WO2021085805A1 - Anti-release hard moisture absorber composition - Google Patents

Anti-release hard moisture absorber composition Download PDF

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Publication number
WO2021085805A1
WO2021085805A1 PCT/KR2020/009318 KR2020009318W WO2021085805A1 WO 2021085805 A1 WO2021085805 A1 WO 2021085805A1 KR 2020009318 W KR2020009318 W KR 2020009318W WO 2021085805 A1 WO2021085805 A1 WO 2021085805A1
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Prior art keywords
moisture
chloride
oxide
weight
release
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PCT/KR2020/009318
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French (fr)
Korean (ko)
Inventor
안광호
정영진
Original Assignee
(주)티케이이엔에스
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Publication of WO2021085805A1 publication Critical patent/WO2021085805A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S45/00—Arrangements within vehicle lighting devices specially adapted for vehicle exteriors, for purposes other than emission or distribution of light
    • F21S45/30—Ventilation or drainage of lighting devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/166—Magnesium halide, e.g. magnesium chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide

Definitions

  • the present invention relates to a hard release-resistant desiccant composition and a moisture absorbing product comprising the same, and in particular, by controlling the composition ratio of metal chloride, metal oxide, cellulose derivative, and lipid to a specific range, it has a high moisture absorption rate and a low release rate, It relates to a release-resistant hard desiccant composition capable of minimizing a change in volume according to the present invention, and a moisture-absorbing product including the same.
  • the desiccant is incorporated into the container and is used to absorb moisture in the container to maintain good storage conditions of objects in the container, and is applied to preserve products sensitive to moisture such as pharmaceuticals, food, semiconductors, and metal machinery.
  • a desiccant is composed by incorporating a moisture absorbing component into a packaging material and sealing the packaging material, and the moisture absorbing power of the desiccant is determined by the moisture absorbing power of the moisture absorbing component contained in the packaging material. It is also very important to manage it so that it does not work.
  • the current automobile industry has used a method in which an anti-fog coating agent and a bentonite-based desiccant are mounted in a lamp housing such as a dust cover and used.
  • deterioration such as whitening or flow phenomenon occurs due to outdoor ultraviolet rays, temperature, and humidity of the anti-fog coating agent, and in this case, there is a problem of replacing the automotive lamp module.
  • the general bentonite-based desiccant absorbs certain moisture and then releases moisture again in a high-temperature, low-humidity environment when the lamp is operated, causing condensation on the inner surface of the lamp lens.
  • the inner wall of the container exerts pressure on the desiccant due to the constraints of the space inside the container, thereby being absorbed inside the desiccant.
  • Existing liquid moisture absorption may leak out of the packaging. Therefore, in order to improve this problem, a characteristic of minimizing the expansion rate due to moisture absorption, such as a sponge, is required, and a new function of a desiccant is required that also possesses such characteristics.
  • the present invention was devised to solve the above problems, and in detail, by controlling the composition ratio of metal chlorides, metal oxides, cellulose derivatives and lipids within a specific range, while maintaining a high moisture absorption rate, suppressing external leakage due to water release. And, it relates to a release-resistant hard desiccant composition capable of minimizing a volume change due to moisture absorption, and a moisture absorption product including the same.
  • the present invention relates to a hard release-resistant moisture absorbent composition and a moisture absorbent product comprising the same.
  • One aspect of the present invention relates to a hard release-resistant desiccant composition
  • a hard release-resistant desiccant composition comprising 30 to 70% by weight of a metal chloride, 20 to 50% by weight of a metal oxide, 1 to 10% by weight of a cellulose derivative, and 5 to 20% by weight of a lipid. will be.
  • the metal chloride is characterized in that one or more selected from calcium chloride, magnesium chloride, lithium chloride, strontium chloride, yttrium chloride and copper chloride,
  • the metal oxide is characterized in that one or more selected from calcium oxide, barium oxide, magnesium oxide, strontium oxide, sodium oxide and potassium oxide,
  • the cellulose derivative is characterized in that any one or more selected from nitrocellulose, acetylcellulose, methylcellulose, ethylcellulose, benzylcellulose, carboxymethylcellulose and hydroxymethylcellulose.
  • the lipid is characterized in that any one or more selected from beeswax, lanolin, candelilla, petrolatum, polyethylene wax, polypropylene wax, polyamide wax, carnova wax, paraffin wax, and polytetrafluoroethylene wax.
  • the moisture absorption product including the release-resistant hard desiccant composition has a volume change rate of 120% or less measured under the conditions of 50°C and 95% relative humidity, and the moisture release rate and moisture absorption measured under the conditions of 50°C and 95% relative humidity. It is characterized in that the rate is 0.8% or less and 160% or more, respectively.
  • the moisture absorption product manufactured according to the present invention maintains a high moisture absorption rate by controlling the composition ratio of metal chlorides, metal oxides, cellulose derivatives and lipids within a specific range, while corrosion, rust prevention, and external leakage of the product due to moisture release in high temperature environments. It can be used effectively as a moisture absorption product embedded in automobile lamps as it can suppress the volume change due to moisture absorption and minimize the volume change caused by moisture absorption.
  • release resistant means that the absorbed liquid does not spill out.
  • the release-resistant hard absorbent composition according to the present invention is characterized by comprising a metal chloride, a metal oxide, a cellulose derivative, and a lipid.
  • the metal chloride absorbs moisture in the atmosphere based on high deliquescent property, and can improve rust prevention in some cases, and mainly alkali metal or alkaline earth metal chlorides are exemplified.
  • metal chlorides examples include calcium chloride, magnesium chloride, lithium chloride, strontium chloride, yttrium chloride, and copper chloride, and these may be used alone or in combination of two or more.
  • magnesium chloride may be more preferably included as the metal chloride.
  • the magnesium chloride (MgCl 2 ) has the most excellent hygroscopicity due to its high moisture absorption rate up to 1.5 times or more compared to other metal chlorides.
  • anhydrides there are 2, 4, 6, 8, 10, 12 hydrates, etc., usually hexahydrate ( It exists in the form of MgCl 2 ⁇ 6H 2 O).
  • the magnesium chloride is relatively easy to obtain as a main component of bittern, which is a by-product after salt is extracted from seawater, and has excellent deliquescent properties, so it is most preferred for the desiccant composition according to the present invention.
  • the method for preparing the metal chloride is not limited. However, in order for the metal chloride to have deliquescent properties, it must be used in a dried state, so a drying process must be included in the manufacturing process for this purpose. At this time, the detailed conditions of the drying process are not limited in the present invention, and drying in an oven set at a temperature of 150° C. or higher, vacuum drying, freeze drying, or the like is preferable.
  • the metal chloride does not limit the manufacturing process.
  • Zedlikka's "Preparation of Magnesia (+99% MgO) by Lutner-HCl-making method” Engel-Ruthner Industrianlagen Aktiengesellschaft, Aichholzgasse 51-53, A-1120 Vienna, pages 5-7 ), etc., by first leaching the gotostone several times with hydrochloric acid, and then filtering out various impurities.
  • the metal chloride may further contain a silicon compound. Since the silicon compound can immobilize corrosion products such as metal ions and chlorine ions generated in the process of absorption of metal chlorides, the rust prevention effect can be greatly improved.
  • the type of the silicon compound is not limited, but zeolite is preferably used.
  • the zeolite is a crystalline aluminum silicate mineral and has a property of strongly adsorbing polar substances according to the action of cations in the crystal structure, so it adsorbs not only corrosion products but also moisture, and molecules smaller than the micropores due to the micropores of a certain size. It can be adsorbed by selectively passing through.
  • the silicon compound first dissolves a metal chloride in water to prepare a solution, and then a porous zeolite is mixed therein and sprayed to form droplets having a predetermined average particle diameter, and then dried to form a metal chloride- It can be prepared with a mixed moisture adsorption component of a silicon compound.
  • the silicon compound is preferably added in an amount of 100 to 500 parts by weight based on 100 parts by weight of a metal chloride. In the above range, stable moisture adsorption ability can be expressed, and rust prevention performance can be greatly improved.
  • the metal chloride is preferably contained in an amount of 30 to 70% by weight, more preferably 45 to 55% by weight, based on 100% by weight of the total composition. If less than 30% by weight is added, the moisture adsorption performance is greatly degraded, and if it is added more than 70% by weight, liquefied corrosion products may be released due to an excessive increase in deliquescent properties.
  • the metal oxide itself has high deliquescent properties, adsorbs moisture, and prevents the initial liquefaction of magnesium chloride due to a reaction to be described later.
  • metal oxide examples include one or more selected from calcium oxide, barium oxide, magnesium oxide, strontium oxide, sodium oxide, and potassium oxide, and these may be used alone or in combination of two or more.
  • magnesium oxide may be included as the metal oxide.
  • the magnesium oxide forms a needle-shaped hydration product to absorb the initially liquefied metal chloride to maintain a solid shape.
  • the magnesium oxide reacts with the metal chloride, more specifically, magnesium chloride to proceed with a solidification reaction.
  • metal chloride especially magnesium chloride
  • the magnesium chloride is liquefied at the same time as moisture absorption due to the defrosting phenomenon, and the aqueous solution generated through the liquefaction function acts as a corrosion product, greatly reducing rust prevention.
  • the aqueous solution of magnesium chloride forms magnesium oxide and magnesia cement, and a hydration reaction proceeds to become a solid, thereby inhibiting the decomposition of the initial metal chloride, thereby preventing liquefaction.
  • the composition absorbs water more and more, and after that, the deliquescent phenomenon of the metal chloride stops. Therefore, due to this mechanism, unlike the conventional metal chloride or silica gel, side effects of re-release of absorbed moisture can be suppressed, and rust prevention properties are also improved.
  • the metal oxide is preferably added in an amount of 20 to 50% by weight, more preferably 30 to 40% by weight, based on 100% by weight of the total composition. If it is added less than 20% by weight, it is difficult to control the high deliquescent properties of the metal chloride, so that the rust prevention effect may be greatly reduced, and if it is added in more than 50% by weight, the hygroscopicity may be lowered due to a solidification phenomenon caused by a rapid magnesia reaction.
  • the metal chloride or metal oxide is preferably added in the form of a powder.
  • the specific surface area (BET) of the metal chloride or metal oxide is not limited, but the specific surface area (BET) is preferably 10 m 2 /g or more, more preferably 40 m 2 /g or more.
  • the cellulose derivative is to compensate for the disadvantages of the metal oxide or metal chloride, and the cured product produced by absorbing moisture by the metal oxide or metal chloride forms a hydration product having needle formation, which is caused by expansion of the contents.
  • the packaging material is open or damaged. Therefore, by adding a high molecular weight cellulose derivative together to suppress the disadvantages of the hydration product, it is possible to secure the moisture absorption capacity of the cellulose derivative itself, and at the same time prevent damage to the packaging material due to hardening of metal oxides and metal chlorides.
  • the cellulose derivative since the cellulose derivative itself has electrostatic repulsion and hydrophilicity at the same time, it can have a certain level of dehumidification properties regardless of changes in relative humidity.
  • examples of the cellulose derivatives include nitrocellulose, acetylcellulose, methylcellulose, ethylcellulose, benzylcellulose, carboxymethylcellulose and hydroxymethylcellulose, among which carboxymethylcellulose is used. Since it has -COONa having electrostatic repulsion and -OH having hydrophilicity in itself, it is preferable because it can accommodate a larger amount of water molecules along with expansion between internal structures.
  • a modified cellulose derivative may be prepared by esterification or etherification of some of the hydroxyl groups (-OH) in general cellulose.
  • Representative etherified cellulose derivatives include carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose, and esterified cellulose derivatives include cellulose nitrate and cellulose acetate.
  • the cellulose derivative is not limited in shape and the like like the metal chloride or metal oxide.
  • the cellulose derivative may be in a granular form, and the size of the cellulose derivative may preferably have an average diameter of 0.1 to 20 ⁇ m.
  • the cellulose derivative is preferably added in an amount of 1 to 10% by weight, more preferably 3 to 7% by weight, based on 100% by weight of the total composition. If less than 1% by weight is added, the rate of formation of magnesia cement during the initial moisture absorption process of the composition can be rapidly accelerated and the packaging material may be damaged.If it is added in excess of 10% by weight, the packaging material is rather damaged due to excessive volume increase of the composition during the moisture absorption process. It can be the cause.
  • moisture absorbed by the lipid may be released as the composition changes from a solid to a liquid, which serves to prevent this.
  • it has the effect of a lubricant to increase processability by reducing the viscosity of the composition.
  • the lipid is not limited to the type, for example, selected from beeswax, lanolin, candelilla, petrolatum, polyethylene wax, polypropylene wax, polyamide wax, carnova wax, paraffin wax, and polytetrafluoroethylene wax. Any one or a plurality may be used. Among these, it is preferable to use polyethylene wax for the effect of anti-moisture release and for uniform dispersion of the composition.
  • the lipid is preferably 5 to 20% by weight, more preferably 5 to 15% by weight of the total composition 100% by weight. If it is added less than 5% by weight, it is difficult to prevent liquefaction of the composition due to temperature change, and if it is added in more than 20% by weight, a corrosion product may occur due to phase separation between other components and lipids after curing of the composition.
  • the release-resistant hard desiccant composition according to the present invention may further include various kinds of additives in addition to it.
  • the additive may further include a catalyst of a type known per se, a surface-active additive, an emulsifier, a reaction retarder, a pigment, a dye, a flame retardant, an anti-aging agent, a scorch inhibitor, a plasticizer, an antibacterial agent, a filler, and the like.
  • the amount of the additive is not limited, and the amount of the additive may be freely adjusted for each component.
  • the additive is preferably added in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total composition for each component.
  • the present invention can provide a moisture-absorbing product comprising the release-resistant hard desiccant composition.
  • the moisture absorbing product may be provided in a packaging material having an accommodation space therein and a form sealed inside the packaging material.
  • the packaging material may be a breathable film composed of one or a plurality of layers.
  • the packaging material may have a double-layer structure in which a coating layer including a synthetic latex is formed on a breathable film.
  • the air permeable packaging material has good heat resistance.
  • a coating solution containing 30 to 40% by weight of synthetic latex, 2 to 10% by weight of ethylene vinyl acetate material, 50 to 60% by weight of solvent, and 1 to 5% by weight of other substances is applied on the breathable film by a known method.
  • the double-layer structure may be formed, and after applying the coating solution, a drying process may be performed according to a known method, if necessary.
  • the synthetic latex for forming the coating layer preferably corresponds to an acrylic latex adhesive and/or an acrylic latex resin, and more specifically, there is no separate limitation as long as appropriate specifications known to those skilled in the art are adopted.
  • the ethylene vinyl acetate material for forming the coating layer preferably corresponds to a hot melt adhesive including ethylene vinyl acetate, and also suitable specifications known to those skilled in the art may be adopted.
  • other materials are curing agents, inorganic fillers, and/or additive resins, and examples of curing agents include amine-based curing agents, acid anhydride-based curing agents, phenolic curing agents, and dicyandiamide-based curing agents.
  • the inorganic filler may be at least one or more selected from the group consisting of calcium carbonate, magnesium carbonate, talc, mica, kaolin, graphite, and silica
  • the additive resin is illustratively It may be at least one selected from the group consisting of terpene phenol resin, hydrogenated rosin, petroleum resin, xylene resin, and coumarone resin.
  • the solvent may be at least one selected from the group consisting of toluene, acetone, and methyl ethyl ketone.
  • the thickness of the coating layer is not limited in the present invention, but is preferably 1 ⁇ m to 50 ⁇ m, more preferably 5 ⁇ m to 10 ⁇ m.
  • the breathable film of the packaging film of the breathable packaging material included in the moisture absorption product of the present invention includes at least one selected from the group consisting of Tyvek, polypropylene nonwoven fabric, polyethylene nonwoven fabric, polyethylene terephthalate nonwoven fabric, paper and cloth. can do.
  • Tyvek polypropylene nonwoven fabric
  • polyethylene nonwoven fabric polyethylene terephthalate nonwoven fabric
  • paper and cloth can do.
  • use of a breathable film made of Tyvek is preferred.
  • the packaging film of the breathable packaging material included in the moisture absorption product of the present invention may preferably have a double-layer structure in which a coating layer is formed on the breathable film made of Tyvek.
  • the moisture absorption product manufactured according to the present invention has a volume change rate of 120% or less measured under conditions of 50°C and 95% relative humidity by adjusting the composition ratio of metal chlorides, metal oxides, cellulose derivatives and lipids to a specific range as described above.
  • 50° C. and 95% relative humidity may have a moisture release rate and a moisture absorption rate of 0.8% or less and 160% or more, respectively.
  • the specimen After the specimen was subjected to moisture absorption for 48 hours under a temperature of 23 ⁇ 2°C and 50 ⁇ 5% relative humidity, it was dried again in an oven set at 70 ⁇ 2°C for 2 hours, and the moisture absorption rate at each drying temperature was measured. That is, by performing initial moisture absorption and then drying, the moisture absorption rates were measured at the beginning and after drying, respectively, and the release rate was calculated by substituting each moisture absorption rate in Equation 2 below. For example, the 90% release rate means that 90% of the moisture absorbed initially remains after drying.
  • the dimensional change rate according to moisture absorption was measured by measuring the dimensions (L wet ) of the specimens for each sample under the same conditions as the measurement of the absorption rate, and measuring the dimensions of the initial specimens (L dry ) and substituted into Equation 3 below.
  • the specimen was visually confirmed after 7 days exposure at 50 ⁇ 2°C and 95 ⁇ 5% relative humidity using a thermo-hygrostat.
  • a desiccant was prepared by uniformly mixing the composition fertilizers shown in Table 2 below. Subsequently, 35 g of the desiccant of Examples 1 to 7 and Comparative Examples 1 to 7 were added to a breathable packaging material having a length and width of 100 mm, respectively, and then processed at a temperature of 120° C. using a heat sealer to prepare a specimen. At this time, the specimen of Comparative Example 1 was a commercial product (decican, HM). The physical properties of the prepared specimens were measured and described in Tables 3 to 4 below.
  • Example 1 36.91 56.16 68.27 76.39 83.34 88.84 96.81 162.3 119.5
  • Example 2 36.54 52.24 62.51 69.58 72.10 79.97 85.83 134.9 119.6
  • Example 3 36.93 56.18 68.53 76.40 84.11 89.27 97.54 164.1 119.3
  • Example 4 36.92 56.18 67.52 75.34 82.07 85.65 94.27 155.3 119.2
  • Example 5 36.54 56.20 67.80 75.19 81.92 85.52 94.30 158.1 119.7
  • Example 6 36.53 56.02 67.49 75.27 81.36 85.12 93.96 157.2 119.5
  • Example 7 36.54 56.08 67.54 75.14 81.55 85.31 92.42 152.9 120.1 Comparative Example
  • the desiccant prepared according to the present invention can effectively absorb moisture in the atmosphere based on high deliquescent properties. Specifically, it can be seen that Examples 1 and 3, in which the content of the metal chloride is maintained in an appropriate range, have a degree of difference, but have a moisture absorption rate of 160% or more. However, it can be seen that in Example 2 in which the metal oxide was added in an excessive amount, the moisture absorption rate was relatively decreased. This is presumed to be because the solidification phenomenon occurred quickly due to the magnesia reaction.
  • Example 1 when compared with the commercially available desiccant (Comparative Example 1), the moisture absorbent prepared through Example 1 confirmed that there was no significant difference in volume change even after the moisture absorbency test. Specifically, the moisture absorbent of Example 1 almost did not change in volume even after moisture absorption, but it can be seen that the volume of the moisture absorbing agent of Comparative Example 1 was large enough to cause deformation of the case.
  • the desiccant prepared according to the present invention shows excellent values in the release rate.
  • Example 1 in which the amounts of metal chlorides, metal oxides, cellulose derivatives, and lipids were added satisfies the present invention shows the most excellent release rate
  • Comparative Examples 2 to 7 in which the amount of the composition was added out of the standard showed a large release rate. You can see it fall.

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  • Organic Chemistry (AREA)
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Abstract

The moisture-absorbing product produced according to the present invention allows control of the proportions of a metal chloride, a metal oxide, a cellulose derivative, and a lipid within predetermined ranges, thus maintains a high moisture absorption rate and, at the same time, inhibits corrosion, rusting, and leakage of a product to the outside, caused by moisture release in a high-temperature environment or the like, and can minimize a change in volume caused by moisture absorption and thus be usefully employed as a moisture-absorbing product to be contained in an automobile lamp.

Description

내방출성 경질 흡습제 조성물Release-resistant hard desiccant composition
본 발명은 내방출성 경질 흡습제 조성물 및 이를 포함하는 흡습제품에 관한 것으로, 상세하게는 금속염화물, 금속산화물, 셀룰로스 유도체 및 지질의 조성비를 특정 범위로 조절함으로써 높은 흡습율 및 낮은 방출율을 가지고, 흡습에 따른 부피변화를 최소화할 수 있는 내방출성 경질 흡습제 조성물 및 이를 포함하는 흡습제품에 관한 것이다.The present invention relates to a hard release-resistant desiccant composition and a moisture absorbing product comprising the same, and in particular, by controlling the composition ratio of metal chloride, metal oxide, cellulose derivative, and lipid to a specific range, it has a high moisture absorption rate and a low release rate, It relates to a release-resistant hard desiccant composition capable of minimizing a change in volume according to the present invention, and a moisture-absorbing product including the same.
흡습제는 용기에 내입되어 용기내의 수분을 흡습하여 용기 내에 있는 물체의 보관상태를 양호하게 유지하기 위해 사용되는 것으로, 의약품 및 식품, 반도체, 금속 기계 등 습기에 민감한 제품을 보존하기 위해 적용되고 있다.The desiccant is incorporated into the container and is used to absorb moisture in the container to maintain good storage conditions of objects in the container, and is applied to preserve products sensitive to moisture such as pharmaceuticals, food, semiconductors, and metal machinery.
일반적으로 흡습제는, 포장재 안에 흡습 성분을 내입하고 포장재를 밀봉하여 구성되는 것으로, 흡습제의 흡습력은 포장재 안에 내입된 흡습성분의 흡습력에 의해 결정되며, 또한 이에 못지 않게 포장재 안으로 흡수된 수분을 외부로 유출되지 않게 관리하는 것도 매우 중요한 일이다.In general, a desiccant is composed by incorporating a moisture absorbing component into a packaging material and sealing the packaging material, and the moisture absorbing power of the desiccant is determined by the moisture absorbing power of the moisture absorbing component contained in the packaging material. It is also very important to manage it so that it does not work.
특히 자동차 산업이 발달함에 따라 자동차 운송 및 보관 시 헤드램프, 리어램프 및 안개등 등의 결로의 문제점이 계속해서 발생하고 있으며, 이로 인한 산업적 손실이 증대되고 있다.In particular, as the automobile industry develops, condensation problems such as headlamps, rear lamps, and fog lights continue to occur during transportation and storage of automobiles, and industrial losses are increasing.
자동차의 램프는 우천 시와 같이 습도가 높은 환경에서 부품 내외부의 온도차가 큰 경우, 램프 렌즈 온도가 낮아지게 되면, 램프 내부의 수분이 응축되어 렌즈 내부 표면에 미세한 물방울이 맺혀 김이 서리게 된다. 이로 인한 광산란 현상은 자동차 안전 운행에 큰 장애가 되고 있다.When the temperature difference between the inside and outside of the parts is large in an environment of high humidity, such as in rainy weather, when the lamp lens temperature decreases, moisture inside the lamp condenses and fine water droplets form on the inner surface of the lens, resulting in fogging. The resulting light scattering phenomenon is a major obstacle to the safe operation of automobiles.
이러한 문제를 해결하기 위해서 현 자동차 산업은 방담코팅제와 벤토나이트계 흡습제를 더스트 커버와 같은 램프 하우징 내에 장착하여 사용하는 방법을 이용하여 왔다. 하지만 방담코팅제는 옥외의 자외선, 온도와 습도 등에 의해서 백화나 흐름 현상과 같은 열화가 발생하며, 이러한 경우 자동차 램프 모듈을 교체하는 문제점이 발생하였다. 또한 일반 벤토나이트계 흡습제는 일정 수분을 흡습한 후, 램프의 가동 시 고온 저습의 환경에서 수분을 재방출하여 램프 렌즈의 내부 표면의 결로 현상을 야기하는 문제가 있다.In order to solve this problem, the current automobile industry has used a method in which an anti-fog coating agent and a bentonite-based desiccant are mounted in a lamp housing such as a dust cover and used. However, deterioration such as whitening or flow phenomenon occurs due to outdoor ultraviolet rays, temperature, and humidity of the anti-fog coating agent, and in this case, there is a problem of replacing the automotive lamp module. In addition, there is a problem in that the general bentonite-based desiccant absorbs certain moisture and then releases moisture again in a high-temperature, low-humidity environment when the lamp is operated, causing condensation on the inner surface of the lamp lens.
여기에 기존의 염화칼슘 또는 염화마그네슘만으로 구성된 흡습제의 경우에는 흡습성은 강하지만 흡습 후 액체 상태의 흡습액이 흘러 용기 내부에 있는 물체에 치명적인 문제를 야기 시킬 수 있다. In the case of an existing desiccant composed only of calcium chloride or magnesium chloride, it has strong hygroscopicity, but after moisture absorption, a liquid absorbent liquid may flow, causing a fatal problem to the object inside the container.
이러한 단점을 보완하기 위해 콘크리트의 원료인 산화칼슘 또는 산화마그네슘과 혼합하는 경우, 흡습 시 콘크리트화로 경화되나, 이때 흡습제의 부피가 팽창되고 초과 흡수된 수분은 그대로 액상으로 남게 되고(조해성), 종국에는 이러한 액상의 물질이 유출의 문제를 일으킬 수 있다.In order to compensate for these shortcomings, when mixing with calcium oxide or magnesium oxide, which is a raw material for concrete, it is hardened by concrete formation when moisture is absorbed, but at this time, the volume of the desiccant expands and the excess absorbed moisture remains in a liquid state (deliquescent property). These liquid substances can cause spillage problems.
나아가, 용기에 내입되어 있는 흡습제가 흡습액이 증가됨에 따라 부피가 팽창되면 용기 내부의 공간의 제약으로 인해 용기의 내벽이 흡습제에 압력을 가하게 되는 결과를 초래하게 되고, 이로 인해 흡습제 내부에 흡습되어 있던 액상의 흡습액이 포장재 외부로 유출될 수 있다. 따라서 이러한 문제를 개선하기 위해서는 스폰지와 같은 흡습에 따른 팽창율을 최소화하는 특성이 필요하며, 이러한 특성도 함께 보유하는 새로운 기능의 흡습제가 요구된다.Furthermore, if the volume of the desiccant contained in the container expands as the moisture absorbent increases, the inner wall of the container exerts pressure on the desiccant due to the constraints of the space inside the container, thereby being absorbed inside the desiccant. Existing liquid moisture absorption may leak out of the packaging. Therefore, in order to improve this problem, a characteristic of minimizing the expansion rate due to moisture absorption, such as a sponge, is required, and a new function of a desiccant is required that also possesses such characteristics.
본 발명은 상기와 같은 문제점을 해결하기 위해 안출된 것으로, 상세하게는 금속염화물, 금속산화물, 셀룰로스 유도체 및 지질의 조성비를 특정 범위로 조절함으로써 높은 흡습율을 유지하면서 수분 방출에 의한 외부 유출을 억제하며, 흡습에 따른 부피변화를 최소화할 수 있는 내방출성 경질 흡습제 조성물 및 이를 포함하는 흡습제품에 관한 것이다.The present invention was devised to solve the above problems, and in detail, by controlling the composition ratio of metal chlorides, metal oxides, cellulose derivatives and lipids within a specific range, while maintaining a high moisture absorption rate, suppressing external leakage due to water release. And, it relates to a release-resistant hard desiccant composition capable of minimizing a volume change due to moisture absorption, and a moisture absorption product including the same.
본 발명은 내방출성 경질 흡습제 조성물 및 이를 포함하는 흡습제품에 관한 것이다.The present invention relates to a hard release-resistant moisture absorbent composition and a moisture absorbent product comprising the same.
본 발명의 일 양태는 금속염화물 30 내지 70 중량%, 금속산화물 20 내지 50 중량%, 셀룰로스 유도체 1 내지 10 중량% 및 지질 5 내지 20 중량%를 포함하는 것을 특징으로 하는 내방출성 경질 흡습제 조성물에 관한 것이다.One aspect of the present invention relates to a hard release-resistant desiccant composition comprising 30 to 70% by weight of a metal chloride, 20 to 50% by weight of a metal oxide, 1 to 10% by weight of a cellulose derivative, and 5 to 20% by weight of a lipid. will be.
본 발명에서 상기 금속염화물은 염화칼슘, 염화마그네슘, 염화리튬, 염화스트론튬, 염화이트륨 및 염화구리에서 선택되는 어느 하나 또는 복수인 것을 특징으로 하며,In the present invention, the metal chloride is characterized in that one or more selected from calcium chloride, magnesium chloride, lithium chloride, strontium chloride, yttrium chloride and copper chloride,
상기 금속산화물은 산화칼슘, 산화바륨, 산화마그네슘, 산화스트론튬, 산화나트륨 및 산화칼륨에서 선택되는 어느 하나 또는 복수인 것을 특징으로 하며,The metal oxide is characterized in that one or more selected from calcium oxide, barium oxide, magnesium oxide, strontium oxide, sodium oxide and potassium oxide,
상기 셀룰로스 유도체는 니트로셀룰로스, 아세틸셀룰로스, 메틸셀룰로스, 에틸셀룰로스, 벤질셀룰로스, 카르복시메틸셀룰로스 및 하이드록시메틸셀룰로스 중에서 선택되는 어느 하나 또는 복수인 것을 특징으로 한다.The cellulose derivative is characterized in that any one or more selected from nitrocellulose, acetylcellulose, methylcellulose, ethylcellulose, benzylcellulose, carboxymethylcellulose and hydroxymethylcellulose.
또한 상기 지질은 밀랍, 라놀린, 칸델릴라, 바셀린, 폴리에틸렌 왁스, 폴리프로필렌 왁스, 폴리아미드 왁스, 카노바 왁스, 파라핀 왁스 및 폴리테트라플루오로에틸렌 왁스에서 선택되는 어느 하나 또는 복수인 것을 특징으로 한다.In addition, the lipid is characterized in that any one or more selected from beeswax, lanolin, candelilla, petrolatum, polyethylene wax, polypropylene wax, polyamide wax, carnova wax, paraffin wax, and polytetrafluoroethylene wax.
또한, 상기 내방출성 경질 흡습제 조성물을 포함하는 흡습제품은 50℃, 상대습도 95%의 조건에서 측정한 부피변화율이 120% 이하이며, 50℃, 상대습도 95%의 조건에서 측정한 수분방출율 및 흡습율이 각각 0.8% 이하, 160% 이상인 것을 특징으로 한다.In addition, the moisture absorption product including the release-resistant hard desiccant composition has a volume change rate of 120% or less measured under the conditions of 50°C and 95% relative humidity, and the moisture release rate and moisture absorption measured under the conditions of 50°C and 95% relative humidity. It is characterized in that the rate is 0.8% or less and 160% or more, respectively.
본 발명에 따라 제조된 흡습제품은 금속염화물, 금속산화물, 셀룰로스 유도체 및 지질의 조성비를 특정 범위로 조절함으로써 높은 흡습율을 유지하면서 고온 등의 환경에서 수분 방출에 의한 부식, 방청, 생성물의 외부 유출을 억제하며, 흡습에 따른 부피변화를 최소화할 수 있어 자동차 램프에 내장되는 흡습제품으로 유용하게 사용될 수 있다.The moisture absorption product manufactured according to the present invention maintains a high moisture absorption rate by controlling the composition ratio of metal chlorides, metal oxides, cellulose derivatives and lipids within a specific range, while corrosion, rust prevention, and external leakage of the product due to moisture release in high temperature environments. It can be used effectively as a moisture absorption product embedded in automobile lamps as it can suppress the volume change due to moisture absorption and minimize the volume change caused by moisture absorption.
이하, 실시예 및 비교예를 들어 본 발명에 따른 내방출성 경질 흡습제 조성물 및 이를 포함하는 흡습제품을 더욱 상세히 설명한다. 다만 다음에 소개되는 구체예들은 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 예로서 제공되는 것이다.Hereinafter, examples and comparative examples will be described in more detail with respect to the release-resistant hard desiccant composition according to the present invention and a moisture-absorbing product including the same. However, specific examples introduced below are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art.
따라서 본 발명은 이하 제시되는 구체예들에 한정되지 않고 다른 형태로 구체화될 수도 있으며, 이하 제시되는 구체예들은 본 발명의 사상을 명확히 하기 위해 기재된 것일 뿐, 본 발명이 이에 제한되는 것은 아니다. Therefore, the present invention is not limited to the specific examples presented below and may be embodied in other forms, and the specific examples presented below are only described to clarify the spirit of the present invention, and the present invention is not limited thereto.
이때, 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.At this time, unless there are other definitions in the technical terms and scientific terms used, they have the meanings commonly understood by those of ordinary skill in the technical field to which this invention belongs, and unnecessarily obscure the subject matter of the present invention in the following description. Description of possible known functions and configurations will be omitted.
또한 명세서 및 첨부된 특허청구범위에서 사용되는 단수 형태는 문맥에서 특별한 지시가 없는 한 복수 형태도 포함하는 것으로 의도할 수 있다.In addition, the singular form used in the specification and the appended claims may be intended to include the plural form unless otherwise indicated in the context.
본 발명에서 "내방출성"이라는 용어는, 흡수된 액체가 유출되지 않는다는 것을 의미한다.In the present invention, the term "release resistant" means that the absorbed liquid does not spill out.
본 발명에 따른 내방출성 경질 흡습제 조성물 금속염화물, 금속산화물, 셀룰로스 유도체 및 지질을 포함하는 것을 특징으로 한다.The release-resistant hard absorbent composition according to the present invention is characterized by comprising a metal chloride, a metal oxide, a cellulose derivative, and a lipid.
본 발명에서 상기 금속염화물은 높은 조해성을 바탕으로 대기 중의 수분을 흡수하는 것으로, 경우에 따라서 방청성을 향상시킬 수 있으며, 주로 알칼리금속 또는 알칼리토금속의 염화물을 들 수 있다.In the present invention, the metal chloride absorbs moisture in the atmosphere based on high deliquescent property, and can improve rust prevention in some cases, and mainly alkali metal or alkaline earth metal chlorides are exemplified.
상기 금속염화물의 예를 들면, 염화칼슘, 염화마그네슘, 염화리튬, 염화스트론튬, 염화이트륨 및 염화구리 등이 있으며, 이들은 단독으로 또는 둘 이상 혼합하여 사용하여도 무방하다.Examples of the metal chlorides include calcium chloride, magnesium chloride, lithium chloride, strontium chloride, yttrium chloride, and copper chloride, and these may be used alone or in combination of two or more.
본 발명에서 상기 금속염화물로 더욱 바람직하게는 염화마그네슘을 포함할 수 있다. 상기 염화마그네슘(MgCl2)은 다른 금속염화물에 비해 최대 1.5배 이상 흡습율이 높아 가장 우수한 흡습성을 가지며, 무수물 이외에 2, 4, 6, 8, 10, 12 수화물 등이 있으며, 보통은 6 수화물(MgCl2·6H2O)의 형태로 존재한다. In the present invention, magnesium chloride may be more preferably included as the metal chloride. The magnesium chloride (MgCl 2 ) has the most excellent hygroscopicity due to its high moisture absorption rate up to 1.5 times or more compared to other metal chlorides. In addition to anhydrides, there are 2, 4, 6, 8, 10, 12 hydrates, etc., usually hexahydrate ( It exists in the form of MgCl 2 ·6H 2 O).
상기 염화마그네슘은 해수에서 소금을 채취한 후의 부산물인 간수의 주성분으로 비교적 수득하기 쉬우며, 우수한 조해성을 가지므로 본 발명에 따른 흡습제 조성물에 가장 바람직하다.The magnesium chloride is relatively easy to obtain as a main component of bittern, which is a by-product after salt is extracted from seawater, and has excellent deliquescent properties, so it is most preferred for the desiccant composition according to the present invention.
본 발명에서 상기 금속염화물은 제조방법을 한정하지 않는다. 다만 상기 금속염화물이 조해성을 갖기 위해서는 반드시 건조된 상태에서 사용되어야 하므로, 이를 위해 제조공정 중에 건조과정이 필수적으로 포함되어야 한다. 이때 상기 건조공정의 상세 조건은 본 발명에서 한정하지 않으며, 150℃이상의 온도로 설정된 오븐에서 건조시키거나 진공건조, 동결건조 등을 이용하는 것이 좋다.In the present invention, the method for preparing the metal chloride is not limited. However, in order for the metal chloride to have deliquescent properties, it must be used in a dried state, so a drying process must be included in the manufacturing process for this purpose. At this time, the detailed conditions of the drying process are not limited in the present invention, and drying in an oven set at a temperature of 150° C. or higher, vacuum drying, freeze drying, or the like is preferable.
본 발명에서 상기 금속염화물은 제조공정을 한정하지 않는다. 일예로, 염화알루미늄의 경우 제들릭카의 "루트너-HCl-제조법에 의한 마그네시아(+99% MgO)의 제조"(Andritz-Ruthner Industrianlagen Aktiengesellschaft, Aichholzgasse 51-53, A-1120 비엔나, 페이지 5-7) 등에 기재된 방법과 같이 먼저 고토석을 염화수소산으로 수 회 침출시킨 후, 여러 불순물을 여과함으로써 수득할 수 있다.In the present invention, the metal chloride does not limit the manufacturing process. For example, in the case of aluminum chloride, Zedlikka's "Preparation of Magnesia (+99% MgO) by Lutner-HCl-making method" (Andritz-Ruthner Industrianlagen Aktiengesellschaft, Aichholzgasse 51-53, A-1120 Vienna, pages 5-7 ), etc., by first leaching the gotostone several times with hydrochloric acid, and then filtering out various impurities.
또한 상기 금속염화물은 규소화합물을 더 혼합하여도 좋다. 상기 규소화합물은 금속염화물의 흡습 과정에서 생성되는 금속이온, 염소이온 등의 부식 생성물을 고정화할 수 있기 때문에 방청효과를 크게 높일 수 있다.Further, the metal chloride may further contain a silicon compound. Since the silicon compound can immobilize corrosion products such as metal ions and chlorine ions generated in the process of absorption of metal chlorides, the rust prevention effect can be greatly improved.
본 발명에서 상기 규소화합물은 종류를 한정하지 않으나, 바람직하게는 제올라이트를 사용하는 것이 좋다. 상기 제올라이트는 결정질 알루미늄 규산염광물로, 결정구조 내에 있는 양이온의 작용에 따라 극성물질을 강하게 흡착하는 성질을 가지므로 부식 생성물뿐만 아니라 수분도 함께 흡착하며, 일정 크기의 미세기공으로 인해 상기 미세기공보다 작은 분자를 선택적으로 통과시켜 흡착할 수 있다.In the present invention, the type of the silicon compound is not limited, but zeolite is preferably used. The zeolite is a crystalline aluminum silicate mineral and has a property of strongly adsorbing polar substances according to the action of cations in the crystal structure, so it adsorbs not only corrosion products but also moisture, and molecules smaller than the micropores due to the micropores of a certain size. It can be adsorbed by selectively passing through.
본 발명에서 상기 규소화합물은 먼저 금속염화물을 물에 용해시켜 용액을 제조한 후, 여기에 다공성 제올라이트를 혼합하고 이를 분사시켜 소정의 평균입경을 갖는 액적 형태로 형성한 뒤, 이를 건조시켜 금속염화물-규소화합물의 혼합 수분흡착성분으로 제조할 수 있다.In the present invention, the silicon compound first dissolves a metal chloride in water to prepare a solution, and then a porous zeolite is mixed therein and sprayed to form droplets having a predetermined average particle diameter, and then dried to form a metal chloride- It can be prepared with a mixed moisture adsorption component of a silicon compound.
본 발명에서 상기 규소화합물은 금속염화물 100 중량부 대비 100 내지 500 중량부 첨가하는 것이 바람직하다. 상기 범위에서 안정적인 수분흡착능을 발현할 수 있으며 방청성능이 크게 향상될 수 있다.In the present invention, the silicon compound is preferably added in an amount of 100 to 500 parts by weight based on 100 parts by weight of a metal chloride. In the above range, stable moisture adsorption ability can be expressed, and rust prevention performance can be greatly improved.
본 발명에서 상기 금속염화물은 전체 조성물 100 중량% 대비 30 내지 70 중량%, 더욱 바람직하게는 45 내지 55 중량% 포함하는 것이 좋다. 30 중량% 미만 첨가하는 경우 수분의 흡착성능이 크게 떨어지며, 70 중량% 초과 첨가하는 경우 조해성의 과도한 증가로 인해 액상화된 부식 생성물이 방출될 수 있다.In the present invention, the metal chloride is preferably contained in an amount of 30 to 70% by weight, more preferably 45 to 55% by weight, based on 100% by weight of the total composition. If less than 30% by weight is added, the moisture adsorption performance is greatly degraded, and if it is added more than 70% by weight, liquefied corrosion products may be released due to an excessive increase in deliquescent properties.
본 발명에서 상기 금속산화물은 그 자체로도 높은 조해성을 가져 수분을 흡착하며, 후술할 반응으로 인해 염화마그네슘의 초기 액화현상을 방지할 수 있다.In the present invention, the metal oxide itself has high deliquescent properties, adsorbs moisture, and prevents the initial liquefaction of magnesium chloride due to a reaction to be described later.
상기 금속산화물의 예를 들면, 산화칼슘, 산화바륨, 산화마그네슘, 산화스트론튬, 산화나트륨 및 산화칼륨에서 선택되는 어느 하나 또는 복수를 포함하며, 이들은 단독으로 또는 둘 이상 혼합하여 사용하여도 무방하다.Examples of the metal oxide include one or more selected from calcium oxide, barium oxide, magnesium oxide, strontium oxide, sodium oxide, and potassium oxide, and these may be used alone or in combination of two or more.
본 발명에서 상기 금속산화물로 더욱 바람직하게는 산화마그네슘을 포함할 수 있다. 상기 산화마그네슘은 바늘 형상의 수화생성물을 형성시켜 초기에 액화된 금속염화물을 흡수시켜 고체 형상을 유지하게 한다. 또한 상기 산화마그네슘은 상기 금속염화물, 더욱 상세하게는 염화마그네슘과 반응하여 고체화 반응을 진행하게 된다. In the present invention, more preferably magnesium oxide may be included as the metal oxide. The magnesium oxide forms a needle-shaped hydration product to absorb the initially liquefied metal chloride to maintain a solid shape. In addition, the magnesium oxide reacts with the metal chloride, more specifically, magnesium chloride to proceed with a solidification reaction.
이를 더욱 상세히 설명하면, 금속염화물, 특히 염화마그네슘은 높은 조해성으로 인해 습기가 조금만 있어도 흡습하는 성질이 있어 높은 흡습기능을 부여할 수 있다. 다만 상기 염화마그네슘은 조해현상으로 인해 흡습과 동시에 액화현상이 진행되는데, 상기 액화현상을 통해 생성되는 수용액은 부식생성물로 작용하여 방청성을 크게 떨어뜨리게 된다. 그러나 산화마그네슘이 혼합되면 상기 염화마그네슘의 수용액이 산화마그네슘과 마그네시아 시멘트를 형성하여 고체가 되는 수화반응이 진행됨으로써 초기 금속염화물의 조해성을 억제시켜 액화현상을 방지할 수 있다. 이러한 마그네시아 시멘트를 형성하기 위해 조성물은 물을 더욱 더 흡수하게 되며, 그 이후 금속염화물의 조해현상은 정지하게 된다. 따라서 이러한 메커니즘으로 인해 기존의 금속염화물 또는 실리카겔과는 달리 흡수했던 수분을 재방출하는 부작용을 억제할 수 있으며, 방청성 또한 향상되게 된다.To explain this in more detail, metal chloride, especially magnesium chloride, has a property of absorbing moisture even with a small amount of moisture due to its high deliquescent property, so that a high moisture absorption function can be imparted. However, the magnesium chloride is liquefied at the same time as moisture absorption due to the defrosting phenomenon, and the aqueous solution generated through the liquefaction function acts as a corrosion product, greatly reducing rust prevention. However, when magnesium oxide is mixed, the aqueous solution of magnesium chloride forms magnesium oxide and magnesia cement, and a hydration reaction proceeds to become a solid, thereby inhibiting the decomposition of the initial metal chloride, thereby preventing liquefaction. In order to form such magnesia cement, the composition absorbs water more and more, and after that, the deliquescent phenomenon of the metal chloride stops. Therefore, due to this mechanism, unlike the conventional metal chloride or silica gel, side effects of re-release of absorbed moisture can be suppressed, and rust prevention properties are also improved.
본 발명에서 상기 금속산화물은 전체 조성물 100 중량% 대비 20 내지 50 중량%, 더욱 바람직하게는 30 내지 40 중량% 첨가하는 것이 바람직하다. 20 중량% 미만 첨가하는 경우 금속염화물의 높은 조해성을 제어하기 어려워 방청효과가 크게 저하될 수 있으며, 50 중량% 초과 첨가하는 경우 급격한 마그네시아 반응으로 인한 고결현상으로 인해 흡습성이 떨어질 수 있다.In the present invention, the metal oxide is preferably added in an amount of 20 to 50% by weight, more preferably 30 to 40% by weight, based on 100% by weight of the total composition. If it is added less than 20% by weight, it is difficult to control the high deliquescent properties of the metal chloride, so that the rust prevention effect may be greatly reduced, and if it is added in more than 50% by weight, the hygroscopicity may be lowered due to a solidification phenomenon caused by a rapid magnesia reaction.
본 발명에서 상기 금속염화물 또는 금속산화물은 분말형태로 첨가하는 것이 바람직하다. 이때 상기 금속염화물 또는 금속산화물의 비표면적(BET)은 제한되지 않으나 비표면적(BET)이 10 ㎡/g 이상인 것이 바람직하며, 더욱 바람직하게는 40㎡/g 이상인 것이 좋다.In the present invention, the metal chloride or metal oxide is preferably added in the form of a powder. At this time, the specific surface area (BET) of the metal chloride or metal oxide is not limited, but the specific surface area (BET) is preferably 10 m 2 /g or more, more preferably 40 m 2 /g or more.
본 발명에서 상기 셀룰로스 유도체는 금속산화물 또는 금속염화물의 단점을 보완하기 위한 것으로, 금속산화물 또는 금속염화물이 수분을 흡수하여 생성된 경화체는 바늘 형성을 가지는 수화생성물이 형성되며, 이는 내용물의 팽창에 의해 포장재가 벌어지거나 손상되는 문제점을 가진다. 따라서 이러한 수화생성물의 단점을 억제하기 위해 고분자량의 셀룰로스 유도체를 함께 첨가함으로써 셀룰로스 유도체 자체의 수분흡수력을 확보함과 동시에 금속산화물과 금속염화물의 경화에 따른 포장재의 파손 등을 방지할 수 있다.In the present invention, the cellulose derivative is to compensate for the disadvantages of the metal oxide or metal chloride, and the cured product produced by absorbing moisture by the metal oxide or metal chloride forms a hydration product having needle formation, which is caused by expansion of the contents. There is a problem in that the packaging material is open or damaged. Therefore, by adding a high molecular weight cellulose derivative together to suppress the disadvantages of the hydration product, it is possible to secure the moisture absorption capacity of the cellulose derivative itself, and at the same time prevent damage to the packaging material due to hardening of metal oxides and metal chlorides.
또한 상기 셀룰로스 유도체는 그 자체로 정전기적 반발력과 친수성을 동시에 가지므로, 상대습도의 변화에 관계없이 일정 수준의 제습특성을 함께 가질 수 있다.In addition, since the cellulose derivative itself has electrostatic repulsion and hydrophilicity at the same time, it can have a certain level of dehumidification properties regardless of changes in relative humidity.
본 발명에서 상기 셀룰로스 유도체로 예를 들면, 니트로셀룰로스, 아세틸셀룰로스, 메틸셀룰로스, 에틸셀룰로스, 벤질셀룰로스, 카르복시메틸셀룰로스 및 하이드록시메틸셀룰로스 등을 들 수 있으며, 이들 중 카르복시메틸셀룰로스를 사용하는 것이 그 자체 내에 정전기적 반발력을 가지는 -COONa와 친수성을 가지는 -OH를 동시에 갖고 있어 내부구조간의 팽창과 함께 더 많은 함량의 물분자를 수용할 수 있어 바람직하다.In the present invention, examples of the cellulose derivatives include nitrocellulose, acetylcellulose, methylcellulose, ethylcellulose, benzylcellulose, carboxymethylcellulose and hydroxymethylcellulose, among which carboxymethylcellulose is used. Since it has -COONa having electrostatic repulsion and -OH having hydrophilicity in itself, it is preferable because it can accommodate a larger amount of water molecules along with expansion between internal structures.
상기 셀룰로스 유도체는 제조방법을 한정하지 않는다. 일예로, 일반 셀룰로스 내 수산기(-OH) 중 일부를 에스테르화 또는 에테르화하여 개질 셀룰로스 유도체를 제조할 수 있다. 대표적인 에테르화 셀룰로스 유도체는 카르복시메틸셀룰로스, 하이드록시에틸셀룰로스, 하이드록시프로필셀룰로스 등이 있으며, 에스테르화 셀룰로스 유도체는 질산 셀룰로스, 셀룰로스 아세테이트 등이 있다.The method for preparing the cellulose derivative is not limited. For example, a modified cellulose derivative may be prepared by esterification or etherification of some of the hydroxyl groups (-OH) in general cellulose. Representative etherified cellulose derivatives include carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose, and esterified cellulose derivatives include cellulose nitrate and cellulose acetate.
또한 상기 셀룰로스 유도체는 상기 금속염화물 또는 금속산화물과 마찬가지로 형태 등을 한정하지 않는다. 예를 들어 상기 셀룰로스 유도체는 과립형일 수 있으며, 그 크기는 0.1 내지 20㎛의 평균직경을 갖는 것이 좋다.In addition, the cellulose derivative is not limited in shape and the like like the metal chloride or metal oxide. For example, the cellulose derivative may be in a granular form, and the size of the cellulose derivative may preferably have an average diameter of 0.1 to 20 μm.
상기 셀룰로스 유도체는 전체 조성물 100 중량% 중 1 내지 10 중량%, 더욱 바람직하게는 3 내지 7 중량% 첨가하는 것이 바람직하다. 1 중량% 미만 첨가하는 경우 조성물의 초기 흡습 과정에서의 마그네시아 시멘트 생성속도가 급격히 빨라져 포장재 등이 파손될 수 있으며, 10 중량% 초과 첨가하는 경우 흡습과정에서의 조성물의 과도한 부피 증가로 인해 오히려 포장재의 파손 원인이 될 수 있다.The cellulose derivative is preferably added in an amount of 1 to 10% by weight, more preferably 3 to 7% by weight, based on 100% by weight of the total composition. If less than 1% by weight is added, the rate of formation of magnesia cement during the initial moisture absorption process of the composition can be rapidly accelerated and the packaging material may be damaged.If it is added in excess of 10% by weight, the packaging material is rather damaged due to excessive volume increase of the composition during the moisture absorption process. It can be the cause.
본 발명에서 상기 지질은 상기 조성물 주변의 온도 변화가 발생하는 경우, 조성물이 고체에서 액체로 변화함에 따라 흡습된 수분이 방출될 수 있는데, 이를 방지하는 역할을 한다. 또한 조성물의 점도를 줄여 가공성을 높이는 활제의 효과도 가진다.In the present invention, when a temperature change around the composition occurs, moisture absorbed by the lipid may be released as the composition changes from a solid to a liquid, which serves to prevent this. In addition, it has the effect of a lubricant to increase processability by reducing the viscosity of the composition.
본 발명에서 상기 지질은 종류에 한정하지 않으며, 일예로 밀랍, 라놀린, 칸델릴라, 바셀린, 폴리에틸렌 왁스, 폴리프로필렌 왁스, 폴리아미드 왁스, 카노바 왁스, 파라핀 왁스 및 폴리테트라플루오로에틸렌 왁스 등에서 선택되는 어느 하나 또는 복수일 수 있다. 이들 중 폴리에틸렌 왁스를 사용하는 것이 수분의 내방출성 효과 및 조성물의 균일한 분산을 위해서 바람직하다.In the present invention, the lipid is not limited to the type, for example, selected from beeswax, lanolin, candelilla, petrolatum, polyethylene wax, polypropylene wax, polyamide wax, carnova wax, paraffin wax, and polytetrafluoroethylene wax. Any one or a plurality may be used. Among these, it is preferable to use polyethylene wax for the effect of anti-moisture release and for uniform dispersion of the composition.
본 발명에서 상기 지질은 전체 조성물 100 중량% 중 5 내지 20 중량%, 더욱 바람직하게는 5 내지 15 중량% 포함하는 것이 바람직하다. 5 중량% 미만 첨가하는 경우 온도 변화에 따른 조성물의 액상화를 막기 어려우며, 20 중량% 초과 첨가하는 경우 조성물의 경화 후 다른 성분과 지질과의 상분리가 발생하여 부식 생성물이 발생할 수 있다.In the present invention, the lipid is preferably 5 to 20% by weight, more preferably 5 to 15% by weight of the total composition 100% by weight. If it is added less than 5% by weight, it is difficult to prevent liquefaction of the composition due to temperature change, and if it is added in more than 20% by weight, a corrosion product may occur due to phase separation between other components and lipids after curing of the composition.
본 발명에 따른 내방출성 경질 흡습제 조성물은 이외에도 다양한 종류의 첨가제를 더 포함할 수 있다. 구체적으로, 상기 첨가제는 그 자체로 공지된 유형의 촉매, 표면-활성 첨가제, 유화제, 반응 지연제, 안료, 염료, 난연제, 노화방지제, 스코치 억제제, 가소제, 항균제, 충전제 등을 더 포함할 수 있다. The release-resistant hard desiccant composition according to the present invention may further include various kinds of additives in addition to it. Specifically, the additive may further include a catalyst of a type known per se, a surface-active additive, an emulsifier, a reaction retarder, a pigment, a dye, a flame retardant, an anti-aging agent, a scorch inhibitor, a plasticizer, an antibacterial agent, a filler, and the like. .
상기 첨가제는 첨가량을 한정하지 않으며, 각 성분별로 첨가량을 자유롭게 조절하여도 좋다. 일예로 상기 첨가제는 각 성분별로 전체 조성물 100 중량부 대비 0.01 내지 10 중량부 첨가하는 것이 좋다. The amount of the additive is not limited, and the amount of the additive may be freely adjusted for each component. As an example, the additive is preferably added in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total composition for each component.
본 발명은 상기 내방출성 경질 흡습제 조성물을 포함하는 흡습제품을 제공할 수 있다. 구체적으로 상기 흡습제품은 내부에 수용 공간을 가지는 포장재와, 상기 포장재의 내부에 밀봉되어 있는 형태로 구비될 수 있다.The present invention can provide a moisture-absorbing product comprising the release-resistant hard desiccant composition. Specifically, the moisture absorbing product may be provided in a packaging material having an accommodation space therein and a form sealed inside the packaging material.
본 발명에서 상기 포장재는 하나 또는 복수의 층으로 이루어진 통기성 필름일 수 있다. 예를 들어 상기 포장재는 합성라텍스를 포함하는 코팅층이 통기성 필름 상에 형성된 이중막 구조일 수 있다. 이 경우 통기성 포장재의 내열성이 양호한 장점이 있으므로 바람직하다. 이 때 합성라텍스 30 내지 40 중량%, 에틸렌 비닐아세테이트 물질 2 내지 10 중량%, 용매 50 내지 60 중량%, 및 기타 물질 1 내지 5 중량%을 포함하는 코팅액을 통기성 필름 상에 공지의 방법으로 도포하는 과정을 거쳐 상기 이중막 구조를 형성할 수 있으며, 코팅액을 도포 후 필요에 따라 공지의 방법에 의한 건조 과정도 거칠 수 있다.In the present invention, the packaging material may be a breathable film composed of one or a plurality of layers. For example, the packaging material may have a double-layer structure in which a coating layer including a synthetic latex is formed on a breathable film. In this case, it is preferable because the air permeable packaging material has good heat resistance. At this time, a coating solution containing 30 to 40% by weight of synthetic latex, 2 to 10% by weight of ethylene vinyl acetate material, 50 to 60% by weight of solvent, and 1 to 5% by weight of other substances is applied on the breathable film by a known method. Through a process, the double-layer structure may be formed, and after applying the coating solution, a drying process may be performed according to a known method, if necessary.
상기 코팅층을 형성하기 위한 합성라텍스는 바람직하게 아크릴 라텍스 점착제 및/또는 아크릴 라텍스 수지에 해당하며, 보다 구체적으로는 당업자에게 공지된 적절한 제원을 채택하는 한 별도의 제한은 없다. 상기 코팅층을 형성하기 위한 에틸렌 비닐아세테이트 물질은 바람직하게 에틸렌 비닐아세테이트를 포함한 핫멜트 접착제에 해당하며, 역시 당업자에게 공지된 적절한 제원이 채택될 수 있다. 상기 코팅층을 형성하기 위한 코팅액의 성분으로 기타 물질은 경화제, 무기필러 및/또는 첨가제 수지이며, 경화제로는 예시적으로 아민계 경화제, 산 무수물계 경화제, 페놀계 경화제 및 디시안 디아미드계 경화제로 이루어진 군으로부터 선택된 적어도 하나 이상일 수 있으며, 무기필러로는 예시적으로 탄산칼슘, 탄산마그네슘, 탈크, 운모, 고령토, 흑연 및 실리카로 이루어진 군으로부터 선택된 적어도 하나 이상일 수 있으며, 첨가제 수지로는 예시적으로 테르펜 페놀수지, 수첨 로진, 석유수지, 크실렌수지 및 쿠마론수지로 이루어진 군으로부터 선택된 적어도 하나 이상일 수 있다. 상기 코팅층을 형성하기 위한 코팅액의 성분으로 용매는 예시적으로 톨루엔, 아세톤 및 메틸에틸케톤으로 이루어진 군으로부터 선택된 적어도 하나 이상일 수 있다.The synthetic latex for forming the coating layer preferably corresponds to an acrylic latex adhesive and/or an acrylic latex resin, and more specifically, there is no separate limitation as long as appropriate specifications known to those skilled in the art are adopted. The ethylene vinyl acetate material for forming the coating layer preferably corresponds to a hot melt adhesive including ethylene vinyl acetate, and also suitable specifications known to those skilled in the art may be adopted. As a component of the coating solution for forming the coating layer, other materials are curing agents, inorganic fillers, and/or additive resins, and examples of curing agents include amine-based curing agents, acid anhydride-based curing agents, phenolic curing agents, and dicyandiamide-based curing agents. It may be at least one or more selected from the group consisting of, and the inorganic filler may be at least one or more selected from the group consisting of calcium carbonate, magnesium carbonate, talc, mica, kaolin, graphite, and silica, and the additive resin is illustratively It may be at least one selected from the group consisting of terpene phenol resin, hydrogenated rosin, petroleum resin, xylene resin, and coumarone resin. As a component of the coating solution for forming the coating layer, the solvent may be at least one selected from the group consisting of toluene, acetone, and methyl ethyl ketone.
상기 코팅층의 두께는 본 발명에서 한정하지 않으나 바람직하게 1 ㎛ 내지 50 ㎛, 보다 바람직하게는 5 ㎛ 내지 10 ㎛인 것이 바람직하다.The thickness of the coating layer is not limited in the present invention, but is preferably 1 µm to 50 µm, more preferably 5 µm to 10 µm.
본 발명의 흡습제품에 포함되는 통기성 포장재의 포장필름의 통기성 필름에 있어, 상기 통기성 필름은 타이벡, 폴리프로필렌 부직포, 폴리에틸렌 부직포, 폴리에틸렌테레프탈레이트 부직포, 종이 및 천으로 이루어진 군으로부터 선택된 적어도 하나 이상을 포함할 수 있다. 포장재에 양호한 내열성을 부여하는 측면에서는, 타이벡으로 이루어진 통기성 필름의 사용이 바람직하다. 이에 따라 본 발명의 흡습제품에 포함되는 통기성 포장재의 포장필름은 바람직하게 타이벡으로 이루어진 통기성 필름 상에 코팅층이 형성된 이중막 구조일 수 있다.In the breathable film of the packaging film of the breathable packaging material included in the moisture absorption product of the present invention, the breathable film includes at least one selected from the group consisting of Tyvek, polypropylene nonwoven fabric, polyethylene nonwoven fabric, polyethylene terephthalate nonwoven fabric, paper and cloth. can do. In terms of imparting good heat resistance to the packaging material, use of a breathable film made of Tyvek is preferred. Accordingly, the packaging film of the breathable packaging material included in the moisture absorption product of the present invention may preferably have a double-layer structure in which a coating layer is formed on the breathable film made of Tyvek.
본 발명에 따라 제조된 흡습제품은 상기와 같이 금속염화물, 금속산화물, 셀룰로스 유도체 및 지질의 조성비를 특정 범위로 조절함에 따라 50℃, 상대습도 95%의 조건에서 측정한 부피변화율이 120% 이하이며, 50℃, 상대습도 95%의 조건에서 측정한 수분방출율 및 흡습율이 각각 0.8% 이하, 160% 이상일 수 있다.The moisture absorption product manufactured according to the present invention has a volume change rate of 120% or less measured under conditions of 50°C and 95% relative humidity by adjusting the composition ratio of metal chlorides, metal oxides, cellulose derivatives and lipids to a specific range as described above. , 50° C. and 95% relative humidity may have a moisture release rate and a moisture absorption rate of 0.8% or less and 160% or more, respectively.
이하, 실시예 및 비교예를 들어 본 발명을 더욱 상세히 설명한다. 다만, 하기 실시예 및 비교예는 본 발명을 더욱 상세히 설명하기 위한 하나의 예시일 뿐, 본 발명이 하기 실시예 및 비교예에 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following Examples and Comparative Examples are only one example for describing the present invention in more detail, and the present invention is not limited to the following Examples and Comparative Examples.
하기 실시예 및 비교예를 통해 제조된 시편의 물성을 다음과 같이 측정하였다.The physical properties of the specimens prepared through the following Examples and Comparative Examples were measured as follows.
(시료)(sample)
실시예 및 비교예에 사용된 시료의 제원은 하기 표 1과 같다.The specifications of the samples used in Examples and Comparative Examples are shown in Table 1 below.
구분division 조성물Composition 제조사manufacturer 제품명product name 비고Remark
AA 염화마그네슘Magnesium chloride 알드리치Aldrich -- 순도 94%94% purity
BB 산화마그네슘Magnesium oxide (주)대명케미칼Daemyung Chemical Co., Ltd. -- CAS.NO : 1309-48-4CAS.NO: 1309-48-4
CC 카르복시메틸셀룰로스Carboxymethylcellulose 신원상사Shinwon Corporation -- CAS.NO : 9004-32-4CAS.NO: 9004-32-4
DD 폴리에틸렌왁스Polyethylene wax SFCSFC LH1200LH1200 연화점 : 109±3℃Softening point: 109±3℃
(흡습율)(Moisture absorption rate)
항온항습기를 이용하여 50±2 ℃ 온도 및 95±5 % 상대습도 하에서 시편을 7일간 노출시킨 후 24시간 마다 각각의 무게를 측정하였으며, 측정된 무게를 하기 식 1에 대입하여 흡습율을 계산하였다.After exposing the specimen for 7 days at 50±2 ℃ temperature and 95±5% relative humidity using a thermo-hygrostat, each weight was measured every 24 hours, and the measured weight was substituted into Equation 1 below to calculate the moisture absorption rate. .
Figure PCTKR2020009318-appb-M000001
Figure PCTKR2020009318-appb-M000001
(내방출율)(Resistant release rate)
시편을 23±2℃ 온도 및 50±5% 상대습도 하에서 48시간 흡습시킨 후, 이를 다시 70±2℃로 설정된 오븐에서 2시간 건조 시키고 각각의 건조 온도에서의 흡습율을 측정하였다. 즉, 초기 흡습을 진행하고 이후 건조를 거침으로서, 초기와 건조 후의 흡습율을 각각 측정하였으며, 내방출율은 하기의 식 2에 각각의 흡습율을 대입하여 계산하였다. 일예로 내방출율 90%는 초기에 흡습한 수분의 90%가 건조 후에 잔류하는 것을 의미한다.After the specimen was subjected to moisture absorption for 48 hours under a temperature of 23±2°C and 50±5% relative humidity, it was dried again in an oven set at 70±2°C for 2 hours, and the moisture absorption rate at each drying temperature was measured. That is, by performing initial moisture absorption and then drying, the moisture absorption rates were measured at the beginning and after drying, respectively, and the release rate was calculated by substituting each moisture absorption rate in Equation 2 below. For example, the 90% release rate means that 90% of the moisture absorbed initially remains after drying.
Figure PCTKR2020009318-appb-M000002
Figure PCTKR2020009318-appb-M000002
(부피변화율)(Volume change rate)
수분 흡습에 따른 치수 변화율은 흡수율의 측정과 동일한 조건에서 시료별 시편에 대한 치수(Lwet)를 측정하고, 초기 시편의 치수(Ldry)를 측정하여 하기 식 3에 대입하였다. The dimensional change rate according to moisture absorption was measured by measuring the dimensions (L wet ) of the specimens for each sample under the same conditions as the measurement of the absorption rate, and measuring the dimensions of the initial specimens (L dry ) and substituted into Equation 3 below.
Figure PCTKR2020009318-appb-M000003
Figure PCTKR2020009318-appb-M000003
또한 시편을 커버형 보호용기에 삽입한 후, 항온항습기를 이용하여 50±2℃ 온도 및 95±5 % 상대습도 하에서 7일간 노출시킨 후 육안으로 시편을 확인하였다.In addition, after inserting the specimen into the cover-type protective container, the specimen was visually confirmed after 7 days exposure at 50±2℃ and 95±5% relative humidity using a thermo-hygrostat.
(실시예 1 내지 7, 비교예 1 내지 7)(Examples 1 to 7, Comparative Examples 1 to 7)
하기 표 2에 기재된 조성비료 균일하게 혼합하여 흡습제를 제조하였다. 이어서 길이와 너비가 각각 100㎜인 통기성 포장재에 실시예 1 내지 7 및 비교예 1 내지 7의 흡습제 35g을 투입한 후, 열실링기를 이용하여 120℃의 온도에서 가공하여 시편을 제조하였다. 이때 비교예 1의 시편은 시판제품(데시칸, HM)을 사용하였다. 제조된 시편의 물성을 측정하여 하기 표 3 내지 4에 기재하였다.A desiccant was prepared by uniformly mixing the composition fertilizers shown in Table 2 below. Subsequently, 35 g of the desiccant of Examples 1 to 7 and Comparative Examples 1 to 7 were added to a breathable packaging material having a length and width of 100 mm, respectively, and then processed at a temperature of 120° C. using a heat sealer to prepare a specimen. At this time, the specimen of Comparative Example 1 was a commercial product (decican, HM). The physical properties of the prepared specimens were measured and described in Tables 3 to 4 below.
조성물(중량%)Composition (% by weight)
AA BB CC DD
실시예 1Example 1 5050 3535 55 1010
실시예 2Example 2 4040 4545 55 1010
실시예 3Example 3 6060 2525 55 1010
실시예 4Example 4 5353 3535 22 1010
실시예 5Example 5 4747 3535 88 1010
실시예 6Example 6 5757 3535 55 33
실시예 7Example 7 4848 3535 55 1212
비교예 1Comparative Example 1 기존제품(데시칸, HM)Existing product
비교예 2Comparative Example 2 8080 55 55 1010
비교예 3Comparative Example 3 2525 6060 55 1010
비교예 4Comparative Example 4 5050 3535 -- 1515
비교예 5Comparative Example 5 4545 3030 1515 1010
비교예 6Comparative Example 6 5050 4242 55 33
비교예 7Comparative Example 7 4343 3030 55 2222
중량(g)Weight(g) 흡습율(%)Moisture absorption rate (%) 부피변화율(%)Volume change rate (%)
초기Early 1일차Day 1 2일차Day 2 3일차Day 3 4일차Day 4 5일차Day 5 7일차Day 7
실시예 1Example 1 36.9136.91 56.1656.16 68.2768.27 76.3976.39 83.3483.34 88.8488.84 96.8196.81 162.3162.3 119.5119.5
실시예 2Example 2 36.5436.54 52.2452.24 62.5162.51 69.5869.58 72.1072.10 79.9779.97 85.8385.83 134.9134.9 119.6119.6
실시예 3Example 3 36.9336.93 56.1856.18 68.5368.53 76.4076.40 84.1184.11 89.2789.27 97.5497.54 164.1164.1 119.3119.3
실시예 4Example 4 36.9236.92 56.1856.18 67.5267.52 75.3475.34 82.0782.07 85.6585.65 94.2794.27 155.3155.3 119.2119.2
실시예 5Example 5 36.5436.54 56.2056.20 67.8067.80 75.1975.19 81.9281.92 85.5285.52 94.3094.30 158.1158.1 119.7119.7
실시예 6Example 6 36.5336.53 56.0256.02 67.4967.49 75.2775.27 81.3681.36 85.1285.12 93.9693.96 157.2157.2 119.5119.5
실시예 7Example 7 36.5436.54 56.0856.08 67.5467.54 75.1475.14 81.5581.55 85.3185.31 92.4292.42 152.9152.9 120.1120.1
비교예 1Comparative Example 1 36.8536.85 57.8357.83 69.6669.66 75.3175.31 79.4979.49 82.3482.34 86.9786.97 136.0136.0 122.4122.4
비교예 2Comparative Example 2 36.5136.51 49.2249.22 65.4765.47 69.5469.54 73.3073.30 75.2175.21 79.2079.20 116.9116.9 95.395.3
비교예 3Comparative Example 3 36.5136.51 47.2247.22 62.4762.47 65.5465.54 67.3067.30 69.2169.21 70.2070.20 92.392.3 119.2119.2
비교예 4Comparative Example 4 37.1037.10 55.2455.24 61.6561.65 64.1664.16 67.1267.12 68.9868.98 69.4269.42 87.187.1 119.1119.1
비교예 5Comparative Example 5 37.1437.14 57.8857.88 70.2470.24 77.1477.14 83.1083.10 87.5487.54 95.2495.24 156.4156.4 147.2147.2
비교예 6Comparative Example 6 36.5236.52 56.0756.07 67.5167.51 75.2875.28 81.3181.31 85.1685.16 93.8593.85 157.0157.0 98.298.2
비교예 7Comparative Example 7 36.5436.54 56.0556.05 67.4867.48 75.2975.29 81.3581.35 85.1485.14 93.9093.90 157.0157.0 97.597.5
상기 표 3과 같이 본 발명에 따라 제조된 흡습제는 높은 조해성을 바탕으로 대기 중의 수분을 효과적으로 흡수할 수 있음을 알 수 있다. 구체적으로 금속염화물의 함량이 적정 범위를 유지하는 실시예 1, 3은 정도의 차이는 있으나 흡습율이 160% 이상 유지함을 알 수 있다. 다만 금속산화물이 약간 과량으로 첨가된 실시예 2는 흡습율이 상대적으로 하락한 것을 알 수 있다. 이는 마그네시아 반응으로 인해 고결현상이 빨리 발생하였기 때문으로 추측된다.As shown in Table 3, it can be seen that the desiccant prepared according to the present invention can effectively absorb moisture in the atmosphere based on high deliquescent properties. Specifically, it can be seen that Examples 1 and 3, in which the content of the metal chloride is maintained in an appropriate range, have a degree of difference, but have a moisture absorption rate of 160% or more. However, it can be seen that in Example 2 in which the metal oxide was added in an excessive amount, the moisture absorption rate was relatively decreased. This is presumed to be because the solidification phenomenon occurred quickly due to the magnesia reaction.
또한 실시예 1을 통해 제조된 흡습제는 시판 중인 흡습제(비교예 1)과 비교 시 흡습율 시험 후에도 부피 변화에 큰 차이가 없음을 확인하였다. 구체적으로 실시예 1의 흡습제는 흡습 후에도 거의 부피 변화가 일어나지 않았으나, 비교예 1의 흡습제는 케이스의 변형이 일어날 정도로 부피가 크게 증가한 것을 확인할 수 있다.In addition, when compared with the commercially available desiccant (Comparative Example 1), the moisture absorbent prepared through Example 1 confirmed that there was no significant difference in volume change even after the moisture absorbency test. Specifically, the moisture absorbent of Example 1 almost did not change in volume even after moisture absorption, but it can be seen that the volume of the moisture absorbing agent of Comparative Example 1 was large enough to cause deformation of the case.
중량(g)Weight(g) 방출율(%)Emission rate (%)
초기Early 흡습 후 중량Weight after moisture absorption 건조 후 중량Weight after drying
실시예 1Example 1 36.7536.75 42.7742.77 42.6842.68 0.210.21
실시예 2Example 2 36.7536.75 46.8746.87 45.2545.25 0.840.84
실시예 3Example 3 36.7836.78 46.5446.54 45.2245.22 0.860.86
실시예 4Example 4 36.6936.69 46.8746.87 45.3045.30 0.840.84
실시예 5Example 5 36.7936.79 46.3446.34 45.1945.19 0.880.88
실시예 6Example 6 36.7436.74 46.7246.72 45.3545.35 0.860.86
실시예 7Example 7 36.7736.77 46.5446.54 45.2145.21 0.860.86
비교예 1Comparative Example 1 36.8536.85 43.7643.76 43.6543.65 0.250.25
비교예 2Comparative Example 2 36.7236.72 45.2145.21 45.2245.22 1.001.00
비교예 3Comparative Example 3 36.7436.74 44.9544.95 45.0145.01 1.011.01
비교예 4Comparative Example 4 36.7536.75 45.0145.01 45.2045.20 1.021.02
비교예 5Comparative Example 5 36.7536.75 45.2345.23 45.5245.52 1.031.03
비교예 6Comparative Example 6 36.7636.76 45.0145.01 45.0345.03 1.001.00
비교예 7Comparative Example 7 36.7536.75 44.9844.98 44.7844.78 0.970.97
상기 표 4와 같이 본 발명에 따라 제조된 흡습제는 내방출율에서도 우수한 수치를 보이고 있다. 특히 금속염화물, 금속산화물, 셀룰로스 유도체 및 지질의 첨가량이 본 발명을 만족하는 실시예 1은 가장 우수한 내방출율을 보이고 있으며, 이에 반해 조성물의 첨가량이 기준을 벗어나는 비교예 2 내지 7은 내방출율이 크게 떨어지는 것을 확인할 수 있다.As shown in Table 4 above, the desiccant prepared according to the present invention shows excellent values in the release rate. In particular, Example 1 in which the amounts of metal chlorides, metal oxides, cellulose derivatives, and lipids were added satisfies the present invention shows the most excellent release rate, whereas Comparative Examples 2 to 7 in which the amount of the composition was added out of the standard showed a large release rate. You can see it fall.

Claims (6)

  1. 금속염화물 30 내지 70 중량%, 금속산화물 20 내지 50 중량%, 셀룰로스 유도체 1 내지 10 중량% 및 지질 5 내지 20 중량%를 포함하는 것을 특징으로 하는 내방출성 경질 흡습제 조성물.Metal chloride 30 to 70% by weight, metal oxide 20 to 50% by weight, cellulose derivative 1 to 10% by weight and 5 to 20% by weight of lipids, characterized in that it comprises a hard release-resistant moisture absorbent composition.
  2. 제 1항에 있어서,The method of claim 1,
    상기 금속염화물은 염화칼슘, 염화마그네슘, 염화리튬, 염화스트론튬, 염화이트륨 및 염화구리에서 선택되는 어느 하나 또는 복수인 것을 특징으로 하는 내방출성 경질 흡습제 조성물.The metal chloride is one or more selected from calcium chloride, magnesium chloride, lithium chloride, strontium chloride, yttrium chloride and copper chloride.
  3. 제 1항에 있어서,The method of claim 1,
    상기 금속산화물은 산화칼슘, 산화바륨, 산화마그네슘, 산화스트론튬, 산화나트륨 및 산화칼륨에서 선택되는 어느 하나 또는 복수인 것을 특징으로 하는 내방출성 경질 흡습제 조성물.The metal oxide is one or more selected from calcium oxide, barium oxide, magnesium oxide, strontium oxide, sodium oxide, and potassium oxide.
  4. 제 1항에 있어서,The method of claim 1,
    상기 셀룰로스 유도체는 니트로셀룰로스, 아세틸셀룰로스, 메틸셀룰로스, 에틸셀룰로스, 벤질셀룰로스, 카르복시메틸셀룰로스 및 하이드록시메틸셀룰로스 중에서 선택되는 어느 하나 또는 복수인 것을 특징으로 하는 내방출성 경질 흡습제 조성물.The cellulose derivative is one or more selected from nitrocellulose, acetylcellulose, methylcellulose, ethylcellulose, benzylcellulose, carboxymethylcellulose and hydroxymethylcellulose.
  5. 제 1항에 있어서,The method of claim 1,
    상기 지질은 밀랍, 라놀린, 칸델릴라, 바셀린, 폴리에틸렌 왁스, 폴리프로필렌 왁스, 폴리아미드 왁스, 카노바 왁스, 파라핀 왁스 및 폴리테트라플루오로에틸렌 왁스에서 선택되는 어느 하나 또는 복수인 것을 특징으로 하는 내방출성 경질 흡습제 조성물.The lipid is one or more selected from beeswax, lanolin, candelilla, petrolatum, polyethylene wax, polypropylene wax, polyamide wax, carnova wax, paraffin wax, and polytetrafluoroethylene wax. Hard desiccant composition.
  6. 제 1항에 있어서,The method of claim 1,
    상기 내방출성 경질 흡습제 조성물을 포함하는 흡습제품은,A moisture absorption product comprising the release-resistant hard desiccant composition,
    50℃, 상대습도 95%의 조건에서 측정한 부피변화율이 120% 이하이며, 50℃, 상대습도 95%의 조건에서 측정한 수분방출율 및 흡습율이 각각 0.8% 이하, 160% 이상인 것을 특징으로 하는 내방출성 경질 흡습제 조성물.Characterized in that the volume change rate measured at 50°C and 95% relative humidity is 120% or less, and the moisture release rate and moisture absorption rate measured at 50°C and 95% relative humidity are 0.8% or less and 160% or more, respectively. Release-resistant hard desiccant composition.
PCT/KR2020/009318 2019-10-29 2020-07-15 Anti-release hard moisture absorber composition WO2021085805A1 (en)

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