the temperature maintaining function of the present invention is a composite functional material expressing both the temperature holding function and the shock absorbing property by mixing a phase change material, a crosslinking agent, and a conventional rubber additive on the shock absorbing polymer substrate. It is characterized in that the manufacturing.

In particular, by providing shock-absorbing compound material with temperature retention function, two products maximized to one product, providing a new compound function material that overcomes the limitations of the material having only one function each existed. Like insoles, it can be applied to various applications such as electric, electronics, industrial and building materials, as well as parts requiring both temperature maintenance and shock absorption.

In addition, since it contains a phase change material, it is an excellent material that can be expected to increase thermal efficiency, temperature control, and energy saving effect.

Claims (8)

A shock absorbing composite functional material having a temperature maintaining function, which is based on a shock absorbing polymer material, wherein a crosslinking agent, a general rubber additive, and a phase change material are mixed. The method of claim 1, wherein the base material of the shock absorbing polymer material is a styrenic block copolymer, styrene / butadiene rubber, 1,2-polybutadiene, acrylic rubber, epoxidized natural rubber, polyvinyl chloride resin, polyvinyl chloride / nitrile. A shock absorbing composite material having a temperature maintaining function, characterized in that one or more selected from rubber composites and butyl rubbers are used. 3. The impact having a temperature holding function according to claim 2, wherein one or more selected from materials such as thermoplastic elastomers, rubbers, and polyolefins can be added to the base of the shock absorbing polymer material by up to 30% by weight. Absorbent composite function material. The styrene-based block copolymer according to claim 2, wherein the styrene-based block copolymer is a polystyrene, and the soft block is saturated or unsaturated polyisoprene, and the glass transition point of the soft block is around -20 to 20 ° C. Shock-absorbing composite material having a temperature maintaining function, characterized in that used as. The styrene / butadiene rubber of the components constituting the substrate is a solution-polymerized solution, and has a glass transition point in the range of -40 to -10 ° C. The 1,2-polybutadiene is synth. An impact-absorbing composite material having a temperature maintaining function, characterized in that it has an stereoscopic structure of acrylic, and that acrylic rubber is a copolymer of an alkyl ester of acrylic acid and a crosslinkable monomer containing a small amount of chlorine. The shock absorbing composite functional material according to claim 1, wherein the phase change material has a phase transition temperature in the range of -5.5 to 40 ° C and is prepared in the form of microcapsules. The shock absorbing composite functional material having a temperature maintaining function according to claim 1, wherein the crosslinking agent is selected from a sulfur crosslinking mechanism and an organic peroxide crosslinking mechanism. The shock absorbing composite functional material having a temperature maintaining function according to claim 1, wherein the crosslinking agent is not added when the substrate is composed of only a thermoplastic material and is molded using a conventional thermoplastic material molding process.