WO2021100964A1 - Phenolic foam insulation material and preparation method therefor - Google Patents

Phenolic foam insulation material and preparation method therefor Download PDF

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Publication number
WO2021100964A1
WO2021100964A1 PCT/KR2019/017652 KR2019017652W WO2021100964A1 WO 2021100964 A1 WO2021100964 A1 WO 2021100964A1 KR 2019017652 W KR2019017652 W KR 2019017652W WO 2021100964 A1 WO2021100964 A1 WO 2021100964A1
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Prior art keywords
foam insulation
phenolic
neutralizing agent
phenolic foam
inorganic neutralizing
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PCT/KR2019/017652
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French (fr)
Korean (ko)
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박재동
김성남
김태현
나성원
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(주)하이코리아
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009—Use of pretreated compounding ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3402—Details of processes or apparatus for reducing environmental damage or for working-up compositions comprising inert blowing agents or biodegradable components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/35—Component parts; Details or accessories
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E04B1/78—Heat insulating elements
    • E04B1/80—Heat insulating elements slab-shaped

Definitions

  • the disclosed content relates to a phenolic foam insulation and a method of manufacturing the same, and more particularly, to a phenolic foam insulation and a method of manufacturing the same, which suppresses the occurrence of corrosion of the metal material when contacting the metal material, and has a low formaldehyde residual rate.
  • phenolic foam insulation Since phenolic foam insulation has excellent heat insulation and fire resistance properties, it is used as a heat insulation material for building materials. Such phenolic foam insulation is disclosed in Korean Patent Publication No. 10-1408965 (2014.06.11.) and Korean Registered Patent Publication No. 10-1916285 (2018.11.01.).
  • Conventional phenolic foam insulation materials contain an acid catalyst inside the foam by using an organic acid as a curing agent, so when exposed to moisture such as rainwater, the acid catalyst may be extracted from the phenolic resin foam by water.
  • a metal material comes into contact with the phenolic foam insulation material, it is difficult to apply it as a core material of a sandwich panel because it causes a problem that the metal is corroded.
  • the phenolic resin used as a raw material for phenolic foam insulation contains unreacted phenol and formaldehyde.
  • formaldehyde it is a first-class carcinogen, which is harmful to the human body and carries an odor. Therefore, a phenolic foam insulation material that satisfies the standards for emission of pollutants from construction materials in the Enforcement Regulations of the Indoor Air Quality Management Act in Korea (indoor air quality process test standard test method 0.02 mg/m2 ⁇ h or less) is required.
  • Disclosed is to provide a phenolic foam insulation having a high pH value compared to the conventional phenolic foam insulation while maintaining excellent insulation properties.
  • phenolic foam insulation By removing unreacted formaldehyde remaining inside the phenolic foam insulation, it is intended to provide a phenolic foam insulation suitable for the emission standard of contaminants (0.02mg/m2 ⁇ h or less) of building materials in the Enforcement Regulations of the Indoor Air Quality Control Act in Korea.
  • a phenolic foam insulation formed by foaming and curing an expandable phenolic resin composition
  • an expandable phenolic resin composition comprising a phenolic resin, a blowing agent, an acid catalyst, and an inorganic neutralizing agent, wherein the inorganic neutralizing agent is aluminum hydroxide, zinc oxide, calcium carbonate And at least one selected from the group consisting of magnesium carbonate, and the inorganic neutralizing agent is coated with a binder.
  • the foamable phenolic resin composition may include 100 parts by weight of a phenol resin, 6 to 8 parts by weight of a foaming agent, 6 to 10 parts by weight of an acid catalyst, and 3 to 10 parts by weight of an inorganic neutralizing agent.
  • the binder may include a water-soluble resol, and may have two or more functional groups capable of reacting with phenol and an inorganic neutralizing agent.
  • urea or melamine may be further included in the foamable phenolic resin composition.
  • the content disclosed as one other embodiment is a method of manufacturing a phenolic foam insulation, characterized in that the phenolic foam insulation is the phenolic foam insulation according to any one of claims 1 to 3, and includes the following steps (A) to (C). It describes the manufacturing method of the phenolic foam insulation.
  • (C) a step of removing formaldehyde by spraying an oxygen catalyst in the chamber at 30 to 50° C. for 6 to 12 hours in a chamber;
  • the oxygen catalyst in the step (C) may be a titanium phosphate-based compound.
  • the phenolic foam insulation prepared by the above manufacturing method may have a pH of 6 or more, and a formaldehyde emission amount of 0.02 mg/m 2 ⁇ h or less.
  • the phenolic foam insulation and its manufacturing method as described above can prevent cell cracking and deterioration of insulation performance due to the use of an inorganic neutralizing agent, and can suppress the occurrence of metal corrosion when contacted with a metal material.
  • an inorganic neutralizing agent e.g., a metal oxide
  • by removing unreacted formaldehyde inside the phenolic foam insulation it can be safely used as an indoor finishing material as it conforms to the pollutant emission standard (0.02 mg/m2 ⁇ h or less) of building materials in the Enforcement Regulations of the Domestic Indoor Air Quality Control Act.
  • FIG. 1 illustrates a structure of a multi-stage conveyor inside an alkali chamber according to an embodiment of the disclosure.
  • FIG. 2 is an enlarged view of an upper portion of a multi-stage conveyor inside an alkali chamber according to an embodiment of the disclosure.
  • a foamable phenolic resin composition containing a phenolic resin, a foaming agent, an acid catalyst, and an inorganic neutralizing agent coated with a phenolic binder is foamed and cured, and then heated in a chamber sprayed with ammonia and an oxygen catalyst to a pH of 6
  • a chamber sprayed with ammonia and an oxygen catalyst to a pH of 6
  • the phenolic resin is preferably a resol-type resin, and the resol-type resin may be prepared by reacting a phenolic compound and an aldehyde in the presence of a catalyst.
  • Phenol compounds include phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, resorcinol, and the like
  • aldehydes include formaldehyde, furfural, and acetaldehyde.
  • the molar ratio of phenol and aldehyde is not particularly limited, but it is preferable that an excessive amount of aldehyde is added to reduce unreacted phenol and aldehyde.
  • the remaining aldehyde may be reacted by adding urea or melamine, and it is preferable to add 10 to 70 parts by weight of urea or melamine based on 100 parts by weight of the aldehyde.
  • an alkali metal, an alkaline earth metal catalyst, or an amine may be used, and at least one selected from the group consisting of lithium hydroxide, potassium hydroxide, or barium hydroxide is preferably used in terms of resistance to water degradation and prevention of metal corrosion.
  • the phenolic resin used to prepare the disclosed phenolic foam insulation has a weight average molecular weight of 600 to 800 Mw, a viscosity of 700 to 9000 cps, and a resin content of 80 to 85%.
  • the blowing agent can be a hydrocarbon-based or a mixture of hydrocarbons, and it is preferable to use a blowing agent having an ozone depletion potential (ODP) of 0.11 or less for domestic eco-friendly product certification. More preferably, there are cyclopentane and chloropropane, and may be used alone or in combination.
  • the amount of the blowing agent is suitably 6 to 8 parts by weight per 100 parts by weight of the phenolic resin. If it is less than 6 parts by weight, the foaming rate is low and the thermal insulation property is lowered, and if it exceeds 8 parts by weight, the size of the foamed cell increases, and the strength and cell density of the insulating material are deteriorated.
  • the acid catalyst benzene sulfonic acid, methylbenzene sulfonic acid, phenol sulfonic acid, xylene sulfonic acid, and the like may be used as the acid hardening agent.
  • the amount of the acid catalyst is suitable for 6 to 10 parts by weight, and the amount can be adjusted according to the length of the foam tunnel and the thickness of the insulating material. In the case of using less than 6 parts by weight, the curing time is delayed and the production speed is lowered, and a uniform and robust closed cell structure cannot be created. If it is used in excess of 10 parts by weight, foaming proceeds immediately after spraying the raw material, and the product cannot be produced.
  • the inorganic neutralizing agent at least one selected from the group consisting of aluminum hydroxide, zinc oxide, calcium carbonate, and magnesium carbonate may be used, and when the inorganic neutralizing agent is used, a phenolic binder is coated to increase the bonding strength between the phenol and the inorganic neutralizing agent. It is desirable to use the one that has been used.
  • the phenolic binder preferably has two or more functional groups capable of reacting with phenol and inorganic neutralizing agents.Since it has adhesiveness to glass, silica, alumina, etc. and also has heat resistance, when using a phenolic binder as a binder between a phenolic resin and an inorganic material It is possible to protect the phenolic foam insulation from deterioration by preventing the occurrence of inorganic components inside the cell and cracking inside the cell.
  • the inorganic neutralizing agent As a method of coating the inorganic neutralizing agent with a phenolic binder, there is a method of gelling or curing after applying a composition containing a water-soluble resol to the inorganic neutralizing agent. According to the above method, there is an effect of increasing the pH and improving flame retardancy. It is preferable to use 3 to 10 parts by weight of the inorganic neutralizing agent coated with a phenolic binder, and when using less than 3 parts by weight, the neutralization effect is insignificant, and when used in excess of 10 parts by weight, long-term thermal insulation performance decreases. .
  • the foamable phenolic resin composition for manufacturing the disclosed phenolic foam insulation may further include a foaming agent, urea, plasticizer, and other additives if necessary.
  • the disclosed phenolic foam insulation is manufactured including the following process.
  • the cotton material natural fibers, polyester fibers, polyethylene fibers, glass fibers, nonwoven fabrics, paper, metal foil, and the like may be used.
  • (B) A process of manufacturing a molded article by placing a double conveyor at the top of the sprayed raw material at a height suitable for the final thickness of the insulating material, passing it continuously through a foaming tunnel of 50 to 70 m, heating it to 40 to 60°C, and foaming and curing it. .
  • the height suitable for the final thickness may vary depending on the use of the insulating material, and when used as an interior material of a building, it is preferably 20 to 200 mm.
  • the moving speed of the tunnel is preferably 3 to 5 m/min.
  • the size to be cut to suit the use of the phenolic foam insulation may vary, and in consideration of work convenience and productivity, it is preferable to be 1200 x 600 or 1200 x 1200.
  • the interval of the multi-stage conveyor is 20 to 40 mm, and alkaline volatiles are simultaneously sprayed into the passage through which hot air flows inside the chamber to evenly maintain the alkaline volatiles inside the chamber, and are aged for 12 to 24 hours at 50 to 60°C. .
  • the aging condition is less than 50°C or less than 12 hours, neutralization of residual acidic content is insufficient, and if it exceeds 60°C or more than 24 hours, it is not preferable in terms of energy cost and productivity.
  • ammonia concentration: 2 to 10% by weight
  • a titanium phosphate-based compound is preferable as the oxygen catalyst, and formaldehyde and ammonia odor released from the phenolic foam insulation material can be sufficiently removed under the temperature and time conditions of the chamber.
  • Resol-type phenolic resin 100 parts by weight (Kangnam Chemical PF-6000), foaming agent 6 parts by weight (chloropropane), acid catalyst 7 parts by weight (methylbenzenesulfonic acid, Kangnam Chemical NEOCAT C-4) and inorganic neutralizing agent (water-soluble resol)
  • foaming agent 6 parts by weight chloropropane
  • acid catalyst 7 parts by weight methylbenzenesulfonic acid, Kangnam Chemical NEOCAT C-4
  • inorganic neutralizing agent water-soluble resol
  • the prepared molded article was cut into a size of 1200 x 600, laminated in an alkali chamber, and then aged at 55° C. for 18 hours in an ammonia (concentration: 2 to 10% by weight) atmosphere.
  • the aging molded article was subjected to a post-treatment process at 40° C. for 8 hours while spraying a titanium phosphate compound in the chamber.
  • the physical properties of the product were measured by the following measurement method by making a specimen of 300 x 300 phenolic foam monolithic material.
  • the phenolic foam insulation produced by the method of manufacturing the disclosed phenolic foam insulation has an excellent initial thermal conductivity of 0.020W/mk or less, less deterioration in long-term thermal conductivity, and has a pH of 6 or more. Corrosion can be prevented even when in contact with the body, and formaldehyde emission is less than 0.02 mg/m2 ⁇ h, providing a safe phenolic foam insulation material that is not harmful to the human body.
  • the disclosed contents are applicable to manufacturing and related fields of phenolic foam insulation.

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Abstract

Disclosed is a phenolic foam insulation material prepared by expanding and curing an expandable phenolic resin composition containing a phenolic resin, an expanding agent, an acidic catalyst, and an inorganic neutralizing agent, wherein the inorganic neutralizing agent is at least one selected from the group consisting of aluminum hydroxide, zinc oxide, calcium carbonate, and magnesium carbonate, and the inorganic neutralizing agent is coated with a binder. Such a phenolic foam insulation material and a preparation method therefor can prevent cell cracking and insulation performance degradation caused by the use of an inorganic neutralizing agent and can suppress the occurrence of metal corrosion upon contact with metal materials. In addition, the removal of unreacted formaldehyde inside the phenolic foam insulation material can lead to a safe use as an insulation material.

Description

페놀폼 단열재 및 이의 제조방법Phenolic foam insulation and its manufacturing method
개시된 내용은 페놀폼 단열재 및 이의 제조방법에 관한 것으로, 보다 구체적으로는 금속 재료와 접촉시 금속 재료의 부식 발생을 억제하고, 포름알데하이드 잔존율이 낮은 페놀폼 단열재 및 이의 제조방법에 관한 것이다.The disclosed content relates to a phenolic foam insulation and a method of manufacturing the same, and more particularly, to a phenolic foam insulation and a method of manufacturing the same, which suppresses the occurrence of corrosion of the metal material when contacting the metal material, and has a low formaldehyde residual rate.
본 명세서에서 달리 표시되지 않는 한, 이 섹션에 설명되는 내용들은 이 출원의 청구항들에 대한 종래 기술이 아니며, 이 섹션에 포함된다고 하여 종래 기술이라고 인정되는 것은 아니다. Unless otherwise indicated herein, the content described in this section is not prior art to the claims of this application, and inclusion in this section is not admitted to be prior art.
페놀폼 단열재는 우수한 단열성과 내화 특성을 갖기 때문에, 건축 재료의 단열재 용도로 사용되고 있다. 이러한 페놀폼 단열재는 한국 등록특허공보 제10-1408965호(2014.06.11.)와 한국 등록특허공보 제10-1916285호(2018.11.01.) 등에 개시된다. 종래의 페놀폼 단열재는 경화제로 유기산을 사용하여 발포체 내부에 산 촉매를 함유하고 있어 빗물과 같은 수분에 노출된 경우에 상기 산 촉매가 물에 의해 페놀 수지 발포체로부터 추출되는 경우가 있다. 금속 재료가 상기 페놀폼 단열재와 접촉시 금속이 부식되는 문제를 일으키는 단점이 있어 샌드위치 패널의 심재로 적용이 어렵다.Since phenolic foam insulation has excellent heat insulation and fire resistance properties, it is used as a heat insulation material for building materials. Such phenolic foam insulation is disclosed in Korean Patent Publication No. 10-1408965 (2014.06.11.) and Korean Registered Patent Publication No. 10-1916285 (2018.11.01.). Conventional phenolic foam insulation materials contain an acid catalyst inside the foam by using an organic acid as a curing agent, so when exposed to moisture such as rainwater, the acid catalyst may be extracted from the phenolic resin foam by water. When a metal material comes into contact with the phenolic foam insulation material, it is difficult to apply it as a core material of a sandwich panel because it causes a problem that the metal is corroded.
그리고, 최근 국내 유통되는 페놀폼 단열재에 포름알데히이드가 발포체 내에 잔존하는 문제점이 발생하여 이에 대한 우려가 증가하고 있다. 페놀폼 단열재의 원료로 사용되는 페놀 수지에는 미반응의 페놀과 포름알데히드가 포함되어 있는데, 포름알데히드의 경우 1급 발암물질로서 인체에 유해고 악취를 수반하는 물질이다. 따라서, 국내 실내공기질 관리법 시행규칙의 건축자재의 오염물질 방출 기준(실내공기질공정시험기준 시험법 0.02㎎/㎡·h이하)을 만족하는 페놀폼 단열재가 요구된다.In addition, there is a growing concern about the problem that formaldehyde remains in the foam in the phenolic foam insulating material distributed in Korea recently. The phenolic resin used as a raw material for phenolic foam insulation contains unreacted phenol and formaldehyde. In the case of formaldehyde, it is a first-class carcinogen, which is harmful to the human body and carries an odor. Therefore, a phenolic foam insulation material that satisfies the standards for emission of pollutants from construction materials in the Enforcement Regulations of the Indoor Air Quality Management Act in Korea (indoor air quality process test standard test method 0.02 mg/m²·h or less) is required.
개시된 내용은 우수한 단열성을 유지하면서, 종래의 페놀폼 단열재와 비교하여 높은 pH 값을 갖는 페놀폼 단열재를 제공하는 것에 있다.Disclosed is to provide a phenolic foam insulation having a high pH value compared to the conventional phenolic foam insulation while maintaining excellent insulation properties.
또한, 페놀폼 단열재 내부에 잔존하는 미반응 포름알데히드를 제거하여 국내 실내공기질 관리법 시행규칙의 건축자재의 오염물질 방출 기준(0.02㎎/㎡·h이하)에 적합한 페놀폼 단열재를 제공함에 있다.In addition, by removing unreacted formaldehyde remaining inside the phenolic foam insulation, it is intended to provide a phenolic foam insulation suitable for the emission standard of contaminants (0.02mg/㎡·h or less) of building materials in the Enforcement Regulations of the Indoor Air Quality Control Act in Korea.
하나의 실시예로서 개시된 내용은 페놀 수지, 발포제, 산 촉매 및 무기 중성화제를 포함하는 발포성 페놀 수지 조성물을 발포, 경화시켜 이루어지는 페놀폼 단열재로서, 상기 무기 중성화제는 수산화알루미늄, 산화아연, 탄산칼슘 및 탄산마그네슘으로 이루어지는 군에서 선택되는 적어도 하나이며, 상기 무기 중성화제가 결합제로 코팅된 것을 특징으로 하는 페놀폼 단열재에 대해 기술하고 있다.Disclosed as an embodiment is a phenolic foam insulation formed by foaming and curing an expandable phenolic resin composition comprising a phenolic resin, a blowing agent, an acid catalyst, and an inorganic neutralizing agent, wherein the inorganic neutralizing agent is aluminum hydroxide, zinc oxide, calcium carbonate And at least one selected from the group consisting of magnesium carbonate, and the inorganic neutralizing agent is coated with a binder.
바람직하기로는, 상기 상기 발포성 페놀 수지 조성물은 페놀 수지 100 중량부, 발포제 6 내지 8 중량부, 산 촉매 중량부 6 내지 10 중량부 및 무기 중성화제 3 내지 10 중량부로 이루어질 수 있다.Preferably, the foamable phenolic resin composition may include 100 parts by weight of a phenol resin, 6 to 8 parts by weight of a foaming agent, 6 to 10 parts by weight of an acid catalyst, and 3 to 10 parts by weight of an inorganic neutralizing agent.
더 바람직하기로는, 상기 결합제는 수용성 레졸을 포함하고, 페놀 및 무기 중성화제와 반응할 수 있는 2 이상의 관능기를 가지는 것일 수 있다.More preferably, the binder may include a water-soluble resol, and may have two or more functional groups capable of reacting with phenol and an inorganic neutralizing agent.
더욱 바람직하기로는, 상기 발포성 페놀 수지 조성물에 요소 또는 멜라민이 더 포함될 수 있다.More preferably, urea or melamine may be further included in the foamable phenolic resin composition.
하나의 다른 실시예로서 개시된 내용은 페놀폼 단열재의 제조방법으로서, 페놀폼 단열재가 청구항 1 내지 3 중 어느 한 항에 기재된 페놀폼 단열재이고, 하기 공정 (A) 내지 (C)를 포함하는 것을 특징으로 하는 페놀폼 단열재의 제조방법에 대해 기술하고 있다.The content disclosed as one other embodiment is a method of manufacturing a phenolic foam insulation, characterized in that the phenolic foam insulation is the phenolic foam insulation according to any one of claims 1 to 3, and includes the following steps (A) to (C). It describes the manufacturing method of the phenolic foam insulation.
(A) 페놀 수지, 발포제, 산 촉매 및 무기 중성화제를 포함하는 발포성 페놀 수지 조성물을 발포, 경화하여 성형체를 제조하는 공정;(A) a step of foaming and curing a foamable phenol resin composition containing a phenol resin, a foaming agent, an acid catalyst, and an inorganic neutralizing agent to produce a molded article;
(B) 상기 발포, 경화된 성형체를 알칼리 챔버에 넣고 50 내지 60℃에서 12 내지 24시간 숙성하는 공정; 및(B) a step of placing the foamed and cured molded article in an alkali chamber and aging at 50 to 60°C for 12 to 24 hours; And
(C) 상기 숙성된 성형체를 챔버에서 30 내지 50℃에서 6 내지 12시간 동안 산소촉매를 분무하여 포름알데히드를 제거하는 공정;(C) a step of removing formaldehyde by spraying an oxygen catalyst in the chamber at 30 to 50° C. for 6 to 12 hours in a chamber;
바람직하기로는, 상기 (C)공정의 산소촉매는 인산티타늄계 화합물인 것일 수 있다.Preferably, the oxygen catalyst in the step (C) may be a titanium phosphate-based compound.
더욱 바람직하기로는, 상기 제조방법으로 제조되는 페놀폼 단열재는 pH가 6 이상이며, 포름알데히드 방출량이 0.02㎎/㎡·h 이하일 수 있다.More preferably, the phenolic foam insulation prepared by the above manufacturing method may have a pH of 6 or more, and a formaldehyde emission amount of 0.02 mg/m 2 ·h or less.
이상에서와 같은 페놀폼 단열재 및 이의 제조방법은 무기 중성화제 사용에 의한 셀 균열 및 단열 성능저하를 예방하고, 금속 재료와 접촉 시 금속의 부식 발생을 억제할 수 있다. 또한 페놀폼 단열재 내부 미반응 포름알데히드를 제거하여 국내 실내공기질 관리법 시행규칙의 건축자재의 오염물질 방출 기준(0.02㎎/㎡·h이하)에 적합하여 실내 마감재료로 안전하게 사용할 수 있다.The phenolic foam insulation and its manufacturing method as described above can prevent cell cracking and deterioration of insulation performance due to the use of an inorganic neutralizing agent, and can suppress the occurrence of metal corrosion when contacted with a metal material. In addition, by removing unreacted formaldehyde inside the phenolic foam insulation, it can be safely used as an indoor finishing material as it conforms to the pollutant emission standard (0.02 mg/m²·h or less) of building materials in the Enforcement Regulations of the Domestic Indoor Air Quality Control Act.
본 실시 예들의 효과는 이상에서 언급한 효과들로 제한되지 않으며, 언급되지 않은 또 다른 효과들은 청구범위의 기재로부터 통상의 기술자에게 명확하게 이해될 수 있을 것이다.The effects of the present embodiments are not limited to the above-mentioned effects, and other effects that are not mentioned will be clearly understood by those skilled in the art from the description of the claims.
도 1은 개시된 내용의 일 실시 예에 따른 알칼리 챔버 내부 다단 컨베이어 구조를 나타낸 것이다. 1 illustrates a structure of a multi-stage conveyor inside an alkali chamber according to an embodiment of the disclosure.
도 2는 개시된 내용의 일 실시 예에 따른 알칼리 챔버 내부 다단 컨베이어 상부의 확대도이다.2 is an enlarged view of an upper portion of a multi-stage conveyor inside an alkali chamber according to an embodiment of the disclosure.
이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Hereinafter, a preferred embodiment of the present invention and the physical properties of each component will be described in detail, but this is for explaining in detail enough that one of ordinary skill in the art can easily carry out the invention, This does not mean that the technical spirit and scope of the present invention are limited.
페놀폼 단열재Phenolic foam insulation
개시된 페놀폼 단열재는 페놀 수지, 발포제, 산 촉매, 페놀 결합제가 코팅된 무기 중성화제를 함유하는 발포성 페놀 수지 조성물을 발포, 경화시킨 후 이를 암모니아 및 산소촉매로 분무된 챔버 내에서 가열시켜 pH가 6 이상이며, 발포체 내부에 포름알데히드를 제거한 페놀폼 단열재이다.In the disclosed phenolic foam insulation, a foamable phenolic resin composition containing a phenolic resin, a foaming agent, an acid catalyst, and an inorganic neutralizing agent coated with a phenolic binder is foamed and cured, and then heated in a chamber sprayed with ammonia and an oxygen catalyst to a pH of 6 This is the above, and it is a phenolic foam insulation with formaldehyde removed from the inside of the foam.
상기 페놀 수지는 레졸형 수지가 바람직하고, 레졸형 수지는 페놀 화합물과알데히드가 촉매 존재하에 반응에 의해 제조될 수 있다. 페놀 화합물로는 페놀, 크레졸, 자일레놀, 파라알킬페놀, 파라페닐페놀, 레졸시놀 등이 있으며, 알데히드로는 포름알데히드, 푸르푸랄, 아세트알데히드 등이 있다.The phenolic resin is preferably a resol-type resin, and the resol-type resin may be prepared by reacting a phenolic compound and an aldehyde in the presence of a catalyst. Phenol compounds include phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, resorcinol, and the like, and aldehydes include formaldehyde, furfural, and acetaldehyde.
이때, 상기 페놀과 알데히드의 몰비는 특별히 한정되지 않으나, 미반응의 페놀과 알데히드를 감소시키기 위해 알데히드가 과량 첨가되는 것이 바람직하다.At this time, the molar ratio of phenol and aldehyde is not particularly limited, but it is preferable that an excessive amount of aldehyde is added to reduce unreacted phenol and aldehyde.
상기 미반응 알데히드의 제거를 위하여 남은 알데히드를 요소 또는 멜라민을 첨가하여 반응시킬 수 있으며, 이때 요소 또는 멜라민은 알데히드 100중량부에 대해 10 내지 70중량부를 첨가하는 것이 바람직하다.In order to remove the unreacted aldehyde, the remaining aldehyde may be reacted by adding urea or melamine, and it is preferable to add 10 to 70 parts by weight of urea or melamine based on 100 parts by weight of the aldehyde.
상기 촉매로는 알칼리 금속, 알칼리토류 금속 촉매 또는 아민류가 사용될 수 있으며, 수산화리튬, 수산화칼륨 또는 수산화바륨으로 이루어지는 군에서 선택되는 적어도 하나를 사용하는 것이 내수열화 및 금속 부식 방지 면에서 바람직하다.As the catalyst, an alkali metal, an alkaline earth metal catalyst, or an amine may be used, and at least one selected from the group consisting of lithium hydroxide, potassium hydroxide, or barium hydroxide is preferably used in terms of resistance to water degradation and prevention of metal corrosion.
개시된 페놀폼 단열재의 제조에 사용되는 페놀수지는 중량평균분자량이 600 내지 800Mw이며, 점도가 700 내지 9000cps, 수지 함량이 80 내지 85%인 것이 바람직하다.The phenolic resin used to prepare the disclosed phenolic foam insulation has a weight average molecular weight of 600 to 800 Mw, a viscosity of 700 to 9000 cps, and a resin content of 80 to 85%.
발포제는 탄화수소계 및 탄화수소 혼합물을 사용할 수 있으며, 국내 친환경제품 인증을 위한 ODP(오존층 파괴 지수, ozone depletion potential) 0.11이하인 발포제 사용이 바람직하다. 더욱 바람직하게 시클로펜탄, 클로로프로판이 있으며 단독 또는 혼합하여 사용할 수 있다. 발포제의 양은 페놀수지 100중량부당 6 내지 8 중량부가 적합하다. 6중량부 미만이면, 발포율이 낮아 단열성이 저하되며, 8중량부 초과의 경우 발포셀의 크기가 커지고 단열재의 강도 및 셀 조밀도가 저하되는 단점이 있다. The blowing agent can be a hydrocarbon-based or a mixture of hydrocarbons, and it is preferable to use a blowing agent having an ozone depletion potential (ODP) of 0.11 or less for domestic eco-friendly product certification. More preferably, there are cyclopentane and chloropropane, and may be used alone or in combination. The amount of the blowing agent is suitably 6 to 8 parts by weight per 100 parts by weight of the phenolic resin. If it is less than 6 parts by weight, the foaming rate is low and the thermal insulation property is lowered, and if it exceeds 8 parts by weight, the size of the foamed cell increases, and the strength and cell density of the insulating material are deteriorated.
상기 산 촉매는 산경화제로서 벤젠설폰산, 메틸벤젠설폰산, 페놀 설폰산, 자일렌 설폰산 등이 사용될 수 있다. 산 촉매의 양은 6 내지 10 중량부가 적합하며 발포터널의 길이와 단열재의 두께에 따라 양을 조절할 수 있다. 6 중량부 미만 사용의 경우 경화 시간이 지연되어 생산속도가 저하되며 균일하고 견고한 Closed 형태의 셀구조가 생성되지 못한다. 10중량부 초과로 사용시 원료 분사 후 바로 발포가 진행되어 제품을 생산 할 수 없다. As the acid catalyst, benzene sulfonic acid, methylbenzene sulfonic acid, phenol sulfonic acid, xylene sulfonic acid, and the like may be used as the acid hardening agent. The amount of the acid catalyst is suitable for 6 to 10 parts by weight, and the amount can be adjusted according to the length of the foam tunnel and the thickness of the insulating material. In the case of using less than 6 parts by weight, the curing time is delayed and the production speed is lowered, and a uniform and robust closed cell structure cannot be created. If it is used in excess of 10 parts by weight, foaming proceeds immediately after spraying the raw material, and the product cannot be produced.
상기 무기 중성화제는 수산화알루미늄, 산화아연, 탄산칼슘 및 탄산마그네슘으로 이루어지는 군에서 선택되는 적어도 하나를 사용할 수 있으며, 상기 무기 중성화제 사용 시 페놀과 무기 중성화제의 결합력을 증대하기 위해 페놀 결합제가 코팅된 것을 사용하는 것이 바람직하다. As the inorganic neutralizing agent, at least one selected from the group consisting of aluminum hydroxide, zinc oxide, calcium carbonate, and magnesium carbonate may be used, and when the inorganic neutralizing agent is used, a phenolic binder is coated to increase the bonding strength between the phenol and the inorganic neutralizing agent. It is desirable to use the one that has been used.
상기 페놀 결합제는 페놀 및 무기 중성화제와 반응할 수 있는 2 이상의 관능기를 가지는 것이 바람직한데, 유리, 규상, 알루미나 등에 대한 접착성이 있으며 내열성도 있기 때문에 페놀 결합제를 페놀 수지와 무기질 재료의 결합제로 사용시 셀 내부의 무기 성분 탈락 및 셀 내부의 균열 발생을 방지하여 열화로부터 페놀폼 단열재를 보호할 수 있다.The phenolic binder preferably has two or more functional groups capable of reacting with phenol and inorganic neutralizing agents.Since it has adhesiveness to glass, silica, alumina, etc. and also has heat resistance, when using a phenolic binder as a binder between a phenolic resin and an inorganic material It is possible to protect the phenolic foam insulation from deterioration by preventing the occurrence of inorganic components inside the cell and cracking inside the cell.
상기 무기 중성화제에 페놀 결합제를 코팅하는 방법으로는 무기 중성화제에 수용성 레졸을 포함하는 조성물을 도포한 후 겔화 또는 경화하는 방법이 있다. 상기 방법에 의하면 pH가 상승하고 난연성이 향상되는 효과가 있다. 페놀 결합제가 코팅된 무기 중성화제는 페놀 수지 100중량부에 대해서 3 내지 10중량부를 사용하는 것이 바람직하며 3중량부 미만 사용시 중성화 효과가 미미하고, 10중량부 초과 사용시 장기 단열성능 저하의 원인이 된다.As a method of coating the inorganic neutralizing agent with a phenolic binder, there is a method of gelling or curing after applying a composition containing a water-soluble resol to the inorganic neutralizing agent. According to the above method, there is an effect of increasing the pH and improving flame retardancy. It is preferable to use 3 to 10 parts by weight of the inorganic neutralizing agent coated with a phenolic binder, and when using less than 3 parts by weight, the neutralization effect is insignificant, and when used in excess of 10 parts by weight, long-term thermal insulation performance decreases. .
개시된 페놀폼 단열재 제조를 위한 발포성 페놀 수지 조성물에는 상기 페놀 수지, 발포제, 산 촉매, 페놀 결합제가 코팅된 무기 중성화제 외에도 필요한 경우 정포제, 요소, 가소제 및 기타 첨가제가 더 포함될 수 있다.In addition to the inorganic neutralizing agent coated with the phenolic resin, the foaming agent, the acid catalyst, and the phenolic binder, the foamable phenolic resin composition for manufacturing the disclosed phenolic foam insulation may further include a foaming agent, urea, plasticizer, and other additives if necessary.
페놀폼 단열재의 제조 방법Manufacturing method of phenolic foam insulation
개시된 페놀폼 단열재는 하기의 공정을 포함하여 제조된다. The disclosed phenolic foam insulation is manufactured including the following process.
(A) 페놀수지, 발포제, 산 촉매 및 페놀 결합제가 코팅 된 무기 중성화제를 혼합 및 교반하고, 이를 연속 컨베이어 위 면재에 분사시키는 공정.(A) A process of mixing and stirring an inorganic neutralizing agent coated with a phenolic resin, a foaming agent, an acid catalyst, and a phenolic binder, and spraying it onto the plate on a continuous conveyor.
이때, 상기 면재로는 천연 섬유, 폴리에스테르 섬유, 폴리에틸렌 섬유, 유리 섬유, 부직포, 종이, 금속박 등이 사용될 수 있다.At this time, as the cotton material, natural fibers, polyester fibers, polyethylene fibers, glass fibers, nonwoven fabrics, paper, metal foil, and the like may be used.
(B) 분사된 원료의 상단에 단열재의 최종 두께에 맞는 높이로 더블 컨베이어를 위치시킨 후 50 내지 70m의 발포터널에 연속적으로 통과시켜 40 내지 60℃로 가열하며 발포 및 경화 시켜 성형체를 제조하는 공정.(B) A process of manufacturing a molded article by placing a double conveyor at the top of the sprayed raw material at a height suitable for the final thickness of the insulating material, passing it continuously through a foaming tunnel of 50 to 70 m, heating it to 40 to 60°C, and foaming and curing it. .
이때, 최종 두께에 맞는 높이는 단열재의 용도에 따라 달라질 수 있으며, 건축물의 내장재로 사용되는 경우에는 20 내지 200mm인 것이 바람직하다.At this time, the height suitable for the final thickness may vary depending on the use of the insulating material, and when used as an interior material of a building, it is preferably 20 to 200 mm.
또한, 효율적인 생산을 위하여 터널의 이동속도는 3 내지 5m/min이 바람직하다.In addition, for efficient production, the moving speed of the tunnel is preferably 3 to 5 m/min.
(C) 발포 경화된 성형체를 일정한 크기로 절단하는 공정.(C) The process of cutting the foam-hardened molded article into a certain size.
이때, 페놀폼 단열재의 용도에 맞도록 절단하는 크기는 달라질 수 있으며, 작업 편의성 및 생산성을 고려시 1200 x 600 또는 1200 x 1200인 경우가 바람직하다.At this time, the size to be cut to suit the use of the phenolic foam insulation may vary, and in consideration of work convenience and productivity, it is preferable to be 1200 x 600 or 1200 x 1200.
(D) 절단된 성형체를 다단 컨베이어를 통해 일정한 간격으로 배열시킨 후 알칼리 챔버에 넣고 가열 및 숙성시키는 공정.(D) A process of arranging the cut molded articles at regular intervals through a multi-stage conveyor, placing them in an alkali chamber, and heating and aging them.
이때, 다단 컨베이어의 간격은 20 내지 40mm로 하고, 챔버 내부 열풍이 유입되는 통로에 알칼리성 휘발물을 동시에 분사시켜 챔버 내부의 알칼리성 휘발물을 고르게 유지시키며 50 내지 60℃에서 12시간 내지 24시간 숙성한다. At this time, the interval of the multi-stage conveyor is 20 to 40 mm, and alkaline volatiles are simultaneously sprayed into the passage through which hot air flows inside the chamber to evenly maintain the alkaline volatiles inside the chamber, and are aged for 12 to 24 hours at 50 to 60°C. .
상기 숙성조건이 50℃미만이거나 12시간 미만이면 잔류 산성분의 중화가 불충분하고, 60℃ 초과하거나 24시간을 초과하면 에너지 비용 및 생산성 측면에서 바람직하지 못하다.If the aging condition is less than 50°C or less than 12 hours, neutralization of residual acidic content is insufficient, and if it exceeds 60°C or more than 24 hours, it is not preferable in terms of energy cost and productivity.
상기 알칼리성 휘발물로는 암모니아(농도: 2 내지 10중량%)를 사용하는 것이 안전성 및 경제성 관점에서 바람직하다.As the alkaline volatile matter, it is preferable to use ammonia (concentration: 2 to 10% by weight) from the viewpoint of safety and economy.
(E) 숙성된 성형체를 챔버의 온도를 30 내지 50℃로 하고, 6시간 내지 12시간 산소촉매 용액을 분무하여 숙성시키는 공정.(E) A process in which the temperature of the chamber is set at 30 to 50°C, and an oxygen catalyst solution is sprayed for 6 to 12 hours to age the aged molded article.
이때, 상기 산소촉매로는 인산티타늄계 화합물이 바람직하며, 상기 챔버의 온도 및 시간 조건에서 페놀폼 단열재에서 방출된 포름알데히드와 암모니아 냄새를 충분히 제거할 수 있다. At this time, a titanium phosphate-based compound is preferable as the oxygen catalyst, and formaldehyde and ammonia odor released from the phenolic foam insulation material can be sufficiently removed under the temperature and time conditions of the chamber.
이하 실시예 및 비교예를 바탕으로 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 의해 제한되는 것은 아니다. Hereinafter, the present invention will be described in more detail based on 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 by the following Examples and Comparative Examples.
[실시예][Example]
레졸형 페놀수지 100 중량부(강남화성 PF-6000), 발포제 6 중량부(클로로프로판), 산 촉매 7중량부(메틸벤젠설폰산, 강남화성 NEOCAT C-4) 및 무기 중성화제(수용성 레졸을 코팅한 수산화알루미늄) 10 중량부를 믹서에 공급한 후 교반하고 컨베이어 상부의 면재에 분사한 다음, 발포터널을 통과시키며 발포 및 경화하여 성형품을 제조하였다.Resol-type phenolic resin 100 parts by weight (Kangnam Chemical PF-6000), foaming agent 6 parts by weight (chloropropane), acid catalyst 7 parts by weight (methylbenzenesulfonic acid, Kangnam Chemical NEOCAT C-4) and inorganic neutralizing agent (water-soluble resol) After supplying 10 parts by weight of coated aluminum hydroxide) to the mixer, agitating and spraying it on the top of the conveyor, then foaming and curing while passing through a foam tunnel to prepare a molded article.
제조된 성형품을 1200 x 600 크기로 절단하고, 알칼리 챔버에 적층 후 암모니아(농도: 2 내지 10중량%) 분위기에서 55℃에서 18시간 숙성하였다.The prepared molded article was cut into a size of 1200 x 600, laminated in an alkali chamber, and then aged at 55° C. for 18 hours in an ammonia (concentration: 2 to 10% by weight) atmosphere.
상기 숙성을 거친 성형품을 챔버 내에서 인산티타늄계 화합물을 분무하며 40℃에서 8시간 후처리 공정을 수행하였다.The aging molded article was subjected to a post-treatment process at 40° C. for 8 hours while spraying a titanium phosphate compound in the chamber.
[비교예 1][Comparative Example 1]
무기 중성화제로 결합제를 사용하지 않은 수산화알루미늄을 사용한 것을 제외하고는 실시예와 동일하게 제조하였다.It was prepared in the same manner as in Examples, except that aluminum hydroxide without using a binder was used as an inorganic neutralizing agent.
[비교예 2][Comparative Example 2]
무기 중성화제를 사용하지 않고, 알칼리 숙성 공정 및 산소촉매 숙성 공정을 실시하지 않은 것을 제외하고는 실시예와 동일하게 제조하였다.It was prepared in the same manner as in Examples, except that the inorganic neutralizing agent was not used and the alkali aging process and the oxygen catalyst aging process were not performed.
[비교예 3][Comparative Example 3]
알칼리 숙성 공정 및 산소촉매 숙성 공정을 실시하지 않은 것을 제외하고는 실시예와 동일하게 제조하였다.It was prepared in the same manner as in Examples, except that the alkali aging process and the oxygen catalyst aging process were not performed.
[비교예 4][Comparative Example 4]
산소촉매 숙성 공정을 실시하지 않은 것을 제외하고는 실시예와 동일하게 제조하였다.It was prepared in the same manner as in Examples, except that the oxygen catalyst aging process was not performed.
[실시예] 및 [비교예 1] 내지 [비교예 4]의 조성을 아래 [표 1]에 나타내었다.The composition of [Example] and [Comparative Example 1] to [Comparative Example 4] is shown in [Table 1] below.
구 분division 실시예(중량부)Example (parts by weight) 비교예 1(중량부)Comparative Example 1 (parts by weight) 비교예 2(중량부)Comparative Example 2 (parts by weight) 비교예 3(중량부)Comparative Example 3 (parts by weight) 비교예 4(중량부)Comparative Example 4 (parts by weight)
원료Raw material 페놀수지Phenolic resin 100100 100100 100100 100100 100100
발포제blowing agent 66 66 66 66 66
산 촉매Acid catalyst 77 77 77 77 77
일반무기 중성화제General weapon neutralizer ×× 1010 ×× ×× ××
페놀결합제가코팅된중성화제Neutralizer coated with phenolic binder 1010 ×× ×× 1010 1010
공정fair 알칼리 숙성 공정Alkaline aging process ○○ ○○ ×× ×× ○○
후 처리 공정(산소촉매)Post-treatment process (oxygen catalyst) ○○ ○○ ×× ×× ××
상기 [실시예] 및 [비교예 1] 내지 [비교예 4]를 시험한 결과를 아래 [표 2]에 나타내었다.The results of testing [Example] and [Comparative Example 1] to [Comparative Example 4] are shown in [Table 2] below.
구분division 실시예Example 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4
초기 열전도율(W/Mk)Initial thermal conductivity (W/Mk) 0.0190.019 0.0210.021 0.0190.019 0.0190.019 0.0190.019
28일 후 열전도율(W/Mk)Thermal conductivity (W/Mk) after 28 days 0.0210.021 0.0280.028 0.0210.021 0.0210.021 0.0210.021
산소지수 (%)Oxygen Index (%) 4141 4141 3939 4141 4141
pHpH 66 66 33 44 66
포름알데히드(mg/m2·h)Formaldehyde (mg/m 2 ·h) 0.010.01 0.010.01 0.050.05 0.050.05 0.030.03
제품의 물성은 300 x 300 페놀폼 단연재의 시편을 제작하여 다음과 같은 측정방법으로 측정하였다. The physical properties of the product were measured by the following measurement method by making a specimen of 300 x 300 phenolic foam monolithic material.
1) 초기 열전도율(W/mK)은 KS L 9016에 의해 측정하였다.1) Initial thermal conductivity (W/mK) was measured by KS L 9016.
2) 28일 경과 후 열전도율(W/mK)은 KS M ISO 4898에 의해 측정하였다.2) After 28 days, the thermal conductivity (W/mK) was measured by KS M ISO 4898.
3) 산소지수는 KS M ISO 4589-2에 의해 측정하였다.3) The oxygen index was measured according to KS M ISO 4589-2.
4) pH는 KS ISO 3071에 의해 측정하였다.4) The pH was measured according to KS ISO 3071.
5) 포름알데히드(실내공기질공정시험기준 ㎎/㎡·h)은 EN 02131.1에 의해 측정하였다.5) Formaldehyde (indoor air quality process test standard mg/m2·h) was measured according to EN 02131.1.
상기 [표 2] 에서 보이는 바와 같이 개시된 페놀폼 단열재의 제조방법에 의하여 제조된 페놀폼 단열재는 초기 열전도율이 0.020W/mk이하로 우수하고, 장기 열전도율의 저하가 적으며, pH가 6이상이어서 금속과의 접촉시에도 부식을 방지할 수 있고, 포름알데히드 방출량이 0.02㎎/㎡·h 이하로서 인체에 유해성이 없는 안전한 페놀폼 단열재를 제공할 수 있다.As shown in [Table 2], the phenolic foam insulation produced by the method of manufacturing the disclosed phenolic foam insulation has an excellent initial thermal conductivity of 0.020W/mk or less, less deterioration in long-term thermal conductivity, and has a pH of 6 or more. Corrosion can be prevented even when in contact with the body, and formaldehyde emission is less than 0.02 mg/m2·h, providing a safe phenolic foam insulation material that is not harmful to the human body.
개시된 내용은 예시에 불과하며, 특허청구범위에서 청구하는 청구의 요지를 벗어나지 않고 당해 기술분야에서 통상의 지식을 가진 자에 의하여 다양하게 변경 실시될 수 있으므로, 개시된 내용의 보호범위는 상술한 특정의 실시 예에 한정되지 않는다.The disclosed contents are only examples, and since various changes can be made by those of ordinary skill in the art without departing from the gist of the claims claimed in the claims, the scope of protection of the disclosed contents is limited to the above-described specific It is not limited to the embodiment.
개시된 내용은 페놀폼 단열재 제조 및 관련 분야에 적용 가능하다.The disclosed contents are applicable to manufacturing and related fields of phenolic foam insulation.

Claims (7)

  1. 페놀 수지, 발포제, 산 촉매 및 무기 중성화제를 포함하는 발포성 페놀 수지 조성물을 발포, 경화시켜 이루어지는 페놀폼 단열재로서,As a phenolic foam heat insulator formed by foaming and curing a foamable phenolic resin composition containing a phenolic resin, a foaming agent, an acid catalyst, and an inorganic neutralizing agent,
    상기 무기 중성화제는 수산화알루미늄, 산화아연, 탄산칼슘 및 탄산마그네슘 으로 이루어지는 군에서 선택되는 적어도 하나이며,The inorganic neutralizing agent is at least one selected from the group consisting of aluminum hydroxide, zinc oxide, calcium carbonate, and magnesium carbonate,
    상기 무기 중성화제가 결합제로 코팅된 것을 특징으로 하는 페놀폼 단열재.Phenolic foam insulation, characterized in that the inorganic neutralizing agent is coated with a binder.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 발포성 페놀 수지 조성물은 페놀 수지 100 중량부, 발포제 6 내지 8 중량부, 산 촉매 중량부 6 내지 10 중량부 및 무기 중성화제 3 내지 10 중량부를 포함하는 것을 특징으로 하는 페놀폼 단열재.The foamable phenolic resin composition comprises 100 parts by weight of a phenol resin, 6 to 8 parts by weight of a foaming agent, 6 to 10 parts by weight of an acid catalyst, and 3 to 10 parts by weight of an inorganic neutralizing agent.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 결합제는 수용성 레졸을 포함하고, 페놀 및 무기 중성화제와 반응할 수 있는 2 이상의 관능기를 가지는 것을 특징으로 하는 페놀폼 단열재.The binder comprises a water-soluble resol, and a phenol foam insulation, characterized in that it has two or more functional groups capable of reacting with phenol and an inorganic neutralizing agent.
  4. 청구항 1에 있어서,The method according to claim 1,
    상기 발포성 페놀 수지 조성물에 요소 또는 멜라민이 더 포함된 것을 특징으로 하는 페놀폼 단열재.Phenol foam insulation, characterized in that the urea or melamine is further included in the expandable phenolic resin composition.
  5. 청구항 1 내지 4 중 어느 한 항에 따른 페놀폼 단열재의 제조방법에 있어서, 하기 공정 (A) 내지 (C)를 포함하는 것을 특징으로 하는 페놀폼 단열재의 제조방법:In the manufacturing method of the phenolic foam insulation according to any one of claims 1 to 4, the method of manufacturing a phenolic foam insulation comprising the following steps (A) to (C):
    (A) 페놀 수지, 발포제, 산 촉매 및 무기 중성화제를 포함하는 발포성 페놀 수지 조성물을 발포, 경화하여 성형체를 제조하는 공정;(A) a step of foaming and curing a foamable phenol resin composition containing a phenol resin, a foaming agent, an acid catalyst, and an inorganic neutralizing agent to produce a molded article;
    (B) 상기 발포, 경화된 성형체를 알칼리 챔버에 넣고 50 내지 60℃에서 12 내지 24시간 숙성하는 공정; 및(B) a step of placing the foamed and cured molded article in an alkali chamber and aging at 50 to 60°C for 12 to 24 hours; And
    (C) 상기 숙성된 성형체를 챔버에서 30 내지 50℃에서 6 내지 12시간 동안 산소촉매를 분무하여 포름알데히드를 제거하는 공정;(C) a step of removing formaldehyde by spraying an oxygen catalyst in the chamber at 30 to 50° C. for 6 to 12 hours in a chamber;
  6. 청구항 5에 있어서,The method of claim 5,
    상기 (C)공정의 산소촉매는 인산티타늄계 화합물인 것을 특징으로 하는 페놀폼 단열재의 제조방법.The oxygen catalyst in the step (C) is a method for producing a phenolic foam insulation, characterized in that the titanium phosphate-based compound.
  7. 청구항 5에 있어서,The method of claim 5,
    상기 페놀폼 단열재는 pH가 6 이상이며, 포름알데히드 방출량이 0.02㎎/㎡·h 이하로 제조되는 것을 특징으로 하는 페놀폼 단열재의 제조방법.The phenolic foam insulation has a pH of 6 or more and a formaldehyde emission amount of 0.02 mg/m2·h or less.
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