KR101656255B1 - Eco-friendly and high functional Rubber Composition for Cleaning and Releasing Mold of Enhanced detergency - Google Patents

Abstract

The present invention relates to a rubber composition for cleaning an environmentally-friendly, highly functional mold having improved cleaning power for removing contaminants remaining in a mold in a process of continuously molding a thermosetting resin. More particularly, And a cleaning auxiliary agent contained in an amount less than that of the cleaning agent to accelerate and improve the action of the cleaning agent. Thus, it is possible to provide an environment-friendly and environmentally friendly working environment for the cleaning of the mold, and at the same time, To a rubber composition for cleaning an environmentally-friendly, highly functional mold having improved cleaning power.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a rubber composition for cleaning an environmentally-

The present invention relates to a rubber composition for cleaning an environmentally-friendly, highly functional mold having improved cleaning power for removing contaminants remaining in a mold in a process of continuously molding a thermosetting resin. More particularly, And a cleaning auxiliary agent contained in an amount less than that of the cleaning agent to accelerate and improve the action of the cleaning agent. Thus, it is possible to provide an environment-friendly and environmentally friendly working environment for the cleaning of the mold, and at the same time, A rubber composition for cleaning an environmentally-friendly, highly functional mold having improved cleaning power.

In a mold used for molding a product by using a thermosetting resin as a raw material by compressing and heating the same, a part of the contaminants and the molding material introduced during the working process are carbonized and remain so that it acts as a contaminant in repetitive work processes, Not only cause some defects in the molded product, but also cause the quality of the product to deteriorate during the continuous molding process. Therefore, after the molding operation is performed for a predetermined period or a predetermined number of times, a work for removing the contaminants remaining in the mold (so-called "cleaning operation") must be performed.

As a method for efficiently performing such a cleaning operation, a sheet containing a cleaning component has been developed and much research has been conducted on the composition used in the production of such a sheet. U.S. Patent No. 3,476,599 proposes a thermosetting resin composition for cleaning a mold in which a thermosetting resin is used as a base and an aminoalcohol compound having an amino group and a hydroxyl group is added thereto as a cleaning agent. However, in the curing process of the sheet for cleaning, the amino group of the aminoalcohol compound, which is a detergent, is decomposed to generate an amine-based gas, thereby causing odor and smoke generation.

As one method for solving this problem, Korean Patent Laid-Open Publication No. 1988-7799 proposes a rubber composition for mold cleaning using an uncrosslinked rubber as a base material and an imidazole-based or imidazoline-based compound as a cleaning agent . Although the above-mentioned cleaning composition solves the above-mentioned problems to some extent, the problem is not fundamentally solved because the scent due to the decomposition of the curing agent (mainly organic peroxide) used in the crosslinking of the uncrosslinked rubber is severely generated. Further, the detergent is limited to an imidazole-based or imidazoline-based compound, which limits the cleaning power.

Therefore, there is a high demand for a rubber composition for cleaning a mold that provides an environment-friendly working environment that is smokeless and odorless during the cleaning operation of a mold than a conventional cleaning sheet and exhibits high cleaning performance.

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and the technical problems required from the past.

The present application is based on the finding that when a rubber composition for cleaning a mold is used which contains a curing agent, an adsorbent, a cleaning agent, and a cleaning assistant which is contained in an uncrosslinked rubber in a smaller amount than the above-mentioned cleaning agent and assists the action of the cleaning agent, The inventors of the present invention have completed the present invention by confirming that the washing power is remarkably increased while the working environment is improved by suppressing the generation of irritating odor and smoke generated from the hardening agent and the like.

In order to achieve the above object, the rubber composition for cleaning a mold according to the present invention comprises 0.5 to 6 parts by weight of a curing agent, 5 to 150 parts by weight of an adsorbent, 0.5 to 30 parts by weight of a cleaning agent, And 0.1 to 7 parts by weight of a cleaning adjuvant which is contained in a smaller amount and assists the action of the cleaning agent.

The uncrosslinked rubber is a component which is crosslinked in the mold by the action of a hardener when heat and pressure are applied and is removed in a state containing or adhering contaminants in the mold. The kind of the uncrosslinked rubber is particularly limited if it is such an uncrosslinked rubber Butadiene rubber (BR), nitrile rubber (NBR), ethylene-propylene terpolymer rubber (EPT), ethylene-propylene rubber (EPM), ethylene- One or a mixture of two or more selected from the group consisting of propylene diene monomer rubber (EPDM), styrene-butadiene rubber (SBR), polyisoprene rubber (IR), silicone rubber (Q) and fluorinated rubber (FKM) Can be used. Specifically, it may be an ethylene-propylene terpolymer rubber (EPT), a butadiene rubber (BR), a styrene-butadiene rubber (SBR), a nitrile rubber (NBR) or a mixture thereof.

The above-mentioned curing agent may be an organic peroxide, phenol resin, sulfur, or the like, which is a component serving to induce such curing when the uncrosslinked rubber is cured while undergoing a crosslinking reaction by heat and pressure. Specifically, it may be an organic peroxide, and the kind of the organic peroxide may be selected according to the mold temperature in consideration of the half-life temperature. Such organic peroxides include, but are not limited to, for example, 2,5-dimethyl-2,5-bis- (t-butylperoxy) t-butylperoxy), dt-butylperoxide, 2,5-dimethyl-2,5-bis- (t-butylperoxy) - (t-butylperoxy) -hexane, t-buthylcumylperoxide, bis- (t-buthylperoxy-i-propyl) benzene, dicumylperoxide, 4,4-di-t-buthylperoxy-n-buthylvalerate, t-butylperoxybenzoate, T-buthylperoxybenzoate, 1,1-di-t-buthylperoxy-3,3,5-trimethylcyclohexane, dibenzoyl- Di-benzoylperoxide, bis- (2,4-dichlorobenzoyl) -peroxide and the like can be used. Of these, bis (t-butylperoxy-i-propyl) benzene and 4,4-di-t-butylperoxy-n-butyl valerate were obtained by copolymerization of ethylene-propylene diene monomer (EPDM) Particularly preferred for mixed rubber cleaning compositions.

As described above, the content of the curing agent is 0.5 to 6 parts by weight, and if it is less than 0.5 parts by weight, the initiation of curing or the curing rate can not be promoted. If the amount of the curing agent is more than 6 parts by weight, excessive crosslinking occurs, the mechanical properties such as the tear strength are largely lowered, which is generally undesirable.

The rubber composition according to the present invention also includes an adsorbent for adsorbing and removing various odor and smoke components generated in a cleaning operation (a work for applying a heat and pressure to a mold for cleaning a mold made of a rubber composition according to the present invention into a mold) do. Such an adsorbent has a high adsorption power and a large specific surface area for the odor and smoke components. The odor and smoke generated during the operation are inevitably caused by various factors such as, for example, decomposition of the curing agent and decomposition of the detergent. In the composition according to the present invention, an adsorbent having fine pores and a large specific surface area is added The problem caused by this can be solved. The adsorbent has a specific surface area of at least 200 m 2 / g or more. In addition, it is possible to exhibit a more excellent adsorption force by having a lot of fine pores.

Examples of the adsorbent include clay (silica), silica gel, activated carbon, zeolite, ion exchange resin, acidic clay and the like. In some cases, they may be used in the form of a mixture of two or more thereof. In particular, the adsorbent used in the present invention may be zeolite, silica gel, or acidic white clay having a specific surface area of not less than 200 m < 2 > / g and not being colored. More specifically, it may be a fine powder silica gel or zeolite have. The fine powder silica gel can solve the problem of kneading with uncrosslinked rubber by pulverizing silica gel particles in micrometer (㎛) units in advance in meters (mm), and the zeolite X type and zeolite Y type have a specific surface area (about 500 ㎡ / g) is large, but it is expensive, so that the manufacturing cost of the composition of the present invention can be lowered by mixing with zeolite A type. On the other hand, since activated carbon and ion exchange resin have a very large specific surface area (about 600 m 2 / g or more), they are excellent in adsorption power, but are preferably used in combination with other adsorbent components since they are blackish and expensive.

The amount of the adsorbent is 5 to 150 parts by weight, and if it is less than 5 parts by weight, the ability to remove odor and smoke is deteriorated. If it is more than 150 parts by weight, mixing with the uncrosslinked rubber is difficult, It is not preferable because it can not be easily removed from the mold at a distance.

On the other hand, the cleaning agent, which serves to substantially remove contaminants from the mold, is not particularly limited as long as it performs such action. For example, methylene chloride, diethylene glycol monobutylether Ethyl acetoaldehyde, ethyl diglycol, ethanoic acid, formic acid, ammonium dodecylbenzene sulfonate, 1-methoxy-2 1-methoxy-2-propanol, methyl alcohol, dodecylbenzene sulfonic acid, acetone, 2- (2-butoxyethoxy) ethanol diethylene glycol mono (2-butoxyethoxy) ethanol diethylene glycol monobutylether (BDG), ethanol amine (MEA), 2-aminoethanol (MEA), 2-diethylamino ethanol : DEAE), 2- 2-methoxyethanol, 2-ethoxylethanol, 2-propoxyethanol, dimethyl sulfoxide (DMS), 2- (2-aminoethylamino (2-aminoethylamino) ethanol, N-methyl pyrrolidinone (NMP), 1-phenoxy-2-propanol (PGPhE), mesityl Mesityloxide, and 4-hydroxy-4-methyl-2-pentanone, and amine-alcohol-based compounds. And more specifically, methylene chloride, acetone, 2-methoxyethanol (EM), dimethylsulfoxide (DMS), N-methylpyridinone (NMP), 1-phenoxy-2-propanol (PGPhE) Mesityl oxide, 4-hydroxy-4-methyl-2-pentanone, or mixtures of two or more thereof.

Conventionally, as described above, an amine alcohol compound, an imidazole compound, or an imidazoline compound is selectively used as a cleaning agent. However, the inventors of the present invention have found that when one kind of cleaning compound is used as a cleaning agent, It was confirmed that a more excellent cleaning effect can be obtained when a mixture of cleaning compounds of different kinds is used as a cleaning agent. Thus, more particularly, two or more mixtures of different cleansing compounds are used as detergents. Here, the mutual ratios of the mixed cleansing compounds may be in the range of 1:99 to 99: 1 by weight, particularly in the range of 5:95 to 95: 5.

As described above, the amount of the detergent is 0.5 to 30 parts by weight. If the amount of the detergent is less than 0.5 parts by weight, it is difficult to obtain sufficient detergency. If the amount of the detergent is more than 30 parts by weight, surplus detergent remains on the mold surface, There is a problem in that it is not preferable.

Meanwhile, the inventors of the present application have conducted intensive research and have found that when using a cleaning adjuvant which is contained in a smaller amount than the cleaning agent together with the above-mentioned cleaning agent to promote and improve the action of the cleaning agent, And showed an effect of significantly reducing the odor generated in the cleaning agent.

Such a cleaning aid may be, in particular, a nonionic surfactant.

In one example, the nonionic surfactant may be an alkylamine ethoxylate compound having a molecular formula of C ₂₃ H ₃₈ N ₂ O ₈ . The alkyl amine ethoxylate compound having the molecular formula of C ₂₃ H ₃₈ N ₂ O ₈ has a reversible surfactant. In the caustic solution, the amine ethoxylate serves as a surfactant. In the acidic solution, There is a property of losing its surface activity. These properties make it easier to separate the emulsified oil from the aqueous material, so that the compounds are known to be mainly used for industrial laundry or metal cleaning.

In another example, the nonionic surfactant may be an alkylphenol ethoxylate-based compound represented by the following formula (1), more specifically, the following R may be an octylphenol ethoxylate-based compound having 8 carbon atoms, and the following x May be an integer of 3 to 10.

(1)

(One)

In this formula,

R is alkyl of 4 to 10 carbon atoms, and x is an integer of 1 to 55. [

The alkylphenol ethoxylate-based compound of the above formula (1) is a substance having wettability, cleansing property and oil emulsifying property to water, and can be used at a wide range of temperatures and can be used in various forms such as liquid, paste, There are properties that can be used in compounds. Therefore, it is known that the compound can be used in a variety of industrial cleaning applications ranging from a soft detergent to a heavy industrial product, and in particular has a good effect on the cleaning of hard surfaces and metals.

In another example, the nonionic surfactant may be an alcohol alkoxylate compound having a molecular formula of C ₁₂ H ₃₀ O ₂ , and more specifically, a substance of the following formula 2.

[CH ₃ CH ₂ OCH ₂ (CH ₂ ) ₆ CH ₂ OH] * [CH ₄ ] * [CH ₄ ] (2)

The alcohol alkoxylate compound having a molecular formula of C ₁₂ H ₃₀ O ₂ is a water-soluble nonionic surfactant having excellent performance and processability, and has characteristics of excellent wettability, cleansing property and fast dissolution rate. Because of these properties, it is known that the compounds can be used in a variety of industrial applications, from household detergents to industrial laundry detergents as well as hard surface and metal detergents and degreasing agents.

Such a cleaning aid does not have a clear mechanism such as how it interacts with the cleaning agent. However, when used together with the cleaning agent, the cleaning agent has a detergency as compared with the addition amount thereof It can be seen that it is remarkably improved. Therefore, the rubber composition according to the present invention including the above-described cleaning aid has an advantage that it can have a better or similar cleaning power even when the amount of the cleaning agent is reduced as compared with the conventional rubber composition.

The content of the cleaning adjuvant may be 0.1 to 7 parts by weight, specifically 0.5 to 3 parts by weight, as described above. If the amount is less than 0.1 part by weight, it is difficult to obtain the improved cleaning power. If the amount is more than 7 parts by weight, it may act as another contaminant, but the cleaning power is not improved.

At least one of the detergent and the cleaning aid may be applied to the adsorbent as described above or may be impregnated or impregnated or impregnated with a detergent or a cleaning aid present in a predominantly liquid state, This is because it is difficult to knead uniformly with the rubber.

On the other hand, the inventors of the present application have found that when the cleaning agent and the cleaning auxiliary agent further include an expanding agent, which is an alcohol-based material such as water and / or methanol or ethanol, the detergency is further improved.

Cleaning operation, in general, the temperature and the 15 pressure kgf / cm ² to 100 kgf / cm ² for placing a unit for mold cleaning made of the mold cleaning rubber composition on the mold, from 150 to 200 ℃ 2 to 10 Min to cure the unit into the shape of the mold. When the swelling agent is added together with the detergent, the washing power can be further improved because the temperature applied to the unit during the washing operation is higher than the boiling point of the swelling agent. Therefore, the swelling agent is vaporized at a temperature higher than the boiling point, To the surface, that is, to promote the blooming effect. That is, when only the cleaning agent is used, the cleaning agent that is present inside and can not effectively act on the contaminant may be eluted to the surface to contact the contaminant.

When such an expanding agent is further included in the rubber composition according to the present invention, the content of the expanding agent may be 1 to 10 parts by weight based on 100 parts by weight of the uncrosslinked rubber. If the amount is less than 1 part by weight, it is difficult to obtain the above effect. If the amount is more than 10 parts by weight, the kneading operation is difficult and the mold surface is contaminated.

Furthermore, the inventors of the present application have found that when a strong acid such as hydrochloric acid, sulfuric acid, nitric acid, bromic acid, or a strong alkali such as sodium hydroxide or potassium hydroxide is used in combination with a detergent and a cleaning aid, Respectively. It is believed that the strong acid or strong base (hereinafter occasionally referred to as " cleaning catalyst ") added together with the detergent serves as a catalyst in the cleaning process. That is, in a rubber composition for cleaning a mold containing only a cleaning agent and a cleaning aid component, the cleaning agent directly dissolves the contaminants, or when the detergent penetrates between the mold and the contaminants, The cleaning process is carried out in such a manner that it is attached to and removed from the rubber. On the other hand, when the cleaning catalyst is used together with a cleaning agent and a cleaning aid, the cleaning catalyst enhances the penetration of the cleaning agent and the cleaning aid while promoting the pulverization of the contaminants, thereby greatly improving the cleaning power.

The cleaning catalyst may be contained in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the cleaning agent. As such a cleansing catalyst, a strong acid or a strong base as described above may be selectively used, and in detail, KOH may be used.

The content of the cleaning agent containing the cleaning catalyst may also be 0.5 to 30 parts by weight as described above.

Meanwhile, the conventional uncrosslinked rubber composition for mold washing may contain an inorganic filler. This is because the viscosity of the lowered composition is added to the uncrosslinked rubber by adding a detergent and a releasing agent to the Mooney viscosity ) In order to maintain the balance of various components. Such fillers are generally added in an amount proportional to the amount of detergent and release agent added. However, these prior art inorganic fillers have low adsorptivity and low specific surface area to the odor and smoke components generated in the operation, and thus can not attain the object of the present invention at all. On the other hand, the adsorbent of the present invention exhibits not only adsorption to odor and smoke components but also effects of addition of the conventional inorganic filler.

Of course, in some cases, in order to increase the balance of the components of the composition in accordance with the increase in viscosity, the composition of the present invention may contain 5 to 50 parts by weight of the inorganic filler as in the prior art, based on 100 parts by weight of the uncrosslinked rubber May be added. Examples of such an inorganic filler include silica, talc, alumina, potassium carbonate, calcium carbonate, aluminum hydroxide, titanium oxide, and carbon black.

In addition, other compounds or mixtures may be added to the rubber composition for cleaning a mold according to the present invention within a range not deteriorating its physical properties.

INDUSTRIAL APPLICABILITY The rubber composition for mold cleaning of the present invention contains a curing agent, an adsorbent, a cleaning agent, and a cleaning assistant which is contained in an uncrosslinked rubber in a smaller amount than the above cleaning agent and assists the action of the cleaning agent, And a high-performance detergent, thereby greatly improving the working environment and the efficiency, thereby improving the productivity.

Hereinafter, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.

≪ Example 1 >

30 g of a mixed detergent (monoethanolamine (MEA), 25 g of N-methylpyrrolidone (NMP) and 35 g of dimethylsulfoxide (DMSO)) was added to 1000 g of the butadiene rubber (BR) (300 g of silica, 50 g of titanium oxide), and an adsorbent (zeolite X type 400 g) as a curing agent (30 g of 4,4-di-t-butylperoxy-n-butyl valerate) Kneader) and a roll mill. At this time, an auxiliary cleaning agent (Triton RW 10 g) was applied to the adsorbent and impregnated.

≪ Example 2 >

A kneaded product was prepared in the same manner as in Example 1, except that 10 g of Triton XL-80N was used as the auxiliary cleaning agent in Example 1 above.

≪ Example 3 >

A kneaded product was prepared in the same manner as in Example 1, except that 10 g of Triton X-100 was used as the auxiliary cleaning agent in Example 1 above.

<Example 4>

In order to confirm the effect of the swelling agent, 25 g of water and ethanol were mixed one by one to the composition of Example 1, and a kneaded product was prepared in the same manner as in Example 1.

&Lt; Example 5 >

In order to confirm the effect of the cleaning catalyst, 5 g of KOH was further added as a cleaning catalyst to the composition of Example 4 to prepare a kneaded product in the same manner as in Example 1.

&Lt; Comparative Example 1 &

A kneaded product was prepared in the same manner as in Example 1, except that the auxiliary cleaning agent was not used in Example 1.

<Experimental Example 1>

The kneaded materials prepared in Examples 1 to 5 and Comparative Example 1 were charged into an experimental mold (MQFP 28 x 28) contaminated with an epoxy molding compound (EMC) and cured at 180 ° C and a pressure of 60 kg / cm ² for 450 seconds , And a cleaning operation was performed on the mold. This operation was repeated until the contaminants on the mold were completely removed.

In this cleaning operation, the irritating odor and the degree of occurrence of fogging were confirmed, and the washing power against the contaminants of the mold was confirmed. The results are shown in Table 1 below. The following results are obtained by performing the same method five times and averaging.

Cleaning power Example 5? Example 4 ??? Example 1? Example 2? Example 3
≥ Comparative Example 1 Smell and smoke Except for Comparative Example 1,

As shown in Table 1, it can be seen that the cleaning performance of the compositions according to Examples 1 to 5 including the cleaning assistant is significantly improved as compared with the case where the cleaning assistant is not included.

Further, it can be seen that the cleaning power of Example 1 is higher than that of the cleaning assistants of Examples 2 and 3 (Examples 2 and 3), and that the cleaning agents of Examples 4 and 5 It can be seen that the cleaning performance in the case of using the rubber composition according to the present invention is more excellent.

Furthermore, when the cleaning auxiliary agent is used, it can be seen that there is no generation of odor and haze during the cleaning operation.

Claims (11)

0.5 to 6 parts by weight of a curing agent, 5 to 150 parts by weight of an adsorbent, 0.5 to 30 parts by weight of a cleaning agent, and 0.1 to 7 parts by weight of a cleaning aid, based on 100 parts by weight of the uncrosslinked rubber,
The curing agent is an organic peroxide,
The adsorbent is a zeolite or silica gel having a specific surface area of 200 m ² / g or more,
The cleaning agent is a mixture of two or more different kinds of cleaning compounds,
The cleaning aid may be an alkylamine ethoxylate compound having the molecular formula C ₂₃ H ₃₈ N ₂ O ₈ , an alkylphenol ethoxylate compound having the formula 1, or an alcohol alkoxylate having a molecular formula C ₁₂ H ₃₀ O ₂ Wherein the rubber compound is a compound of the following formula:

(One)
In this formula,
R is alkyl of 4 to 10 carbon atoms, and x is an integer of 1 to 55. [ delete delete delete delete The rubber composition for cleaning a mold according to claim 1, wherein the alcohol alkoxylate compound is a substance of the following formula 2:
[CH ₃ CH ₂ OCH ₂ (CH ₂ ) ₆ CH ₂ OH] * [CH ₄ ] * [CH ₄ ] (2) The rubber composition for cleaning a mold according to claim 1, wherein the rubber composition for cleaning the mold further comprises an expanding agent. 8. The rubber composition for cleaning a mold according to claim 7, wherein the swelling agent is water, an alcohol-based material, or a mixture of water and an alcohol-based material. The rubber composition for cleaning a mold according to claim 7, wherein the swelling agent is contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the uncrosslinked rubber. The rubber composition for cleaning a mold according to claim 1, wherein the rubber composition for cleaning a metal further comprises a cleaning catalyst for strong acid or strong alkali. The rubber composition for cleaning a mold according to claim 10, wherein the cleaning catalyst is KOH.