CN1274780C - Water-resistant adhesive composite for wood - Google Patents
Water-resistant adhesive composite for wood Download PDFInfo
- Publication number
- CN1274780C CN1274780C CN 03123885 CN03123885A CN1274780C CN 1274780 C CN1274780 C CN 1274780C CN 03123885 CN03123885 CN 03123885 CN 03123885 A CN03123885 A CN 03123885A CN 1274780 C CN1274780 C CN 1274780C
- Authority
- CN
- China
- Prior art keywords
- binder composition
- weight
- weight parts
- tackiness agent
- comparative example
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention provides an adhesive having a long working life, and excellent waterproof and heatproof properties. The adhesive composition comprises (A) and (B), (A) 100 pts.wt. vinyl acetate resin emulsion-based adhesive obtained by carrying out emulsion polymerization of 100 pts.wt. vinyl acetate monomer with 0.1-10 pts.wt. carboxy group containing monomer by using a carboxy group-modified polyvinyl alcohol as a protective colloid, and (B) 0.05-60 pts.wt. N,N-diglycidylamino group-containing compound represented by general formula (1).
Description
Technical field
The present invention relates to be used for the wooden MR adhesive composition of using that timber is particularly made laminated wood.
Background technology
In the past, as the timber MR adhesive, known had formaldehyde resin class tackiness agents such as urea-formaldehyde resins tackiness agent, melamine-formaldehyde resin tackiness agent, phenol-formaldehyde resin tackiness agent, resorcinol formaldehyde resin adhesive.
But, always remaining free formaldehyde in the above-mentioned formaldehyde resin class tackiness agent.Therefore, use in the above-mentioned formaldehyde resin class tackiness agent adherent goods and can discharge formaldehyde.Formaldehyde is the cause material that causes bad building (sick house) syndromes, chemical substance allergy etc., can be influential to human body, and this is the problem that this class tackiness agent exists.
For solve the problem that above-mentioned formaldehyde resin class tackiness agent exists, developed do not use formaldehyde, have water tolerance, stable on heating tackiness agent, the aquosity polymer isocyanic ester binder composition is for example arranged.Described aqueous macromolecule-isocyanate class binder composition is a host with water-based emulsion resin, water-based latex resin etc., cooperates the isocyanate compound as linking agent to form again in this host.
But, in above-mentioned aqueous macromolecule-isocyanate class binder composition, in described host, directly cooperate described linking agent, mix the moisture vigorous reaction that contains in the two described isocyanate compound in back and the said composition and foam.So cause viscosity to increase along with foaming, make the coating operation become very difficult.In addition, in above-mentioned host, directly cooperate the aqueous macromolecule-isocyanate class binder composition of described linking agent type, cause water tolerance, thermotolerance significantly to reduce along with the process of time.Therefore, there is short problem of serviceable time (usable time) in above-mentioned aqueous macromolecule-isocyanate class binder composition.
Given this, a kind of water-resistant adhesive is disclosed in special public clear 51-30577 number of Japanese patent laid-open publication gazette, this tackiness agent is with after isocyanate ester compound or isocyanates polymer dissolution are in hydrophobic organic solvent, again the solution that forms is dispersed in the aqueous solution or water-based emulsion that contains polyvinyl alcohol, obtains water-resistant adhesive.Utilize the water-resistant adhesive of above-mentioned communique record, can prevent the vigorous reaction of isocyanate ester compound or isocyanic ester base polymer and moisture, problems such as above-mentioned foaming, viscosity rising can not take place.
But the water-resistant adhesive of above-mentioned communique record is because described hydrophobic organic solvent has the strong stimulation smell, in the coating operation or emit this hydrophobic organic solvent from these water-resistant adhesive adherent goods.Therefore the water-resistant adhesive of putting down in writing in the described communique has the danger that becomes bad synthetic building syndrome, chemical substance allergy inducement because of emitting of described hydrophobic organic solvent causes environmental pollution, so also be not suitable for using.
In addition, for solving the problem of above-mentioned formaldehyde resin class tackiness agent, in the special public clear 51-28655 communique of Japanese patent laid-open publication gazette, disclose a kind of binder composition, formed by the mixture that contains the water-soluble cpds of 2 above epoxy group(ing) in carboxylic polymkeric substance, multivalent metal hydroxides or polyvalent metal oxides, the molecule.So the binder composition of putting down in writing in the described communique can not become and brings out bad synthetic building syndrome, the hypersensitive reason of chemical substance because of not containing formaldehyde.
But the binder composition of putting down in writing in the above-mentioned communique is because used described multivalent metal hydroxides, so have strong basicity.Therefore, with the former thereby variable color of the binder composition adherent timber of described communique record,, also be inconvenient to use if this binder composition is attached on the skin and also can causes the contact dermatitis in the coating operation because of alkali pollution.
Summary of the invention
The present invention is for solving the problem of above-mentioned existence, problems such as the variable color that a kind of irritating smell that does not produce because of formaldehyde or organic solvent is provided, causes because of alkali pollution, contact dermatitis, foaming, viscosity rising, and usable time is long, the wooden MR adhesive composition of using of water tolerance, excellent heat resistance.
For realizing this purpose, the invention provides the following wooden MR adhesive composition of using.
The wooden MR adhesive composition of using of the 1st embodiment of the present invention is characterized in that forming by following (A) with (B):
(A) be protective colloid with carboxy-modified polyvinyl alcohol, letex polymerization VAM 100 weight parts and contain polyvinyl acetate resin emulsion class tackiness agent 100 weight parts that monomer 0.1～10 weight part of carboxyl obtains,
(B) as 4 officials with tertiary amine nitrogen atom can epoxy compounds general formula (1) expression contain N, compound 0.05～60 weight part of N-diepoxy propyl group amino,
In the formula, D is a kind of divalent group selecting from the group that the branched alkylidene of the straight-chain alkyl-sub-of carbonatoms 1～12, carbonatoms 1～12, phenylene, alkyl substituted phenylene, halogen substituted phenylene, alkylidene group diphenylene are formed.
The 1st embodiment binder composition of the present invention is a host with low price, self normality bonding force, polyvinyl acetate resin emulsion class tackiness agent that ageing resistance is good.Described binder composition is the described material with 4 officials energy epoxy compounds formation of tertiary amine nitrogen atom that cooperates in described host as linking agent.
The 1st embodiment binder composition of the present invention is a host with described polyvinyl acetate resin emulsion class tackiness agent, and described polyvinyl acetate resin emulsion class tackiness agent is that protective colloid letex polymerization VAM and the monomer that contains carboxyl form with carboxy-modified polyvinyl alcohol.Therefore described binder composition can obtain having concurrently stable on heating good adhesivepropertieies such as water tolerance, heatproof water-based, anti-boiling property.
In addition, above-mentioned binder composition is combined with the 4 officials energy epoxy compounds that has the tertiary amine nitrogen atom concurrently in described host, do not contain formaldehyde or organic solvent.Therefore, above-mentioned binder composition does not have the danger of inducements such as becoming bad synthetic building syndrome, chemical substance allergy.
In addition, do not contain isocyanate compound in the above-mentioned composition, rise so can prevent foaming, viscosity that isocyanate compound and reaction of moisture cause.In addition, do not contain multivalent metal hydroxides in the aforesaid combination, so can prevent skin inflammationes such as pH rises, alkali pollution causes variable color or contact dermatitis.
In above-mentioned polyvinyl acetate resin emulsion class tackiness agent, with respect to described VAM 100 weight parts, if described carboxylic monomer less than 0.1 weight part that contains then can't obtain sufficient cross-linking density, when making above-mentioned binder composition, can't obtain sufficient water tolerance, thermotolerance.In addition, above-mentioned polyvinyl acetate resin emulsion class tackiness agent with respect to described VAM 100 weight parts, if the described carboxylic monomer that contains surpasses 100 weight parts, then is difficult to obtain stable emulsion.In addition, even obtain stable emulsion, the polymerization degree is also low, when making above-mentioned binder composition, can't obtain sufficient adhesiveproperties.
In the 1st embodiment binder composition of the present invention, with respect to described polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, if described use level with 4 officials energy epoxy compounds of tertiary amine nitrogen atom is lower than 0.05 weight part, then the curing of this binder composition becomes insufficient, water tolerance, thermotolerance, weather resistance, and the aspects such as closely bonding property of timber can't obtain sufficient adhesiveproperties.In addition, with respect to described polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, if described use level with 4 officials energy epoxy compounds of tertiary amine nitrogen atom is higher than 60 weight parts, then the viscosity of this binder composition significantly increases, coating reduces, except that influencing operability, water tolerance, thermotolerance, weather resistance, and the aspects such as closely bonding property of timber also can't obtain sufficient adhesiveproperties.In addition, also can cause the price of this binder composition to raise.
The wooden of the 2nd embodiment of the present invention is that the host in the tackiness agent of above-mentioned the 1st embodiment is changed into by following (a) and the title complex (b) formed with MR adhesive:
(a) above-mentioned polyvinyl acetate resin emulsion class tackiness agent;
(b) modification synthetic rubber latex, this latex are by the conjugated diolefine of selecting from divinyl or isoprene, can are that the carboxylic monomer copolymerization that contains of 0.1～20 weight % forms with the vinyl monomer of this conjugated diolefine copolymerization with respect to the total amount of this conjugated diolefine and vinyl monomer.Above-mentioned wooden be to contain the described polyvinyl acetate resin emulsion class tackiness agent that (contains 5 weight %) more than the 5 weight % to being lower than 100 weight % with MR adhesive with respect to above-mentioned title complex total amount, contain the title complex of the modification synthetic rubber latex that is lower than 95 weight %.
The binder composition of the 2nd embodiment of the present invention contains the described modification synthetic rubber latex of above-mentioned scope amount in described host, can obtain better thermotolerance.Described modification synthetic rubber latex, even only contain minute quantity in described host, the stable on heating effect of described binder composition also can be improved.But if described modification synthetic rubber latex surpasses 95 weight % with respect to the host total amount, then the closely bonding property of this binder composition and timber significantly reduces, and can't obtain sufficient adhesiveproperties.
In addition, described modification synthetic rubber latex, if the wherein said insufficient total amount 0.1 weight % that contains carboxylic monomer with respect to described conjugated diolefine and vinyl monomer, described binder composition just can't obtain sufficient water tolerance and thermotolerance.On the other hand, if the described carboxylic monomer that contains is higher than 20 weight % with respect to the total amount of described conjugated diolefine and vinyl monomer, then the poor stability during latex polymerization can not obtain good latex.Having good stability when making polymerization must have special device, operation etc., is difficult to avoid price to raise.
Below describe embodiment of the present invention in detail.
The binder composition of the present invention's the 1st embodiment, form by following (A) with (B):
(A) be protective colloid with carboxy-modified polyvinyl alcohol, letex polymerization VAM 100 weight parts and contain polyvinyl acetate resin emulsion class tackiness agent 100 weight parts that monomer 0.1～10 weight part of carboxyl obtains,
(B) as 4 officials with tertiary amine nitrogen atom can epoxy compounds general formula (1) expression contain N, compound 0.05～60 weight part of N-diepoxy propyl group amino,
In the formula, D is a kind of divalent group selecting from the group that the branched alkylidene of the straight-chain alkyl-sub-of carbonatoms 1～12, carbonatoms 1～12, phenylene, alkyl substituted phenylene, halogen substituted phenylene, alkylidene group diphenylene are formed.
The carboxylic monomer that contains with described VAM letex polymerization is not particularly limited, but preferably use vinylformic acid, methacrylic acid, phthalic acid, toxilic acid, methylene-succinic acid etc.The described carboxylic monomer that contains can use separately, also can more than 2 kinds or 2 kinds and use.
Be used for described VAM and the described described protective colloid that contains the carboxylic monomer letex polymerization,, be not particularly limited so long as carboxy-modified polyvinyl alcohol gets final product.As described protective colloid, usually can use following several: make with vinyl acetate as ethene unsaturated carboxylic acid (phthalic acid, toxilic acid, methylene-succinic acid also can be acid anhydrides) copolymerization such as the vinyl ester monomers of representative and vinylformic acid, methacrylic acid, phthalic acid, toxilic acid, methylene-succinic acids after, carry out the random copolymers that saponification obtains; Or has the segmented copolymer that the described ethene unsaturated carboxylic acid of radical polymerization obtains under the existence of polyvinyl alcohol analog copolymer of thiol group endways.As described vinyl ester monomer, except that vinyl acetate, can also use formic acid ethene, vinyl propionate, Versatic acid (band branched paraffin carboxylic acid) ethene, trimethylacetic acid ethene etc.
The polymerization degree for described carboxy-modified polyvinyl alcohol is not particularly limited, but in order to play the effect of protective colloid, preferred degree of polymerization is in 50～4000 scope, more preferably in 100～3000 scope.
The modification amount of carrying out modification for the carboxyl that utilizes described carboxy-modified polyvinyl alcohol also is not particularly limited, but in order to play the effect of protective colloid, preferably in the scope of 0.1～50 mole of %, in the scope particularly preferably in 0.5～10 mole of %.If utilize the modification amount of described carboxyl to be lower than 0.1 mole of %, then in described polyvinyl acetate resin emulsion class tackiness agent, can not get sufficient cross-linking density, when making described binder composition, can't obtain sufficient water tolerance, thermotolerance.In addition, if utilize the modification amount of described carboxyl to be higher than 10 moles of %, viscosity rises easily when then making described binder composition, and usable time shortens.
In addition, described carboxy-modified polyvinyl alcohol in the scope of harmless described protective colloid performance, also can be the product with the copolymerization of copolymerization of ethylene unsaturated monomer.As described copolymerization of ethylene unsaturated monomer, for example can enumerate ethene, iso-butylene, vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, trimethylammonium-(3-acrylamide-3-dimethyl propyl)-ammonium chloride, ethyl vinyl ether, butyl vinyl ether, N-vinyl pyrrolidone, vinylchlorid, bromine ethene, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, sodium vinyl sulfonate, sodium allyl sulfonate etc.
Described carboxy-modified polyvinyl alcohol; in the scope of harmless described protective colloid performance; can use the following terminal-modified thing that obtains: in the presence of mercaptan compounds such as mercaptan acetate, thiohydracrylic acid; make vinyl ester monomer and the copolymerization of ethene unsaturated carboxylic acid such as vinyl acetate, the more terminal-modified thing that the multipolymer saponification is obtained.
Described VAM and described when containing the carboxylic monomer letex polymerization, also can with described carboxy-modified polyvinyl alcohol simultaneously and use tensio-active agent.The kind of described tensio-active agent is not particularly limited, but preferred nonionic class tensio-active agent.
Described VAM and the described polymerizing catalyst that uses when carboxylic monomer carries out letex polymerization that contains, be not particularly limited, but preferably use superoxide such as hydrogen peroxide, persulphates such as Potassium Persulphate, Sodium Persulfate, reductive agents such as tartrate, formic acid, oxalic acid.Described polymerizing catalyst can use separately, also can more than 2 kinds or 2 kinds and use.
Usage quantity for above-mentioned polymerizing catalyst is not particularly limited, but with respect to described VAM and described total amount 100 weight parts that contain carboxylic monomer, preferably uses in the scope of 0.01～2 weight part.In addition, the resinous principle of the polyvinyl acetate resin emulsion class tackiness agent that obtained by the above-mentioned emulsion polymerization is not particularly limited, but is preferably 35～65 weight %.
As the N that contains by general formula (1) expression, N-diepoxy propyl group aminocompound for example can be enumerated N, N, N ', N '-Fourth Ring oxygen propyl group quadrol, N, N, N ', N '-Fourth Ring oxygen propyl group hexamethylene-diamine, 1,3-two (N, N-diepoxy propyl group amino methyl) hexanaphthene, 1-(N, N-diepoxy propyl group amino methyl)-1,5,5-trimethylammonium-3-(N, N-diepoxy propyl group amino) hexanaphthene, N, N, N ', N '-Fourth Ring oxygen propyl group-1, the 4-phenylenediamine, (N, N, N ', N '-Fourth Ring oxygen propyl group) diaminotoluene, N, N, N ', N '-Fourth Ring oxygen propyl group-1, the 3-dimethylphenylene diamine, N, N, N ', N '-Fourth Ring oxygen propyl group-4, the 4-diaminodiphenyl-methane, and halogen two replaces body or halogen four replaces body, N, N, N ', N '-Fourth Ring oxygen propyl group-4,4 '-diamino triphenyl methane, two (N, N-diepoxy propyl group amino-benzene oxygen phenyl) sulfone, two (N, N-diepoxy propyl group amino trimethylene methyl)-nine (butyleneglycols), two (N, N-diepoxy propyl group amino-phenol) sulfone, 4 '-(N, N-diepoxy propyl group amino) 4 ' of Phenylsulfonic acid-(N, N-diepoxy propyl group amino) phenylester, two (N, N-diepoxy propyl group amino trimethylene methyl) aklylene glycol etc.Wherein, preferably use N, N, N ', N '-Fourth Ring oxygen propyl group-1,3-dimethylphenylene diamine, 1,3-two (N, N-diepoxy propyl group amino methyl) hexanaphthene etc.
In addition, can also use N, what N-diepoxy propyl group amino-2,4-two (epoxypropyl oxygen base) aniline replaced above-mentioned general formula (1) expression contains N, N-diepoxy propyl group aminocompound.
The binder composition of the present invention's the 2nd embodiment, will use above-mentioned vinyl acetate base resin emulsion class tackiness agent to change into by following (a) and the title complex of (b) forming as host separately in above-mentioned the 1st embodiment tackiness agent:
(a) described polyvinyl acetate resin emulsion class tackiness agent;
(b) modification synthetic rubber latex, this latex are by the conjugated diolefine of selecting from divinyl or isoprene, can are that the carboxylic monomer copolymerization that contains of 0.1～20 weight % forms with the vinyl monomer of this conjugated diolefine copolymerization with respect to the total amount of this conjugated diolefine and vinyl monomer.The binder composition of the 2nd embodiment uses and contains the described polyvinyl acetate resin emulsion class tackiness agent that (contains 5 weight %) more than the 5 weight % to being lower than 100 weight % with respect to above-mentioned title complex total amount, contains the title complex of the modification synthetic rubber latex that is lower than 95 weight %.The binder composition of the 2nd embodiment by these title complex 100 weight parts and as described 4 officials with tertiary amine nitrogen atom can epoxy compounds general formula (1) expression contain N, N-diepoxy propyl group aminocompound 0.05～60 weight part is formed.
In the 2nd embodiment, the expression of described poly (vinyl acetate) emulsions class tackiness agent and above-mentioned general formula (1) contain N, N-diepoxy propyl group aminocompound, can use with the 1st embodiment in identical compound.
Described modification synthetic rubber latex, be by the 1st composition-by the conjugated diolefine of selecting in divinyl or the isoprene, the 2nd composition-can with the vinyl monomer of this conjugated diolefine copolymerization, the 3rd composition-contain carboxylic monomer, the terpolymer of forming is undertaken carboxy-modified by described the 3rd composition.
As the vinyl monomer of described the 2nd composition, vinylbenzene, styrene derivatives, vinyl cyanide, chloroprene, acrylate, methacrylic ester, vinyl acetate, ethene, vinylchlorid, vinylidene chloride, inclined to one side sym-dibromoethane, ethylene-vinyl ether etc. are for example arranged.Described vinyl monomer can use separately, also can more than 2 kinds or 2 kinds and use.
As the carboxylic monomer that contains of described the 3rd composition, vinylformic acid, methacrylic acid, butenoic acid, methylene-succinic acid, methylene-succinic acid monoesters, fumaric acid, fumaric monoalkylester, methylfumaric acid, methylfumaric acid monoesters etc. are for example arranged.The described carboxylic monomer that contains can use separately, also can more than 2 kinds or 2 kinds and use.
Described modification synthetic rubber latex for reaching carboxy-modified purpose, with respect to the total amount of described conjugated diolefine and vinyl monomer, contains the carboxylic monomer that contains of 0.1～20 weight %, and more preferably contains the carboxylic monomer that contains of 0.2～10 weight %.
The binder composition of described each embodiment can cooperate the water-based latex, the water-based emulsion resin that add other as required.As described water-based latex, water-based emulsion resin, 1 kind of latex selecting in 3-hexadiene isoprene, iso-butylene, acrylate, methacrylic ester, vinyl acetate, ethene, vinylchlorid, vinylidene chloride, bromine ethene, sym-dibromoethane, ethyl vinyl ether, butyl vinyl ether are formed partially the group or emulsion resin are for example arranged from vinylbenzene, divinyl, chloroprene, 1.But described water-based latex, water-based emulsion resin also can be copolymer latex or emulsion resin that the resin more than 2 kinds of the copolymerization selected from described group is formed.
In addition, the binder composition of above-mentioned each embodiment, in the scope that does not influence described purpose, can contain various additives such as organic solvent, softening agent, membrane-forming agent, pigment extender, filler, extender, pigment, dyestuff, paste, tackifier, dispersion agent, emulsifying agent, wetting agent, defoamer, frostproofer, sanitas, mould inhibitor, rust-preventive agent.As above-mentioned organic solvent, toluene, dimethylbenzene, butylacetate, carbitol etc. are for example arranged.In addition, as softening agent, phthalic acid ester, polyethyleneglycol phenyl ether etc. are for example arranged.As pigment extender or filler, can enumerate clay, talcum powder, lime carbonate, mica, silicic acid powder, wood powder etc.As extender, wheat-flour, W-Gum etc. are for example arranged.In addition, for example can enumerate white pigment or tinting pigments such as titanium oxide as pigment.As paste or tackifier polyvinyl alcohol, Natvosol, methylcellulose gum, carboxymethyl cellulose, starch, dextrin etc. are for example arranged.Frostproofer for example has ethylene glycol etc.
The binder composition of above-mentioned each embodiment, can be used as laminated wood, ply condensation material (LVL), decorative sheet, composite material, shaving board wood fibre sheet materials such as (particle board), the wood adhesive of carpenter work manufacturing usefulness such as furniture, building product, sporting goods is especially suitable for use as the laminated wood tackiness agent.
Except that above-mentioned timber, binder composition of the present invention can also be applicable to fluting board (corrugated board), paper, cloth, metal, glass, wolline plate, plastic plate, inorganic board, cement class inorganic board be equal to-material between or bonding between the differing materials.Described plastic plate for example has vinyl chloride resin plate, ABS plate, FRP plate, styrene resin plate etc.In addition, as described inorganic board, rock wool mineral fibreboard, plasterboard, calcium silicate boards etc. such as (rock woo1) are for example arranged, cement class inorganic board for example has eternit (slate) plate, paper pulp cement plate, concrete slab etc.
Binder composition of the present invention can also be as being coated with application composition or coating composition.
Embodiment
Below provide embodiments of the invention and comparative example.
Embodiment 1
In the present embodiment, pure water 566g and carboxy-modified polyvinyl alcohol (being designated hereinafter simply as c-PVC) 35g at first pack in the reaction vessel that stirrer, reflux condensing tube, thermometer and dropping funnel are housed, 90 ℃ of following heated and stirred 1 hour, obtain the c-PVC aqueous solution.The polymerization degree of above-mentioned c-PVC is 1700, and 98 moles of % of saponification deg are the random copolymerization modified vinyl alcohols that contain 2 moles of % of toxilic acid.
10 quality % (the acetate monomer 38.7g that in the above-mentioned c-PVC aqueous solution of water-cooled to 65 ℃, adds the mixture of forming by acetate monomer 387g and vinylformic acid 8g then, vinylformic acid 0.8g), reach 20 quality % (hydrogen peroxidase 10 .58g of the polymerizing catalyst of forming by hydrogen peroxide 2.9g and tartrate 1g, tartrate 0.2g), be warming up to 70 ℃ after adding and carry out prepolymerization.Next whole surpluses of said mixture were added dropwise in 3 hours continuously in the reaction solution after the above-mentioned prepolymerization, in 3.5 hours, drip whole surpluses of above-mentioned polymerizing catalyst simultaneously continuously, carry out letex polymerization.80 ℃ of following slakings 1 hour, as protective colloid, synthesize carboxy-modified polyvinyl acetate resin emulsion class tackiness agent after the above-mentioned emulsion polymerization with carboxy-modified polyvinyl alcohol.The resin portion of above-mentioned polyvinyl acetate resin emulsion class tackiness agent is divided into 43 weight %, and viscosity is 22000mPas/23 ℃.
Next will as 4 officials of containing the tertiary amine nitrogen atom can epoxy compounds as shown in the formula the N shown in (2), N, N ', the N '-Fourth Ring oxygen propyl group-m-xylene diamine (Gas of Mitsubishi (ガ ス) KCC's system, trade(brand)name: TETRAD-X) 1.5 weight parts are heated to 35 ℃ in advance, join in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts that are preheating to 35 ℃, stir, make binder composition, carry out paste producing.
At the veneer that water ratio is laminated in the following order 0.7mm on the Liu An material of 5～8 weight %, 1.7mm, 0.7mm are thick, at the binder composition that coating present embodiment in the both sides of bonding plane obtains, glue spread is 330g/m then
2(two sides), 20 ℃ are descended airtight stacking 10 minutes, at 20 ℃, 10kg/cm
2Colding pressing under bonding 20 minutes, 110 ℃, 8kg/cm
2Hot pressing under bonding 60 seconds, obtain being used to estimate the test sample sheet of adhesiveproperties.
Next estimate the adhesiveproperties of the above-mentioned test sample sheet of paste producing after 5 minutes, after 120 minutes.Above-mentioned adhesiveproperties is based on the tackiness agent timber stretching of JIS JIS K 6851 and cuts off intensity, estimates its normality intensity, water-fast intensity, heatproof water intensity and the anti-intensity of boiling repeatedly.
Above-mentioned normality intensity is that test sample is measured the intensity that obtains under the condition determination of 20 ℃ of room temperatures.In addition, above-mentioned water-fast intensity is test sample to be soaked after 3 days take out in 20 ℃ water, soaks under the state and directly measures the intensity that obtains under the condition determination of 20 ℃ of room temperatures.Above-mentioned heatproof water intensity is test sample is soaked 3 hours in 60 ℃ water after, to cool off in 20 ℃ water, soaks after the taking-up under the state and directly measures the intensity that obtains under the condition determination of 20 ℃ of room temperatures.The anti-intensity of boiling repeatedly is test sample to be soaked take out after 4 hours 60 ℃ air drying 24 hours in boiling water, in boiling water, soak the water of putting into 20 ℃ after 4 hours again and cool off, soak after the taking-up under the state and directly under the condition determination of 20 ℃ of room temperatures, measure the intensity that obtains.
The evaluation result of paste producing after 5 minutes is as shown in table 1, and the evaluation result after 120 minutes is as shown in table 2.Unit in the table is bonding strength (kgf/cm
2).In addition, this moment, the shared percentage of the area that fractures of wooden part was that xylem divides fracture rate (%), represented in bracket.
Comparative example 1
In this comparative example, the pure water 498g that at first in the reaction vessel that stirrer, reflux condensing tube, thermometer and dropping funnel are housed, packs into, with embodiment 1 in the identical c-PVC35g of material that uses, 90 ℃ of following heated and stirred 1 hour, obtain the c-PVC aqueous solution.
Then, water is cooled to add in 65 ℃ the above-mentioned c-PVC aqueous solution acetate monomer 39.5g and, is warmed up to 70 ℃ then and carries out prepolymerization as the Potassium Persulphate 0.08g of polymerizing catalyst.In above-mentioned prepolymerization reaction solution, drip continuously acetate monomer 355.5g then in 3 hours and, carry out letex polymerization as 1% Potassium peroxide solution 72g of polymerizing catalyst.80 ℃ of following slakings 1 hour, as protective colloid, synthetic carboxyl did not have the polyvinyl acetate resin emulsion class tackiness agent of modification with carboxy-modified polyvinyl alcohol then.The resin of above-mentioned polyvinyl acetate resin emulsion class tackiness agent partly accounts for 43 weight %, and viscosity is 32000mPas/23 ℃.
Next 4 officials that contain tertiary amine nitrogen atom identical with the compound of use among the embodiment 1 can be preheating to 35 ℃ by epoxy compounds 1.5 weight parts, join in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts that are preheating to 35 ℃, stir, make binder composition, carry out paste producing.
Next with the binder composition that obtains in this comparative example, estimate the adhesiveproperties of paste producing after 5 minutes, after 120 minutes similarly to Example 1.The evaluation result of paste producing after 5 minutes is as shown in table 1, and the evaluation result after 120 minutes is as shown in table 2.
Comparative example 2
Except c-PVA being replaced with the polymerization degree is 1700, the unmodified polyethylene alcohol of 98 moles of % of the saponification deg (Kuraray of Co., Ltd. (Network ラ レ) system, trade(brand)name: PVA117), with comparative example 1 identical synthetic carboxy-modified polyvinyl acetate resin emulsion class tackiness agent.The resin portion of above-mentioned polyvinyl acetate resin emulsion class tackiness agent is divided into 43 weight %, and viscosity is 2000mPas/23 ℃.
The above-mentioned polyvinyl acetate resin emulsion class tackiness agent that in using this comparative example, obtains then, identical with comparative example 1, make binder composition, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in this comparative example after paste producing 5 minutes, 120 minutes adhesiveproperties.5 minutes evaluation result is as shown in table 1 after the paste producing, and the evaluation result after 120 minutes is as shown in table 2.
Comparative example 3
Except c-PVA being replaced with the polymerization degree is 1700, the unmodified polyethylene alcohol of 98 moles of % of the saponification deg (Kuraray of Co., Ltd. (Network ラ レ) system, trade(brand)name: PVA117) replace it outside, with the unmodified polyvinyl acetate resin emulsion of comparative example 1 identical synthetic carboxyl class tackiness agent.The resin portion of above-mentioned polyvinyl acetate resin emulsion class tackiness agent is divided into 43 weight %, and viscosity is 29000mPas/23 ℃.
The above-mentioned polyvinyl acetate resin emulsion class tackiness agent that in using this comparative example, obtains then, identical with comparative example 1, make binder composition, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in this comparative example after paste producing 5 minutes, 120 minutes adhesiveproperties.5 minutes evaluation result is as shown in table 1 after the paste producing, and the evaluation result after 120 minutes is as shown in table 2.
Comparative example 4
In this comparative example, at first with the 15% polyvinyl alcohol water solution (Kuraray of Co., Ltd. (Network ラ レ) system, trade(brand)name: PVA217) 100 weight parts, salt of wormwood (eastern efflorescence of day Industrial Co., Ltd, trade(brand)name: NS100) (Asahi Chemical Industry Co., Ltd's system, trade(brand)name: DL-612) 100 weight parts are mixed and made into host for 60 weight parts, styrene butadiene copolymer latex.
Next in being preheating to 35 ℃ above-mentioned host 100 weight parts, add 35 ℃ (Sumitomo Bayer (バ イ エ Le) Co., Ltd.'s system of the polymethylene polyphenyl base polymeric polyisocyanate as linking agent that is preheating to, trade(brand)name: Sumidule (ス ミ ジ ユ one Le) 44V-20) 85 weight parts and n-butyl phthalate 15 weight parts, binder composition is made in stirring, carries out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in this comparative example after paste producing 5 minutes, 120 minutes adhesiveproperties.5 minutes evaluation result is as shown in table 1 after the paste producing, and the evaluation result after 120 minutes is as shown in table 2.
Table 1
| Normality intensity | Water-fast intensity | Heatproof water intensity | The anti-intensity of boiling repeatedly | |
| Embodiment 1 | 18.7(100) | 11.4(70) | 11.7(70) | 11.6(75) |
| Comparative example 1 | 16.1(95) | 5.4(0) | 4.2(0) | Peel off |
| Comparative example 2 | 18.0(100) | 3.0(0) | Peel off | Peel off |
| Comparative example 3 | 17.1(90) | 3.6(0) | Peel off | Peel off |
| Comparative example 4 | 18.2(100) | 11.0(80) | 12.1(85) | 11.1(70) |
Table 2
| Normality intensity | Water-fast intensity | Heatproof water intensity | The anti-intensity of boiling repeatedly | |
| Embodiment 1 | 18.5(100) | 12.0(60) | 11.0(80) | 11.8(80) |
| Comparative example 1 | 17.2(100) | 5.5(0) | 4.0(0) | Peel off |
| Comparative example 2 | 17.1(100) | 3.1(0) | Peel off | Peel off |
| Comparative example 3 | 17.0(100) | 3.4(0) | Peel off | Peel off |
| Comparative example 4 | 17.6(100) | 7.5(10) | 5.5(0) | 3.5(0) |
By table 1 and table 2 as can be known, the binder composition of the embodiment of the invention 1 possesses good adhesiveproperties aspect water tolerance, thermotolerance, and this adhesiveproperties deterioration do not occur through 120 minutes yet after paste producing, and usable time is long.
With respect to the foregoing description 1; use the binder composition of the comparative example 1 of the unmodified polyvinyl acetate resin emulsion of carboxyl class tackiness agent; use the binder composition of the unmodified polyvinyl alcohol of carboxyl as the comparative example 2 of the carboxy-modified polyvinyl acetate resin emulsion class tackiness agent of protective colloid letex polymerization formation; when using the binder composition of comparative example 3 of the unmodified polyvinyl acetate resin emulsion of the carboxyl class tackiness agent that the unmodified polyvinyl alcohol of carboxyl forms as the protective colloid letex polymerization, can not obtain in water tolerance; the sufficient adhesiveproperties in thermotolerance aspect.
In addition, use the binder composition of isocyanate ester compound as the comparative example 4 of linking agent, possessed good adhesiveproperties aspect water tolerance, thermotolerance in 5 minutes after the paste producing, but the adhesiveproperties of water tolerance, thermotolerance aspect is low after 120 minutes, usable time is short.
Embodiment 2
In the present embodiment, except in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, adding 4 officials energy epoxy compounds, 3 weight parts that contain the tertiary amine nitrogen atom,, carry out paste producing with the embodiment 1 identical binder composition of making.
Identical with embodiment 1 then, estimate the binder composition that obtains in the present embodiment after paste producing 5 minutes adhesiveproperties.The result is as shown in table 3.
Embodiment 3
4 officials of containing the tertiary amine nitrogen atom that use among the embodiment 1 can be replaced with 1 shown in the following formula (3) by epoxy compounds, 3-two (N, N-diepoxy propyl group amino methyl) hexanaphthene (Gas of Mitsubishi (ガ ス) KCC's system, trade(brand)name: TERAD-C), in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, add this 4 official energy epoxy compounds, 3 weight parts, in addition with the embodiment 1 identical binder composition of making, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in the present embodiment after paste producing 5 minutes adhesiveproperties.The result is as shown in table 3.
Comparative example 5
The 4 officials energy epoxy compounds that contains the tertiary amine nitrogen atom that uses among the embodiment 1 is replaced with Resins, epoxy (Asahi Denka Kogyo K. K's system of dihydroxyphenyl propane diepoxy propyl ether type, trade(brand)name: ADEKA EP-4100), in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, add these Resins, epoxy 3 weight parts, in addition with the embodiment 1 identical binder composition of making, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in this comparative example after paste producing 5 minutes adhesiveproperties.The result is as shown in table 3.
Comparative example 6
The 4 officials energy epoxy compounds that contains the tertiary amine nitrogen atom that uses among the embodiment 1 is replaced with Resins, epoxy (Toto Kasei KK's system of the poly-epoxypropyl amine type shown in the following formula (4), trade(brand)name: EPO TOHTO YH-434) replace, in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, add these Resins, epoxy 3 weight parts, in addition with the embodiment 1 identical binder composition of making, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in this comparative example after paste producing 5 minutes adhesiveproperties.The result is as shown in table 3.
Comparative example 7
The 4 officials energy epoxy compounds that contains the tertiary amine nitrogen atom that uses among the embodiment 1 is replaced with Resins, epoxy (Nagasechemtech (Na ガ セ ケ system テ Star Network) Co., Ltd.'s system of glycerine three glycidyl ethers types, trade(brand)name: Denachol (デ Na コ one Le) EX-314), in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, add these Resins, epoxy 3 weight parts, in addition with the embodiment 1 identical binder composition of making, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in this comparative example after paste producing 5 minutes adhesiveproperties.The result is as shown in table 3.
Comparative example 8
The 4 officials energy epoxy compounds that contains the tertiary amine nitrogen atom that uses among the embodiment 1 is replaced with Resins, epoxy (Toto Kasei KK's system of phenolic aldehyde glycidyl ethers type, trade(brand)name: EPO TOHTOYDPN-638), in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, add these Resins, epoxy 3 weight parts, in addition with the embodiment 1 identical binder composition of making, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in this comparative example after paste producing 5 minutes adhesiveproperties.The result is as shown in table 3.
Comparative example 9
The 4 officials energy epoxy compounds that contains the tertiary amine nitrogen atom that uses among the embodiment 1 is replaced with Resins, epoxy (Toto Kasei KK's system of Bisphenol F diepoxy propyl ether type, trade(brand)name: EPOTOHTO YDF-170), in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, add these Resins, epoxy 3 weight parts, in addition with the identical binder composition of making of example I, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in this comparative example after paste producing 5 minutes adhesiveproperties.The result is as shown in table 3.
Table 3
| Normality intensity | Water-fast intensity | Heatproof water intensity | The anti-intensity of boiling repeatedly | |
| Embodiment 2 | 17.0(100) | 13.2(90) | 11.6(80) | 12.0(90) |
| Embodiment 3 | 16.8(100) | 12.8(100) | 11.8(90) | 11.9(90) |
| Comparative example 5 | 15.4(100) | 2.0(0) | Peel off | Peel off |
| Comparative example 6 | 16.0(100) | 2.9(0) | Peel off | Peel off |
| Comparative example 7 | 17.0(100) | 8.2(20) | 7.5(15) | 6.0(0) |
| Comparative example 8 | 16.9(100) | 4.0(0) | Peel off | Peel off |
| Comparative example 9 | 17.4(100) | 2.0(0) | Peel off | Peel off |
As shown in Table 3, the binder composition of the embodiment of the invention 2,3 possesses good adhesiveproperties aspect water tolerance, thermotolerance.
With respect to the foregoing description 2,3, the binder composition of the comparative example 5～9 of the Resins, epoxy beyond using shown in the general formula (1) can not obtain sufficient adhesiveproperties aspect water tolerance, thermotolerance.
Embodiment 4
In the present embodiment, in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, add 4 officials energy epoxy compounds, 5 weight parts that contain the tertiary amine nitrogen atom, in addition, carry out paste producing with the embodiment 1 identical binder composition of making.
Identical with embodiment 1 then, estimate the binder composition that obtains in the present embodiment after paste producing 5 minutes adhesiveproperties.The result is as shown in table 4.And list after the binder composition paste producing of embodiment 1,25 minutes adhesiveproperties evaluation result in the table 4 once more.
Embodiment 5
In the present embodiment, in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, add 4 officials energy epoxy compounds, 0.5 weight part that contains the tertiary amine nitrogen atom, in addition, carry out paste producing with the embodiment 1 identical binder composition of making.
Identical with embodiment 1 then, estimate the binder composition that obtains in the present embodiment after paste producing 5 minutes adhesiveproperties.The result is as shown in table 4.
Embodiment 6
In the present embodiment, in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, add 4 officials energy epoxy compounds, 60 weight parts that contain the tertiary amine nitrogen atom, in addition, carry out paste producing with the embodiment 1 identical binder composition of making.
Identical with embodiment 1 then, estimate the binder composition that obtains in the present embodiment after paste producing 5 minutes adhesiveproperties.Press 330g/m
2The present embodiment that the amount on (two sides) took by weighing after the paste producing 5 minutes obtains binder composition, coats on the above-mentioned test sample with the hand roller of band glue, judges its coating, and the result is no reticulate pattern, and coating is good.The result is as shown in table 4.
Comparative example 10
In this comparative example, only use above-mentioned polyvinyl acetate resin emulsion class tackiness agent, do not use the 4 officials energy epoxy compounds that contains the tertiary amine nitrogen atom fully, in addition, carry out paste producing with the embodiment 1 identical binder composition of making.
Identical with embodiment 1 then, estimate the binder composition that obtains in the present embodiment after paste producing 5 minutes adhesiveproperties.The result is as shown in table 4.
Comparative example 11
In this comparative example, in above-mentioned polyvinyl acetate resin emulsion class tackiness agent 100 weight parts, add 4 officials energy epoxy compounds, 80 weight parts that contain the tertiary amine nitrogen atom, in addition, carry out paste producing with the embodiment 1 identical binder composition of making.
Identical with embodiment 1 then, estimate the binder composition that obtains in the present embodiment after paste producing 5 minutes adhesiveproperties.Press 330g/m
2The present embodiment that the amount on (two sides) took by weighing after the paste producing 5 minutes obtains binder composition, coats on the above-mentioned test sample with the hand roller of band glue, judges its coating, and the result is the viscosity height, reticulate pattern is arranged, and coating is bad.The result is as shown in table 4.
Table 4
| 4 officials can epoxy compounds | Normality intensity | Water-fast intensity | Heatproof water intensity | The anti-intensity of boiling repeatedly | Coating | |
| Embodiment 1 | 1.5 | 18.7(100) | 11.4(70) | 11.8(70) | 11.6(75) | - |
| Embodiment 2 | 3 | 17.0(100) | 13.2(90) | 11.6(80) | 12.0(90) | - |
| Embodiment 4 | 5 | 17.2(100) | 13.8(100) | 11.6(100) | 12.2(100) | - |
| Embodiment 5 | 0.5 | 17.3(100) | 7.2(25) | 8.2(55) | 7.8(45) | - |
| Embodiment 6 | 60 | 18.6(100) | 13.1(100) | 12.8(100) | 9.4(30) | Well |
| Comparative example 10 | 0 | 16.0(100) | 3.8(0) | Peel off | Peel off | - |
| Comparative example 11 | 80 | 12.4(40) | 6.0(10) | 6.2(10) | 5.0(0) | Bad |
4 officials energy epoxy compounds: the addition (weight part) in polyvinyl acetate resin emulsion class tackiness agent 100 weight parts
As shown in Table 4, the coating of the binder composition in the embodiment of the invention 1,2,4～6 is good, possesses good binder performance aspect water tolerance, thermotolerance.
With respect to the various embodiments described above, the binder composition that does not contain the comparative example 10 of 4 officials energy epoxy compounds fully can not obtain sufficient adhesiveproperties aspect water tolerance, thermotolerance.In addition, with respect to the various embodiments described above, the addition of 4 officials energy epoxy compounds is very high above the viscosity of the binder composition of the comparative example 11 of the scope of the invention, occurs reticulate pattern during coating, is difficult to coating, can not obtain sufficient adhesiveproperties.
Embodiment 7
In the present embodiment, the polyvinyl acetate resin emulsion class tackiness agent that uses among the embodiment 1 is replaced with the mixture of these polyvinyl acetate resin emulsion class tackiness agent 80 weight parts and carboxy-modified styrene butadiene synthetic rubber latex (being designated hereinafter simply as c-SBR) 20 weight parts composition, in addition with the embodiment 1 identical binder composition of making, carry out paste producing.Above-mentioned c-SBR is the ter-polymers that divinyl 43 weight %, vinylbenzene 52 weight % and vinylformic acid 5 weight % form, and solid state component accounts for 50 weight %.
Identical with embodiment 1 then, estimate the binder composition that obtains in the present embodiment after paste producing 5 minutes adhesiveproperties.The result is as shown in table 5.
Embodiment 8
In the present embodiment, the polyvinyl acetate resin emulsion class tackiness agent that uses among the embodiment 1 is replaced with the mixture of the same c-SBR 50 weight parts composition that uses among these polyvinyl acetate resin emulsion class tackiness agent 50 weight parts and the embodiment 7, in addition with the embodiment 1 identical binder composition of making, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in the present embodiment after paste producing 5 minutes adhesiveproperties.The result is as shown in table 5.
Embodiment 9
In the present embodiment, the polyvinyl acetate resin emulsion class tackiness agent that uses among the embodiment 1 is replaced with the mixture of the same c-SBR 80 weight parts formation of using among these polyvinyl acetate resin emulsion class tackiness agent 20 weight parts and the embodiment 7, in addition with the embodiment 1 identical binder composition of making, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in the present embodiment after paste producing 5 minutes adhesiveproperties.The result is as shown in table 5.
Comparative example 12
In the present embodiment, with the polyvinyl acetate resin emulsion class tackiness agent that uses among the embodiment 1 replace with embodiment 6 in the same c-SBR that uses, except not using this polyvinyl acetate resin emulsion class tackiness agent fully, with the embodiment 1 identical binder composition of making, carry out paste producing.
The binder composition that obtains in this comparative example, owing to do not use this polyvinyl acetate resin emulsion class tackiness agent fully, viscosity is very low, can not coat on the above-mentioned veneer, can't estimate adhesiveproperties with method similarly to Example 1.The result is as shown in table 5.
Comparative example 13
The c-SBR that uses among the embodiment 7 is replaced with the unmodified styrene butadiene synthetic rubber of carboxyl latex (Asahi Chemical Industry Co., Ltd's system, trade(brand)name: DL612), in addition with the embodiment 7 identical binder compositions of making, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in the present embodiment after paste producing 5 minutes adhesiveproperties.The result is as shown in table 5.
Table 5
| Normality intensity | Water-fast intensity | Heatproof water intensity | The anti-intensity of boiling repeatedly | |
| Embodiment 7 | 18.2(100) | 14.1(55) | 11.6(80) | 12.8(90) |
| Embodiment 8 | 17.6(100) | 13.8(50) | 11.4(85) | 12.2(95) |
| Embodiment 9 | 11.9(100) | 12.7(65) | 11.7(70) | 11.6(90) |
| Comparative example 12 | - | - | - | - |
| Comparative example 13 | 16.0(95) | 8.6(45) | 10.6(45) | 6.3(25) |
As shown in Table 5, the binder composition of the embodiment of the invention 7～9 in water tolerance, thermotolerance, particularly possesses good adhesiveproperties by anti-thermotolerance aspect of boiling the intensity embodiment repeatedly.
With respect to the binder composition of the foregoing description 6～8, the viscosity of the binder composition of comparative example 12 is very low, and the coating difficulty is not suitable for as tackiness agent.In addition, use the binder composition of the comparative example 13 of the unmodified styrene butadiene synthetic rubber of carboxyl latex, can not obtain sufficient adhesiveproperties aspect water tolerance, the thermotolerance.
Embodiment 10
In the present embodiment, the polyvinyl acetate resin emulsion class tackiness agent that uses among the embodiment 1 is replaced with the mixture of the same c-SBR 50 weight parts composition that uses among these polyvinyl acetate resin emulsion class tackiness agent 50 weight parts and the embodiment 7, in these mixture 100 weight parts, add 4 officials energy epoxy compounds, 60 weight parts that contain the tertiary amine nitrogen atom, in addition with the embodiment 1 identical binder composition of making, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in the present embodiment after paste producing 5 minutes adhesiveproperties.In addition, with the binder composition that obtains in the present embodiment, by judging its coating with embodiment 6 identical methods, the result is no reticulate pattern, and coating is good.The result is as shown in table 6.
Write down after the paste producing relevant 5 minutes adhesiveproperties evaluation result in the table 6 once more with the binder composition of embodiment 8.
Comparative example 14
In this comparative example, with embodiment 10 in add 4 officials that contain the tertiary amine nitrogen atom in mixture 100 weight parts formed of identical polyvinyl acetate resin emulsion class tackiness agent and c-SBR can epoxy compounds 80 weight parts, in addition with the embodiment 1 identical binder composition of making, carry out paste producing.
Identical with embodiment 1 then, estimate the binder composition that obtains in this comparative example after paste producing 5 minutes adhesiveproperties.In addition, with the binder composition that obtains in this comparative example, by judging its coating with embodiment 6 identical methods, the result is for reticulate pattern occurring, and coating is bad.The result is as shown in table 6.
Table 6
| 4 officials can epoxy compounds | Normality intensity | Water-fast intensity | Heatproof water intensity | The anti-intensity of boiling repeatedly | Coating | |
| Embodiment 8 | 1.5 | 17.6(100) | 13.8(50) | 11.4(85) | 12.2(95) | - |
| Embodiment 10 | 60 | 19.8(100) | 16.6(100) | 15.4(80) | 11.5(75) | Well |
| Comparative example 14 | 80 | 18.5(32) | 8.8(15) | 7.8(10) | 6.5(0) | Bad |
4 officials energy epoxy compounds: the addition (weight part) in polyvinyl acetate resin emulsion class tackiness agent 100 weight parts
As shown in Table 6, the binder composition coating of embodiment 8,10 related to the present invention is good, possesses good adhesiveproperties aspect water tolerance, thermotolerance.
With respect to the various embodiments described above, the addition of 4 officials energy epoxy compounds is very high above the binder composition viscosity of the comparative example 14 of the scope of the invention, occurs reticulate pattern during coating, and the coating difficulty can not obtain sufficient adhesiveproperties.
Embodiment 11
In the present embodiment, use the binder composition of embodiment 1, preparation similarly to Example 1, get 2 test sample sheets that are of a size of 9cm * 28cm, wherein 2 Outboard Sections of a test sample sheet are respectively with after the even coating of the pure water of 5g, with vinyl film parcel, in being 90% air, 40 ℃, relative humidity placed 14 days.After above-mentioned processing, the variable color difference between test sample sheet after the judgment processing and the untreated test sample sheet with the naked eye.The result is as shown in table 7.
Embodiment 12
In the present embodiment, remove to use the binder combination beyond the region of objective existence of embodiment 7, with embodiment 11 identical processing, the variable color difference between test sample sheet after the judgment processing and the untreated test sample sheet with the naked eye.The result is as shown in table 7.
Comparative example 15
In this comparative example, at first with the iso-butylene-maleic anhydride-maleimide (Kuraray of Co., Ltd. (Network ラ レ) system, trade(brand)name: Isoban (ィ ソ バ Application) 304, mol ratio 1: 0.5: 0.5) 50 weight parts, 25% ammoniacal liquor, 20 weight parts and pure water 70 weight parts mix, and 85～90 ℃ of following stirrings made its dissolving in 2 hours.Then, said mixture is cooled to below 50 ℃, add saleratus (eastern efflorescence of day Industrial Co., Ltd system, trade(brand)name: NS100) 140 weight parts, styrene butadiene synthetic rubber latex (Japanese Zeon (ゼ オ Application) Co., Ltd.'s system, trade(brand)name: Nipol LX 430, resin part 49 weight %) 140 weight parts and pure water 60 weight parts, fully stir, make host.
Then with respect to above-mentioned host 100 weight parts, interpolation is as glycerine three epoxypropyl ether type epoxies (Nagasechemtech (Na ガ セ ケ system テ Star Network) Co., Ltd.'s system of linking agent, trade(brand)name Denachol (デ Na コ one Le) EX-314) 5 weight parts, binder composition is made in stirring, carries out paste producing.
Next, the binder combination beyond the region of objective existence that remove to use this comparative example to obtain, with embodiment 11 identical processing, the variable color difference between test sample sheet after the judgment processing and the untreated test sample sheet with the naked eye.The result is as shown in table 7.
Comparative example 16
In this comparative example, with respect to host 100 weight parts of comparative example 15 identical preparations, as linking agent, adding identical 4 officials that contain the tertiary amine nitrogen atom that use with embodiment can epoxy compounds 1.5 weight part, binder composition is made in stirring, carries out paste producing.
Next, remove the binder combination beyond the region of objective existence that uses this comparative example to obtain, with embodiment 11 identical processing, with the naked eye the variable color difference between test sample after the judgment processing and the untreated test sample.The result is as shown in table 7.
Comparative example 17
In this comparative example, at first with the iso-butylene-maleic anhydride (Kuraray of Co., Ltd. (Network ラ レ) system, trade(brand)name: Isoban (イ ソ バ Application) 304, mol ratio 1: 1) 50 weight parts, pure water 85 weight parts and sodium hydroxide 20 weight parts mix, and 85～90 ℃ are stirred down and made its dissolving in 2 hours.Then, said mixture is cooled to below 50 ℃, add slaked lime 70 weight parts, styrene butadiene synthetic rubber latex (Japanese Zeon (ゼ オ Application) Co., Ltd.'s system, trade(brand)name: Nipol LX 430, resin part 49 weight %) 150 weight parts and pure water 60 weight parts, fully stir, make host.Then except using above-mentioned host, according to comparative example 15 complete same methods, make binder composition, carry out paste producing.
Next, remove the binder combination beyond the region of objective existence that uses this comparative example to obtain, with embodiment 11 identical processing, with the naked eye the variable color difference between test sample after the judgment processing and the untreated test sample.The result is as shown in table 7.
Comparative example 18
In this comparative example, with respect to the comparative example 17 identical host of making 100 weight parts, as linking agent, add with embodiment in identical 4 officials that contain the tertiary amine nitrogen atom that use can epoxy compounds 1.5 weight parts, the viscose binder composition is made in stirring, carries out paste producing.
Then, remove the binder combination beyond the region of objective existence that uses this comparative example to obtain, with embodiment 11 identical processing, with the naked eye the variable color difference between test sample after the judgment processing and the untreated test sample.The result is as shown in table 7.
Table 7
| The variable color degree | |
| Embodiment 11 | ○ |
| Embodiment 12 | ○ |
| Comparative example 15 | × |
| Comparative example 16 | × |
| Comparative example 17 | × |
| Comparative example 18 | × |
Variable color degree: zero ... variable color is not found in expression
* ... variable color is found in expression
As shown in Table 7, the binder composition of the embodiment of the invention 11,12 (embodiment 1,7) does not make test sample sheet generation variable color.
With respect to the binder composition of the foregoing description 11,12 (embodiment 1,7), the binder composition that contains the comparative example 15～18 of overbased materials in the host can make the test sample sheet that the variable color that is caused by alkali pollution takes place.
Claims (6)
1, the wooden MR adhesive composition of using is characterized in that forming by following (A) with (B):
(A) be protective colloid with carboxy-modified polyvinyl alcohol, letex polymerization VAM 100 weight parts and contain polyvinyl acetate resin emulsion class tackiness agent 100 weight parts that monomer 0.1～10 weight part of carboxyl obtains,
(B) as 4 officials with tertiary amine nitrogen atom can epoxy compounds general formula (1) expression contain N, compound 0.05～60 weight part of N-diepoxy propyl group amino,
In the formula, D is a kind of divalent group selecting from the group that the branched alkylidene of the straight-chain alkyl-sub-of carbonatoms 1～12, carbonatoms 1～12, phenylene, alkyl substituted phenylene, halogen substituted phenylene, alkylidene group diphenylene are formed.
2, the wooden MR adhesive composition of using as claimed in claim 1, the wherein said N that contains, N-diepoxy propyl group aminocompound are the N by formula (2) expression, N, and N ', N '-Fourth Ring oxygen propyl group-m-xylene diamine,
3, the wooden MR adhesive composition of using as claimed in claim 1, the wherein said N that contains, N-diepoxy propyl group aminocompound are by 1 of formula (3) expression, 3-two (N, N-diepoxy propyl group amino methyl) hexanaphthene,
4, the wooden MR adhesive composition of using is characterized in that forming by following (A) with (B):
(A) by following (a) and title complex 100 weight parts (b) formed:
(a) be protective colloid with carboxy-modified polyvinyl alcohol, letex polymerization VAM 100 weight parts and contain the polyvinyl acetate resin emulsion class tackiness agent that monomer 0.1～10 weight part of carboxyl obtains;
(b) modification synthetic rubber latex, this latex are by the conjugated diolefine of selecting from divinyl or isoprene, can are that the carboxylic monomer copolymerization that contains of 0.1～20 weight % forms with the vinyl monomer of this conjugated diolefine copolymerization with respect to the total amount of this conjugated diolefine and vinyl monomer;
With respect to this title complex total amount contain 5 weight % or more than the 5 weight % to the described polyvinyl acetate resin emulsion class tackiness agent that is lower than 100 weight %, contain the modification synthetic rubber latex that is lower than 95 weight %,
(B) as 4 officials with tertiary amine nitrogen atom can epoxy compounds general formula (1) expression contain N, compound 0.05～60 weight part of N-diepoxy propyl group amino,
In the formula, D is a kind of divalent group selecting from the group that the branched alkylidene of the straight-chain alkyl-sub-of carbonatoms 1～12, carbonatoms 1～12, phenylene, alkyl substituted phenylene, halogen substituted phenylene, alkylidene group diphenylene are formed.
5, the wooden MR adhesive composition of using as claimed in claim 4, wherein said modification synthetic rubber latex is modified phenylethylene-divinyl synthetic rubber latex.
6, the wooden MR adhesive composition of using as claimed in claim 4, the wherein said N that contains, N-diepoxy propyl group aminocompound are the N by formula (2) expression, N, and N ', N '-Fourth Ring oxygen propyl group-m-xylene diamine,
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002158183A JP3907183B2 (en) | 2002-05-30 | 2002-05-30 | Water-resistant adhesive composition for wood |
| JP158183/2002 | 2002-05-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1461785A CN1461785A (en) | 2003-12-17 |
| CN1274780C true CN1274780C (en) | 2006-09-13 |
Family
ID=29773640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03123885 Expired - Fee Related CN1274780C (en) | 2002-05-30 | 2003-05-30 | Water-resistant adhesive composite for wood |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3907183B2 (en) |
| CN (1) | CN1274780C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4263570B2 (en) * | 2003-09-19 | 2009-05-13 | 株式会社オーシカ | Water-resistant adhesive composition for wood |
| JP4284138B2 (en) * | 2003-09-19 | 2009-06-24 | 株式会社オーシカ | Water-resistant adhesive composition for wood |
| US7868123B2 (en) * | 2007-11-19 | 2011-01-11 | Ethicon, Inc. | Derivatized tertiary amines and uses thereof |
| JP2012236980A (en) * | 2011-04-28 | 2012-12-06 | Nitto Denko Corp | Aqueous dispersion type tacky adhesive composition and tacky adhesive sheet |
| JP6405182B2 (en) * | 2014-10-14 | 2018-10-17 | 株式会社オーシカ | Method for bonding porous materials |
| EP3650502A4 (en) * | 2017-07-04 | 2020-07-22 | Denka Company Limited | Polymer latex composition and use thereof |
| CN110643309A (en) * | 2019-10-28 | 2020-01-03 | 顶立新材料科技有限公司 | Preparation method of environment-friendly metal laminated wood veneer aqueous adhesive |
| CN113461853A (en) * | 2021-06-25 | 2021-10-01 | 山东顶立新材料科技有限公司 | Environment-friendly plate alignment adhesive polymerization emulsion and preparation method thereof |
-
2002
- 2002-05-30 JP JP2002158183A patent/JP3907183B2/en not_active Expired - Fee Related
-
2003
- 2003-05-30 CN CN 03123885 patent/CN1274780C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003342545A (en) | 2003-12-03 |
| JP3907183B2 (en) | 2007-04-18 |
| CN1461785A (en) | 2003-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1041102C (en) | Emulsion polymer blend | |
| CN1200976C (en) | Heat resistant compsns. | |
| CN1193874C (en) | Image obtaining membrane for printing and thermal transfer printing | |
| CN1663973A (en) | Aqueous emulsion and uses thereof | |
| CN1221621C (en) | Adhesive compositions containing graft copolymers | |
| CN1124741A (en) | Sheet of acrylic acid or the like, adhesive sheet of acrylic acid or the like and production of same | |
| CN101065849A (en) | Easily adhesive polyester film for solar cell back surface-protecting film and solar cell back surface-protecting film obtained using the same | |
| CN1690097A (en) | Acrylic resin | |
| CN1427867A (en) | Use of boron derivative as heat-activated catalyst for polymerisation and/or crosslinking of silicon by hydrogenative condensation | |
| CN101068879A (en) | Hybrid thermosetting composition | |
| CN1769344A (en) | Thermosetting resin composition, and prepreg, metal-clad laminated board and printed wiring board using the same | |
| CN1969025A (en) | Adhesive composition, method for bonding to a metal surface and rubber to metal adhesive | |
| CN1608083A (en) | Synthetic resin emulsion, easily water-swellable pressure-sensitive adhesive compositions containing the same and process for production of the emulsion | |
| CN1274780C (en) | Water-resistant adhesive composite for wood | |
| CN1376182A (en) | Process for improving the toughness of PCT formulations by adding rubber impact modifiers | |
| CN1086009C (en) | Process for preparing copolymer emulsion, its product and use thereof | |
| CN1287569A (en) | Coating composition | |
| CN1303874A (en) | Composition of aqueous emulsion and adhesive composition | |
| CN1228444A (en) | Method for producing aqueous emulsion of polyurethane | |
| CN1217968C (en) | Aquious carbaminate-olefine hybrid polymer dispersing liquid and its prepn and use | |
| CN1239615C (en) | Curable resin composition | |
| CN100345887C (en) | Pre-impregnating agents for high-resistant and elastic composite fibres | |
| CN1182766A (en) | Prime coating agent composition | |
| CN1053628A (en) | Make the compacting prepress sealer that uses in the conjugate fiber sheet material | |
| CN1761710A (en) | Irradiated, oxidized olefin polymer coupling agents |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060913 Termination date: 20150530 |
|
| EXPY | Termination of patent right or utility model |