KR101743239B1 - Forming additive and forming composition having the same - Google Patents

Abstract

20 to 35 parts by weight of azodicarbonamide, 15 to 35 parts by weight of a toluene sulfoamide formaldehyde resin, 5 to 20 parts by weight of zinc p-toluene sulfonate, and 5 to 15 parts by weight of a urea compound, A composition for a foam comprising an expanding additive composition is presented.

Description

[0001] The present invention relates to a foaming additive composition and a foaming composition containing the foaming additive composition,

The present invention relates to a foam additive composition and a foam composition containing the foam additive composition, and more particularly to a foam additive composition which maintains hardness, improves the modulus of elasticity and lowers the specific gravity while increasing the foaming efficiency of the foam, To a composition for a foam.

Bubbles are formed inside a substance to absorb shock, or a substance made of a material such as a sponge is called a foam.

Foam has attracted attention from the aspect of light weight in the beginning and it has been mainly used for various packaging materials and daily necessities. Recently, however, the demand for foam has been rapidly increasing, such as automobile related parts, construction related parts and shoes related parts.

However, in the conventional foam, since the composition comprising resin or elastomer is obtained by simply foaming, the mechanical strength is lowered, and there is a limit such as deterioration in long-term use.

Therefore, it is still desired to develop a foam having improved mechanical strength, which is improved in foaming efficiency, is lightweight, maintains hardness and high elasticity, or is further improved.

A problem to be solved by the present invention is to provide a foaming additive composition which improves the foaming efficiency of a foam while improving hardness and elastic modulus, and a composition for a foam comprising the foaming additive composition.

To solve this problem, according to one aspect of the present invention, there is provided a foaming additive composition of the following embodiments.

A first embodiment is a composition comprising 20 to 35 parts by weight of azodicarbonamide, 15 to 35 parts by weight of a toluene sulfonamide formaldehyde resin, 5 to 20 parts by weight of zinc p-toluene sulfonate, and 5 to 15 parts by weight of a urea compound Foaming additive compositions.

A second embodiment relates to a foamed additive composition in a first embodiment wherein the urea compound is urea.

In a third embodiment, in the first or second embodiment, the foamed additive composition comprises 15 to 30 parts by weight of magnesium carbonate, 2 to 12 parts by weight of a metal oxide, 1 to 10 parts by weight of a crosslinking agent, 0.1 to 100 parts by weight of a brightener, 2 parts by weight of a pigment, and 0.1 to 2 parts by weight of a pigment.

According to another aspect of the present invention there is provided a composition for a foam of the following embodiments.

A fourth embodiment relates to a composition for a foam comprising the foamed additive composition of any one of the first to third embodiments.

The fifth embodiment is, in the fourth embodiment,

Wherein the foam composition contains 1 to 30 parts by weight of the foamed additive composition per 100 parts by weight of the ethylene vinyl acetate copolymer alone or a mixture of the ethylene vinyl acetate copolymer and the olefin based polymer.

The foamed additive composition according to an embodiment of the present invention includes a reinforcing material for preventing a decrease in elastic modulus and hardness and a foaming promoter for increasing a foaming rate, Can be improved.

As a result, the foam obtained according to the foamable composition of one embodiment of the present invention may have improved properties such as hardness, modulus of elasticity, and other physical properties, while increasing the foaming efficiency without increasing the production cost.

Hereinafter, the present invention will be described in detail. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.

Therefore, the configurations shown in the embodiments described herein are merely the most preferred embodiments of the present invention, and are not intended to represent all of the technical ideas of the present invention, so that various equivalents And variations are possible.

The foaming additive composition according to one aspect of the present invention comprises 20 to 35 parts by weight of azodicarbonamide, 15 to 35 parts by weight of a toluene sulfonamide formaldehyde resin, 5 to 20 parts by weight of zinc p-toluene sulfonate, 15 parts by weight.

The azodicarbonamide is a kind of azo type blowing agent and has a decomposition temperature of 130 to 200 ° C. Usually, the amount of the blowing agent used is determined by the amount of the decomposed gas. For example, the azodicarbonamide system is 200 to 230 ml / g.

The content of the azodicarbonamide may be 20 to 35 parts by weight, specifically 22 to 32 parts by weight. When the content of the azodicarbonamide is less than 20 parts by weight, the resulting foam has a high hardness and a high specific gravity. When the content of the foaming agent is more than 35 parts by weight, the hardness is low and the mechanical properties are significantly reduced, The performance may be degraded.

The toluene sulfonamide formaldehyde resin is a filler that is a physical property improving agent that plays a role in reinforcing the lowering of the elastic modulus and hardness of the obtained foam. That is, in the case of conventional foams, there is a disadvantage in that the physical properties are lowered as the foaming efficiency becomes larger. However, according to the present invention, by adding toluene sulfonamide formaldehyde resin together with azodicarbonamide as a foaming agent, It is possible to improve all properties such as low specific gravity and high elasticity while increasing the efficiency.

 Examples of the toluene sulfonamide formaldehyde resin include ortho (o-) toluene sulfoamide formaldehyde resin, para (p-) toluene sulfoamide formaldehyde resin, ortho / para (o / p-) toluene sulfo Amide formaldehyde resins, and the like, but are not limited thereto.

The content of the toluene sulfonamide formaldehyde resin may be 15 to 35 parts by weight, and more specifically 20 to 30 parts by weight.

The zinc p-toluenesulfonate serves as a foaming promoter to increase the foaming rate.

The content of the zinc p-toluenesulfonate may be 5 to 20 parts by weight, and more specifically 7 to 17 parts by weight.

The urea compound acts as a foaming promoter for increasing the foaming rate and at the same time enhances the foaming uniformity.

Examples of the urea compound include urea derivatives such as urea, surfaced treated urea and the like, and commercially available CELLEX-TS may be used, but the present invention is not limited thereto.

The content of the urea compound may be 5 to 15 parts by weight, and more specifically 7 to 12 parts by weight.

According to one embodiment of the present invention, the foamed additive composition may further include various additional components to reduce the product cost and improve the performance of the foamed product.

Such additional components include, but are not limited to, magnesium carbonate, metal oxides, crosslinking agents, brighteners, pigments, and the like.

The metal oxide serves to improve processing properties and improve the physical properties of the foam. Specifically, the metal oxide may be one or more selected from the group consisting of cadmium oxide, zinc oxide, magnesium oxide, silver oxide, tin oxide, You can choose to use it. Particularly, the metal oxide also acts as a decomposition auxiliary agent for the foaming agent.

The cross-linking agent is preferably a peroxide-based cross-linking agent capable of sufficiently collecting decomposed gas generated at a decomposition temperature of the blowing agent at a decomposition temperature or higher and imparting high-temperature viscoelasticity to the resin. The crosslinking agent is preferably used in an amount of 0.8 to 1.4 wt% It is effective to use the part. If the content of the cross-linking agent is less than 0.8 part by weight, the cross-linking agent is partially uncured and the high temperature viscoelasticity of the resin can not be maintained during the decomposition of the blowing agent. Thus, the mechanical properties are decreased and the foam formation is difficult. When the cross- There is a problem that the appearance of the foamed article becomes poor due to over-crosslinking and the improvement of the adhesive force is insignificant.

The peroxide type crosslinking agent preferably has a 10-minute half-life temperature of 130 to 200 ° C, and examples thereof include t-butylperoxyisopropyl carbonate, t-butylperoxylaurate, t-butylperoxyacetate Butyl diperoxyphthalate, t-dibutylperoxymaleic acid, cyclohexanoneperoxide, t-butylcumylperoxide, t-butylhydroperoxide, t-butylperoxybenzoate, dicumylperoxide, 1 , 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, 2,5-dimethyl- t-butylperoxy) valerate, or?,? - bis (t-butylperoxy) diisopropylbenzene.

The brightening agent is a fluorescent whitening agent. The brightening agent absorbs light in the UV region and emits fluorescence at a wavelength in the range of 400 to 500 nm. The whitening agent acts to whiten whiteness by optical action do. Examples of the fluorescent brightener include 1,4-bis (2-benzoxazolyl) naphthalene and the like.

The pigment is added for coloring the resulting foam, and various pigments can be applied depending on the desired color. Examples of such pigments are ultramarine-blue and the like.

According to one embodiment of the present invention, the additional components include 15 to 30 parts by weight of magnesium carbonate, 2 to 12 parts by weight of a metal oxide, 1 to 10 parts by weight of a crosslinking agent, 0.1 to 2 parts by weight of a brightener and 0.1 to 2 parts by weight of a pigment May be further included.

 According to one aspect of the present invention, there is provided a composition for a foam comprising the aforementioned foam additive composition.

The composition for a foam may contain 1 to 30 parts by weight of the foamed composition in an amount of 100 parts by weight of an ethylene vinyl acetate copolymer alone or a mixture of an ethylene vinyl acetate copolymer and an olefin polymer, Can be included.

When the foamed additive composition satisfies such a content range, the foaming performance can be increased, and the low specific gravity can be obtained, and all the properties including hardness and elasticity can be improved and improved.

It is effective that the ethylene vinyl acetate copolymer has a vinyl acetate content of 15 to 28% by weight and a melt flow index of 0.5 to 6.0 g / 10 min.

The olefin-based polymer may have a melt flow rate of 1.0 to 5.0 (g / 10 min, 190 DEG C / 2.16 kg) and a Mooney viscosity (121 DEG C) of 0.8 to 1.0 MU. Polyethylene resin, etc. Specifically, LC100, LC170, LC180, LC370, and LC670 of LG Chem may be used.

The content of the olefinic polymer may be in the range of 5 to 50 parts by weight based on 100 parts by weight of the ethylene vinyl acetate copolymer. When the range is satisfied, the product properties and the adhesive properties can be improved and the mechanical properties can be improved .

The composition for a foam may further include a foaming agent, a crosslinking agent, a metal oxide, a stearic acid compound, a brightener, a pigment, calcium carbonate, magnesium carbonate, and the like.

The foaming agent may be an azo compound such as azodicarbonamide having a decomposition temperature of 130 to 200 DEG C, a nitroso compound such as N, N'-dinitrosopentamethylenetetraamine, azobisisobutyronitrile, p- P-phenylbenzene sulfonyl hydrazide, pn, p'-oxybis (benzenesulfonylhydrazide) -based compounds, and diazo amino azobenzene.

The content of the blowing agent may be determined in consideration of the expansion ratio and specific gravity of the foam, and may be, for example, 1 to 100 parts by weight, based on 100 parts by weight of the ethylene vinyl acetate copolymer alone or a mixture of the ethylene vinyl acetate copolymer and the olefin- 10 parts by weight of the blowing agent may be used, and the amount of the blowing agent used may be determined according to the amount of the decomposed gas. For example, 200 to 230 ml / g of azodicarbonamide type, 130 to 170 ml / g of modified azodicarbonamide type, 240 ml / g of nitroso type, p, p'-oxybis (benzenesulfonylhydrazide) The system shows an amount of decomposition gas of 125 ml / g.

When the content of the blowing agent is less than 1 part by weight, the obtained foam has a high hardness and a high specific gravity. When the content of the blowing agent is more than 10 parts by weight, the hardness is lowered and the mechanical properties are significantly reduced, There is a problem that the required performance is deteriorated. In the case of press molding, there may arise a problem of forming an unstable foam cell in which the foam blows due to a sudden expansion exceeding the high temperature viscoelasticity limit of the resin.

The crosslinking agent is preferably a peroxide type crosslinking agent capable of sufficiently collecting decomposed gas generated at a temperature higher than the decomposition temperature of the foaming agent and imparting high temperature viscoelasticity to the resin.

The cross-linking agent may be used in an amount of 0.3 to 2 parts by weight per 100 parts by weight of the ethylene vinyl acetate copolymer alone or a mixture of the ethylene vinyl acetate copolymer and the olefin-based polymer. When the content of the cross-linking agent is less than 0.3 part by weight, the cross-linking agent is partially uncured and the high temperature viscoelasticity of the resin is not maintained during decomposition of the blowing agent. Thus, the mechanical properties are decreased and the foam is difficult to form. When the cross- And the appearance of the foam may be poor due to crosslinking.

The peroxide type crosslinking agent is preferably one having a 10-minute half-life temperature of 130 to 200 DEG C, for example, t-butylperoxyisopropyl carbonate, t-butylperoxylaurate, t-butylperoxyacetate Butyl diperoxyphthalate, t-dibutylperoxymaleic acid, cyclohexanoneperoxide, t-butylcumylperoxide, t-butylhydroperoxide, t-butylperoxybenzoate, dicumylperoxide, 1 , 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, 2,5-dimethyl- t-butylperoxy) valerate, or?,? - bis (t-butylperoxy) diisopropylbenzene.

The metal oxide is added to improve processing properties of the foam and to improve physical properties. The metal oxide is added in an amount of 0.5 to 5 parts by weight per 100 parts by weight of the ethylene vinyl acetate copolymer alone or a mixture of the ethylene vinyl acetate copolymer and the olefin based polymer Is preferably used. If the content of the metal oxide is less than 0.5 parts by weight, foaming characteristics of the foaming agent may be poor. When the content of the metal oxide is more than 5 parts by weight, dispersion characteristics of the metal oxide may be deteriorated.

The metal oxide may be selected from the group consisting of cadmium oxide, zinc oxide, magnesium oxide, silver oxide, tin oxide, lead oxide and calcium oxide. Particularly, the metal oxide also acts as a decomposition auxiliary agent for the foaming agent.

The stearic acid compound is added in order to improve the crosslinking and foaming properties and improve the working characteristics in the obtained foam, and it is preferable that the stearic acid compound is added to the ethylene vinyl acetate copolymer alone, It is preferable to use 3 parts by weight. When the content of the stearic acid compound is less than 0.5 parts by weight, crosslinking and foaming properties become poor. When the content of stearic acid is more than 3 parts by weight, mechanical properties of the foam are deteriorated. Examples of the stearic acid compound include, but are not limited to, zinc stearic acid and the like.

Further, pigments or brighteners may be used for imparting hue to the foam or for enhancing the whitening effect. Examples of the brightener include fluorescent brighteners such as 1,4-bis (2-benzoxazolyl) naphthalene, titanium dioxide and the like And various pigments such as ultramarine-blue may be applied as the pigment.

The content of the brightener may be 0.1 to 3 parts by weight, and the content of the pigment may be 0.1 to 2 parts by weight based on 100 parts by weight of the ethylene vinyl acetate copolymer alone or a mixture of the ethylene vinyl acetate copolymer and the olefin polymer. have.

In addition, according to one embodiment of the present invention, a filler may be further added to reduce the unit cost of the product and to improve the mechanical properties, and the filler may be at least one selected from the group consisting of wonder, clay, talc, mica, titanium oxide, Indium, tin oxide, or silica.

According to one embodiment of the present invention, the foamed additive composition comprises 20 to 35 parts by weight of azodicarbonamide, 15 to 35 parts by weight of a toluene sulfonamide formaldehyde resin, 5 to 20 parts by weight of zinc p-toluene sulfonate, And 5 to 15 parts by weight of the compound at room temperature under conditions such as a pulverizer or a mixer.

According to an embodiment of the present invention, the composition for a foam comprises 1 to 30 parts by weight of the foamed additive composition per 100 parts by weight of the ethylene vinyl acetate copolymer alone, or a mixture of the ethylene vinyl acetate copolymer and the olefin- Kneaded, and extruded into a pellet form. At this time, as described above, the foam composition may further contain a foaming agent, a crosslinking agent, a metal oxide, a stearic acid compound, a brightener, a pigment, calcium carbonate, magnesium carbonate and the like.

Specifically, the composition containing the above components is kneaded at room temperature using a ban-bury mixer generally used for kneading, and kneaded using a kneader, an open roll mill, callender), or the kneaded composition may be produced in the form of a pellet through a uniaxial or biaxial screw extruder at a temperature of 90 to 100 ° C.

The composition for a foam obtained in the above-described manner is heated at a temperature of, for example, 140 to 148 占 폚, specifically, 144 to 146 占 폚 under a pressure of 142 to 160 kg / cm2, specifically, 148 to 152 kg / Min, more specifically, for 44 minutes to 46 minutes, to form a final foamed sponge.

The foaming additive composition of the present invention and the foam composition containing the foaming additive composition of the present invention as described above can be used as foams for shoes, and particularly as foams for shoe midsole. Also, the composition for foam of the present invention can be applied to building materials such as an interlayer noise material, safety articles such as life vests, and the like, and can also be applied to low specific gravity rubber products requiring high release.

According to an embodiment of the present invention, the final foam (for example, a sponge) obtained by foaming the composition for foam of the present invention is skived again using a press device, and then the sponge is cut Then, the cut sponge is put into a shoe mold mold mold and compressed into various thicknesses (for example, 200, 190, 180, 160 mm to 100 mm) according to the application (for example, a compression time is 3 to 20 minutes More specifically 8 to 10 minutes, cooling time 1 to 30 minutes, particularly 5 to 25 minutes, more specifically 10 minutes, pressure 130 to 160 kg / cm 2, more specifically 135 to 155 kg / (150 kg / cm2), it can be applied to the production of a material for shoes (Phylon) having excellent physical properties.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the following examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

Example 1

Preparation of foaming additive composition

22 parts by weight of azodicarbonamide as a foaming agent and 29 parts by weight of o / p-toluenesulfonamide formaldehyde resin were first pulverized at a room temperature by a pulverizer, transferred to a mixer, and then p-toluene sulfonate (CELLEX-TS , 8 parts by weight of urea (CELEX-A), 18 parts by weight of magnesium carbonate, 3 parts by weight of zinc oxide, 4 parts by weight of porous silica (Zerosil, Rhodia Silica Korea) having a specific surface area of 140 to 170 m & 5 parts by weight of dicumyl peroxide as a crosslinking agent, 0.5 parts by weight of KCB (Hostalux KCB, 1,4-bis (2-benzooxazolyl) naphthalene) as a pigment brightening agent and 0.5 part by weight of Ultramarine Blue Manufactured by Daicikase Co., Ltd.) were mixed at room temperature to prepare a foaming additive composition.

Preparation of Composition for Foam

25 parts by weight of an ethylene vinyl acetate copolymer (vinyl acetate content 21%), 30 parts by weight of an ethylene vinyl acetate copolymer (vinyl acetate content 18%), 5 parts by weight of low density polyethylene (LDPE), 3 parts by weight of magnesium carbonate, , 0.8 part by weight of zinc stearate, 0.43 part by weight of dicumyl peroxide, 3 parts by weight of modified azodicarbonamide (CELLCOM-JTR), 1.5 parts by weight of titanium dioxide, Ultramarine Blue 0.152 part by weight of K-408, 0.025 part by weight of 2B-RED and 2.94 parts by weight of the foamed additive composition (CELLCOM-JTR) were added together at room temperature to prepare a composition for foam .

Production of foam

The composition for the foam was prepared into a composition in the form of a pellet through an extruder at 90 to 100 캜.

Then, the pellet-form composition was press-molded under the conditions of a mold temperature of 145 ° C and a pressure of 150 kg / cm 2 for 44 minutes to 46 minutes to prepare a shoe foam (sponge).

Then, the above-prepared shoe foam was compressed to 50% to 62.5% of the initial thickness at a compression time of 10 minutes, a cooling time of 10 minutes, and a pressure of 150 kg / cm2 to prepare a high quality shoe middle material (Phylon).

Comparative Example 1

The composition for a foam and a foam for shoes using the same were prepared in the same manner as in Example 1, except that the foam additive composition prepared in Example 1 was not added.

Then, the above-prepared shoe foam was compressed to 50% of the initial thickness at a compression time of 10 minutes, a cooling time of 10 minutes, and a pressure of 150 kg / cm2 to prepare a high-grade shoe midsole material (Phylon).

Property evaluation

The specific gravity, hardness, and compression set of the shoe soles produced in Example 1 and Comparative Example 1 were measured by the following methods, and the results are shown in Table 1 below.

(1) Specific gravity

ASTM D-297.

(2) Hardness Asker C

ASTM D-2240.

(3) Compression Set

The degree of permanent deformation of the foam by a long-term compressive load is measured and measured according to ASTM D-395.

Specific gravity (g / cc) Hardness Asker C Compression Set (%) Example 1 0.16 to 0.167 55 ~ 57 40.6 Comparative Example 1 0.19-0.22 49 ~ 53 53.2

Referring to Table 1, in Example 1 obtained by incorporating the foamed additive composition according to one embodiment of the present invention, the specific gravity was much lower than that of Comparative Example 1, and it was greatly improved even in the case of a compression set (passing 70 or less) It was confirmed that the elasticity is excellent and the specific gravity is lowered and the hardness is increased, so that a chemically favorable mutation phenomenon is exhibited.

Claims (5)

20 to 35 parts by weight of azodicarbonamide, 15 to 35 parts by weight of a toluene sulfoamide formaldehyde resin, 5 to 20 parts by weight of zinc p-toluene sulfonate, and 5 to 15 parts by weight of a urea compound. The method according to claim 1,
Wherein said urea compound is urea. The method according to claim 1,
Wherein the foamed additive composition further comprises 15 to 30 parts by weight of magnesium carbonate, 2 to 12 parts by weight of a metal oxide, 1 to 10 parts by weight of a crosslinking agent, 0.1 to 2 parts by weight of a brightener, and 0.1 to 2 parts by weight of a pigment Composition. A foam composition for foam comprising the foamed additive composition of any one of claims 1 to 3. 5. The method of claim 4,
Wherein the foam composition comprises 1 to 30 parts by weight of the foamed additive composition per 100 parts by weight of the ethylene vinyl acetate copolymer alone or a mixture of the ethylene vinyl acetate copolymer and the olefin based polymer.