CN1227243A - Method for producing adhesive, adhesive, and laminate products - Google Patents
Method for producing adhesive, adhesive, and laminate products Download PDFInfo
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- CN1227243A CN1227243A CN 98124081 CN98124081A CN1227243A CN 1227243 A CN1227243 A CN 1227243A CN 98124081 CN98124081 CN 98124081 CN 98124081 A CN98124081 A CN 98124081A CN 1227243 A CN1227243 A CN 1227243A
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Abstract
The invention discloses an adhesive and a method for producing adhesive it. The primary adhesive is produced at a relatively low temperature with a high reliability. The adhesive is excellent in bonding strength, especially initial bonding strength and is not reduced even in a condition of repeating braising and boiling. It is suitable for binding wood board and veneer in order to produce laminated products. The method of producing the adhesive is: adding (B) a polyvinyl alcohol powder to (A) an aqueous emulsion to produce primary adhesive; and adding (C) a polyvalent isocyanate-based compound to the mixture.
Description
The present invention relates to produce the method for aqueous binder, also relate to aqueous binder and laminated product.Specifically, the present invention relates to have high bond strength, the aqueous binder of especially high initial adhesion strength, and the method for producing aqueous binder, in the method, the main adhesive component that is produced has high stability, in addition, can produce this main adhesive component at a lower temperature.This method power consumption is low, tackiness agent productive rate height.
Basically the tackiness agent of forming by water-soluble polymers, water miscible liquid and isocyanate compound release formaldehyde not, it is different from conventional aminoplastics based adhesive, even at room temperature it is pressed in for some time short on the matrix, it also has very high bond strength and water-repellancy, therefore it be suitable as wood, glued board and various plastics tackiness agent (for example, see disclosed Japanese patent application (JP-A) clear-48-94739 and clear-50-69139).
In this case, Japanese Industrial Standards (JIS) stipulate the wooden tackiness agent that comprises water-soluble polymers and isocyanate compound recently.
This type of tackiness agent is gone up not release formaldehyde substantially.Therefore, it is with than the tackiness agent of aminoresin based adhesive to human body and environment milder recently, and is especially well-known as producing tackiness agent in the glued board.
People have prepared the conventional tackiness agent that comprises water-soluble polymers, water miscible liquid and isocyanate compound by following manner and have been applied so far.At first the water-soluble polymers polyvinyl alcohol is dissolved in the water by heating, the preparation aqueous solution joins it in the water miscible liquid then, prepares the primary binder component, just before using tackiness agent, the linking agent isocyanate compound is joined in the primary binder component.Yet,, more effectively produce more and more necessity of primary binder component along with the exploitation and the production-scale expansion of recent production line.In this case, if can produce the primary binder component under relatively low temperature, so, the energy consumption that water-soluble polymer dissolves is prepared the aqueous solution of polymkeric substance in water will reduce, and in addition, the productive rate of primary binder component will improve.If like this, can more effectively produce the primary binder component.Especially,, and make its dissolving in the short period of time and obtain the primary binder component, the production performance of that tackiness agent and all will improve with the processing characteristics of tackiness agent if can under relatively low temperature, join water-soluble polymers in the water miscible liquid.In addition, if like this, also will produce other advantage, promptly the place of adhesive application is unrestricted, or says, may on-the-spot preparation tackiness agent.
Above-mentioned conventional tackiness agent does not possess good initial adhesion strength, therefore need provide the tackiness agent with good initial adhesion strength.
The invention solves the existing problem of conventional tackiness agent in the above-mentioned prior art, a kind of method of producing aqueous binder is provided, the primary binder component of wherein being produced has high stability, in addition, can produce the primary binder component under relatively lower temp.The energy consumption of this method is low, the productive rate height of tackiness agent.In addition, the present invention also provides a kind of especially aqueous binder of initial adhesion strength of good bond strength that has, even under the condition of boiling repeatedly, this tackiness agent also keeps its good adhesive strength.
Purpose of the present invention reaches by the method for producing tackiness agent, this method comprises adding (B) pva powder in (A) water miscible liquid, this pva powder solubleness of 1 hour in 40 ℃ of water is not less than 50% weight, surface tension under its 1% weightaqueous solution form is not less than 45mN/m, so just prepared the primary binder component, then to wherein adding polyisocyanate compounds (C).
In the method, preferably (B) joined in (A) preparation primary binder component not being higher than 60 ℃ following.
In the method, also the granularity of preferably polyethylene alcohol powder (B) is not more than 500 μ m.
Except above-mentioned purpose, another object of the present invention provides a kind of tackiness agent with long pot life.This purpose realizes by a kind of like this tackiness agent, this tackiness agent comprises (A) water miscible liquid, (B) polyvinyl alcohol, (C) polyisocyanate compounds, wherein the carboxyl number of this polyvinyl alcohol is the 0.2-5% mole, its solubleness of 1 hour in 40 ℃ of water is not less than 50% weight, and the surface tension under the aqueous solution form of 1% weight is not less than 45mN/m.
The water miscible liquid (A) that constitutes aqueous binder of the present invention can be any of letex polymerization type water miscible liquid; this emulsion is preparation like this; make the ethylenically unsaturated monomers and the letex polymerization in the aqueous solution of dienes monomer of free redical polymerization; this aqueous solution contains one or more conventional negatively charged ion; positively charged ion; both sexes or non-ionic dispersing agent; low-molecular-weight surfactant and various types of polyvinyl alcohol; water-soluble polymerss such as Natvosol (protective colloid); or water miscible liquid (A) is the water miscible liquid that the back emulsification by polymkeric substance prepares, for example typical polyaminoester emulsion.The water miscible liquid of these types can be used separately, or uses together.
In constituting the letex polymerization type water miscible liquid of aqueous binder of the present invention, the ethylenically unsaturated monomers that is used for disperse phase comprises: for example alkene such as ethene, propylene, iso-butylene etc.; Haloolefin such as vinylchlorid, vinylidene chloride, vinyl fluoride, vinylidene fluoride etc.; Vinyl ester such as vinyl formate, vinyl-acetic ester, propionate, alkanecarboxylic acid vinyl acetate (Vinyl Versatate), new vinyl acetate acid etc.; Vinylformic acid and ester thereof are as methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, the positive butyl ester of propylene ester, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, vinylformic acid dodecane ester, vinylformic acid octadecane ester, hydroxyethyl acrylate, vinylformic acid hydroxypropyl ester, hydroxybutyl acrylate, vinylformic acid hydroxypropyl ester chlorination trimethyl ammonium etc.; Methacrylic acid and ester thereof, as methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, methacrylic acid 2-(ethyl hexyl) ester, methacrylic acid dodecane ester, methacrylic acid octadecane ester, methacrylic acid hydroxyethyl ester, hydroxypropyl methacrylate, hydroxyethyl methacrylate butyl ester, hydroxypropyl methacrylate chlorination trimethyl ammonium etc.; Acrylic amide, as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N,N-DMAA, acrylamido-2-methyl propane sulfonic acid and sodium salt thereof, chlorination trimethylammonium-(3-acrylamido-3-dimethyl propyl) ammonium, chlorination 3-acrylamidopropyl trimethyl ammonium, chlorination 3-methacrylamido oxypropyl trimethyl ammonium, N methacrylamide, N-ethyl acrylamide, diacetone acrylamide etc.; Nitrile such as vinyl cyanide, methacrylonitrile etc.; Allylic cpd is as allyl acetate, chlorallylene etc.; Styrene compound is as vinylbenzene, alpha-methyl styrene, p-methylstyrene sulfonic acid and sodium salt and sylvite etc.; And the N-vinyl pyrrolidone etc.The dienes monomer comprises: for example, and divinyl, isoprene, chloroprene etc.
These water miscible liquids are preferably: comprise the aqueous polymer dispersion of dienes monomeric unit such as divinyl etc., for example, the styrene-butadiene copolymer emulsion; The polymer emulsion that comprises (methyl) acrylate monomeric units, for example, the water miscible liquid of (methyl) acrylate-acrylate copolymer; Comprise for example polymer emulsion of vinyl-acetic ester etc. of vinyl ester monomers unit, for example, the water miscible liquid of vinyl-vinyl acetate copolymer etc.
Constitute the letex polymerization of the letex polymerization type water miscible liquid of aqueous binder of the present invention for preparation, can use conventional emulsion polymerisation process, wherein, the top monomer of mentioning is heated then and stirs all simultaneously or join continuously in the reactor that water, dispersion agent as mentioned above and polymerization starter exist; Perhaps use such method, the aqueous solution by making monomer and dispersion agent and emulsification and the emulsion for preparing in advance join in the reactor continuously.
There is no particular limitation for polymerization starter.For example, operable is any in the following material: Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen peroxide, 2,2 '-azo two (2-amidine propane) dihydrochloride, cumene hydroperoxide, benzoyl peroxide, peroxidation isopropyl benzene etc., they can use separately, or use with following reductive agent: sodium bisulfite, tartrate, L-xitix, formaldehyde sodium sulfoxylate, ferrous sulfate, or use other similar materials of redox system form.
For letex polymerization type water miscible liquid and back oil-in-water type water miscible liquid, constitute in the water miscible liquid of aqueous binder of the present invention, the amount of dispersion agent does not have particular restriction.Yet, per 100 weight parts monomers in the common emulsion, the amount of dispersion agent is the 0.2-50 weight part, is preferably the 0.5-20 weight part.If the amount of dispersion agent is less than 0.2 weight part, the stability of emulsion and the polymerization stability of Aquo System will reduce.But if greater than 50 weight parts, the viscosity stability of the tackiness agent of preparation will reduce.
Polyvinyl alcohol (PVA) powder (B) that is used for production aqueous binder of the present invention must be such: it is not less than 50% weight in 1 hour solubleness of 40 ℃ of water, and the surface tension under 1% weightaqueous solution form is not less than 45mN/m.The PVA powder that this requirement is satisfied in use just may prepare the primary binder component at low temperatures, and does not cause or seldom cause cohesion, therefore, can reduce preparation primary binder component required energy, as described in the following embodiment.In this way the low temperature viscosity stability of the primary binder component of Sheng Chaning is good.In addition, have fabulous initial adhesion strength by polyisocyanates being joined the tackiness agent of producing in this primary binder component, even under the condition of boiling repeatedly, its bond strength does not reduce yet.And, along with the increase of the variation adhesive viscosities of time is very little.Preferably, the solubleness of PVA powder is at least 60% weight, more preferably at least 70% weight.The surface tension of preferred PVA powder is at least 50mN/m, and more preferably it is between 50-7mN/m.If use solubleness less than 50% weight, or surface tension prepares the primary binder component at low temperatures less than the PVA of 45mN/m, mixed system will condense so, the initial adhesion strength of the tackiness agent of being produced and the bond strength under conditions of cooking repeatedly thereof all will be lower, can clearly find out this point from following described comparative example's data.
The PVA that satisfies above-mentioned solubleness requirement can obtain by degree of hydrolysis, the polymerization degree, granularity and the carboxyl-content of suitably controlling PVA.The PVA that satisfies above-mentioned surface tension requirement can obtain by degree of hydrolysis, the polymerization degree and the carboxyl-content of suitably controlling PVA.Therefore, according to all class factors of producing PVA, can obtain to satisfy the PVA that solubleness requires and surface tension requires.Specifically, the degree of hydrolysis of PVA can be at least 70% mole, is preferably the 80-96% mole; Its polymerization degree can be 100-8000, is preferably 400-4000.
The used PVA of the present invention is preferably pulverous, and its granularity is not more than 500 μ m.Saved with pulverous PVA and PVA to be added to the water and to be heated and to prepare the step of the PVA aqueous solution, and reduced the energy consumption of production tackiness agent of the present invention.In addition, can see obviously that from the following embodiment that mentions the tackiness agent of being produced has good initial adhesion strength, even under the condition of boiling repeatedly, this bond strength does not reduce yet.
The carboxyl-content that is used for PVA of the present invention is preferably the 0.2-5% mole, more preferably the 0.3-5% mole.
As satisfy above-mentioned condition, the polymerization degree is the preferred example of 1700 PVA, can should be mentioned that: degree of hydrolysis is not less than 87% mole, preferably is not less than 94% mole, its granularity is not more than the unmodified PVA of 200 μ m; Being not less than 85% mole, carboxyl-content with degree of hydrolysis is the PVA that 0.2-5% mole and granularity are not more than 500 μ m.
Here alleged PVA solubleness is such: add the PVA of 10% weight in 40 ℃ water, stirred 1 hour, filter by the metal net shaped filter of 200 purposes then, measure the amount of residue, obtain the filtering degree of PVA thus.It shows the solubleness of the PVA that represents with weight percentage.
Here the surface tension of alleged PVA is such: the surface tension of measuring the PVA aqueous solution (20 ℃) of 1% weight with Wilhelmy-type tonometer.It shows the surface tension with the PVA of mN (milli newton)/m (rice) expression.
The PVA that is used for shown type of the present invention can obtain by the whole bag of tricks.For example, make vinyl ester with any conventional polymerization process polymerization in mass polymerization, solution polymerization, suspension polymerization, letex polymerization or other similar approach, make the hydrolysis under alkalescence or acidic conditions of resulting polymkeric substance, obtain being not less than 70% mole degree of hydrolysis.So just obtained the PVA that wants.In the method, used method for hydrolysis does not have particular restriction.For example, any known belt (belt-type) or slurry type hydrolysis can be used.Vinyl ester comprises for example vinyl formate, vinyl-acetic ester, propionate, new vinyl acetate acid etc., but vinyl-acetic ester preferably.
In addition, also can make the polymerization in the presence of thiol compound such as thiol-acetic acid, thiohydracrylic acid or analogue of vinyl ester monomers such as vinyl-acetic ester or analogue, then the PVA that is terminal groups modification to resulting polymkeric substance hydrolysis.It also can be used for the present invention.
For the PVA (B) that constitutes tackiness agent of the present invention, the PVA that most preferably has following character: carboxyl-content is the 0.2-5% mole in the molecule, its solubleness of 1 hour in 40 ℃ of water is not less than 50% weight, surface tension under its 1% weightaqueous solution form is not less than 45mN/m, and such PVA will cause better result.PVA with the carboxyl-content that is limited can prolong the working life of the tackiness agent that comprises this type of PVA, so the processing property of this tackiness agent is good.Carboxy-modified PVA can obtain with the whole bag of tricks.Yet, usually preferred here use is: by make vinyl ester monomers as be vinyl-acetic ester copolymerization in the presence of alkene class unsaturated carboxylic acid such as vinylformic acid, methacrylic acid, fumaric acid, toxilic acid (acid anhydride), methylene-succinic acid (acid anhydride) or analogue, any random copolymers that resulting multipolymer hydrolysis is made then; By making alkene class unsaturated carboxylic acid (mentioning) in the presence of the end capped PVA polymkeric substance of thiol, carry out the segmented copolymer that radical polymerization makes as above-mentioned; And with vinylformic acid or class Michael adducts with thing, it is incorporated into carboxyl in the PVA polymkeric substance by the aftertreatment reaction and prepares.
Part or all of carboxyl among the PVA can be with the form of an alkali metal salt of itself and sodium, potassium or analogue and is existed.Carboxyl-content among the PVA is preferably the 0.3-5% mole, more preferably the 0.5-5% mole.
The PVA (B) that constitutes tackiness agent of the present invention can be the multipolymer form with any other alkene class unsaturated comonomer, as long as it does not surmount following requirement: its solubleness of 1 hour in 40 ℃ of water is not less than 50% weight, and its surface tension under 1% weightaqueous solution form is not less than 45mN/m.Alkene class unsaturated comonomer comprises, for example, acrylamide, Methacrylamide, chlorination trimethylammonium-(3-acrylamido-3-dimethyl propyl) ammonium, acrylamido-2-methyl propane sulfonic acid and sodium salt thereof, N-vinyl pyrrolidone, sodium vinyl sulfonate, sodium allyl sulfonate etc.
In order to obtain best result, the granularity of the PVA in the tackiness agent of the present invention (B) preferably is not more than 500 μ m, and mixes with water miscible liquid (A) and prepare the primary binder component.It is desirable to, the granularity of PVA is 300 μ m to the maximum, and better is to be 200 μ m to the maximum, it would be desirable to be 100 μ m to the maximum.The lower limit of PVA granularity preferably is at least 40 μ m, more preferably is at least 50 μ m.As mentioned above, use the PVA powder of granularity in this limited range can under less energy-consumption, produce the primary binder component, and can produce high-quality tackiness agent.The method for preparing this type of PVA powder has no particular limits.For example, PVA controlled lapping in any known wet type or dry grinding machine, perhaps the thin PVA powder that forms naturally in the method for routine production PVA is carried out physics and sieve after the hydrolysis.The drying conditions of PVA powder does not have particular restriction.Yet in view of its dissolution rate, the PVA powder preferably be not higher than under 80 ℃ the temperature, more preferably be not higher than under 50 ℃ the temperature dry.Here alleged PVA granularity refers to its mean particle size.Briefly, the PVA powder is sieved by Japanese Industrial Standards (JIS) sieve, be divided into several parts, measure the weight of each part.The weight data integration of each part, can obtain 50% o'clock granularity (mean particle size) of integrated value thus.
The polymerization degree that constitutes the PVA (B) of aqueous binder of the present invention does not have particular restriction.But, consider the dissolution rate of PVA and the bond strength of tackiness agent, it is desirable to, the polymerization degree that is used for PVA of the present invention is 100-8000, is preferably 200-4000.
Aqueous binder of the present invention comprises the primary binder component, and contains polyisocyanates (C), and wherein the primary binder component comprises water miscible liquid (A) and PVA (B).Should contain at least 2 isocyanate group in polyisocyanates (C) molecule, such isocyanic ester for example comprises, toluene diisocynate (TDI), hydrogenation TDI, TriMethylolPropane(TMP)-the TDI adducts (for example, Bayer ' s Desmodur L (trade(brand)name)), three isocyanic acid triphenyl methanes, methylene-bis (isocyanic acid diphenyl) (MDI), hydrogenation MDI, MDI polymkeric substance, 1, hexamethylene-diisocyanate, eylylene diisocyanate, 4,4-dicyclohexyl methane diisocyanate, isophorone diisocyanate, etc.Here also can use isocyanate-terminated prepolymer by polyol and excessive polyisocyanic acid polyisocyanate polyaddition are prepared.Polyisocyanate compound (C) can directly join in the primary binder component, or with adding wherein behind the solvent cut, this solvent is an inert to isocyanic ester, as dibutyl phthalate, toluene or analogue.The polyisocyanate compound (C) that joins in the primary binder component makes resulting tackiness agent have fabulous bond strength and water tolerance.
In aqueous binder of the present invention, water miscible liquid (A) is preferably 99.5/0.5-50/50 with the solid weight of PVA (B) than (A)/(B) usually.Content about polyisocyanate compound in the tackiness agent (C) it is desirable to, and the solid weight of { (A)+(B) }/(C) is than being 100/0.5-100/100, more preferably 100/1-100/80.If the amount of polyisocyanate compound is less than this limited range, the bond strength of tackiness agent and water tolerance are all with variation.Yet if greater than this limited range, will shorten the working life that has added the tackiness agent of polyisocyanate compound, cause this tackiness agent inapplicable thus.
If desired, aqueous binder of the present invention can contain any water-soluble polymers, for example starch, treated starch, Sumstar 190, sodiun alginate, carboxymethyl cellulose, methylcellulose gum, Walocel MT 20.000PV, maleic anhydride-isobutylene copolymers, maleic anhydride-styrol copolymer, maleic anhydride-methyl ethylene ether copolymer etc., and be generally used for thermosetting resin in the conventional tackiness agent, as urea-formaldehyde resin, urea-melamine-formaldehyde resin, resol etc.
If desired, aqueous binder of the present invention also can contain any filler, as clay, kaolin, talcum, lime carbonate, wood powder etc.; Carrier such as flour etc.; Pigment such as titanium dioxide etc. and any other anticorrosive additive, rust-preventive agent etc.
The present invention also provides a kind of method of producing aqueous binder, this method comprises: be not higher than under 60 ℃ and the following condition, add PVA powder (B) (as noted above) in water miscible liquid (A), preparation primary binder component is then to wherein adding polyisocyanate compound (C).In the method for the invention, the stability of the primary binder component of being produced is high, in addition, can produce the primary binder component under relatively low temperature.Therefore, in the method, the energy consumption of producing the primary binder component has reduced, and the productivity of aqueous binder is higher.In the method, preferably not being higher than 50 ℃, under 45 ℃ temperature, the PVA powder is joined preparation primary binder component in the water miscible liquid.The ideal minimum temperature is at least 5 ℃, more preferably is at least 10 ℃.The PVA powder is being joined in the step of water miscible liquid,, will reduce its solubleness, therefore should avoid assembling if expansible PVA particle aggregation forms accumulative PVA coarse grain together.For this reason, for example, preferably before the PVA powder joins in the water miscible liquid, in the PVA powder, add inorganics such as lime carbonate or analogue earlier.
This aqueous binder can be used for bonding various matrix, so that produce various laminated products.The preferred example that can use the matrix of this tackiness agent comprises: wood, glued board, paper, fiber, various plastics etc.The example of preferred laminated product comprises: layer of wood stampings, layer of plywood stampings.The amount of the tackiness agent of being used on the matrix can suitably be determined according to the condition of the laminated product of being wanted.
For tackiness agent is coated on the matrix, for example, can use coating method in any one in the methods such as brushing, roller coat.After the tackiness agent coating, matrix can be with the mode drying of any needs.For example, they are can be at room temperature dry, or under up to 200 ℃ temperature heat drying.Even at room temperature dry, tackiness agent of the present invention also has good adhesive strength.
Illustrate in greater detail the present invention below with reference to embodiment and comparative example, but these embodiment are not construed as limiting to scope of the present invention.Unless specifically indicate, all " umbers " and " % " in these embodiment and comparative example all are weight part or weight percentage.Embodiment 1:
(its polymerization degree is 1700 to add PVA powder (1) in the copolymer emulsion (solids content that Kuraray Co. makes is 55% OM-4200) of ethane-acetic acid ethyenyl ester, degree of hydrolysis is 95mol%, granularity is 90 μ m, solubleness is 88% weight, with surface tension is 55mN/m) 5 parts (relative solids content is 100 parts a emulsion), stir 1 hour down with preparation primary binder component at 40 ℃.In this primary binder component, add 15 parts of polymethylene multi-phenenyl isocyanates (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) (solids content is 100 parts a primary binder component relatively), the preparation tackiness agent.Under following condition, this is experimentized.Resulting experimental data is listed in table 1-3.Experiment condition: 1, the low temperature viscosity stability of primary binder component:
The primary binder component was placed 7 days down at 5 ℃, observe its outward appearance then.
Zero: no change.
*: gelation.2, the state of primary binder component:
The primary binder component is coated on the sheet glass, makes it on sheet glass, form film, detect by an unaided eye
Its state.
Zero does not find cohesion.
Δ finds to have some cohesion.
* find that cohesion is very serious.3, clingtest
The bond strength of experiment tackiness agent under following condition.
By adherent matrix: water-content is birch/birch (straight burr plate) of 8%.
The amount of tackiness agent: 250g/m
2(two sides coating).
The lamination time: 1 minute.
The condition of exerting pressure: 20 ℃ of pressurizations 24 hours down, pressure is 10kg/m
2(only consider to be used under the normal condition to measure the experiment slice of bond strength and be used to measure the experiment slice of bond strength repeatedly under the conditions of cooking).
According to JIS K-6852 experiment laminate samples, to measure the compression shear bond strength.Bond strength under the normal condition:
Under 20 ℃ sample solidifies 7 days, direct experiment then.Bond strength under the conditions of cooking repeatedly:
Under 20 ℃, sample solidifies 7 days, be immersed in then in the boiling water 4 hours, under 60 ℃ of air dry 20 hours then, be immersed in again in the boiling water 4 hours, be immersed at last in the water of room temperature to cooling.When it is still wet, the sample of so handling is experimentized, measure bond strength.Initial adhesion strength:
After lamination is intact, under 20 ℃, use 10kg/cm
2Pressure sample is exerted pressure, carry out bond strength experiment then immediately.4, viscosity changes:
This shows, has increased 40 ℃ of viscosity of placing 2 hours tackiness agent down.The more little tackiness agent of viscosity increase is long more its working life, and processing property is good more.Embodiment 2
(its polymerization degree is 500, and degree of hydrolysis is 88.2mol%, and sulfhydryl content is 4.5 * 10 the PVA of 5 parts of sulfydryl terminals
-5Mol/g-PVA) and 100 parts of ion exchanged waters join and be used for the glass reactor that polymeric is equipped with agitator, nitrogen conduit and thermometer, heating makes its dissolving.After the cooling, the pH value of gained solution is adjusted to 3.0, then, is heated to 70 ℃ under the situation of nitrogen blasting to wherein adding sulfuric acid.Keeping stirring velocity is 150 rev/mins, to wherein adding 10 parts of methyl methacrylates and 10 parts of n-butyl acrylates, and to the potassium persulfate solution that wherein adds 10 part 1%, the trigger monomer polymerization.Polymerization began back 1 hour, and 40 parts of methyl methacrylates, 38 parts of n-butyl acrylates and 2 parts of methacrylic acid hydroxyethyl esters were added drop-wise in the reaction mixture with constant speed in 2 hours.Add the back mixture heating up to up to 80 ℃, and under this temperature, kept 1 hour.The result obtains methyl methacrylate-n-butyl acrylate that solids concn is 48.5% (AcrylEm)-methacrylic acid hydroxyethyl ester copolymer emulsion.In this emulsion, add 5 parts of (100 parts of solids contents with emulsion are benchmark) PVA powder (1), stirred 1 hour down, preparation primary binder component at 40 ℃.In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 1-3.Embodiment 3
In styrene-butadiene copolymer emulsion (solids content that Asahi chemical industrial company makes is 50% DL-612), add 5 parts of (100 parts of solids contents with emulsion are benchmark) PVA powder (1), stirred 1 hour preparation primary binder component down at 40 ℃.In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 1-3.Embodiment 4
Prepare the primary binder component according to the mode identical with embodiment 3, different is with PVA powder (2) (its polymerization degree is 550, and degree of hydrolysis is 88mol%, and granularity is 200 μ m, solubleness be 90% and surface tension be 50mN/m) replace PVA powder (1).In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 1-3.Embodiment 5
Prepare the primary binder component according to the mode identical with embodiment 3, different is, and (its polymerization degree is 1700 to PVA powder (3) with 2.5 parts of (100 parts of solids contents with emulsion are benchmark) PVA powder (1) and 2.5 parts (100 parts of solids contents with emulsion are benchmark), degree of hydrolysis is 88mol%, granularity is 100 μ m, solubleness be 95% and surface tension be 52mN/m) replace 5 parts of PVA powder (1).In this primary binder component, add polymethylene multi-phenenyl isocyanate (MillionateMR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 1-3.Embodiment 6
Prepare the primary binder component according to the mode identical, different be to use 10 parts of (100 parts of solids contents with emulsion are benchmark) PVA powder (1) with embodiment 3.In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 1-3.Embodiment 7
Prepare the primary binder component according to the mode identical, different be to use 1 part of (100 parts of solids contents with emulsion are benchmark) PVA powder (1) with embodiment 3.In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 1-3.Embodiment 8
Prepare tackiness agent according to the mode identical, the different 3 parts of polymethylene multi-phenenyl isocyanates (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) that are to use with embodiment 3.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 1-3.Embodiment 9
Prepare tackiness agent according to the mode identical with embodiment 3, different is the lime carbonate that adds 5% weight in advance in PVA powder (1).Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 1-3.The comparative example 1
Prepare the primary binder component according to the mode identical with embodiment 3, different is that (its polymerization degree is 1700 to PVA powder (4) with 5 parts (100 parts of solids contents with emulsion are benchmark), degree of hydrolysis is 70mol%, granularity is 600 μ m, solubleness be 99% and surface tension be 42mN/m) replace PVA powder (1).In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 1-3.The comparative example 2
Prepare the primary binder component according to the mode identical with embodiment 3, different is that (its polymerization degree is 1700 to PVA powder (5) with 5 parts (100 parts of solids contents with emulsion are benchmark), degree of hydrolysis is 95mol%, granularity is 600 μ m, solubleness be 45% and surface tension be 55mN/m) replace PVA powder (1).In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 1-3.The comparative example 3
Prepare tackiness agent according to the mode identical with embodiment 3, different is is 5 parts of (solids content of emulsion relatively) PVA powder (1) of the PVA aqueous solution (PVA concentration is 10%) replacement of 5 parts (100 parts of solids contents with emulsion are benchmark) with solid PVA content, wherein the PVA aqueous solution is by pouring in the water at 95 ℃ of following PVA powder (1), stirs then 1 hour and prepares.
Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 1-3.The comparative example 4
Prepare tackiness agent according to the mode identical with embodiment 3, different is is 5 parts of (solids content of emulsion relatively) PVA powder (1) of the PVA aqueous solution (PVA concentration is 10%) replacement of 5 parts (100 parts of solids contents with emulsion are benchmark) with solid PVA content, wherein the PVA aqueous solution is by (its polymerization degree is 1700 at 95 ℃ of following PVA powder (6), degree of hydrolysis is 98mol%, granularity is 600 μ m, solubleness is 21%, with surface tension be 60mN/m) pour in the water, stirred then 1 hour and prepare.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 1-3.Embodiment 1-1
(its polymerization degree is 1700 to PVA powder (1-1) to add 5 parts (100 parts of solids contents with emulsion are benchmark) in ethane-acetic acid ethyenyl ester copolymer emulsion (solids content that Kuraray Co. makes is 55% OM-4200), degree of hydrolysis is 95mol%, the modification degree of maleic anhydride is 2mol%, granularity is 300 μ m, solubleness is 90%, with surface tension be 60mN/m), stirred 1 hour down preparation primary binder component at 40 ℃.In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 4-6.Embodiment 2-1
(its polymerization degree is 500, and degree of hydrolysis is 88.2mol%, and sulfhydryl content is 4.5 * 10 5 parts of end capped PVA of sulfydryl
-5Mol/g-PVA) and 100 parts of ion exchanged waters join and be used for the glass reactor that polymeric is equipped with agitator, nitrogen conduit and thermometer, heating makes its dissolving.After the cooling, the pH value of gained solution is adjusted to 3.0, then, is heated to 70 ℃ under the situation of nitrogen blasting to wherein adding sulfuric acid.Keeping stirring velocity is 150 rev/mins, to wherein adding 10 parts of methyl methacrylates and 10 parts of n-butyl acrylates, to the over cure sour water potassium solution that wherein adds 10 part 1%, trigger monomer polymerization.Polymerization began back 1 hour, and 40 parts of methyl methacrylates, 38 parts of n-butyl acrylates and 2 parts of methacrylic acid hydroxyethyl esters were added drop-wise in the reaction mixture with constant speed in 2 hours.Add the back mixture heating up to up to 80 ℃, and under this temperature, kept 1 hour.The result obtains methyl methacrylate-n-butyl acrylate that solids concn is 48.5% (Acryl Em)-methacrylic acid hydroxyethyl ester copolymer emulsion.In this emulsion, add 5 parts of (100 parts of solids contents with emulsion are benchmark) PVA powder (1-1), stirred 1 hour down, preparation primary binder component at 40 ℃.In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 4-6.Embodiment 3-1
In styrene-butadiene copolymer emulsion (solids content that Asahi chemical industrial company makes is 50% DL-612), add 5 parts of (100 parts of solids contents with emulsion are benchmark) PVA powder (1-1), stirred 1 hour preparation primary binder component down at 40 ℃.In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 4-6.Embodiment 4-1
Prepare the primary binder component according to the mode identical with embodiment 3-1, different is with PVA powder (2-1), (its polymerization degree is 550, degree of hydrolysis is 62mol%, methylene-succinic acid modification degree is 3mol%, granularity is 350 μ m, solubleness be 95% and surface tension be 51mN/m) replace PVA powder (1-1).In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 4-6.Embodiment 5-1
Prepare the primary binder component according to the mode identical with embodiment 3-1, different is, and (its polymerization degree is 1800 to PVA powder (3-1) with 2.5 parts of (100 parts of solids contents with emulsion are benchmark) PVA powder (1-1) and 2.5 parts (100 parts of solids contents with emulsion are benchmark), degree of hydrolysis is 88mol%, methylene-succinic acid modification degree is 1mol%, granularity is 300 μ m, solubleness be 95% and surface tension be 55mN/m) replace 5 parts of PVA powder (1-1).In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that NipponPolyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 4-6.Embodiment 6-1
Prepare the primary binder component according to the mode identical, different be to use 10 parts of (100 parts of solids contents with emulsion are benchmark) PVA powder (1-1) with embodiment 3-1.In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 4-6.Embodiment 7-1
Prepare the primary binder component according to the mode identical, different be to use 1 part of (100 parts of solids contents with emulsion are benchmark) PVA powder (1) with embodiment 3-1.In this primary binder component, add polymethylene multi-phenenyl isocyanate (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) 15 parts (100 parts of solids contents with the primary binder component are benchmark), the preparation tackiness agent.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 4-6.Embodiment 8-1
Prepare tackiness agent according to the mode identical, the different 3 parts of polymethylene multi-phenenyl isocyanates (the Millionate MR-100 (trade(brand)name) that Nippon Polyurethane Co. makes) that are to use with embodiment 3-1.Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 4-6.Embodiment 9-1
Prepare tackiness agent according to the mode identical with embodiment 3-1, different is the lime carbonate that adds 5% weight in advance in PVA powder (1-1).Experimentize and estimate according to the mode identical with embodiment 1.Resulting experimental data is listed in table 4-6.
As above-mentioned described in detail, the invention provides tackiness agent, even and under the condition of boiling repeatedly, its degree of adhesion does not reduce yet with the especially high initial adhesion strength of high bond strength.The present invention also provides the method for producing tackiness agent, and the stability of the primary binder component that this method is produced is high, and this primary binder component can be produced under relatively low temperature.The energy consumption of this method is low, the productive rate height of tackiness agent.When the PVA that contains carboxyl is used for this method, prolonged the working life of the tackiness agent of being produced, therefore improved the processing characteristics of tackiness agent.
Therefore, tackiness agent of the present invention is applicable to bonding various matrix, especially is fit to timber and glued board.Except can being used for it timber and timber bonding, tackiness agent of the present invention also can be used for the bonding of timber and paper, fiber product, inorganic board, various plastics etc.
Table 1
| The primary binder component | Polyisocyanate compound | ||
| Emulsion | PVA powder (per 100 parts of solids contents of emulsion) | Polymethylene multi-phenenyl isocyanate (MR-100) (/ per 100 parts of main active ingredients) | |
| Embodiment 1 | ?OM-4200 | (1) 5 part of PVA | ????15 |
| Embodiment 2 | ?Acryl?Em | (1) 5 part of PVA | ????15 |
| Embodiment 3 | ?DL-612 | (1) 5 part of PVA | ????15 |
| Embodiment 4 | ?DL-612 | (2) 5 parts of PVA | ????15 |
| Embodiment 5 | ?DL-612 | (3) 2.5 parts of (1) 2.5 part of PVA of PVA | ????15 |
| Embodiment 6 | ?DL-612 | (1) 10 part of PVA | ????15 |
| Embodiment 7 | ?DL-612 | (1) 1 part of PVA | ????15 |
| Embodiment 8 | ?DL-612 | (1) 5 part of PVA | ?????3 |
| Embodiment 9 | ?DL-612 | (1) 5 part of PVA (*) | ????15 |
| The comparative example 1 | ?DL-612 | (4) 5 parts of PVA | ????15 |
| The comparative example 2 | ?DL-612 | (5) 5 parts of PVA | ????15 |
| The comparative example 3 | ?DL-612 | 5 parts of aqueous solution (with regard to solids content) of PVA (1) | ????15 |
| The comparative example 4 | ?DL-612 | The aqueous solution (with regard to solids content) that PVA is (6) 5 parts | ????15 |
(*) add 5% weight lime carbonate OM-4200 in advance: ethane-acetic acid ethyenyl ester copolymer emulsion (solids content: DL-612 55%): styrene-butadiene copolymer emulsion (solids content: Acryl Em 50%): methyl methacrylate/n-butyl acrylate/hydroxyethyl acrylate
Copolymer emulsion (solids content: 48.5%)
Table 2
| Degree of hydrolysis (mol%) | The polymerization degree | Granularity (μ m) | Solubleness (%) | Surface tension (mN/m) | |
| PVA powder (1) | ????95 | ?1700 | ????90 | ????88 | ????55 |
| PVA powder (2) | ????88 | ??550 | ????200 | ????90 | ????50 |
| PVA powder (3) | ????88 | ?1700 | ????100 | ????95 | ????52 |
| PVA powder (4) | ????70 | ?1700 | ????600 | ????99 | ????42 |
| PVA powder (5) | ????95 | ?1700 | ????600 | ????45 | ????55 |
| PVA powder (6) | ????98 | ?1700 | ????600 | ????21 | ????60 |
Table 3
| The primary binder component | Tackiness agent | |||||
| The low temperature viscosity stability of primary binder component (after placing 7 days under 5 ℃) | The state of primary binder component (according to the film that on sheet glass, forms) | Initial adhesion strength (kg/cm 2) | Bond strength (kg/cm under the usual terms 2) | Bond strength (kg/cm under the conditions of cooking repeatedly 2) | The viscosity no-load voltage ratio (doubly) of tackiness agent | |
| Embodiment 1 | ????○ | ????○ | ????30 | ????190 | ????100 | ????2.2 |
| Embodiment 2 | ????○ | ????○ | ????28 | ????195 | ????110 | ????2.1 |
| Embodiment 3 | ????○ | ????○ | ????32 | ????160 | ????105 | ????2.1 |
| Embodiment 4 | ????○ | ????○ | ????28 | ????180 | ????85 | ????2.2 |
| Embodiment 5 | ????○ | ????○ | ????29 | ????200 | ????110 | ????2.1 |
| Embodiment 6 | ????○ | ????○ | ????30 | ????190 | ????85 | ????2.1 |
| Embodiment 7 | ????○ | ????○ | ????31 | ????180 | ????90 | ????2.2 |
| Embodiment 8 | ????○ | ????○ | ????30 | ????190 | ????80 | ????2.2 |
| Embodiment 9 | ????○ | ????○ | ????28 | ????190 | ????100 | ????2.1 |
| The comparative example 1 | ????○ | ????× | ????14 | ????180 | ????85 | ????6.0 |
| The comparative example 2 | ????○ | ????× | ????15 | ????160 | ????60 | ????2.1 |
| The comparative example 3 | ????○ | ????○ | ????18 | ????170 | ????90 | ????2.1 |
| The comparative example 4 | ????× | ????○ | ????13 | ????170 | ????96 | ????2.1 |
Table 4
| The primary binder component | Polyisocyanate compound | ||
| Emulsion | PVA powder (per 100 parts of solids contents of/emulsion) | Polymethylene multi-phenenyl isocyanate (MR-100) (in/per 100 parts of main active ingredients) | |
| Embodiment 1-1 | ????OM-4200 | 5 parts of PVA (1-1) | ????15 |
| Embodiment 2-1 | ????Acryl?Em | 5 parts of PVA (1-1) | ????15 |
| Embodiment 3-1 | ????DL-612 | 5 parts of PVA (1-1) | ????15 |
| Embodiment 4-1 | ????DL-612 | 5 parts of PVA (2-1) | ????15 |
| Embodiment 5-1 | ????DL-612 | 2.5 parts of 2.5 parts of PVA of PVA (1-1) (3-1) | ????15 |
| Embodiment 6-1 | ????DL-612 | 10 parts of PVA (1-1) | ????15 |
| Embodiment 7-1 | ????DL-612 | 1 part of PVA (1-1) | ????15 |
| Embodiment 8-1 | ????DL-612 | 5 parts of PVA (1-1) | ????3 |
| Embodiment 9-1 | ????DL-612 | 5 parts of PVA (1-1) (*) | ????15 |
(*) add the lime carbonate of 5% weight in advance.OM-4200: ethane-acetic acid ethyenyl ester copolymer emulsion (solids content: DL-612 55%): styrene-butadiene copolymer emulsion (solids content: Acryl Em 50%): methyl methacrylate/n-butyl acrylate/hydroxyethyl acrylate
Copolymer emulsion (solids content: 48.5%)
Table 5
| Carboxyl-content (mole %) | Degree of hydrolysis (mol%) | The polymerization degree | Granularity (μ m) | Solubleness (%) | Surface tension (mN/m) | |
| ?PVA(1-1) | Maleic anhydride (2) | ????95 | ????1700 | ????300 | ????90 | ????60 |
| ?PVA(2-1) | Methylene-succinic acid (3) | ????62 | ????550 | ????350 | ????95 | ????51 |
| ?PVA(3-1) | Methylene-succinic acid (1) | ????88 | ????1800 | ????300 | ????95 | ????55 |
Table 6
| The primary binder component | Tackiness agent | |||||
| The low temperature viscosity stability of primary binder component (after placing 7 days under 5 ℃) | The state of primary binder component (according to the film that on sheet glass, forms) | Initial adhesion strength (kg/cm 2) | Bond strength (kg/cm under the usual terms 2) | Bond strength (kg/cm under the conditions of cooking repeatedly 2) | The viscosity no-load voltage ratio (doubly) of tackiness agent | |
| Embodiment 1-1 | ????○ | ????○ | ????28 | ????200 | ????110 | ????1.8 |
| Embodiment 2-1 | ????○ | ????○ | ????28 | ????195 | ????110 | ????1.9 |
| Embodiment 3-1 | ????○ | ????○ | ????30 | ????200 | ????110 | ????1.8 |
| Embodiment 4-1 | ????○ | ????○ | ????32 | ????190 | ????100 | ????1.8 |
| Embodiment 5-1 | ????○ | ????○ | ????30 | ????205 | ????95 | ????1.9 |
| Embodiment 6-1 | ????○ | ????○ | ????29 | ????200 | ????100 | ????1.8 |
| Embodiment 7-1 | ????○ | ????○ | ????28 | ????195 | ????100 | ????1.8 |
| Embodiment 8-1 | ????○ | ????○ | ????30 | ????180 | ????85 | ????1.9 |
| Embodiment 9-1 | ????○ | ????○ | ????31 | ????200 | ????105 | ????1.9 |
Claims (7)
1, a kind of method of producing tackiness agent, this method comprises adding (B) pva powder in (A) water miscible liquid, this pva powder solubleness of 1 hour in 40 ℃ of water is not less than 50% weight, the surface tension of its 1% weightaqueous solution form is not less than 45mN/m, preparation primary binder component is then to wherein adding (C) polyisocyanate compound.
2, produce the method for tackiness agent according to claim 1, wherein, the primary binder component is not to be higher than under 60 ℃ the temperature, prepares in (A) by (B) joined.
3, produce the method for tackiness agent according to claim 1, wherein, the granularity of pva powder (B) is not more than 500 μ m.
4, a kind of tackiness agent, this tackiness agent comprises (A) water miscible liquid, (B) polyvinyl alcohol and (C) polymeric polyisocyanate, wherein the carboxyl number of (B) polyvinyl alcohol is the 0.2-5% mole, its solubleness of 1 hour in 40 ℃ of water is not less than 50% weight, and the surface tension of its 1% weightaqueous solution form is not less than 45mN/m.
5, the laminated product that obtains with the tackiness agent of claim 4.
6, the wooden laminated product that obtains with the tackiness agent of claim 4.
7, the layer of plywood stampings that obtain with the tackiness agent of claim 4.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35256697 | 1997-12-22 | ||
| JP352564/97 | 1997-12-22 | ||
| JP352564/1997 | 1997-12-22 | ||
| JP352566/1997 | 1997-12-22 | ||
| JP35256497 | 1997-12-22 | ||
| JP352566/97 | 1997-12-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1227243A true CN1227243A (en) | 1999-09-01 |
| CN1106437C CN1106437C (en) | 2003-04-23 |
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ID=26579656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98124081A Expired - Lifetime CN1106437C (en) | 1997-12-22 | 1998-12-22 | Method for producing adhesive, adhesive, and laminate products |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN1106437C (en) |
| ID (1) | ID21591A (en) |
| MY (1) | MY133097A (en) |
| NZ (1) | NZ333047A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360629C (en) * | 2002-04-28 | 2008-01-09 | 王学谦 | Multifunctional aqueous adhesive and its prepn |
| CN100413904C (en) * | 2005-12-20 | 2008-08-27 | 南开大学 | Soluble cross-linked polyvinyl alcohol polyurethane and synthesis method thereof |
| CN108659758A (en) * | 2018-05-24 | 2018-10-16 | 广东东美实业有限公司 | A kind of composite plate formaldehyde-free rubber water formula |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5716149B2 (en) * | 1973-10-08 | 1982-04-03 | ||
| JPS62119285A (en) * | 1985-11-19 | 1987-05-30 | Mitsui Toatsu Chem Inc | Adhesive composition |
| CN1032352A (en) * | 1987-10-09 | 1989-04-12 | 肖绪汉 | White emulsion binder and preparation method thereof |
| JPH023488A (en) * | 1988-06-14 | 1990-01-09 | Showa Denko Kk | Adhesive |
| CN1041965A (en) * | 1988-10-21 | 1990-05-09 | 薜志纯 | Improving acrylic resin binding agent |
| EP0367120A1 (en) * | 1988-10-28 | 1990-05-09 | Air Products And Chemicals, Inc. | Vinyl laminating adhesive composition |
| US5092953A (en) * | 1989-03-21 | 1992-03-03 | Air Products And Chemicals, Inc. | Aqueous vinyl chloride-ethylene copolymer/polyisocyanate adhesive compositions for wood composites |
| JP3474303B2 (en) * | 1995-03-24 | 2003-12-08 | 株式会社クラレ | Wood adhesive |
| JPH08269426A (en) * | 1995-04-03 | 1996-10-15 | Kuraray Co Ltd | Compounded composition and adhesive |
-
1998
- 1998-11-27 NZ NZ33304798A patent/NZ333047A/en not_active IP Right Cessation
- 1998-12-17 MY MYPI9805706 patent/MY133097A/en unknown
- 1998-12-22 CN CN98124081A patent/CN1106437C/en not_active Expired - Lifetime
- 1998-12-22 ID IDP981663A patent/ID21591A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360629C (en) * | 2002-04-28 | 2008-01-09 | 王学谦 | Multifunctional aqueous adhesive and its prepn |
| CN100413904C (en) * | 2005-12-20 | 2008-08-27 | 南开大学 | Soluble cross-linked polyvinyl alcohol polyurethane and synthesis method thereof |
| CN108659758A (en) * | 2018-05-24 | 2018-10-16 | 广东东美实业有限公司 | A kind of composite plate formaldehyde-free rubber water formula |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1106437C (en) | 2003-04-23 |
| MY133097A (en) | 2007-10-31 |
| ID21591A (en) | 1999-06-24 |
| NZ333047A (en) | 2000-02-28 |
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