CN1839037A - Time released curing system - Google Patents

Time released curing system Download PDF

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Publication number
CN1839037A
CN1839037A CNA038271168A CN03827116A CN1839037A CN 1839037 A CN1839037 A CN 1839037A CN A038271168 A CNA038271168 A CN A038271168A CN 03827116 A CN03827116 A CN 03827116A CN 1839037 A CN1839037 A CN 1839037A
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China
Prior art keywords
weight
curable adhesive
phosphite
adhesive
lauxite
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Granted
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CNA038271168A
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Chinese (zh)
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CN1839037B (en
Inventor
J·P·陈
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Hexion Research Belgium SA
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Borden Chemical Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
    • C08G12/12—Ureas; Thioureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C09D161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/249925—Fiber-containing wood product [e.g., hardboard, lumber, or wood board, etc.]
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249982—With component specified as adhesive or bonding agent
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249982—With component specified as adhesive or bonding agent
    • Y10T428/249985—Composition of adhesive or bonding component specified
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/249991—Synthetic resin or natural rubbers
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31942—Of aldehyde or ketone condensation product
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31942—Of aldehyde or ketone condensation product
    • Y10T428/31949—Next to cellulosic
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31942—Of aldehyde or ketone condensation product
    • Y10T428/31949—Next to cellulosic
    • Y10T428/31957—Wood

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

Abstract

Disclosed is a solidifiable urea formaldehyde adhesive compound, which comprises urea formaldehyde resin and orthophosphorous acid aromatic ester with various concentration respectively, can be used as a coating-type abrasive filler or apply to wood engineering, by the way of release with the passing of time. The invention of solidifiable adhesive will enable to achieve the desired working schedule or shorten the time for solidification under or close to the urea formaldehyde environment.

Description

The curing system of Shi Fanging in time
Invention field
The present invention relates to the grinding agent that is used to apply and the curable urea-formaldehyde adhesive composition of Engineered Wood Product Manufacturing goods.Said composition comprises curable Lauxite and aryl phosphite.
Background of invention
The present invention relates to abrasive article, grinding agent gravel wherein thin layer or that be more typically individual layer is bonded on the backing.For example, this product is the grinding agent that applies, and more generally is called as " sand paper " and fiber abrasive pad.Usually, glue or thermosetting resin such as phenolic resins (" PF resin ") and Lauxite (" UF resin ") have been used for formulation for coating material.The UF resin is more cheap than phenolic resins, has been used to reduce the cost of grinding agent product.But the present UF resin system that the grinding agent product that is used to apply is made does not provide desired working time and hardening time under environment or the condition near environment.The curable urea-formaldehyde adhesive composition that discharges is in time just being sought in the grinding agent industry that applies, and having enough working times, and can solidify faster so that picture rich in detail and non-crimping sand paper to be provided.
Known phenol resin composition can solidify at ambient temperature, and solidifies fast under suitable higher temperature.These resins, as license in the United States Patent (USP) 5,296,520 of Gerber, use the aryl phosphite latent acid catalyst that the controlled working time of hardening phenolic resin is provided at ambient temperature.But Gerber finds that urea and other amide compound are that the resin with aryl phosphite curing agent carries out the very effective retarding agent that environment temperature is hardened.
Yet the UF resin is different with phenolic resins, has very different chemical property and manufacture method separately.The nitrogen of UF resin by urea and the condensation prepared of the carbonyl reaction of formaldehyde.On the contrary, a kind of exemplary novolac polymer is the fragrance replacement by a plurality of activation points of phenol, is replaced by formaldehyde at first, then the phenolic resins of preparation with other reactive intermediate reaction.In the preparation of phenolic resins, catalyst such as highly basic, zinc acetate and borate can be used to provide the resol of phenolic aldehyde, and strong acid can be used to provide the novolac of phenolic aldehyde.Can use strong acid catalyst, for example sulfuric acid prepares the UF resin.Structurally, phenolic resins is highly fragrant, and comprises fragrant end group.On the contrary, the UF resin is an amino resins, basically right and wrong fragrance.About curing properties, the novolac polymer scope comprises from the thermosetting resol to thermoplasticity line style novolaks.The UF resin is a thermosetting resin.Therefore, pointed as the Gerber that quotes previously, the chemical property of PF resin is not the omen of UF resin chemical property.
The UF precondensate can mix with the liquid phenolic resin system.But this system is carried out catalysis by alkaline environment (pH is greater than 7) is provided, and in contrast, unmixing urea aldehyde prepolymer uses acid catalyst.
Therefore, need to use the curable urea-formaldehyde adhesive composition of potential acid hardening component, it will provide desired working time and hardening time under environment or the condition near environment.It is wondrous and unexpected to the improvement based on the adhesive composition of urea aldehyde that result described below provides.
Summary of the invention
In one embodiment of the invention, provide curable adhesive composition, it comprises:
Lauxite; With
Aryl phosphite.
In another embodiment of the present invention, curable adhesive composition is provided,
It comprises:
Lauxite; With
Aryl phosphite, its amount is the about 0.05 weight %～about 15 weight % based on total resin weight.
Detailed Description Of The Invention
According to one embodiment of the invention, provide the curable adhesive composition of the aryl phosphite that uses various concentration.The distinct advantages of this curing system comprises: the improvement of urea-formaldehyde adhesive color, thus improved final products as the outward appearance in sand paper; Solidify faster, thereby saved energy in the industry of Engineered Wood Product Manufacturing goods.Color improvement is because the aryl phosphite component to a great extent.The aryl phosphite that plays antioxidant action is known as the stabilizing agent in the multiple polymers.
In another embodiment of the invention, provide the curable urea-formaldehyde adhesive composition that discharges in time.Have been found that aryl phosphite, for example triphenyl phosphite plays the promoter effect in preformed curable adhesive, but is the mode that discharges with in time, and wherein decisive parameter is a temperature.For example, curing system is stable under about 70 °F (about 21 ℃), but quickens at about 80 (about 27 ℃) above curing reaction.Working time be about 0.5 hour～more than 100 hours.The spendable amount of aryl phosphite of the present invention is the about 0.05 weight %～based on about 15 weight % of total resin weight based on total resin weight.Lauxite is particularly useful in adhesive composition.Thereby, grinding agent product and Engineered Wood Product Manufacturing purposes that this curable adhesive composition that discharges in time can be used for applying.
In this article term " sclerosis " and " curing " but mutual alternative ground use.
Aryl phosphite curing agent of the present invention is the ester of phosphorous acid, and it has: two aromatics organic ester groups and acidic hydrogen, three aromatic ester groups or two aromatic ester groups and an alkyl group.As an illustration, curing agent can be dibasic phosphite ester such as hydrogen phosphite diphenyl ester (" DPP "), or trisubstituted phosphite ester such as triphenyl phosphite (" TPP ").
In the presence of water, aryl phosphite of the present invention controllably is hydrolyzed into stronger acid product in a period of time, and finally is hydrolyzed into phosphorous acid.Phosphorous acid is that dissociation constant pKa is 1.20 strong acid.The acidity of phosphorous acid is enough to provide the environment temperature sclerosis of Lauxite or hardens near environment temperature.
Aryl phosphite curing agent of the present invention can be represented by general formula (I)
(Ar-O) 2-P-OX
(I)
Wherein Ar is an aryl, and X is selected from hydrogen, aryl or alkyl.Herein with document in, have the aryl phosphite of two ester groups and a hydrogen atom, hydrogen phosphite diphenyl ester is for example also mentioned with ester group and the title of omitting hydrogen, for example phosphorous acid diphenyl ester (" DPP ") simply.Useful aryl phosphite curing agent comprises: hydrogen phosphite diphenyl ester (DPP), hydrogen phosphite diformazan phenyl ester (preferred between or contraposition), the hydrogen phosphite phenyl is to the toluene ester, hydrogen phosphite phenyl m-tolyl ester, hydrogen phosphite dinaphthyl ester, phosphorous acid diphenyl isopropyl ester, phosphorous acid diphenyl methyl esters, the own ester of phosphorous acid two (p-methylphenyl), triphenyl phosphite (TPP), tricresyl phosphite (toluene) ester, the different monooctyl ester of phosphorous acid diphenyl, phosphorous acid diphenyl 2-Octyl Nitrite, phosphorous acid diphenyl isodecyl ester, phosphorous acid diphenyl cyclohexyl, phosphorous acid 2-chloroethyl diphenyl ester etc.A kind of useful commercial DPP solution is DOVERPHOS 213, can be from Dover Chemical Corp., and Dover, Ohio buys.A kind of useful commercial TPP solution is DOVERPHOS 10, can be from Dover Chemical Corp., and Dover, Ohio buys.
By change total moisture content, use retarding agent or promoter additive, specific phosphorous acid curing agent and amount and temperature, can in wide region, change working time of resin.The working time of room temperature of the present invention or environment temperature hardening composition can be about 15 minutes extremely up to about 20 hours.Can use the Shore Instrument ﹠amp that is positioned at New York; The D type hardness tester meter of Manufacturing Company is measured Shore D hardness.Another method of testing of measures ambient temperature sclerosis uses rod to be coated with machine, wherein described in the qualitative flow program of hereinafter mentioning (Qualitative FlowProcedure), in mixed 24 hours or shorter time, the composition of being made up of Lauxite, aryl phosphite and water is " rigid (stick hard) adheres ".The environment temperature hardening composition is preferably those compositions with hydrogen phosphite diaryl ester, triaryl phosphites or phosphorous acid diaryl mono alkyl ester.Available about 1%～10% water prehydrolysis triaryl phosphites or phosphorous acid diaryl mono alkyl ester based on aryl phosphite weight.The pre-solvolysis of available water, alkanol, glycol and composition thereof has the phosphite ester of three organic substituents.Aryl phosphite of the present invention can be prepared with promoter.But these preliminary treatment will weaken release performance in time of the present invention.
Preferably with aryl phosphite with three organic substituents, as triaryl phosphites or phosphorous acid diaryl mono alkyl ester as potential curing agent, at ambient temperature hardenable compositions is provided the stationary phase of prolongation, and under the temperature that suitably improves, for example be not higher than under 60 ℃ the temperature, for example under about 35 ℃～50 ℃, provide quick-hardening.Thereby, depending on the level of aryl phosphite, this curing agent can keep fluid 5 hours or the longer time under about 23 ℃ temperature, but solidified fast under higher temperature.But, by using the hydrogen phosphite diaryl ester of low concentration, or the water of low concentration, or use with retarding agent, hydrogen phosphite diaryl ester and triaryl phosphites or phosphorous acid diaryl mono alkyl ester also can have the environment temperature stationary phase of prolongation, then quick-hardening under the temperature that suitably improves.
Basis is the viscosity of Lauxite, aryl phosphite and water, can keep flowing several hours at ambient temperature extremely up to the time more than 100 hours, and it is based on the concentration of aryl phosphite.
The amount of the aryl phosphite that uses among the present invention can change in wide region.For example, in curable urea-formaldehyde adhesive of the present invention, the amount of the aryl phosphite of preferable range can be the about 0.05 weight %～about 15 weight % based on total resin weight.When using DPP, preferred scope is based on about 0.1 weight %～about 2 weight % of total resin weight; Most preferred scope is based on about 0.30 weight %～about 2 weight % of total resin weight.When using TPP, preferred scope is based on about 0.25 weight %～about 5 weight % of total resin weight.
Lauxite of the present invention (" UF resin ") is a water-base resin, can use the sclerosis of curing agent or promoter.For example, the U of useful UF resin: the F mol ratio is about 1: 1～about 1: 3.5.The pH of UF resin of the present invention can be about 4～about 9.In the present invention, can use formaldehyde scavenger, urea for example, its can by after join in the Lauxite.The UF resin of modification can be used for adhesive of the present invention.
But employed Lauxite in the useful in the present invention application of adhesive precursor composition, but can form by urea or any urea derivative and any aldehyde that can be become with coating, they can react with the speed of accelerating one in the presence of catalyst, and the abrasive article with the acceptable nonferromagnetic substance of desired use is provided.This resin comprises the product of aldehyde and urea.As already pointed out, Lauxite is preferred in grinding agent industry, this thermal property owing to them, availability, low cost and be easy to processing.Lauxite is preferably 30～95% solids, and more preferably 60～80% solids are before adding entry and catalyst, viscosity is about 125～about 1500cps (Brookfield viscometer, No. 3 rotors, 30rpm, 25 ℃), molecular weight (number average) is at least about 200, and preferred about 200～700.
Be used for preferred Lauxite of the present invention and be known to Borden Chemical, Inc., Columbus, the trade names of OH " AL3029 ".This is a kind of unmodified (promptly not containing furfural) Lauxite, and 65% solid viscosity (Bu Shi, No. 3 rotors, 30rpm, 25 ℃) is 325cps, and free formaldehyde content is 0.1～0.5 weight %.
By using and phosphorous acid acid identical or acid stronger acid, i.e. pK aBe 1.20 or following acid, with the pH of Lauxite be reduced to about 4 or more than, have higher pK with use aAcid compare, increased hardening of resin speed with aryl phosphite.PK aBe 1.2 or following acid can mention sulfamic acid, oxalic acid, dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid and phenol sulfonic acid illustratively.Ammonium chloride can be used as the source of hydrochloric acid and/or cushioning liquid component.Acid with more weak than phosphorous acid acidity reduces pH as acetate, formic acid, benzoic acid and salicylic acid, and the acid that has the acidity that is equal to or greater than phosphorous acid with use is compared, and causes the lower activity to phosphite ester.
[0022] in curable adhesive of the present invention, also can use catalyst.The example of useful catalysts includes but not limited to Lewis acid, for example aluminium chloride etc.Preferred those are selected from the Lewis acid of aluminium chloride, iron chloride (III) and copper chloride (II).Particularly preferably be Lewis acid aluminium chloride, be non-hydrated form (AlCl 3) or six hydrated form (AlCl 36H 2O).Useful catalysts also comprises moisture organic amine salt or ammonium ion salt.If use ammonium ion salt, it is preferably ammonium ion (NH 4 +) and halogen ion such as chlorion (Cl -), fluorine ion (F -), bromide ion (Br -) salt that waits.Particularly preferred ammonium ion salt is ammonium chloride (NH 4Cl).Ammonium sulfate ((NH 4) 2SO 4), ammonium peroxydisulfate ((NH 4) 2S 2O 8), ATS (Ammonium thiosulphate) ((NH 4) 2S 2O 3) and ammonium nitrate (NH 4NO 3) be considered to be suitable for the present invention, especially with AlCl as co-catalyst 3When being used in combination, can be used as useful ammonium ion salt.Usually use and the preferred in some cases mixture that uses inorganic and organic salt.
Sclerous reaction of the present invention needs water, so that the aryl phosphite hydrolysis for example finally is hydrolyzed into phosphorous acid.Total moisture content in the composition promptly can be used for the water of hydrolysis phosphite ester, can in wide region, change, and as the water of about 0.15～5 weight portion of every weight portion aryl phosphite, the water of about 0.3～3 weight portion of preferred every weight portion phosphite ester.The total moisture content that needs can be from any composition in the composition, Lauxite for example, or can in composition, add extra water.
Composition of the present invention can comprise filler, modifier and the aggregation that uses with Lauxite usually.Aggregate material can be granular materials, as the material of granular, powder or sheet form.Suitable aggregate material includes but not limited to: sand, aluminium oxide, zirconia, silica, zircon sand, olivine sand, carborundum, silicon nitride, boron nitride, bauxite, quartz, chromite and corundum and composition thereof.For some application, preferred low-density aggregate material such as vermiculite, perlite and float stone.For other application, preferred high-density aggregation body comprises: quartz sand, gravel, rubble and disconnected brick.Can use filler such as mica, kaolin, wollastonite and barite.Composition of the present invention can be used to make the abrasive article of coating, paper.
But useful in the present invention application of adhesive composition can comprise filler, fiber, lubricant, grinding aid, antistatic additive, wetting agent and other additive such as surfactant, pigment, dyestuff, coupling agent, plasticizer, dispersant and suspending agent.Select these amount of substances to obtain desired character, for example improve the wettable of abrasive particles.Perhaps, can not use these additives to be formed with the adhesive precursor composition of usefulness, and only before being coated on the substrate, additive is mixed in the adhesive precursor.
Adhesive composition of the present invention can comprise formaldehyde scavenger such as urea and ammonium compounds.
In the abrasive article of being everlasting, use filler, to reduce cost and to improve dimensional stability and other physical property.Filler can be selected from the packing material of the nonferromagnetic substance of any rheological property that can not influence adhesive precursor nocuously or resulting abrasive article.Preferred filler comprises calcium silicates, aluminum sulfate, hibbsite, ice crystal, magnesia, kaolin, quartz and glass.Filler as grinding aid is ice crystal, potassium fluoborate, feldspar and sulphur.Can various amounts use filler, restrictive condition only is that abrasive article keeps acceptable engineering properties (as flexibility and toughness).
But can be the above-mentioned application of adhesive precursor composition of cured form by introducing, prepare the abrasive article of coating of the present invention.Backing can be polymer film, the scraps of paper or laminate.
Use for timber engineering, for example composite plate etc. can be used ligno-cellulosic materials.The example of ligno-cellulosic materials includes but not limited to, the wood-fibred of wood-fibred, wooden thin slice, wood fiber bundle, wood chip and wooden particle, straw, bagasse, bark, recovery, paper fiber of recovery and composition thereof.The composite plate of preparation is known as fiberboard, wood shavings fiberboard, particieboard (strandboard), directed particieboard, flakeboard, particle particieboard (particleboard) etc.
Several contrast experiments have illustrated purposes of the present invention.These experiments are grinding agent and timber application design; Therefore, in adhesive formula, introduce co-catalyst.The unit of curable adhesive A-B component is based on the UF resin that is set to given quality, and all other components are set to the umber of the given UF resin of every quality then.Use sclerosis experiment, its viscosity measurement and the observation of curable adhesive A-B to be shown in table 1.Use Brookfield viscometer, the DV-11+ type, the #18 rotor, 20rpm determines the viscosity reading, viscosity unit is centipoise (cps).The time of all reaction time by all components initial mixing begins to calculate.
The contrast adhesive A
AL3029R 70
Water 7
25% ammonium chloride 3.64
28% aluminium chloride 0.49
With the abundant blending ingredients of said sequence, place 15～20 ℃ bath then at ambient temperature.After 5 hours, the viscosity of reactant mixture is 116.8cps from initial mixing.After 5 hours 30 minutes, mixture placed 32 ℃ stove.After 6 hours 10 minutes, the viscosity of reactant mixture is 136.5cps.
Curable adhesive A1
AL3029R 70
Water 7
25% ammonium chloride 3.64
28% aluminium chloride 0.49
DOVERPHOS 10 0.84
With the abundant blending ingredients of said sequence, place 15～20 ℃ bath then at ambient temperature.After 4 hours 55 minutes, the viscosity of reactant mixture is 122.7cps from initial mixing.After 5 hours 20 minutes, mixture placed 32 ℃ stove.After 6 hours 5 minutes, the viscosity of reactant mixture is 149.4cps.
Curable adhesive A2
AL3029R 70
Water 7
25% ammonium chloride 3.64
28% aluminium chloride 0.49
DOVERPHOS 10 1.26
With the abundant blending ingredients of said sequence, place 15～20 ℃ bath then at ambient temperature.After 4 hours 50 minutes, the viscosity of reactant mixture is 128.3cps from initial mixing.After 5 hours 10 minutes, mixture placed 32 ℃ stove.After 6 hours, the viscosity of reactant mixture is 159.2cps.
Curable adhesive A3
AL3029R 70
Water 7
25% ammonium chloride 3.64
28% aluminium chloride 0.49
DOVERPHOS 10 3.5
With the abundant blending ingredients of said sequence, place 15～20 ℃ bath then at ambient temperature.After 4 hours 50 minutes, the viscosity of reactant mixture is 156.3cps from initial mixing.After 5 hours 5 minutes, mixture placed 32 ℃ stove.After 6 hours, the viscosity of reactant mixture is 208.2cps.
Curable adhesive A4
AL3029R 70
Water 7
25% ammonium chloride 3.64
28% aluminium chloride 0.49
DOVERPHOS 213 0.21
With the abundant blending ingredients of said sequence, place 15～20 ℃ bath then at ambient temperature.After 4 hours 45 minutes, the viscosity of reactant mixture is 188.2cps from initial mixing.After 4 hours 55 minutes, mixture placed 32 ℃ stove.After 6 hours, the viscosity of reactant mixture is 456.5cps.Viscosity continues to increase second with about 3.5cps/.
Contrast adhesive B
AL3029R 70
Water 7
25% ammonium chloride 3.64
28% aluminium chloride 0.49
With the abundant blending ingredients of said sequence, place 15～20 ℃ bath then at ambient temperature.After 4 hours 15 minutes, the viscosity of reactant mixture is 116cps from initial mixing.After 4 hours 30 minutes, mixture placed 32 ℃ stove.After 5 hours 10 minutes, the viscosity of reactant mixture is 125.4cps.
Curable adhesive B1
AL3029R 70
Water 7
25% ammonium chloride 3.64
28% aluminium chloride 0.49
DOVERPHOS 213 0.07
With the abundant blending ingredients of said sequence, place 15～20 ℃ bath then at ambient temperature.After 4 hours 10 minutes, the viscosity of reactant mixture is 121.8cps from initial mixing.After 4 hours 20 minutes, mixture placed 32 ℃ stove.After 5 hours, the viscosity of reactant mixture is 139.2cps.
Curable adhesive B2
AL3029R 70
Water 7
25% ammonium chloride 3.64
28% aluminium chloride 0.49
DOVERPHOS 213 0.14
With the abundant blending ingredients of said sequence, place 15～20 ℃ bath then at ambient temperature.After 4 hours 10 minutes, the viscosity of reactant mixture is 130.1cps from initial mixing.Then, mixture is placed 32 ℃ stove.After 4 hours 50 minutes, the viscosity of reactant mixture is 164.3cps.
Curable adhesive B3
AL3029R 70
Water 7
25% ammonium chloride 3.64
28% aluminium chloride 0.49
DOVERPHOS 213 0.84
With the abundant blending ingredients of said sequence, place 15～20 ℃ bath then at ambient temperature.After 2 hours 40 minutes, gel has taken place in reactant mixture from initial mixing, and is still soft.
Table 1 viscosity measurement and observation
Adhesive/time 2/ temperature Phosphite ester level (%) 1 Viscosity (cps) % increase/control experiment
A/5 hour/15 ℃ -- 116.8
A/6 hour 10 minutes/32 ℃ -- 136.5
A1/4 hour 55 minutes/15 ℃ 1.2(TPP) 122.7
A1/6 hour 5 minutes/32 ℃ 1.2(TPP) 149.4 9.4
A2/4 hour 50 minutes/15 ℃ 1.8(TPP) 128.3
A2/6 hour/32 ℃ 1.8(TPP) 159.2 16.6
A3/4 hour 50 minutes/15 ℃ 5.0(TPP) 156.3
A3/6 hour/32 ℃ 5.0(TPP) 208.2 52.5
A4/4 hour 45 minutes/15 ℃ 0.3(DPP) 188.2
A4/6 hour/32 ℃ 0.3(DPP) 456.5 334
B/4 hour 15 minutes/15 ℃ -- 116
B/5 hour 10 minutes/32 ℃ -- 124.5
B1/4 hour 10 minutes/15 ℃ 0.1(DPP) 121.8
B1/5 hour/32 ℃ 0.1(DPP) 139.2 11.8
B2/4 hour 10 minutes/15 ℃ 0.2(DPP) 130.1
B2/4 hour 50 minutes/32 ℃ 0.2(DPP) 164.3 32.0
B3/2 hour 40 minutes/15 ℃ 1.2(DPP) Immeasurability, gel
1Based on weight resin; Phosphite ester is expressed as DPP or TPP
2For each embodiment, the time is accumulated
Shown in above table 1, adhesive composition of the present invention can be designed to solidify in the mode that discharges in time, can be used for the grinding agent product of Production Example as applying.The curing properties that has compared the adhesive of aryl phosphite with varying level.When having the aryl phosphite of reduced levels in the adhesive, observing viscosity has unexpected raising.For example, for 0.2～0.3% DPP level, viscosity has increased by 32% and 334% respectively.Under higher DPP level, sclerosis even faster.In addition, for 1.8 and 5.0% TPP level, viscosity has increased by 17% and 52% respectively.The temperature that increases and the aryl phosphite of effective dose also can promote the curing in the adhesive of the present invention together.
According to principle of the present invention, curable urea-formaldehyde adhesive composition is disclosed, it comprises the aryl phosphite curing agent that plays the promoter effect in the mode that discharges in time.The curable urea-formaldehyde adhesive composition of the Shi Fanging abrasive article that can be used for for example applying in time.Though above embodiment is that they are not meant to limit the scope of accessory claim as representative of the present invention.It will be apparent to one skilled in the art that in the scope that does not depart from spirit of the present invention and accessory claim and can make improvements.

Claims (20)

1, curable adhesive composition, it comprises:
Lauxite; With
Aryl phosphite.
2, the curable adhesive of claim 1, wherein the amount of aryl phosphite existence is the about 0.05 weight %～about 15 weight % based on total resin weight.
3, the curable adhesive of claim 1, wherein the ratio of the urea of Lauxite and formaldehyde is about 1: 1～about 1: 3.5.
4, the curable adhesive of claim 1, wherein curable adhesive also comprises at least a catalyst.
5, the curable adhesive of claim 1, wherein the pH of Lauxite is about 4～about 9.
6, the curable adhesive of claim 2, wherein the pH of Lauxite is about 4～about 9.
7, the curable adhesive of claim 3, wherein the pH of Lauxite is about 4～about 9.
8, the curable adhesive of claim 1, wherein aryl phosphite is selected from phosphorous acid diphenyl ester and triphenyl phosphite.
9, the curable adhesive of claim 4, wherein at least a catalyst is selected from aluminium chloride and ammonium chloride.
10, the curable adhesive of claim 4, wherein at least a catalyst are the combinations of aluminium chloride and ammonium chloride.
11, curable adhesive composition comprises:
Lauxite, the ratio of its urea and formaldehyde are about 1: 1～about 1: 3.5;
25% ammonium chloride solution, its amount is the about 2 weight %～about 10 weight % based on total resin weight;
28% liquor alumini chloridi, its amount is the about 0.1 weight %～about 2 weight % based on total resin weight;
Water, its amount is the about 5 weight %～about 20 weight % based on total resin weight; With
Aryl phosphite, its amount is the about 0.05 weight %～about 15 weight % based on total resin weight.
12, the curable adhesive of claim 11, wherein aryl phosphite is selected from phosphorous acid diphenyl ester and triphenyl phosphite.
13, the curable adhesive of claim 12, wherein aryl phosphite is the phosphorous acid diphenyl ester, and further, wherein the amount of phosphorous acid diphenyl ester existence is the about 0.1 weight %～about 2 weight % based on total resin weight.
14, the curable adhesive of claim 13, wherein the amount of phosphorous acid diphenyl ester existence is the about 0.30 weight %～about 2 weight % based on total resin weight.
15, the curable adhesive of claim 12, wherein aryl phosphite is a triphenyl phosphite, and further, wherein the amount of triphenyl phosphite existence is the about 0.25 weight %～about 5 weight % based on total resin weight.
16, the abrasive article of coating that comprises the cure adhesive of claim 1.
17, the abrasive article of coating that comprises the cure adhesive of claim 11.
18, the Engineered Wood Product Manufacturing goods that comprise the cure adhesive of claim 1.
CN038271168A 2003-09-26 2003-09-26 Time released curing system Expired - Fee Related CN1839037B (en)

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GB1573114A (en) * 1976-12-08 1980-08-13 Ici Ltd Paper
US4528344A (en) * 1984-05-21 1985-07-09 Ppg Industries, Inc. Low molecular weight resins from nonaromatic polyols and aminoplasts
DE4035249A1 (en) * 1990-11-06 1992-05-07 Gruenzweig & Hartmann MOLDED PART FROM MINERAL WOOL FOR THE CULTIVATION OF PLANTS
CN1077676A (en) * 1992-04-16 1993-10-27 青州市木器厂 Wood-based plate
DE69303027T2 (en) * 1992-09-15 1996-12-19 Minnesota Mining & Mfg Coated abrasives made from coatable urea-aldehyde compositions containing a cocatalyst and methods of making same
KR100353308B1 (en) * 1994-03-15 2002-12-28 프라운호퍼-게젤샤프트 츄어 푀르더룽 데어 안게반텐 포르슝에.파우. Methods for reproducing sawdust and fiber from materials, including small pieces of wood, used furniture, residues of wood products, wood waste and other wood
US6133403A (en) * 1996-12-23 2000-10-17 Borden Chemical, Inc. Reactive diluents for acid curable phenolic compositions
US6224800B1 (en) * 1998-12-17 2001-05-01 Bayer Corporation Extended polymethylene poly(phenylisocyanate) resin binders for the production of wood composite products

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WO2005039874A1 (en) 2005-05-06
CN1839037B (en) 2010-08-18
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AU2003272722A1 (en) 2005-05-11
BR0318512A (en) 2006-09-12
CA2470193A1 (en) 2005-03-26

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