CN1090218C - Preparation processes of adhesive for lignocellulose and lignocellulose pressed board - Google Patents
Preparation processes of adhesive for lignocellulose and lignocellulose pressed board Download PDFInfo
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- CN1090218C CN1090218C CN98107065A CN98107065A CN1090218C CN 1090218 C CN1090218 C CN 1090218C CN 98107065 A CN98107065 A CN 98107065A CN 98107065 A CN98107065 A CN 98107065A CN 1090218 C CN1090218 C CN 1090218C
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- lignocellulose
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- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S528/905—Polymer prepared from isocyanate reactant has adhesive property
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Described in the present invention is a process for the preparation of an adhesive for a lignocellulose pressed board, which comprises injecting a first stream formed of (A) an organic isocyanate compound and a second stream formed of (B) a reactive emulsifier and (C) an emulsifying medium and optionally a mold release agent into a mixing chamber under a high pressure of 40 to 300 kg/cm<SP>2</SP> and then mixing them. According to this invention, a preparation process of an adhesive optimum for the continuous process suited for the industrial production is provided. Owing to good releasability of the invention adhesive at the time of hot pressing, this adhesive is suited for the industrial production of a high-quality and inexpensive lignocellulose pressed board with good productivity.
Description
The present invention relates to a kind of preparation method of the tackiness agent that is used for mainly the heating platen made by lignocellulose and with the method for described tackiness agent production lignocellulose presspahn.
When lignocellulose was the wood chip attitude, mainly the presspahn of being made by lignocellulose was called " shaving board ".Except shaving board, the slicer board of large size wood chip and the directed stranded plate (OSB) that is arranged in a row of fines (bundle) have wherein been used in addition.Under the situation of lignified fiber, they are made into the sheet material such as division board, medium density fibre board (MDF) (MDF) or hardboard.These sheet materials are as material, furniture component or the automobile component of flooring material, wall material, door material, sound-proof material, thermal insulation material, tatami core.
As producing shaving board, slicer board, directed stranded plate, fiberboard such as hardboard, medium density fibre board (MDF) or division board, the tackiness agent or the caking agent of dregs plate of making by dregs or Chinese sorghum plate (will be generically and collectively referred to as " plate " later on) usefulness of making by kaoliang stalk, thermosetting resin such as urea resin, melamine resin, urea melamine, phenol melamine resin and resol (will be generically and collectively referred to as " formaldehyde based resin tackiness agent " later on) up to the present are used widely.
The characteristics of formaldehyde based resin tackiness agent are to have the bond properties of the excellence under the low cost and can solidify in the short relatively time.Is a problem with the formaldehyde that discharges in the bonding hot pressing product of formaldehyde based resin tackiness agent in the viewpoint of environment.From reducing the purpose of burst size of methanal, the free formaldehyde content that can reduce in the tackiness agent (reduces formaldehyde and phenol in the resin glue, trimeric cyanamide, or the mol ratio of urea) or when mixing the formaldehyde based resin tackiness agent, use formaldehyde trap or like that.Yet these measures also do not bring gratifying result.
On the other hand, the open № 131538/1982 and 147567/1982 of Japanese Patent, United States Patent (USP) № 35557263,3636199, mention in 3870665,3919017 and 3930110 and the like use non-carboxaldehyde radicals and also can give the isocyanic ester based adhesive of sheet material with the physicals of excellence.
When using organic polymeric polyisocyanate to make the wooden cellulose-based material of tackiness agent hot pressing, because its this tackiness agent of excellent bounding force clings platen, damaged compacted products, and then caused the very big destruction of product commodity value but also the expensive labour of needs removes the settling on the platen.
In order to improve the ability that organic polymeric polyisocyanate breaks away from the platen metal, and then overcome the problems referred to above, worked out and add additive therein.For example, what be mentioned as organic polyisocyanate ester additive has alkyl phosphate or a pyrophosphate (the open № 018068/1991 of Japanese Patent), sulfonated bodies (the open № 038309/1993 of Japanese Patent), wax and liquid ester (the open № 054390/1992 of Japanese Patent), aliphatic carboxylic acid (the open № 36430/1983 of Japanese Patent), polysiloxane compound (the open № 86225/1986 of Japanese Patent), fatty acid polymer (United States Patent (USP) № 4772442 and 4933232) and the like.
In addition, also there is proposition before hot pressing, release agent to be directly used in the method for platen, this method is by using metal fatty acid salt (the open № 34026/1996 of Japanese Patent), use high boiling polyol (German patent DE-1653178), use has the polysiloxane film (English Patent № 135992) of functional group, coat tetrafluoroethylene (United States Patent (USP) № 4374791) or formation abscission layer like that and work, but these methods can not meet the demands.
At some board mills, organic polymeric polyisocyanate based adhesive top layer that the internal layer and formaldehyde based resin commonly used is used for of platen contact contacts with platen that only is used to get along well.
As the other method that overcomes the problems referred to above, the inventor just uses organic polymeric polyisocyanate, the invention that polyvalent alcohol, linking agent, catalyzer and inner pattern releasing agent applicable are made feedstock production urethane resin product molded or that be shaped has proposed patent application (the open № 245622/1985 of Japanese Patent).Because it comprises the at the most Zinic stearas of 5 part weight of adding based on 100 parts of polyvalent alcohol weight, and it is one and obtains cellular polyurethane and method for producing elastomers by injecting metal pattern that this method can't satisfy purpose of the present invention.In addition, the inventor just uses the mold release compositions (the open № 137953/1988 of Japanese Patent) of the zinc salt that contains aliphatic carboxylic acid that is dissolved in polyvalent alcohol, but also just use metal-salt and N by higher fatty acid, N, the mold release compositions that N '-three (2-hydroxypropyl) quadrol is formed (the open № 72757/1988 of Japanese Patent) has been applied for patent.Because the zinc salt of aliphatic carboxylic acid or the metal-salt of higher fatty acid are with respect to amount (parts by weight) difference of polyvalent alcohol, polyvalent alcohol is made up of diverse, adopted non-aqueous system and mold release compositions is used as preparation polyurethane products molded or that be shaped, they can not satisfy purpose of the present invention.
Comprise in the organic isocyanate compound at one and to add thinner and prepare binder composition with increasing amount, the method that then said composition is used for the lignocellulose sill, organic isocyanate compound and thinner adopt interrupter method mixing and emulsification or mixing and emulsification in static mixer in mixing tank usually.
Because the high reaction activity of organic isocyanate compound, form in the conduit that polymeric articles between organic isocyanate and the thinner and the like flows through with binder composition in mixing tank or static mixer, cause that like this conduit stops up, deposition at the equipment inwall, the variation of flow velocity in operation interruption and/or the pipeline causes being difficult to stable operation in operation.Removing settling need spend huge labour and time and see that from economic point of view the output minimizing that causes owing to circuit failure also is unwelcome.
In order to overcome the problems referred to above, the open № 279303/1990 of Japanese Patent disclosed a kind of in static mixer the emulsion binder composition rapidly itself and cellulosic fibrous bundle are mixed method and the equipment thereof of producing hard board then.In this method, dividing plate is installed and when cleaning, is cleaned static mixer with liquid wash by each input hole place of organic isocyanate compound and thinner in static mixer.This method still needs routine cleaning with static mixer and needs the defective of spended time with the liquid wash static mixer.And then, cause must stopping to supply with cellulosic fibrous bundle owing to can not when cleaning, prepare binder composition.Therefore aforesaid method is not suitable for continuous production efficiently.
Disclosed in the open № 276501/1988 of Japanese Patent that biliquid jet mixer that a kind of use is made up of at two jet pipes of pipeline extended spot cross arrangement is finished emulsification and the method for the tackiness agent production shaving board that obtains.Because spraying pressure is low, mixing and emulsification are not easy fully, mixing device need cause curing in device with the input hole of avoiding two kinds of a kind of the other side of entering in the jetting fluid for a kind of special shape, simultaneously because this mixing tank is not equipped with washing unit, behind the long-term mixing tank of use continuously, the polymerization product of organic isocyanate compound clings and is deposited on hybrid chamber inevitably, and this is to cause change in flow and the reason of circuit failure as stopping up, and this method is still with defective.
Therefore, above-mentioned every kind of method comprises different problems and cannot stand use in the actual production place.At present, see there is not a kind of gratifying method from the viewpoint of various operations, economy and physicals.
The tackiness agent application that the inventor just is made up of organic isocyanate, polyethers and water patent (number of patent application 38396/97 (AU), 973309/97 (ID), 39777/97 (TH), 328826/97 (NZ), 97.116939/97 (CN) ,/97 (MY)).This tackiness agent has excellent performance, but because organic isocyanate is easy to react with other binder component, and the reaction product of the binder component of organic isocyanate and other as scale deposition on the inwall of mixing tank or pipeline, this tackiness agent need improve to adapt to use steady in a long-term.
Purpose of the present invention is exactly to overcome operation that above-mentioned ordinary method can not overcome fully and the problem in the physicals, and provides a kind of inwall that can not be deposited on mixing tank or pipeline owing to the polymerization product of organic isocyanate compound to cause the preparation method of organic polyisocyanate binders of circuit failure; And a kind of use of high efficiency, low cost can not be deposited on the platen when hot-pressed board thereby has the production method that the excellent tackiness agent that breaks away from performance is produced high quality sheet material.
As the result who furthers investigate based on overcoming the problems referred to above, the inventor has found a kind of tackiness agent of the heating platen made by lignocellulose and method of producing this plate of being used for mainly, more particularly, it is a kind of by organic isocyanate compound and a kind of emulsification are mixed, and the emulsifying mixture of gained prepared a kind of binder composition, the first kind of liquid stream that is about to be made up of the organic isocyanate compound and flowed by second kind of liquid that reactive emulsifying agent and emulsification are formed under high pressure is ejected in the hybrid chamber, then its mixing and emulsification is obtained tackiness agent; And a kind ofly use described tackiness agent to produce the method for heating platen and finished the present invention.
Purpose that the present invention is more deep and advantage can be fully understood from the detailed description below in conjunction with accompanying drawing, wherein:
Fig. 1 and 2 is actually used in the synoptic diagram of the preparation facilities of tackiness agent of the present invention for explanation; Fig. 3 is the synoptic diagram of the preparation section of explanation tackiness agent of the present invention; Fig. 4 is for producing the synoptic diagram of medium density fibre board (MDF) (MDF) with an example of device among explanation the present invention.
The present invention comprises following invention and embodiment.
(1) a kind of method for preparing the lignocellulose presspahn with tackiness agent, described tackiness agent is by (A) a kind of organic isocyanate compound, (B) a kind of reactive emulsifying agent, (C) a kind of emulsification is formed, and this method comprises first kind of liquid will being made up of described organic isocyanate compound (A) and flows and flowed at high pressure 40-300Kg/cm by second kind of liquid that described reactive emulsifying agent (B) and described emulsification (C) are formed
2Under be ejected in the hybrid chamber, then described liquid stream is mixed.
(2), wherein also be included in described first kind or the second kind of liquid stream and add releasing agent (D) as (1) described method.
(3) as (1) or (2) described method, wherein said hybrid chamber is furnished with mechanical washing unit.
(4) as (3) described method, the bar that inserts in hybrid chamber and take out that wherein said mechanical washing unit coincide by a mechanically operated inside complete and described hybrid chamber cleans the inwall of described hybrid chamber.
(5) arbitrary being selected from as (1) to (3) described method, wherein said emulsification (C) is for water or comprise water at least.
(6) arbitrary being selected from as (1) to (5) described method, wherein said reactive emulsifying agent (B) is for a kind of polyethers and/or polyester polyol or comprise a kind of polyethers and/or polyester polyol at least.
(7) as (6) described method, wherein said reactive emulsifying agent (B) comprises a kind of polyethers and/or polyester polyol at least; Described polyethers and/or polyester polyol have 2-8 functional group, and repeated structural unit (CH
2-CH
2-amount O) accounts for the 5-70% of polyethers and/or polyester polyol weight; And per 100 parts of organic isocyanate compounds (A) weight, the ratio of described polyethers and/or polyester polyol is the 0.01-70 parts by weight.
(8) as (6) described method, wherein said reactive emulsifying agent (B) comprises a kind of polyethers and/or polyester polyol at least; Comprise a nitrogen-atoms in described polyethers and/or the polyester polyol molecule; The ratio of described nitrogen-atoms is the 0.1-12.0wt% based on polyethers and/or polyester polyol.
(9) as (6) described method, wherein said polyether glycol is by adding alkylene oxide at least a compound that is selected from trolamine, diethanolamine, monoethanolamine, ortho-toluene diamine, toluylenediamine, ditan diamines and polyphenol polymethylene polyamine; And in described alkylene oxide, the quantity of oxyethane is for being the 5-70 parts by weight based on per 100 parts of described polyether glycols of weight.
(10) arbitrary being selected from as (2) to (9) described method, wherein said releasing agent (D) is at least a material that is selected from the metal-salt with the saturated of 8-28 carbon atom and/or unsaturated aliphatic carboxylic acid.
(11) as (10) described method, the metal-salt of the saturated and/or unsaturated aliphatic carboxylic acid of the wherein said 8-28 of a having carbon atom is at least a combination that is selected from a kind of material in the group that comprises sad, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid and docosoic acid and is selected from the another kind of material in the group that comprises zinc, iron, aluminium, calcium, zirconium, magnesium, barium, nickel, copper and cobalt.
(12) arbitrary being selected from as (2) to (11) described method, the amount that wherein said releasing agent (D) adds is that per described organic isocyanate compounds of 100 parts of weight (A) are the 1-150 parts by weight.
(13) arbitrary being selected from as (1) to (12) described method, wherein said organic isocyanate compound (A) is the polymethylene polyphenyl polymeric polyisocyanate.
(14) a kind of method of producing the lignocellulose presspahn, comprise lignocellulose sill and arbitrary being selected from as the described lignocellulose presspahn of claim (1) to (12) are mixed with tackiness agent, make pad with resulting mixture, will fill up hot pressing then.
(15) a kind of lignocellulose presspahn of making as (14) described method.
The present invention will obtain more detailed description hereinafter.
In the present invention, the lignocellulose presspahn is under high pressure a kind of organic isocyanate compound, a kind of reactive emulsifying agent and a kind of emulsification to be ejected in the hybrid chamber that is equipped with mechanical washing unit as a kind of production of product, and with resulting mixture mixing and emulsification, so obtain a kind of tackiness agent; Then described tackiness agent is used for the lignocellulose sill, becomes pad, hot pressing and surface grinding subsequently.
The example of lignocellulose sill comprises the production shaving board, the string shape bits that slicer board and directed stranded plate are used, pulverized dirt and sheet bits; Produce the fiber that hardboard, medium density fibre board (MDF) or division board are used; With the agricultural-food such as kaoliang stalk, bagasse and husk.The material of more than enumerating can be used alone or in combination.
As organic isocyanate compound (A), any material with an isocyanate groups may be used to the present invention.Object lesson comprises tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, HDI, Xylene Diisocyanate, isophorone diisocyanate, norbornylene vulcabond, with polymethylene polyphenyl polymeric polyisocyanate (polymeric MDI), and with the compound modified isocyanate compound that contains a reactive hydrogen at least.From economic point of view, wherein polymeric MDI is preferred.
As being used for reactive emulsifying agent of the present invention (B), if can with described organic isocyanate compound reaction and play the emulsifying agent effect all can be used for the present invention without restriction.Because emulsifying agent has function like this, consider that from the physicals of consistency, foam performance and the plate of economic and organic isocyanate compound polyethers and/or polyester polyol are preferred.
As polyethers and/or polyester polyol (being generically and collectively referred to as polyvalent alcohol hereinafter), can use the mixture of polyether glycol or polyester polyol or use polyether glycol and polyester polyol separately.On the other hand, also can use the polyether-polyester polyol.
As making polyvalent alcohol used in this invention, as long as comprise 2-8 functional group, have the 24-800mgKOH/g hydroxyl value, and have 5-70wt%, more preferably repeating unit (the CH of 10-60wt% ratio with respect to polyvalent alcohol weight
2CH
2-O-) all be preferred.
Be no less than 5% repeating unit and bring good emulsifying property, and no more than 70% repeating unit makes and makes the sheet material with good physical and become possibility.
Can be used for polyether glycol of the present invention prepares by a kind of means that are known as the ordinary method of preparation polyvalent alcohol, this method adds alkylene oxide such as oxyethane, propylene oxide, butylene oxide ring or the Styrene oxide 98min. that contains an epoxy group(ing) in the molecule in as the low-molecular weight compound that has two reactive hydrogens at least of initiator under the situation that is with or without the existence of catalyzer such as alkali-metal oxyhydroxide or tertiary amine.
The example of initiator comprises amine initiator and non-amine initiator.The amine initiator of enumerating comprises thanomin such as monoethanolamine, diethanolamine, and trolamine, and such as 1, the 2-quadrol, diethylenetriamine, ortho-toluene diamine, toluylenediamine, 4,4 '-ditan diamines, 2, the amine of 4 '-ditan diamines and many many phenyl of methyl polyamine and so on.They can be used alone or in combination.
The non-amine initiator of enumerating comprises sucrose, alcohol is glycerol, tetramethylolmethane, sorbyl alcohol, trihydroxymethyl propane, two glycerol, propylene glycol, dipropylene glycol, Diethylene Glycol, ethylene glycol, 1 for example, 4-butyleneglycol and 1,2-butyleneglycol, and phenol for example Resorcinol, dihydroxyphenyl propane and linear phenolic resin.
In the present invention, the amine initiator of more than enumerating is preferred.Also can with the amine initiator and arbitrary more than the non-amine initiator enumerated combine use.
The ratio of nitrogen-atoms is preferably 0.1-12.0wt% in the polyvalent alcohol, is more preferably 1.0-10wt%.The ratio that is no less than 0.1wt% can form effective emulsification.And on the other hand, when the no more than 12.0wt% of ratio, react suitable and tackiness agent prepares easily.
Polyester polyol can be by the addition reaction between acid anhydrides and the alcohol, the polycondensation between polycarboxylic acid and the alcohol or add alkylene oxide and obtain in acid.
The example of acid anhydrides comprises maleic anhydride, succinyl oxide, trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydride, itaconic anhydride, phthalic anhydride, Pyroglutaric acid, glutaconic anhydride, anhydride diethylene glycol, citraconic anhydride, biphenyl acid anhydrides, phenylacetic anhydride.The example of polycarboxylic acid comprises toxilic acid, terephthalic acid, dimethyl terephthalic acid, iso-phthalic acid, fumaric acid, oxalic acid, propanedioic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, certain herbaceous plants with big flowers diacid, citric acid and trimellitic acid.What be used for alcohol of the present invention comprises alcohol for example, phenol and as the alkylene oxide affixture of initiator, more than all enumerate respectively.
As a function of reactive emulsifying agent among the present invention, organic isocyanate compound (A) is dissolved in emulsification (C) or emulsification is important, and need to reach reactive emulsifying agent of this function.Reactive emulsifying agent (B) has adopted reactive emulsifying agent that can satisfy above-mentioned purpose, and reactive emulsifying agent that can also show the surface active ability except above-mentioned functions is more suitable for using.Specifically, " tensio-active agent " can be used as an example and enumerates, and anion surfactant, cats product, and nonionogenic tenside and the like can adopt.
The object lesson of tensio-active agent comprises anion surfactant such as fatty acid soaps, rosined soap, alkylsulfonate, alkylbenzene sulfonate, two alkylaryl sulfonates, alkylthio Succinic Acid, polyoxyethylene alkylsulfonate and polyoxyethylene alkylaryl sulfonate; Segmented copolymer with tensio-active agent such as polyethylene oxide alkyl ethers, polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitol fatty acid ester and ethylene oxide propylene oxide.The present invention is not limited to these tensio-active agents.These tensio-active agents can be used alone or in combination.
Be used for giving an example of emulsification of the present invention (C), comprise that also alcohol is as ethanol, methyl alcohol and propyl alcohol except water; Varsol such as benzene, toluene and hexane; With polar solvent such as N, dinethylformamide, N,N-dimethylacetamide, ethylene carbonate, propylene carbonate and furfural.On the other hand, can use mixture, when using aqueous mixture, preferably use the water that is no less than content 50wt% more than more than one media of enumerating.From viewpoint economic and safety, water is preferred use the in these media.When making water, the scope of pH value (hydrionic concentration) can drop in the scope of 1-13.
According to method of the present invention, lignocellulose can be by use organic isocyanate (A) with tackiness agent, reactive emulsifying agent (B), and emulsification (C) prepares.And then, can add releasing agent (D).
When component (D) is not used as component of tackiness agent, can advise after releasing agent is used for platen, finishing again compacting, binder composition and the like can not be deposited on the platen when sheet material hot pressing like this.Can use as releasing agent and to know.For example, all can be used as can enumerating of component of the present invention (D).When releasing agent joins in the tackiness agent, there is no need to use it for platen.
In the method for the invention, any releasing agent that can address the above problem all is fit to use.The example of preferred releasing agent (D) comprises metal-salt and the wax with the saturated of 8-28 carbon atom and/or unsaturated aliphatic carboxylic acid among the present invention.
About having the metal-salt of the saturated of 8-28 carbon atom and/or unsaturated aliphatic carboxylic acid, having arbitrary aliphatic carboxylic acid single, double and three functional group can use.Wherein, the linear aliphatic family monocarboxylic acid with 12-22 carbon atom is preferred.That object lesson comprises is sad, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, linolic acid, linolenic acid, eicosanoic acid, Lignoceric acid and docosoic acid.The example of metal component comprises zinc, iron, aluminium, calcium, zirconium, magnesium, barium, nickel, copper and cobalt.Be selected from the component of at least a acid in the above group of enumerating and the component of at least a metal respectively and can combine use.In other words, can be used alone or in combination the metal-salt of carboxylic acid, this salt is made up of a kind of acid constituents and a kind of metal component that is selected from the above preferred metal group that is selected from the above preferred carboxylic acid group.
The metal-salt with the saturated of 8-28 carbon atom and/or unsaturated aliphatic carboxylic acid as component (D) can be present in as in the tackiness agent of the present invention.It can be with the form adding of metal-salt or with the independently form adding of aliphatic carboxylic acid and metallic compound.
The example that is used as the wax of component (D) comprises gama wax, brazil wax, rice wax, Japan tallow, palm wax, beeswax, wool wax, spermaceti, montanin wax, ceresine, ceresin, paraffin, Vaseline, Fu-Tuo wax, polyethylene wax, modified waxes and hydrogenation wax, and the mixture between them.
The metal-salt with the saturated of 8-28 carbon atom and/or unsaturated aliphatic carboxylic acid as releasing agent (D) can join reactive emulsifying agent, polyethers and/or polyester polyol in reactive emulsifying agent (B), emulsification (C), any in the mixture of the water in the emulsification (C) and reactive emulsifying agent (B) and emulsification (C).Metal-salt with the saturated of 8-28 carbon atom and/or unsaturated aliphatic carboxylic acid can use with emulsified dose of emulsive form on demand.Here, any emulsifying agent commonly used can use.Object lesson comprises anion surfactant such as fatty acid soaps, rosined soap, alkylsulfonate, alkylbenzene sulfonate, two alkylaryl sulfonates, alkylthio Succinic Acid, polyoxyethylene alkylsulfonate and polyoxyethylene alkylbenzene sulfonate; Segmented copolymer with tensio-active agent such as polyethylene oxide alkyl ethers, polyoxyethylene alkyl phenylate, polyoxyethylene sorbitol fatty acid ester and ethylene oxide propylene oxide.The present invention is not limited to the above tensio-active agent of enumerating.These tensio-active agents can be used alone or in combination.
When releasing agent (D) dissolves in isocyanic ester as wax or analogue, can add it in first kind of liquid stream.Wax or analogue can use with emulsified dose of emulsive form, and can add it in second kind of liquid stream.
Below will set forth the of the present invention method of tackiness agent described above of using with a kind of tackiness agent of raw material preparing.
Fig. 1 and 2 is actually used in the synoptic diagram of the preparation facilities of tackiness agent of the present invention for explanation; Fig. 3 is the synoptic diagram of the preparation section of explanation tackiness agent of the present invention; Fig. 4 produces the synoptic diagram of medium density fibre board (MDF) with an example of device for explanation the present invention.
The preparation facilities of tackiness agent of the present invention (will be called " mixing device " later on) comprises the opening for feed of using as the organic isocyanate compound feeding of first kind of liquid stream 1 as shown in Figure 1; By reactive emulsifying agent, as polyethers and/or polyether glycol (B), and emulsification (C) and selectable releasing agent (D) be pre-mixed obtain mixture flow to the opening for feed 2 of material usefulness as second kind of liquid; Hybrid chamber 5; A cleaning rod 4 that is designed to fit like a glove and handles with hydraulic efficiency plant or pneumatics with hybrid chamber; Vacuum breaker 3; With nozzle 6.
In addition, be illustrated in figure 3 as attaching device for example first kind of liquid stream under high pressure be fed to high-pressure pump used in the hybrid chamber 20; Second kind of liquid stream under high pressure is fed to high-pressure pump used in the same chamber 19.The engine that the hydraulic efficiency plant of manipulation cleaning rod or pneumatics are used and the switchboard of engine provide but also can be used as attaching device not for example.
Hereinafter with reference to Fig. 1,2 and 3 describe the preparation method of tackiness agent of the present invention.Fig. 1 is actually used in the synoptic diagram of the preparation facilities of tackiness agent of the present invention for explanation, and is the cross-sectional view of hybrid chamber when the preparation tackiness agent; Fig. 2 is actually used in the synoptic diagram of the preparation facilities of tackiness agent of the present invention for explanation, and is the cross-sectional view of explanation hybrid chamber when cleaning; Fig. 3 is the synoptic diagram of the preparation section of explanation tackiness agent of the present invention; Fig. 4 is for producing the synoptic diagram of medium density fibre board (MDF) (MDF) with an example of device among explanation the present invention.
It below is the explanation that is used for the Ref. No. of figure.
1. the opening for feed of organic isocyanate compound
2. the opening for feed of reactive emulsifying agent and emulsification
3. vacuum breaker
4. cleaning rod
5. hybrid chamber
6. nozzle
11. the head tank of reactive emulsifying agent
12. the head tank of emulsification
13. the head tank of organic isocyanate compound
14. the gravitation tank of reactive emulsifying agent
15. the gravitation tank of emulsification
16. the mixing tank of reactive emulsifying agent and emulsification
17. the gravitation tank of the mixed platform thing of reactive emulsifying agent and emulsification
18. the gravitation tank of organic isocyanate compound
19. pressure pump
20. pressure pump
21. mixing device
30. feeder
31. pulp digester
32. refiner
33. gas blow pipe
34. first cyclone
35. air-lock
36. side-groove
37. mixer
38. second cyclone
39. fiber storage tank
40. building mortion
Use travelling belt 41. be shaped
42. precompressed
43. hot pressing
The schematic diagram of the mixing arrangement when Fig. 1 prepares adhesive for explanation. Described mixing arrangement is by the charging aperture 1 of organic isocyanate compound, charging aperture 2, check-valves 3, cleaning rod 4, hybrid chamber 5 and the nozzle 6 of reactive emulsifying agent and emulsification (as long as need also component (D)).
Organic isocyanate compound (A), is dosed in the mixing chamber 5 (hereinafter referred to as " hybrid chamber ") that mechanical washing device is housed then as the first liquid stream by the compression pump pressurization. By being pre-mixed reactive emulsifying agent, such as polyethers and/or PEPA (B), emulsification (C) and releasing agent (D) and the mixture that obtains, with another compression pump pressurization, then as the second liquid stream from charging aperture 2 chargings. First and second kinds of liquid streams that enter hybrid chamber under high pressure are mixed into the emulsification shape immediately, thereby obtain adhesive composition of the present invention. It is by nozzle 6 discharging/injections.
The expulsion pressure that enters the hybrid chamber of the present invention that mechanical washing device is housed preferably drops on 40-300Kgf/cm2Scope in. When expulsion pressure less than 40Kgf/cm2The time, be difficult for obtaining abundant mixing and emulsification. On the other hand, because at 300Kgf/cm2Expulsion pressure under can fully mix and emulsification, and surpass this value expulsion pressure can not mix and emulsification in bring better result, thereby industrial unhelpful, above 300Kgf/cm2Expulsion pressure be not preferred.
In injection apparatus of the present invention as shown in Figure 1, the cross section that the first and the second liquid flow to the used outlet of hybrid chamber is much narrower than hybrid chamber. For example, in No. four chambeies that Switzerland ISOTHERM AG produces, each cross section that the first and the second liquid flow to into the used outlet of hybrid chamber is 0.64mm3, and the cross section of hybrid chamber is 3.8m3 The pressure at the outlet nozzle place of hybrid chamber is normal pressure, can not reduce fully at hybrid chamber because of collision so be used for the pressure that the first and the second liquid flows to the pump of material, thereby the first liquid stream flows with the second liquid and mixes. Therefore the pressure that is ejected in the hybrid chamber of the present invention refers to that the first and the second liquid flow to the pressure summation of the pump of material usefulness.
Fig. 2 is the schematic diagram of explanation mixing arrangement when cleaning. When hybrid chamber cleans, when being the preparation end of adhesive, the cleaning rod 4 that is designed to fit like a glove with hybrid chamber is blocked the charging aperture of the first and the second liquid stream, thereby when stoping mixed occurrence, wipe the organic isocyanate polymerization product that is deposited on the hybrid chamber wall, clean thus the inside of hybrid chamber. For example hydraulic pressure or air pressure insert or take out bar 4 mechanically. When cleaning the inside of hybrid chamber 5, the pump that is used for the first and the second liquid stream can stop or be transformed under the low pressure and moves. Can in bar 4, dispose the circulation port of the first and the second liquid stream usefulness, and can when cleaning, improve circulation with pump. On the other hand, also can check-valves be received respectively in the nearby side of hybrid chamber on the first and the second liquid stream to prevent that when the raw material charging goes wrong a kind of liquid from can not enter into the pipe of another kind of liquid.
Adhesive can be furnished with in the barrel mixer of agitation means by the lignocellulosic sill is packed into, then when blender rotates adhesive is sprayed onto on the material; Perhaps allow the lignocellulosic sill with air blast or like thatly make it mobile, then adhesive is sprayed or be added drop-wise on the resulting lignocellulosic bundle, and be used for the lignocellulosic sill.
In per step operation, interpolation surfactant and/or stabilizing agent under the degree of the present invention can not damaged.
Mixed proportion about the relative organic isocyanate compound (A) of reactive emulsifying agent (B), preferably add 0.01-70 part weight based on per 100 weight portion organic isocyanate compounds (A), more preferably the component of 1-30 part weight (B). Quantity is not less than 0.01 weight portion makes the organic isocyanate compound have good dispersiveness, and when no more than 70 weight portion of quantity, gained sheet material has good physical property.
Mixed proportion about the relative emulsification (C) of reactive emulsifying agent (B) preferably adds 0.002-50 part weight based on per 100 weight portion emulsification (C), more preferably the component of 0.01-30 part weight (B). Because can find out the effect of adding reactive emulsifying agent, reactive emulsifying agent (B) that quantity is not less than 0.002 weight portion is preferred. The quantity that surpasses 50 parts of weight is not preferred, does not bring further improvement because add this quantity, thereby industrial unhelpful.
Mixed proportion about the relative organic isocyanate compound with emulsification (C) of reactive emulsifying agent (B) (A), preferably add 10-2000 part weight based on per 100 weight portion organic isocyanate compounds (A), more preferably the component of 30-800 part weight (B) and summation (C). When the total amount of (B)+(C) is not less than 10 weight portion, demonstrated the diluting effect of organic isocyanate compound (A). On the other hand, when total amount is not more than 2000 weight portion, can produce the heating platen with good physical.
In the present invention, can add component (D). During interpolation, based on per 100 weight portion organic isocyanate compounds (A), when component (D) is saturated and/or adds 1-100 part during the slaine of unsaturated aliphatic carboxylic acid, and the releasing agent (D) that adds 1-150 part when being wax. Quantity is not less than 1 weight portion can bring improvement at stripping result, and the quantity that surpasses 150 weight portions industrial be unhelpful because the just fully demoulding when 150 weight portion.
Mixed proportion about the relative organic isocyanate compound of reactive emulsifying agent (A) that formed by reactive emulsifying agent (B) and releasing agent (D) and emulsification (C), based on per 100 weight portion organic isocyanate compounds (A), preferred 10-500 part weight, the more preferably summation of the component of 30-300 part weight (B)+(C)+(D) of adding. As component (B), when total amount (C) and (D) is not less than 10 weight portion, the diluting effect of organic isocyanate compound (A) has appearred. When total amount is not more than 500 weight portion, can produce the heating platen with good physical.
In above-mentioned per step operation, interpolation surfactant and/or stabilizing agent under the degree of the present invention can not damaged.
Mixed proportion about the relative emulsification of reactive emulsifying agent (C) that formed by polyethers and/or PEPA (B) and releasing agent (D), preferably add 0.002-50 part weight based on per 100 weight portion emulsification (C), more preferably the summation of reactive emulsifying agent (B)+(D) of 0.01-30 part weight. When the quantity of reactive emulsifying agent (B) was not less than 0.002 weight portion, the effect of adding reactive emulsifying agent had occurred. The quantity that surpasses 50 weight portions is not preferred because this quantity can not be brought further improvement, thereby industrial be unhelpful.
The quantity of lignocellulosic sill and adhesive is with the physical property of the water content of lignocellulosic sill and expectation and different. Can realize that adhesive mixed uniformly quantity in the lignocellulosic sill all can adopt. The content of adhesive is preferably the 1-30wt% based on per 100 parts of absolute lignocellulosic sills in weighing.
When the content of adhesive was no less than 1wt%, adhesive can work. Because sheet material has sufficient physical property when the content of adhesive is 30wt%, it is not preferred using the adhesive that surpasses 30wt% because this industrial be unhelpful.
Producing by the present invention in the method for lignocellulosic pressboard, the mixture of lignocellulosic sill and adhesive will stand hot pressing after shaping. This mixture can be configured as individual layer or composite bed. The quantity of adhesive can change as required. If necessary, can be in stacked rear precompressed; Or the precompressed bed course is folded.
At this moment, adhesive of the present invention can be used for the skin of next-door neighbour's platen, be used for internal layer and will break away from the slightly poor another kind of adhesive of performance, thereby form a kind of sandwich construction.
In order to allow heat import in the material that will suppress, both can also can hot pressing between the curved surface platen at smooth platen. From continuous production and viewpoint cheaply, the compacting between smooth platen is preferred. Hot pressing can be finished by the mode of continuous or multistep.
After the hot pressing, the outermost surface of plate will be ground to required thickness.
The process units of medium density fibre board (MDF) as shown in Figure 4 is the example that the inventive method realizes industrial applications. As shown in Figure 4, wood piece, for example, wood chip is admitted in the boiling vessel softening, and wooden destroyed in the wood chip. Then the wood chip of gained is sent in the conche, wherein wood chip for example decomposes the fibroblast dimension at disk when a direction or both direction rotate.
The fiber of the humidity of heat is sent in the blender by a so-called air blowing pipeline. In the air blowing pipeline, do not add adhesive, add reactive emulsifying agent such as screening agent or fire retardant. Adhesive then adds between air blowing pipeline and burner, for example the position of Fig. 4 arrow indication. Also can in the air blowing pipeline, drip or spray adhesive of the present invention, then wood fibre and adhesive be mixed. Owing to following reason, this adhesive that is comprised of water-based emulsion by method preparation of the present invention is fit to spray by the air blowing pipeline. At first, the fiber of humidity that has been heated to the heat of a specified temp has improved the temperature that adds the water-based emulsion of adhesive composition, can regulate like this water content in the wood fibre that has coated adhesive. The second, wood fibre has been wiped the adhesive that is deposited on the air blowing channel wall in the huge turbulent flow of air blowing pipeline, thus the cleaning of the pipeline inside that can keep blowing. The 3rd, because flow velocity is large in the air blowing pipeline, need not changes many times mixing and can obtain even coating.
The fiber that flows through the air blowing pipeline will stand partial dehydration. In order after dehydration, fiber to be separated, the first cyclone cluster and air-lock have been installed from air-flow. Then fiber enters batch mixer. Adhesive and auxiliary agent such as releasing agent, fire retardant and screening agent can be packed in the batch mixer and fiber mixes. Have one to carry out churned mechanically agitation means in rotation in batch mixer, adhesive and auxiliary agent spray and obviously can obtain to mix with the even of fiber downwards or from suitable direction. After adding required reactive emulsifying agent, this fiber enters in second cyclone that air-lock is housed by a side-groove and then sends into the used storage tank of fiber that adhesive coats.
The used storage tank of the fiber that adhesive coats is sent into fiber at least in a fiber that adhesive is coated is made the building mortion of pad. The pad of making is like this suppressed by a prepressing device at first at least, then by a hot-press arrangement it is hot pressed into final thickness. At this moment adhesive solidifies because of heat, produces required sheet material. If necessary, this plate can be through surface grinding to adjust thickness and surface appearance.
The example of the mixing arrangement with a hybrid chamber that concrete production adhesive is used comprises Switzerland ISOTHERM AG, U.S. GASMER, GLASS-CLAFT and CLAUS MUFFI, the mixing arrangement that CANON and ToHo machine Co., Ltd produce. Any all being fit to of more than enumerating, use.
In the present invention, can expect and be combined with antioxidant, ultra-violet absorber, fire retardant, stabilizing agent, surfactant, plasticizer, silane coupler, polyvinyl alcohol, metallic catalyst, external release agent, synthetic rubber latex and/or acrylic emulsion in the scope of advantage not damaging the present invention.
Embodiment
Below will do more detailed description to the present invention by embodiment.Yet should keep the present invention firmly in mind and be not limited to or be limited at these embodiment.In an embodiment, showed with wood fibre producd fibers plate, but can use example of the present invention with other lignocellulose sill easily produces various sheet materials.Unless specifically indicate, all titles " part " or " umber " and " % " are meant weight part or parts by weight and weight percentage.
The condition identical with the production that is used for Comparative Examples sheet material is expressed as follows:
Raw material: pulverized dirt or wood fibre (water content: 7.0%, be called wood chip later on)
The composition of sheet material: individual layer (pulverized dirt) or three layers (wood fibre)
The thickness of sheet material (part that removal grinds away): 15mm
The water content of pad: 16%.
Hot pressing temperature: 180 ℃
Pressing pressure: 35Kg/cm
2
Press time: 2.5 minutes
Prefabricated density: 700Kg/m
3
The assessment test
1. transverse strength
To suppress sample be cut into the wide and 275mm of 50mm long (span: batten 225mm), carry out the anti-crawl agentdefiection test with reference to " testing method of shaving board " among the JIS-A-5908 then.The result of transverse strength shows in table.
2. the transverse strength under the humidity (test A)
The same with above method, will suppress sample and be cut into batten.Then batten was immersed in 70 ± 3 ℃ the hot water 2 hours, and soaked 1 hour in the water at normal temperatures again.Carry out the anti-crawl agentdefiection test with not dried batten.The gained result shows as wet transverse strength (A) in table.
3. dispersed assessment
Get a part in order to the tackiness agent of top method preparation do sample then with visual observation MDI to assess its dispersing property.
4. stripping strength
Stripping strength is tested with reference to the method for explanation among JIS A 5905 and the MISA 5908.
5. to the assessment of operate continuously
Continuous production sheet material 50 hours is deposited on the raw material of producing the tackiness agent in the pipeline and being deposited on the polishing plate with visual observation then and assesses.
6. comprehensive evaluation
Productivity and physicals to sheet material are assessed.In every assessment, be judged as good sheet material and be decided to be the A level, and at least in one not satisfied sheet material be decided to be the B level.
Embodiment 1
At first, will be as polymeric MDI (A) (" Cosmonate M-200 ", the trade(brand)name of first kind of liquid stream; The product of Mitsui chemical company); With initiator quadrol (EDA) as second kind of liquid stream, the segmented copolymer of the propylene oxide/oxyethane (content of oxyethane: 40%, hydroxyl value: 252mgKOH/g), the emulsification that is dissolved in the water (C) concentration is that (non-volatile matter: 31%) soluble in water is the mixture that 8% solution is formed with solid content meter concentration, at 100Kgf/cm for the water-based emulsion of 20% solution and Zinic stearas
2Pressure under pack into one and have spray gun (" SP-300 rifle ", trade(brand)name; The product of ISOTHERM AG; Has an aperture that first and second kinds of liquid streams is ejected into the 0.45mm in the hybrid chamber; Dispose a diameter and be 1.1mm No. four hybrid chambers) the chamber in.When stirring then, the mixture with gained in a mixing tank sprays on the wood fibre of pulverizing.The flowing fluid ratio that first liquid stream and second kind of liquid flow is 8: 12 and the total amount of polymeric MDI and polyvalent alcohol is 6% of a timber over-dry weight.The fiber that tackiness agent is applied is shaped on a polishing steel plate then, precompressed subsequently 30 seconds, and sheet metal thickness will be 500% of plate product thickness like this.Prefabricating plate will carry out hot pressing under above-mentioned condition then.
After the hot pressing, the adhesion situation is not found settling on the observation polishing steel plate.To carry out the comparison and the assessment of physicals with reference to the appraisal procedure of explanation among the JIS A 5905 (fiber) through hot pressed sheet material.Its physicals is as shown in table 1 as a result is no more than No. 30 and (refers to that this plate is not less than 30N/mm in the transverse strength of length direction and cross-sectional direction
2, this is the JIS standard of assessment physicals).Use same polishing plate to repeat above operation.Even repeat 50 times, do not observe the settling on the polishing steel plate yet.
In addition, at per 10 minutes by operate continuously when in mixing device, inserting or taking out cleaning rod and clean 50 hours with spray gun.After 50 hours, both in hybrid chamber, also in jet pipe, observed the settling of the polymerization product that polymeric MDI and water and the like formation is arranged.Approximately needed clean for 1 second.Needn't when cleaning hybrid chamber, allow the entire job line stop, and this have brought good productivity.
Except used hydroxyl groups number becomes 447mgKOH/g, according to producing sheet material with embodiment 1 identical method.As shown in table 1, the physicals of sheet material and productivity are all good.
Embodiment 3
The initiator of using except polyvalent alcohol become ortho-toluene diamine (ODT) (content of oxyethane: 40%, hydroxyl value: 447mgKOH/g), according to producing sheet material with embodiment 1 identical method.As shown in table 1, the physicals of gained sheet material and productivity are all good.
Embodiment 4
The initiator of using except polyvalent alcohol become ortho-toluene diamine/glycerol (G) (mol ratio: 5: 1) (content of oxyethane: 50%, hydroxyl value: 452mgKOH/g), according to producing sheet material with embodiment 1 identical method.As shown in table 1, the physicals of gained sheet material and productivity are all good.
Embodiment 5
The initiator of using except polyvalent alcohol become toluylenediamine (MTD) (content of oxyethane: 40%, hydroxyl value: 255mgKOH/g), according to producing sheet material with embodiment 1 identical method.As shown in table 1, the physicals of gained sheet material and productivity are all good.
The initiator of using except polyvalent alcohol becomes 4,4, and-ditan diamines (MDA) (content of oxyethane: 40%, hydroxyl value: 452mgKOH/g), according to producing sheet material with embodiment 1 identical method.As shown in table 1, the physicals of gained sheet material and productivity are all good.
Embodiment 7
Except with glycerol (the G) (content of oxyethane: 40%, hydroxyl value: 56mgKOH/g) as the initiator of polyvalent alcohol, the concentration of reactive emulsifying agent is decided to be 5%, the urethanum of in the urethanum field, the knowing/urea production catalyzer azo bicyclooctane that adds 0.005% quantity, and the flowing fluid ratio of first liquid stream and second kind of liquid stream is decided to be 1: 1, according to the identical method production sheet material of embodiment 1.As shown in table 1, the physicals of gained sheet material and productivity are all good.
Embodiment 8
Except pulverized dirt is used as the lignocellulose sill, according to making sheet material with embodiment 1 identical method.The sheet material of making like this has good physicals, (refers to that this number plate is not less than 18N/mm in the transverse strength of length direction and cross-sectional direction No. 18 that equal at least among the JIS-A-5908
2, this is the JIS evaluation criteria about physicals); And simultaneously, it has good productivity.
Embodiment 9
Make releasing agent component (D) without Zinic stearas during except the preparation tackiness agent and when compacting, on polishing plate, coat a kind of fluorine-based external release agent (" mould cover W-833 ", trade(brand)name; The product of Asahi Glass Co., Ltd.), according to making sheet material with embodiment 1 identical method.As shown in table 1, the sheet material of making like this has good physicals and productivity.
Embodiment 10
Except using " polyethylene wax 220MP " place of magnesium stearate zinc to make releasing agent, according to making sheet material with embodiment 1 identical method.As shown in table 1, the sheet material of making like this has good physicals and productivity.
Comparative Examples 1
Except in being equipped with the mixing tank of stirring parts, mix in batches with the preparation tackiness agent, according to preparing tackiness agent and produce sheet material with it with embodiment 1 identical method.As shown in table 1, the sheet material of making like this has good physicals and productivity.
Need 5 hours ability to use up tackiness agent in the mixing tank fully.Greatly about producing back 15 minutes, yet the sheet material that makes like this has the good physicals that can reduce later on.After producing 5 hours, polyureas, promptly the reaction product of MDI and water is deposited on the inside of mixing tank, at this moment needs to end board materials production and cleans.
Comparative Examples 2
Except in the static mixing jar, first and second kinds of liquid streams being mixed with the preparation tackiness agent, according to preparing tackiness agent and produce sheet material with it with embodiment 1 identical method.As the sampling of a part of tackiness agent that obtains like this and the result of visual observation, find to still have not emulsive MDI so emulsifying property insufficient.Behind the continuous production 5 hours, polyureas, promptly the reaction product of MDI and water is deposited on the inside of static mixing jar, at this moment needs to end board materials production and cleans.
Comparative Examples 3
Except the spraying pressure that will enter hybrid chamber when preparing tackiness agent is decided to be 30Kgf/cm
2, according to preparing tackiness agent and produce sheet material with it with embodiment 1 identical method.As the sampling of a part of tackiness agent that obtains like this and the result of visual observation, find to still have not emulsive MDI so emulsifying property insufficient.In addition, the sheet material physicals that obtains like this is low.
Comparative Examples 4
Except the spraying pressure that will enter hybrid chamber when preparing tackiness agent is decided to be 30Kgf/cm
2, according to preparing tackiness agent and produce sheet material with it with embodiment 8 identical methods.As the sampling of a part of tackiness agent that obtains like this and the result of visual observation, find to still have not emulsive MDI so emulsifying property insufficient.In addition, the sheet material physicals that obtains like this is low.
Obviously as described above, method of the present invention can avoid the polymer deposition of organic isocyanate in mixing tank and pipeline when the preparation isocyanate adhesive.Simultaneously, provide a kind of can be during tackiness agent in preparation owing to pipe blocking does not cause circuit failure, and be fit to the industrial quantity-produced best approach.Method of the present invention provides a kind of tackiness agent that has good detachment when hot pressing, so this method is fit to industrial production high quality and the cheap lignocellulose presspahn with good productivity.Table 1
* has used external release agent
| Ligno-cellulosic materials | The organic isocyanate compound | Reactive emulsifier | Dispersion medium | Releasing agent | Blending means | Blend pressure Kgf/cm 2 | The dispersed evaluation | Clean | The physicals N/mm of sheet material 2 | Continuity test | Comprehensive assessment | |||
| Do transverse strength | Wet transverse strength (A) | Stripping strength | ||||||||||||
| Embodiment 1 | Wood fibre | Polymeric MDI | EDA base PPG | Water | Zinic stearas | Collision type mixes | 100 | Good | 1 time/10 minutes | 42.0 | 23.0 | 1.2 | Good | A |
| Embodiment 2 | Wood fibre | Polymeric MDI | EDA base PPG | Water | Zinic stearas | Collision type mixes | 100 | Good | 1 time/10 minutes | 41.0 | 22.0 | 1.3 | Good | A |
| Embodiment 3 | Wood fibre | Polymeric MDI | OTG base PPG | Water | Zinic stearas | Collision type mixes | 100 | Good | 1 time/10 minutes | 39.0 | 23.0 | 1.4 | Good | A |
| Embodiment 4 | Wood fibre | Polymeric MDI | OTD/G PPG | Water | Zinic stearas | Collision type mixes | 100 | Good | 1 time/10 minutes | 38.0 | 20.0 | 0.9 | Good | A |
| Embodiment 5 | Wood fibre | Polymeric MDI | MTD base PPG | Water | Zinic stearas | Collision type mixes | 100 | Good | 1 time/10 minutes | 41.0 | 21.0 | 1.1 | Good | A |
| Embodiment 6 | Wood fibre | Polymeric MDI | MDA base PPG | Water | Zinic stearas | Collision type mixes | 100 | Good | 1 time/10 minutes | 25.0 | 17.0 | 0.8 | Good | A |
| Embodiment 7 | Wood fibre | Polymeric MDI | G PPG+ catalyzer | Water | Zinic stearas | Collision type mixes | 100 | Good | 1 time/10 minutes | 42.0 | 23.0 | 1.2 | Good | A |
| Embodiment 8 | Pulverized dirt | Polymeric MDI | EDA base PPG | Water | Zinic stearas | Collision type mixes | 100 | Good | 1 time/10 minutes | 42.0 | 23.0 | 1.2 | Good | A |
| Embodiment 9 | Wood fibre | Polymeric MDI | EDA base PPG | Water | ** | Collision type mixes | 100 | Good | 1 time/10 minutes | 43.0 | 21.0 | 1.3 | Good | A |
| Embodiment 10 | Wood fibre | Polymeric MDI | EDA base PPG | Water | Polyethylene wax | The collision mixture | 100 | Good | 1 time/10 minutes | 44.0 | 21.0 | 1.4 | Good | A |
| Comparative Examples 1 | Wood fibre | Polymeric MDI | EDA base PPG | Water | Zinic stearas | Batch-mixed | Normal pressure | Good | 1 time/5 hours | 37.0 | 17.0 | 0.7 | Difference | B |
| Comparative Examples 2 | Wood fibre | Polymeric MDI | EDA base PPG | Water | Zinic stearas | Static mixer | 1 | Difference | 1 time/5 hours | 31.0 | 14.0 | 0.6 | Difference | B |
| Comparative Examples 3 | Wood fibre | Polymeric MDI | EDA base PPG | Water | Zinic stearas | Collision type mixes | 30 | Difference | 1 time/10 minutes | 25.0 | 13 0 | 0.4 | Good | B |
| Comparative Examples 4 | Pulverized dirt | Polymeric MDI | EDA base PPG | Water | Zinic stearas | Collision type mixes | 30 | Difference | 1 time/10 minutes | 17.0 | 11.0 | 0.4 | Good | B |
Claims (14)
1. a lignocellulose presspahn is with the preparation method of tackiness agent, described tackiness agent comprises a kind of organic isocyanate compound of 100 weight parts (A), 0.01-70 (B) of weight part a kind of to comprise reactive emulsifying agent of at least a polyethers and/or polyester polyol and (C) a kind of emulsification, this method comprises first kind of liquid stream being made up of described organic isocyanate compound (A) of 100 weight parts and second kind of liquid being made up of described reactive emulsifying agent (B) and described emulsification (C) of 10-2000 weight part is flowed at high pressure 40-300Kg/cm
2Under be ejected in the hybrid chamber, then described liquid stream is mixed.
2. the method for claim 1 wherein also is included in described first kind or second kind of liquid stream and adds releasing agent (D).
3. method as claimed in claim 1 or 2, wherein said hybrid chamber is furnished with mechanical washing unit.
4. method as claimed in claim 3, the bar that inserts in hybrid chamber and take out that wherein said mechanical washing unit coincide by a mechanically operated inside complete and described hybrid chamber cleans the inwall of described hybrid chamber.
5. method as claimed in claim 4, wherein said emulsification (C) is for water or comprise water at least.
6. the method for claim 1, wherein said reactive emulsifying agent (B) comprises a kind of polyethers and/or polyester polyol at least; Described polyethers and/or polyester polyol have 2-8 functional group and repeating unit (CH
2-CH
2-O), repeating unit (CH
2-CH
2-amount O) accounts for the 5-70% of polyethers and/or polyester polyol weight; And the ratio of described polyethers and/or polyester polyol is that per 100 parts of weight organic isocyanate compounds (A) are the 0.01-70 parts by weight.
7. the method for claim 1, wherein said reactive emulsifying agent (B) comprises a kind of polyethers and/or polyester polyol at least; Comprise a nitrogen-atoms in described polyethers and/or the polyester polyol molecule; The ratio of described nitrogen-atoms is the 0.1-12.0% based on polyethers and/or polyester polyol.
8. method as claimed in claim 6, wherein said polyether glycol prepares by add alkylene oxide at least a compound that is selected from trolamine, diethanolamine, monoethanolamine, ortho-toluene diamine, toluylenediamine, ditan diamines and polyphenyl polymethylene polyamines; And in the described alkylene oxide, the quantity of oxyethane is for being the 5-70 parts by weight based on per 100 parts of described polyether glycol weight.
9. as claim 2 and each described method of 4-8, wherein said releasing agent (D) is at least a material and the wax that is selected from the metal-salt with the saturated of 8-28 carbon atom and/or unsaturated aliphatic carboxylic acid.
10. method as claimed in claim 9, the metal-salt of the saturated and/or unsaturated aliphatic carboxylic acid of the wherein said 8-28 of a having carbon atom are at least a combination that is selected from a kind of material in the group that comprises sad, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid and docosoic acid and is selected from the another kind of material in the group that comprises zinc, iron, aluminium, calcium, zirconium, magnesium, barium, nickel, copper and cobalt.
11. method as claimed in claim 10, the amount that wherein said releasing agent (D) adds is that the described organic isocyanate compounds of per 100 weight parts (A) are the 1-150 parts by weight.
12. method as claimed in claim 11, wherein said organic isocyanate compound (A) is the polymethylene polyphenyl polymeric polyisocyanate.
13. a method of producing the lignocellulose presspahn comprises each described lignocellulose presspahn among lignocellulose sill and the claim 1-11 is mixed with tackiness agent, makes pad with resulting mixture, will fill up hot pressing then.
14. lignocellulose presspahn that method as claimed in claim 13 is made.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37849/97 | 1997-02-21 | ||
| JP37848/97 | 1997-02-21 | ||
| JP3784897 | 1997-02-21 | ||
| JP3784997 | 1997-02-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1196374A CN1196374A (en) | 1998-10-21 |
| CN1090218C true CN1090218C (en) | 2002-09-04 |
Family
ID=26377006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98107065A Expired - Lifetime CN1090218C (en) | 1997-02-21 | 1998-02-21 | Preparation processes of adhesive for lignocellulose and lignocellulose pressed board |
Country Status (6)
| Country | Link |
|---|---|
| KR (1) | KR100258821B1 (en) |
| CN (1) | CN1090218C (en) |
| ID (1) | ID19930A (en) |
| MY (1) | MY135306A (en) |
| NZ (1) | NZ329794A (en) |
| TW (1) | TW473529B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091019C (en) * | 1999-01-22 | 2002-09-18 | 南京林业大学 | Method for producing wheat straw flakeboard |
| JP4632166B2 (en) * | 2001-01-31 | 2011-02-16 | 日本ポリウレタン工業株式会社 | Adhesive composition for lignocellulosic hot-press molded body and method for producing hot-press molded body using the same |
| KR100391247B1 (en) * | 2001-06-01 | 2003-07-12 | 금호미쓰이화학 주식회사 | Binder for molding board of lignocellulose |
| CN101827910B (en) * | 2007-08-31 | 2013-04-17 | 三井化学株式会社 | Mold release agent composition for thermocompression molding and process for producing board |
| US20110027534A1 (en) * | 2008-03-14 | 2011-02-03 | Masanori Ogawa | Mold release sheet and molded articles |
| CN114653563B (en) * | 2022-02-11 | 2023-04-14 | 北新国际木业有限公司 | Surface flame-retardant treatment method for OSB (oriented strand board) and flame-retardant OSB |
| CN115141343B (en) * | 2022-09-05 | 2023-01-13 | 万华化学集团股份有限公司 | Composition, adhesive composition material thereof, aldehyde-free artificial board and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54131696A (en) * | 1978-03-29 | 1979-10-12 | Ici Ltd | Water emulisible isocyanate composition and production of sheet and formed product |
| GB2075038A (en) * | 1980-05-02 | 1981-11-11 | Ici Ltd | Isocyanate-containing emulsions and their use in a process for manufacturing sheets or moulded bodies |
| JPH04372685A (en) * | 1991-06-21 | 1992-12-25 | Koyo Sangyo Kk | Adhesive and bonding method |
| CN1127003A (en) * | 1993-07-14 | 1996-07-17 | 帝国化学工业公司 | Polyisocyanate composition |
| CN1138613A (en) * | 1995-06-21 | 1996-12-25 | 光洋产业株式会社 | Adhesive for air-permeable adherend |
-
1998
- 1998-02-18 NZ NZ329794A patent/NZ329794A/en unknown
- 1998-02-18 MY MYPI98000669A patent/MY135306A/en unknown
- 1998-02-20 TW TW087102394A patent/TW473529B/en not_active IP Right Cessation
- 1998-02-20 KR KR1019980005355A patent/KR100258821B1/en not_active IP Right Cessation
- 1998-02-21 CN CN98107065A patent/CN1090218C/en not_active Expired - Lifetime
- 1998-02-23 ID IDP980252A patent/ID19930A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54131696A (en) * | 1978-03-29 | 1979-10-12 | Ici Ltd | Water emulisible isocyanate composition and production of sheet and formed product |
| GB2075038A (en) * | 1980-05-02 | 1981-11-11 | Ici Ltd | Isocyanate-containing emulsions and their use in a process for manufacturing sheets or moulded bodies |
| JPH04372685A (en) * | 1991-06-21 | 1992-12-25 | Koyo Sangyo Kk | Adhesive and bonding method |
| CN1127003A (en) * | 1993-07-14 | 1996-07-17 | 帝国化学工业公司 | Polyisocyanate composition |
| CN1138613A (en) * | 1995-06-21 | 1996-12-25 | 光洋产业株式会社 | Adhesive for air-permeable adherend |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100258821B1 (en) | 2000-06-15 |
| ID19930A (en) | 1998-08-27 |
| KR19980071561A (en) | 1998-10-26 |
| CN1196374A (en) | 1998-10-21 |
| MY135306A (en) | 2008-03-31 |
| TW473529B (en) | 2002-01-21 |
| AU695177B1 (en) | 1998-08-06 |
| NZ329794A (en) | 1999-01-28 |
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Effective date of registration: 20160415 Address after: 1-5-2, East Xinqiao, Tokyo, Japan Patentee after: MITSU CHEMICALS INC. Address before: Tokyo, Japan, Japan Patentee before: Mitsui Chemical Industry Co., Ltd. |
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Granted publication date: 20020904 |
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