CN1526526A - Resin composition for impregnating wood and impregnated wood - Google Patents
Resin composition for impregnating wood and impregnated wood Download PDFInfo
- Publication number
- CN1526526A CN1526526A CNA2004100076651A CN200410007665A CN1526526A CN 1526526 A CN1526526 A CN 1526526A CN A2004100076651 A CNA2004100076651 A CN A2004100076651A CN 200410007665 A CN200410007665 A CN 200410007665A CN 1526526 A CN1526526 A CN 1526526A
- Authority
- CN
- China
- Prior art keywords
- methyl
- acrylate copolymer
- resin combination
- timber
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The resin composition for a timber impregnation comprises a resin composition containing a (meth)acrylate polymer component and a radically polymerizable monomer component wherein the (meth)acrylate polymer component indispensably contains a crosslinking (meth)acrylate polymer having at least one radically polymerizable double bond in the molecule.
Description
Technical field
The present invention relates to impregnated timber and solidify after with the incorporate impregnated timber of timber with resin combination, timber and the incorporate prewood of cured resin.
Background technology
In recent years, in the building trade of buildings such as dwellings and office, people wish the living space back to nature more and more strongly, and the natural texture that timber had gains great popularity.And, the building materials of wood type are also had higher requirement at building material industry.
Yet, if the building materials of this wood type are not treated just directly use, because timber is inferior to the durability of heat, water (moisture), mechanical shock etc., so after the building materials construction, phenomenons such as variable color, rotten, bending that change in size causes, surface checking, breakage might take place once long in the time, thereby it can not keep good quality for a long time as building materials.Therefore, study at present, can keep natural texture that timber has, usability etc., can improve the chemical treatment timber to the durability of heat, water (moisture), mechanical shock etc. of timber again.
In chemical treatment timber, prewood, be with liquid curing resin, free radical polymerization monomer (below, be commonly referred to as monomer) be cured after the impregnated timber that becomes to grade and obtain, because it can bring into play the characteristic that timber has, improve intensity and durability, so be widely used with construction timber etc. with the upholstery of material etc. as flooring board and stair.
As the impregnated timber resin combination, general use will contain that the unsaturated polyester (UP) of styrene etc. or poly-(methyl methacrylate) etc.s (methyl) acrylate copolymer dissolve and the acrylic acid slurries that obtain (for example, Japan Patent disclose the communique spy open flat 4-144704 number) etc. in the free radical polymerization monomer composition that methyl methacrylate (MMA) waits.Yet because the weatherability deficiency of unsaturated polyester resin is used under the prewood occasion of this resin dipping in the place of solar light irradiation, time one length will variable color.Also have, though aforesaid propylene wintercherry liquid weatherability is relatively good, but owing to contain a large amount of volatility MMA,, can not form cured resin well at wood surface and film so MMA volatilizees from wood surface during resin solidification, still film from cured resin as the timber of base material and to expose, cause bad order (inequality of filming), perhaps, follow the volume shrinkage mass of curing also to increase owing to contain a large amount of monomers, so at impregnated timber and after solidifying, timber can bend, ftracture.
Also have, behind these resin combination impregnated timbers when solidifying, when in the part that wood surface exists with air directly contacts, airborne oxygen can hinder Raolical polymerizable, thereby curing can not be carried out (curing property is low) fully, phenomenon of blocking may take place in residual tack (adhesivity), reduction usability in the polishing operation.
Summary of the invention
Problem to be solved by this invention is: a kind of impregnated timber resin combination is provided, can forms and not only have excellent curing, but also be used for prewood and have the cured resin of durability to film.
Impregnated timber resin combination of the present invention, it is the resin combination that contains (methyl) acrylate copolymer composition and free radical polymerization monomer composition, it is characterized in that in (methyl) acrylate copolymer composition, must be included in bridging property (methyl) acrylate copolymer that has at least one free-radical polymerised pair of key in the molecule.
The present invention also comprises, with above-mentioned impregnated timber with the resin combination impregnated timber after, make the manufacture method of the prewood that this resin combination solidifies and the prewood that obtains according to this manufacture method.
Constitute according to foregoing invention, can provide can form curing property good, guarantee the impregnated timber resin combination that prewood has the cured resin of enough durability to film.Simultaneously, the prewood that obtains is superior in quality, phenomenons such as minority generation bad order, bending, cracking.Thereby prewood of the present invention has excellent hear resistance, and has the durability for factors such as heat, water (moisture), mechanical shocks, and the building materials that are suitable as floor timber etc. are with timber etc.
The specific embodiment
The impregnated timber that the present inventor is solidified after to impregnated timber with resin combination (below, be commonly referred to as resin combination) result that furthers investigate, find: a kind of (methyl) acrylate copolymer composition, this composition is included in bridging property (methyl) acrylate copolymer that has at least one free-radical polymerised pair of key in the molecule, also use and the good curing of resin combination oblatio of formation with free yl polymerizating monomer, and on the prewood that uses this resin combination to obtain, the cured resin that the forms oblatio of filming has enough durability as prewood, and bad order does not take place, crooked, phenomenons such as cracking.Moreover impregnated timber of the present invention is with " impregnated timber " of resin combination, be meant this resin combination from wood surface permeate into, all or part of inner and surperficial space of timber of filling up.Also have, " polymer " of the present invention is not limited only to bipolymer, also comprises the multiple copolymer that ternary is above.
Impregnated timber of the present invention with (methyl) acrylate copolymer composition of resin combination (below, be commonly referred to as A) in, must be included in bridging property (methyl) acrylate copolymer that has at least one free-radical polymerised pair of key in the molecule (below, be commonly referred to as A1), promptly this bridging property (methyl) acrylate copolymer (A1) contains at least one free-radical polymerised pair of key.Resin combination is if contain this bridging property (methyl) acrylate copolymer (A1), when then being heating and curing since between the polymer (A1) or with free radical polymerization monomer composition polymerization reaction take place, so can form the cured coating film of densification, high rigidity.Simultaneously, owing to improved curing, even also can solidify fully at the air contact-making surface.And the if tree oil/fat composition contains plasticizer (will mention in the back), owing to improved the intermiscibility with plasticizer, the white casse that the separation of plasticizer causes when being difficult to solidify.
When synthesizing cross-linked property (methyl) acrylate copolymer (A1), at first, synthetic non-crosslinked does not promptly have free-radical polymerised pair of key, (methyl) acrylate copolymer (A2) in the molecule.This (methyl) acrylate copolymer (A2) is, must contain the monomer component radical polymerization of (methyl) acryl monomer (a1) and the polymer that obtains.Above-mentioned monomer (a1) has, for example, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) propyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentenyl 2-ethoxyethyl acetate, (methyl) acrylic acid methoxyl group diethylene glycol (DEG) ester, (methyl) acrylic acid ethoxydiglycol ester, (methyl) phenoxyethyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylate such as (methyl) acrylic acid hydroxy butyl ester can use one of them or multiple mixing to use.
Also have, when the polymerization of (methyl) acrylate copolymer (A2), with above-mentioned monomer (a1) together, be necessary to use unsaturated monocarboxylic acids such as (methyl) acrylic acid, butenoic acid, the unsaturated dicarboxylic acid of maleic acid, fumaric acid, itaconic acid etc. and the carboxylic monomers (a2) such as monoesters of these unsaturated dicarboxylic acids; (methyl) glycidyl acrylate, glycidyl acrylate ether etc. contain the monomer (a3) of glycidyl.By using these monomers (a2) or monomer (a3), can on the side chain of (methyl) acrylate copolymer (A2), import carboxyl or glycidyl.And,, can obtain (methyl) acrylate copolymer (A1) that molecule contains free-radical polymerised pair of key by making the carboxyl on this side chain and above-mentioned monomer (a3) reacts or glycidyl and above-mentioned monomer (a2) on this side chain are reacted.Using monomer (a2) to use under the occasion of monomer component as (methyl) acrylate copolymer (A2), do not contain monomer (a3) in this monomer component, otherwise too.This is because the cause of gelation takes place in the polymerization way.
Above-mentioned monomer (a2) or (a3), (methyl) acrylate copolymer (A2) with monomer component 100 quality % in, be preferably 0.5～20 quality %.If less than 0.5 quality %, then the double bond content in bridging property (methyl) acrylate copolymer (A1) very little, so may residual stickness when resin combination solidifies, cause usability to reduce.More preferably lower limit is 0.8 quality %, and further the preferred lower limit value is 1.0 quality %.On the other hand, aforementioned proportion is if surpass 20 quality %, and then the durability of the prewood that is obtained by resin combination might descend.Preferred higher limit is 15 quality %, and further preferred higher limit is 10 quality %.
In addition; when synthesizing above-mentioned (methyl) acrylate copolymer (A2); not damage effect degree of being of the present invention; can and use (methyl) acryloyl group monomer with free-radical polymerised pair of key (a4) in addition, (methyl) acryloyl group for example has styrene, AMS, vinyltoluene, N-vinyl pyrrolidone, alpha-olefin etc.
As the synthetic method of (methyl) acrylate copolymer composition (A2), can use general polymerisation.For example, polymerisation in bulk (Bulk polymerization), polymerisation in solution, suspension polymerisation, emulsion polymerisation etc.Reaction conditions such as reaction temperature during above-mentioned polymerisation and reaction time are suitably set and are got final product.Also have, above-mentioned polymerisation is preferably carried out under nitrogen atmosphere.And, preferably add chain-transferring agent and carry out in order to adjust mean molecule quantity.Have as above-mentioned chain-transferring agent, thio-compounds such as mercaptopropionic acid, lauryl mercaptan, benzenethiol also have α-styrene dimer body, carbon tetrachloride etc.Addition as above-mentioned chain-transferring agent can suitably be set according to the kind of chain-transferring agent and the kind of monomer component.But, to monomer component 100 mass parts, preferably in the scope of 0.01～15 mass parts.
In above-mentioned polymerisation, preferably use radical polymerization initiator.As having of above-mentioned polymerization initiator, organic peroxides such as benzoyl peroxide, laurylperoxide base formyl, t-butyl peroxybenzoate, cumene hydroperoxide also have the azo compound of azodiisobutyronitrile etc. etc.Moreover, in the polymerization way, finishing reaction, the mixture that obtains (methyl) acrylate copolymer (A2) and unreacted monomer just can.
Obtaining (methyl) acrylate copolymer (A2) by polymerization afterwards, as above-mentioned, by carboxyl and above-mentioned monomer (a3) reaction that makes this (methyl) acrylate copolymer (A2), perhaps make the glycidyl and above-mentioned monomer (a2) reaction of this (methyl) acrylate copolymer (A2), can obtain (methyl) acrylate copolymer (A1) that molecule contains free-radical polymerised pair of key.When reaction, select known esterification catalyst for use.
The mean molecule quantity of bridging property (methyl) acrylate copolymer (A1) is preferred, with number-average molecular weight (Mn) 5,000～500,000 scope.If number-average molecular weight less than 5,000, the durability of prewood may descend.The lower limit of above-mentioned number-average molecular weight (Mn) is preferably 10,000.On the other hand, if number-average molecular weight surpasses 500,000, then the viscosity of resin combination uprises, to impregnation of timber decline.Thereby the higher limit of number-average molecular weight (Mn) is preferably 100,000, more preferably 50,000.
Also have, in bridging property (methyl) acrylate copolymer (A1), be equivalent to contain this polymer molecular weight (below, be commonly referred to as the polymer molecular weight of each two key) of the two keys of a polymerizability, preferably 200～100,000 scope.When the polymer molecule quantity not sufficient 200 of each two key, the durability of the prewood that is obtained by resin combination may be not enough.Preferred lower limit is 500, and further preferred lower limit is 1,000.On the other hand, the polymer molecular weight of each two key is if surpass 100,000, can residual tack when then resin combination solidifies, and usability may descend.Preferred higher limit is 80,000, and further preferred higher limit is 50,000.If the polymer molecular weight that will make each the two key in bridging property polymer (methyl) acrylic acid (A1) is in above-mentioned scope, suitably molecular weight of adjustment (methyl) acrylate copolymer (A2) and above-mentioned monomer (a3) and consumption (a2) get final product.
(methyl) acrylate copolymer composition (A) of resin combination of the present invention, can be only to be made of above-mentioned bridging property (methyl) acrylic acid (A1), also can be the mixture of (methyl) acrylate copolymer (A2) of above-mentioned bridging property (methyl) acrylate copolymer (A1) and non-crosslinked.In the occasion of mix using, in (methyl) acrylate copolymer composition (A) 100 quality %, preferably make bridging property (methyl) acrylate copolymer (A1) account for 30 quality % or more than the 30 quality %.If bridging property (methyl) acrylate copolymer (A1) deficiency can not be brought into play fully and solidify property improvement effect and durability raising effect.
In the resin combination of the present invention, with above-mentioned (methyl) acrylate copolymer composition (A) together, with free radical polymerization monomer composition (hereinafter referred to as B) as essential composition.This free radical polymerization monomer composition (B) is by Raolical polymerizable taking place with above-mentioned bridging property (methyl) acrylate copolymer (A1), forming of cross-linked structure or multiple monomer and form.For example contain in this free radical polymerization monomer composition (B), when synthetic (methyl) acrylate copolymer (A2), can be used as monomer and the above-mentioned monomer (a1)～(a4) that uses.
Can also contain in the free radical polymerization monomer composition (B), ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol (DEG) two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, two (methyl) acrylic acid DPG ester, two (methyl) acrylic acid tripropylene glycol ester, polypropylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, 1,3-butanediol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,10-decanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 2, two [4-((methyl) acryloyl-oxy ethyoxyl) phenyl] propane of 2-, 2, two [4-((methyl) acryloyl-oxy polyethoxy) phenyl] propane of 2-, glycerine two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, alkylene oxide addition product two (methyl) acrylate of bisphenol-A, alkylene oxide addition product two (methyl) acrylate of trimethylolpropane, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, butanediol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, double trimethylolpropane four (methyl) acrylate etc. contains polyfunctional group free radical polymerization monomer (a5).
Wherein, consider from prewood durability aspect, preferred polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, 2 of using, two [4-((methyl) acryloyl-oxy polyethoxy) phenyl] propane of 2-, alkylene oxide addition product two (methyl) acrylate of bisphenol-A, alkylene oxide addition product two (methyl) acrylate of trimethylolpropane, polytetramethylene glycol two (methyl) diester acrylates are more preferably used polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate.
Free radical polymerization monomer composition of the present invention (B), in order to improve the close property of timber and resin, durability with the prewood that obtains, the free radical polymerization monomer (a6) that preferably contains hydroxyl, the free radical polymerization monomer of hydroxyl (a6) for example have (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester, (alpha-hydroxymethyl) methyl acrylate, (alpha-hydroxymethyl) ethyl acrylate, (alpha-hydroxymethyl) butyl acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate etc.The ratio of the monomer of hydroxyl (a6) is with free radical polymerization monomer composition (B) during as 100 quality %, preferably in the scope of 10～99 quality %.If the ratio of the monomer of hydroxyl is lower than 10 quality %, the impregnation of timber rate is descended, but, can cause again in the decline of air contact-making surface curing property if surpass 99 quality %.The lower limit of the monomer of hydroxyl (a6) is 20 quality % more preferably, more preferably 30 quality %.And higher limit is 95 quality % more preferably, more preferably 90 quality %.
Resin combination of the present invention also can contain plasticizer (below, be commonly referred to as C).Raolical polymerizable does not take place with (methyl) acrylate copolymer composition (A) or free radical polymerization monomer composition (B) in the free-radical polymerised organic compound of this plasticizer (C) right and wrong, can use the known compound as the plasticizer of various resins.If this plasticizer (C) is added in the resin combination, even then its volume and shape change resin combination along with cure shrinkage, prewood moisture absorption or moisture releasing, the cured coating film that obtains also changes with its variation, thereby can more effectively prevent the cracking and the bending of prewood.
Object lesson as plasticizer of the present invention (C) has, ester type compounds such as the reactant of O-phthalic acid alkyl ester, aromatic carboxylic acid esters, aliphatic two alkaline acid esters, aliphatic ester derivatives, phosphate, carboxylic acid and epoxide, saturated polyester, polycaprolactone, polyether ester; The compound of ether-containing keys such as poly-(oxyalkylene) glycol, polyethylene dimethoxym ethane, xylene formaldehyde resin; Polyamide; Polyurethane; Vinyl compound such as chlorinated paraffin wax, styrene, alkene, vinyl chloride, vinylacetate and copolymer thereof, its graft polymers, its crosslinked body etc. can use one of them or multiple mixing to use.
Wherein, set out the compound and the chlorinated paraffin wax of preferred above-mentioned ester type compound, ether-containing key with the good viewpoint of the intermiscibility in the resin combination at impregnated timber.Also have, the compatibility of timber and resin combination, the good viewpoint of dipping property are set out, preferred poly-(oxyalkylene) glycol, polyether ester, chlorinated paraffin wax.Plasticizer of the present invention (C) is and the different material of above-mentioned (methyl) acrylate copolymer composition (A).
Impregnated timber of the present invention contains with resin combination, as (methyl) acrylate copolymer composition (A) and the free radical polymerization monomer composition (B) of essential composition.With preferred embodiment, this resin combination also contains plasticizer (C).At impregnated timber with resin combination not under the situation of plasticizer-containing (C), in total amount 100 mass parts of (methyl) acrylate copolymer composition (A) and free radical polymerization monomer composition (B), preferred (methyl) acrylate copolymer composition (A) accounts for 5～70 mass parts.If (methyl) acrylate copolymer composition (A) is lower than 5 mass parts, can cause the usability variation by residual tack when then resin combination solidifies.Therefore, the lower limit of (methyl) acrylate copolymer composition (A) is 7 mass parts more preferably, more preferably 10 mass parts.On the other hand, (methyl) acrylate copolymer composition (A) is if surpass 70 mass parts, then resin combination viscosity increase, to impregnation of timber decline.Therefore, the higher limit of (methyl) acrylate copolymer composition (A) is 60 mass parts more preferably, more preferably 50 mass parts.
Under the occasion of resin combination plasticizer-containing (C), (A), in total amount 100 mass parts of (B), (C) composition, the cooperation ratio of (methyl) acrylate copolymer composition (A) is preferably 10～60 mass parts, more preferably 20～40 mass parts.If (methyl) acrylate copolymer composition (A) is lower than 10 mass parts, cause the bad order of prewood when then solidifying easily, opposite if surpass 60 mass parts, then resin combination viscosity increase, to impregnation of timber decline.
Also have,, in total amount 100 mass parts of (A), (B), (C) composition, be preferably 10～80 mass parts, more preferably 20～70 mass parts as the cooperation ratio of free radical polymerization monomer composition (B).If free radical polymerization monomer composition (B) composition is lower than 10 mass parts, the viscosity of resin combination increases, to impregnation of timber decline, and is opposite if surpass 80 mass parts, can cause prewood to solidify the back bad order.
The cooperation ratio of plasticizer (C), total amount 100 mass parts for (A), (B), (C) composition are preferably 10～80 mass parts, more preferably 15～50 mass parts.If plasticizer (C) composition is lower than 10 mass parts, then prewood bends easily and ftractures, and is opposite if surpass 80 mass parts, then can cause the durability of prewood to descend, and can not select for use.
In order to make impregnated timber of the present invention, preferably cooperate curing agent (radical polymerization initiator) in resin combination at impregnated timber of the present invention with carrying out polymerization, curing after the resin combination impregnated timber.Above-mentioned curing agent has, for example, methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butyl hydroperoxide, tert-butyl hydroperoxide 2 ethyl hexanoic acid ester, benzoyl peroxide, tert-butyl hydroperoxide isobutyl ester, 1, two (peroxidating of the uncle's hexyl) cyclohexanes, 1 of 1-, two (tert-butyl hydroperoxides) 3 of 1-, 3,5-trimethyl-cyclohexane, t-butyl peroxy-laurate, the own ester of benzylhydroperoxide uncle, the different propylene carbonate of tert-butyl hydroperoxide, 1, azo-compounds such as the peroxide of the different propylene carbonate of 1-dimethylpropyl peroxidating etc. or azodiisobutyronitrile.These compounds are by heating beginning polymerisation.
Also available other light trigger replaces above-mentioned thermal polymerization, as carrying out polymerizing curable with active energy beam.Benzoin and alkyl ethers thereof such as benzoin, benzoin methylether, benzoin ethyl ether are arranged as Photoepolymerizationinitiater initiater; Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 1, acetophenones such as 1-dichloroacetophenone, 4-(1-tert-butyl group dioxy-1-Methylethyl) acetophenone; Quinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; 2,4-dimethyl thioxanthones, 2, thioxanthene ketones such as 4-diisopropyl thioxanthones, 2-clopenthixal ketone; Ketal classes such as acetyl phenyl dimethyl ketal, benzyl dimethyl ketal; Benzophenone, 4-(1-tert-butyl group dioxy-1-Methylethyl) benzophenone, 3, benzophenones such as 3 ', 4,4 ' ,-four (tert-butyl group dioxy carbonyl) benzophenone; 2-methyl isophthalic acid-[4-(first sulfo-) phenyl]-2-morpholino propyl group-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; Acylphosphine oxide class and xanthene ketone etc.
As the use amount of above-mentioned curing agent, for resin combination 100 mass parts, preferably in the scope of 0.1～10 mass parts.If the use amount of curing agent is lower than 0.1 mass parts, curing may not be carried out fully, in addition, if use amount surpasses 10 mass parts, just may bring the problem of the storage stability aspect of composition.The lower limit of curing dose is 0.5 mass parts more preferably, and 0.8 mass parts more preferably, higher limit be 8 mass parts, 5 mass parts more preferably more preferably.
Impregnated timber of the present invention except that the plasticizer (C) of above-mentioned (methyl) acrylate copolymer composition (A), free radical polymerization monomer composition (B) and adding as required, can also contain other compound and additive with in the resin combination.Compound and additive as other have, and for example, antioxidant, ultra-violet absorber, ultra-violet stabilizer, antistatic additive, coloring pigment, dyestuff, elastomer, curing catalysts, cure retarder etc. are arranged.The amount of other compound and additive is controlled in the scope of not damaging effect of the present invention and gets final product, with respect to said composition 100 mass parts, preferably in the scope of 0.01～50 mass parts.
Impregnated timber of the present invention is preferred with resin combination, and the viscosity in the time of 25 ℃ is below 100Pas.If surpass 100Pas, then become high viscosity and make operating difficulties such as liquor charging and can bring problem in the manufacturing.The higher limit of viscosity is 50Pas more preferably, more preferably 10Pas.
With impregnated timber resin combination of the present invention,, for example, be placed on and make it to solidify, just obtain prewood in the composition behind the dipping regulating timber behind the moisture according to known method.The present invention does not have restriction especially to impregnating resin composition timber.For example, entering the coffin-die assortment class can be used, the coniferous tree of China fir, conifer, ponderosa pine, Chinese juniper, port orford cedar, Taiwan Chinese juniper etc., leaf woods such as kalopanax septemlobus, Manchurian ash, oaklet, elm, beech, birch, Ju and maple any.
As to the timber pickling method for compositions, for example, infusion process, decompression injection method, pressurization injection method, decompression/pressurization injection method, coating infusion process (settled process, pressurization) etc. are arranged, suitably select according to the shape and the purposes of timber.Shape to timber is not particularly limited.The thin plate of usefulness such as wood plate is made the prewood aspect from industrialization over the ground, and suitable depth is 0.2～30mm.
Impregnated timber of the present invention uses resin combination to the impregnation of timber amount, according to setting aptly the desired intensity of prewood, durability.But, for Kimura's 100 mass parts, preferably with composition dipping 2～200 mass parts.If amount of composition is lower than 2 mass parts, then the intensity of prewood, durability may be not enough, and if surpass 200 mass parts, then because the heating when solidifying may cause Wood Discoloration.The lower limit of the pickup of composition is 5 mass parts more preferably, 10 mass parts more preferably, and higher limit is 150 mass parts more preferably, more preferably 100 mass parts.
After impregnated timber usefulness resin combination impregnated timber of the present invention, the curing that resin combination solidifies is had, for example, use the heating means of heat/pressure compacting, hot blast, infrared ray etc., use the illuminating method of ultraviolet ray, electron ray, radioactive ray isoreactivity energy line etc.
Embodiment
Below, exemplify embodiment and specifically describe the present invention.But, scope of the present invention is not limited to these embodiment.Moreover, below, unless otherwise noted, " % " expression " quality % " and " part " expression " mass parts ".
Synthesis example 1
In the reactor of being furnished with thermometer, cooling tube, wireway and agitator, add 95 parts of methyl methacrylates, as 5 parts of the methacrylic acids of the monomer that contains carboxyl with as after 4 parts of the dodecyl mercaptans of chain-transferring agent, in the nitrogen replacement reactor.Then, with after the said mixture warming while stirring to 80 ℃, add 2 as polymerization initiator, 1 part of 2 '-azodiisobutyronitrile carries out 4 hours polymerisations, obtains the mixture of carboxylic metering system polymer and unreacted monomer.
Then, in the mixture of above-mentioned carboxylic (methyl) acrylate copolymer and unreacted monomer, as 10 parts of (methyl) glycidyl acrylates of monomer interpolation that contain glycidyl, as esterification catalyst 0.03 part of zinc octoate of interpolation with as after 0.01 part of the polymerization terminator interpolation hydroquinones, be warming up to 100 ℃, under air atmosphere, carry out 5 hours esterifications.Like this, obtain having in the molecule bridging property (methyl) the acrylate copolymer No.1 of free-radical polymerised pair of key and the mixture of unreacted monomer.Say that again unreacted monomer directly uses as the free radical polymerization monomer composition like this.The solid formation branch concentration of this mixture is 52%, the polymer molecular weight of each two key of bridging property (methyl) acrylate copolymer No.1 is 700, and number-average molecular weight (Mn) is 17,000.The mensuration of molecular weight has adopted gel permeation chromatography (GPC, TOSOH Co., Ltd. system).
Synthesis example 2
With the same reaction vessel of synthesis example 1 in, add after 1 part of 99 parts of methyl methacrylates and the methacrylic acid, carry out polymerization equally with synthesis example 1, obtain the mixture of carboxylic (methyl) acrylate copolymer and unreacted monomer.Then, in this mixture, add after 0.01 part of 7 parts of GMAs, 0.03 part of zinc octoate and the hydroquinones, carry out esterification equally with synthesis example 1, obtain the mixture of bridging property (methyl) acrylate copolymer No.2 and unreacted monomer.The solid formation branch concentration of this mixture is 60%, the polymer molecular weight of each two key of bridging property (methyl) acrylate copolymer No.2 is 4,900, number-average molecular weight is 18,000.
Synthesis example 3
With the same reaction vessel of synthesis example 1 in, after 3 parts of 100 parts of adding methyl methacrylates and the methacrylic acids, carry out polymerization equally with synthesis example 1, obtain having non-crosslinked (methyl) the acrylate copolymer No.3 of carboxyl and the mixture of unreacted monomer.This contrast with the solid formation branch concentration of mixture be 60%, the number-average molecular weight of non-crosslinked (methyl) acrylate copolymer No.3 is 20,000.
Synthesis example 4
With the same reaction vessel of synthesis example 1 in, add bisphenol type epoxy compound (trade name " EpototoYD-901 ", Dongdu changes into corporate system, average epoxy equivalent 456) 456 parts, 86 parts of methacryloxyethyl acids, as 2.3 parts of the triethylamines of esterification catalyst with as hydroquinones 0.1 part of polymerization terminator.Then, while be blown into air, be warming up to 115 ℃, reacted 6 hours, obtain the contrast vinyl acetate of acid value 7.0mgKOH/g, number-average molecular weight 990 to this mixture.
Synthesis example 5
With the same reaction vessel of synthesis example 1 in, add 98 parts of methyl methacrylates, as 2 parts of methacrylic acids that contain the monomer of carboxyl, as 100 parts of the toluene of solvent, as after 1 part of the mercaptopropionic acid of chain-transferring agent, in the nitrogen replacement reactor.Then,, add, 0.4 part of 2 '-azodiisobutyronitrile, carry out 2.5 hours polymerisations as 2 of polymerization initiator with after the said mixture warming while stirring to 80 ℃.Afterwards, be warming up to 90 ℃ again, add 2, heating is 3 hours behind 0.15 part of 2 '-azodiisobutyronitrile, adds 0.6 part of hydroquinones, obtains carboxylic (methyl) acrylic polymers.Then, in above-mentioned carboxylic (methyl) acrylic polymers, after adding 0.4 part of 4 parts of (methyl) glycidyl acrylate, tetraphenylphosphonium chloride, while be blown into the toluene solution that air is warming up to 100 ℃, reaction 5.5 hours, has obtained having in the molecule bridging property (methyl) the acrylate copolymer No.5 of the two keys of polymerism to this mixture.The polymer molecular weight of each two key of the solid formation branch concentration 43% of this polymer solution, viscosity 1750mPaS, acid value 3.0, this (methyl) acrylate copolymer No.5 is 3,600, number-average molecular weight is 25,000.
Experiment No.1～No.11
As impregnated timber resin combination of the present invention, resin that synthesis example 1～4 is obtained and free radical polymerization monomer composition mix by the proportioning shown in the table 1 and obtain resin combination.In table 1,, separate expression according to polymer and unreacted monomer the polymeric blends that obtains in the synthesis example.Also have, in experiment No.8,28 parts of bridging properties (methyl) acrylate copolymer No.2 and 28 parts of non-crosslinkeds (methyl) acrylate copolymer No.3 mixing back are used as (methyl) acrylate copolymer.The solid formation branch concentration of being somebody's turn to do (methyl) acrylate copolymer is 56%.
Then,, allocate 3 parts of " Perbutyl O " (trade name, peroxide polymerization initiator, Nof Corp.'s systems) into, obtain joining the resin combination that contains curing agent as curing agent to 100 parts of above-mentioned resin combinations.Then, be that the oaklet material veneer of 0.6mm is put in the pressure reduction vessel with the pressure-reduction outlet that is connected with vavuum pump and resin combination inlet with thickness, the degassing is 30 minutes under the negative pressure of 20 * 102Pa (15Torr).Join the resin combination that contains curing agent while keeping this decompression state to inject, make it to flood fully oaklet material veneer, left standstill 3 hours after turning back to normal pressure, take out the oaklet material veneer of resin combination dipping, remove after the unnecessary resin combination liquid, with thickness is two faces that 25 μ m PET (PET) films are clamped this veneer of oaklet material, under 125 ℃, 1MPa compacting, solidified 10 minutes.Remove the PET film, obtain prewood.With the method shown in following, estimate the prewood that obtains, the results are shown in Table 3.
Experiment No.12～No.18
Press the match ratio shown in the table 2, bridging property (methyl) the acrylate copolymer No.5 that will obtain in synthesis example 5, free radical polymerization monomer and plasticizer mix, at 70～90 ℃, 1.33 * 10
4Under the Pa (100mmHg), bleeding removed toluene in 2 hours, obtained resin combination, and evaluation result sees Table 4.
Evaluation method
(1) viscosity
With the Brookfield viscometer of JIS (JIS) K7117-1 appointment, measure viscosity down at 25 ℃.
(2) impregnation rate
The impregnation rate of composition is calculated according to following numerical expression:
Impregnation rate (%)=100 * [(quality of prewood)-(the not quality of impregnating resin timber)]/(the not quality of impregnating resin timber)
(3-1) surface state of prewood (whether toughness)
With finger touch prewood surface, estimate the prewood surface state according to sense of touch.
Zero ... it is tack-free,
* ... sticking hand.
(3-2) surface state of prewood (in the polishing operation, whether obstruction being arranged)
Strike with the hand grinding machine (Hand sander) (sand paper #240, Japanese Ryobi (RYOBI) corporate system) 20 times come and go the friction prewoods the surface, come visual assessment according to whether stopping up the sandpaper eye.
Zero ... do not stop up the sandpaper eye;
△ ... sandpaper eye chocking-up degree is slight;
* ... sandpaper eye chocking-up degree is serious.
(4) heat resistant test I
One side with sand paper (#240) friction prewood, on the thick glued board of the 15mm that has been coated with the polyurethanes bonding agent in advance, the above-mentioned prewood of mounting, and on after mounting thickness is the PET film of 25 μ m, at 125 ℃, 1MPa thermo-compressed 5 minutes, the bonding prewood of the glued board that obtains is put into 80 ± 3 ℃ thermostat, took out once every 24 hours, visual assessment face checking situation.
Zero ... almost do not ftracture;
△ ... observe slight cracking;
* ... observe serious cracking.
(5) case hardness
Use the pencil scratch hardness tester, with the pencil-lead that has loaded the 1kgf load, on the prewood surface that obtains, scratch (cut) 5 times, scuffing number of times that affirmation is found out in the scuffing on surface less than 2 times pencil in, the concentration mark of hard pencil as case hardness.
(6-1) prewood surface state (having or not the inequality of filming).
Estimate the uniformity of prewood surface coating according to visual observations.
Zero ... be formed with uniform resin coating film on the timber;
* ... the part that do not form uniform resin coating film on the timber, has still wood surface is exposed.
(6-2) prewood surface state (muddiness that has or not solidfied material).
Estimated the muddiness of prewood surface coating according to visual observations.
Zero ... be formed with transparent resin coating film on the timber;
△ ... be formed with the resin coating film of white casse a little on the timber;
* ... the resin coating film white casse that forms on the timber.
(7) heat resistant test II
Press the proportioning resin composition modulation shown in the table 2,, allocate " Perbutyl O " 2 parts into, obtained the curing agent resin composition containing as curing agent to 100 parts of this resin combinations.Then, be that the oaklet material veneer of 0.6mm is put in the pressure reduction vessel with the pressure-reduction outlet that is connected with vavuum pump and resin combination inlet, 20 * 10 with thickness
2The degassing is 30 minutes under the negative pressure of Pa (15Torr).While keeping this decompression state to inject the curing agent complexing compositions, make it to flood fully oaklet material veneer, left standstill 3 hours after turning back to normal pressure.Take out the oaklet material veneer of resin combination dipping, remove unnecessary resin combination liquid, on the thick glued board of the 15mm that has been coated with the polyurethanes bonding agent in advance, the above-mentioned prewood of mounting, and on after mounting thickness is the PET film of 25 μ m, 125 ℃, 1MPa thermo-compressed 10 minutes, make resin solidification.The glued board crimping prewood that obtains is put into 80 ± 3 ℃ thermostat, took out once, visualization, evaluation face checking situation every 24 hours.
In addition, for experiment No.17～No.18, heat resistant test II will be carried out in the following manner after the resin photocuring.In above-mentioned curing agent resin composition containing, replace " Perbutyl O " use " Darocurel173 " (trade name, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, Photoepolymerizationinitiater initiater, Germany Merck corporate system) 2 parts, with similarly above-mentioned, with resin dipping oaklet material veneer.The oaklet material veneer that taking-up is flooded with resin combination, remove after the unnecessary resin combination liquid, with thickness is that the PET film of 25 μ m covers two face, the speed that makes it then with 2m/min is the 10cm place, below of the high-pressure UV lamps (80W/cm) of 2kW by power output, makes resin solidification.Then, above-mentioned prewood behind photocuring is thrown off the PET film, this prewood of mounting on the thick glued board of the 15mm that has been coated with the polyurethanes bonding agent in advance, then mounting thickness was the PET film of 25 μ m on the prewood of this mounting, 125 ℃, 1MPa thermo-compressed 5 minutes.
Zero ... almost do not ftracture;
△ ... observe slight cracking;
* ... observe serious cracking.
(8) size changing rate
With the magic ink square of 10cm * 10cm that on prewood, draws, and accurately measure its four limits, in 25 ℃ deionized water, soak after 24 hours and take out.Timber is put into 80 ± 3 ℃ thermostat 8 hours, measure the length on four limits of square of drawing then, according to following formula driven dimension rate of change.
(size changing rate) (%)=(soak in the water and after the heating measured value)/(initial measured value) * 100.
Can find out from table 3, can fully guarantee impregnation rate with resin combination, not find the generation of the phenomenon such as cracking, obstruction on prewood surface as the impregnated timber of experiment No.1～8 of example of the present invention.Also have, dipping and solidify the prewood that this impregnated timber obtains after with resin combination, its hear resistance is good, and case hardness is also high, and durability is good.
On the other hand, in experiment No.9, owing to used (methyl) acrylate copolymer of non-crosslinked, thus viscosity residual (surface cure is low), blockage phenomenon in the polishing operation.Also have, in experiment No.10, because not with addition of (methyl) acrylate copolymer, so overall performance is inferior.Experiment No.11 has been to use the example of vinylester resin, and its overall performance is still not as example of the present invention.
Also have, can find out, added the impregnated timber resin combination in experiment No.12～18 of example of the present invention of plasticizer, can fully guarantee impregnation rate, in the difficult defectives such as inequality, white casse of filming in prewood surface from table 4.As can be known with this impregnated timber with resin combination dipping and the prewood after solidifying, its hear resistance is good, size changing rate is also low.Especially, compare with table 3, the resin combination that adds plasticizer has better hear resistance.
Table 1
| Experiment No. | Resin combination proportioning (part) | |||||||
| The kind of polymer and amount | Free radical polymerization monomer | |||||||
| Unreacted monomer (MMA) | ????HEMA | ????MMA | ????HPMA | ?PE-200 | ?9EG-A | |||
| ????1 | Bridging property (methyl) acrylate copolymer No.1 | ????52 | ????48 | ????50 | ????- | ????- | ????- | ????- |
| ????2 | Bridging property (methyl) acrylate copolymer No.2 | ????60 | ????40 | ????50 | ????- | ????- | ????- | ????- |
| ????3 | Bridging property (methyl) acrylate copolymer No.1 | ????52 | ????48 | ????30 | ????20 | ????- | ????- | ????- |
| ????4 | Bridging property (methyl) acrylate copolymer No.2 | ????60 | ????40 | ????- | ????- | ????50 | ????- | ????- |
| ????5 | Bridging property (methyl) acrylate copolymer No.2 | ????60 | ????40 | ????- | ????- | ????- | ????50 | ????- |
| ????6 | Bridging property (methyl) acrylate copolymer No.1 | ????52 | ????48 | ????30 | ????- | ????- | ????- | ????20 |
| ????7 | Bridging property (methyl) acrylate copolymer No.2 | ????60 | ????40 | ????- | ????- | ????30 | ????- | ????20 |
| ????8 | Bridging property (methyl) acrylate copolymer No.2 non-crosslinked (methyl) acrylate copolymer No.3 | ????28 ????28 | ????44 | ????50 | ????- | ????- | ????- | ????- |
| ????9 | Non-crosslinked (methyl) acrylate copolymer No.3 | ????60 | ????40 | ????50 | ????- | ????- | ????- | ????- |
| ????10 | Do not have | ????0 | ????- | ????50 | ????50 | ????- | ????- | ????- |
| ????11 | Vinyl acetate | ????100 | ????- | ????30 | ????20 | ????- | ????- | ????- |
MMA: methyl methacrylate; HPMA: hydroxypropyl methacrylate; 9EG-A: polyethyleneglycol diacrylate (common prosperity chemical company system);
HEMA: hydroxyethyl methacrylate; PE-200: polyethylene glycol monomethacrylate (Nof Corp.'s system)
Table 2
| Experiment No. | Resin combination proportioning (part) | ||||||||||
| The kind of polymer and amount | Free radical polymerization monomer | Plasticizer | |||||||||
| ????HEMA | ????MMA | ???9EG-A | ????LMA | ???HEA | ????HPA | ?RS-700 | ???K-43 | ?PP-400 | |||
| ????12 | Bridging property (methyl) acrylate copolymer No.5 | ??25 | ????26 | ????9 | ????- | ????- | ???- | ????- | ????40 | ????- | ????- |
| ????13 | Bridging property (methyl) acrylate copolymer No.5 | ??25 | ????40 | ????9 | ????10 | ????- | ???- | ????- | ????16 | ????- | ????- |
| ????14 | Bridging property (methyl) acrylate copolymer No.5 | ??25 | ????40 | ????9 | ????- | ????10 | ???- | ????- | ????- | ????16 | ????- |
| ????15 | Bridging property (methyl) acrylate copolymer No.5 | ??25 | ????40 | ????9 | ????- | ????- | ???- | ????- | ????- | ????- | ????26 |
| ????16 | Bridging property (methyl) acrylate copolymer No.5 | ??25 | ????40 | ????9 | ????10 | ????- | ???- | ????- | ????- | ????16 | ????- |
| ????17 | Bridging property (methyl) acrylate copolymer No.5 | ??26 | ????- | ????16 | ????- | ????- | ???40 | ????- | ????18 | ????- | ????- |
| ????18 | Bridging property (methyl) acrylate copolymer No.5 | ??26 | ????- | ????9 | ????10 | ????- | ???- | ????37 | ????18 | ????- | ????- |
HEMA: hydroxyethyl methacrylate; RS-700: commodity " Adekasaiza-RS-700 " (rising sun electrification corporate system);
MMA: methyl methacrylate; K-43: commodity " EnbaraK-43 " (aginomoto Fine-techno corporate system);
9EG-A: polyethyleneglycol diacrylate (common prosperity chemical company system); LMA: lauryl methacrylate;
HPA: acrylic acid hydroxypropyl ester; HEA: hydroxy-ethyl acrylate;
PP-400: polypropylene glycol (Mn=460, Sanyo changes into corporate system)
Table 3
| Experiment No. | Viscosity (mPas) | Impregnation rate (%) | The prewood surface state | Heat resistant test I | Case hardness | |||
| Sticking hand | Stop up | 24 hours | 48 hours | 72 hours | ||||
| ??1 | ????1800 | ????95 | ????○ | ????○ | ??○ | ??△ | ??× | ??2H |
| ??2 | ????2500 | ????93 | ????○ | ????○ | ??○ | ??○ | ??△ | ??2H |
| ??3 | ????1700 | ????89 | ????○ | ????○ | ??○ | ??△ | ??× | ??2H |
| ??4 | ????2700 | ????91 | ????○ | ????○ | ??○ | ??○ | ??△ | ??2H |
| ??5 | ????3100 | ????83 | ????○ | ????○ | ??○ | ??○ | ??△ | ??2H |
| ??6 | ????2600 | ????87 | ????○ | ????○ | ??○ | ??△ | ??× | ??2H |
| ??7 | ????3000 | ????85 | ????○ | ????○ | ??○ | ??○ | ??△ | ??2H |
| ??8 | ????2800 | ????81 | ????○ | ????○ | ??○ | ??○ | ??△ | ??2H |
| ??9 | ????2000 | ????90 | ????× | ????△ | ??○ | ??× | ??× | ??2H |
| ??10 | ????10 | ????75 | ????× | ????× | ??× | ??× | ??× | ??4B |
| ??11 | ????1000 | ????91 | ????× | ????× | ??× | ??× | ??× | ??H |
Table 4
| Experiment No. | Viscosity (mPas) | Impregnation rate (%) | The prewood surface state | Heat resistant test I | Heat resistant test II | Size changing rate (%) | |||||
| The inequality of filming | White casse | 24 hours | 48 hours | 72 hours | 24 hours | 48 hours | 72 hours | ||||
| ????12 | ????1000 | ????95 | ????○ | ????○ | ??○ | ??○ | ??△ | ??○ | ??○ | ??△ | ????2.2 |
| ????13 | ????1200 | ????90 | ????○ | ????△ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ????1.6 |
| ????14 | ????1250 | ????85 | ????○ | ????○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ????2.0 |
| ????15 | ????1300 | ????80 | ????○ | ????○ | ??○ | ??○ | ??△ | ??○ | ??○ | ??△ | ????1.8 |
| ????16 | ????1800 | ????84 | ????○ | ????○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ????2.2 |
| ????17 | ????890 | ????80 | ????○ | ????○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ????2.0 |
| ????18 | ????930 | ????83 | ????○ | ????○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ????2.1 |
Claims (6)
1, a kind of impregnated timber resin combination, it is the resin combination that contains (methyl) acrylate copolymer composition and free radical polymerization monomer composition, it is characterized in that: in this (methyl) acrylate copolymer composition, must be included in bridging property (methyl) acrylate copolymer that has a free-radical polymerised pair of key in the molecule at least.
2, impregnated timber resin combination according to claim 1, it is characterized in that: described impregnated timber also contains plasticizer with resin combination.
3, impregnated timber resin combination according to claim 2 is characterized in that: when (methyl) acrylate copolymer composition, free radical polymerization monomer composition and plasticizer three's total amount is 100 parts, contain 10～80 parts in plasticizer.
4, impregnated timber resin combination according to claim 1 and 2 is characterized in that: part or all of above-mentioned free radical polymerization monomer composition is the free radical polymerization monomer that contains hydroxyl.
5, a kind of manufacture method of prewood is characterized in that: after using the resin combination impregnated timber with the described impregnated timber of claim 1, this resin combination is solidified.
6, a kind of prewood, manufacture method according to claim 5 makes.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003056789 | 2003-03-04 | ||
| JP200356789 | 2003-03-04 | ||
| JP2003141814 | 2003-05-20 | ||
| JP2003141814 | 2003-05-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1526526A true CN1526526A (en) | 2004-09-08 |
| CN1281388C CN1281388C (en) | 2006-10-25 |
Family
ID=34315580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410007665 Expired - Fee Related CN1281388C (en) | 2003-03-04 | 2004-02-26 | Resin composition for impregnating wood and impregnated wood |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1281388C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127216A (en) * | 2010-12-30 | 2011-07-20 | 东北林业大学 | Method for preparing polymerizable wood modifier having polar long ether chain and two terminal alkenyls |
| CN101108501B (en) * | 2006-07-20 | 2012-02-29 | 雅马哈株式会社 | Method of forming a wooden mold as well as wooden structure, vehicle interior material, and acoustic structure processed by the method |
| CN104723423A (en) * | 2013-12-20 | 2015-06-24 | 阿姆斯特郎世界工业公司 | Biobased impregnating composition and products comprising same |
| CN104723425A (en) * | 2013-12-20 | 2015-06-24 | 阿姆斯特郎世界工业公司 | Wood products impregnated with monomer based compositions |
| CN104924383A (en) * | 2015-04-30 | 2015-09-23 | 湖南栋梁木业有限公司 | Modification technology capable of improving strength and weather fastness of wood |
| CN110978181A (en) * | 2019-10-21 | 2020-04-10 | 中国林业科学研究院林产化学工业研究所 | Method for improving performance of fast-growing wood by using bio-based rigid monomer |
| CN115026919A (en) * | 2022-05-17 | 2022-09-09 | 水木山海科技(佛山)有限责任公司 | Preparation method of plastic composite compressed wood |
| CN117086967A (en) * | 2023-09-04 | 2023-11-21 | 华南农业大学 | Manufacturing method and application of reinforced and toughened plastic wood |
-
2004
- 2004-02-26 CN CN 200410007665 patent/CN1281388C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108501B (en) * | 2006-07-20 | 2012-02-29 | 雅马哈株式会社 | Method of forming a wooden mold as well as wooden structure, vehicle interior material, and acoustic structure processed by the method |
| CN102127216A (en) * | 2010-12-30 | 2011-07-20 | 东北林业大学 | Method for preparing polymerizable wood modifier having polar long ether chain and two terminal alkenyls |
| CN102127216B (en) * | 2010-12-30 | 2012-07-25 | 东北林业大学 | Method for preparing polymerizable wood modifier having polar long ether chain and two terminal alkenyls |
| CN104723423A (en) * | 2013-12-20 | 2015-06-24 | 阿姆斯特郎世界工业公司 | Biobased impregnating composition and products comprising same |
| CN104723425A (en) * | 2013-12-20 | 2015-06-24 | 阿姆斯特郎世界工业公司 | Wood products impregnated with monomer based compositions |
| AU2014274559B2 (en) * | 2013-12-20 | 2015-11-26 | Armstrong Flooring, Inc. | Wood products impregnated with monomer based compositions |
| CN104924383A (en) * | 2015-04-30 | 2015-09-23 | 湖南栋梁木业有限公司 | Modification technology capable of improving strength and weather fastness of wood |
| CN110978181A (en) * | 2019-10-21 | 2020-04-10 | 中国林业科学研究院林产化学工业研究所 | Method for improving performance of fast-growing wood by using bio-based rigid monomer |
| CN115026919A (en) * | 2022-05-17 | 2022-09-09 | 水木山海科技(佛山)有限责任公司 | Preparation method of plastic composite compressed wood |
| CN117086967A (en) * | 2023-09-04 | 2023-11-21 | 华南农业大学 | Manufacturing method and application of reinforced and toughened plastic wood |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1281388C (en) | 2006-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2007536403A (en) | Radiation curable coatings for metal substrates from polyfunctional acrylate oligomers | |
| US20230357474A1 (en) | Acrylic Emulsions Modified with Functional (Meth)acrylates to Enable Crosslinking | |
| CN1281388C (en) | Resin composition for impregnating wood and impregnated wood | |
| JP7245824B2 (en) | Polymer, oxygen absorber and resin composition using the same | |
| CN1271140C (en) | Curable resin composition, process for preparing low polymer with acrylyl, substituted methacrylic acid radical and beta-dicarbonyl and its polymerizing process | |
| WO2013184413A1 (en) | Coating compositions | |
| TW201716523A (en) | Topcoat composition, method of coating substrates with the same, and substrate | |
| JP4888027B2 (en) | Curing agent for radical polymerization type thermosetting resin, molding material containing the same, and curing method thereof | |
| EP2448982B1 (en) | Process for the preparation of radiation curable compositions | |
| JP2003212975A (en) | Curable composition | |
| CN1239547C (en) | Curable unsaturated resin composition | |
| JP5151179B2 (en) | Active energy ray-curable composition, printed matter using the composition, and molded decorative sheet molded product | |
| JP2005001372A (en) | Resin composition for timber impregnation | |
| JP2007112985A (en) | Radically curable resin composition | |
| JPH10219089A (en) | Curing composition and surface-cured wooden decorative panel | |
| JP2007246700A (en) | Resin composition for decorative sheet and thermosetting resin coating paper and decorative sheet | |
| JP4147467B2 (en) | Unsaturated polyester resin composition for decorative plate and decorative plate | |
| JP2004098362A (en) | Wood imprepnation composition | |
| JP2006176715A (en) | Composition for decorative laminate and decorative laminate using the same resin composition for decorative laminate | |
| JP2005178254A (en) | Method for producing woody decorative plate | |
| JP2009062401A (en) | Uv-curable hard coat resin composition, film for molding, and manufacturing method of molded article | |
| JP2005255816A (en) | Photocurable coating material composition for woody material | |
| JPH02153913A (en) | Acrylic syrup composition | |
| WO2020141348A1 (en) | (meth)acrylate-functionalized branched polyalpha-olefins | |
| JP4769377B2 (en) | RESIN COMPOSITION FOR COMPOSITE WOOD AND METHOD FOR PRODUCING COMPOSITE WOOD |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |