CN1104482C - Adhesive for lignocellulose forming board and its manufacturing method - Google Patents
Adhesive for lignocellulose forming board and its manufacturing method Download PDFInfo
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- CN1104482C CN1104482C CN97116939A CN97116939A CN1104482C CN 1104482 C CN1104482 C CN 1104482C CN 97116939 A CN97116939 A CN 97116939A CN 97116939 A CN97116939 A CN 97116939A CN 1104482 C CN1104482 C CN 1104482C
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- binding agent
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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
- C09J175/08—Polyurethanes from polyethers
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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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
-
- 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
- C09J2401/00—Presence of cellulose
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
In a process for producing a board by using an isocyanate adhesive according to the present invention, a stable emulsion can be obtained by using an polether polyol, which has been obtained by the addition of an alkylene oxide to an amine compound, or a polyester polyol contained in its molecule a nitrogen compound upon emulsification of an organic polyisocyanate in water.The use of the aqueous emulsion so obtained or the aqueous emulsion further containing a metallic salt of an aliphatic carboxylic acid having 2 to 28 carbon atoms as an adhesive, particularly, as an adhesive for a lignocellulose material brings about an improvement in the physical properties .
Description
The present invention relates to binding agent, particularly relate to binding agent and the manufacture method thereof used as the thermal pressing moulded board of main raw material with lignocellulose.
Use is with the moulding product of lignocellulose as main raw material, be called particle board in the wooden occasion of chipping of lignocellulose, except that particle board, at the slicer board that uses full length film, make strip (fibrous bundle) be called heat-insulating shield, middle proportion fiberboard (MDF), hardboard, produce these moulding product and use with component materials as flooring board, wall material, door material, sound-proof material, lagging material, matting material, furniture material, automobile along the orientation fibers bundle plate (OSB) of a direction arrangement, the occasion of wood fibre (cellulosic).
In the past, be used to make the binding agent or the tackiness agent of jowar stem plate that rice husk plate that fiberboard such as particle board, slicer board, OSB, hardboard, MDF and heat-insulating shield and moulding rice husk constitute and moulding jowar stem constitute etc. (below be called plate), being extensive use of is heat cured urea resin, melmac, urea melmac, phenolic aldehyde melmac, resol etc. (below be called the diaion binding agent).
These resins are cheap, have cohesiveness good, with short period solidified characteristic.But the formaldehyde that the goods after these diaion binding agents hot-forming are emitted is considered as problem on environment, though proposed to be used to reduce the improvement of formaldehyde discharging amount, also insufficient.
And on the other hand, as non-formaldehyde system and give the binding agent of good plate rerum natura, also propose to be used for the isocyanate-based binding agent (No. 131538/1982, patent disclosure, No. 147567/1982, patent disclosure, United States Patent (USP) No. 3557263, No. 3636199, No. 3870665, No. 3919017, No. 3930110 specification sheetss etc.) of plate.
But, as lignocellulose based material binding agent, use organic polymeric polyisocyanate, in hot-forming occasion, because its good cohesiveness, and produce this binding agent attached on the heat dish.Because adhering to of this binding agent, forming composition sustains damage, and significantly loss is as the value of commodity.In addition, also spending a large amount of labours from heat dish removal dirt settling.
In order to address these problems, also carrying out for improving, to the Study on Additive of organic polymeric polyisocyanate interpolation from the release property of the metal of heat dish.For example, propose the alkylphosphonic that adds to organic polymeric polyisocyanate or pyrophosphate salt (No. 018068/1989, patent announcement), sulfonated compound (patent is announced No. 038309/1991), wax and liquid ester (patent is announced No. 054390/1990), aliphatic carboxylic acid (No. 36430/1983, patent disclosure), polysiloxane compound (No. 86205/1986, patent disclosure), fatty acid polymer (No. 4772442, No. 4933232 each specification sheetss of United States Patent (USP)) etc., but also do not obtained effect of sufficient.
In addition, additive method has been proposed in the method for the direct release agent application of thermotropism dish before the hot pressing.For example, the release layer (No. 34026/1996, patent announcement) that form to use metallic soap is arranged, use high boiling polyol (No. 1653178 specification sheetss of German Patent), use polysiloxane film (No. 135992 specification sheetss of English Patent), utilize the lining (No. 4374791 specification sheetss of United States Patent (USP)) of tetrafluoroethylene etc. with functional group, but all insufficient.
Therefore, a part of plate factory also adopts in forming several layers of plate during fabrication, and only using organic polymeric polyisocyanate in the interior layer that does not contact the heat dish is binding agent, and the manufacture method of the upper layer that contact with heat dish use diaion in the past.
In addition, being disclosed in plate is in the binding agent with MDI, and with the method (No. 30306/1985, patent disclosure, No. 34026/1996, patent disclosure, No. 78049/1997, patent disclosure) of aliphatic carboxylic acid metal-salt, but, the shortcoming that the poor stability of adhesive composition and press time can not lack is arranged respectively, for purpose of the present invention, still can not become sufficient solution.
But, above-mentioned any method all exists the solvabilities in organic polymeric polyisocyanate such as aliphatic carboxylic acid metal-salt and wax, alkylphosphonic, polysiloxane low separately, variety of issues such as release property difference, the not anti-actual on-the-spot use of making, at present, on the engineering, economically, all unsatisfied technology on the rerum natura.
The problem that the present invention wants to solve provides novel binding agent, especially solve on the unappeasable engineering of previous methods, problem physically, even using organic polymeric polyisocyanate is binding agent, also can the non-cohesive hot method of coiling, making high-quality plate at an easy rate.
The inventor has carried out research with keen determination in order to solve the above problems, and the result finds relevant binding agent of the present invention, particularly with the heating platen binding agent of lignocellulose as main raw material, and uses the heating platen of this binding agent and their manufacture method.
The present invention is by using the polyvalent alcohol that contains from the nitrogen-atoms of amine compound residue in the molecule of polyether glycol and/or polyester polyol, not only can regulate the reactivity of adhesive composition, and when using as internal mold release with specific saturated or metallic salts of unsaturated carboxylate, the favorable dispersity of internal mold release, and energy conditioned reaction, release property becomes good with multiplying each other more, find that thus this binding agent is the adhering to of heat dish during with the undirected hot pressing of a spot of internal mold release compacting, the heating platen binding agent that productivity is good, thus the present invention finished.
The inventor has carried out research with keen determination in order to solve above-mentioned problem, thereby has finished the present invention.The invention reside in provides
(a) binding agent, it is characterized in that, it comprises water-in-oil emulsion, described water-in-oil emulsion contains organic polymeric polyisocyanate based compound (A) and polyether glycol and/or polyester polyol (B), with respect to 100 parts by weight (A), (B) be 1～70 parts by weight, the hydroxyl valency of this polyether glycol and/or polyester polyol is 24～800mgKOH/g, is the amino polyol that contains nitrogen compound in the molecule.
And then, the present invention includes the invention and the embodiment of following (b)～(e).
(b) (a) in the record binding agent, it is characterized in that, this polyether glycol is that alkylene oxide is added in select from trolamine, diethanolamine, Monoethanolamine MEA BASF, ortho-toluene diamine, toluylenediamine, ditan diamines, polyphenyl polymethylene polyamines at least a or more than one the compound, with respect to the weight of polyether glycol, the addition content of the oxyethane in this alkylene oxide is 5～70 parts by weight.
(c) (a) or (b) binding agent of record is characterized in that organic isocyanate based compound (A) is a polymethylene polyphenyl base polymeric polyisocyanate.
(d) (a) binding agent of putting down in writing in～(c) each, it is characterized in that the ratio of the nitrogen-atoms in polyether glycol and/or the polyester polyol (B) is 0.1～12.0% all (weight), sense radix (B) is 2～8, with respect to the weight of (B), (CH in its structure
2CH
2-O-) repeating unit is 5～70%.
(e) (a) binding agent of putting down in writing in～(d) each, it is characterized in that, contain organic isocyanate based compound (A), polyether glycol and/or polyester polyol (B) and have the saturated of 8～28 carbon atoms and/or unsaturated aliphatic carboxylic metallic salt (C), wherein, with respect to 100 parts by weight (A), (B) be 1～70 parts by weight,, (C) be 1～150 parts by weight with respect to 100 parts by weight (B).
(f) (e) binding agent of record is characterized in that having the saturated of 8～28 carbon atoms and/or unsaturated aliphatic carboxylic metallic salt (C) is an aqueous emulsion.
(g) (a) binding agent of putting down in writing in～(f) each is characterized in that, this binding agent is the lignocellulose binding agent.
The manufacture method of the binding agent of putting down in writing in (h) (a)～(g) each is characterized in that, binding agent is with water, organic isocyanate based compound (A) and polyether glycol and/or polyester polyol (B) emulsification.
(i) (h) manufacture method of binding agent of record is characterized in that, binding agent so that with have the saturated of 8～28 carbon atoms and/or unsaturated aliphatic carboxylic metallic salt (C) mixes.
(j) manufacture method of lignocellulose profiled sheeting is characterized in that, the binding agent put down in writing in each of (a)～(f) with after ligno-cellulosic materials mixes, is carried out the hot pressing compacting and obtains.
(k) the lignocellulose profiled sheeting that adopts the manufacture method of the lignocellulose profiled sheeting of (j) to obtain.
(1) (a) the lignocellulose profiled sheeting binding agent of putting down in writing in～(f) each, it is characterized in that, have the saturated of 8～28 carbon atoms and/or unsaturated aliphatic carboxylic metallic salt (C) and be by sad, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, linolic acid, linolenic acid, eicosanoic acid, Lignoceric acid, docosoic and zinc, iron, aluminium, calcium, zirconium, magnesium, barium, nickel, copper or cobalt constitute at least a more than.
Below, illustrate in greater detail the present invention.
Binding agent among the present invention is the binding agent that is made of the pure and mild water of organic isocyanate based compound, polyether glycol and/or polyester polyols, perhaps by organic isocyanate based compound, polyether glycol and/or polyester polyol, water and have the saturated of 8～28 carbon atoms or the unsaturated aliphatic carboxylic metallic salt constitutes.This binding agent is useful as the binding agent of lignocellulose profiled sheeting (below be also referred to as plate) especially.
Lignocellulose profiled sheeting among the present invention is the binding agent that coating contains organic isocyanate based compound, polyether glycol and/or the pure and mild water of polyester polyols on ligno-cellulosic materials, perhaps be coated in the mentioned component and then contain binding agent with the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt, yet carry out the hot pressing compacting, obtain the lignocellulose profiled sheeting of its goods.
As ligno-cellulosic materials, can enumerate primary products such as the fibrous bundle sheet, stippled plate, thin slice and the fiber that in hardboard, MDF, heat-insulating shield, uses that in particle board, slicer board, OSB, use and jowar stem, bagasse, rice husk.These raw materials may be used alone, two or more kinds can also be used in combination.
As (A) organic isocyanate based compound in the present invention, it can be material with isocyanate group, specifically, for example can enumerate tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 1, hexamethylene-diisocyanate, Xylene Diisocyanate, isophorone diisocyanate, norbornylene vulcabond, polymethylene polyphenyl base polymeric polyisocyanate (polycondensation MDI) are perhaps with having the modified isocyanate of 1 above compound bearing active hydrogen with above-mentioned isocyanate compound modification.Wherein, on economy, MDI is better with polycondensation.
As (B) polyether glycol and/or the polyester polyol that use in the present invention, official's energy radixes such as preferably terminal OH base and terminal amino group are 2～8, hydroxyl valency (OHv) is 24～800mgKOH/g, contain the polyether glycol and/or the polyester polyol of nitrogen compound in molecule.In addition, sense radix (B) is 2～8, with respect to (B), and (the CH in its structure
2CH
2-O-) repeating unit better is 5～70% (weight), preferably 10～60% (weight).
Above-mentioned ethylene oxide content is more than 5%, and emulsifying property is good, and below 70%, the intermiscibility of polymeric polyisocyanate is good, is gratifying.
In addition, the ratio of the nitrogen-atoms in above-mentioned (B) polyether glycol and/or the polyester polyol, better be 0.1～12.0% (weight), 1.0～10.0% (weight) preferably, more than 0.1% (weight), can carry out emulsification effectively, below 12.0% (weight), reaction suitably, binding agent easy to manufacture.
As polyether glycol, the known method that employing is made as common polyvalent alcohol, at catalyst-free, perhaps with alkali metal hydroxide, tertiary amine etc. as catalyzer, the alkylene oxide that will have epoxy group(ing) in oxyethane, propylene oxide, butylene oxide ring, Styrene oxide 98min. equimolecular adds that to reduce to be in the low molecular compound with 2 active hydrogens of initiator and make.
Above-mentioned initiator can be enumerated as ethanolamines such as the Monoethanolamine MEA BASF of amine series initiators, diethanolamine, trolamines, 1,2-quadrol, diethylenetriamine, ortho-toluene diamine, toluylenediamine, 4,4 '-ditan diamines, 2, amines such as 4 '-ditan diamines, poly-methyl polyphenylene polyamines, they can use separately, perhaps can mix use.
In addition, also can with non-amine series initiators, be glycerine, sucrose, tetramethylolmethane, Sorbitol Powder, trimethyl propane, two glycerine, propylene glycol, dipropylene glycol, Diethylene Glycol, ethylene glycol, 1,4-butyleneglycol, 1, alcohols such as 2-butyleneglycol, phenolic aldehyde such as quinhydrones, dihydroxyphenyl propane, line style phenolic aldehyde etc. mix use.
Preferred in the present invention initiator is above-mentioned amine series initiators, though in these amine series initiators with non-amine series initiators and usefulness, also without any obstruction.
In addition, polyester polyol obtains with the cocondensation reaction of addition reaction, polycarboxylic acid and the alcohol of alcohol or to polycarboxylic acid addition alkylene oxide by acid anhydrides.
Acid anhydrides can be enumerated maleic anhydride, succinyl oxide, trihemellitic acid acid anhydride, PMA, itaconic anhydride, phthalate anhydride, Pyroglutaric acid, glutaconic anhydride, di-alcohol acid anhydrides, pyrocitric acid acid anhydride, diphenic acid acid anhydride, toluene acid anhydrides etc.Polycarboxylic acid for example can be enumerated toxilic acid, terephthalic acid, dimethyl terephthalic acid, m-phthalic acid, fumaric acid, oxalic acid, propanedioic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, citric acid, trihemellitic acid etc.In addition,, can use the alcohols of in above-mentioned initiator, enumerating, perhaps the alkylene oxide affixture of above-mentioned initiator as alcohol.
(C's) has the saturated of 8～28 carbon atoms or a unsaturated aliphatic carboxylic metallic salt in the present invention, can use the carboxylic acid of arbitrary sense radix of one, two, three as sour composition, wherein, the straight chain aliphatics monocarboxylic acid that preferably has 12～22 carbon atoms.For example can enumerate aliphatic carboxylic acids such as sad, lauric acid, tetradecanoic acid, palmitinic acid, oleic acid, linolic acid, linolenic acid, eicosanoic acid, Lignoceric acid, docosoic.In addition, can enumerate zinc, iron, aluminium, calcium, zirconium, magnesium, barium, nickel, copper, cobalt etc. as metal ingredient.These can be selected from the group separately of sour composition, metal ingredient makes up more than at least a and uses.That is, the carboxylic metallic salt that constitutes of sour composition of selecting from the group that above-mentioned preferred carboxylic acid is formed and the metal ingredient selected from the group that above-mentioned preferred metal is formed may be used alone, can also be two or more kinds in combination.
The object lesson of above-mentioned carboxylic metallic salt for example can be enumerated zinc, iron, aluminium, calcium, zirconium, magnesium, the barium salt of aliphatic carboxylic acids such as sad, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, docosoic.As above-mentioned aliphatic carboxylic acid, the aliphatic carboxylic acid of arbitrary sense radix of one, two, three can use, but to have straight chain aliphatics monocarboxylic acid the best of 12～22 carbon atoms.
(C) have the saturated of 8～28 carbon atoms or a unsaturated aliphatic carboxylic metallic salt, in binding agent of the present invention, can the metal-salt form exist, can add with the state of metal-salt and use, also can add aliphatic carboxylic acid and metallic compound respectively and use.
In addition, have the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt (C), as required, also can use emulsifying agent to use as emulsification.Emulsifying agent as this occasion, it can be the general emulsifying agent that uses, can lift anion surfactants such as fatty acid soaps, RA rosin acid, alkylsulfonate, alkyl benzene sulfonate, di alkylaryl sulfonate, alkyl sulfo succinate, polyoxy allylic alkylation vitriol, polyxyethylated arylsulphonate, tensio-active agents such as Voranol EP 2001, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid esters, oxygen ethylene oxy propylene block copolymer, but the present invention is not limited to these tensio-active agents.In addition, these tensio-active agents can use separately, also can be used in combination more than two kinds.
And then, also can use stablizer as required.This moment is as stablizer; so long as can make stablizer just passable with the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt (C) and these emulsifying agent stabilizations; can use the natural high moleculer eompound, the synthetic macromolecular compound that form protective colloid, for example gelatin, Sudan Gum-arabic, carboxymethyl cellulose, polyvinyl alcohol etc.
Having the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt (C) can add in organic isocyanate based compound, polyether glycol or water any, in addition, also can add in the binding agent of forming by organic isocyanate based compound, polyether glycol and water.
About the ratio of mixture of (A) organic isocyanate based compound with (B) polyether glycol and/or polyester polyol, with respect to 1 equivalent isocyanate group of organic isocyanate, Ahew is good with 0.02 to 1.2.More than 0.02, organic polymeric polyisocyanate mixes in water, and below 1.2, the rerum natura of plate is good, is suitable.
Of the present invention have lignocellulose profiled sheeting that the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt and water the form manufacture method with binding agent by (A) organic isocyanate based compound, (B) polyether glycol and/or polyester polyol, (C), and promptly the modulation of mentioned component is as follows.
In the present invention, do not limit the emulsifying water method of (A) organic isocyanate based compound especially and (C) have the blending means of the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt, for example, (A) organic isocyanate based compound, (B) polyether glycol and/or three kinds of whiles of the pure and mild water of polyester polyols high-speed mixing can be carried out emulsification; Also can add (B) polyether glycol and/or polyester polyol and dissolving in water, high-speed mixing (A) organic isocyanate based compound carries out emulsification then; Also can be with (B) polyether glycol and/or polyester polyol with after (A) organic isocyanate based compound mix, high-speed stirring limit, limit is added to and is carried out emulsification in the water.
In addition, can with (A) organic isocyanate based compound, (B) polyether glycol and/or polyester polyol, have four kinds in the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt (C) and water simultaneously high-speed mixing carry out emulsification; Also (C) can be had after the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt be dispersed in the water in advance, add also dissolving (B) polyether glycol and/or polyester polyol, high-speed mixing (A) organic isocyanate based compound carries out emulsification; Also (B) polyether glycol and/or polyester polyol and (C) can be had the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt and mix the back and mix with water, emulsification is carried out in the interpolation of limit high-speed mixing (A) organic isocyanate based compound limit; After also can in (A) organic isocyanate based compound, mixing (C) and having the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt, be blended in water and (B) carry out emulsification in the mixed solution of polyether glycol and/or polyester polyol; Also can be on one side (B) polyether glycol and/or polyester polyol, (A) organic isocyanate based compound, (C) be had after the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt mix, carry out emulsification in the water Yi Bian add to; After also can being dissolved in (B) polyether glycol and/or polyester polyol in the water, mix (A) organic isocyanate based compound, mix (C) then and have the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt.
In addition, in each stage, can use tensio-active agent, stablizer not damage scope of the present invention.Hybrid mode is not added special qualification, no matter no matter but the batch-type continous way can, for example can use homogenizer, static mixer etc.
Employed amount of moisture is also different because of the amount of moisture of lignocellulose based material, but can be that binding agent can be blended in the amount in the lignocellulose based material equably, preferably 1～300% of binder amount (weight).
The ratio of mixture of organic isocyanate based compound (A) and polyether glycol and/or polyester polyol (B) with respect to 100 parts by weight (A), (B) is the scope of 1～70 parts by weight, preferably the scope of 5～50 parts by weight.(B) more than 1 parts by weight, easily form the water-in-oil emulsion of stabilization, and below 70 parts by weight, the plate rerum natura is good.
In addition, (A) organic isocyanate based compound and (B) usage rate of polyether glycol and/or pure and mild water miscible liquid of polyester polyols and lignocellulose based material, weight ratio by (A) and effective constituent (B) and lignocellulose based material, better be 2: 100～30: 100 scope, preferably 3: 100～20: 100 scope.With respect to 100 parts by weight lignocellulose based materials, effective constituent can obtain the effect as binding agent more than 2 parts by weight, below 30 parts by weight, obtains sufficient plate rerum natura.
In the present invention, (B) polyether glycol and/or polyester polyol and (C) have the ratio of the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metallic salt, with respect to 100 parts by weight (B), (C) better be 1～150 parts by weight, preferably 2～120 parts by weight.(C) more than 1 parts by weight, stripping result is arranged, when hot pressing is suppressed, be difficult for attached to the heat dish on, be suitable therefore, in addition, below 150 parts by weight, obtain sufficient detachment.
As in the present invention lignocellulose based material and the blending means that by (A) organic polymeric polyisocyanate based compound, (B) polyether glycol, water and/or (C) has the binding agent that the saturated of 8～28 carbon atoms or unsaturated aliphatic carboxylic metal-salt form, hope is jet binder in mixing tank, and perhaps using similarly, device is blended in binding agent in the lignocellulose based material equably.At this moment, if desired, also can dilute, form the solution shape, but, be good to form the aqueous solution from economy, secure context with solvent and water.
In the manufacture method of lignocellulose profiled sheeting of the present invention, the mixture of binding agent and lignocellulose based material carries out hot pressing after moulding, can forming process become several layers from individual layer when moulding.In addition, after moulding, also can before hot pressing, carry out presuppression.Can change the content of binding agent as required.In addition, if necessary, also can after stacked, carry out presuppression, and also can carry out stacked before, carry out the laminate of presuppression stacked.In addition, the face that can only contact hot dish cart layer at this moment uses binding agent of the present invention, uses the bad binding agent of release property at internal layer, makes multilayered structure.
Promptly form the lignocellulose layer that contains binding agent of the present invention at outermost layer, internal layer also can use as the lignocellulose layer that contains binding agent of the present invention, perhaps also can be used as the lignocellulose layer that uses other binding agents.No matter the lignocellulose layer of internal layer is that individual layer or multilayer can.In addition, if needed, after stacked, can carry out presuppression, in addition also can be before stacked, carry out the laminate of presuppression stacked.
Be formed on the method that outermost layer contains the lignocellulose layer of binding agent of the present invention, can when moulding, form, in addition also can be below the heat dish after formation contains the lignocellulose layer of binding agent of the present invention, place the lignocellulose layer that uses other binding agents thereon, form the lignocellulose layer that contains binding agent of the present invention more thereon.Also can be with they form layers simultaneously continuously.
Heat preferably spreads all in the formed material during hot pressing, and shape also simultaneously can be up and down dull and stereotyped, also can be crooked shape, but from continuous production, cost aspect, dull and stereotyped compacting is suitable.In addition, as required, the part that contacts with binding agent of the present invention when moulding for example can apply external release agent on code disc and pressing plate.Not using is that the occasion of (C) of internal mold release is effective especially, in addition with (C) and with also improving release property.As this external release agent, can use the general remover that uses when common moulding, especially releasing agent that uses when urethanum RIM moulding etc. can exemplify out fluorine-containing wax, hydrocarbon system wax, polysiloxane series and their releasing agents such as mixture particularly.
The outermost layer of the plate after the hot pressing as required, can carry out precision work with surface grinding to desirable thickness.
In addition, the lignocellulose layer that is removed, after fully separating, the ligno-cellulosic materials that can be used as raw material re-uses.
In addition, in the present invention, in the scope of not damaging desired effect, can use antioxidant, UV light absorber, softening agent, silane coupling agent, polyvinyl alcohol, metal catalyst, external release agent, synthetic rubber latax, acrylic emulsion simultaneously.
Below, illustrate in greater detail the present invention according to embodiment, but these embodiment not any limitation of the invention.Evaluation result in embodiment and the comparative example is shown in table 1～2.In example only otherwise specify that in advance all umbers and ratio all are benchmark with weight.In addition, the co-manufactured condition of the plate of narration performance in relatively below.
Raw material: stippled plate or wood fibre (water ratio 4.0% below is called sheet)
Plate structure: three layers (wood fibres) that individual layer (stippled plate) or top layer/heart layer/top layer is formed
▲ added the moisture in the table, be phase jljl ▲
Thickness of slab (except the means of abrasion): 15mm
Laminate water ratio: 16%
Hot pressing temperature: 180 ℃
Pressing pressure: 35Kg/cm
2
Press time: 2 minutes and 30 seconds
Set density: 700kg/cm
3
Evaluation test
1. bending strength
According to the project of the test film of " particle board JIS-A-5908 ", block into the test film of wide 50mm, long 275mm (spacing 225mm) from type test portion, carry out anti-reflecting bending strength test.The result represents as bending strength.
2. the bending strength when moistening (A test)
With the method identical, from type test portion truncation test sheet with 1.Then test film was soaked 2 hours in 70 ± 3 ℃ warm water, in normal-temperature water, soak after 1 o'clock again, carry out anti-reflecting bending strength test with wetted former state state.The bending strength of result when moistening represented.
3. the bending strength when moistening (B test)
With the method identical, from type test portion truncation test sheet with 1.Then test film was soaked in boiling water 2 hours, in normal-temperature water, soak after 1 hour again, carry out anti-reflecting bending strength test with wetted former state state.The bending strength of result when moistening represented.
4. release property test
Use steel burr dish during hot pressing, the attachment state of the burr dish of Visual Confirmation sheet after hot pressing.Should operate at most and repeat 30 times, and be recorded to and see the number of times that adheres to.
5. synthetic determination
The moulding of synthetic determination plate, the rerum natura of plate.The evaluation symbol of expression result of determination is as follows.
Zero: can make plate, and rerum natura is a good state out of questionly
△: can make plate, but rerum natura is a good state not
*: can profiled sheeting, but exist produce foul smell etc. or the like the state of problem
* *: can not be made the state of plate
Embodiment 1
Put into 60g (1mol) quadrol (EDA) in the SUS autoclave, behind nitrogen replacement, the 504g that packs into (9mol) propylene oxide (PO) was 110 ℃ of reactions 4 hours.Outgas then, the 0.3g that packs into is as the potassium hydroxide (KOH) of catalyzer, confirm nitrogen replacement after, dissolve at 90～110 ℃, append the 396g that packs into (9mol) oxyethane (EO) again, 110 ℃ of reactions 4 hours.Adopt the resulting polyvalent alcohol of ordinary method purifying, obtain propylene oxide (PO)/oxyethane (EO) block copolymerization PPG (ethylene oxide content 43%, hydroxyl valency 230mgKOH/g).
Then, the propylene oxide of the synthetic/ethylene oxide block copolymerization PPG of dissolving 14.8 parts by weight in the water of 117 parts by weight, on one side high-speed stirring drops into 59.2 umber polycondensation MDI[Mitsuis east on one side and presses chemistry (strain) manufacturing, trade(brand)name コ ス モ ネ-ト M-200 again) carry out emulsification.After 5 minutes, use the resulting water miscible liquid of stippled plate spraying coating of 820 umbers of spray gun in mixing tank.
Then apply the external release agent (モ-Le De ス パ Star ト W823 of fluorine system, Asahi Glass society (strain) makes), use mixing tank that above-mentioned emulsion is mixed on the stippled plate, the sheet that forms is molded into equably the square of 30cm size, covering steel burr dish on the exsiccant steel burr dish, carry out hot pressing with above-mentioned condition.Beginning to begin the needed time to hot pressing from emulsification is 20 minutes.After the hot pressing, observe attachment state, but do not see and adhering to steel burr dish.In addition, the plate after hot-forming is used as physical property measurement.Re-use identical burr dish and repeat above-mentioned profiled sheeting manufacturing operation.Even 50 times repeatedly, on steel burr dish, do not observe dirt settling yet.
Embodiment 2
In the method for embodiment 1, the addition mole number of PO/EO is become 4mol/5mol, obtain the polyvalent alcohol of table 1 record.Use this polyvalent alcohol, the evaluation of binding agent is carried out in operation similarly to Example 1.Even the profiled sheeting manufacturing operation is repeated 50 times, also not observing on steel burr dish has dirt settling.
Embodiment 3
Method according to embodiment 1, except becoming with ortho-toluene diamine (OTD)/glycerine (G) (mol ratio 5: 1) as the initiator of polyvalent alcohol and the polyvalent alcohol (ethylene oxide content: 50% that obtains, hydroxyl valency: 452mgKOH/g), carry out 1 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 4
According to the method for embodiment 1, except becoming with the initiator of methyl tolylene diamine (MTD) as polyvalent alcohol, and the polyethers that obtains (ethylene oxide content: 40%, hydroxyl valency: 449mgKOHg), carry out 1 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 5
According to the method for embodiment 1, except becoming with 4,4 '-ditan diamines (MDA) as the initiator of polyvalent alcohol and the polyvalent alcohol that obtains (ethylene oxide content: 40%, hydroxyl valency: 452mgKOH/g), carry out 1 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 6
According to the method for embodiment 1, except become with ortho-toluene diamine (OTD) as the initiator of polyvalent alcohol and the polyvalent alcohol that obtains (ethylene oxide content: 40%), hydroxyl valency: 280mgKOH/g), carry out 1 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 7
According to the method for embodiment 1, except become with Monoethanolamine MEA BASF (MEOA) as the initiator of polyvalent alcohol and the polyvalent alcohol that obtains (ethylene oxide content: 60%, hydroxyl valency: 280mgKOH/g), carry out 1 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also seen dirt settling.
Embodiment 8
According to the method for embodiment 1, except become with trolamine (TEOA) as the initiator of polyvalent alcohol and the polyvalent alcohol that obtains (ethylene oxide content: 40%, hydroxyl valency: 713mgKOH/g), carry out 1 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also seen dirt settling.
Embodiment 9
Method according to embodiment 1, except becoming with mol ratio is the polyvalent alcohol (ethylene oxide content: 45% that the mixture of ortho-toluene diamine (OTD)/Monoethanolamine MEA BASF (MEOA) of 1: 1 obtains as the initiator of polyvalent alcohol, hydroxyl valency: 280mgKOH/g), carry out 1 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also seen dirt settling.
Embodiment 10
The 17.4 umber polyvalent alcohols that use in an embodiment, 2.5 umber phthalate anhydrides at 15 hours synthesizing polyester polyvalent alcohols of 220 ℃ of esterifications, except using this polyvalent alcohol, are carried out 1 identical operations with embodiment.Repeat 50 times even profiled sheeting is made operation, on steel burr dish, also do not see dirt settling.
Embodiment 11
With quadrol as initiator, the propylene oxide that is used in an embodiment/epoxyethane block copolymer PPG (ethylene oxide content: 43%, hydroxyl valency: 230mgKOH/g), use this multipolymer, the quantitative change of polyvalent alcohol is become 17.8 parts by weight, polycondensation MDI is become 71.1 parts by weight, replace stippled plate with wood fibre, amount of resin: top layer/heart layer /=8/4 (%), carry out the moulding ratio: three formable layers of top layer/heart layer/top layer=25/50/25 (%), in addition, with the condition identical with embodiment 1 with the MDF moulding.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 12
According to the method for embodiment 1,, carry out 1 identical operations with embodiment except the hydroxyl groups valency is become the 450mgKOH/g.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 13
Method according to embodiment 1, except becoming with ortho-toluene diamine (OTD)/glycerine (G) (mol ratio 5: 1) as the initiator of polyvalent alcohol and the polyvalent alcohol (ethylene oxide content: 50% that obtains, hydroxyl valency: 452mgKOH/g), carry out 11 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 14
According to the method for embodiment 1, except become with toluylenediamine (MTD) as the initiator of polyvalent alcohol and obtain polyethers (ethylene oxide content: 40%, hydroxyl valency: 449mgKOH/g), carry out 11 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 15
According to the method for embodiment 1, except becoming with 4,4 '-ditan diamines (MDA) as the initiator of polyvalent alcohol and the polyethers that obtains (ethylene oxide content: 40%, hydroxyl valency: 452mgKOH/g), carry out 11 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 16
According to the method for embodiment 1, except become with ortho-toluene diamine (OTD) as the initiator of polyvalent alcohol and the polyvalent alcohol that obtains (ethylene oxide content: 40%, hydroxyl valency: 280mgKOH/g), carry out 11 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 17
According to the method for embodiment 1, except become with Monoethanolamine MEA BASF (MEOA) as the initiator of polyvalent alcohol and the polyvalent alcohol that obtains (ethylene oxide content: 60%, hydroxyl valency: 280mgKOH/g), carry out 11 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 18
According to the method for embodiment 1, except become with trolamine (TEOA) as the initiator of polyvalent alcohol and the polyvalent alcohol that obtains (ethylene oxide content: 40%, hydroxyl valency: 713mgKOH/g), carry out 1 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 19
Method according to embodiment 1, except the mixture that becomes ortho-toluene diamine (OTD)/Monoethanolamine MEA BASF (MEOA) with 1: 1 mol ratio as the initiator of polyvalent alcohol and the polyvalent alcohol (ethylene oxide content: 45% that obtains, hydroxyl valency: 280mgKOH/g), carry out 11 identical operations with embodiment.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Comparative example 1
According to the method for embodiment 1, except become the polyethers that obtains as the initiator of polyvalent alcohol with glycerine (ethylene oxide content: 40%, hydroxyl valency: 450mgKOH/g), carry out 1 identical operations, use stippled plate to be molded into plate with embodiment.But, do not solidify with this condition of molding forming composition, when removing pressing pressure, produce sound, plate crumbles.Therefore do not carry out later plate evaluation of physical property.
Comparative example 2
Method according to embodiment 1, but become with glycerine as the initiator of polyvalent alcohol and the polyethers (ethylene oxide content: 40% that obtains, hydroxyl valency: 450mgKOH/g), when emulsification, use the Triethylene Diamine (TEDA) of 1.0 parts by weight as urethane esterification catalyzer, except above-mentioned, carry out 1 identical operations, use stippled plate to be molded into plate with embodiment.But, after emulsification in 5 minutes, emulsion foaming, tackify.Forming composition after the hot pressing forms pimple, has pruned many places and has formed convex-concave on the surface.Therefore do not carry out later plate evaluation of physical property.Known occasion at so a large amount of use amine catalysts can not obtain satisfied forming composition.
Comparative example 3
Method according to embodiment 1, but become with certain oil as the initiator of polyvalent alcohol and the polyethers (ethylene oxide content: 40% that obtains, hydroxyl valency: 450mgKOH/g), when emulsification, use the Triethylene Diamine of 0.5 parts by weight as urethane esterification catalyzer, except above-mentioned, carry out in the same manner with embodiment, use stippled plate to be molded into plate.After emulsification in 5 minutes, emulsion does not change in appearance, carries out hot pressing.But the plate in hot pressing or after the hot pressing produces and thinks that the amine that is caused by catalyzer is smelly, worsens operating environment.
Comparative example 4
Use high-speed stirring on one side, replace polycondensation MDI and polyvalent alcohol, be identically formed plate with embodiment 1 Yi Bian make self-emulsifying type polycondensation MDI (chemistry (strain) manufacturing, trade(brand)name UR-4000 are pressed in Mitsui east) in water, carry out emulsive emulsifying water binding agent.The rerum natura of forming composition is good, but than embodiment difference.
Comparative example 5
According to the method for embodiment 1, except becoming the polyethers (the nitrogen-atoms ratio in the polyvalent alcohol is 18.9%) that makes the hydroxyl groups valency reach 1516mgKOH/g and obtain, carry out 1 identical operations with embodiment.But, when making binding agent, the adhesive composition foaming, therefore the generating portion precipitation can not be coated on the stippled plate, thereby not carry out later profiled sheeting manufacturing operation.
Even (be that the comparative example that can not make is made in expression below the lower limit of hydroxyl groups valency.)
Embodiment 20
At first, the quadrol (EDA) that uses with embodiment 1 is as initiator, propylene oxide/epoxyethane block copolymer PPG (ethylene oxide content 43% with 14.8 parts by weight, hydroxyl valency 230mgKOH/g), Zinic stearas (St-Zn) as 6.0 parts by weight of internal mold release is dispersed in the water of 117 parts by weight, one side high-speed stirring is carried out emulsification Yi Bian drop into the polycondensation MDI (chemistry (strain) manufacturing, trade(brand)name コ ス モ ネ-ト M-200 are pressed in Mitsui east) of 59.2 parts by weight again.After 5 minutes, use the resulting water-in-oil emulsion of stippled plate spraying coating of 820 parts by weight of spray gun in mixing tank.
Then, the stippled plate that is coated with above-mentioned water-in-oil emulsion is processed into the square of 30cm size equably,, carries out hot pressing with above-mentioned condition covering steel burr dish on the exsiccant steel burr dish.From emulsification begin to the time that hot pressing begins to need be 20 minutes.After the hot pressing, observation is adhered to steel burr dish, but does not see and adhering to.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.In addition, the plate after hot-forming re-uses identical burr dish and repeats above-mentioned operation as rerum natura usefulness relatively.Even repeat 50 times, on steel burr dish, do not observe dirt settling yet.
Embodiment 21
According to the method for embodiment 1, except becoming the polyethers that the hydroxyl groups valency becomes 450mgKOH/g, carry out 20 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 22
According to the method for embodiment 1, except become with methyl tolylene diamine (MTD) as the initiator of polyvalent alcohol and the polyethers that obtains (ethylene oxide content: 40%, hydroxyl valency: 447mgKOH/g), carry out 20 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 23
Method according to embodiment 1, except becoming with ortho-toluene diamine (OTD)/glycerine (G) (mol ratio 5: 1) as the initiator of polyvalent alcohol and the polyethers (ethylene oxide content: 50% that obtains, hydroxyl valency: 452mgKOH/g), carry out 20 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 24
According to the method for embodiment 1, except become with toluylenediamine (MTD) as the initiator of polyvalent alcohol and the polyethers that obtains (ethylene oxide content: 40%, hydroxyl valency: 255mgKOH/g), carry out 20 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 25
According to the method for embodiment 1, except becoming with 4,4 '-ditan diamines (MDA) as the initiator of polyvalent alcohol and the polyethers that obtains (ethylene oxide content: 40%, hydroxyl valency: 452mgKOH/g), carry out 20 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 26
According to the method for embodiment 1, except become with ortho-toluene diamine (OTD) as the initiator of polyvalent alcohol and the polyethers that obtains (ethylene oxide content: 40%, hydroxyl valency: 280mgKOH/g), carry out 20 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 27
According to the method for embodiment 1, except become with triethylamine (TEOA) as the initiator of polyvalent alcohol and the polyethers that obtains (ethylene oxide content: 40%, hydroxyl valency: 713mgKOH/g), carry out 20 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 28
Method according to embodiment 1, except becoming with the mixture of ortho-toluene diamine (OTD)/Monoethanolamine MEA BASF (MEOA) (mol ratio 1: 1) as the initiator of polyvalent alcohol and the polyethers (ethylene oxide content: 45% that obtains, hydroxyl valency: 280mgKOH/g), carry out 20 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 29
The 17.4 umber polyvalent alcohols that use from embodiment 1,2.5 umber phthalate anhydrides except using this polyester polyol, carry out 20 identical operations with embodiment at 15 hours synthesizing polyester polyvalent alcohols of 220 ℃ of esterifications.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 30
Use nonionogenic tenside, make the propylene oxide/epoxyethane block copolymer PPG (ethylene oxide content: 43% that in embodiment 1, uses as polyvalent alcohol, hydroxyl valency: 230mgKOH/g), 6.0 umber is dispersed in as the Zinic stearas (St-Zn) of internal mold release in 3 times the water, uses this dispersion liquid.The amount of its polyvalent alcohol reaches 17.8 parts by weight, and polycondensation MDI reaches 71.1 parts by weight, replaces the particle sheet with wood fibre, addition top layer/heart layer=8/4 (%), moulding ratio: top layer/heart layer/top layer=25/50/25 (%) three layers.In addition, form MDF with the condition identical with embodiment 20.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 31
According to the method for embodiment 1,, carry out 30 identical operations with embodiment except the hydroxyl groups valency is become the 450mgKOH/g.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 32
According to the method for embodiment 1, except become use with ortho-toluene diamine as the initiator of polyvalent alcohol and the polyethers that obtains (ethylene oxide content: 40%, hydroxyl valency: 447mgKOH/g), carry out 30 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 33
Method according to embodiment 1, except become use with ortho-toluene diamine (OTD)/glycerine (G) (mol ratio 5: 1) as the initiator of polyvalent alcohol and the polyethers (ethylene oxide content: 50% that obtains, hydroxyl valency: 452mgKOH/g), carry out 30 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 34
According to the method for embodiment 1, except become with toluylenediamine (MTD) as the initiator of polyvalent alcohol and the polyvalent alcohol that obtains (ethylene oxide content: 40%, hydroxyl valency: 255mgKOH/g), carry out 30 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 35
According to the method for embodiment 1, except becoming with 4,4 '-ditan diamines (MDA) as the initiator of polyvalent alcohol and the polyvalent alcohol that obtains (ethylene oxide content: 40%, hydroxyl valency: 452mgKOH/g), carry out 30 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 36
According to the method for embodiment 1, except become with ortho-toluene diamine (OTD) as the initiator of polyvalent alcohol and the polyvalent alcohol that obtains (ethylene oxide content: 40%, hydroxyl valency: 280mgKOH/g), carry out 30 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 37
According to the method for embodiment 1, except become with trolamine (TEOA) as the initiator of polyvalent alcohol and the polyvalent alcohol that obtains (ethylene oxide content: 40%, hydroxyl valency: 713mgKOH/g), carry out 30 identical operations with embodiment.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Embodiment 38
Method according to embodiment 1, except becoming with the mixture of ortho-toluene diamine (OTD)/Monoethanolamine MEA BASF (MEOA) (mol ratio 1: 1) as the initiator of polyvalent alcohol and the polyvalent alcohol (ethylene oxide content: 45% that obtains, hydroxyl valency: 280mgKOH/g), carry out operation together with embodiment 30.Owing to use internal mold release simultaneously, carry out the demoulding under the external release agent not applying.Even the profiled sheeting manufacturing operation is repeated 50 times, on steel burr dish, is not also observed dirt settling.
Table 1
| The lignocellulose based material | Isocyanic ester | Polyvalent alcohol | Water | Releasing agent | Catalyzer | |
| Kind umber water ratio % | The kind umber | Initiator hydroxyl valency nitrogen content EO content umber mg/KOH/g % % | Umber | Outside inner kind kind amount % | Kind (amount) | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 13 embodiment 14 embodiment 15 embodiment 16 embodiment 17 embodiment 18 embodiment 19 | Stippled plate 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) | M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 71.1 M-200 71.1 M-200 71.1 M-200 71.1 M-200 71.1 M-200 71.1 M-200 71.1 M-200 71.1 M-200 71.1 | EDA 230 3.1 43 14.8 EDA 450 5.5 50 14.8 OTD/G 452 4.9 50 14.8 MTD 449 5.6 40 14.8 MDA 452 5.6 40 14.8 OTD 280 3.5 40 14.8 MEOA 280 3.1 60 14.8 TEOA 713 11.9 40 14.8 OTD/MEOA 280 3.3 45 14.8 esters 180 2.7 35 17.4 EDA 230 3.1 43 17.8 EDA 450 5.5 50 17.8 OTD/G 452 4.9 50 17.8 MTD 449 5.6 40 17.8 MDA 452 5.6 40 17.8 OTD 280 3.5 40 17.8 MEOA 280 3.1 60 17.8 TEOA 713 11.9 40 17.8 OTD/MEOA 280 3.3 45 17.8 | 117 117 117 117 117 117 117 117 117 117 117 117 117 117 117 117 117 117 117 | Fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system-fluorine system- | — — — — — — — — — — — — — — — — — — — |
| Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 comparative examples 5 | Stippled plate 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) | M-200 59.2 M-200 59.2 M-200 59.2 UR-4000 74.0 M-200 59.2 | G 450 0.0 40 14.8 G 450 0.0 40 14.8 G 450 0.0 40 14.8 — — — — — EDA 1516 18.9 40 14.8 | 117 117 117 117 117 | Fluorine system-fluorine system-fluorine system-fluorine system-fluorine system- | TEDA1.0 TEDA0.5 — — |
Table 2
| The lignocellulose based material | Isocyanic ester | Polyvalent alcohol | Water | Releasing agent | Catalyzer | |
| Kind umber water ratio % | The kind umber | Initiator hydroxyl valency nitrogen content EO content umber mgKOH/g % % | Umber | Outside inner kind kind % | Kind (amount) | |
| Embodiment 20 embodiment 21 embodiment 22 embodiment 23 embodiment 24 embodiment 25 embodiment 26 embodiment 27 embodiment 28 implementation columns 29 embodiment 30 embodiment 31 embodiment 32 embodiment 33 embodiment 34 embodiment 35 embodiment 36 embodiment 37 embodiment 38 | Stippled plate 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) stippled plates 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) wood fibres 820 (4) | M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 59.2 M-200 71.1 M-200 71.1 M-200 71.1 M-200 71.1 M-200 71.1 M-200 71.1 M-200 71.1 M-200 71.1 M-200 71.1 | EDA 230 3.1 43 14.8 EDA 450 5.5 50 14.8 MTD 447 5.5 40 14.8 OT/G 452 4.9 50 14.8 MTD 255 3.2 40 14.8 MDA 452 5.6 40 14.8 OTD 280 3.5 40 14.8 TEOA 713 11.9 40 14.8 OTD/MEOA 280 3.3 45 14.8 fat 180 2.7 35 17.4 EDA 230 3.1 43 17.8 EDA 450 5.5 50 17.8 MTD 447 5.5 40 17.8 OTD/G 452 4.9 50 17.8 MTD 255 5.6 40 17.8 MDA 452 5.6 40 17.8 OTD 280 3.5 40 17.8 TEOA 713 11.9 40 17.8 OTD/MEOA 280 3.3 45 17.8 | 117 117 117 117 117 117 117 117 117 117 117 117 117 117 117 117 117 117 117 | -zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6-zinc stearate 6 | — — — — — — — — — — — — — — — — — — — |
Table 3
| The moistening B bending strength of the moistening A bending strength of density water ratio state bending strength stripping strength can release times g/cm 3 ％ N/mm 2 N/mm 2 N/mm 2 N/mm 2Inferior | Foul smell | Synthetic determination | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 13 embodiment 14 embodiment 15 embodiment 16 embodiment 17 implementation columns 18 embodiment 19 | 0.692 8.8 26.2 19.6 15.6 0.56 ＞50 0.701 8.9 27.1 19.2 15.7 0.54 ＞50 0.691 9.0 23.2 18.2 15.0 0.49 ＞50 0.701 9.0 26.3 19.0 16.0 0.52 ＞50 0.689 8.9 26.1 19.0 16.3 0.50 ＞50 0.701 8.9 26.2 16.9 13.5 0.48 ＞50 0.695 8.9 24.2 17.1 12.6 0.47 ＞50 0.699 8.9 23.9 16.9 12.8 0.50 ＞50 0.707 9.0 23.2 19.0 13.8 0.51 ＞50 0.721 8.8 23.9 18.2 14.1 0.57 ＞50 0.689 8.9 43.2 21.0 18.5 0.49 ＞50 0.704 7.8 46.4 22.3 19.1 0.72 ＞50 0.695 7.7 42.9 22.0 18.6 0.65 ＞50 0.713 8.0 40.2 22.8 18.3 0.72 ＞50 0.706 7.9 44.3 23.1 18.9 0.69 ＞50 0.702 8.1 42.9 23.8 18.5 0.65 ＞50 0.689 7.6 41.0 22.2 19.0 0.65 ＞50 0.711 7.5 39.8 23.7 18.2 0.68 ＞50 0.703 8.1 42.5 22.3 18.8 0.71 ＞50 | Do not have | ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ |
| Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 comparative examples 5 | Explosion takes place when the demoulding, therefore not carrying out physical property measurement-plate surface has convex-concave, do not carry out the foaming of plate evaluation of physical property-0.697 9.0 19.8 9.8 8.0 0.51＞50 0.706 8.9 16.8 9.8 7.7 0.51＞50 adhesive compositions, produce precipitation, therefore can not be coated on the stippled plate- | -there is the amine foul smell to have the amine foul smell not have | ×× ×× × △ ×× |
Table 4
| The moistening B bending strength of the moistening A bending strength of density water ratio state bending strength stripping strength can release times g/cm 3 ％ N/mm 2 N/mm 2 N/mm 2 N/mm 2Inferior | Foul smell | Synthetic determination | |
| Implementation column 20 embodiment 21 embodiment 22 embodiment 23 embodiment 24 embodiment 25 embodiment 26 embodiment 27 embodiment 28 embodiment 29 embodiment 30 embodiment 31 embodiment 32 embodiment 33 embodiment 34 embodiment 35 embodiment 36 embodiment 37 embodiment 38 | 0.692 8.8 26.2 19.6 16.6 0.57 ＞50 0.701 8.9 27.1 19.2 15.7 0.58 ＞50 0.689 9.2 25.7 18.8 15.7 0.53 ＞50 0.691 9.0 23.2 18.2 14.9 0.49 ＞50 0.695 9.1 26.2 19.1 15.1 0.54 ＞50 0.701 9.0 26.3 19.0 16.0 0.61 ＞50 0.711 8.9 23.2 18.3 15.4 0.58 ＞50 0.709 8.8 24.1 18.5 16.7 0.55 ＞50 0.708 8.7 23.7 18.7 16.0 0.53 ＞50 0.704 9.1 24.6 18.9 16.0 0.55 ＞50 0.697 9.0 42.4 23.2 18.6 0.72 ＞50 0.702 8.9 41.9 22.9 18.2 0.69 ＞50 0.721 9.1 40.9 22.9 17.9 0.63 ＞50 0.706 8.9 41.7 22.9 18.4 0.76 ＞50 0.711 8.8 39.9 21.7 18.4 0.80 ＞50 0.717 8.9 40.4 24.3 17.6 0.78 ＞50 0.700 9.0 41.1 23.4 18.6 0.69 ＞50 0.702 8.8 41.3 22.6 18.8 0.66 ＞50 0.709 8.7 41.5 22.9 18.9 0.65 ＞50 | Do not have | ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ |
Claims (11)
1. binding agent, it comprises water-in-oil emulsion, described water-in-oil emulsion contains organic isocyanate based compound (A) and polyether glycol and/or polyester polyol (B), it is characterized in that, with respect to 100 parts by weight (A), (B) be 1～70 parts by weight, this polyether glycol and/or polyester polyol are that the hydroxyl valency is 24～800mgKOH/g, contains the amino polyol of nitrogen compound in molecule.
2. binding agent according to claim 1, it is characterized in that, this polyether glycol is that alkylene oxide is added in one or more the compound of selecting from the poly-methyl polyamines of trolamine, diethanolamine, Monoethanolamine MEA BASF, ortho-toluene diamine, toluylenediamine, ditan diamines, polyphenylene, with respect to the weight of polyether glycol, the addition content of the oxyethane in this alkylene oxide is 5～70 parts by weight.
3. binding agent according to claim 1 and 2 is characterized in that, organic isocyanate based compound (A) is a polymethylene polyphenyl base polymeric polyisocyanate.
4. according to each described binding agent in the claim 1～3, it is characterized in that the nitrogen-atoms ratio in polyether glycol and/or the polyester polyol (B) is 0.1～12.0% all (weight), sense radix (B) is 2～8, with respect to the parts by weight of (B), (CH in its structure
2CH
2-O-) repeating unit is 5～70%.
5. according to each described binding agent in the claim 1～4, it is characterized in that, contain organic isocyanate based compound (A), polyether glycol and/or polyester polyol (B) and have the saturated of 8～28 carbon atoms and/or unsaturated aliphatic carboxylic metallic salt (C), wherein, with respect to 100 parts by weight (A), (B) be 1～70 parts by weight,, (C) be 1～150 parts by weight with respect to 100 parts by weight (B).
6. binding agent according to claim 5 is characterized in that, has the saturated of 8～28 carbon atoms and/or unsaturated aliphatic carboxylic metallic salt (C) is an aqueous emulsion.
7. according to each described binding agent in the claim 1～6, it is characterized in that this binding agent is the lignocellulose binding agent.
8. according to the manufacture method of each described binding agent in the claim 1～7, it is characterized in that binding agent is to make water and organic isocyanate based compound (A), polyether glycol and/or polyester polyol (B) carry out emulsification and obtain.
9. the manufacture method of binding agent according to claim 8 is characterized in that, binding agent be further mix have the saturated of 8～28 carbon atoms and/or unsaturated aliphatic carboxylic metallic salt and.
10. the manufacture method of lignocellulose profiled sheeting is characterized in that,, carries out hot pressing and obtains the lignocellulose profiled sheeting with after the lignocellulose based material mixes according to each described binding agent in the claim 1～6.
11. the lignocellulose profiled sheeting that adopts the manufacture method of lignocellulose profiled sheeting according to claim 10 to obtain.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP255069/1996 | 1996-09-26 | ||
| JP25506996 | 1996-09-26 | ||
| JP255069/96 | 1996-09-26 | ||
| JP255788/96 | 1996-09-27 | ||
| JP25578896 | 1996-09-27 | ||
| JP255788/1996 | 1996-09-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1180092A CN1180092A (en) | 1998-04-29 |
| CN1104482C true CN1104482C (en) | 2003-04-02 |
Family
ID=26542006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97116939A Expired - Lifetime CN1104482C (en) | 1996-09-26 | 1997-09-26 | Adhesive for lignocellulose forming board and its manufacturing method |
Country Status (7)
| Country | Link |
|---|---|
| KR (1) | KR100255788B1 (en) |
| CN (1) | CN1104482C (en) |
| AU (1) | AU690497B1 (en) |
| ID (1) | ID18329A (en) |
| MY (1) | MY115553A (en) |
| NZ (1) | NZ328826A (en) |
| TW (1) | TW470766B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100391247B1 (en) * | 2001-06-01 | 2003-07-12 | 금호미쓰이화학 주식회사 | Binder for molding board of lignocellulose |
| JP5577013B2 (en) * | 2007-06-06 | 2014-08-20 | 三井化学株式会社 | Solventless laminating adhesive and method for producing composite film |
| EP3510091A4 (en) * | 2016-09-09 | 2020-04-08 | Robert N. Clausi | Surface modifying agent formulation |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2610552A1 (en) * | 1975-03-12 | 1976-09-23 | Ici Ltd | METHOD OF MANUFACTURING PLATES OR MOLDED OBJECTS |
| CA1021705A (en) * | 1974-05-08 | 1977-11-29 | Pinckney Molded Plastics | Three-level stacking container |
| EP0342781A2 (en) * | 1988-05-16 | 1989-11-23 | Director-General Of The Agency Of Industrial Science And Technology | New polyurethane and process for preparing same |
| CN1102421A (en) * | 1993-07-12 | 1995-05-10 | 拜尔公司 | New compositions useful as binders for the production of composite materials |
| CN1119020A (en) * | 1993-03-05 | 1996-03-20 | 国际壳牌研究有限公司 | Polymer polyols |
| CN1120848A (en) * | 1993-04-13 | 1996-04-17 | 帝国化学工业公司 | Polyurethane foams |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5233009A (en) * | 1991-11-07 | 1993-08-03 | Miles Inc. | Polyurethanes comprising the reaction of an isocyanate terminated prepolymer and a polyol mixture comprising triols and an organic diamine |
| JPH06218035A (en) * | 1993-01-28 | 1994-08-09 | Mitsubishi Rayon Co Ltd | Biomedical adhesive |
| DE4446334A1 (en) * | 1994-12-23 | 1996-06-27 | Bayer Ag | Reclosable cellulosic materials |
-
1997
- 1997-09-23 AU AU38396/97A patent/AU690497B1/en not_active Ceased
- 1997-09-24 NZ NZ328826A patent/NZ328826A/en unknown
- 1997-09-24 MY MYPI97004454A patent/MY115553A/en unknown
- 1997-09-26 KR KR1019970049010A patent/KR100255788B1/en not_active IP Right Cessation
- 1997-09-26 TW TW086114177A patent/TW470766B/en not_active IP Right Cessation
- 1997-09-26 CN CN97116939A patent/CN1104482C/en not_active Expired - Lifetime
- 1997-09-26 ID IDP973309A patent/ID18329A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1021705A (en) * | 1974-05-08 | 1977-11-29 | Pinckney Molded Plastics | Three-level stacking container |
| DE2610552A1 (en) * | 1975-03-12 | 1976-09-23 | Ici Ltd | METHOD OF MANUFACTURING PLATES OR MOLDED OBJECTS |
| EP0342781A2 (en) * | 1988-05-16 | 1989-11-23 | Director-General Of The Agency Of Industrial Science And Technology | New polyurethane and process for preparing same |
| CN1119020A (en) * | 1993-03-05 | 1996-03-20 | 国际壳牌研究有限公司 | Polymer polyols |
| CN1120848A (en) * | 1993-04-13 | 1996-04-17 | 帝国化学工业公司 | Polyurethane foams |
| CN1102421A (en) * | 1993-07-12 | 1995-05-10 | 拜尔公司 | New compositions useful as binders for the production of composite materials |
Also Published As
| Publication number | Publication date |
|---|---|
| ID18329A (en) | 1998-03-26 |
| KR19980025012A (en) | 1998-07-06 |
| AU690497B1 (en) | 1998-04-23 |
| MY115553A (en) | 2003-07-31 |
| KR100255788B1 (en) | 2000-05-01 |
| CN1180092A (en) | 1998-04-29 |
| NZ328826A (en) | 1998-02-26 |
| TW470766B (en) | 2002-01-01 |
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