KR102571596B1 - Fire retardant composition for wood and wood-based materials using high concentrations of boron compounds mixed phenolic formaldehyde resin, wood and wood-based materials using the same and manufacturing method thereof - Google Patents

Fire retardant composition for wood and wood-based materials using high concentrations of boron compounds mixed phenolic formaldehyde resin, wood and wood-based materials using the same and manufacturing method thereof Download PDF

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KR102571596B1
KR102571596B1 KR1020220036881A KR20220036881A KR102571596B1 KR 102571596 B1 KR102571596 B1 KR 102571596B1 KR 1020220036881 A KR1020220036881 A KR 1020220036881A KR 20220036881 A KR20220036881 A KR 20220036881A KR 102571596 B1 KR102571596 B1 KR 102571596B1
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wood
flame retardant
boric acid
borate
phenolic resin
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강석구
양승민
윤시원
최병훈
구영모
이화형
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사단법인 우디즘목재이용연구소
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/163—Compounds of boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2200/00—Wooden materials to be treated
    • B27K2200/10—Articles made of particles or fibres consisting of wood or other lignocellulosic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/30—Fireproofing

Abstract

본 발명에 따른 목재 및 목질재료용 난연제 조성물은 붕산(Boric acid), 붕산염(Sodium borate), 페놀수지(Phenilic resin) 및 물을 포함하는 것을 특징으로 한다.
본 발명에 따른 난연목재 또는 난연목질재료의 제조방법은, S1) 목재 또는 목질재료를 준비하는 단계; S2) 페놀수지· 붕산붕산염 화합물의 목재 난연제를 제조하는 단계; S3) 상기 S2)단계에서 얻어지는 페놀수지· 붕산붕산염 화합물의 목재 난연제를 상기 목재 또는 목질재료에 주입하는 단계; S4) 주입처리된 상기 목재 또는 목질재료를 건조-경화하는 단계;를 포함하는 것을 특징으로 한다.The flame retardant composition for wood and wood-based materials according to the present invention is characterized by comprising boric acid, sodium borate, phenolic resin and water.
A method for manufacturing flame retardant wood or wood material according to the present invention includes the steps of S1) preparing wood or wood material; S2) preparing a wood flame retardant of a phenolic resin borate compound; S3) injecting the wood flame retardant of the phenolic resin boric acid borate compound obtained in step S2) into the wood or wood material; S4) drying-curing the wood or wood material subjected to injection treatment; characterized in that it comprises a.

Description

고농도 붕소 및 페놀수지 화합물을 이용한 목재 및 목질재료용 난연제 조성물, 이를 이용한 난연목재 또는 난연목질재료, 및 그 제조방법{Fire retardant composition for wood and wood-based materials using high concentrations of boron compounds mixed phenolic formaldehyde resin, wood and wood-based materials using the same and manufacturing method thereof} Fire retardant composition for wood and wood-based materials using high concentrations of boron compounds mixed phenolic formaldehyde resin , wood and wood-based materials using the same and manufacturing method thereof}

본 발명은 목재 및 목질재료용 난연제 조성물과 이를 이용한 난연목재 및 난연목질재료에 관한 것으로, 상세하게는 고농도의 붕소화합물 즉 붕산(Boric acid)과 붕산염(sodium borate)의 무기질 약제와 페놀수지로 이루어지는 목재 및 목질재료용 난연제 조성물과, 이를 사용하여 무기질 처리에 따른 접착력 약화현상이나 수분에 약한 성질을 개선하는 난연목재 또는 난연목질재료의 제조방법에 관한 것이다.The present invention relates to a flame retardant composition for wood and wood materials and a flame retardant wood and flame retardant wood material using the same. It relates to a flame retardant composition for wood and wood materials, and a method for manufacturing flame retardant wood or wood material using the same to improve adhesion weakening or moisture resistance due to inorganic treatment.

목재는 환경친화적이고 인체친화적이며 지속가능한 재료로서 원시시대로부터 최근까지 생활도구와 각종 용구를 포함, 가구와 목조건물에 널리 사용되고 있어 인간과 뗄레야 뗄 수 없는 깊은 관계를 갖고 있다. 더욱이 최근에 지구환경문제로 온난화가 진행되면서 이산화탄소의 통조림인 목재가 다시 각광을 받기 시작하면서 목재를 오래 사용할 수 있는 목재건물의 사용 등을 권장하기 시작하였다. 그러나 이러한 목재는 썩거나 불에 타는 단점을 갖고 있다. 이러한 단점을 보완하기 위해 특히 화재에 대한 내화성능을 부여하기 위해 여러 가지 난연관련 연구가 계속되어 왔다.Wood is an environment-friendly, human-friendly, and sustainable material that has been widely used in furniture and wooden buildings, including living tools and various tools from the primitive times to the present, and has a deep relationship that is inseparable from humans. Moreover, recently, as global warming progresses due to global environmental problems, wood, a can of carbon dioxide, has begun to come into the limelight again, and the use of wood buildings that can use wood for a long time has begun to be recommended. However, these woods have the disadvantage of rotting or burning. In order to compensate for these disadvantages, in particular, various flame retardant studies have been conducted in order to impart fire resistance to fire.

붕산(Boric acid)과 붕산염(sodium borate)은 Gay-Lussac이 1823년에 내화성능을 발견한 이래, 목재, 종이 및 목질재료의 난연처리와 목재방부제, 흰개미방제에 널리 사용되어 왔다. 1970년대에 Minalith, Pyresote 라는 이름으로 붕산, 붕사, 무기염류의 혼합약제를 미국 AWPA에서 사용하였으며, 국내 대학 교과서(이등, 1981)에도 일찍이 소개하고 있다. 그런데 지금까지 붕소계열의 약제는 낮은 용해도로 인해 8% (Wt%) 이하의 낮은 함량(손 등 2013, 정 등 2018, 대한민국 특허 10-2015-0124482)으로 사용되어 내화약제의 보조제로만 사용되고 있다(이 1981, 목재공학 향문사, 손동원 외 2013: 붕산 붕사 각 3%, 친환경난연목재 제조기술개발. 산림과학원 연구보고 13∼20, 정영진 등: Fire Sci. Eng., Vol. 32, No. 2, pp. 1∼6, 2018: 4% ) (특허 대한민국 10-2015-0124482: 붕산 0.4∼1 중량%, 붕산염 1∼5중량%, 특허 대한민국 10-2021-0064800 : 붕산 0.6∼0.7 중량%, 붕사 0.1∼1 중량%). Boric acid and sodium borate have been widely used for flame retardant treatment of wood, paper and wood materials, wood preservatives, and termite control since Gay-Lussac discovered fire resistance in 1823. In the 1970s, a mixture of boric acid, borax, and inorganic salts under the name of Minalith and Pyresote was used in the US AWPA, and was introduced early in domestic university textbooks (Lee Deung, 1981). However, so far, boron-based drugs have been used only as adjuvants for fire-resistant chemicals, being used at a low content of 8% (Wt%) or less (Son et al. 2013, Jeong et al. 2018, Korean Patent No. 10-2015-0124482) due to their low solubility ( Lee 1981, Wood Engineering Hyangmunsa, Son Dong-won et al. 2013: Boric acid borax 3% each, eco-friendly fire retardant wood manufacturing technology development, Forest Science Institute Research Report 13~20, Jung Young-jin et al.: Fire Sci. Eng., Vol. 32, No. 2, pp 1~6, 2018: 4%) (Patent Korea 10-2015-0124482: boric acid 0.4~1 wt%, borate 1~5 wt%, Patent Korea 10-2021-0064800: boric acid 0.6~0.7 wt%, borax 0.1 -1% by weight).

그 주된 이유는 첫째 상온에서 물에 대한 용해도가 낮고(붕산 4.72g, 붕사 4.71g 20℃), 둘째로 용해도를 높이기 위하여 온도를 높여, 고온용해처리시 목재표면에 침전 결정이 생겨 침투를 방해하고 백화현상으로 인하여 목재표면이 오염이 된다. (예 80℃: 용해도 붕산 23.6g, 붕사 44.3g). 셋째로 처리재를 물에 접촉하면 약제의 용탈성(침출성)이 매우 높고, 넷째로 붕산·붕산염의 목재처리는 동일재료뿐 아니라 이종 재료간에도 접착형성을 방해하여 강도저하를 가져오는 것으로 알려져 있다(Laks et al. 1990).The main reason for this is, firstly, low solubility in water at room temperature (boric acid 4.72g, borax 4.71g 20℃), and secondly, the temperature is increased to increase the solubility, so during high-temperature melting treatment, precipitation crystals are formed on the surface of the wood, which hinders penetration. The wood surface is contaminated due to efflorescence. (Example 80°C: solubility boric acid 23.6 g, borax 44.3 g). Thirdly, when the treatment material comes into contact with water, the dissolution (leachability) of the drug is very high, and fourthly, boric acid and borate wood treatment is known to reduce the strength by interfering with the formation of adhesion between different materials as well as the same material. (Laks et al. 1990).

본 발명은 상기한 문제점을 해결하기 위한 것으로, 불에 약한 목재의 단점을 보완하고 처리 후 표면의 상태가 깨끗이 유지되면서 물에 의한 용탈이 되지 않고 치수안정성과 난연성능을 부여하는 고농도 페놀-붕소계 목재 난연제 조성물, 이를 이용한 난연목재 및 그 제조방법을 제공하는데 있다.The present invention is intended to solve the above problems, a high concentration phenol-boron system that compensates for the disadvantages of wood, which is vulnerable to fire, and provides dimensional stability and flame retardancy without being leached by water while maintaining a clean surface state after treatment. It is to provide a wood flame retardant composition, a flame retardant wood using the same, and a manufacturing method thereof.

본 발명에 따른 목재 및 목질재료용 난연제 조성물은 붕산(Boric acid), 붕산염(Sodium borate), 및 수용성 페놀수지(Phenolic resin)를 포함하여 이루어지는 것을 특징으로 한다.The flame retardant composition for wood and wood-based materials according to the present invention is characterized by comprising boric acid, sodium borate, and a water-soluble phenolic resin.

또한, 상기 조성물은 고형분기준으로 상기 페놀수지는 16-36 wt%, 붕산(Boric acid)은 8-18 wt%, 붕산염(Sodium borate) 10-22 wt%로, 붕산·붕산염은 18-40wt%를 포함한다. 이하, 구성성분의 함량은 고형분 기준으로 한다.In addition, the composition contains 16-36 wt% of the phenol resin, 8-18 wt% of boric acid, 10-22 wt% of sodium borate, and 18-40 wt% of boric acid and borate based on solid content. includes Hereinafter, the contents of components are based on solid content.

상기 페놀수지는 수지반응기에 페놀, 포르마린, 물을 투입하고 수산화나트륨(NaOH)으로 pH를 10.7에서 11.0으로 조정하고 반응시켜 제조된 액상형 레졸(resol)형인 것을 특징으로 한다.The phenolic resin is characterized in that it is a liquid resol type prepared by adding phenol, formalin, and water to a resin reactor, adjusting the pH from 10.7 to 11.0 with sodium hydroxide (NaOH), and reacting.

상기 페놀수지는 상기 수지반응기에서 상기 페놀과 상기 포르마린은 페놀:포르마린(35%)로 몰비 1:1.63~2.4(mol)로 투입하고 수산화나트륨(NaOH)으로 pH를 10.7에서 11.0으로 조정하고, 70℃∼80℃에서 반응시켜 제조된 액상형 레졸(resol)형인 것을 특징으로 한다.The phenolic resin was added in the resin reactor at a molar ratio of 1:1.63 to 2.4 (mol) as phenol:formarin (35%), the pH was adjusted from 10.7 to 11.0 with sodium hydroxide (NaOH), and 70 It is characterized in that it is a liquid resol type prepared by reacting at ℃ to 80 ℃.

또한, 레조르시놀 또는 비스페놀을 더 포함하고, 상기 레조르시놀 또는 비스페놀은 페놀과의 공축합수지 제조가 가능한 액상형 레졸(resol)형인 것을 특징으로 한다.In addition, it further includes resorcinol or bisphenol, and the resorcinol or bisphenol is characterized in that it is a liquid resol type capable of preparing a co-condensation resin with phenol.

또한, 상기 레조르시놀은 10-40wt% 포함하는 것을 특징으로 한다.In addition, the resorcinol is characterized in that it contains 10-40wt%.

또한, 상기 레조르시놀은 23∼33 wt%, 페놀수지 15∼21wt%로 레조르시놀·페놀수지는 38∼54 wt%, 붕산(Boric acid)은 6.8∼10.9 wt%, 붕산염(Sodium borate)은 8.5∼13.7 wt%로서 붕산·붕산염은 15.3∼24.6 wt%를 포함하는 것을 특징으로 한다.In addition, the resorcinol is 23 to 33 wt%, the phenolic resin is 15 to 21 wt%, the resorcinol phenolic resin is 38 to 54 wt%, boric acid is 6.8 to 10.9 wt%, and borate (Sodium borate) It is characterized by containing 8.5 to 13.7 wt% of silver and 15.3 to 24.6 wt% of boric acid and borate salts.

또한, 상기 붕산 및 붕산염을 혼합하여 붕산·붕산염 혼합물을 만들고 상기 붕산·붕산염 혼합물은 붕산붕산염 용액으로 붕산 25.53wt%, 붕산염(붕사) 31.91wt%를 물에 넣어 온도를 90℃∼100℃까지 높여 투명하게 물에 잘 녹는 붕산·붕산염 혼합물을 만들어 페놀수지에 혼합하여 반응하는 것을 특징으로 한다.In addition, the boric acid and borate are mixed to make a boric acid-borate mixture, and the boric acid-borate mixture is a borate solution by adding 25.53 wt% of boric acid and 31.91 wt% of borate (borax) into water to raise the temperature to 90 ° C. to 100 ° C. It is characterized by making a transparent water-soluble boric acid-borate mixture and reacting by mixing it with a phenolic resin.

또한, 본 발명에 따른 난연목재 또는 난연목질재료의 제조방법은 In addition, the method for producing flame retardant wood or flame retardant wood material according to the present invention

S1) 목재 또는 목질재료를 준비하는 단계;S1) preparing wood or wood material;

S2) 페놀수지· 붕산붕산염 화합물의 목재 난연제를 제조하는 단계;S2) preparing a wood flame retardant of a phenolic resin borate compound;

S3) 상기 S2)단계에서 얻어지는 페놀수지· 붕산붕산염 화합물의 목재 난연제를 상기 목재 또는 목질재료에 주입하는 단계; 및S3) injecting the wood flame retardant of the phenolic resin boric acid borate compound obtained in step S2) into the wood or wood material; and

S4) 주입처리된 상기 목재 또는 목질재료를 건조,경화하는 단계;S4) drying and curing the injected wood or wood material;

를 포함하는 것을 특징으로 한다.It is characterized in that it includes.

또한, 상기 S2) 단계는 S2-1) 페놀수지를 제조하는 단계; S2-2) 붕산과 붕산염을 용매에 혼합하여 붕산·붕산염 혼합물을 제조하는 단계; S2-3) 상기 붕산·붕산염 혼합물과 상기 페놀수지를 혼합하여 반응하는 단계;를 포함한다.In addition, the step S2) may include: S2-1) preparing a phenolic resin; S2-2) preparing a boric acid-borate mixture by mixing boric acid and borate in a solvent; S2-3) mixing and reacting the boric acid-borate mixture and the phenol resin;

또한, S5) 목질요소에 따라 열압공정을 거쳐 최종목질재료를 제조하는 단계를 더 포함하는 것을 특징으로 한다.In addition, S5) characterized in that it further comprises the step of manufacturing a final wood-based material through a hot-pressing process according to wood-based elements.

또한, 상기 목재 또는 목질재료는 원목에서 얻은 단판, 판재, 파티클, 스트랜드 및 섬유와 이들로부터 만든 합판, 단판적층재(LVL), 집성재, 구조용 직교집성판(CLT), 파티클보드, 스트랜드보드, 섬유판인 것을 특징으로 한다.In addition, the wood or wood-based material is veneer, plate, particle, strand and fiber obtained from hardwood and plywood made from them, veneer laminate (LVL), laminated material, orthogonal laminated board (CLT) for structure, particle board, strand board, Characterized in that it is a fiberboard.

또한, 상기 S2-1) 페놀수지를 제조하는 단계는 수지반응기에 페놀 94g(1몰), 35% 포르마린 139.5∼205.7g(1.63-2.4 mol), 물 14∼20g을 투입하고 수산화나트륨(NaOH)으로 pH를 10.7에서 11.0로 조정하고, 70℃∼80℃에서 반응시켜 액상형 레졸(resol)형을 만드는 것을 특징으로 한다.In addition, in the step of S2-1) preparing a phenol resin, 94 g (1 mol) of phenol, 139.5 to 205.7 g (1.63-2.4 mol) of 35% formalin, and 14 to 20 g of water were added to a resin reactor, and sodium hydroxide (NaOH) It is characterized by adjusting the pH from 10.7 to 11.0 and reacting at 70 ° C to 80 ° C to make a liquid resol type.

또한, 상기 S2-2) 단계에서 붕산, 붕산염을 물에 넣어 온도를 90℃∼100℃까지 높이고, 투명하게 될 때까지 물에 잘 녹는 붕산·붕산염 혼합물들을 만든 후에, S2-3) 단계에서 상기 제조된 페놀수지에 페놀수지 16∼36 wt%, 붕산(Boric acid) 8∼18 wt%, 붕산염(Sodium borate) 10∼22 wt%로, 붕산·붕산염이 18∼40wt%의 비율로 되도록 혼합하여 반응시켜 만든 것을 특징으로 한다.In addition, in step S2-2), boric acid and borate are added to water to raise the temperature to 90 ° C. to 100 ° C., and after making boric acid and borate mixtures that are well soluble in water until they become transparent, in step S2-3), 16-36 wt% of phenolic resin, 8-18 wt% of boric acid, 10-22 wt% of sodium borate, and 18-40 wt% of boric acid and borate are mixed with the prepared phenolic resin. It is characterized by being made by reacting.

또한, 상기 S2) 단계에서 페놀수지· 붕산붕산염 화합물을 제조한 후 상기 페놀수지· 붕산붕산염 화합물에 레조르시놀을 추가하여 목재 난연제를 제조하는 것을 특징으로 한다.In addition, after preparing the phenol resin boric acid borate compound in step S2), resorcinol is added to the phenol resin boric acid borate compound to produce a wood flame retardant.

또한, 상기 S3) 단계에서 주입방법은 상압에서 확산침투하는 것을 특징으로 한다.In addition, the injection method in step S3) is characterized by diffusion and penetration at normal pressure.

또한, 상기 S3) 단계에서 주입방법은 가압감압방법으로 이루어지고, 주가압은 10∼25kg/㎠ 로 30∼120분 까지 처리하는 것을 특징으로 한다.In addition, the injection method in the step S3) is made of a pressure reduction method, and the main pressure is characterized in that it is treated for 30 to 120 minutes at 10 to 25 kg / cm 2 .

또한, 상기 S3) 단계에서 주가압 전후로 전배기 30분, 후배기 10∼30분을 하는 것을 특징으로 한다.In addition, it is characterized in that in the step S3), before and after the main pressure, 30 minutes of the previous exhaust period and 10 to 30 minutes of the rear exhaust period are performed.

또한, 상기 S4) 단계에서는 주입처리된 상기 목재 또는 목질재료를 상온에서 안정화시키고, 50~70℃에서 일정기간 동안 건조단계를 거친 후, 100-150℃에서 수지를 경화시키는 경화단계를 포함하는 것을 특징으로 한다.In addition, the step S4) includes a curing step of stabilizing the injected wood or woody material at room temperature, drying at 50 to 70 ° C for a certain period of time, and then curing the resin at 100 to 150 ° C. to be characterized

또한, 상기 S5) 단계에서는 단판(veneer)은 합판 또는 단판적층재(LVL)로, 판재는 집성재 또는 구조용 직교집성판(CLT)으로, 파티클은 파티클보드로, 스트랜드는 스트랜드보드로, 섬유는 섬유판으로 제조하는 것을 특징으로 한다.In addition, in the step S5), the veneer is plywood or veneer laminate (LVL), the plate material is laminated material or structural orthogonal laminated board (CLT), the particle is particle board, the strand is strand board, and the fiber is Characterized in that it is made of fiberboard.

따라서 상기와 같이 구성되는 본 발명에 따른 난연제 조성물은 페놀수지의 영향으로 무기질 약제를 사용하지만 무기질 처리에 따른 접착력 약화현상이나 수분에 약한 성질이 개선되면서, 고농도의 붕산·붕산염 혼합물과 페놀수지의 반응 화합물은 상온(25-30℃)에서 최대 2개월간 보존되는 목재 난연제 조성물을 제공하면서 기존의 붕산, 붕산염의 무기 약제를 내화약제로 사용할 경우 8% (Wt%)이하로 조성되면서 보조약제로 사용하는 것과는 달리 40중량%까지의 고농도로 조성이 되며, 주약제(내화접착제)로 사용할 수 있다. 따라서 농도가 높은 조성의 붕산·붕산염에 의한 혼합물과 페놀수지와의 반응 화합물에 의한 난연제는 목재의 내화효과를 극대화 할 수 있는 접착제가 될 수 있다.Therefore, the flame retardant composition according to the present invention configured as described above uses an inorganic agent due to the influence of the phenolic resin, but the weakening of adhesion due to the inorganic treatment or the property of being weak to moisture is improved, and the reaction between the high-concentration boric acid and borate mixture and the phenolic resin The compound provides a wood flame retardant composition that is preserved for up to 2 months at room temperature (25-30 ° C), and is used as an auxiliary agent when the existing boric acid or borate inorganic agent is used as a fire-resistant agent at 8% (Wt%) or less. Unlike that, it is composed at a high concentration of up to 40% by weight, and can be used as a main agent (fireproof adhesive). Therefore, a flame retardant made of a mixture of boric acid and borate in high concentration and a reaction compound with phenolic resin can be an adhesive that can maximize the fire resistance effect of wood.

본 발명에 따르면 접착력 약화현상이나 수분에 약한 성질이 개선되며 물에 의하여 잘 용탈되지 않고 치수안정성이 높고 난연성이 향상되는 목재 난연제 조성물, 난연목재 및 그 제조방법이 제공된다.According to the present invention, there is provided a wood flame retardant composition, flame retardant wood, and a method for manufacturing the same, which improve adhesion weakening or moisture resistance, are not easily leached by water, have high dimensional stability, and improve flame retardancy.

도 1은 본 발명의 실시예에 따라 난연 처리된 목재 사진이다. 무처리 목재와 차이없이 목재의 무늬가 잘 살아있다.
도2는 목재 판재의 무처리판재와 난연처리 판재의 용탈시험(KS M 1701) 전후의 비교사진이다.
도 3은 무처리파티클보드와 난연처리파티클보드의 용탈처리시험(KS M 1701-2018) 전후의 비교 사진이다. 무처리파티클보드의 용탈시험 결과 1의 오른쪽은 두께팽윤율 48%로서 두께가 많이 부풀어올라 있는데 반하여 난연처리파티클보드(2의 오른쪽)은 두께팽윤율이 12%로서 치수안정성이 매우 높음을 보여주고 있다.
도 4는 본 발명의 실시예에 따라 난연처리된 목재의 콘칼로리메타의 착화 시험 결과의 표면 모습들이다. 높은 온도에 의하여 표면은 탄화층이 형성되어 있고 뒷면은 깨끗한 것을 볼 수 있다.
도 5는 본 발명에 따른 난연목재 또는 난연목질재료의 제조공정 흐름도이다.
도 6 내지 도14는 본 발명의 실시예에 따라 난연처리된 목재의 KS F ISO 5660-1에서 제시하고 있는 콘칼로리메타의 성능시험에 의한 총열방출율(THR)과 열방출율(HRR)의 결과 그래프이다. 모두 난연등급 이상의 기준을 만족시켜 주고 있다.1 is a photograph of wood treated with flame retardancy according to an embodiment of the present invention. The pattern of the wood is well preserved, no difference from untreated wood.
Figure 2 is a comparative photograph before and after the leaching test (KS M 1701) of the untreated board and the flame retardant treatment of the wooden board.
Figure 3 is a comparative photograph before and after the leaching treatment test (KS M 1701-2018) of untreated particle board and flame retardant treated particle board. As a result of the leaching test of the untreated particle board, the thickness swelling rate on the right side of 1 is 48%, and the thickness is swollen a lot, whereas the flame retardant treated particle board (right side of 2) has a thickness swelling rate of 12%, showing very high dimensional stability. there is.
Figure 4 is the surface appearance of the ignition test results of the cone calorimeter of the flame-retardant treated wood according to an embodiment of the present invention. It can be seen that the carbonized layer is formed on the surface due to the high temperature and the back surface is clean.
Figure 5 is a flow chart of the manufacturing process of flame retardant wood or flame retardant wood material according to the present invention.
6 to 14 are graphs of the results of the total heat release rate (THR) and heat release rate (HRR) by the performance test of the cone calorie meter presented in KS F ISO 5660-1 of the flame-retardant treated wood according to an embodiment of the present invention. am. All of them satisfy the standard of flame retardant grade or higher.

이하 본 발명을 상세하게 설명한다. 본 명세서 및 특허청구범위에 사용된 용어는 사전적 의미나 통상적인 의미로 한정되는 것은 아니며 본 발명의 기술적 사항에 부합하는 의미로 해석되어야 한다. Hereinafter, the present invention will be described in detail. The terms used in this specification and claims are not limited to the dictionary meaning or conventional meaning, and should be interpreted as meaning consistent with the technical details of the present invention.

본 발명에 따른 목재 및 목질재료용 난연제 조성물은 붕산(Boric acid), 붕산염(Sodium borate), 수용성 페놀수지(Phenol formaldehyde resin) 및 물을 포함한다.The flame retardant composition for wood and wood-based materials according to the present invention includes boric acid, sodium borate, water-soluble phenolic resin and water.

그리고, 난연제 조성물에서 페놀수지(Phenolic resin)(고형분)는 16-36 wt%, 붕산(Boric acid)(고형분) 8-18 wt%, 붕산염(Sodium borate)(고형분)은 10-22 wt%로 붕산·붕산염(전체고형분)은 18-40wt%를 포함하여 이루어질 수 있다.And, in the flame retardant composition, phenolic resin (solid content) is 16-36 wt%, boric acid (boric acid) (solid content) 8-18 wt%, borate (sodium borate) (solid content) is 10-22 wt% Boric acid and borate salts (total solid content) may be made including 18-40wt%.

상기 페놀수지는 액상형 레졸(resol)형이고, 본 발명에서 난연제 조성물은 레조르시놀(resorcinol) 또는 비스페놀을 더 포함할 수 있다. 레조르시놀 또는 비스페놀은 페놀과의 공축합수지 제조가 가능한 액상형 레졸(resol)형이다.The phenolic resin is a liquid resol type, and in the present invention, the flame retardant composition may further include resorcinol or bisphenol. Resorcinol or bisphenol is a liquid resol type capable of preparing a cocondensation resin with phenol.

난연제 조성물에서 레조르시놀은 10-40wt% 포함할 수 있다.In the flame retardant composition, resorcinol may be included in an amount of 10 to 40 wt %.

또한, 난연제 조성물에서 레조르시놀 수지(고형분)은 23∼33 wt%, 페놀수지(고형분) 15∼21wt%로 레조르시놀·페놀수지(전체고형분)은 38∼54 wt%, 붕산(Boric acid) (고형분) 6.8∼10.9 wt%, 붕산염(Sodium borate)(고형분)은 8.5 ∼ 13.7 wt%로서 붕산·붕산염 (전체고형분)은 15.3∼24.6 wt%를 포함하여 이루어질 수 있다. In addition, in the flame retardant composition, the resorcinol resin (solid content) is 23 to 33 wt%, the phenol resin (solid content) is 15 to 21 wt%, the resorcinol/phenol resin (total solid content) is 38 to 54 wt%, boric acid (boric acid) ) (solid content) 6.8 to 10.9 wt%, borate (sodium borate) (solid content) is 8.5 to 13.7 wt%, boric acid · borate (total solid content) may include 15.3 to 24.6 wt%.

붕산 및 붕산염을 혼합하여 붕산·붕산염에 의한 혼합물을 만들고 이 붕산·붕산염에 의한 혼합물은 일예로서 붕산·붕산염 용액으로 붕산 25.53wt%, 붕산염(붕사) 31.91wt%를 물에 넣어 온도를 90℃∼100℃까지 높여 투명하게 물에 잘 녹는 붕산·붕산염에 의한 혼합물을 만들어 페놀수지에 혼합하여 반응할 수 있다.A mixture of boric acid and borate is prepared by mixing boric acid and borate, and the mixture of boric acid and borate is, as an example, a solution of boric acid and borate by adding 25.53 wt% of boric acid and 31.91 wt% of borate (borax) into water and raising the temperature to 90 ° C. By raising the temperature to 100℃, a mixture of boric acid and borate that is transparently soluble in water can be made and mixed with phenolic resin to react.

그 다음, 상기와 같은 본 발명의 목재 및 목질재료용 난연제 조성물의 제조방법에 대해 상세하게 설명한다. 본 발명의 목재 및 목질재료용 난연제 조성물로서 난연 약제는 페놀수지를 제조하는 단계와, 붕산과 붕산염을 용매에 혼합하여 붕산·붕산염 혼합물을 제조하는 단계, 그리고 붕산·붕산염 혼합물과 페놀수지를 혼합하여 반응하는 세 단계를 포함하여 제조된다.Next, the method for preparing the flame retardant composition for wood and wood-based materials of the present invention as described above will be described in detail. As a flame retardant composition for wood and wood materials of the present invention, the flame retardant agent comprises the steps of preparing a phenolic resin, mixing boric acid and borate in a solvent to prepare a boric acid/borate mixture, and mixing the boric acid/borate mixture and the phenolic resin. It is prepared by including three reaction steps.

페놀수지를 제조할 때, 실온에서 반응기에 페놀, 포르말린, 증류수를 투입하고 pH를 조정하여 소정온도에서 소정시간동안 반응시켜 레졸형 페놀수지를 제조한다.When preparing a phenolic resin, phenol, formalin, and distilled water are put into a reactor at room temperature, and the pH is adjusted and reacted at a predetermined temperature for a predetermined time to prepare a resol-type phenolic resin.

수지반응기에 페놀과 포르마린은 페놀:포르마린으로 몰비 1:1.63~2.4(mol)로 투입할 수 있다. 구체적인 일예로 실온에서 반응기에 페놀 94g(1몰), 포르마린 35% 139.5-205.7g(1.63-2.4 mol), 증류수 14-20g을 투입하여 pH를 NaOH로 10.7에서 11로 조정하여 온도 70-80℃에서 1시간 반응시켜 pH가 매우 높고, 낮은 온도와 짧은 반응시간을 적용한 중간산물로서의 레졸(resol)형 페놀수지(수지 고형분: 51-53.4%, pH:10.7-10.98, 점도: 32-38.4 cp)를 만든다. Phenol and formalin may be added to the resin reactor at a molar ratio of 1:1.63 to 2.4 (mol) as phenol:formarin. As a specific example, 94 g (1 mol) of phenol, 139.5-205.7 g (1.63-2.4 mol) of 35% formalin, and 14-20 g of distilled water were added to the reactor at room temperature, the pH was adjusted from 10.7 to 11 with NaOH, and the temperature was 70-80 ° C. Resol-type phenolic resin (resin solid content: 51-53.4%, pH: 10.7-10.98, viscosity: 32-38.4 cp) as an intermediate product with a very high pH by reacting for 1 hour at a low temperature and short reaction time makes

또한 페놀을 대신하여 레조르시놀, 비스페놀 등 페놀유도체가 사용될 수 있으며 페놀과 혼용을 하여 레조르시놀·페놀 공축합수지의 제조도 가능하다. In addition, phenol derivatives such as resorcinol and bisphenol can be used instead of phenol, and resorcinol-phenol co-condensation resin can be prepared by mixing with phenol.

상기 붕산·붕산염 혼합물을 제조하는 단계에서는 붕산, 붕산염(붕사)을 넣고 소정온도까지 높여 투명하게 될 때까지 물에 잘 녹는 붕산·붕산염에 의한 혼합물을 제조한다.In the step of preparing the boric acid-borate mixture, boric acid and borate (borax) are added and raised to a predetermined temperature to prepare a mixture of boric acid and borate, which is well soluble in water, until it becomes transparent.

붕산·붕산염 혼합물로서 붕산·붕산염 용액은 구체적인 일예로 붕산 25.53wt%, 붕산염 (붕사) 31.91wt%를 물(42.56wt%)에 넣어 온도를 90℃-100℃까지 높여, 투명하게 될 때까지 물에 잘 녹는 붕산·붕산염에 의한 혼합물을 제조할 수 있다.As a boric acid-borate mixture, the boric acid-borate solution is a specific example by adding 25.53wt% of boric acid and 31.91wt% of borate (borax) to water (42.56wt%) and raising the temperature to 90℃-100℃, until the water becomes transparent. It is possible to prepare a mixture of boric acid and borate salts that are easily soluble in

붕산·붕산염 혼합물과 페놀수지를 혼합하여 반응하는 단계에서는 전술한 바와 같이 각각 제조된 붕산·붕산염 혼합물과 페놀수지를 혼합하여 반응한다.In the step of mixing and reacting the boric acid/borate mixture and the phenol resin, the prepared boric acid/borate mixture and the phenol resin are mixed and reacted as described above.

본 실시예에서는 상기 제조된 폐놀수지에 온도를 60℃로 유지시키면서, 페놀수지 고형분 16-36 wt%, 붕산(Boric acid) 고형분 8-18 wt%, 붕산염(Sodium borate) 고형분은 10-22 wt%로 붕산·붕산염 전체고형분이 18-40 wt%의 비율이 되도록 혼합하여 두 시간 반응시켜 내수형 목재 난연제 조성물을 만들게 되는데 액상형으로 20-30℃의 온도에서 최대 2개월간 보존 가능하다. In this embodiment, while maintaining the temperature of the prepared phenolic resin at 60 ℃, phenolic resin solid content of 16-36 wt%, boric acid (Boric acid) solid content of 8-18 wt%, borate (Sodium borate) solid content of 10-22 wt% In %, the total solid content of boric acid and borate is mixed to a ratio of 18-40 wt% and reacted for two hours to make a water-resistant wood flame retardant composition, which can be stored for up to 2 months at a temperature of 20-30 ° C in liquid form.

또는 이렇게 만든 페놀수지·붕산붕산염혼합물을 60℃로 유지한 상태에서 레조르시놀을 10-40wt% 첨가하여 2시간 더 반응시켜 20-30℃의 온도에서 보관하는 내수형 레조르시놀페놀수지·붕산붕산염혼합물의 난연제 조성물의 제조도 가능하다. Alternatively, a water-resistant type resorcinol phenolic resin boric acid that is stored at a temperature of 20-30 ° C by adding 10-40 wt% of resorcinol and reacting for 2 hours while maintaining the phenolic resin boric acid borate mixture thus prepared at 60 ° C. It is also possible to prepare flame retardant compositions of borate mixtures.

이렇게 만든 페놀레조르시놀수지·붕산붕산염 혼합물 또는 레조르시놀페놀수지·붕산붕산염 혼합물의 경우, 페놀수지 고형분이 낮고 레조르시놀수지 고형분도 낮아 페놀수지 고형분과 레조르시놀 고형분의 합이 30wt% 이하로 되는 경우는 난연처리 제품의 난연효과와 치수안정 쪽으로 접착보다는 난연처리에 중요성을 두는 경우가 되며, 페놀수지 고형분과 레조르시놀 고형분의 합이 40wt% 이상이 되면 접착이 주가 되고 동시에 난연효과가 부차적으로 작용하게 되므로, 합판이나 집성재의 제조시 사용하는 일반 접착제처럼 경화제와 필러를 첨가하여 냉압 또는 열압을 할 수 있다. 이 경우에는 목질재료에 사용하는 일반 접착제처럼 사용하므로 난연제의 주입처리에 따른 복잡한 공정과는 달리 공정이 단순하다. 이러한 난연접착제는 합판이나 집성재의 제조시 접착층(glue line)이 형성되기 직전에 인접 경계면의 목질부분으로 액상의 난연조성물이 일부 확산되어 들어가며, 또한 접착층 자체가 난연층이 형성되므로 접착층이 많을수록 난연층이 많게 되므로 난연층이 많은 합판은 집성재보다 보다 유리하게 작용하게 된다. 따라서 난연합판의 난연접착층이 많을수록 오래도록 화재 속에서 버틸 수 있게 하여 주는 역할을 담당하게 한다. 따라서 합판뿐만 아니라 구조재로 사용하는 CLT의 내부에 이러한 난연합판이 들어있는 경우에, 화재시 구조물이 용도별 부재별로 일정 시간 이상 버틸 수 있게 하는 내화구조 역할을 충분히 할 수 있게 된다. In the case of the phenolresorcinol resin boric acid borate mixture or the resorcinol phenol resin boric acid borate mixture thus prepared, the phenolic resin solid content is low and the resorcinol resin solid content is low, so that the sum of the phenolic resin solid content and the resorcinol solid content is 30 wt% or less. When the flame retardant effect and dimensional stability of the flame retardant treated product are more important than adhesion, the flame retardant treatment is more important. Since it acts as a secondary function, it can be cold-pressed or hot-pressed by adding a hardener and a filler like a general adhesive used in the manufacture of plywood or laminated materials. In this case, since it is used like a general adhesive used for wood materials, the process is simple, unlike the complicated process of injecting flame retardants. In this flame retardant adhesive, a liquid flame retardant composition is partially diffused into the wood part of the adjacent interface immediately before the glue line is formed during the manufacture of plywood or laminated material, and the flame retardant layer itself is formed, so the more the adhesive layer is, the more flame retardant it is. Since there are many layers, plywood with many flame retardant layers acts more advantageously than laminated materials. Therefore, as the number of flame retardant adhesive layers of the flame retardant plate increases, it plays a role in enabling it to withstand fire for a long time. Therefore, when such a flame retardant board is contained inside the CLT used as a structural material as well as the plywood, it is possible to play a sufficient role as a fire resistant structure that allows the structure to withstand a certain period of time for each member for each use in case of fire.

그 다음으로 본 발명에 따른 난연목재 또는 난연목질재료 및 그 제조방법에 대해 설명한다. 도 5는 본 발명에 따른 난연목재 또는 난연목질재료의 제조공정 흐름도이다.Next, the flame retardant wood or flame retardant wood material and its manufacturing method according to the present invention will be described. Figure 5 is a flow chart of the manufacturing process of flame retardant wood or flame retardant wood material according to the present invention.

본 발명에 따른 난연목재 또는 난연목질재료의 제조방법은 S1) 목재 또는 목질재료를 준비하는 단계; S2) 페놀수지· 붕산붕산염 화합물의 목재 난연제를 제조하는 단계; S3) 상기 S2)단계에서 얻어지는 페놀수지· 붕산붕산염 화합물의 목재 난연제를 상기 목재 또는 목질재료에 주입하는 단계; S4) 주입처리된 상기 목재 또는 목질재료를 건조-경화하는 단계;를 포함하여 이루어진다.A method for manufacturing a flame retardant wood or wood material according to the present invention comprises the steps of S1) preparing wood or wood material; S2) preparing a wood flame retardant of a phenolic resin borate compound; S3) injecting the wood flame retardant of the phenolic resin boric acid borate compound obtained in step S2) into the wood or wood material; S4) drying-hardening the wood or wood material subjected to injection treatment;

또한, S2) 단계는 페놀수지를 제조하는 단계; 붕산과 붕산염을 용매에 혼합하여 붕산·붕산염 혼합물을 제조하는 단계; 상기 붕산·붕산염 혼합물과 상기 페놀수지를 혼합하여 반응하는 단계;를 포함하여 이루어진다.In addition, step S2) is a step of preparing a phenolic resin; Preparing a boric acid-borate mixture by mixing boric acid and borate in a solvent; and mixing and reacting the boric acid-borate mixture and the phenol resin.

또한, 추가적으로 S5) 목질요소(particle, fiber, veneer, board)에 따라 열압공정을 거쳐 최종목질재료를 제조하는 단계를 더 포함할 수 있다. In addition, S5) manufacturing a final wood material through a hot pressing process according to wood elements (particle, fiber, veneer, board) may be further included.

본 발명의 난연목재 및 난연목질재료의 제조방법으로는 먼저 목재 또는 목질재료를 준비한다. 목재는 사용하는 방법에 따라 여러가지 요소로 구분된다. 목재를 제제하여 판재나 각재로 켤 수 있고, 얇은 판 즉 단판(veneer)으로 깎거나 켤 수 있으며, 파티클(particle)이나 파이버(fiber)로 마쇄 또는 파쇄시켜 만들 수 있다. 이들 목재요소(particle, fiber, veneer, board)를 가지고 목질재료를 만들게 되는데, 즉 파티클로는 파티클보드, 파이버로는 파이버보드, 스트랜드(strand)로는 스트랜드보드(OSB), 단판(veneer)으로는 합판(plywood), 단판적층재(LVL, laminated veneer lumber), 판재로는 집성재(laminated lumber, glue-laminated timber, glulam)와 구조용 직교집성판(CLT: cross laminated timber) 등의 목질재료를 제조하게 되며 이 공정(혼합, 주입, 도장, 피목등)에 맞게 난연약제를 처리하게 된다.In the method for manufacturing flame retardant wood and flame retardant wood material of the present invention, wood or wood material is first prepared. Wood is classified into several elements depending on how it is used. Wood can be prepared and turned into boards or squares, cut or turned into thin boards, that is, veneers, and can be made by grinding or crushing into particles or fibers. Wood materials are made with these wood elements (particle, fiber, veneer, board), that is, particleboard is particleboard, fiber is fiberboard, strand is strandboard (OSB), veneer is veneer. Manufactures wood materials such as plywood, laminated veneer lumber (LVL), laminated lumber, glue-laminated timber, glulam, and cross laminated timber (CLT) for boards. And the flame retardant is treated according to this process (mixing, injection, painting, skin, etc.).

다음으로 난연약제를 준비하는 단계로서 전술한 바와 같은 목재 및 목질재료용 난연제 조성물을 제조한다. Next, as a step of preparing a flame retardant, a flame retardant composition for wood and wood-based materials as described above is prepared.

다음은 페놀수지· 붕산붕산염 화합물을 상기 목재 및 목질재료에 주입하는 단계로서, 주입방법은 목질요소와 두께에 따라 상온에서 확산침투하는 방법으로부터 가압방법과 배기와 가압처리를 같이 하는 방법이 결정된다. The following is a step of injecting phenolic resin boric acid borate compound into the wood and wood materials. Depending on the wood element and thickness, the injection method is determined from diffusion and penetration at room temperature to pressurization and exhaust and pressurization. .

판재는 수종에 따라 가압만 10∼25 kg/㎠에서 두 시간 행하거나, 감압·가압방법으로 전배기 (0.08 MPa) 30분, 가압 15∼25 kg/㎠의 압력에 한 시간, 후배기 (0.08 MPa) 10-30분을 시행한다. 이 때 온도는 상온으로부터 60℃가 일반적이다. 기성제품인 합판, 단판 적층재나 집성재도 판재에 준하여 처리한다. 단판인 경우는 수종에 따라 10∼25 kgf/㎠의 압력으로 30분∼120분 처리한다. 파티클이나 파이버는 난연제를 혼합기(MIXER)에서 혼합하면서 30분간 회전시켜 마찰과 내부확산을 통하여 주입 도포시킨다. Depending on the species, the plate is either pressurized only at 10~25 kg/cm2 for two hours, or decompressed and pressurized for 30 minutes in the former exhaust (0.08 MPa), one hour in the pressure of 15~25 kg/cm2, and post exhaust (0.08 MPa). MPa) 10-30 minutes. At this time, the temperature is generally 60 ° C from room temperature. Ready-made plywood, veneer laminates, and laminates are treated in the same way as plate materials. In the case of a single plate, it is treated for 30 to 120 minutes at a pressure of 10 to 25 kgf/cm2 depending on the species. Particles or fibers are injected and applied through friction and internal diffusion by rotating the flame retardant for 30 minutes while mixing in a mixer (MIXER).

다음은 난연제가 주입처리된 목재 및 목질재료를 건조-경화하는 단계로서, 목재요소와 수종, 심변재, 두께에 따라 50-70℃, 바람직하게는 60℃에서 일정기간 동안 건조, 양생시켜 안정화하는 단계와 난연제 내의 페놀수지를 100∼150℃에서 경화시키는 단계를 거치게 된다. 판재는 일예로 60℃에서 24∼48시간 건조 양생하고 105℃에서 24시간 경화시켜 난연처리 목재를 제조할 수 있다. 단판은 두께가 얇기 때문에 일예로 60℃에서 12∼24시간 건조 양생하고 105℃에서 6∼12시간 경화시켜 난연단판을 제조한다. 파티클이나 파이버는 일예로 60℃에서 12∼24시간 건조 후, 105∼150℃에서 30분∼2시간 경화 처리시킨다. The next step is to dry and harden the wood and wood materials injected with the flame retardant, which are dried and cured for a certain period of time at 50-70 ° C, preferably 60 ° C, depending on the wood element, tree species, heart sapwood, and thickness to stabilize and a step of curing the phenolic resin in the flame retardant at 100 to 150°C. For example, the board may be dried and cured at 60° C. for 24 to 48 hours and cured at 105° C. for 24 hours to produce flame retardant treated wood. Since the veneer is thin, for example, a flame retardant veneer is prepared by drying and curing at 60 ° C for 12 to 24 hours and curing at 105 ° C for 6 to 12 hours. Particles or fibers are, for example, dried at 60°C for 12 to 24 hours and then cured at 105 to 150°C for 30 minutes to 2 hours.

다음은 건조·경화한 목재 및 목질재료에서 목재 및 판재는 처리된 그대로 사용할 수 있으나 단판(veneer), 파티클, 파이버는 물론 판재도 다음 단계인 열압공정을 거쳐 최종목질재료를 제조하는 단계를 거치게 된다. Next, in the dried and hardened wood and wood materials, wood and boards can be used as they have been processed, but veneers, particles, fibers, and boards go through the next step, the hot-pressing process, to manufacture final wood materials. .

처리된 판재는 집성재나 구조용 직교집성판(CLT)을 만들게 되는데 레조르시놀 접착제나 페놀레조르시놀 공축합 접착제를 사용하여 만들게 된다. 처리된 단판(veneer)은 접착제를 사용하여 합판과 단판적층재(LVL)를 만들게 된다. 처리된 파티클이나 파이버는 접착제를 사용하여 통상적인 열압스케쥴을 사용하여 파티클보드나 파이버보드를 제조한다. 일예를 들면 난연처리된 파티클에 멜라민수지(고형분 53%) 10%와 경화제 NH4Cl 20% 용액 3%를 첨가하여 매트 성형 후, 열압기에서 175℃에서 45-30-20 kg/㎠(2-3.3-2분)7분30초의 열압스케쥴을 적용, 열압하여 난연파티클보드를 제조하게 된다. The treated boards are made into laminated materials or structural orthogonal laminated boards (CLT), which are made using resorcinol adhesives or phenolresorcinol co-condensation adhesives. The treated veneer is then made into plywood and veneer (LVL) using adhesives. The treated particles or fibers are then bonded to form particleboard or fiberboard using a conventional hot press schedule. For example, after molding a mat by adding 10% of melamine resin (53% solid content) and 3% of a 20% solution of a curing agent NH 4 Cl to the flame retardant treated particles, 45-30-20 kg/cm2 (2 -3.3-2 minutes) apply a hot pressure schedule of 7 minutes and 30 seconds to produce flame retardant particle board.

본 발명에 따른 목재 및 목질재료를 위한 난연제 조성물, 난연 목재 및 난연목질재료의 제조방법은 환경에 대한 부담을 줄이면서 난연성능을 향상시킬 수 있으며, 목재 및 목질재료의 본래의 물성을 향상시키고 목재의 자연적인 무늬와 심미성을 유지하여 목조주택, 목재가구, 목재문화재, 각종 생활용구에 이르기까지 그 적용이 모두 가능하다.The flame retardant composition for wood and wood materials and the method for manufacturing flame retardant wood and flame retardant wood materials according to the present invention can improve flame retardant performance while reducing the burden on the environment, improve the original physical properties of wood and wood materials, and It can be applied to wooden houses, wooden furniture, wooden cultural assets, and various living utensils by maintaining the natural pattern and aesthetics of the product.

이하, 실시예를 통하여 본 발명을 보다 상세히 설명하기로 한다. 이들 실시예는 오로지 이 발명을 보다 구체적으로 설명하기 위한 것으로, 이 발명의 취지에 따라 이 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 당 업계에서 통상의 지식을 가진 자에게 있어서는 자명한 것이다.Hereinafter, the present invention will be described in more detail through examples. These examples are only for explaining the present invention in more detail, and it is obvious to those skilled in the art that the scope of the present invention is not limited by these examples according to the purpose of the present invention. .

[실시예 1] 난연판재처리[Example 1] Flame retardant plate reprocessing

라디에타 소나무 판재(100 mm *10mm *400mm, 길이방향 실링)를 목재 난연제 조성물이 채워진 가압주입기에 넣고 43℃에서 전배기(0.08 MPa) 30분, 가압 20 ㎏/㎠ 의 압력으로 1 시간, 후배기 (0.08 MPa) 10분 처리하여 감압-가압처리하였다. 난연제는 페놀수지(Phenolic resin) 고형분이 20.8 wt%, 붕산(Boric acid) 고형분 15.3 wt%, 붕산염(Sodium borate) 고형분은 19.2 wt%로 붕산·붕산염 전체고형분이 34.5 wt%로 만든 붕산·붕산염 고형분의 양이 페놀수지 고형분보다 1.66배가 많은 난연제를 사용하였다.Radiata pine board (100 mm * 10 mm * 400 mm, longitudinal sealing) was put into a pressurized injector filled with a wood flame retardant composition, and at 43 ° C. for 30 minutes with a pre-exhaust (0.08 MPa), 1 hour at a pressure of 20 kg / ㎠, and a post-exhaust (0.08 MPa) for 10 minutes and reduced pressure-pressure treatment. The flame retardant is a phenolic resin solid content of 20.8 wt%, boric acid solid content of 15.3 wt%, and boric acid solid content of 19.2 wt%, and the total solid content of boric acid and borate is 34.5 wt%. A flame retardant with an amount of 1.66 times more than the solid content of the phenolic resin was used.

상기 내화처리를 통해 주입된 판재는 60℃에서 24시간 건조 양생하고 105℃에서 24시간 경화시켜 난연처리 목재를 제조하였다. 난연처리된 판재의 콘칼로리미터의 내화성 결과는 다음과 같다. The board injected through the fireproof treatment was dried and cured at 60 ° C for 24 hours and cured at 105 ° C for 24 hours to prepare flame retardant treated wood. The fire resistance results of the cone calorimeter of the flame retardant treated board are as follows.

중량증가율(WPG : weight percent gain)은 48.28%였고, 착화시간은 100초, 중량감소율은 8.24%로서 KS F ISO 5660-1에서 제시하고 있는 콘칼로리미터 성능시험을 한 결과 도6((a):총열방출율(THR), (b):열방출율(HRR))과 같이 난연등급을 만족시켰다 The weight percent gain (WPG) was 48.28%, the ignition time was 100 seconds, and the weight loss rate was 8.24%. As a result of the cone calorimeter performance test presented in KS F ISO 5660-1, Figure 6 ((a) : Total heat release rate (THR), (b): Heat release rate (HRR))

일반적인 물성(난연판재/무처리판재)은 밀도 0.60/0.42 g/㎠, 함수율 8.81/7.83 %였다. 또한 난연처리 판재의 중량증가율은 48.28 %였는데 반하여 용탈처리시험(KS M 1701-2018)의 결과는 중량감소율이 28.12±0.026 %로 난연제가 제품 속에 그대로 많이 남아 있어 용탈저항성이 매우 높아지는 효과가 있었다. 도2는 무처리판재와 난연처리 판재의 용탈시험 전후 비교사진으로서 10회의 용탈처리에 의하여 무처리판재(1의 오른쪽)는 목재표면이 심하게 갈라져 있으나 난연처리재(2의 오른쪽)는 처리전과 같이 깨끗함으로 치수안정이 대단히 높다는 것을 보여주고 있다.General physical properties (flame retardant board/untreated board) were density of 0.60/0.42 g/cm2 and moisture content of 8.81/7.83%. In addition, the weight increase rate of the flame retardant treated board was 48.28%, whereas the result of the leaching treatment test (KS M 1701-2018) showed that the weight loss rate was 28.12 ± 0.026%, and the flame retardant remained in the product as it was, so the leaching resistance was very high. Figure 2 is a comparative photograph of the untreated board and the flame retardant treated board before and after the leaching test, and the untreated board (right side of 1) is severely cracked by the leaching treatment 10 times, but the flame retardant treated board (right side of 2) is as before treatment. It shows that the dimensional stability is very high with cleanliness.

[실시예 2] 라디에타파인 판재 난연처리후 집성재 제조[Example 2] Manufacture of laminated material after flame retardant treatment of radiata pine plate

라디에타 소나무 판재 (100 mm *10mm *400mm, 길이방향 실링)를 목재난연제 조성물이 채워진 가압주입기에 넣고 60℃에서 가압 14 ㎏/㎠ 의 압력으로 2 시간, 가압처리하였다. 난연제는 페놀수지(Phenolic resin) 고형분이 20.8 wt%, 붕산(Boric acid) 고형분 15.3 wt%, 붕산염(Sodium borate) 고형분은 19.2 wt%로 붕산·붕산염 전체고형분이 34.5 wt%로 만든 붕산·붕산염 고형분의 양이 페놀수지 고형분보다 1.66배가 많은 난연제를 사용하였으며, 처리된 라디에타 소나무(Radieta pine, 10mm 두께)의 중량증가율(WPG)은 63.76%였다. 주입된 판재는 60℃에서 24시간 건조 양생하고 105℃에서 24시간 경화시켜 난연 처리 목재를 제조하였다. 난연처리된 판재의 집성재 제조는 2매로 S사의 페놀 수지를 사용하여(도포량 200g/㎡, 150℃,10kgf/㎠, 35min.) 열압하여 제조하였다.A radiata pine board (100 mm * 10 mm * 400 mm, longitudinal sealing) was put into a pressure injector filled with a wood flame retardant composition and subjected to pressure treatment at 60° C. under a pressure of 14 kg/cm 2 for 2 hours. The flame retardant is a phenolic resin solid content of 20.8 wt%, boric acid solid content of 15.3 wt%, and boric acid solid content of 19.2 wt%, and the total solid content of boric acid and borate is 34.5 wt%. The amount of flame retardant was 1.66 times higher than the phenolic resin solid content, and the weight gain (WPG) of the treated Radieta pine (10 mm thick) was 63.76%. The injected board was dried and cured at 60 ° C for 24 hours and cured at 105 ° C for 24 hours to prepare flame retardant treated wood. The laminated material of the flame retardant treated board was prepared by hot pressing using 2 sheets of S company's phenol resin (coating amount 200g/m 2 , 150 °C, 10 kgf/cm 2 , 35 min.).

난연처리된 라디에타파인 집성재의 콘칼로리미터의 내화성 결과는 다음과 같다. The fire resistance results of the cone calorimeter of the flame retardant treated radiata pine laminate are as follows.

착화시간은 착화가 되지 않았으며, 중량감소율(600초)은 7.16%를 나타냈고, KS F ISO 5660-1에서 제시하고 있는 콘칼로리미터 성능시험을 한 결과 도7((a):총열방출율(THR), (b):열방출율(HRR))과 같이 준불연등급을 만족시켰다.The ignition time was not ignited, the weight loss rate (600 seconds) was 7.16%, and as a result of the cone calorimeter performance test presented in KS F ISO 5660-1, Figure 7 ((a): total heat release rate ( THR), (b): heat release rate (HRR)) satisfied the semi-flammable grade.

일반적인 물성(난연집성재/ 무처리집성재)은 밀도 0.60/0.42 g/㎠, 함수율 8.81/7.83 %였다. General physical properties (flame retardant laminated material/untreated laminated material) were 0.60/0.42 g/cm2 density and 8.81/7.83% moisture content.

[실시예 3] 단판 난연처리 후 합판제조[Example 3] Manufacture of plywood after veneer flame retardant treatment

낙엽송 단판(2.4mm두께)을 목재 난연제가 채워진 가압주입기에 넣고 60℃에서 가압 14 ㎏/㎠ 의 압력으로 2 시간, 가압처리하였다. 액상 난연제는 페놀수지 고형분 20.8 wt%, 붕산(Boric acid) 고형분 15.3 wt%, 붕산염(Sodium borate) 고형분은 19.2 wt%로 붕산·붕산염 전체고형분이 34.5 wt%의 조성으로 제조된 난연제를 사용하였다. 상기 내화처리를 통해 주입된 단판은 60℃에서 24시간 건조 양생하고 105℃에서 24시간 경화시켰다. 이렇게 처리된 난연 처리 단판을 사용하여 5매합판(페놀수지 도포량 200g/㎡, 150℃, 10kgf/㎠, 20min.)을 열압하여 제조하였다. 난연 처리된 단판으로 제조된 합판의 콘 칼로리미터의 내화성과 물성의 결과는 다음과 같다.A larch veneer (2.4 mm thick) was put into a pressure injector filled with wood flame retardant and subjected to pressure treatment at 60° C. at a pressure of 14 kg/cm 2 for 2 hours. The liquid flame retardant was prepared with a composition of 20.8 wt% of phenolic resin solid content, 15.3 wt% of boric acid solid content, 19.2 wt% of sodium borate solid content, and 34.5 wt% of boric acid/borate solid content. The veneer injected through the fireproof treatment was dried and cured at 60 ° C for 24 hours and cured at 105 ° C for 24 hours. Five plywood (phenolic resin coating amount 200 g / m 2, 150 ° C., 10 kgf / cm 2, 20 min.) was prepared by hot pressing using the flame retardant treated veneer treated as described above. The results of fire resistance and physical properties of the cone calorimeter of plywood made of flame retardant treated veneer are as follows.

중량증가율(WPG : weight percent gain)은 30.09% 였고, 착화성은 99초였으며, 중량감소율(300초)은 13.28%였고, KS F ISO 5660-1에서 제시하고 있는 콘칼로리미터 성능시험을 한 결과 도8((a):총열방출율(THR), (b):열방출율(HRR))과 같이 난연등급을 만족시켰다.The weight percent gain (WPG) was 30.09%, the ignition quality was 99 seconds, the weight loss rate (300 seconds) was 13.28%, and the results of the cone calorimeter performance test presented in KS F ISO 5660-1 8 ((a): total heat release rate (THR), (b): heat release rate (HRR)).

일반적인 물성(난연합판/ 무처리합판)은 밀도 0.75±0.11/0.67±0.04 g/㎠, 함수율 9.05±0.04/9.53±0.07 %, 인장전단접착력은 0.89±0.12/1.19 ±0.26 N/㎟ 그리고 내수인장강도는 0.82/0.84 N/㎟였다. 따라서 난연처리로 인하여 합판 밀도는 높아지고 난연제 처리로 인한 접착력의 저하는 없었으며, 붕산·붕산염 혼합물만의 처리재는 재단시 바로 접착부위가 떨어지는데 반해 새로 개발된 페놀수지·붕산붕산염화합물 난연제와는 크게 차이가 남을 알 수 있었다.General physical properties (flame-resistant board/untreated plywood) are density 0.75±0.11/0.67±0.04 g/cm2, moisture content 9.05±0.04/9.53±0.07 %, tensile shear adhesion 0.89±0.12/1.19 ±0.26 N/㎟ and water resistance The strength was 0.82/0.84 N/mm 2 . Therefore, the density of the plywood increased due to the flame retardant treatment, and there was no decrease in adhesive strength due to the flame retardant treatment, and while the treated material with only boric acid and borate mixture immediately fell off during cutting, it is significantly different from the newly developed phenolic resin and borate borate compound flame retardant. was able to know others.

[실시예 4] 기성 합판 난연 처리[Example 4] Ready-made plywood flame retardant treatment

합판의 기성제품(낙엽송 2.4㎜ 두께 단판 13매합판, 크기 (T)30*(W)100*(L)300mm, 라디에타파인 2.4mm 두께 단판 9매 합판, (T)21*(W)100*(L)300mm)과 난연제를 가압기에 넣고 60℃에서 가압 14 ㎏/㎠ 의 압력으로 2시간, 난연제를 가압 처리하였다. 난연제는 붕산, 붕산염 고형분/페놀수지 고형분이 1.66으로, 페놀수지(Phenolic resin) 고형분이 20.8 wt%, 붕산(Boric acid) 고형분 15.3 wt%, 붕산염(Sodium borate) 고형분은 19.2 wt%로 붕산·붕산염 전체고형분이 34.5 wt%로 만든 내수형 목재 난연제를 사용하였다. Ready-made products of plywood (larch 2.4mm thick veneer 13 plywood, size (T)30*(W)100*(L)300mm, radiata pine 2.4mm thick veneer 9 veneer plywood, (T)21*(W)100* (L) 300mm) and the flame retardant were put into a pressurizer, and the flame retardant was pressurized at 60 ° C. for 2 hours at a pressure of 14 kg / cm 2 . The flame retardant is boric acid, borate solid content / phenolic resin solid content of 1.66, phenolic resin solid content of 20.8 wt%, boric acid solid content of 15.3 wt%, and borate solid content of borate (Sodium borate) solid content of 19.2 wt%. A water-resistant wood flame retardant made with a total solid content of 34.5 wt% was used.

상기 내화처리를 통해 주입된 판재는 60℃에서 24시간 건조 양생하고 105℃에서 24시간 경화시켜 난연처리 목재를 제조하였다.The board injected through the fireproof treatment was dried and cured at 60 ° C for 24 hours and cured at 105 ° C for 24 hours to prepare flame retardant treated wood.

난연처리된 라디에타파인 합판의 콘칼로리미터의 내화성 결과는 다음과 같다.The fire resistance results of the cone calorimeter of the flame retardant treated radiata pine plywood are as follows.

착화시간은 140초이고, 중량감소율(300초)은 9.2%를 나타냈고, KS F ISO 5660-1에서 제시하고 있는 콘칼로리미터 성능시험을 한 결과 도9((a):총열방출율(THR), (b):열방출율(HRR))와 같이 난연등급을 만족시켰다.The ignition time was 140 seconds, the weight loss rate (300 seconds) was 9.2%, and the result of the cone calorimeter performance test presented in KS F ISO 5660-1 Figure 9 ((a): total heat release rate (THR) , (b): heat release rate (HRR)) satisfied the flame retardancy grade.

일반적인 물성(난연합판/무처리합판)은 밀도 0.69/0.51 g/㎠, 함수율 7.70/7.44 %였다. 내화제에 의한 중량증가율(WPG : weight percent gain)은 36.3% 였다.General physical properties (fire retardant board/untreated plywood) were density 0.69/0.51 g/cm2 and moisture content 7.70/7.44%. The weight percent gain (WPG) by the fire retardant was 36.3%.

또한 난연 처리된 낙엽송 합판의 콘 칼로리미터의 내화성 결과는 다음과 같았다.In addition, the fire resistance results of the cone calorimeter of the flame retardant treated larch plywood were as follows.

착화시간은 187초이고, 중량감소율(300초)은 7.94%를 나타냈고, KS F ISO 5660-1에서 제시하고 있는 콘 칼로리미터 성능시험을 한 결과 도10((a):총열방출율(THR), (b):열방출율(HRR))과 같이 난연 등급을 만족시켰다.The ignition time was 187 seconds, the weight reduction rate (300 seconds) was 7.94%, and the result of the cone calorimeter performance test presented in KS F ISO 5660-1 Figure 10 ((a): total heat release rate (THR) , (b): heat release rate (HRR)).

밀도 0.75±0.03/0.67±0.08g/㎠(난연합판/무처리합판), 함수율 9.05±0.12/9.53±0.10%, 인장 전단 접착력은 1.98±0.37/2.09 N/㎟ 그리고 내수 인장 강도는 0.82±0.078/0.84 N/㎟였다. 따라서 난연 처리로 인하여 합판 밀도는 높아지고 난연제 처리로 인한 접착력의 저하는 없었음을 알 수 있었다. 또한, 난연 처리 합판의 내화제 처리에 의한 중량증가율은 22.46±0.49%였는데 반하여 용탈 시험의 결과는 중량감소율이 7.2±0.27% 밖에 되지 않아 상당량의 난연제가 제품속에 그대로 남아 있어 용탈 저항성이 매우 높아졌음을 알 수 있었다. Density 0.75±0.03/0.67±0.08g/cm2 (flame-resistant board/untreated plywood), moisture content 9.05±0.12/9.53±0.10%, tensile shear adhesion 1.98±0.37/2.09 N/㎟ and water resistance tensile strength 0.82±0.078 /0.84 N/mm2. Therefore, it was found that the density of the plywood increased due to the flame retardant treatment and there was no decrease in adhesive strength due to the flame retardant treatment. In addition, the weight increase rate of the flame retardant treated plywood by the fireproofing agent treatment was 22.46 ± 0.49%, whereas the result of the leaching test showed that the weight loss rate was only 7.2 ± 0.27%, and a considerable amount of the flame retardant remained in the product, so the leaching resistance was very high. And it was found.

[실시예 5] 난연 파티클보드 제조[Example 5] Manufacturing of flame retardant particle board

난연제는 페놀수지(Phenolic resin) 고형분이 20.8 wt%, 붕산(Boric acid) 고형분 15.3 wt%, 붕산염(Sodium borate) 고형분은 19.2 wt%로 붕산·붕산염 전체고형분이 34.5 wt%로 만든 붕산·붕산염 고형분의 양이 페놀수지 고형분보다 1.66배가 많은 난연제를 사용하였다. 이 난연제를 전건 파티클에 대하여 30%, 50%로 도포기에서 혼합하여 처리시킨 후, 60℃에서 24시간 건조 후 150℃에서 30분 처리시켜 경화시켰다. 이 파티클에 멜라민수지(고형분 53%)를 파티클 전건중량의 10%와 경화제 NH4Cl 20% 용액을 수지 중량의 3%로 첨가하여 매트 성형 후, 열압기에서 175℃에서 45-30-20 kg/㎠의 압력과 (2-3.3-2분)7분30초의 열압시간 스케쥴을 적용, 열압하여 난연 파티클보드를 제조하였다. 30% 난연 처리된 파티클 보드의 콘칼로리미터의 내화성능 결과는 다음과 같았다.The flame retardant is a phenolic resin solid content of 20.8 wt%, boric acid solid content of 15.3 wt%, and boric acid solid content of 19.2 wt%, and the total solid content of boric acid and borate is 34.5 wt%. A flame retardant with an amount of 1.66 times more than the solid content of the phenolic resin was used. The flame retardant was treated by mixing 30% and 50% of the pre-dried particles in an applicator, dried at 60 ° C for 24 hours, and then cured by treating at 150 ° C for 30 minutes. Melamine resin (solid content: 53%) is added to the particles at 10% of the dry weight of the particles and 20% of the curing agent NH 4 Cl solution is added at 3% of the weight of the resin to form a mat, and then 45-30-20 kg at 175℃ in a hot press. A flame retardant particle board was prepared by hot pressing by applying a pressure of / cm 2 and a hot pressing time schedule of (2-3.3-2 minutes) 7 minutes and 30 seconds. The fire resistance performance results of the cone calorimeter of the 30% flame retardant treated particle board were as follows.

착화시간은 42초이고, 중량감소율(300초)은 13.42%를 나타냈고, KS F ISO 5660-1에서 제시하고 있는 콘 칼로리미터 성능시험을 한 결과 도11((a):총열방출율(THR), (b):열방출율(HRR))과 같이 난연 등급을 만족시켰다.The ignition time was 42 seconds, the weight loss rate (300 seconds) was 13.42%, and the result of the cone calorimeter performance test presented in KS F ISO 5660-1 Figure 11 ((a): total heat release rate (THR) , (b): heat release rate (HRR)).

50% 난연 처리된 파티클 보드의 콘칼로리미터의 내화성능 결과는 다음과 같다. The fire resistance performance results of the cone calorimeter of the 50% flame retardant treated particle board are as follows.

착화시간은 착화가 전혀 되지 않았고, 중량감소율(600초)은 24.39%를 나타냈고, KS F ISO 5660-1에서 제시하고 있는 콘 칼로리미터 성능시험을 한 결과 도12((a):총열방출율(THR), (b):열방출율(HRR))와 같이 준불연 등급을 만족시켰다.The ignition time did not ignite at all, the weight loss rate (600 seconds) was 24.39%, and as a result of the cone calorimeter performance test presented in KS F ISO 5660-1, Figure 12 ((a): Total heat release rate ( THR), (b): heat release rate (HRR)) satisfied the semi-nonflammable rating.

일반적인 물성(30wt%난연파티클보드/50wt%난연파티클보드/무처리파티클보드)은 밀도 0.92±0.05/1.01±0.07/0.81±0.06 g/㎠, 함수율 6.733±0.19 /7.267±0.64/6.81±0.42%, 휨강도는 21.894±1.89/23.605±1.76/22.783±0.70 N/㎟ 그리고 습윤휨강도는 7.01±0.67/7.56±0.81/6.53±0.97 N/㎟, 박리강도는 0.81±0.05/0.904±0.07/0.97±0.09 N/㎟였다. General physical properties (30wt% flame retardant particle board/50wt% flame retardant particle board/untreated particle board) are density 0.92±0.05/1.01±0.07/0.81±0.06 g/cm2, moisture content 6.733±0.19/7.267±0.64/6.81±0.42% , the flexural strength was 21.894±1.89/23.605±1.76/22.783±0.70 N/㎟, the wet flexural strength was 7.01±0.67/7.56±0.81/6.53±0.97 N/㎟, and the peel strength was 0.81±0.05/0.904±0.07/0.9 7±0.09 It was N/mm2.

지금까지 보고된 예로서 Yalinkilic.M.K 등(1998)은 붕산·붕사처리(4.7%처리) 파티클보드가 미처리파티클보드보다 내부접착력이 42.4% 감소한다고 보고하였는데 이 실시예의 비교치로서 실험한 붕산·붕산염용액만을 갖고 파티클중량의 40%를 난연처리한 파티클보드의 박리강도는 0.27 N/㎟로서 무처리파티클보드 0.97 N/㎟에 비교하면 72.2%가 감소하였는데 반하여 개발된 폐놀·붕산붕산염난연제처리는 파티클전건중량의 30%, 50%를 처리하였는데도 무처리에 비하여 통계적으로 차이가 없었다(F=1.826). 또한 여기서 습윤 휨강도는 무처리에 비하여 처리량이 증가함에 따라 오히려 증가하여 물에 습윤시 휨강도는 무처리에 비하여 높아짐을 알 수 있었으며, 개발된 페놀수지· 붕산·붕산염 화합물의 난연제를 처리한 파티클 보드의 용탈 처리 시험(KS M 1701-2018)의 결과 (30%난연파티클보드/ 50%난연파티클보드)의 중량감소(WPL: weight percent loss)는 10.16±0.03%/15.26±0.05%로 중량증가율에 비교하면 많은 난연제가 파티클보드 내에 그대로 남아 있어 높은 용탈저항성을 나타냈을 뿐만 아니라 도3의 1의 오른 쪽은 무처리 파티클 보드의 용탈시험 결과 두께팽윤율 48±0.8%로서 두께가 많이 부풀어올라 있는데 반하여 50% 난연 처리 파티클 보드(2의 오른쪽)는 두께 팽윤율이 12±0.3%로서 치수안정이 매우 높음을 보여주고 있다. 따라서 개발된 본 페놀수지· 붕산·붕산염 화합물의 난연제 처리는 페놀수지의 영향으로 붕산·붕산염을 목재 내부에 가두어 두거나 이들을 실링하여 붕소에 의한 접착력 감소와 물에 대한 단점을 보완하여 치수안정에 도움을 주어, 붕산·붕산염 난연제 처리 만으로의 내부결합력이 떨어지는 단점을 보완하게 되었음을 알 수 있었다. As an example reported so far, Yalinkilic.M.K et al. (1998) reported that the particle board treated with boric acid and borax (4.7% treated) decreased the internal adhesion by 42.4% compared to the untreated particle board. The peel strength of the particle board treated with flame retardant treatment for 40% of the particle weight with only solution was 0.27 N/mm2, which was 72.2% lower than that of 0.97 N/mm2 of untreated particle board. Even though 30% and 50% of the dry weight were treated, there was no statistical difference compared to no treatment (F=1.826). In addition, it was found that the wet flexural strength increased as the amount of treatment increased compared to the untreated case, and the flexural strength when wet with water increased compared to the untreated case. As a result of the leaching treatment test (KS M 1701-2018) (30% flame retardant particle board / 50% flame retardant particle board), the weight percent loss (WPL) was 10.16±0.03%/15.26±0.05%, compared to the weight increase rate. If you do, many flame retardants remain in the particle board, not only showing high leaching resistance, but also the right side of 1 in FIG. The % flame retardant treated particle board (right of 2) shows very high dimensional stability with a thickness swelling rate of 12±0.3%. Therefore, the flame retardant treatment of this phenolic resin, boric acid, and borate compound developed by the influence of the phenolic resin traps boric acid and borate inside the wood or seals them to compensate for the decrease in adhesion caused by boron and the disadvantages against water, thereby helping to stabilize the dimensions. Given, it was found that the disadvantage of poor internal bonding strength only with boric acid and borate flame retardant treatment was supplemented.

[실시예 6] 페놀-레조르시놀수지·붕산-붕산염혼합물(PRB: phenol-resorecinol resin· boron complex) 난연제의 낙엽송 단판 난연처리[Example 6] Flame retardant treatment of larch veneer with phenol-resorcinol resin boron complex (PRB) flame retardant

페놀 94g(1몰), 포르마린 35% 171.4g(2.0mol), 물 15g을 수지반응기에 넣고, NaOH로 pH를 11로 조정하여 70℃에서 1시간 반응시켜 액상형 레졸(resol)형 페놀수지(고형분 51.7%, pH 11.0, 점도 24.3 cps)를 만들고, 붕산·붕산염 용액은 붕산 25.53wt%, 붕산염(붕사) 31.91wt%을 넣어 온도를 90℃-100℃까지 높여, 투명하게 될 때까지 물에 잘 녹는 붕산·붕산염 혼합물들을 만든 후에, 온도를 60℃로 유지시킨 상태에서 상기 제조된 페놀수지와 두 시간 반응시켜 폐놀수지 고형분이 23.4 wt%에, 붕산(Boric acid) 고형분 14.03 wt%, 붕산염(Sodium borate) 고형분은 17.54 wt%로 붕산·붕산염 전체고형분이 31.57 wt%의 비율이 되도록 만든다. 계속 온도를 60℃로 유지하면서 여기에 레조르시놀을 10g을 추가하여 15분간 교반하여 녹인 후 두 시간 더 반응시켜 만들면 폐놀수지 고형분이 21.3 wt%, 레조르시놀수지고형분이 9.1 wt%로 전체수지고형분이 30.4 wt%, 붕산(Boric acid) 고형분 12.8 wt%, 붕산염(Sodium borate) 고형분은 15.9 wt%로 붕산·붕산염 전체고형분이 28.7 wt%의 비율이 되는 내수형 페놀-레조르시놀수지·붕산-붕산염 목재 난연제(pH 7.35, 점도 36.9 cps)가 제조된다. Put 94 g (1 mol) of phenol, 171.4 g (2.0 mol) of formalin 35%, and 15 g of water into a resin reactor, adjust the pH to 11 with NaOH, and react at 70 ° C for 1 hour to obtain a liquid resol-type phenolic resin (solid content) 51.7%, pH 11.0, viscosity 24.3 cps), and for the boric acid/borate solution, add 25.53wt% of boric acid and 31.91wt% of borate (borax), raise the temperature to 90℃-100℃, and immerse well in water until it becomes transparent. After making the soluble boric acid and borate mixtures, the prepared phenolic resin was reacted with the prepared phenolic resin for two hours while the temperature was maintained at 60 ° C to obtain a phenolic resin solid content of 23.4 wt%, boric acid solid content of 14.03 wt%, borate (Sodium borate) The solid content is 17.54 wt%, so that the total solid content of boric acid and borate is 31.57 wt%. While maintaining the temperature at 60 ° C, add 10 g of resorcinol, stir for 15 minutes to dissolve, and then react for two more hours. Water-resistant type phenol-resorcinol resin and boric acid with solid content of 30.4 wt%, boric acid solid content of 12.8 wt%, and sodium borate solid content of 15.9 wt%, and the total solid content of boric acid and borate is 28.7 wt% -Borate wood flame retardant (pH 7.35, viscosity 36.9 cps) is prepared.

낙엽송 단판 (2.4mm두께)을 상기 목재 난연제가 채워진 가압주입기에 넣고 40℃에서 가압 25 ㎏/㎠ 의 압력으로 1시간, 가압처리 하였다. 내화처리를 통해 주입된 단판은 60℃에서 24시간 건조 양생하고 105℃에서 24시간 경화시켰다. 이렇게 처리된 난연 처리 단판을 사용하여 5매합판(페놀수지 도포량 200g/㎡, 150℃, 10kgf/㎠, 20min.)을 열압하여 제조하였다. 난연 처리된 단판으로 제조된 합판의 콘 칼로리미터의 내화성과 물성의 결과는 다음과 같다.A larch veneer (2.4 mm thick) was put into a pressure injector filled with the wood flame retardant and subjected to pressure treatment at 40° C. at a pressure of 25 kg/cm 2 for 1 hour. Veneers injected through fireproofing were dried and cured at 60 ° C for 24 hours and cured at 105 ° C for 24 hours. Five plywood (phenolic resin coating amount 200 g / m 2, 150 ° C., 10 kgf / cm 2, 20 min.) was prepared by hot pressing using the flame retardant treated veneer treated as described above. The results of fire resistance and physical properties of the cone calorimeter of plywood made of flame retardant treated veneer are as follows.

착화시간은 131초이고, 중량감소율(300초)은 14.28%를 나타냈고, KS F ISO 5660-1에서 제시하고 있는 콘 칼로리미터 성능시험을 한 결과 도13((a):총열방출율(THR), (b):열방출율(HRR))과 같이 난연 등급을 만족시켰다. The ignition time was 131 seconds, the weight loss rate (300 seconds) was 14.28%, and the result of the cone calorimeter performance test presented in KS F ISO 5660-1 Figure 13 ((a): Total heat release rate (THR) , (b): heat release rate (HRR)).

일반적인 물성(난연처리합판/무처리합판)은 밀도 0.70±0.05/0.67±0.04 g/㎠, 함수율 7.70±0.06/9.53±0.07 %였다. 내화제에 의한 중량증가율(WPG : weight percent gain)은 33.18±0.01%였다. 인장 전단 접착력은 0.99±0.08/1.19±0.26 N/㎟였다.General physical properties (flame retardant treated plywood/untreated plywood) were density 0.70±0.05/0.67±0.04 g/cm2 and moisture content 7.70±0.06/9.53±0.07%. The weight percent gain (WPG) by the fire retardant was 33.18±0.01%. The tensile shear adhesion was 0.99±0.08/1.19±0.26 N/mm2.

[실시예 7] 레조르시놀 페놀수지·붕산붕산염혼합물(RPB: resorecinol-phenol resin· boron complex)의 난연접착제로 제조한 난연합판제조[Example 7] Preparation of flame retardant board made of flame retardant adhesive of resorcinol-phenol resin boron complex (RPB)

페놀 94g(1몰), 포르마린 35% 171.4g(2.0mol), 물 15g을 수지반응기에 넣고, NaOH 로 pH를 11로 조정하여 70℃에서 1시간 반응시켜 액상형 레졸(resol)형 페놀수지(고형분 51.7%, pH 11.0, 점도 24.3 cps)를 만들고, 붕산·붕산염 용액은 붕산 25.53wt%, 붕산염 (붕사) 31.91wt%을 넣어 온도를 90℃-100℃까지 높여, 투명하게 될 때까지 물에 잘 녹는 붕산·붕산염 혼합물들을 만든 후에 온도를 60℃로 유지시킨 상태에서 상기 제조된 페놀수지와 반응시켜 폐놀수지 고형분이 23.4 wt%에, 붕산(Boric acid) 고형분 14.03 wt%, 붕산염(Sodium borate) 고형분은 17.54 wt%로 붕산·붕산염 전체고형분이 31.57 wt%의 비율이 되도록 두 시간 반응시킨다. 이 후 온도를 계속 60℃로 유지하면서 레조르시놀을 30g추가하여 15분간 교반하여 녹인 후 두 시간 반응시켜 만든 내수형 목재 난연접착제를 제조하였다. 이렇게 제조된 난연접착제로서의 레조르시놀·페놀공축합수지(Phenolic resin)의 조성은 페놀수지 고형분 18.6 wt% 와 레조르시놀수지 고형분 28.6 wt%로 접착제 전체고형분은 47.2 wt%, 붕산(Boric acid) 고형분 9.1 wt%, 붕산염(Sodium borate) 고형분은 11.4 wt%, 붕산·붕산염 전체고형분이 20.5 wt%, 나머지가 증류수 32.3 wt%이었다. 이 난연접착제는 접착층이 경화되어 내화층이 되어 난연효과를 줄 뿐만 아니라 이 접착제로부터 난연성분이 인접한 구성 목질재료 즉 단판이나 판재에 확산되어 난연성능을 같이 부과하게 된다. 이렇게 제조된 레조르시놀-페놀공축합수지· 붕산붕산염 혼합물(RPB) 난연접착제의 pH는 7.62, 점도는 48.3 cps였다. 두께 2.4㎜의 라디에타소나무 단판에 중량비로 난연접착제 100: 소맥분 15: 경화제 30중량부의 비율로 조제된 난연접착제를 도포량 200 g/㎡으로 도포하여 5매합판을 제조하였으며, 합판열압조건은 10 ㎏f/㎠, 150℃, 20분으로 하였다. 제조된 합판의 표면에 레조르시놀·페놀공축합수지· 붕산·붕산염 혼합물(RPB) 난연접착제를 도포량 300 g/㎡으로 도포하여 코팅하고 25-30℃에서 24시간 건조한 후 150℃에서 30분간 경화시켰다. Put 94 g (1 mol) of phenol, 171.4 g (2.0 mol) of formalin 35%, and 15 g of water into a resin reactor, adjust the pH to 11 with NaOH, and react at 70 ° C for 1 hour to obtain a liquid resol-type phenolic resin (solid content) 51.7%, pH 11.0, viscosity 24.3 cps), and for the boric acid/borate solution, add 25.53wt% of boric acid and 31.91wt% of borate (borax), raise the temperature to 90℃-100℃, and immerse well in water until it becomes transparent. After making soluble boric acid and borate mixtures, the temperature was maintained at 60 ° C and reacted with the prepared phenolic resin to obtain a phenolic resin solid content of 23.4 wt%, boric acid solid content of 14.03 wt%, and sodium borate solid content Silver is 17.54 wt% and reacted for two hours so that the total solid content of boric acid and borate is 31.57 wt%. Thereafter, while maintaining the temperature at 60 ° C., 30 g of resorcinol was added, stirred for 15 minutes to melt, and then reacted for two hours to prepare a water-resistant wood flame retardant adhesive. The composition of the resorcinol-phenol co-condensation resin as a flame retardant adhesive thus prepared is 18.6 wt% of phenolic resin solid content and 28.6 wt% of resorcinol resin solid content, and the total adhesive solid content is 47.2 wt%, boric acid The solid content was 9.1 wt%, the solid content of sodium borate was 11.4 wt%, the total solid content of boric acid and borate was 20.5 wt%, and the remainder was 32.3 wt% of distilled water. This flame-retardant adhesive not only gives a flame-retardant effect by hardening the adhesive layer to become a fire-resistant layer, but also imparts flame-retardant performance by spreading the flame-retardant component from the adhesive to adjacent constituent wood materials, that is, veneer or plate. The pH of the resorcinol-phenol cocondensation resin·boric acid borate mixture (RPB) flame retardant adhesive thus prepared was 7.62 and the viscosity was 48.3 cps. A flame retardant adhesive prepared in a weight ratio of 100: wheat flour 15: 30 parts by weight of curing agent was applied to a radiata pine veneer with a thickness of 2.4 mm at a coating amount of 200 g / ㎡ to prepare 5 plywood, and the plywood hot pressure condition was 10 kgf /cm 2 , 150° C., 20 minutes. On the surface of the prepared plywood, resorcinol·phenol co-condensation resin·boric acid·borate mixture (RPB) flame retardant adhesive was applied and coated in an amount of 300 g/㎡, dried at 25-30℃ for 24 hours, and then cured at 150℃ for 30 minutes made it

제조된 합판의 내화성은 KS F ISO 5660-1에서 제시하고 있는 콘칼로리미터 성능시험을 한 결과 도14((a):총열방출율(THR), (b):열방출율(HRR))와 같이 난연등급 기준을 만족시켰다. As a result of the cone calorimeter performance test presented in KS F ISO 5660-1, the fire resistance of the manufactured plywood is flame retardant as shown in Figure 14 ((a): total heat release rate (THR), (b): heat release rate (HRR)) The grading criterion was met.

제조된 합판의 일반적인 물성(난연합판/무처리합판)은 밀도 0.65±0.01/0.43±0.03 g/㎠, 함수율 4.7±0.15/4.8±0.20 % 로 난연제 주입에 따라 밀도가 높아졌으며, 비내수의 상태 인단 전단 접착력은 1.10±0.26/1.18±0.30 N/㎟ 로 나타났으며 t-검정 결과(t=0.34) 두 집단의 비내수 인장 전단 접착력은 통계적으로 유의한 차이를 보이지 않았다. The general physical properties of the manufactured plywood (flame retardant board/untreated plywood) are density 0.65±0.01/0.43±0.03 g/cm2, moisture content 4.7±0.15/4.8±0.20%, the density increased by injection of flame retardant, and non-waterproof state. The shear shear adhesion was 1.10±0.26/1.18±0.30 N/mm2, and the t-test result (t=0.34) showed no statistically significant difference in the non-waterproof tensile shear adhesion of the two groups.

내수 인단 전단 접착력은 0.99±0.09/0.98±0.09 N/㎟ 로 나타났으며 t-검정 결과 (t=0.07) 두 집단의 내수 인장 전단 접착력은 통계적으로 유의한 차이가 나타나지 않았다. 따라서 난연접착제에 의한 난연합판제조는 난연제에 의한 접착력 저하가 나타나지 않고 합판제조가 잘 제조되었을 뿐만 아니라 KS F ISO 5660-1에서 제시하고 있는 콘칼로리미터 난연등급 기준을 만족시키는 결과를 나타냈다. The water resistance shear adhesion was 0.99±0.09/0.98±0.09 N/㎟, and the t-test result (t=0.07) showed no statistically significant difference in the water resistance tensile shear adhesion between the two groups. Therefore, in the flame retardant plate production using the flame retardant adhesive, the adhesive strength was not deteriorated by the flame retardant, the plywood was well manufactured, and the cone calorimeter flame retardancy standard presented in KS F ISO 5660-1 was satisfied.

상기 실시예 1~7에 따라 제조된 난연 처리 목재 및 목질재료에 대하여 KS F ISO 5660-1에서 제시하고 있는 콘칼로리미터 성능시험 결과 도6 내지 도14에서 보는 바와 같이 모두 난연등급이상의 규격을 만족시켰다. 여기서 난연등급이란 콘칼로리미터로 측정할 때 50kW의 열에 대하여 5분간 측정하여 열방출율은 200kW/㎡이하이어야 하며 총열방출량은 8MJ/㎡을 만족하는 것이며 준불연등급은 50kW의 열에 대하여 10분간 측정하여 열방출율은 200kW/㎡이하이어야 하며 총열방출량은 8MJ/㎡을 만족하는 것이다. As shown in FIGS. 6 to 14, as a result of the cone calorimeter performance test presented in KS F ISO 5660-1 for the flame retardant treated wood and wood materials manufactured according to Examples 1 to 7, all of them satisfy the standards of flame retardancy grade or higher. made it Here, the flame retardant grade is measured with a cone calorimeter for 5 minutes at 50 kW of heat, the heat release rate must be less than 200 kW / ㎡, and the total heat emission satisfies 8 MJ / ㎡. The heat release rate must be less than 200 kW/m2 and the total heat release amount satisfies 8 MJ/m2.

도 4는 무처리 목재와 본 발명의 실시예에 따른 난연처리된 목재의 콘칼로리메타의 착화 시험 결과의 표면 모습들이다. 본 발명의 실시예에 따른 난연처리된 목재의 경우 높은 온도에 의하여 표면은 탄화층이 형성되어 있으나 뒷면은 깨끗한 것을 볼 수 있고, 무처리 판재 등에 비해 탄화층의 두께가 대폭 감소하는 것을 알 수 있다.Figure 4 is the surface appearance of the ignition test results of the cone calorimeter of untreated wood and flame retardant treated wood according to an embodiment of the present invention. In the case of flame retardant treated wood according to an embodiment of the present invention, a carbonized layer is formed on the surface due to high temperature, but the back side is clean, and it can be seen that the thickness of the carbonized layer is significantly reduced compared to untreated boards. .

본 발명에서는 전술한 바와 같이 난연성능을 배가하고 고농도의 붕산·붕산염 혼합물의 고형분을 안정적으로 사용하기 위해 이를 수용하는 담체로서 페놀수지를 사용하여 안정된 난연제를 생성하게 할 뿐만 아니라, 붕산·붕산염의 무기질 처리에 따른 접착력 약화현상이나 수분에 약한 성질을 개선시키는 역할을 하고, 이러한 붕산·붕산염의 혼합물과의 안정된 페놀수지 화합물의 친접착성 난연약제가 제조되어, 목재의 자연무늬와 표면을 그대로 깨끗이 유지하고, 물에 잘 용탈되지 않고 치수안전성이 있는 난연목재 및 난연목질재료가 제조되고 이산화탄소의 통조림인 목재를 건축물에 오랫동안 사용하여 지구 온난화방지와 탄소중립 방안으로서도 크게 기여하리라 기대된다.In the present invention, as described above, in order to double the flame retardant performance and stably use the solid content of the high-concentration boric acid-borate mixture, a phenolic resin is used as a carrier for accommodating it to produce a stable flame retardant, as well as inorganic substances of boric acid and borate. It plays a role in improving the weakening of adhesive power or the property of being weak to moisture due to treatment, and a stable phenolic resin compound with a mixture of boric acid and borate salts is manufactured to produce a flame retardant agent with an affinity for adhesion, keeping the natural pattern and surface of wood clean. It is expected that it will contribute greatly to preventing global warming and carbon neutrality by using wood, which is canned carbon dioxide, for a long time in buildings, and flame retardant wood and flame retardant wood materials that are not easily leached by water and have dimension stability are manufactured.

이상과 같이, 본 명세서와 도면에는 이 발명의 구체적인 실시예를 설명하기 위하여 특정 용어를 사용하여 개시하였으나 발명의 이해를 돕기 위한 일반적인 의미에서 사용한 것으로 이 발명의 범위를 한정하고자 하는 것은 아니며 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게는 자명한 것이다. As described above, although specific terms have been disclosed in this specification and drawings to describe specific embodiments of the present invention, they are used in a general sense to help understanding of the present invention and are not intended to limit the scope of the present invention. It is obvious to those skilled in the art.

Claims (23)

붕산(Boric acid), 붕산염(Sodium borate), 및 수용성 페놀수지(Phenolic resin)를 포함하고,
상기 페놀수지는 16-36 wt%, 붕산(Boric acid)은 8-18 wt%, 붕산염(Sodium borate) 10-22 wt%로, 붕산·붕산염 혼합물은 18-40wt%를 포함하는 것을 특징으로 하는 목재 및 목질재료용 난연제 조성물.Contains boric acid, sodium borate, and water-soluble phenolic resin,
The phenol resin is 16-36 wt%, boric acid is 8-18 wt%, borate is 10-22 wt%, and the boric acid borate mixture is 18-40 wt% Characterized in that it contains A flame retardant composition for wood and wood-based materials. 붕산(Boric acid), 붕산염(Sodium borate), 및 수용성 페놀수지(Phenolic resin)와 레조르시놀을 포함하고
상기 레조르시놀은 23∼33 wt%, 페놀수지 15∼21wt%로 레조르시놀·페놀수지 혼합물은 38∼54 wt%, 붕산(Boric acid)은 6.8∼10.9 wt%, 붕산염(Sodium borate)은 8.5∼13.7 wt%로서 붕산·붕산염 혼합물은 15.3∼24.6 wt%를 포함하는 것을 특징으로 하는 목재 및 목질재료용 난연제 조성물.It contains boric acid, sodium borate, and water-soluble phenolic resin and resorcinol.
The resorcinol is 23 to 33 wt%, the phenol resin is 15 to 21 wt%, the resorcinol-phenol resin mixture is 38 to 54 wt%, boric acid is 6.8 to 10.9 wt%, and borate is A flame retardant composition for wood and wood-based materials, characterized in that the boric acid-borate mixture contains 15.3 to 24.6 wt% as 8.5 to 13.7 wt%. 제1항 또는 제2항에 있어서,
상기 페놀수지는 수지반응기에 페놀, 포르마린, 물을 투입하고 수산화나트륨(NaOH)으로 pH를 10.7에서 11.0으로 조정하고 제조된 액상형 레졸(resol)형인 것을 특징으로 하는 목재 및 목질재료용 난연제 조성물.According to claim 1 or 2,
The phenolic resin is a flame retardant composition for wood and wood materials, characterized in that the liquid resol type prepared by adding phenol, formalin, and water to a resin reactor and adjusting the pH from 10.7 to 11.0 with sodium hydroxide (NaOH). 제3항에 있어서,
상기 페놀수지는 상기 수지반응기에서 상기 페놀과 상기 포르마린은 페놀:포르마린으로 몰비 1:1.63~2.4로 투입하고, 수산화나트륨(NaOH)으로 pH를 10.7에서 11.0으로 조정하고, 70℃∼80℃에서 반응시켜 제조된 액상형 레졸(resol)형인 것을 특징으로 하는 목재 및 목질재료용 난연제 조성물.According to claim 3,
The phenolic resin was added in the resin reactor at a molar ratio of 1:1.63 to 2.4 for the phenol and the formalin as phenol:formarin, the pH was adjusted from 10.7 to 11.0 with sodium hydroxide (NaOH), and the reaction was performed at 70° C. to 80° C. A flame retardant composition for wood and woody materials, characterized in that it is a liquid resol type prepared by 제2항에 있어서,
상기 레조르시놀은 페놀과의 공축합수지 제조가 가능한 액상형 레졸(resol)형인 것을 특징으로 하는 목재 및 목질재료용 난연제 조성물.According to claim 2,
The flame retardant composition for wood and wood-based materials, characterized in that the resorcinol is a liquid resol type capable of preparing a co-condensation resin with phenol. 삭제delete 삭제delete 제1항에 있어서,
상기 붕산 및 붕산염을 혼합하여 붕산·붕산염 혼합물을 만들고 상기 붕산·붕산염 혼합물은 붕산붕산염 용액으로 붕산 25.53wt%, 붕산염 31.91wt%를 물에 넣어 온도를 90℃∼100℃까지 높여 투명하게 물에 잘 녹는 붕산·붕산염 혼합물을 만들어 페놀수지에 혼합하여 반응하는 것을 특징으로 하는 목재 및 목질재료용 난연제 조성물.According to claim 1,
The boric acid and borate are mixed to make a boric acid-borate mixture, and the boric acid-borate mixture is a borate solution by adding 25.53 wt% of boric acid and 31.91 wt% of borate into water and raising the temperature to 90 ℃ to 100 ℃ so that the water is transparent. A flame retardant composition for wood and wood-based materials, characterized by making a soluble boric acid-borate mixture and reacting by mixing with a phenolic resin. S1) 목재 또는 목질재료를 준비하는 단계;
S2) 페놀수지· 붕산·붕산염 혼합물의 목재 난연제를 제조하는 단계;
S3) 상기 S2)단계에서 얻어지는 페놀수지· 붕산·붕산염 혼합물의 목재 난연제를 상기 목재 또는 목질재료에 주입하는 단계; 및
S4) 주입처리된 상기 목재 또는 목질재료를 건조,경화하는 단계;
를 포함하고,
상기 목재 난연제는 페놀수지 16∼36 wt%, 붕산(Boric acid) 8∼18 wt%, 붕산염(Sodium borate) 10∼22 wt%로, 붕산·붕산염 혼합물이 18∼40wt%를 포함하는 것을 특징으로 하는 난연목재 또는 난연목질재료의 제조방법.S1) preparing wood or wood material;
S2) preparing a wood flame retardant of a mixture of phenolic resin, boric acid and borate;
S3) injecting the wood flame retardant of the mixture of phenol resin, boric acid and borate obtained in step S2) into the wood or wood-based material; and
S4) drying and curing the injected wood or wood material;
including,
The wood flame retardant comprises 16 to 36 wt% of phenolic resin, 8 to 18 wt% of boric acid, 10 to 22 wt% of sodium borate, and 18 to 40 wt% of boric acid and borate mixture. Method for producing flame retardant wood or flame retardant wood material. S1) 목재 또는 목질재료를 준비하는 단계;
S2) 페놀수지· 붕산·붕산염 혼합물에 레조르시놀을 혼합하여 목재 난연제를 제조하는 단계;
S3) 상기 S2)단계에서 얻어지는 레조르시놀·페놀수지· 붕산·붕산염 혼합물의 목재 난연제를 상기 목재 또는 목질재료에 주입하는 단계; 및
S4) 주입처리된 상기 목재 또는 목질재료를 건조,경화하는 단계;
를 포함하고,
상기 목재 난연제는 레조르시놀 23∼33 wt%, 페놀수지 15∼21wt%로 레조르시놀·페놀수지 혼합물은 38∼54 wt%, 붕산(Boric acid)은 6.8∼10.9 wt%, 붕산염(Sodium borate)은 8.5∼13.7 wt%로서 붕산·붕산염 혼합물은 15.3∼24.6 wt%를 포함하는 것을 특징으로 하는 난연목재 또는 난연목질재료의 제조방법.S1) preparing wood or wood material;
S2) preparing a wood flame retardant by mixing resorcinol with a phenolic resin·boric acid·boric acid mixture;
S3) injecting a wood flame retardant of a mixture of resorcinol·phenolic resin·boric acid·boric acid obtained in step S2) into the wood or wood-based material; and
S4) drying and curing the injected wood or wood material;
including,
The wood flame retardant is 23 to 33 wt% of resorcinol, 15 to 21 wt% of phenolic resin, 38 to 54 wt% of resorcinol-phenolic resin mixture, 6.8 to 10.9 wt% of boric acid, and sodium borate ) is 8.5 to 13.7 wt%, and the boric acid-borate mixture contains 15.3 to 24.6 wt%. 제9항 또는 제10항에 있어서,
상기 S2) 단계는
S2-1) 붕산과 붕산염을 용매에 혼합하여 붕산·붕산염 혼합물을 제조하는 단계; 및
S2-2) 상기 붕산·붕산염 혼합물과 페놀수지를 혼합하여 반응하는 단계;를 포함하는 난연목재 또는 난연목질재료의 제조방법.The method of claim 9 or 10,
The step S2) is
S2-1) preparing a mixture of boric acid and borate by mixing boric acid and borate in a solvent; and
S2-2) mixing and reacting the boric acid/borate mixture with a phenolic resin; a method for producing a flame retardant wood or wood material including a flame retardant. 제9항 또는 제10항에 있어서,
S5) 상기 목재 또는 목질재료를 열압공정을 거쳐 최종목질재료를 제조하는 단계를 더 포함하는 것을 특징으로 하는 난연목재 또는 난연목질재료의 제조방법.The method of claim 9 or 10,
S5) The method of manufacturing a flame-retardant wood or wood-based material, characterized in that it further comprises the step of manufacturing a final wood-based material through a hot pressing process of the wood or wood-based material. 제9항 또는 제10항에 있어서,
상기 목재 또는 목질재료는 원목에서 얻은 단판, 판재, 파티클, 스트랜드 및 섬유와 이들로부터 만든 합판, 단판적층재(LVL), 집성재, 구조용 직교집성판(CLT), 파티클보드, 스트랜드보드, 섬유판인 것을 특징으로 하는 난연목재 또는 난연목질재료의 제조방법.The method of claim 9 or 10,
The wood or wood-based material is veneer, plate, particle, strand, and fiber obtained from hardwood, and plywood, veneer laminate (LVL), laminated material, structural orthogonal laminated board (CLT), particle board, strand board, and fiber board made therefrom. Method for producing flame retardant wood or flame retardant wood material, characterized in that. 제11항에 있어서,
상기 S2-2)단계 전에 페놀수지를 제조하는 단계를 포함하고, 상기 페놀수지를 제조하는 단계는 수지반응기에 페놀, 포르마린, 물을 투입하고 수산화나트륨(NaOH)으로 pH를 10.7에서 11.0로 조정하고 반응시켜 액상형 레졸(resol)형을 만드는 난연목재 또는 난연목질재료의 제조방법.According to claim 11,
A step of preparing a phenolic resin before the step S2-2), wherein the step of preparing the phenolic resin is to add phenol, formalin, and water to a resin reactor, adjust the pH from 10.7 to 11.0 with sodium hydroxide (NaOH), A method for producing a flame retardant wood or flame retardant wood material by reacting to form a liquid resol. 제11항에 있어서,
상기 S2-1) 단계에서 붕산, 붕산염을 물에 넣어 온도를 90℃∼100℃까지 높이고, 투명하게 될 때까지 물에 잘 녹는 붕산·붕산염 혼합물들을 만든 후에, S2-2) 단계에서 상기 제조된 페놀수지에 페놀수지 16∼36 wt%, 붕산(Boric acid) 8∼18 wt%, 붕산염(Sodium borate) 10∼22 wt%로, 붕산·붕산염 혼합물이 18∼40wt%의 비율로 되도록 혼합하여 반응시켜 만든 난연목재 또는 난연목질재료의 제조방법.According to claim 11,
In step S2-1), boric acid and borate are added to water to raise the temperature to 90 ° C. to 100 ° C., and after making boric acid and borate mixtures that are well soluble in water until they become transparent, in step S2-2), the prepared 16-36 wt% of phenolic resin, 8-18 wt% of boric acid, 10-22 wt% of sodium borate, and 18-40 wt% of boric acid/borate mixture are mixed and reacted with phenolic resin Method for manufacturing flame retardant wood or flame retardant wood material made by 삭제delete 제9항 또는 제10항에 있어서,
상기 S3) 단계에서 주입방법은 상압에서 확산침투하는 것을 특징으로 하는 난연목재 또는 난연목질재료의 제조방법.The method of claim 9 or 10,
The method of manufacturing flame retardant wood or flame retardant wood material, characterized in that the injection method in step S3) is diffusion and penetration at normal pressure. 제9항 또는 제10항에 있어서,
상기 S3) 단계에서 주입방법은 가압감압방법으로 이루어지고, 주가압은 10∼25kg/㎠ 로 30∼120분 까지 처리하는 것을 특징으로 하는 난연목재 또는 난연목질재료의 제조방법.The method of claim 9 or 10,
In the step S3), the injection method is a pressure reduction method, and the main pressure is 10 to 25 kg / cm 2 and processed for 30 to 120 minutes. 제18항에 있어서,
상기 S3) 단계에서 주가압 전후로 전배기 30분, 후배기 10∼30분을 하는 것을 특징으로 하는 난연목재 또는 난연목질재료의 제조방법.According to claim 18,
Method for producing flame retardant wood or flame retardant wood material, characterized in that in step S3), 30 minutes before and after main pressure, and 10 to 30 minutes after exhaust. 제9항 또는 제10항에 있어서,
상기 S4) 단계에서는 주입처리된 상기 목재 또는 목질재료를 상온에서 안정화시키고, 50~70℃에서 일정기간 동안 건조단계를 거친 후, 100-150℃에서 수지를 경화시키는 경화단계를 포함하는 난연목재 또는 난연목질재료의 제조방법.The method of claim 9 or 10,
In the step S4), the injected wood or wood material is stabilized at room temperature, subjected to a drying step at 50 to 70 ° C for a certain period of time, and then cured at 100 to 150 ° C. Manufacturing method of flame retardant wood material. 제12항에 있어서,
상기 S5) 단계에서는 단판(veneer)은 합판 또는 단판적층재(LVL)로, 판재는 집성재 또는 구조용 직교집성판(CLT)으로, 파티클은 파티클보드로, 스트랜드는 스트랜드보드로, 섬유는 섬유판으로 제조하는 것을 특징으로 하는 난연목재 또는 난연목질재료 제조방법.According to claim 12,
In the step S5), the veneer is plywood or veneer laminate (LVL), the plate material is laminated material or structural orthogonal laminated board (CLT), the particle is particle board, the strand is a strand board, and the fiber is a fiber board Method for producing flame retardant wood or flame retardant wood material, characterized in that for manufacturing. 제9항 또는 제10항에 따라 제조되는 난연목재.Flame retardant wood produced according to claim 9 or 10. 제9항 또는 제10항에 따라 제조되는 난연목질재료.A flame-retardant wood-based material prepared according to claim 9 or 10.
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