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WO2018141034A1 - Formaldehyde scavenger composition for wood laminate, process for manufacturing wood laminate with reduced formaldehyde emission and improved mechanical properties, and wood laminate - Google Patents

Formaldehyde scavenger composition for wood laminate, process for manufacturing wood laminate with reduced formaldehyde emission and improved mechanical properties, and wood laminate Download PDF

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Publication number
WO2018141034A1
WO2018141034A1 PCT/BR2017/050020 BR2017050020W WO2018141034A1 WO 2018141034 A1 WO2018141034 A1 WO 2018141034A1 BR 2017050020 W BR2017050020 W BR 2017050020W WO 2018141034 A1 WO2018141034 A1 WO 2018141034A1
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Prior art keywords
formaldehyde
parts
composition
laminate
alkanolamine
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PCT/BR2017/050020
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French (fr)
Portuguese (pt)
Inventor
Bruno Cesar Ortiz UGARTE
Giulio Pieter FORMENTI
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Isogama Industria Quimica Ltda
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Isogama Industria Quimica Ltda
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Priority to PCT/BR2017/050020 priority Critical patent/WO2018141034A1/en
Priority to BR112019016067-1A priority patent/BR112019016067A2/en
Publication of WO2018141034A1 publication Critical patent/WO2018141034A1/en
Anticipated expiration legal-status Critical
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/42Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/05Alcohols; Metal alcoholates
    • C08K5/053Polyhydroxylic alcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/17Amines; Quaternary ammonium compounds

Definitions

  • the present invention pertains to the field of formaldehyde sequestering compositions in wood laminate products, more specifically, to a process of manufacturing wood laminate product with reduced formaldehyde emission and improved mechanical properties by use of an ethanolamine composition. solubilized in a glycol.
  • Panels of lignocellulosic materials such as wood are used in a wide variety of applications, mainly for commercial and residential building materials. All parts of trees, which are the main raw material in all end products of this industry, have some use and value in the process. After a tree cut is made, it can be converted into a very different set of shapes by chipping and / or cutting it into different sizes / consistencies, or combining it with some form of resin, before pressing / molding.
  • the end result of the process is a wood composite developed for specific applications such as low density fiberboard, medium density fiberboard, high density fiberboard, chipboard, plywood, OSBs, OWBs, MDFs, MDPs, HDFs, structural plywood, planks, columns, and T-beams.
  • Formaldehyde is a highly reactive molecule that, when in contact, may be irritating to tissues. Studies in humans and animals indicate that formaldehyde, when inhaled at a certain level, may be irritating to the respiratory tract and eyes, as well as to the skin and gastrointestinal system by direct (contact) and oral route.
  • Wood composite materials are treated in the postpress step with formaldehyde sequestrants such as amino compounds.
  • US 4501628 deals with a method for reducing formaldehyde emission from wood-based composite panels bonded with aminoplast resins.
  • a saline mixture comprising urea or one of its analogues, an easily ammonia-releasing compound and alternatively a catalyst is prepared in fine granular form.
  • the mixture is then added and combined to the dried wood particles prior to the addition of the binder resin.
  • the mixture comprises 12-20 parts of the ammonia generating compound, 65-88 parts of urea or an analog thereof, and 0-15% of the catalyst. From 6 to 22.5% by weight of this mixture is used in relation to the total resin solids.
  • Formaldehyde evolution is alleged to be reduced by 45-80% compared to an untreated control panel, having an adverse effect on physical properties or press time.
  • US Published patent application US20090181260A1 deals with an alkanolamine-modified phenolic resin formulation, the formulation being formed by reaction of a basic catalyst, formaldehyde, water and a benzene-oi to form an intermediate composition to which an alkanolamine is added to reduce the presence of formaldehyde,
  • US 4376807 describes a treatment for wood panels where the wood fibers are bonded with formaldehyde-based resins, the treatment comprising coating at least one side of the panel with a saline solution containing an ammonium cation. as a 10-15% aqueous solution of ammonium bicarbonate. Decomposition of the ammonium salt reacts with free formateide to produce a stable, low volatile reaction product.
  • the treatment can be applied to panels before and after finishing and formaldehyde reduction occurs on both the top surface of the panels and the transverse surface.
  • US Published Patent Application US201 10171482A1 deals with a formaldehyde sequester for wood laminates.
  • the sequestrant contains urea, monobasic ammonium phosphate and dibasic ammonium phosphate.
  • the weight ratio of urea to monobasic ammonium phosphate and dibasic ammonium phosphate is in the range from 5 to 45 / 0.5 to 15/1 to 20.
  • the application range of the sequester is in the range from 1 to 50 g / m 2 on dry basis.
  • the present invention is directed to an alkanolamine-based formalin-sequestering composition in glycolic solvent for use in wood laminates. agglutinated with formaldehyde-containing resins, after the laminate pressing step, said composition comprising between 10 and 99 parts alkanolamine and between 90 and 1 part glycolic solvent per hundred parts composition, including 50 parts alkanolamine and 50 parts solvent between 80 parts alkanolamine and 20 parts glycolic solvent.
  • an object of the invention is an alkanolamine and glycolic solvent composition as a formaldehyde sequester in wood laminates where the wood is agglutinated with urea formaldehyde, melamine formaldehyde or phenol formaldehyde resins.
  • Another object of the invention is a process of manufacturing laminated wood product with reduced formaldehyde emission and improved mechanical properties with the aid of said formaldehyde sequestering composition.
  • Yet another object of the invention is a reduced formaldehyde emission laminate product and improved mechanical properties over prior art products not treated with the composition of the invention.
  • the invention is a formaldehyde sequestering composition for wood laminates comprising an alkanolamine in a non-aqueous hydroxylated solvent such as a glycol.
  • a formaldehyde sequestering composition for wood laminates comprising an alkanolamine in a non-aqueous hydroxylated solvent such as a glycol.
  • wood laminates as plywood, agglomerates, OSBs, OWBs, MDFs, MDPs, HDFs, structural plywood, boards, columns and T-beams and all wood laminates where lignocellulosic material is bonded by formaldehyde-containing resins. , such as phenol-formaldehyde resins and aminoplast resins such as urea-formaldehyde and melamine-formaldehyde resins.
  • the invention also relates to a process of manufacturing laminate wood with reduced formaldehyde emission and improved properties of both swelling and water absorption, as well as tensile properties, over control without application of the composition of the invention.
  • the composition of the invention for formaldehyde sequestration consists of an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine.
  • alkanolamine such as monoethanolamine, diethanolamine or triethanolamine.
  • monoethanolamine is the preferred compound and is not limited thereto.
  • Alkanolamine as monoethanolamine is present in the composition from 10 to 99 parts alkanolamine and 90 to 1 part glycolic solvent, per 100 parts composition, including 50 parts alkanolamine and 50 parts glycolic solvent, and 90 parts. parts alkanolamine and 10 parts glycolic solvent.
  • the anhydrous glycolic solvent useful for the purposes of the invention may be any diol or a triol, but for economic reasons 1,2,3-propanotriol or glycerin has been used in the composition of the invention. Glycerin, being a byproduct of the biodiesel industry, is extremely abundant in the country and therefore of low cost.
  • a non-aqueous solvent such as the glycol of the composition of the invention avoids hydrolysis (reverse cure reaction) of the resin, hydrolysis being an important factor in reducing the physicochemical and mechanical properties of the laminate or panel.
  • compositions are mixed at room temperature under mechanical agitation, forming a homogeneous mixture rapidly due to their chemical affinity.
  • the composition is applied to ready-made panels after curing the resins, immediately at the press exit or shortly after the laminating or panel cooling equipment.
  • the sequestering composition achieves maximum efficiency, as sequestrants applied in the adhesive mixture ("glue tapping", as the jargon of the area) with the wood or applied just before the entry of the laminates or panels in the press act consuming important part of the formaldehyde contained in the resins, reducing their efficiency in the conformation of the panels. This results in panels of lower or higher physical-chemical-mechanical resistance. expensive (due to the need to apply more resin to compensate for the negative effect of the sequester).
  • the proportion of sequestering composition applied to the laminates is between 5 and 70 g / m 2 , including between 30 and 60 g / m 2 and 40 and 50 g / m 2
  • post-press application that is, when formaldehyde has already reacted by cross-linking the prepolymer molecular chains (urea-formaldehyde resin) as advocated in the invention, causes The sequestering composition reacts only with formaldehyde that is free or easily released in ready-made laminates, thereby reducing formaldehyde emission.
  • the laminate is sanded, as is customary for panels of thickness greater than 6 mm.
  • fixing a part of the sequestering composition is removed, exposing surface of high physical-chemical-mechanical resistance.
  • the process of manufacturing wood laminates with reduced formaldehyde emission and improved mechanical physicochemical properties comprises the steps of:
  • composition based on an ethanoamine solubilised in a glycolic solvent, in the ratio of 10 to 99 parts alkanolamine and between 90 and 1 part glycolic solvent per 100 parts of composition, including 50 parts parts of alkanolamine and 50 parts of glycolic solvent, and between 80 parts of alkanolamine and 20 parts of glycolic solvent;
  • step b) Curing the laminate of step b) to obtain a cured laminate
  • step (d) For the cured laminate of step (c), apply the composition of step (a) to the ratio in grams per square meter of surface area between 5 and 70 g / m 2 , including between 30 and 60 g / m 2 and 40 and 50 g / m 2 ;
  • step d) After at least 40 minutes of applying the composition, step d) sanding the laminate;
  • Tests on 350 x 150 x 15 mm MDP (agglomerate) laminates made with urea-formaldehyde resin were treated with the sequestering composition of the invention, which comprised a mixture of 85 parts monoethaneamine and 15 parts glycerin per 100 parts of composition.
  • the composition was applied by roller to the surface weight (dosage) of 45 g / m 2 . After 16 hours the laminates were sanded by removing 0.15 mm from each side. A panel without application was also sanded and analyzed as a control.
  • Formaldehyde emission test results adapted from JIS A 5905 in mg / L, Swelling after immersion in water according to ABNT NBR 14810-2 in%, Water absorption after immersion according to ABNT NBR 14810-2 in% and Internal traction according to ABNT NBR 14810-2 in Kgf / cm 2 are listed in Table 1 below.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

Described is a formaldehyde scavenger composition for wood laminate, containing between 10 and 99 parts of an alkanolamine and between 90 and 1 part of a glycol per hundred parts of composition, the composition being applied after the laminate pressing step in an amount, in grams per square meter of surface area, of between 5 and 70 g/m2. As a result of the process of applying the claimed composition, the laminate produced exhibits reduced formaldehyde emission and improved water absorption and mechanical properties compared to a control laminate. A process for manufacturing a laminate and a wood laminate are also described.

Description

COMPOSIÇÃO SEQUESTRANTE DE FORMALDEÍDO PARA LAMINADO DE MADEIRA, PROCESSO DE MANUFATURA DE LAMINADO DE MADEIRA COM EMISSÃO DE FORMALDEÍDO REDUZIDA E PROPRIEDADES MECÂNICAS MELHORADAS E SEQUESTRANT COMPOSITION OF WOOD LAMINATE FORMALDEHYDE, WOOD LAMINATE MANUFACTURING PROCESS WITH REDUCED FORMALDEHYDE EMISSION AND MECHANICAL PROPERTIES AND

LAMINADO DE MADEIRA WOOD LAMINATE

CAMPO DA INVENÇÃO FIELD OF INVENTION

[001 ] A presente invenção pertence ao campo das composições sequestrantes de formaldeído em produtos laminados de madeira, mais especificamente, a um processo de manufatura de produto laminado de madeira com emissão reduzida de formaldeído e propriedades mecânicas melhoradas pelo uso de uma composição de uma etanolamina solubilizada em um glicol.  [001] The present invention pertains to the field of formaldehyde sequestering compositions in wood laminate products, more specifically, to a process of manufacturing wood laminate product with reduced formaldehyde emission and improved mechanical properties by use of an ethanolamine composition. solubilized in a glycol.

FUNDAMENTOS DA INVENÇÃO BACKGROUND OF THE INVENTION

[002] Painéis de materiais lignocelulósicos como madeira são usados em uma grande variedade de aplicações, principalmente para materiais de construção comercial e residencial. Todas as partes das árvores, que é a principal matéria-prima em todos os produtos finais dessa indústria, têm algum uso e valor no processo. Depois que um corte de árvore é realizado, esta pode ser convertida em um conjunto bastante diferenciado de formas, lascando-a e/ou cortando-a em diferentes tamanhos/consistências, ou combinando-a com alguma forma de resina, antes da prensagem/moldagem. O resultado final do processo é um compósito de madeira desenvolvido para aplicações específicas, como painéis de fibra de baixa densidade, painéis de fibra de média densidade, painéis de fibra de alta densidade, painéis aglomerados, compensados, OSBs, OWBs, MDFs, MDPs, HDFs, compensados estruturais, tábuas, colunas e vigas em T.  [002] Panels of lignocellulosic materials such as wood are used in a wide variety of applications, mainly for commercial and residential building materials. All parts of trees, which are the main raw material in all end products of this industry, have some use and value in the process. After a tree cut is made, it can be converted into a very different set of shapes by chipping and / or cutting it into different sizes / consistencies, or combining it with some form of resin, before pressing / molding. The end result of the process is a wood composite developed for specific applications such as low density fiberboard, medium density fiberboard, high density fiberboard, chipboard, plywood, OSBs, OWBs, MDFs, MDPs, HDFs, structural plywood, planks, columns, and T-beams.

[003] Em se tratando da indústria da prensagem de painéis e a fabricação de materiais baseados em fibra de madeira, um dos maiores desafios é proporcionar baixos níveis de emissão de formol (formaldeído). [003] When it comes to the panel pressing industry and the manufacture of wood fiber based materials, one of the largest The challenge is to provide low levels of formaldehyde emission.

[004] Controles cada vez mais rígidos sobre as emissões de formaldeídos causam um impacto cada vez maior na indústria de compósitos de fibra de madeira/prensagem de painel.  Increasingly tight controls on formaldehyde emissions are having an increasing impact on the wood fiber composite / panel pressing industry.

[005] O formol é uma molécula altamente reativa que, quando em contato, pode ser irritante para os tecidos. Estudos em humanos e animais indicam que o formaldeído, quando inalado a determinado nível pode ser irritante para o aparelho respiratório e olhos, bem como para a pele e sistema gastrointestinal, por via direta (contato) e oral.  [005] Formaldehyde is a highly reactive molecule that, when in contact, may be irritating to tissues. Studies in humans and animals indicate that formaldehyde, when inhaled at a certain level, may be irritating to the respiratory tract and eyes, as well as to the skin and gastrointestinal system by direct (contact) and oral route.

[006] Estudos realizados em voluntários expostos ao formaldeído via respiratória durante curtos períodos de tempo, indicaram a ocorrência de irritação nos olhos, nariz e garganta a uma concentração entre 0.4-3 ppm. Estudos efetuados em macacos e ratos expostos a concentrações mais elevadas de formaldeído, na ordem dos 3-9 ppm, demonstraram que o formaldeído tem a capacidade de originar hiperplasia no epitélio do aparelho respiratório superior. Foi também averiguado o seu efeito em animais expostos durante toda a sua vida, quer por via respiratória, quer quando adicionado na água e verificou-se que este provocava danos em tecidos das vias de entrada (aparelho respiratório superior e gastrointestinal, por exemplo). O Departamento de Saúde e Serviços Humanos (DHHS) determinou que o formaldeído pode ser considerado um razoável carcinogênico humano (NTP). A Agência Internacional para Pesquisa sobre Câncer (IARC) determinou que o formaldeído é cancerígeno para os seres humanos.  Studies in volunteers exposed to formaldehyde via the air for short periods of time indicated irritation of the eyes, nose and throat at a concentration of 0.4-3 ppm. Studies in monkeys and rats exposed to higher formaldehyde concentrations, in the order of 3-9 ppm, have shown that formaldehyde has the ability to cause hyperplasia in the upper respiratory tract epithelium. Its effect on exposed animals throughout their lives, either breathing or when added to water has also been investigated and found to cause damage to the tissues of the airways (eg upper and gastrointestinal respiratory tract). The Department of Health and Human Services (DHHS) has determined that formaldehyde can be considered a reasonable human carcinogen (NTP). The International Agency for Research on Cancer (IARC) has determined that formaldehyde is carcinogenic to humans.

[007] A Agência de Proteção Ambiental (EPA) determinou que o formaldeído é um provável carcinogênico humano com base em evidências limitadas em seres humanos e evidência suficiente em animais de laboratório. [008] A literatura de patentes é abundante em documentos que propõem soluções de composições sequestrantes de formaldeído em painéis de madeira onde as fibras de madeira são coladas com resinas do tipo fenol formaldeído e resinas aminoplasto à base de uréia - formaldeído ou melamina-formaldeído. [007] The Environmental Protection Agency (EPA) has determined that formaldehyde is a likely human carcinogen based on limited evidence in humans and sufficient evidence in laboratory animals. Patent literature abounds in documents proposing solutions for formaldehyde sequestering compositions in wood panels where wood fibers are glued with phenol formaldehyde resins and urea-based formaldehyde or melamine formaldehyde resins.

[009] Em geral a técnica utiliza as seguintes abordagens para a redução dos níveis de formaldeído de painéis compósitos de madeira:  [009] In general the technique uses the following approaches for reducing the formaldehyde levels of wood composite panels:

• a resina ligante, fenol-formaldeído ou aminoplasto, é preparada com teor reduzido de formaldeído;  • the binder resin, phenol formaldehyde or aminoplast, is prepared with reduced formaldehyde content;

• sequestrantes de formaldeído são adicionados à resina ligante; ou  • formaldehyde sequestrants are added to the binder resin; or

• os materiais compósitos de madeira são tratados na etapa pós-prensa com sequestrantes de formaldeído, como os compostos aminados.  • Wood composite materials are treated in the postpress step with formaldehyde sequestrants such as amino compounds.

[0010] Assim, a patente US 4501628 trata de um método para reduzir emissão de formaldeído de painéis compósitos à base de madeira ligados com resinas aminoplasto. Uma mistura salina compreendendo uréia ou um de seus análogos, um composto que libera facilmente amónia e alternativamente um catalisador é preparada em forma granulada fina. A mistura é então adicionada e combinada às partículas de madeira seca antes da adição da resina ligante. A mistura compreende de 12-20 partes do composto gerador de amónia, 65-88 partes de uréia ou um análogo da mesma, e 0-15% do catalisador. De 6 a 22,5% em peso desta mistura é usada em relação aos sólidos totais da resina. É alegado que a evolução de formaldeído é reduzida entre 45- 80% em relação a um painel controle não tratado, em efeito adverso sobre as propriedades físicas ou tempo de prensa.  Thus, US 4501628 deals with a method for reducing formaldehyde emission from wood-based composite panels bonded with aminoplast resins. A saline mixture comprising urea or one of its analogues, an easily ammonia-releasing compound and alternatively a catalyst is prepared in fine granular form. The mixture is then added and combined to the dried wood particles prior to the addition of the binder resin. The mixture comprises 12-20 parts of the ammonia generating compound, 65-88 parts of urea or an analog thereof, and 0-15% of the catalyst. From 6 to 22.5% by weight of this mixture is used in relation to the total resin solids. Formaldehyde evolution is alleged to be reduced by 45-80% compared to an untreated control panel, having an adverse effect on physical properties or press time.

[001 1 ] O pedido de patente publicado norte-americano US20090181260A1 trata de uma formulação de resina fenóiica modificada com uma alcanolamina, a formulação sendo formada pela reação de um catalisador básico, formaideído, água e um benzeno-oi para formar uma composição intermediária à qual uma alcanolamína é adicionada para reduzir a presença de formaideído, US Published patent application US20090181260A1 deals with an alkanolamine-modified phenolic resin formulation, the formulation being formed by reaction of a basic catalyst, formaldehyde, water and a benzene-oi to form an intermediate composition to which an alkanolamine is added to reduce the presence of formaldehyde,

[0012] A patente norte-americana US 4376807 descreve um tratamento para painéis de madeira onde as fibras da madeira são aglutinadas com resinas à base de formaideído, o tratamento compreendendo revestir pelo menos um lado do painel com uma solução salina contendo um cátion de amónio, como uma solução aquosa de 10- 15% de bicarbonato de amónio. A decomposição do sal de amónio reage com o formaideído livre para produzir um produto de reação estável e de baixa volatilidade. O tratamento pode ser aplicado a painéis antes e depois do acabamento e a redução de formaideído ocorre tanto na superfície de topo dos painéis quanto na superfície transversal.  US 4376807 describes a treatment for wood panels where the wood fibers are bonded with formaldehyde-based resins, the treatment comprising coating at least one side of the panel with a saline solution containing an ammonium cation. as a 10-15% aqueous solution of ammonium bicarbonate. Decomposition of the ammonium salt reacts with free formateide to produce a stable, low volatile reaction product. The treatment can be applied to panels before and after finishing and formaldehyde reduction occurs on both the top surface of the panels and the transverse surface.

[0013] O pedido de patente publicado norte-americano US201 10171482A1 trata de um sequestrante de formaideído para laminados de madeira. O sequestrante contém uréia, fosfato de amónio monobásico e fosfato de amónio dibásico. A razão em peso de uréia para fosfato de amónio monobásico e para fosfato de amónio dibásico está na faixa desde 5 a 45/0,5 até 15/1 para 20. A faixa de aplicação do sequestrante está na faixa desde 1 a 50 g/m2 em base seca. US Published Patent Application US201 10171482A1 deals with a formaldehyde sequester for wood laminates. The sequestrant contains urea, monobasic ammonium phosphate and dibasic ammonium phosphate. The weight ratio of urea to monobasic ammonium phosphate and dibasic ammonium phosphate is in the range from 5 to 45 / 0.5 to 15/1 to 20. The application range of the sequester is in the range from 1 to 50 g / m 2 on dry basis.

[0014] Apesar das abordagens propostas, seria útil se a técnica dispusesse de tratamentos alternativos para a redução de formaideído em laminados enquanto as propriedades de absorção de água e propriedades mecânicas são melhoradas em relação a produtos similares não tratados, como uma composição de amina hidroxilada em solvente glicólico para tratamento pós-prensa desses laminados.  Despite the proposed approaches, it would be useful if the technique had alternative treatments for the reduction of formaldehyde in laminates while water absorption properties and mechanical properties are improved over similar untreated products such as a hydroxylated amine composition. in glycolic solvent for postpress treatment of these laminates.

SUMÁRIO DA INVENÇÃO SUMMARY OF THE INVENTION

[0015] De modo amplo, a presente invenção trata de uma composição sequestrante de formaideído à base de uma alcanolamína em solvente glicólico para ser utilizada em laminados de madeira aglutinados com resinas contendo formaldeído, após a etapa de prensagem do laminado, a dita composição compreendendo entre 10 e 99 partes de alcanolamina e entre 90 e 1 parte de solvente glicólico por cem partes de composição, incluindo 50 partes de alcanolamina e 50 partes de solvente glicólico, e entre 80 partes de alcanolamina e 20 partes de solvente glicólico. Broadly, the present invention is directed to an alkanolamine-based formalin-sequestering composition in glycolic solvent for use in wood laminates. agglutinated with formaldehyde-containing resins, after the laminate pressing step, said composition comprising between 10 and 99 parts alkanolamine and between 90 and 1 part glycolic solvent per hundred parts composition, including 50 parts alkanolamine and 50 parts solvent between 80 parts alkanolamine and 20 parts glycolic solvent.

[0016] Assim um objetivo da invenção é uma composição de alcanolamina e solvente glicólico como sequestrante de formaldeído em laminados de madeira onde a madeira é aglutinada com resinas uréia formaldeído, melamina-formaldeído ou fenol-formaldeído.  Thus an object of the invention is an alkanolamine and glycolic solvent composition as a formaldehyde sequester in wood laminates where the wood is agglutinated with urea formaldehyde, melamine formaldehyde or phenol formaldehyde resins.

[0017] Outro objetivo da invenção é um processo de manufatura de produto laminado de madeira com emissão reduzida de formaldeído e propriedades mecânicas melhoradas com auxílio da dita composição sequestrante de formaldeído.  [0017] Another object of the invention is a process of manufacturing laminated wood product with reduced formaldehyde emission and improved mechanical properties with the aid of said formaldehyde sequestering composition.

[0018] Ainda outro objetivo da invenção é um produto laminado com emissão reduzida de formaldeído e propriedades mecânicas melhoradas em relação a produtos do estado da técnica não tratados com a composição da invenção.  Yet another object of the invention is a reduced formaldehyde emission laminate product and improved mechanical properties over prior art products not treated with the composition of the invention.

DESCRIÇÃO DETALHADA DA INVENÇÃO DETAILED DESCRIPTION OF THE INVENTION

[0019] A invenção trata de uma composição sequestrante de formaldeído para laminados de madeira, compreendendo uma alcanolamina em um solvente hidroxilado não aquoso, como um glicol. Úteis para a invenção são os laminados de madeira como compensados, aglomerados, OSBs, OWBs, MDFs, MDPs, HDFs, compensados estruturais, tábuas, colunas e vigas em T e todos os laminados de madeira onde o material lignocelulósico é aglutinado por resinas contendo formaldeído, como resinas fenol-formaldéido e resinas aminoplasto como resinas uréia-formol e melamina-formol.  The invention is a formaldehyde sequestering composition for wood laminates comprising an alkanolamine in a non-aqueous hydroxylated solvent such as a glycol. Useful for the invention are wood laminates as plywood, agglomerates, OSBs, OWBs, MDFs, MDPs, HDFs, structural plywood, boards, columns and T-beams and all wood laminates where lignocellulosic material is bonded by formaldehyde-containing resins. , such as phenol-formaldehyde resins and aminoplast resins such as urea-formaldehyde and melamine-formaldehyde resins.

[0020] A invenção trata também de um processo de manufatura de laminado de madeira com emissão reduzida de formaldeído e propriedades melhoradas tanto de inchamento e absorção de água, como propriedades de tração, em relação a um controle sem aplicação da composição da invenção. [0020] The invention also relates to a process of manufacturing laminate wood with reduced formaldehyde emission and improved properties of both swelling and water absorption, as well as tensile properties, over control without application of the composition of the invention.

[0021 ] Conforme a invenção, a composição da invenção para sequestro de formaldeído consiste de uma alcanolamina como monoetanolamina, dietanolamina ou trietanolamina. Por questões económicas a monoetanolamina é o composto preferido, não estando limitado a este.  According to the invention, the composition of the invention for formaldehyde sequestration consists of an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine. For economic reasons monoethanolamine is the preferred compound and is not limited thereto.

[0022] A alcanolamina como monoetanolamina está presente na composição desde entre 10 e 99 partes de alcanolamina e entre 90 e 1 parte de solvente glicólico, por cem partes de composição, incluindo 50 partes de alcanolamina e 50 partes de solvente glicólico, e entre 90 partes de alcanolamina e 10 partes de solvente glicólico.  Alkanolamine as monoethanolamine is present in the composition from 10 to 99 parts alkanolamine and 90 to 1 part glycolic solvent, per 100 parts composition, including 50 parts alkanolamine and 50 parts glycolic solvent, and 90 parts. parts alkanolamine and 10 parts glycolic solvent.

[0023] O solvente glicólico, anidro, útil para as finalidades da invenção pode ser qualquer, um diol ou um triol, mas por razões económicas foi utilizado na composição da invenção o 1 ,2,3-propanotriol ou glicerina. A glicerina por ser um subproduto da indústria do biodiesel é extremamente abundante no país e, portanto, de baixo custo.  The anhydrous glycolic solvent useful for the purposes of the invention may be any diol or a triol, but for economic reasons 1,2,3-propanotriol or glycerin has been used in the composition of the invention. Glycerin, being a byproduct of the biodiesel industry, is extremely abundant in the country and therefore of low cost.

[0024] Vantajosamente, o uso de um solvente não aquoso como o glicol da composição da invenção evita hidrólise (reação reversa da cura) da resina, a hidrólise sendo fator importante de redução das propriedades físico-químico-mecânicas do laminado ou painel.  Advantageously, the use of a non-aqueous solvent such as the glycol of the composition of the invention avoids hydrolysis (reverse cure reaction) of the resin, hydrolysis being an important factor in reducing the physicochemical and mechanical properties of the laminate or panel.

[0025] Os componentes da composição são misturados à Temperatura ambiente, sob agitação mecânica, formando uma mistura homogénea rapidamente devido a sua afinidade química.  [0025] The components of the composition are mixed at room temperature under mechanical agitation, forming a homogeneous mixture rapidly due to their chemical affinity.

[0026] A composição é aplicada em painéis prontos, após a cura das resinas, imediatamente na saída da prensa ou logo após o equipamento resfriador dos laminados ou painéis. Dessa forma a composição sequestrante alcança máxima eficiência, pois sequestrantes aplicados na mistura de adesivo ("batida de cola", conforme o jargão da área) com a madeira ou aplicados logo antes da entrada dos laminados ou painéis na prensa atuam consumindo parte importante do formaldeído contido nas resinas, reduzindo a eficiência das mesmas na conformação dos painéis, Istoresulta em painéis de resistência físico-química- mecânica inferior ou mais caros (peia necessidade de aplicar maior quantidade de resina para compensar o efeito negativo do sequestrante). [0026] The composition is applied to ready-made panels after curing the resins, immediately at the press exit or shortly after the laminating or panel cooling equipment. Thus the sequestering composition achieves maximum efficiency, as sequestrants applied in the adhesive mixture ("glue tapping", as the jargon of the area) with the wood or applied just before the entry of the laminates or panels in the press act consuming important part of the formaldehyde contained in the resins, reducing their efficiency in the conformation of the panels. This results in panels of lower or higher physical-chemical-mechanical resistance. expensive (due to the need to apply more resin to compensate for the negative effect of the sequester).

[0027] Conforme a invenção, a proporção de composição sequestrante aplicada nos laminados, em gramas por metro quadrado de laminado, está entre 5 e 70 g/m2, incluindo entre 30 e 60 g/m2 e 40 e 50 g/m2. According to the invention, the proportion of sequestering composition applied to the laminates, in grams per square meter of laminate, is between 5 and 70 g / m 2 , including between 30 and 60 g / m 2 and 40 and 50 g / m 2

[0028] Vantajosamente, a aplicação pós prensa (após a cura das resinas), ou seja, quando o formol já reagiu fazendo o entrecruzamento das cadeias moleculares do pré-poiímero (resina uréia-formol) conforme preconizado na invenção, faz com que a composição de sequestrante reaja apenas com o formol que está livre ou facilmente liberável nos laminados prontos, reduzindo dessa forma a emissão de formaldeído.  Advantageously, post-press application (after resin cure), that is, when formaldehyde has already reacted by cross-linking the prepolymer molecular chains (urea-formaldehyde resin) as advocated in the invention, causes The sequestering composition reacts only with formaldehyde that is free or easily released in ready-made laminates, thereby reducing formaldehyde emission.

[0029] Conforme o processo de manufatura de laminados de madeira com emissão de formaldeído reduzida e propriedades mecânicas melhoradas, após pelos menos 40 min da aplicação o laminado é lixado, como é de praxe em painéis de espessura maior que 6 mm. No iixamento parte da composição sequestrante é removida, expondo superfície de alta resistência físico-química-mecânica.  Depending on the process of manufacturing wood laminates with reduced formaldehyde emission and improved mechanical properties, after at least 40 min of application the laminate is sanded, as is customary for panels of thickness greater than 6 mm. In fixing a part of the sequestering composition is removed, exposing surface of high physical-chemical-mechanical resistance.

[0030] Portanto, o processo de manufatura de laminados de madeira com emissão reduzida de formaldeído e propriedades físico- químico mecânicas melhoradas conforme a invenção compreende as etapas de:  Therefore, the process of manufacturing wood laminates with reduced formaldehyde emission and improved mechanical physicochemical properties according to the invention comprises the steps of:

a) Prover uma composição à base de uma etanoiamina soiubiiizada em um solvente giicólico, na proporção de entre 10 e 99 partes de alcanolamina e entre 90 e 1 parte de solvente giicólico por 100 partes de composição, incluindo 50 partes de alcanolamina e 50 partes de solvente glicólico, e entre 80 partes de alcanolamina e 20 partes de solvente glicólico; (a) provide a composition based on an ethanoamine solubilised in a glycolic solvent, in the ratio of 10 to 99 parts alkanolamine and between 90 and 1 part glycolic solvent per 100 parts of composition, including 50 parts parts of alkanolamine and 50 parts of glycolic solvent, and between 80 parts of alkanolamine and 20 parts of glycolic solvent;

b) Prover um laminado de madeira aglutinado por resina à base de fenol-formaldeído ou uréia-formaldeído ou melamina-formaldeído;  (b) providing a resin-bonded wood laminate based on phenol formaldehyde or urea formaldehyde or melamine formaldehyde;

c) Curar o laminado da etapa b), obtendo um laminado curado;  c) Curing the laminate of step b) to obtain a cured laminate;

d) Sobre o laminado curado da etapa c), aplicar a composição da etapa a) na proporção, em grama por metro quadrado de superfície, entre 5 e 70 g/m2, incluindo entre 30 e 60 g/m2 e 40 e 50 g/m2; (d) For the cured laminate of step (c), apply the composition of step (a) to the ratio in grams per square meter of surface area between 5 and 70 g / m 2 , including between 30 and 60 g / m 2 and 40 and 50 g / m 2 ;

e) Após pelo menos 40 minutos da aplicação da composição, etapa d), lixar o laminado; e  e) After at least 40 minutes of applying the composition, step d) sanding the laminate; and

f) Separar e armazenar o laminado com emissão reduzida de formaldeído e propriedades físico-químico- mecânicas melhoradas.  (f) Separate and store laminate with reduced formaldehyde emission and improved physicochemical and mechanical properties.

[0031 ] A invenção será ilustrada a seguir por um Exemplo, que não deve ser considerado limitativo da mesma.  The invention will be illustrated below by an Example, which is not to be construed as limiting thereof.

EXEMPLO  EXAMPLE

[0032] Testes em laminados de MDP (aglomerado) de 350 x 150 x 15 mm fabricados com resina uréia-formol foram tratados com a composição sequestrante da invenção, que compreendia uma mistura de 85 partes de monoetanoiamina e 15 partes de glicerina por cem partes de composição. A composição foi aplicada por meio de rolo na gramatura (dosagem) de 45 g/m2 de superfície. Após 16 horas os laminados foram lixados retirando 0, 15 mm de cada face. Um painel sem aplicação também foi lixado e analisado como controle. Tests on 350 x 150 x 15 mm MDP (agglomerate) laminates made with urea-formaldehyde resin were treated with the sequestering composition of the invention, which comprised a mixture of 85 parts monoethaneamine and 15 parts glycerin per 100 parts of composition. The composition was applied by roller to the surface weight (dosage) of 45 g / m 2 . After 16 hours the laminates were sanded by removing 0.15 mm from each side. A panel without application was also sanded and analyzed as a control.

[0033] Os resultados dos testes de emissão de formaldeído adaptado da norma JIS A 5905em mg/L, Inchamento após imersão em água conforme a Norma ABNT NBR 14810-2 em %, Absorção de água após imersão conforme a Norma ABNT NBR 14810-2 em % e Tração interna conforme a Norma ABNT NBR 14810-2 em Kgf/cm2 estão listados na Tabela 1 a seguir. Formaldehyde emission test results adapted from JIS A 5905 in mg / L, Swelling after immersion in water according to ABNT NBR 14810-2 in%, Water absorption after immersion according to ABNT NBR 14810-2 in% and Internal traction according to ABNT NBR 14810-2 in Kgf / cm 2 are listed in Table 1 below.

TABELA 1  TABLE 1

Figure imgf000010_0001
Figure imgf000010_0001

[0034] Conforme se pode constatar de modo muito nítido, os dados da Tabela 1 indicam melhoria dos parâmetros físico-químico-mecânicos e redução da emissão de formaldeído nos laminados tratados com a composição da invenção. Tal resultado é inesperado, principalmente em relação às propriedades de absorção de água e tração interna. Pois em painéis onde a camada superficial tem em sua composição resina à base de formol, a aplicação de outros sequestrantes com base aquosa conduz à hidrólise da resina, que provoca liberação de formol e redução das propriedades físico-mecânicas. As can be seen very clearly, the data in Table 1 indicate improvement of the physicochemical-mechanical parameters and reduction of formaldehyde emission in laminates treated with the composition of the invention. Such a result is unexpected, especially regarding water absorption and internal traction properties. Because in panels where the surface layer has formaldehyde-based resin, the application of other water-based sequestrants leads to hydrolysis of the resin, which causes formaldehyde release and reduced physical-mechanical properties.

Claims

REIVINDICAÇÕES 1 . Composição sequestrante de formaldeído para laminado de madeira, caracterizada por compreender, para cem partes de composição, entre 10 e 99 partes de uma alcanolamina e entre 90 e 1 parte de solvente glicólico. 1 . Wood laminate formaldehyde sequestering composition, comprising, for one hundred parts of the composition, between 10 and 99 parts of an alkanolamine and between 90 and 1 part glycolic solvent. 2. Composição de acordo com a reivindicação 1 , caracterizada por ser aplicada após a etapa de prensagem do dito laminado de madeira, este sendo aglutinado por resina à base de fenol-formaldeído ou uréia-formaldeído ou melamina-formaldeído.  Composition according to Claim 1, characterized in that it is applied after the pressing step of said wood laminate, which is bonded by phenol-formaldehyde or urea-formaldehyde or melamine-formaldehyde resin. 3. Composição de acordo com a reivindicação 1 , caracterizada por compreender, por cem partes de composição, 80 partes de alcanolamina e 20 partes de solvente glicólico.  Composition according to Claim 1, characterized in that it comprises 100 parts of composition, 80 parts of alkanolamine and 20 parts of glycolic solvent. 4. Composição de acordo com a reivindicação 3, caracterizada por compreender entre 50 partes de alcanolamina e 50 partes de solvente glicólico.  Composition according to Claim 3, characterized in that it comprises between 50 parts alkanolamine and 50 parts glycolic solvent. 5. Composição de acordo com a reivindicação 1 , caracterizada por a alcanolamina ser selecionada dentre monoetanolamina, dietanolamina e trietanolamina.  Composition according to Claim 1, characterized in that the alkanolamine is selected from monoethanolamine, diethanolamine and triethanolamine. 6. Composição de acordo com a reivindicação 5, caracterizada por a alcanolamina ser a monoetanolamina.  Composition according to Claim 5, characterized in that the alkanolamine is monoethanolamine. 7. Composição de acordo com a reivindicação 1 , caracterizada por o glicol ser o 1 ,2,3-propano triol ou glicerina.  Composition according to Claim 1, characterized in that the glycol is 1,2,3-propane triol or glycerin. 8. Processo de manufatura de laminado de madeira com emissão reduzida de formaldeído e propriedades mecânicas melhoradas com auxílio da composição de acordo com a reivindicação 1 , caracterizado por compreender as etapas de:  Process of manufacturing wood laminate with reduced formaldehyde emission and improved mechanical properties with the aid of the composition according to claim 1, characterized in that it comprises the steps of: a) Prover uma composição à base de uma etanolamina solubilizada em um solvente glicólico, na proporção de, para cem partes de composição, entre 10 e 99 partes de alcanolamina e entre 90 e 1 parte de solvente glicólico, incluindo entre 80 partes de alcanolamina e 20 partes de solvente glicólico, e entre 50 partes de alcanolamina e 50 partes de solvente glicólico; a) Provide a composition based on a solubilized ethanolamine in a glycolic solvent, in the ratio of to 100 parts of composition, between 10 and 99 parts alkanolamine and between 90 and 1 part glycolic solvent, including between 80 parts alkanolamine and 20 parts glycolic solvent, and between 50 parts alkanolamine and 50 parts glycolic solvent; b) Prover um laminado de madeira aglutinado por resina à base de fenol-formaldeído ou uréia-formaldeído ou melamina-formaldeído;  (b) providing a resin-bonded wood laminate based on phenol formaldehyde or urea formaldehyde or melamine formaldehyde; c) Curar o laminado da etapa b), obtendo um laminado curado; d) Sobre o laminado curado da etapa c), aplicar a composição da etapa a) na proporção, em grama por metro quadrado de superfície, entre 5 e 70 g/m2, incluindo entre 30 e 60 g/m2 e 40 e 50 g/m2; c) Curing the laminate of step b) to obtain a cured laminate; (d) For the cured laminate of step (c), apply the composition of step (a) to the ratio in grams per square meter of surface area between 5 and 70 g / m 2 , including between 30 and 60 g / m 2 and 40 and 50 g / m 2 ; e) Após pelo menos 40 minutos da aplicação da composição, etapa d), lixar o laminado; e  e) After at least 40 minutes of applying the composition, step d) sanding the laminate; and f) Separar e armazenar o laminado de madeira com emissão reduzida de formaldeído e propriedades físico-químico-mecânicas melhoradas.  f) Sort and store wood laminate with reduced formaldehyde emission and improved physicochemical-mechanical properties. 9. Processo de acordo com a reivindicação 8, caracterizado por a etanolamina ser selecionada dentre monoetanolamina, dietanolamina e trietanolamina.  Process according to Claim 8, characterized in that the ethanolamine is selected from monoethanolamine, diethanolamine and triethanolamine. 10. Processo de acordo com a reivindicação 9, caracterizado por a etanolamina ser a monoetanolamina.  Process according to Claim 9, characterized in that the ethanolamine is monoethanolamine. 1 1 . Processo de acordo com a reivindicação 8, caracterizado por o glicol ser o 1 ,2,3-propanotriol ou glicerina.  1 1. Process according to Claim 8, characterized in that the glycol is 1,2,3-propanethriol or glycerin. 12. Laminado de madeira, caracterizado por ser obtido através do processo de acordo com a reivindicação 8.  Wood laminate, characterized in that it is obtained by the process according to claim 8.
PCT/BR2017/050020 2017-02-03 2017-02-03 Formaldehyde scavenger composition for wood laminate, process for manufacturing wood laminate with reduced formaldehyde emission and improved mechanical properties, and wood laminate Ceased WO2018141034A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2003635A1 (en) * 1989-11-22 1991-05-22 Andrew Blair Wood coating and treating composition
US5635217A (en) * 1991-04-18 1997-06-03 Dr. Wolman Gmbh Wood preservatives
WO2010056441A1 (en) * 2008-11-17 2010-05-20 Dow Global Technologies Inc. Methods for reducing airborne formaldehyde
US9090855B2 (en) * 2010-06-17 2015-07-28 S.C. Johnson & Son, Inc. Anti-bacterial cleaning composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2003635A1 (en) * 1989-11-22 1991-05-22 Andrew Blair Wood coating and treating composition
US5635217A (en) * 1991-04-18 1997-06-03 Dr. Wolman Gmbh Wood preservatives
WO2010056441A1 (en) * 2008-11-17 2010-05-20 Dow Global Technologies Inc. Methods for reducing airborne formaldehyde
US9090855B2 (en) * 2010-06-17 2015-07-28 S.C. Johnson & Son, Inc. Anti-bacterial cleaning composition

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