WO1997017412A1 - Adhesif et panneaux fabriques a l'aide de cet adhesif - Google Patents

Adhesif et panneaux fabriques a l'aide de cet adhesif Download PDF

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Publication number
WO1997017412A1
WO1997017412A1 PCT/JP1996/003240 JP9603240W WO9717412A1 WO 1997017412 A1 WO1997017412 A1 WO 1997017412A1 JP 9603240 W JP9603240 W JP 9603240W WO 9717412 A1 WO9717412 A1 WO 9717412A1
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WO
WIPO (PCT)
Prior art keywords
adhesive
board
formaldehyde
waste liquid
phenol
Prior art date
Application number
PCT/JP1996/003240
Other languages
English (en)
Japanese (ja)
Inventor
Tsuyoshi Kono
Original Assignee
Tsuyoshi Kono
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsuyoshi Kono filed Critical Tsuyoshi Kono
Publication of WO1997017412A1 publication Critical patent/WO1997017412A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C09J161/14—Modified phenol-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates

Definitions

  • the present invention relates to an adhesive using pulp waste liquid, and a lignocellulose-based board such as a particle board or a fiber board using the same.
  • lignin that is produced by separation and purification from valve wastewater.
  • lignin has a cost for purification.
  • the price of commercially available lignin is higher than that of urea and formalin, which are the raw materials for general wood adhesives, and is almost equal to that of I: nol and melamine.
  • Lignin is a component of waste liquid, and using lignin alone does not fundamentally solve the problem of waste liquid treatment.
  • JP-B-54-157798 and JP-B-62-224 require the use of a larger amount of phenol than the valve waste liquid component in order to obtain sufficient strength performance.
  • Japanese Patent Publication No. 51-222497 discloses the use of 50 to 100 parts of phenol per 100 parts of solid content of sulfurous acid valve waste liquid, but the production process is complicated. However, its cost is lower than that of commercially available urea resin adhesives and melamine resin adhesives.
  • pulp is produced not only from wood but also from non-wood such as bamboo, rice straw, wheat straw, ash, flax, and kenaf.
  • non-wood such as bamboo, rice straw, wheat straw, ash, flax, and kenaf.
  • Environmental pollution due to a sudden increase in valve waste liquid has become a problem.
  • the present invention uses a valve waste liquid (black liquor), exhibits excellent strength performance, has a high ratio of components derived from the valve waste liquid, and is extremely economically advantageous as compared with a commercially available thermosetting resin adhesive.
  • An object of the present invention is to provide an adhesive and to provide a lignocellulose-based board having good performance by using such an adhesive.
  • the present inventor has surprisingly found that a pulp waste liquor of a grass plant can be used to produce a board product having a certain degree of strength even if it is directly used as an adhesive for a board such as a particle board.
  • the adhesive having good strength properties was obtained by reacting the pulp waste liquor with phenols and formaldehyde under appropriate conditions.
  • the adhesive of the present invention is an adhesive obtained by reacting pulp waste liquor with phenol X and formaldehyde, and 30% by weight or more of the non-volatile content of the adhesive is derived from grass pulp waste liquor. It is characterized by the following.
  • the present invention provides a method of forming a board by adding and mixing an adhesive containing the above-mentioned adhesive or a component derived from the waste liquid of grass pulp to 30% by weight or more to a small piece of lignocellulosic material, and applying heat and pressure. It also covers lignocellulosic boards, such as characteristic board and fiber board.
  • the valve waste liquid used in the adhesive of the present invention is a so-called black liquor discharged in the valve digestion step, and is composed of hemicellulose, lignin or a decomposition product or modification thereof and a digestion catalyst.
  • a waste liquid containing The pulp waste liquid is It is preferable to use only the waste liquid of the gramineous bulb, but it is also possible to use a mixture of waste liquid other than the gramineous plant such as wood.
  • any kind of gramineous plants such as bamboo, rice straw, wheat straw, bagasse (sugar cane pulp), ash, corn, coriander, etc. can be used, but especially bamboo, rice straw, wheat-based pulp.
  • the use of waste liquid is preferred.
  • Examples of the above pulp waste liquid include so-called chemical pulping methods such as the Kraft method, the sulfurous acid method, and the soda method, semi-chemical valve forming methods, thermomechanical pulping methods, organic solvent methods, etc.
  • the waste liquid in any pulping method that discharges the denatured product can be used, but it is preferable to use the one obtained by alkaline conditions, particularly the one obtained by the soda method or the craft method.
  • hemicellulose is decomposed into hydroxy acid in alkaline cooking, and it is expected that there is a limit to using the waste liquid of Al-Chili cooking as it is as an adhesive.
  • the waste liquid of Arikuri cooking is preferably used.
  • valve waste liquid all plant-derived components in the valve waste liquid serve as active ingredients for adhesive production, and when the valve waste liquid is alkaline, the alkali component serves as a reaction catalyst. Therefore, it is not necessary to remove specific components in the valve waste liquid. However, it is preferable to remove the microfissure of the valve mixed in the waste liquid. Pulp waste liquid is usually about 20% to 50% in degree. It is used after being dehydrated and concentrated.
  • phenols all phenols such as phenol, cresol, xylenol, bisphenol, bisphenol: t-norl F and resorcinol can be used, but from the viewpoint of performance and cost, use of phenol is preferred.
  • the amount used is preferably 100% by weight or less, more preferably 5 to 60% by weight, based on the nonvolatile content of the pulp waste liquor. The amount used may exceed 100% by weight, but it will only increase the cost and cannot improve the physical properties.
  • formaldehyde all formaldehydes such as formalin, paraformaldehyde and polyoxymethylene can be used.
  • the use amount is preferably in the range of 1.2 to 5.0, more preferably 1.8 in terms of the molar ratio to the phenol monomer.
  • a range of -3.5 is particularly preferred.
  • aldehydes such as acetoaldehyde, furfural, benzua 4 It is possible to use aldehyde, glyoxal, etc. in place of formaldehyde in a molar number that does not exceed the amount of formaldehyde.
  • the adhesive of the present invention is preferably one in which the pulp waste liquor is reacted with phenols and formaldehyde under the conditions of pH 9 or more, particularly pH 10 or more.
  • the catalyst any alkali catalyst satisfying such PH conditions can be used, including oxides or hydroxides of alkali metals and alkaline earth metals.
  • the pulp waste liquid used is an alkaline one such as the Kraft method or the soda method, it is not necessary to add the above-mentioned catalyst, which is advantageous.
  • the adhesive of the present invention is a reaction product of the above-mentioned valve waste liquid, phenols and formaldehyde, and contains at least 30% by weight or more, preferably 50% by weight, of a component derived from grassy valve waste liquid in non-volatile components. %, Particularly preferably 60 to 95% by weight. Those containing less than 30% by weight of the components derived from the vegetation waste liquid of the gramineous plant cannot achieve the object of the present invention.
  • the content is used in the production of the adhesive with respect to the non-volatile content of the adhesive.
  • the weight percentage of the non-volatile content of the polished grass valve waste liquid is used in the production of the adhesive with respect to the non-volatile content of the adhesive.
  • the adhesive of the present invention has a structure in which a pulp waste liquid component and a polymer of phenol X and formaldehyde are added with a methylol group.If possible, the pulp waste liquid component and the phenol monomer are alternately polymerized to form a methylol group.
  • a structure with a well-balanced addition is preferred.
  • As an unfavorable structure a large amount of polycondensate consisting of c-nol and formaldehyde alone is mixed, and a large amount of polycondensate consisting only of valve waste liquid components and formaldehyde is mixed.
  • the adhesive having the above preferred structure may be obtained by reacting a reaction product with a valve waste liquid after obtaining a specific reaction product from phenols and formaldehyde, or by mixing a valve waste liquid with a phenol: >>: phenols and formaldehyde. And at the same time under specific conditions.
  • an adhesive obtained by obtaining a specific reaction product from phenols and formaldehyde and then reacting the reaction product with a valve waste liquid has the most preferable structure.
  • the adhesive obtained by reacting the product with the valve waste liquid is as follows.
  • the specific reaction product has a weight-average molecular weight of 120 to 500, preferably 150 to 300, and a content of a methylol derivative of a phenol monomer of 20% or more.
  • it is a reaction product of not less than 40% of phenol;
  • a reaction product has, for example, a molar ratio of formaldehyde to phenol monomer of 1.8 to 3.5, an alkali metal to phenol monomer of 0.1 to 0.5, and a reaction temperature of 50 to 80. For 30 minutes to 2 hours. This specific reaction product is added to the valve waste liquid and reacted at 50 to 95 temperatures for 20 minutes to 5 hours.
  • the adhesive obtained by simultaneously reacting the above-mentioned valve waste liquid with phenols and formaldehyde under specific conditions is as follows: That is, the pulp waste liquid concentrate contains phenols and formaldehyde. , And firstly react at 40 to 85 for 20 minutes to 2 hours, preferably for 45 to 75 at 30 minutes to 1 hour, and then at 50 to 95 at 30 to 8 hours. Let it. The first reaction preferentially forms the methylol form of phenolic monomer.
  • the adhesive of the present invention When the adhesive of the present invention is neutralized to PH57, it separates into a tetrahydrofuran-soluble component and an insoluble component, and the weight-average molecular weight of the soluble component is preferably 500 or more, and is preferably from 800 to 2,000. Is more preferred. Those having an overlapping average molecular weight of less than 500 have low strength performance, and the desired weight average molecular weight is adjusted mainly by the reaction time.
  • the adhesive of the present invention is usually used in the form of a liquid, particularly an aqueous solution or a suspension of water, but can be used in a powder form by dewatering and drying.
  • the adhesive of the present invention is cured by a cross-linking reaction of a methylol group and is usually thermosetting, preferably by heat treatment at a temperature of at least 150, more preferably at a temperature of from 180 to 210. , Curing is achieved.
  • thermosetting it is not necessarily limited to thermosetting.
  • the adhesive can be cured at room temperature by allowing an alkali metal to exist in an amount of 0.5 mol or more based on the mononuclear phenol, and mixing an organic acid ester at the time of use.
  • the adhesive of the present invention can be used in all applications where a conventional thermosetting resin adhesive or binder is used, but is particularly useful as an adhesive for wood such as particle board, fiber board, and plywood. Demonstrate excellent performance,
  • the adhesive of the present invention may be used in combination with other agents such as a water-soluble agent, a release agent, and a flame retardant. Further, the adhesive of the present invention can be used in combination with other synthetic resin adhesives such as urea resin and melamine resin.
  • the board in the present invention is a board, such as a particle board or a fiber board, formed by mixing small pieces of a lignocellulosic substance such as wood with an adhesive, heating and pressurizing.
  • the board of the present invention comprises a small piece of a lignocell mouth substance containing an adhesive containing 30% by weight or more, preferably 50% by weight or more, and particularly preferably 60% by weight or more of a component derived from a pulp waste liquid of a grass family.
  • the non-volatile components are added and mixed at a ratio of 0.5 to 40% base, and heated and pressurized.
  • the above-mentioned adhesive it is preferable to use the above-mentioned adhesive of the present invention.
  • the waste liquid of a grass valve valve itself may be used.
  • Some wood adhesives may be used in combination.
  • the adhesive of the present invention By adding and mixing the adhesive of the present invention to a small piece of lignocellulose material, heating and pressing to form a plate, a practical lignocellulose board such as a particle board or a fiber board can be produced with good performance.
  • the adhesive of the present invention may be added at a ratio of about 0.5 to 40% by weight in terms of nonvolatile content to small pieces of the lignocellulose substance, and usually at a rate of 1 to 20% by weight. It is preferably added.
  • Such a board of the present invention has a mechanical strength equal to or higher than that of a board product using a conventional wood adhesive.
  • the conditions for heating and pressing may be in accordance with a conventional method.
  • additives such as a water solution, a release agent, a preservative, and the like may be used, and these may be previously added to and mixed with the adhesive, or may be added separately from the adhesive during board production. .
  • the reason why the adhesive of the present invention exhibits excellent performance is not necessarily clear,
  • the composition of hemicellulose and lignin specific to gramineous plants can be mentioned.
  • ⁇ Gramineous plants contain a large amount of xylan as hemicellulose.Xylane hydrolyzes, and mostly xylose is hydrolyzed to furfural.
  • Furfural is a substance used as an aldehyde source for furan and phenolic resins, but is industrially used as a suitable raw material for plants of the family Poaceae such as maize transaxles, wheat straw, fir husks, and bacass.
  • Lignin of grasses has a special structure represented by the formula (1) (formula (2) is a lignin that is often contained in coniferous trees, and formula (3) is a lignin that is frequently contained in broad-leaved trees).
  • Lignin of grasses has no methoxy group at the right and left ortho-positions of the phenolic skeleton, so that formaldehyde can easily undergo an addition reaction, and oligomers can be easily formed by co-condensation with phenolic phenol. It is believed that there is.
  • the reason why a pulp waste liquid and a methylol derivative of phenol are preferred is exemplified by the most preferred trimethylol phenol.
  • the trimethylol phenol represented by the formula (4): 1: 1: The dehydration and condensation of the pulp waste component with the pulp waste liquid component tend to form an oligomer in which the phenol monomer represented by the formula (5) and the pulp waste liquid component are alternately polymerized with a methylene group interposed therebetween. Moreover, the methylol necessary for the reaction The ru body remains in the skeleton. In this way, a resin composition of a type that cures by a cross-linking reaction of a methylol group is formed by efficiently using a small amount of phenol and formaldehyde.
  • the molecular weight distribution charts and weight average molecular weights in these Examples and Comparative Examples were obtained by neutralizing a sample with FH5-7 with formic acid and then dissolving the THF (tetrahydrofuran) soluble matter by gel permeation chromatography (manufactured by Shimadzu Corporation). The column was measured using Shimadzu LC Column GPC-801 1500) and the carrier: THF, 1 cc / ai detector, UV.
  • the content of the methylol form of the t-nol monomer is as follows: It was expressed as area% of molecular S distribution chart.
  • Example 6 8 (Calculation of% of non-adherence of used valve waste liquid to non-volatile adhesive)
  • Adhesive IK was produced in the same manner as in Examples -g except that a pulp waste liquid other than 13 Gramineous plants was used.
  • the fi content average molecular weights of these adhesives are also shown in Table 2.
  • FIG. 1 shows a molecular weight distribution chart of the reaction product X.
  • the content of the methylol form of the phenol monomer in the reaction product X was o-methylolphenol 8%, p-methylolphenol + 2,6-dimethylol 8%, 2.4-dimethylolphenol 11%, Trimetic mouth: 29% for t-nor, a total of 56%.
  • the weight average molecular weight was 172.
  • reaction product X was added to the same concentrated solution of grass valve waste liquid as used in Examples 4 to 6 so that the ratio of phenol X in the reaction product X to the nonvolatile matter of the valve waste liquid became 15% by weight. And reacted for 2 hours at 70 to produce adhesives L to N.
  • Table 3 shows the weight average molecular weights.
  • Fig. 2 shows the molecular weight distribution chart of the rice valve waste liquid adhesive of the adhesive N.
  • Examples 12 to 25 and Comparative Examples 5 to 8 show the strength performance of the adhesive of the present invention as a particle board adhesive, and the particles obtained by the method for producing a lignocellulosic board of the present invention. This is an examination of the strength performance of the board.
  • the particle board is made from absolutely dry flakes obtained by cutting the building demolition material using a knife ring flaker (pa 11 man) with a blade of 0.5 mm. After applying and adding a 10% by weight adhesive as a non-volatile content using a spray gun, it is hand-dispersed in a 22 cm square forming box, mat formed, and a lcm size spacer is used (target specific gravity 0). 7 gZ c ⁇ ), pressure was 50 kgf Zcnf at 200 ° C for 15 minutes by zono heating.
  • test pieces obtained by cutting the molded product into a size of 5 ⁇ 20 cm were measured in accordance with JIS A59085.5.
  • Particle boards were manufactured using the adhesives A to H and L to N of the present invention manufactured in Examples 1 to 11, and the bending strength was measured. The results are shown in Table 4.
  • Particle boards were manufactured using the adhesives I to K and ⁇ manufactured in Comparative Examples 1 to 3, and the bending strength was measured. The results are shown in Table 4.
  • the bamboo valve waste liquid concentrate ⁇ and the above-mentioned phenol aldehyde resin adhesive ⁇ are mixed at a ratio such that the non-volatile content of the bamboo pulp waste liquid becomes 40% by weight, and the adhesive 0 is mixed. % To produce adhesive ⁇ . Particle boards were manufactured using these adhesives, and the bending strength was measured. The results are shown in Table 4, Table 4
  • the component derived from the pulp waste liquor in the non-volatile content of the adhesive is 30% or more, especially 50% or more, and even 80% or more, the phenol alcohol resin adhesive Demonstrates strength performance equal to or higher than
  • the weight-average molecule 1 is 120-500, and 20% or more of the non-inhibited portion is phenol:
  • the reaction product of phenol X, which is a methylol form of monomer, with formaldehyde The adhesive reacting to the waste liquid exhibits better strength performance.
  • the board can be manufactured using only the pulp waste liquid of grasses as an adhesive.
  • An adhesive having a weight average molecular weight of 500 or more exhibits good strength performance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Paper (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

Cette invention concerne un adhésif préparé à partir d'une liqueur de pâte résiduelle, lequel adhésif possède d'excellentes qualités de résistance ainsi qu'un contenu élevé en composants dérivés de la liqueur résiduelle, et présente un grand avantage économique par rapport aux adhésifs de résine thermodurcissable disponibles dans le commerce. Cette invention concerne également des panneaux de lignocellulose fabriqués à l'aide de cet adhésif. Cet adhésif comprend une liqueur de pâte résiduelle ainsi qu'un produit issu de la réaction entre un composé phénol et un formaldéhyde, au moins 30 % en poids des composants non volatiles étant dérivés d'une liqueur de pâte résiduelle d'une plante graminée. Ces panneaux de lignocellulose peuvent être réalisés sous forme de panneaux de particules ou de panneaux de fibres, et sont fabriqués en mélangeant l'adhésif susmentionné à de petites particules d'une substance lignocellulosique, puis en pressant ce mélange sous forme d'un panneau, au moins 30 % en poids des composants non volatiles étant dérivés d'une liqueur de pâte résiduelle d'une plante graminée.
PCT/JP1996/003240 1995-11-06 1996-11-06 Adhesif et panneaux fabriques a l'aide de cet adhesif WO1997017412A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7/313636 1995-11-06
JP31363695 1995-11-06

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Publication Number Publication Date
WO1997017412A1 true WO1997017412A1 (fr) 1997-05-15

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WO (1) WO1997017412A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990068760A (ko) * 1999-06-14 1999-09-06 김성호 건축자재용접착본드및그제조방법.
JP3361819B2 (ja) * 1997-05-05 2003-01-07 剛 河野 接着剤及びそれを使用したボード
JP2011099083A (ja) * 2009-11-09 2011-05-19 Kono Shinsozai Kaihatsu Kk エポキシ樹脂

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102618196B (zh) * 2011-01-27 2013-10-16 中国林业科学研究院木材工业研究所 一种生物质胶粘剂的制备方法及其生物质胶粘剂和胶合木板
CN105121495A (zh) * 2013-02-15 2015-12-02 英派尔科技开发有限公司 酚类环氧化合物
WO2014200486A1 (fr) 2013-06-13 2014-12-18 Empire Technology Development Llc Résines phénoliques multifonctionnelles
CN105814014B (zh) 2013-12-02 2018-06-12 英派尔科技开发有限公司 新型双子表面活性剂和它们的用途
CN104293258B (zh) * 2014-03-10 2016-05-18 黄淮学院 一种造纸废液资源化利用的方法及采用该方法生产的胶粘剂
CN110894409A (zh) * 2018-09-12 2020-03-20 上海昶法新材料有限公司 用于建筑模板纸的改性酚醛树脂胶黏剂及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51148731A (en) * 1975-06-17 1976-12-21 Eidai Co Ltd A process for preparing lignin-phenol co-condensation resin adhesive
JPS55160049A (en) * 1979-04-20 1980-12-12 Reichhold Ltd Lignosulfonic acid phenol resin bonding agent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51148731A (en) * 1975-06-17 1976-12-21 Eidai Co Ltd A process for preparing lignin-phenol co-condensation resin adhesive
JPS55160049A (en) * 1979-04-20 1980-12-12 Reichhold Ltd Lignosulfonic acid phenol resin bonding agent

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3361819B2 (ja) * 1997-05-05 2003-01-07 剛 河野 接着剤及びそれを使用したボード
KR19990068760A (ko) * 1999-06-14 1999-09-06 김성호 건축자재용접착본드및그제조방법.
JP2011099083A (ja) * 2009-11-09 2011-05-19 Kono Shinsozai Kaihatsu Kk エポキシ樹脂

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CN1207114A (zh) 1999-02-03
CN1113947C (zh) 2003-07-09

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