WO2012099382A2 - 디에틸헥실사이클로헥산을 포함하는 벽지용 염화비닐계 수지 조성물 - Google Patents

디에틸헥실사이클로헥산을 포함하는 벽지용 염화비닐계 수지 조성물 Download PDF

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Publication number
WO2012099382A2
WO2012099382A2 PCT/KR2012/000412 KR2012000412W WO2012099382A2 WO 2012099382 A2 WO2012099382 A2 WO 2012099382A2 KR 2012000412 W KR2012000412 W KR 2012000412W WO 2012099382 A2 WO2012099382 A2 WO 2012099382A2
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Prior art keywords
weight
vinyl chloride
parts
resin composition
compounds
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PCT/KR2012/000412
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English (en)
French (fr)
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WO2012099382A3 (ko
Inventor
김재송
윤경준
장연수
심기조
Original Assignee
한화케미칼 주식회사
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Priority to EP12736635.9A priority Critical patent/EP2666819B1/en
Priority to JP2013549371A priority patent/JP5650851B2/ja
Priority to US13/980,172 priority patent/US20130303640A1/en
Priority to CN201280005606.3A priority patent/CN103328566B/zh
Publication of WO2012099382A2 publication Critical patent/WO2012099382A2/ko
Publication of WO2012099382A3 publication Critical patent/WO2012099382A3/ko

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/06—Homopolymers or copolymers of vinyl 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Definitions

  • the present invention relates to a vinyl chloride resin composition. More specifically, it minimizes the generation of volatile organic compounds (VOCs), which is highly environmentally safe and does not use phthalate-based plasticizers. It is about vinyl resin compositions.
  • VOCs volatile organic compounds
  • Vinyl chloride resins are homopolymers of vinyl chloride and common polymers containing 50% or more of vinyl chloride, and are one of five general-purpose thermoplastic plastic resins produced by suspension polymerization and emulsion polymerization.
  • Polyvinyl chloride resin is plasticizer, stabilizer, layering agent, blowing agent, blowing agent, pigment, pigment, viscosity depressant, fat sugar (Ti0 2 ) and subsidiary materials with special functions It is widely used in a wide range of applications such as flooring, wallpaper, tarpaulin, artificial leather, toys, and undercarriage coatings by coating and molding in the form of plastisol.
  • wallpaper is the most exposed product in residential and office spaces, and more than 60% of it is manufactured using vinyl chloride resin.
  • the main issue of wallpaper in recent years is environmentally friendly wallpaper.
  • Phthalate-based plasticizers considered as HB grades (best, excellent, good, general) in accordance with the emissions of VOCs (Volatile Organic Compounds) conducted by the Air Cleaning Council (Especially DEHP, BBP, DBP).
  • plastics are prepared by mixing solid materials including vinyl chloride resin, layering agent and pigment, and liquid raw materials including plasticizer, stabilizer and viscosity reducing agent. After the sol is prepared, this plastisol is coated on paper, followed by gelling, printing, foaming and embossing to produce vinyl chloride-based wallpaper.
  • the viscosity of the plastisol is determined by coating characteristics and wallpaper in the coating process. It is the main physical property that determines the productivity, and the lower the viscosity, the better.
  • Volatile organic compounds generated from vinyl chloride-based wallpaper are derived from viscous lowering additives, liquid stabilizers and solvents for oily inks used in printing processes to reduce the viscosity of plastisols.
  • viscous lowering additives liquid stabilizers and solvents for oily inks used in printing processes to reduce the viscosity of plastisols.
  • excessive addition of viscosity-lowering additives can cause not only volatile organic compounds but also quality deterioration of the product.
  • plasticizers are the most liquid components, and these plasticizers are phthalate-based.
  • Di-nononyl phthalate Di-IsoNonyl Phthalate, DINP
  • DIDP Di-Iso-Decyl Phthalate
  • BBP Butyl Benzyl Phthalate
  • DBP Di-n-butyl phthalate
  • DBP Di-n-butyl phthalate
  • DBP Di-n-butyl phthalate
  • DBP Di-n-butyl phthalate
  • DODP dioctyl terephthalate
  • DEHP and BBPJDBP are socially endocrine disruptors (endocrine). As a disruptor, it is suspected of being an environmental hormone, and there is a movement to regulate it.
  • Patent Document 1 Korean Unexamined Patent Publication No. 2008-0105341 (Patent Document 1) describes a nonphthalate plasticizer.
  • DOTP is used alone or in combination with DINP.
  • the DOTP is not a phthalate-based plastic, so it can escape the environmental hormone debate, but has no advantages in terms of wallpaper properties, and has been used as an existing wallpaper manufacturing material.
  • additives stabilizers, viscosity-lowering additives
  • various problems have been found, such as deterioration in foaming during wallpaper production and rapid viscosity rise in winter.
  • the present invention solves the problems of the prior art, and is a vinyl chloride-based composition for wallpaper using di-2-ethylnucleosilphthalate, diisononylphthalate, or dioctyl terephthalate, which are conventionally used as a plasticizer.
  • di-2-ethylnucleosilphthalate, diisononylphthalate, or dioctyl terephthalate which are conventionally used as a plasticizer.
  • the vinyl chloride resin composition according to the present invention minimizes the amount of phthalate-based plasticizers, which have been argued to be harmful to the environment, and breaks down the viscosity of plastisols using diethylnuclear cyclonucleic acid, an eco-friendly plasticizer free from environmental hormone disputes.
  • the vinyl chloride-based resin composition according to the present invention can reduce the amount of the viscosity-lowering additive that causes the occurrence of low-boiling volatile organic compounds, thereby minimizing the occurrence of volatile organic compounds and other low-boiling additives. Volatile organics can be minimized.
  • Diethylnuclear cyclohexane has superior foaming properties to existing vinyl chloride resin compositions.
  • the present invention utilizes these properties to provide a vinyl chloride resin composition having better foaming properties than existing vinyl chloride resin compositions. .
  • plasticizers have a sharp viscosity increase during the winter, and an additional viscosity lowering agent should be added.
  • the vinyl chloride resin composition according to the present invention includes diethylnuclear cyclonucleic acid, In winter, the viscosity does not increase much, and it is very advantageous for the manufacture of environment-friendly products with very low variability at low temperature.
  • the vinyl chloride resin composition according to the present invention was found to be excellent in compatibility with other additives, and thus also has excellent low temperature stability.
  • the vinyl chloride resin composition according to the present invention is an existing vinyl chloride resin composition. It can be used for longer periods of time and shows excellent workability even at low temperatures.
  • vinyl chloride resin compositions optimize the content of the components, including vinyl chloride resins, plasticizers and other additives, enabling the excellent physical properties required when used as interior materials for wallpaper.
  • the present invention is to solve the above problems, 40 to 120 parts by weight of plasticizer, 0.5 to 7 parts by weight of stabilizer, 0.5 to 5 parts by weight of foaming agent, layering agent 30-150 to 100 parts by weight of vinyl chloride resin provides a parts by weight and per ( ⁇ 2) 1 ⁇ 20 parts by weight if the vinyl chloride coefficient including a composition.
  • the present invention relates to 100 parts by weight of vinyl chloride resin.
  • Chloride containing 40 to 120 parts by weight of plasticizer containing diethylnucleic acid cyclonucleic acid, 0.5 to 7 parts by weight of stabilizer, 0.5 to 5 parts by weight of foaming agent, 30 to 150 parts by weight of layering agent, and 1 to 20 parts by weight of (TiO 2 ) Provide vinyl resin compositions.
  • the plasticizer further includes dioctyl terephthalate, diisononyl phthalate, or a mixture thereof, and more specifically, a mixture of diethylnuclear cyclonucleic acid or diethylnuclear cyclonucleic acid and dioctyl terephthalate, or
  • the vinyl chloride-based resin composition according to the present invention has a viscosity of 40% lower than that of the representative phthalate-based plasticizer, di_2-ethylnuclear phthalate, and is tested according to the quality certification regulations of the eco-friendly building materials group established by the Korea Air Cleaning Association. when doing
  • the emission of formaldehyde is less than 0.015 mg / n h, and the emission of total volatile organic compounds is 0.10 mg / n h or less.
  • the vinyl chloride-based resin composition contains diethyl nucleosil cyclonucleic acid, and thus can exhibit excellent coating properties due to low room temperature and low temperature viscosity, excellent foaming properties, and minimize generation of volatile organic compounds.
  • the vinyl chloride resin composition according to the present invention is easy to use due to its excellent foaming properties and excellent low temperature viscosity, and has excellent low temperature storage stability, which makes it possible to use winter working conditions in comparison with conventional vinyl chloride resin composition.
  • the gelling speed is excellent even though the change in low temperature is low, so it is easy to work without changing the thermal conditions of the existing vinyl chloride resin composition manufacturing system.
  • Plasticizers are plasticizers containing diethylhexylcyclonucleic acid, specifically diethylnuclearcyclonucleic acid or diethylnuclearcyclonucleic acid;
  • the mixing ratio of the diethylnuclear cyclonucleic acid and the dioctyl terephthalate mixture is 100: 0 to 10: 90% by weight, and the mixing weight ratio of the diethylnuclear cyclonucleic acid and the diisononyl phthalate mixture is 100: 0 to 10:90 weight. It is good to be%.
  • the vinyl chloride resin composition according to the present invention is as described above.
  • diisononyl phthalate mixture By using diisononyl phthalate mixture, not only the viscosity at room temperature can be lowered, but also the viscosity can be prevented from rising at low temperatures in winter, which minimizes the amount of volatile viscosity-lowering solution additives and has excellent compatibility with additives.
  • diethyl nucleus cyclonucleic acid can improve production speed because the gelling speed is very fast.
  • the vinyl chloride resin composition according to the present invention is contained in 100 parts by weight of vinyl chloride resin.
  • the plasticizer contains less than 40 parts by weight, the viscosity of the plastisol is too high, resulting in a problem of 'coating property deterioration and inflexibility of the product, and 120 parts by weight.
  • the bleeding effect plasticizer coming out of the surface of the molded part
  • the surface is sticky with a dry surface, which can cause problems for the finished and finished products.
  • the vinyl chloride resin composition according to the present invention includes foaming agents, stabilizers, auxiliary stabilizers,
  • the additives may further include additives such as layer additives, land grades (Ti0 2 ), viscosity lowering agents, and the like.
  • the additive may be appropriately selected according to the properties to be improved in the vinyl chloride resin composition, and the composition according to the present invention may include one or more of the above additives.
  • the vinyl chloride resin composition according to the present invention is based on 100 parts by weight of the vinyl chloride resin, the plasticizer 40 to 120 parts by weight, the stabilizer 0.5 to 7 parts by weight, the foaming agent 0.5 to 5 parts by weight, layer Total 30 to 150 parts by weight and 1 to 20 parts by weight (TiO 2 ) Include.
  • the stabilizer is added to prevent various property changes caused by cleavage and crosslinking of the main chain by HC1 separation from polyvinyl chloride to form a polyene structure as a chromophore.
  • Ca-Zn It includes any one or more selected from the group consisting of a compound, a K-Zn compound, a Ba-Zn compound, an organic Tin compound, a metallic soap compound, a phenol compound, a phosphate ester compound or a phosphite ester compound .
  • the stabilizer that can be used in the present invention are Ca-Zn-based compounds; K-Zn compound; Ba-Zn compound; Organic Tin compounds such as mercaptide compounds, maleic acid compounds or carboxylic acid compounds; Metallic soap-based compounds such as Mg-stearate, Ca-stearate, Pb-stearate, Cd-stearate, or Ba-stearate; Phenolic compounds; Phosphoric acid ester compounds; Or phosphorous acid
  • Ca-Zn-based compounds it is an ester compound etc., and it is selectively included according to a use purpose.
  • K-Zn-based compounds preferably Ca-Zn-based composite organic compounds and K-Zn-based composite organic compounds.
  • the vinyl chloride resin is a hybrid polymer containing 50% or more of vinyl chloride homopolymer and vinyl chloride, and is one of five general-purpose thermoplastic resins prepared by suspension polymerization and emulsion polymerization.
  • the vinyl chloride resin used in the present invention is a hybrid polymer containing 50% or more of vinyl chloride homopolymer and vinyl chloride, and is one of five general-purpose thermoplastic resins prepared by suspension polymerization and emulsion polymerization.
  • the polymerization degree is 900 ⁇ 1700 resin produced by microsuspension polymerization or emulsion polymerization.
  • the stabilizer is preferably 0.5 to 7 parts by weight, and more preferably 1 to 4 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of the stabilizer is less than 0.5 parts by weight, there is a problem that the thermal stability is lowered, if more than 7 parts by weight may be expressed more than the required thermal stability.
  • the blowing agent used in the present invention includes any one or more selected from chemical blowing agents, physical blowing agents or mixtures thereof.
  • the chemical blowing agent decomposes above a certain temperature to generate gas.
  • azodicarbonamide azodi isobutyronitrile (azodiisobutyro-nitrile)
  • Examples thereof include sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium carbonate and ammonium carbonate.
  • physical blowing agents include carbon dioxide, nitrogen, argon, water, air and helium.
  • Inorganic foaming agents or aliphatic containing from 1 to 9 carbon atoms Organic blowing agents such as aliphatic hydrocarbons, aliphatic alcohols containing 1 to 3 carbon atoms, and halogenated aliphatic hydrocarbons containing 1 to 4 carbon atoms. Specific examples of such compounds include, aliphatic
  • Hydrocarbon compounds include methane, ethane, propane, normal butane, isobutane, normal pentane, isopentane and neopentane, and aliphatic alcohols with methanol, ethane, normal propanol and isopropanol.
  • 1,1,1,3,3-pentafluoropropane (l, l, l, 3,3-pentafluoropropane, HFC.sub.l3 245fa), pentafluoroethane, difluoromethane ), Perfluoroethane, 2,2-difluoropropane,
  • HCFC-123 1-chloro-1,2,2,2-tetrafluoroethane (1-chloro-1,2,2-tetrafluoroethane, HCFC-124), trichloromonofluoromethane ( trichloromonofluoromethane,
  • the amount of the blowing agent is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride-based resin, but when the content of the blowing agent is too small, the amount of gas for foaming is too small, so that the foaming effect is insignificant or not at all. I can't expect it, In too many cases, too much gas is produced and it is difficult to expect the required properties.
  • the filler of the present invention is used for the purpose of improving the productivity of the vinyl chloride resin composition and the dry touch feeling, and it is calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide or clay. It may include any one or more selected from the group consisting of.
  • the vinyl chloride resin composition according to the present invention may include a viscosity lowering agent as necessary, and specifically, an ester viscosity lowering agent may be used.
  • the filler may preferably contain 30 to 150 parts by weight, and more preferably 50 to 130 parts by weight.
  • the filler is contained in less than 50 parts by weight, the dimension stability and economical efficiency is low, and when included in excess of 130 parts by weight, the foam surface is not good, the processability is reduced.
  • the vinyl chloride resin composition of the present invention is added with (Ti0 2 ) sugar per white to give whiteness and
  • the concealment can be improved.
  • the above-mentioned sugar may preferably contain 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, relative to 100 parts by weight of the vinyl chloride resin. If the sugar content is contained in less than 3 parts by weight, whiteness and concealment is poor, the color does not appear properly after printing, and when contained in more than 15 parts by weight, the foam surface is deteriorated.
  • the vinyl chloride resin composition according to the present invention may be prepared by a generally known method using vinyl chloride resin, the above plasticizer and optionally an additive, and the method is not particularly limited.
  • the vinyl chloride resin composition according to the present invention is environmentally friendly and has excellent foaming properties and workability, including interior materials, such as wallpaper, flooring, artificial leather and floor studs. It can be widely applied.
  • the vinyl chloride resin composition produced by the present technology can be free from environmental controversy by using diethylnuclear cyclonucleic acid, which is a non-phthalate-based plasticizer that replaces the controversial phthalate-based plasticizer. .
  • dioctyl terephthalate which is a phthalate plasticizer and a non-phthalate plasticizer
  • the initial viscosity and the low temperature viscosity are very low and volatile organic compounds (VOC) are less generated.
  • the vinyl chloride resin additive according to the present invention has excellent compatibility with the vinyl chloride resin additive according to the present invention.
  • diethylnuclear cyclonucleic acid can improve the production speed due to the very fast gelling speed. It has the advantage of producing products under the same production conditions as plastisols using 2-ethylnucleosilphthalate.
  • the vinyl chloride resin composition according to the present invention is environmentally friendly and has excellent foaming characteristics and workability, so it is not only used for wallpaper but also for the production of flooring materials, artificial leather, etc., and can be widely applied to flooring materials.
  • FIG. 2 compares the gelling rates of plasticizers (DEHP, DEHCH, DINP, DOTP). Best Mode for Carrying Out the Invention
  • the prepared plastisol was aged for 1 hour in a 25 0 C incubator and the viscosity was measured using a Brookfield viscometer (spindle # 6, 20, 5 RPM). Viscosity with time was assessed after storage in the ° C refrigerator.
  • the change in viscosity over time means the ratio between the initial viscosity and the viscosity after 1 day
  • the change in viscosity over low temperature means the change in viscosity after 1 day at -5 ° C.
  • the foaming refers to the surface of the product, the size of the foaming cell, and the uniformity of the cells.
  • the foam sheet was coated with a 0.2 mm thickness on top of the foam sheet at 40 ° C for 40 seconds and then foamed. The surface state of the prepared foam sheet was visually observed, and the foamed cells were photographed using an electron microscope. Observations were made and the results are indicated by the following symbols.
  • the whiteness of the foam sheet was quantified after measurement using a colorimeter as a key factor in the sharpness of the color in the coloration process.
  • the HB mark refers to organic compounds (TVOC,
  • HCHO is a mark that gives the product a level of certification according to the result of the rigorous and thorough quality certification test by an accredited testing institute according to the quality certification regulation of eco-friendly building materials group established by Korea Air Cleaning Association.
  • the grades are determined by the table below, where the rating is indicated by the number of clover in the certification mark: 5 is the best, 4 is excellent, 3 is good, 2 is general I, 1 is general It is divided into II.
  • the plasticizers of Examples 1 to 4 prepared using diethyl nucleosil cyclonucleic acid as plasticizers are conventional phthalate-based plasticizers, such as di-2-ethylnusil phthalate, diisononyl phthalate, and eco-friendly plasticizers.
  • the viscosity is very low compared to the plastisols of Comparative Examples 1 to 3 prepared with phosphorus dioctyl terephthalate. Appeared low.
  • Viscosity of processing is the viscosity at the time of passing through coater when making wallpaper, wallpaper
  • Examples 1 to 4 and Comparative Examples 1 to 3 the physical property evaluation results according to the diethyl nucleus cyclonucleic acid content showed that di-2-ethylhexyl phthalate 70 was mixed under the condition that 60 parts by weight of diethyl nucleus cyclonucleic acid was mixed. Similar viscosities and physical properties are shown in comparison with those by weight. Therefore, the use of diethylnuclear cyclonucleic acid has the advantage of reducing the amount of plasticizer added by 10 parts by weight.
  • Examples 5 to 10 below are plasticizer diethylnuclear cyclonucleic acid and
  • Example 3 The same procedure as in Example 1 was carried out except that 50 parts by weight of diethylnucleosilcyclonucleic acid and 20 parts by weight of dioctyl terephthalate were used, and the results are shown in Table 3.
  • dioctyl terephthalate When dioctyl terephthalate is mixed, dioctyl terephthalate content
  • Examples 11 to 16 are plasticizer diethylnuclear cyclonucleic acid and
  • the diethylnuclear cyclonucleic acid is not soluble at -15 ° C, and it is confirmed that the excellent low temperature viscosity changes due to the excellent low temperature characteristics. there was.
  • Example 17 In the case of Example 17, in which diethyl nucleus cyclonucleic acid was used alone and no viscosity lowering agent was used, processing viscosity, room temperature viscosity change, low temperature viscosity change, The values of TVOC and HCHO were shown to be good.
  • the diethyl nucleosil cyclohexane of the present invention is similar to di-2-ethylnuclear phthalate, a typical plasticizer, and gelling rate, diisononyl phthalate and di It appeared much faster than octyl terephthalate, which has the advantage that it can be used without changing the special thermal conditions in the existing wallpaper production process.
  • jeonghaejyeoseo is no, gyundung and only this as described later claims claims or parity variants 0 all that are to fall within the scope of the inventive idea something to do.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

본 발명은 가소제로 디에틸헥실사이클로헥산을 포함하는 염화비닐계 수지 조성물에 대한 것으로, 논란이 되고 있는 프탈레이트계 가소제를 대체하여 환경 오염 문제를 방지할 수 있고，종래 프탈레이트계 가소제 및 논프탈레이트계 가소제인 디옥틸테레프탈레이트에 비해 초기점도 및 저온점도가 매우 낮고 저온 경시변화성이 극히 낮아 작업성이 용이하며, 휘발성 유기화합물의 발생이 적어 친환경제품 개발에 널리 적용할 수 있다.

Description

명세서
발명의명칭:디에틸핵실사이클로핵산을포함하는염화비닐계 수지조성물
기술분야
[1] 본발명은염화비닐계수지조성물에관한것으로，더욱상세하게는휘발성 유기화합물 (Volatile Organic Compounds: VOCs)의발생량을최소화하여환경에 대한안전성이높고,프탈레이트계가소제를사용하지않는친환경염화비닐계 수지조성물에관한것이다.
배경기술
[2] 염화비닐계수지는염화비닐의단독중합체및염화비닐을 50%이상함유한 흔성중합체로서,현탁중합과유화중합으로제조되는 5대범용열가소성 플라스틱수지중의하나이다.그중에서유화중합으로제조되는
폴리염화비닐계수지는가소제 (Plasticizer),안정제 (Stabilizer),층전제 (Filler), 발포제 (Blowing Agent),안료 (Pigment),점도조절제 (Viscosity Depressant), 지당 (Ti02)및특수한기능을갖는부원료를흔합하여플라스티졸 (Plastisol) 형태로코팅성형과몰드코팅성형가공법을통해바닥재,벽지，타포린， 인조피혁，장난감 (Toy),자동차하부코팅재등의광범위한분야에사용되고 있다.
[3] 특히，벽지는주거및사무공간에서가장많이노출되는제품으로서， 60% 이상이염화비닐계수지를이용하여제조되고있다.최근벽지의주요쟁점은 친환경벽지에관한것이며，친환경성에대한판단기준은공기청정협의회에서 시행하고있는휘발성유기화합물 (Volatile Organic Compounds: VOCs)의 방출량에따라매겨지는 HB등급 (최우수,우수，양호，일반까지 4단계)과 국내에서환경호르몬의심물질이라고여겨지는프탈레이트계가소제 (특히 DEHP, BBP, DBP)함유여부에따라결정되고있다.
[4] 염화비닐계수지를이용한벽지의제조과정을살펴보면，염화비닐계수지 , 층전제,안료를포함하는고상의원료와가소제,안정제，점도저하제용첨가제를 포함하는액상의원료를흔합하여플라스티졸을제조한다음，이플라스티졸을 종이에코팅하여겔링，인쇄,발포및엠보스공정을거쳐염화비닐계벽지가 생산된다.이때，상기플라스티졸의점도는코팅공정에서코팅특성및벽지의 생산성을결정하는주요물성이며，점도가낮을수록유리하다.
[5] 염화비닐계벽지에서발생되는휘발성유기화합물은플라스티졸의점도를 낮추기위해첨가하는점도저하제용첨가제,액상안정제및인쇄공정에서 사용하는유성잉크의용제에서발생되는것으로,비점이높은가소제의영향은 거의없다.특히점도저하용첨가제를과량첨가할경우휘발성유기화합물 발생뿐만이아니라제품의품질저하의원인이된다.따라서휘발성유기화합물 발생을줄이기위해서는휘발성유기화합물발생의원인이되는점도저하제용 액상첨가제첨가량을최소화할필요가있다.
[6] 벽지용염화비닐계수지조성물중에서가소제는가장많은함량을차지하는 액상성분이며,이러한가소제는프탈레이트계제품인
디 -2-에틸핵실프탈레이트 (Di-2-EthylHexyl Phthalate, DEHP),
디이소노닐프탈레이트 (Di-IsoNonyl Phthalate, DINP),
디이소데실프탈레이트 (Di-Iso-Decyl Phthalate, DIDP),부틸벤질프탈레이트 (Butyl Benzyl Phthalate, BBP),디-엔 -부틸프탈레이트 (Di-n-butyl phthalate, DBP)와 최근들어논프탈레이트계 (non- phthalate)가소제인디옥틸테레탈레이트 (dioctyl terephthalate, DOTP)등이일부사용되고있다.프탈레이트계가소제중 DEHP, BBPJDBP와같은일부제품은사회적으로사람의호르몬작용을방해하거나 흔란시키는내분비계교란물질 (endocrine disrupter)로서환경호르몬으로 의심받고있어이를규제하는움직임이있다.
[7] 대한민국공개특허 2008-0105341(특허문헌 1)에는논프탈레이트계가소제인
DOTP를단독또는 DINP와흔합한것을사용하고있는것이개시되어 있는데， 상기 DOTP는프탈레이트계가소제가아니기때문에환경호르몬논쟁에서 벗어날수는있으나，벽지용물성측면에서장점이없고，기존벽지제조원료로 사용하던첨가제 (안정제，점도저하용첨가제)와의상용성에문제가있으며，벽지 생산시발포성저하，동절기에급격한점도상승등의여러가지문제가 발견되고있다.
발명의상세한설명
기술적과제
[8] 따라서,본발명은상기종래기술의문제점을해결하기위한것으로서종래에 가소제로사용되는디 -2-에틸핵실프탈레이트,디이소노닐프탈레이트,또는 디옥틸테레프탈레이트를사용한벽지용염화비닐계조성물에비하여
플라스티졸의점도가매우낮고기존사용하는첨가제와상용성이우수하면서 휘발성유기화합물의발생을최소화하는
디 (2-에틸핵실)사이클로핵산 -1,4-디카르복실레이트 (DEHCH,
디에틸핵실사이클로핵산)가소제를포함하는친환경염화비닐계수지조성물을 개발하였다.
[9] 본발명에따른염화비닐계수지조성물은환경에유해하다는논쟁을지니고 있는프탈레이트계가소제를최소화하며，환경호르몬논쟁에서자유로운 친환경가소제인디에틸핵실사이클로핵산을사용하여플라스티졸의점도를 획기적으로낮출수있다.이에따라본발명에따른염화비닐계수지조성물은 저비점의휘발성유기화합물발생의원인이되는점도저하용첨가제의 사용량을줄일수있으므로휘발성유기화합물발생을최소화하며,기타 저비점제첨가에따른휘발성유기물을최소화할수있다. [10] 본발명에따른염화비닐계수지조성물에포함되어있는
디에틸핵실사이클로헥산은기존의염화비닐계수지조성물보다우수한발포 특성을가지고있다.본발명은이러한특성을이용하여기존의염화비닐계수지 조성물보다발포특성이우수한염화비닐계수지조성물을제공하게되었다.
[11] 특히종래의가소제들은동절기에급격한점도상승이일어나추가로과량의 점도저하제를첨가해야하나,본발명에따른염화비닐계수지조성물은 디에틸핵실사이클로핵산을포함하므로이를적용한플라스티졸은동절기에도 점도상승이크지않으며，저온경시변화성이극히낮아친환경제품제조에매우 유리하다.
[12] 또한본발명의따른염화비닐계수지조성물은다른첨가제들과의상용성이 우수하여저온안정성또한우수함을발견하였으며，이로인하여본발명에따른 염화비닐계수지조성물은기존의염화비닐계수지조성물보다장기간 /장시간 사용이가능하며，저온에서도우수한작업성을보인다.
[13] 이러한염화비닐계수지조성물은염화비닐계수지，가소제및기타첨가제를 포함하는구성성분의함량을최적으로하여벽지용등의인테리어소재로 사용될경우요구되는우수한물성을구현할수있게해준다.
과제해결수단
[14] 본발명은상기와같은과제를해결하기위하여，염화비닐계수지 100중량부에 대하여가소제 40~120중량부，안정제 0.5~7중량부,발포제 0.5~5중량부，층전제 30-150중량부및지당 (ΉΟ2)1~20중량부를포함하는염화비닐계수지조성물을 제공한다.
[15] 구체적으로본발명은염화비닐계수지 100증량부에대하여
디에틸핵실사이클로핵산을포함하는가소제 40~120중량부，안정제 0.5~7 증량부，발포제 0.5~5중량부，층전제 30~150중량부및지당 (TiO2)l~20중량부를 포함하는염화비닐계수지조성물을제공한다.
[16] 이때，가소제는디옥틸테레프탈레이트，디이소노닐프탈레이트，또는이들의 흔합물을더포함하며，보다구체적으로는디에틸핵실사이클로핵산또는 디에틸핵실사이클로핵산과디옥틸테레프탈레이트의흔합물또는
디에틸핵실사이클로핵산과디이소노닐프탈레이트의흔합물을포함한다.
[17] 본발명에따른염화비닐계수지조성물은대표적인프탈레이트계가소제인 디 _2-에틸핵실프탈레이트에비해점도가 40%낮으며 ,한국공기청정협회가 제정한친환경건축자재단체품질인증규정에의하여테스트할때
포름알데히드의방출량이 0.015 mg/n h미만이고,총휘발성유기화합물의 방출량이 0.10 mg/n h이하이다.
[18] 또한,상기염화비닐계수지조성물은디에틸핵실사이클로핵산을포함하고 있어상온및저온점도가낮아우수한코팅특성을구현할수있으며,발포 물성이우수하고,휘발성유기화합물의발생을최소화할수있어환경에대한 안정성이높다.
[19] 본발명에따른염화비닐계수지조성물은이러한우수한발포특성과더불어 우수한저온점도성으로인하여작업이용이하고,저온저장안정성이우수하여 기존의염화비닐계수지조성물에비하여동절기작업조건이용이하다.또한 저온경시변화성이낮음에도겔링속도는우수하기때문에기존의염화비닐계 수지조성물제조시스템의열적조건을바꾸지않아도작업이용이하다는 장점도가지고있다.
[20] 가소제는디에틸헥실사이클로핵산을포함하는가소제이며，구체적으로는 디에틸핵실사이클로핵산또는디에틸핵실사이클로핵산과
디옥틸테레프탈레이트의혼합물또는디에틸핵실사이클로핵산과디이소노닐 프탈레이트의혼합물을포함한다.보다구체적으로는
디에틸핵실사이클로핵산과디옥틸테레프탈레이트흔합물의흔합증량비는 100 : 0~ 10:90증량%이며，디에틸핵실사이클로핵산과디이소노닐프탈레이트 흔합물의혼합중량비는 100： 0 ~ 10： 90중량 %인것이좋다.
[21] 본발명에따른염화비닐계수지조성물은상기와같은
디에틸핵실사이클로핵산단독，디에틸핵실사이클로핵산과
디옥틸테레프탈레이트흔합물또는디에틸헥실사이클로핵산과
디이소노닐프탈레이트흔합물을사용하여상온에서의점도를낮출뿐만 아니라,동절기의저온에서도점도가상승되는것을방지할수있어，휘발성이 강한점도저하용액상첨가제첨가량을최소화할수있으며，첨가제와의 상용성이우수하다.또한，디에틸핵실사이클로핵산은겔링속도가매우빠르기 때문에생산속도를향상시킬수있다.
[22] 본발명에따른염화비닐계수지조성물은염화비닐계수지 100중량부에
대하여，상기가소제 40 ~ 120중량부,더욱바람직하게는 70 ~ 90중량부를 포함한다. 본발명에따른벽지용염화비닐계수지조성물에서가소제가 40 중량부미만으로포함된경우，플라스티졸의점도가너무높아코팅성이 ' 저하되는문제와제품의유연성이떨어지는문제가있고 120중량부를초과하여 포함된경우，블리딩현상 (bleeding effect,가소제가성형품의표면으로나오는 현상)이일어나기쉽고표면이덜마른상태로끈적거리기때문에가공및 완제품에문제를야기할수있다.
[23] 본발명에따른염화비닐계수지조성물은발포제，안정제 ,보조안정제 ,
층전제，지당 (Ti02),점도저하제등과같은첨가제를더포함할수있다. 상기 첨가제는염화비닐계수지조성물에서향상시키고자하는물성에따라 적합하게선택될수있고，본발명에따른조성물은상기첨가제들을하나이상 포함할수있다.
[24] 더욱구체적으로，본발명에따른염화비닐계수지조성물은염화비닐계수지 100중량부에대하여,상기가소제 40 ~ 120중량부,안정제 0.5 - 7중량부， 발포제 0.5 ~ 5중량부，층전제 30 ~ 150중량부및지당 (TiO2)l~20증량부를 포함한다.
[25] 상기 안정제는 폴리 염화비 닐에서 HC1이 분리 되어 발색단인 폴리 엔 구조를 형성하여 주쇄의 절단，가교 현상을 일으켜 발생하는 여 러 가지 물성 변화를 예방하는 목적으로 첨가되는 것으로， Ca-Zn계 화합물， K-Zn계 화합물, Ba-Zn계 화합물，유기 Tin계 화합물，메탈릭 비누계 화합물，페놀계 화합물, 인산 에스테르계 화합물 또는 아인산 에스테르계 화합물로 이루어진 군으로부터 선택되는 어느 하나 이상인 것을 포함한다. 본 발명에서 사용될 수 있는 안정제로 보다 구체적 인 예는 Ca-Zn계 화합물; K-Zn계 화합물; Ba-Zn계 화합물; 머캡티드 (Mercaptide)계 화합물, 말레인산계 화합물 또는 카르복실산계 화합물과 같은 유기 Tin계 화합물; Mg-스테아레 이트, Ca-스테아레이트, Pb-스테아레 이트， Cd-스테아레 이트, 또는 Ba-스테아레 이트 등과 같은 메탈릭 비누계 화합물; 페놀계 화합물; 인산 에스테르계 화합물; 또는 아인산
에스테르계 화합물 등이며，사용 목적 에 따라 선택적으로 포함된다. 본 발명에서는 특히 Ca-Zn계 화합물， K-Zn계，바람직하게는 Ca-Zn계 복합 유기화합물， K-Zn계 복합 유기화합물을 사용하는 것이 바람직 하다.
[26] 상기 염화비 닐 수지는 염화비 닐의 단독 중합체 및 염화비 닐을 50%이상 함유한 혼성 중합체로서，현탁중합과 유화중합으로 제조되는 5대 범용 열가소성 플라스틱 수지 중의 하나이다. 본 발명에 사용되는 염화비 닐 수지는
미세현탁중합 또는 유화증합에서 제조된 증합도 900~1700인 수지 이다.
[27] 상기 안정 제는 염화비 닐계 수지 100 증량부에 대하여 바람직하게는 0.5 ~ 7 중량부，더욱 바람직하게는 1 ~ 4 증량부가 포함된다. 안정제의 함량이 0.5 중량부 미 만이면，열안정성 이 떨어지는 문제점 이 있고， 7 중량부를 초과하면 필요 이상의 열안정성 이 발현될 수 있다.
[28] 본 발명에서 사용되는 발포제는 화학적 발포제，물리 적 발포제 또는 이들의 혼합물 중에서 선택되는 어느 하나 이상인 것을 포함한다.
[29] 상기 화학적 발포제로는 특정온도 이상에서 분해되 어 가스를 생성하는
화합물이면 특별히 제한하지 않으며 , 아조디카본아미드 (azodicarbonamide), 아조디 이소부티로니트릴 (azodiisobutyro-nitrile),
벤젠설포닐하이드라지드 (benzenesulfonhydrazide),
4,4-옥시 벤젠설포닐-세미카바자이드 (4,4-oxybenzene sulfonyl-semicarbazide), p-를루엔 설포닐 세미-카바자이드 (p-toluene sulfonyl semi-carbazide),
바륨아조디카복실레 이트 (barium azodicarboxylate), Ν,Ν'-디 메틸 -Ν,Ν'- 디 니트로소테 레프탈아미드 (N,N'-dimethyl-N,N'-dinitrosoterephthalamide) 및 트리하이드라지노 트리아진 (trihydrazino triazine) 둥을 예로 들 수 있다. 또한 중탄산나트륨, 중탄산칼륨，중탄산암모늄，탄산나트륨 및 탄산암모늄 둥을 예로 들 수 있다.
[30] 또한, 물리적 발포제로는 이산화탄소，질소, 아르곤，물，공기 및 핼륨 등의
무기발포제 또는 1 내지 9개의 탄소원자를 포함하는 지방족 탄화수소화합물 (aliphatic hydrocarbon), 1 내지 3개의 탄소원자를 포함하는 지 방족 알코올 (aliphatic alcohol) 및 1 내지 4개의 탄소원자를 포함하는 할로겐화 지 방족 탄화수소화합물 (halogenated aliphatic hydrocarbon) 등의 유기 발포제를 들 수 있다. 상기와 같은 화합물들의 구체적 인 예를 들면，지방족
탄화수소화합물로서 메탄, 에 탄，프로판，노말부탄，아이소부탄，노말펜탄， 아이소펜탄 및 네오펜탄 둥이 있으며 , 지방족 알코올로서 메탄올, 에 탄을, 노말프로판올 및 아이소프로판올 둥이 있고, 할로겐화 지 방족
탄화수소화합물로서 메틸플루오라이드 (methyl fluoride),
퍼플루오로메탄 (perfluoromethane), 에 틸 플루오라이드 (ethyl fluoride),
1,1-디플루오로에 탄 (1,1-difluoroethane, HFC- 152a),
1,1,1-트리플루오로에 탄 (l,l,l-trifluoroethane, HFC- 143a),
1,1, 1,2-테트라플투오로에탄 (l,U,2-tetrafluoroethane, HFC- 134a),
1,1，2，2-테트라플루오로에 탄 (l,l,2,2-tetrafluoromethane, HFC- 134),
1，1，1,3，3-펜타플루오로부탄 (U,l,3,3-pentafluorobutane, HFC-365mfc),
1,1,1,3,3-펜타플루오로프로판 (l,l,l,3,3-pentafluoropropane, HFC.sub.l3 245fa), 펜타플루오로에 탄 (pentafluoroethane), 디플루오로메탄 (difluoromethane), 퍼플루오로에탄 (perfluoroethane), 2，2-디플루오로프로판 (2,2-difluoropropane),
1，1，1-트리플루오로프로판 (l,l,l-trifluoropropane),
퍼플루오로프로판 (perfluoropropane), 디클로로프로판 (dichloropropane), 디플루오로프로판 (difluoropropane), 퍼플루오로부탄 (perfluorobutane),
퍼플루오로사이클로부탄 (perfluorocyclobutane), 메틸 클로라이드 (methyl chloride), 메틸렌 클로라이드 (methylene chloride), 에 틸 클로라이드 (ethyl chloride),
1， 1， 1 -트리클로로에 탄 ( 1 , 1， 1 -trichloroethane),
1,1-디클로로 -1-플루오로에 탄 (1,1-dichloro-l-fluoroethane, HCFC-141b),
1-클로로 -1,1-디플루오로에 탄 (l-chloro-U-difluoroethane, HCFC- 142b), 클로로디플루오로메탄 (chlorodifluoromethane, HCFC-22),
1 , 1 -디클로로 -2,2,2-트리플루오로에 탄 ( 1， 1 -dichloro-2,2,2-trifluoroethane,
HCFC- 123)， 1 -클로로 - 1 ,2,2,2-테트라플루오로에 탄 ( 1 -chloro- 1 ,2,2,2-tetrafluoroethan e, HCFC- 124), 트리클로로모노플루오로메탄 (trichloromonofluoromethane,
CFC-11), 디클로로디플루오로메탄 (dichlorodifluoromethane, CFC-12),
트리클로로트리플루오로에 탄 (trichlorotrifluoroethane, CFC-113),
1,1,1-트리플루오로에 탄 (U,l-trifluoroethane)，펜타플루오로에 탄 (pentafluoroethan e), 디 클로로테트라플루오로에 탄 (dichlorotetrafluoroethane, CFC-114),
클루오로헵타플루오로프로판 (chloroheptafluoropropane) 및
디클로로핵사플루오로프로판 (dichlorohexafluoropropane) 등을 들 수 있다.
상기와 같은 발포제의 함량은 염화비 닐계 수지 100 중량부에 대하여 0.5 ~ 5 중량부인 것이 바람직 한데, 발포제의 함량이 너무 적은 경우에는 발포를 하기 위 한 가스의 생성 량이 너무 적어 발포효과가 미미하거나 전혀 기 대할 수가 없고， 너무많은경우에는가스의생성량이너무많아요구되는물성을기대하기 어렵다.
[31] 본발명의충전제는염화비닐계수지조성물의생산성，건조상태의감촉 (Dry touch)감을향상시키는목적으로사용되며 ,탄산칼슘，탈크，이산화티탄,카올린, 실리카,알루미나，수산화마그네슘또는점토로이루어진군에서선택되는어느 하나이상인것을포함한다.
[32] 본발명에따른염화비닐계수지조성물은필요에따라점도저하제를포함할 수있으며,구체적으로는에스테르계점도저하제를사용할수있다.
[33] 상기본발명에따른염화비닐계수지조성물에서상기충전제는바람직하게는 30 - 150중량부，더욱바람직하게는 50 ~ 130중량부포함될수있다. 충전제가 50중량부미만으로포함된경우,치수안정성과경제성이낮아지는문제점이 있고， 130증량부초과하여포함된경우,발포표면이좋지않으며，가공성이 저하되는문제점이있다.
[34] 본발명의염화비닐계수지조성물은지당 (Ti02)을첨가하여백색도및
은폐성을향상시킬수있다.상기지당은염화비닐계수지 100중량부에대하여 바람직하게는 1 ~ 20증량부,더욱바람직하게는 3 - 15중량부가포함될수있다. 지당이 3중량부미만으로포함된경우，백색도및은폐성이떨어져인쇄후 색깔이제대로나오지않으며， 15중량부초과하여포함된경우,발포표면이 저하되는문제점이있다.
[35] 본발명에따른염화비닐계수지조성물은염화비닐계수지 ,상기가소제및 선택적으로첨가제를사용하여일반적으로알려진방법에의하여제조될수 있으며，그방법에있어서특별히한정되지는않는다.
[36] 상술한바와같이，본발명에따른염화비닐계수지조성물은친환경적이며 매우우수한발포특성및작업성을가지고있어이를포함하는인테리어소재, 예를들면，벽지，상재，인조레쟈및바닥재둥에널리적용될수있다.
발명의효과
[37] 이상에서설명한바와같이，본기술로제조된염화비닐계수지조성물은특히 논란이되고있는프탈레이트계가소제를대체하는논프탈레이트계가소제인 디에틸핵실사이클로핵산을사용함으로써환경논란에서자유로을수있다.
[38] 또한디에틸핵실사이클로핵산을사용한염화비닐계조성물은기존
프탈레이트계가소제및논프탈레이트계가소제인디옥틸테레프탈레이트에 비해초기점도및저온점도가매우낮고휘발성유기화합물 (VOC)발생이적어 친환경제품개발에유리하다.
[39] 특히,본발명에따른염화비닐계수지첨가제와의상용성이우수하다.또한， 디에틸핵실사이클로핵산은겔링속도가매우빠르기때문에생산속도를 향상시킬수있다.또한,기존에가장많이사용되는디 -2-에틸핵실프탈레이트를 사용한플라스티졸과동일한생산조건에서제품을생산할수있는장점이있다. [40] 또한본발명에따른염화비닐계수지조성물은친환경적이며매우우수한 발포특성및작업성을가지고있어벽지용뿐만아니라，상재,인조레쟈등의 제조에사용되며,바닥재용에도널리적용될수있다.
도면의간단한설명
[41] 도 1은가소제 (DEHP, DEHCH, DINP, DOTP)의저온저장안정성을측정한
것이다.
[42] 도 2는가소제 (DEHP, DEHCH, DINP, DOTP)의겔링속도를비교한것이다. 발명의실시를위한최선의형태
[43] 본발명을실시여 i에의해상세히설명한다.
[44] 단，하기실시예는본발명을예시하는것일뿐，본발명의내용이하기
실시예에의해한정되는것은아니다.
[45]
[46] (평가)
[47] 점도측정
[48] 제조된플라스티졸을 250C항온오븐에서 1시간동안숙성시킨후 Brookfield 점도계 ( spindle #6， 20, 5 RPM)를이용하여점도를측정하였다.또한제조된 플라스티졸을 -5°C냉장고에보관한후시간에따른점도를평가하였다.
[49] 점도경시변화는초기점도와 1일후점도의비를의미하여，
저온점도경시변화는 -5°C조건에서 1일후점도변화정도를의미한다.
[50]
[51] 발포표면및발포셀 (cell)측정
[52] 발포제품에서가장중요한것은발포성이다.상기발포성은제품의표면,발포 셀 (cell)의크기및셀 (cell)의균일성을말한다.본발명에따른플라스티졸을 어플리케이션을이용하여종이위에 0.2 mm두께로코팅한후 220°C오본에서 40초동안열올가하여발포시켜발포시트를제작하였다.이렇게제작된발포 시트의표면상태는육안관찰을통해,발포 cell은전자현미경을이용하여촬영, 관찰하였으며,결과는하기와같은기호로표시하였다.
[53] (매우우수) ©>0>Δ>Χ(매우불량)
[54]
[55] 백색도측정
[56] 발포시트의백색도는조색공정에서색상의선명도를나타내는주요인자로서 컬러미터 (colorimeter)를이용하여측정한후수치화하였다.
[57]
[58] 열안정성측정
[59] 플라스티졸을어플리케이션을이용하여종이위에 0.2 mm두께로코팅한후， 220°C오본에서 60~100초동안열을가하여황변이발생되는시점을관찰하여, 상대비교를통해열안정성을비교하였다.열안정성은다음과같은기준으로 정리하였다.
[60] (매우우수) ©>0>Δ>Χ(매우불량)
[61]
[62] 저온특성평가
[63] 가소제를 50 vial에주입한후 -15°C에서 4시간방치후꺼내어가소제의 외관을육안으로관찰하였다.
[64]
[65] 겔링속도측정
[66] 제조된플라스티졸을 SVNC장비를이용하여 110°C에서겔링속도를
측정하였다. SVNC장비에서겔링이진행될수록진폭 (amplitude)이감소하는데 이값이감소하는속도를이용하여겔링속도를비교측정하였다.
[67]
[68] HB마크
[69] HB마크는국내외에서생산되는건축자재에대한유기화합물 (TVOC,
HCHO)방출강도를한국공기청정협회가제정한친환경건축자재단체품질인증 규정에의하여공인시험기관에서엄격하고철저한품질인증시험을한후그 결과에따라제품에인증둥급을부여하는마크이다.벽지의인증둥급은아래의 표에의해결정되며,인증마크에클로버개수로등급이표시된다.클로버의 개수가 5개이면최우수, 4개는우수， 3개는양호， 2개는일반 I, 1개는일반 II으로 구분한다.
[70] <표 1>
[71]
Figure imgf000012_0001
[72] (실시 예 1)
[73] 염화비 닐계 수지 (중합도 900인 유화중합수지) 100 중량부에 대하여，가소제로 디에 틸핵실사이클로핵산 60 중량부， K/Zn계 복합안정 제 (KKZ102PF, 우창실업) 3 중량부, 아조디카본아미드 발포제 (DWPX03, 동진세미 켐) 3 중량부，에스테르계 점도저하제 (V5125, ΒΥΚ사) 5 중량부，지당 (R902, Dupont사) 10 중량부 및 평균입균 10/ 인 탄산칼슘 (OM-10, 한국오미 아) 100 중량부를 매티스
믹서 (Mathis mixer)에서 10분 동안 흔합하여 플라스티졸을 제조한 후, 상기 평가에서 기 재된 측정방법에 의하여 물성을 평가하고, 그 결과를 표 2에 나타내었다.
[74] (실시 예 2)
[75] 가소제로 디 에 틸핵실사이클로핵산 70 중량부를 사용하는 것을 제외하고는 실시 예 1과 동일하게 제조하였으며，그 결과를 표 2에 나타내었다.
[76] (실시 예 3)
[77] 가소제로 디 에 틸핵실사이클로핵산 80 증량부를 사용하는 것을 제외하고는 실시 예 1과 동일하게 제조하였으며，그 결과를 표 2에 나타내었다.
[78] (실시 예 4)
[79] 가소제로 디에 틸헥실사이클로핵산 90 증량부를 사용하는 것을 제외하고는 실시 예 1과 동일하게 제조하였으며 , 그 결과를 표 2에 나타내었다.
[80] (비교예 1)
[81] 가소제로 디에틸핵실사이클로핵산 대신에，디 -2-에 틸핵실프탈레 이트 70 중량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를표 2에나타내었다.
[82] (비교예 2)
[83] 가소제로디에틸핵실사이클로핵산대신에，디이소노닐프탈레이트 70
중량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를표 2에나타내었다.
[84] (비교예 3)
[85] 가소제로디에틸핵실사이클로핵산대신에，디옥틸테레프탈레이트 70
중량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며,그 결과를하기표 3에나타내었다.
[86] <표 2>
[87]
Figure imgf000013_0001
상기표 2에서볼수있는바와같이,가소제로디에틸핵실사이클로핵산을 사용하여제조한실시예 1내지 4의플라스티졸은종래의프탈레이트계 가소제인디 -2-에틸핵실프탈레이트,디이소노닐프탈레이트와친환경가소제인 디옥틸테레프탈레이트로제조한비교예 1내지 3의플라스티졸에비하여 점도가매우낮고，특히디 -2-에틸핵실프탈레이트에비해점도가 50%수준으로 낮게나타났다.
[89] 가공점도는벽지제조시코터 (coater)를통과할때의점도로，벽지
제조공정에서매우중요한특성치이다.본발명에따른실시예 1내지 4는상기 비교대상가소제에비해가공점도가매우낮음을확인할수있었다.그리고상온 점도경시변화는비교대상가소제간의차이가크지않았다.
[90] 동절기에기온이내려가면서가소제점도가상승시，이를방지하기위하여 하절기에비해점도를낮추는방안으로액상첨가제를과량첨가함으로써원가 상승및휘발성유기화합물 (VOC)이발생하는문제가있었다.따라서동절기 점도가낮은가소제일수록친환경벽지생산에적합하다고볼수있는관점에서， 디에틸핵실사이클로핵산을가소제로사용한실시예 1내지 4는비교예 1내지
3에비하여저온점도및저온점도경시변화가매우낮아우수함을확인할수 있었다.특히,친환경가소제로사용되고있는디옥틸테레프탈레이트를 가소제로사용한비교예 3과대비시저온점도및저온점도경시변화는매우작기 때문에동절기에디에틸핵실사이클로핵산의저점도특성은더욱부각될수 있다.
[91] 실시예 1내지 4의발포성은모두매우우수하게나타났으며，비교예 1내지 3도 유사한수준이였다.
[92] 열안정성은디이소노닐프탈레이트에비해우수하고디옥틸프탈레이트와
유사하며디옥틸테레프탈레이트에비해서는약간떨어진다.그러나
디이소노닐프탈레이트도폴리염화비닐 (PVC)벽지생산과정에서열안정성이 문제가되지않기때문에디에틸핵실사이클로핵산의열안정성은벽지 제조공정에 있어문제가되지않는다.
[93] 백색도는실시예및비교예모두유사하게나타났다.
[94] 상기실시예 1내지 4그리고비교예 1내지 3에서디에틸핵실사이클로핵산 함량에따른물성평가결과를보면，디에틸핵실사이클로핵산 60증량부를 흔합하는조건에서디 -2-에틸헥실프탈레이트 70중량부를흔합한것과비교시 유사한점도및물성을나타낸다.따라서디에틸핵실사이클로핵산을사용할 경우，가소제첨가량을 10증량부정도줄일수있는장점이 있다.
[95] 또한벽지제조공장에서점도조절을위해추가첨가하는점도저하제첨가량을 줄일수있어친환경벽지생산에유리하다.그리고점도저하제첨가량을 줄임으로써 VOC발생가능성을줄일수있고벽지생산과정에서발생되는 점착 (tacky)현상을방지할수있는장점이있다.
[96] 하기실시예 5내지 10은가소제로디에틸핵실사이클로핵산및
디옥틸테레프탈레이트와의혼합가능성을평가한것으로,상기
디에틸핵실사이클로핵산및디옥틸테레프탈레이트의흔합비를제어하여 실시하였다.
[97] (실시예 5)
[98] 가소제로디에틸핵실사이클로핵산 60중량부및디옥틸테레프탈레이트 10 증량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를표 3에나타내었다.
[99] (실시예 6)
[100] 가소제로디에틸핵실사이클로핵산 50중량부및디옥틸테레프탈레이트 20 중량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를표 3에나타내었다.
[101] (실시예 7)
[102] 가소제로디에틸헥실사이클로핵산 40중량부및디옥틸테레프탈레이트 30 중량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를표 3에나타내었다.
[103] (실시예 8)
[104] 가소제로디에틸핵실사이클로핵산 30중량부및디옥틸테레프탈레이트 40 중량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를표 3에나타내었다.
[105] (실시예 9)
[106] 가소제로디에틸핵실사이클로핵산 20중량부및디옥틸테레프탈레이트 50 중량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를표 3에나타내었다.
[107] (실시예 10)
[108] 가소제로디에틸헥실사이클로핵산 10중량부및디옥틸테레프탈레이트 60 증량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를하기표 3에나타내었다.
[109] <표3>
[110]
실시여 I 설시에 실시에 실시 0靈 설시 0醫 설시 ο|
5 6 7 8 9 10 초기점도 (c
5,050 5,400 5,850 6,800 7.250 7,500
PS) 상온점도
1.08 1.05 1.05 1.06 1.05 1.09 경시변 지온 도
(CPS-5t 31,350 34,050 38,750 43,200 46,450 54細 )
지온정도경
4.63 4.86 4.98 4.53 4.50 4.89 시변학
가 도
(CPS, 500 4,130 4,530 4.990 5,460 6.040 6.810 sec-1)
^^성 Θ Ο ο Θ Ο ο 열 ¾t¾성 Ο ο ο Ο ο ο -도 91.0 90.9 91.0 91.0 91.0 91.0
TVOC 0.05 0.06 0.06 0.07 0.08 0.08
HCHO 0.001 0.001 0.001 0.001 0.001 0.001
[111] 상기표 3에서볼수있듯이,디에틸핵실사이클로핵산에
디옥틸테레프탈레이트를흔합할경우디옥틸테레프탈레이트함량이
증가할수록점도는상승하고,저온점도및저온점도경시변화도약간증가한다. 특히，비교예 3과대비시디옥틸테레프탈레이트에디에틸핵실사이클로핵산을 소량 (10중량 %이상)혼합하면디옥틸테레프탈레이트단독에비해저온 경시변화성이현격히작아진다.
[112] 발포성은디옥틸테레프탈레이트함량이증가할수록약간떨어지지만，벽지 제조시문제가되지않으며 ,열안정성은개선됨을확인할수있었다.따라서，본 발명에따른실시예 5내지 10을통하여디에틸핵실사이클로핵산과
디옥틸테레프탈레이트의혼합물이염화비닐계수지 100증량부에대하여 70 증량부를함유할시상기흔합중량비는 70:0 ~ 10:60인것이바람직함을확인할 수있었다.
[113] 하기실시예 11내지 16은가소제로디에틸핵실사이클로핵산및
디이소노닐프탈레이트와의흔합가능성을평가한것으로，상기
디에틸핵실사이클로핵산및디이소노닐프탈레이트의흔합비를제어하여 실시하였다. [114] (실시예 11)
[115] 가소제로디에틸핵실사이클로핵산 60중량부및디이소노닐프탈레이트 10 중량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를표 3에나타내었다.
[116] (실시예 12)
[117] 가소제로디에틸핵실사이클로핵산 50중량부및디이소노닐프탈레이트 20 중량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를표 3에나타내었다.
[118] (실시예 13)
[119] 가소제로디에틸핵실사이클로핵산 40중량부및디이소노닐프탈레이트 30 중량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를표 3에나타내었다.
[120] (실시예 I4)
[121] 가소제로디에틸핵실사이클로핵산 30중량부및디이소노닐프탈레이트 40 증량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를표 3에나타내었다.
[122] (실시예 15)
[123] 가소제로디에틸핵실사이클로헥산 20중량부및디이소노닐프탈레이트 50 중량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를표 4에나타내었다.
[124] (실시예 16)
[125] 가소제로디에틸핵실사이클로핵산 10중량부및디이소노닐프탈레이트 60 증량부를사용하는것을제외하고는실시예 1과동일하게제조하였으며，그 결과를하기표 4에나타내었다.
[126] (실시예 17)
[127] 염화비닐계수지 (중합도 900인유화중합수지) 100중량부에대하여,가소제로 디에틸핵실사이클로핵산 70중량부, K/Zn계복합안정제 (KKZ102PF,우창실업 ) 3 중량부,아조디카본아미드발포제 (DWPX03,동진세미켐) 3중량부,지당 (R902, Dupont사) 10증량부및평균입균 10 인탄산칼슘 (OM-10,한국오미아) 100 중량부를매티스믹서 (Mathismixer)에서 10분동안흔합하여플라스티졸을 제조한후，상기평가에서기재된측정방법에의하여물성을평가하고,그 결과를표 4에나타내었다.
[128] <표 4> [129]
Figure imgf000018_0001
[130] 상기표 4에서볼수있듯이，디에틸핵실사이클로핵산에
디이소노닐프탈레이트를흔합할경우디이소노닐프탈레이트함량이
증가할수록점도는상승하고,저온점도및저온경시변화성도약간
증가하였으며，디이소노닐프탈레이트흔합에따른발포성변화는크지않았다. 또한,비교예 2와대비시디이소노닐프탈레이트에디에틸핵실사이클로핵산을 소량 (10중량 %이상)흔합하면디이소노닐프탈레이트단독에비해
저온점도경시변화가현격히작아지는것을확인할수있다.
[131] 따라서，본발명에따른실시예 11내지 17을통하여
디에틸헥실사이클로핵산과디이소노닐프탈레이트의흔합물이염화비닐계 수지 100중량부에대하여 70중량부를함유할시상기혼합중량비는 70:0 - 10:60인것이바람직함을확인할수있었다.
[132] 상기실시예를통하여，본발명에서사용되는가소제의저온특성평가 (-15°C) 결과，도 1에서볼수있듯이가소제의저온저장안정성은
디에틸핵실사이클로핵산 >디 -2-에틸핵실프탈레이트 >디옥틸테레프탈레이트 >디이소노닐프탈레이트순으로우수함을나타내었으며， 디에틸핵실사이클로핵산의경우기존프탈레이트계가소제와
디옥틸테레프탈레이트에서문제가되는동절기저장안정성에서매우우수한 특성을보이므로동절기플라스티졸제조시배합시간단축및점도강하효과를 기대할수있음을확인하였다.디에틸핵실사이클로핵산의경우저온에서도 상변화가크지않으나나머지가소제들은부분적으로웅결되어 있다.본 발명에서,디에틸핵실사이클로핵산의경우 -15°C에서도웅결이되지않아, 이러한우수한저온특성으로인해저온점도경시변화특성이우수함을확인할 수있었다.
[133] 디에틸핵실사이클로핵산을단독으로사용하며점도저하제를사용하지않은 실시예 17의경우，점도저하제의미사용으로초기점도가비교적높은반면에 가공점도,상온점도경시변화，저온점도경시변화, TVOC및 HCHO의값이 우수함을보여주었다.
[134] 또한,본발명에서사용되는가소제의겔링속도를비교한결과를도 2에
나타내였으며,겔링속도는디 -2-에틸핵실프탈레이트 >
디에틸핵실사이클로핵산 >디이소노닐프탈레이트 >디옥틸테레프탈레이트 순으로나타났다.본발명의디에틸핵실사이클로헥산은대표적인가소제인 디 -2-에틸핵실프탈레이트와겔링속도가유사하고디이소노닐프탈레이트및 디옥틸테레프탈레이트에비해서는매우빠르게나타났으며,이를통해,기존의 벽지생산공정에서특별한열조건의변동없이사용가능한장점이있다.
[135] 이상과같이본발명에서는구체적인장치도와같이특정된사항들과한정된 실시예및도면에의해설명되었으나이는본발명의보다전반적인이해를돕 7 위해서제공된것일뿐，본발명은상기의실시예에한정되는것은아니며，본 발명이속하는분야에서통상의지식을가진자라면이러한기재로부터다양한 수정및변형이가능하다.
[136] 따라서，본발명의사상은설명된실시예에국한되어정해져서는아니되며, 후술하는특허청구범위뿐아니라이특허청구범위와균둥하거나둥가적변형 0 있는모든것들은본발명사상의범주에속한다고할것이다.

Claims

청구범위
염화비닐계수지 100중량부에대하여디에틸핵실사이클로핵산을 포함하는가소제 40~120중량부，안정제 0.5~7중량부，발포제 0.5-5중량부，층전제 30~150중량부및지당 (TiO2)l~20중량부를 포함하는염화비닐계수지조성물.
제 1항에있어서，
상기가소제는디옥틸테레프탈레이트，디이소노닐프탈레이트， 또는이들의흔합물을더포함하는염화비닐계수지조성물. 제 1항에있어서，
상기안정제는 Ca-Zn계화합물， K-Zn계화합물， Ba-Zn계화합물, 유기 Tin계화합물，메탈릭비누계화합물，페놀계화합물，인산 에스테르계화합물또는아인산에스테르계화합물로이루어진 군으로부터선택되는어느하나이상인것을포함하는염화비닐계 수지조성물.
제 1항에있어서,
상기발포제는화학적발포제,물리적발포제또는이들의흔합물 중에서선택되는어느하나이상인것을포함하는염화비닐계 수지조성물.
제 1항에있어서,
상기층전제는탄산칼슘,탈크，이산화티탄，카올린，실리카， 알루미나,수산화마그네슘또는점토로이루어진군에서선택되는 어느하나이상인것을포함하는염화비닐계수지조성물.
제 1항에 있어서，
상기조성물은포름알데히드의방출량이 0.015 mg/m2h미만이고, 총휘발성유기화합물의방출량이 O.lOmg/rrfh이하인염화비닐계 수지조성물.
제 1항내지제 6항에서선택된어느한항의조성물을포함하여 제조되는인테리어소재.
제 7항에있어서，
상기인테리어소재는벽지，상재，인조레쟈및바닥재를포함하는 인테리어소재.
PCT/KR2012/000412 2011-01-18 2012-01-18 디에틸헥실사이클로헥산을 포함하는 벽지용 염화비닐계 수지 조성물 WO2012099382A2 (ko)

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WO2021010669A1 (ko) * 2019-07-16 2021-01-21 한화솔루션 주식회사 벽지용 염화비닐 수지 조성물

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JP2014502666A (ja) 2014-02-03
WO2012099382A3 (ko) 2012-11-29
EP2666819A2 (en) 2013-11-27
CN103328566A (zh) 2013-09-25
EP2666819B1 (en) 2018-09-05
KR20120083560A (ko) 2012-07-26
CN103328566B (zh) 2016-01-27
US20130303640A1 (en) 2013-11-14

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