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CN100419036C - Water-resistant adhesive composition for wood - Google Patents

Water-resistant adhesive composition for wood Download PDF

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Publication number
CN100419036C
CN100419036C CNB2004800270128A CN200480027012A CN100419036C CN 100419036 C CN100419036 C CN 100419036C CN B2004800270128 A CNB2004800270128 A CN B2004800270128A CN 200480027012 A CN200480027012 A CN 200480027012A CN 100419036 C CN100419036 C CN 100419036C
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carboxy
water
modified
weight parts
adhesive composition
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CN1852956A (en
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岩崎雅春
森永博泰
村田裕司
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Oshika KK
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Oshika KK
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3227—Compounds containing acyclic nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

An inexpensive adhesive composition for wood which emits neither formaldehyde nor an irritative odor, causes neither skin rashes nor wood fouling/discoloration, has a long pot life, and is excellent in water resistance and heat resistance. The composition comprises: a main ingredient comprising a carboxy-modified aqueous emulsion or latex resin and an aqueous solution of a carboxy-modified polyvinyl alcohol polymer; and a compound having an N,N-diglycidylamino group as a tetrafunctional epoxy compound having a tertiary amino nitrogen atom. It comprises 100 pts.wt. of a carboxy-modified aqueous emulsion or latex resin having a modification amount of 0.1 to 20 wt.%, 0.2 to 270 pts.wt., in terms of resin amount, of an aqueous solution of a carboxy-modified polyvinyl alcohol polymer having a modification amount of 0.1 to 10 mol% and a degree of polymerization of 100 to 6,000, and 0 to 700 pts.wt. of a filler, and further contains 3 to 200 pts.wt. of the compound having an N,N-diglycidylamino group per 100 pts.wt. of the main ingredient.

Description

Water-resistant adhesive composition for wood
Technical field
The present invention relates to woodenly, particularly relate to the water-resistant adhesive composition for wood of the secondary processing of the manufacturing that is used for glued board or glued board with water-resistant adhesive (adhesive) composition.
Background technology
That all the time, has used polyvinyl alcohol resin woodenly sticks with glue agent and has obtained widespread use.Described polyvinyl alcohol resin has extremely good cementability for Mierocrystalline cellulose, but its water tolerance and poor heat resistance.Therefore in described polyvinyl alcohol resin, cooperated formaldehyde resin such as urea-formaldehyde resin, resorcinol formaldehyde resin, terpolycyantoamino-formaldehyde resin and given that water tolerance and stable on heating formaldehyde resin class are wooden to stick with glue agent by known to the people.
But, residual in the agent free formaldehyde that derives from this formaldehyde resin arranged wooden the sticking with glue of described formaldehyde resin class, therefore use the bonding product of this tackiness agent can discharge this formaldehyde, thereby cause family expenses material (sick house) complication, chemical substance allergy etc.In addition, stick with glue for the agent for described formaldehyde resin class is wooden, if under the temperature more than 30 ℃ through more than 3 hours, then its viscosity rises, and presents gel state, coating and cementability descend, and therefore have the problem of poor practicability.
For solve described formaldehyde resin class wooden stick with glue the problem that exists in the agent and propose do not use described formaldehyde resin have water tolerance and a stable on heating wooden agent that sticks with glue, known have a following adhesive compound, promptly, the aqueous solution, aqueous emulsifying resin (emulsionresin), water based emulsion resin (latex resin) etc. that will contain polyvinyl alcohol are as host, cooperate the aqueous macromolecule-isocyanate class adhesive compound of making as the isocyanate compound of linking agent in this host.But for described aqueous macromolecule-isocyanate class adhesive compound, react and foam owing in described host, directly cooperating, mix behind the described isocyanate compound this isocyanate compound meeting and water fierceness, and viscosity also can rise, make coating reduce, perhaps passing in time, water-fast cementability and heat-resistant fine adhesive function significantly descend, and therefore exist the spendable time than problems such as weak points.
In order to solve the problem that in described aqueous macromolecule-isocyanate class adhesive compound, exists, in the special public clear 51-30577 communique following tackiness agent has been proposed, promptly, isocyanate ester compound or isocyanates polymer dissolution in having in the hydrophobic solvent of intermiscibility with isocyanate ester compound or isocyanic ester base polymer, are dispersed in the mixture that obtains in the aqueous solution that contains polyvinyl alcohol or the water-based emulsion and the water-resistant adhesive stick of making then.
For described water-resistant adhesive stick, because isocyanate ester compound or isocyanic ester base polymer are dissolved in the hydrophobic solvent in advance, therefore when mixing, can avoid isocyanic ester and water to react with the aqueous solution that contains polyvinyl alcohol or water-based emulsion.Thus, there is not the problem that above-mentioned foaming or viscosity rise or the spendable time is short in the described water-resistant adhesive stick.But, in described water-resistant adhesive stick, have the strong impulse smell, so this irritating smell can cause family expenses material complication, chemical substance allergy etc. again owing to described hydrophobic solvent.
In order to solve the problem that in described aqueous macromolecule-isocyanate class adhesive compound, exists, in the public clear 51-28655 communique of spy, proposed by carboxylic polymkeric substance, multivalent metal hydroxides, in molecule, contained the adhesive compound that the mixture of the water-soluble cpds of 2 above epoxy group(ing) constitutes.But because described multivalent metal hydroxides, described adhesive compound presents the above strong basicity of pH11, and therefore the alkali pollution of timber can take place, if perhaps in operating process this adhesive compound be contacted with skin then can produce macula etc.
In addition, in order to solve the problem that in described aqueous macromolecule-isocyanate class adhesive compound, exists, the present patent application people etc. have proposed following adhesive compound, that is, by the aqueous solution that has the polyvinyl alcohol polymer of carboxyl at intramolecularly, have 4 functional group's epoxy compoundss of tertiary amine groups nitrogen-atoms and have containing the aminoacrylic acid emulsion or having the aqueous adhesive composition that containing of active hydrogen, amino water-borne acrylic resin constituted of active hydrogen.In described aqueous adhesive composition,, can contain the weighting agent Calcium hydrogen carbonate (speciallyying permit communique No. 3048674) for example about 126 weight parts with respect to resinous principle 100 weight parts that in the aqueous solution of described polyvinyl alcohol polymer, contain.
In described aqueous adhesive composition, contain, have active hydrogen contain the aminoacrylic acid emulsion or have containing of active hydrogen amino water-borne acrylic resin and be prepared as follows, promptly, at first preparation has the ACRYLIC EMULSION of carboxyl or has after the water-borne acrylic resin of carboxyl, utilizes group with imine moiety such as alkyl imines to carry out amino modified to described carboxyl.
But, the price height of described ACRYLIC EMULSION or water-borne acrylic resin, thereby can't avoid the increase of described aqueous adhesive composition cost, and, the color of timber is changed owing to remain in described imide compound in this aqueous adhesive composition.
Summary of the invention
The objective of the invention is to solve problem as above, the wooden agent composition that sticks with glue of the cheapness of long, water tolerance of a kind of following serviceable time and excellent heat resistance is provided, this wooden agent composition that sticks with glue can not discharge the formaldehyde or the irritating smell that can cause family expenses material complication, chemical substance allergy etc., and can not cause pollution, the variable color of skin macula or timber, the problem that does not exist foaming, viscosity to rise.
In order to achieve the above object, of the present invention wooden stick with glue the agent composition comprise (A) by do not comprise contain the aminoacrylic acid emulsion or contain amino water-borne acrylic resin, intramolecularly has the host that the aqueous solution of the carboxy-modified polyvinyl alcohol polymer that the carboxy-modified aqueous emulsifying resin of carboxyl or carboxy-modified latex resin that intramolecularly has carboxyl and intramolecularly have carboxyl constitutes, and (B) as 4 functional group's epoxy compoundss with tertiary amine groups nitrogen-atoms, contain N, the compound of N-2-glycidyl amino with what general formula (1) was represented.
Figure C20048002701200061
(in the formula, D represents to be selected from a kind of divalent group in phenylene that ring type alkylidene group, phenylene, the alkyl of straight or branched alkylidene group, the carbonatoms 3～12 of carbonatoms 1～12 replace, the phenylene that halogen replaces)
Adhesive compound of the present invention is, in described carboxy-modified aqueous emulsifying resin or carboxy-modified latex resin, add polyvinyl alcohol resin by carboxy-modified aqueous solutions of polymers after used as host, and in this host, cooperate and contain N, the compound of N-2-glycidyl amino is made, and himself has extremely good cementability for Mierocrystalline cellulose wherein said polyvinyl alcohol resin.
Adhesive compound of the present invention does not have containing the aminoacrylic acid emulsion or having containing of active hydrogen of amino water-borne acrylic resin of active hydrogen even do not use owing to have described composition, can obtain equal therewith adhesiveproperties yet.
Adhesive compound of the present invention is owing to contain described carboxy-modified aqueous emulsifying resin or carboxy-modified latex resin, therefore can obtain good coating and wettability in the wood materials in that this adhesive compound is coated on.In addition, this adhesive compound is being coated in the wood materials, described carboxy-modified aqueous emulsifying resin or carboxy-modified latex resin can prevent described carboxy-modified polyvinyl alcohol polymer and the described N of containing, and the compound of N-2-glycidyl amino is to the excessive permeation of this wood materials.Its result, adhesive compound of the present invention can obtain good water-fast bonding force, heat-resisting bonding force and weather resistance when being used for wood materials bonding.
In addition, adhesive compound of the present invention is to cooperate the described N of containing in described host, and the compound of N-2-glycidyl amino is made, so do not contain formaldehyde or organic solvent, can not cause family expenses material complication, chemical substance allergy etc.In addition, do not contain isocyanate compound in the adhesive compound of the present invention, therefore can prevent the foaming that causes by the reaction of this isocyanate compound and water, the rising of viscosity, can obtain the long serviceable time.In addition, do not contain multivalent metal hydroxides in the adhesive compound of the present invention, so pH can not rise, can prevent the alkali pollution of timber, the macula of skin.
And then, adhesive compound of the present invention is not owing to contain the aminoacrylic acid emulsion or contain amino water-borne acrylic resin, therefore it is cheap, describedly contain the aminoacrylic acid emulsion or contain amino water-borne acrylic resin, be for ACRYLIC EMULSION or have the carboxyl of the water-borne acrylic resin of carboxyl, carry out amino modified and make with group with imine moiety such as alkyl imines with carboxyl.
In water-resistant adhesive composition for wood of the present invention, the carboxy-modified amount for described carboxy-modified aqueous emulsifying resin or carboxy-modified latex resin has no particular limits, and preferred carboxy-modified amount is the scope of 0.1～20 weight %.If the carboxy-modified amount of described carboxy-modified aqueous emulsifying resin or carboxy-modified latex resin less than 0.1 weight %, then is not easy to obtain sufficient water-fast bonding force, heat-resisting bonding force, weather resistance.On the other hand, if carboxy-modified amount surpasses 20 weight %, then generally understand deficient in stability in polyreaction, if will obtain good aqueous emulsifying resin or latex resin, cost can increase inevitably.
In water-resistant adhesive composition for wood of the present invention, have no particular limits preferred 0.1～10 mole of % of carboxy-modified amount, the scope of the polymerization degree preferred 100～6000 for carboxy-modified amount, the polymerization degree of described carboxy-modified polyvinyl alcohol polymer.
In the described carboxy-modified polyvinyl alcohol polymer, when carboxy-modified amount during less than 0.1 mole of %, the cross-linking density step-down is difficult to obtain sufficient water tolerance and thermotolerance and anti-boiling property.On the other hand, when carboxy-modified amount surpasses 10 moles of %, generally lack the stability of polyreaction, if will obtain good polyvinyl alcohol polymer, cost can increase inevitably.
In addition, described carboxy-modified polyvinyl alcohol polymer, its polymerization degree was not easy to obtain sufficient water tolerance and thermotolerance less than 100 o'clock.On the other hand, when the polymerization degree surpasses 6000, generally lack the stability of polyreaction, be not easy to obtain good polyvinyl alcohol polymer.
In addition, the saponification deg for described carboxy-modified polyvinyl alcohol polymer has no particular limits, but if will obtain good water tolerance and thermotolerance, preferably saponification deg is set at the scope of 70～100 moles of %.
In the water-resistant adhesive composition for wood of the present invention, described carboxy-modified polyvinyl alcohol polymer has no particular limits for the use level of described carboxy-modified aqueous emulsifying resin or carboxy-modified latex resin, with respect to resinous principle 100 weight parts that contain in described carboxy-modified aqueous emulsifying resin or the carboxy-modified latex resin, preferably the resinous principle meter that contains in the aqueous solution of described carboxy-modified polyvinyl alcohol polymer according to this polymkeric substance is contained 0.2～270 weight part.The use level of the resinous principle that contains in the aqueous solution of described carboxy-modified polyvinyl alcohol polymer, if surpass 270 weight parts with respect to the resinous principle that contains in described carboxy-modified aqueous emulsifying resin of 100 weight parts or the carboxy-modified latex resin, then can not obtain sufficient water-fast bonding strength and heat-resisting bonding strength and the anti-bonding strength repeatedly of boiling sometimes.
In water-resistant adhesive composition for wood of the present invention, about the described N that contains, the use level of the host that the compound of N-2-glycidyl amino constitutes for the aqueous solution by described carboxy-modified aqueous emulsifying resin or carboxy-modified latex resin and described carboxy-modified polyvinyl alcohol polymer, have no particular limits, preferably with respect to resinous principle 100 weight parts that contain in this host, the described N of containing that contains 3～150 weight part scopes, the compound of N-2-glycidyl amino.As the described N that contains, the use level of the compound of N-2-glycidyl amino is with respect to resinous principle 100 weight parts that contain in the described host, during less than 3 weight parts, the curing of described water-resistant adhesive composition for wood becomes insufficient, can not obtain sufficient water tolerance and thermotolerance, simultaneously weather resistance, also reduce with the performances such as connecting airtight property of timber.On the other hand, as the described N that contains, the use level of the compound of N-2-glycidyl amino is with respect to resinous principle 100 weight parts that contain in the described host, during greater than 150 weight parts, sometimes can not obtain sufficient adhesion strength and material fracture rate, and cost can increase inevitably.
By making water-resistant adhesive composition for wood of the present invention further contain weighting agent, can prevent that the resinous principle excessive permeation can obtain stable adhesiveproperties in this wood materials when being coated on this adhesive compound on the wood materials.Have no particular limits for described weighting agent, and also have no particular limits about use level with respect to the described weighting agent of described carboxy-modified aqueous emulsifying resin or carboxy-modified latex resin, preferably, contain the described weighting agent of 0～700 weight part scope with respect to resinous principle 100 weight parts that in described carboxy-modified aqueous emulsifying resin or carboxy-modified latex resin, contain.When with respect to resinous principle 100 weight parts that in described carboxy-modified aqueous emulsifying resin or carboxy-modified latex resin, contain, when the use level of described weighting agent surpasses 700 weight parts, can not obtain the anti-bonding strength repeatedly of boiling fully sometimes.
Embodiment
Below, embodiments of the present invention are described in further detail.
The water-resistant adhesive composition for wood of present embodiment comprise host and as 4 functional group's epoxy compoundss with tertiary amine groups nitrogen-atoms, contain N, the compound of N-2-glycidyl amino with what general formula (1) was represented.Described host is made of the aqueous solution that intramolecularly has the carboxy-modified polyvinyl alcohol polymer that the carboxy-modified aqueous emulsifying resin of carboxyl or carboxy-modified latex resin that intramolecularly has carboxyl and intramolecularly have carboxyl.
Figure C20048002701200091
(in the formula, D represents to be selected from a kind of divalent group in phenylene that ring type alkylidene group, phenylene, the alkyl of straight or branched alkylidene group, the carbonatoms 3～12 of carbonatoms 1～12 replace, the phenylene that halogen replaces)
As described carboxy-modified aqueous emulsifying resin that uses in the present embodiment or described carboxy-modified latex resin, can use the dispersion liquid of the known polymkeric substance and the multipolymer of unsaturated monomer with carboxyl.As described multipolymer, specifically can enumerate by being selected from vinyl acetate, propionate, ethene, ethylene chloride, vinylidene chloride, ethylene bromide, inclined to one side bromine ethene, ethyl vinyl ether, butyl vinyl ether, vinylbenzene, styrene derivatives, divinyl, vinyl cyanide, chloroprene, 1, the polymkeric substance that the unsaturated monomer more than a kind and 2 kinds in 3-hexadiene, isoprene, iso-butylene, acrylate, the methacrylic ester etc. constitutes.In addition, as with the unsaturated monomer with carboxyl of described polymkeric substance copolymerization, can enumerate the unsaturated monomer more than a kind or 2 kinds in monocarboxylic acids such as ethene unsaturated dicarboxylic acids such as being selected from toxilic acid, toxilic acid monoesters, maleic acid diester, methylene-succinic acid, methylene-succinic acid monoesters, fumaric acid, fumaric monoalkylester, citraconic acid, citraconic acid monoesters, methylfumaric acid, methylfumaric acid monoesters or its ester, Ba Dousuan, vinylformic acid, methacrylic acid etc.
It is the resin of 0.1～20 weight % scope that carboxy-modified aqueous emulsifying resin or described carboxy-modified latex resin for example can suitably use carboxy-modified amount.
In addition, the carboxy-modified polyvinyl alcohol polymer that uses in the present embodiment is so long as the polyvinyl alcohol polymer that has a carboxyl at intramolecularly just has no particular limits.As described carboxy-modified polyvinyl alcohol polymer, for example can suitably use and to implement the saponified random copolymers again after as copolymerization such as the vinyl acetate monomer of representative and ethene unsaturated carboxylic acid, its acid anhydrides or have endways under the existence of vinol series polymer of thiol group with vinyl acetate, make described ethene unsaturated carboxylic acid carry out radical polymerization and the block polymer that obtains.
As described vinyl ester monomers, except described vinyl-acetic ester, can also enumerate vinyl formate, propionate, tertiary ethylene carbonate, new vinyl acetate acid etc.In addition, as described ethene unsaturated carboxylic acid, can enumerate vinylformic acid, methacrylic acid, fumaric acid, toxilic acid, methylene-succinic acid, Ba Dousuan, citraconic acid, equisetic acid or their acid anhydrides etc.
For described carboxy-modified polyvinyl alcohol polymer, modification amount to its polymerization degree, carboxyl has no particular limits, and the suitable use for example polymerization degree is that 100～6000 scope, the modification amount of carboxyl are the carboxy-modified polyvinyl alcohol polymer of 0.1～10 mole of % scope.In addition, just have no particular limits as long as described carboxy-modified polyvinyl alcohol has the saponification deg that is dissolved in the water, suitable usually use saponification deg is the carboxy-modified polyvinyl alcohol of 70～100 moles of % scopes.
In addition, as described carboxy-modified polyvinyl alcohol polymer, in the scope of the adhesiveproperties of the water-resistant adhesive composition for wood that does not damage present embodiment, can use with the ethylene unsaturated monomer copolymerization described carboxy-modified polyvinyl alcohol polymer.As described ethylene unsaturated monomer, can enumerate for example 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, ethylene chloride, ethylene bromide, ethylene fluoride, vinylidene chloride, vinylidene, tetrafluoroethylene, sodium vinyl sulfonate, sodium allyl sulfonate etc.
In addition, described carboxy-modified polyvinyl alcohol polymer can use in the presence of mercaptan compounds such as thioacetic acid, thiohydracrylic acid, with the terminal-modified multipolymer of resaponifying after vinyl ester monomers such as vinyl-acetic ester and the copolymerization of ethene unsaturated carboxylic acid.
In the water-resistant adhesive composition for wood of present embodiment, preferably with respect to resinous principle 100 weight parts that contain in described carboxy-modified aqueous emulsifying resin or the carboxy-modified latex resin, resinous principle with containing in the aqueous solution of described carboxy-modified polyvinyl alcohol polymer by this polymkeric substance contains 0.2～270 weight part scope.
In addition, as the N that contains with general formula (1) expression, the compound of N-2-glycidyl amino, can enumerate N, N, N ', N '-four glycidyl group quadrol, N, N, N ', N '-four glycidyl group hexamethylene-diamine, 1, two (the N of 3-, N-2-glycidyl amino methyl) hexanaphthene, 1-(N, N-2-glycidyl amino methyl) 1,5,5-trimethylammonium-3-(N, N-2-glycidyl amino) hexanaphthene, N, N, N ', N '-four glycidyl group-1, the 4-phenylenediamine, (N, N, N ', N '-four glycidyl group) diaminotoluene, N, N, N ', N '-four glycidyl group-1, the 3-benzene dimethylamine, 2 of its halogen replaces 4 of body or halogen and replaces body, two (N, N-2-glycidyl amino-phenol) sulfone, 4 ' of 4 '-(N, N-2-glycidyl amino) Phenylsulfonic acid-(N, N-2-glycidyl amino) phenyl ester, two (N, N-2-glycidyl amino trimethylene methyl) alkylene glycol etc., wherein suitable N, N, the N ' of using, N '-four glycidyl group-1, the 3-benzene dimethylamine, 1, two (N, N-2-glycidyl amino methyl) hexanaphthenes of 3-etc.
The N that contains with described general formula (1) expression, N-2-glycidyl aminocompound, for example with respect to resinous principle 100 weight parts that contain in the described host, can use the scope of 3～150 weight parts, wherein said host is made of the aqueous solution of described carboxy-modified aqueous emulsifying resin or described carboxy-modified latex resin and described carboxy-modified polyvinyl alcohol polymer.In addition, in the water-resistant adhesive composition for wood of present embodiment, can use N, N-2-glycidyl amino-2, two (glycidyl oxygen) aniline of 4-replace containing N, N-2-glycidyl aminocompound with what described general formula (1) was represented.
The water-resistant adhesive composition for wood of present embodiment can further contain weighting agent.Have no particular limits for described weighting agent, for example can enumerate organic matters such as blood meal, defatted soyflour, walnut powder is weighting agent, clay, kaolin clay, burns till inanimate matter weighting agents such as clay, lime carbonate, talcum, diatomite, sericite, zeolite, gypsum, silicon-dioxide, aluminium hydroxide, aluminum oxide.Described weighting agent can use separately, also can use simultaneously more than 2 kinds.With respect to resinous principle 100 weight parts that contain in described carboxy-modified aqueous emulsifying resin or the carboxy-modified latex resin, described weighting agent for example can use the scope of 0～700 weight part.
In addition, in the water-resistant adhesive composition for wood of present embodiment, in the scope of not damaging adhesiveproperties, toluene can suit to add, dimethylbenzene, butylacetate, the Trivalin SF equal solvent, phthalic acid ester, softening agent such as polyethyleneglycol phenyl ether are made film, wheat-flour, extenders such as W-Gum, white pigments such as titanium oxide, tinting pigment, dyestuff, polyvinyl alcohol, Natvosol, methylcellulose gum, carboxymethyl cellulose, starch, paste or thickening materials such as dextrin, dispersion agent, emulsifying agent, wetting agent, defoamer, ethylene glycol etc. freeze to prevent agent, sanitas, mould inhibitor, a kind of in the rust-preventive agent etc. or more than 2 kinds.
The water-resistant adhesive composition for wood of present embodiment is not owing to contain formaldehyde, organic solvent, therefore do not pollute the environment, how wet and the serviceable time is long, has good water-fast bonding force, even keep water-fast bonding force between also can be often under high temperature the environment.
The following describes embodiments of the invention and comparative example.
Embodiment 1
In the present embodiment, add carboxy-modified styrene butadiene synthetic latex resin (methylene-succinic acid 2.3 weight % with the methylene-succinic acid modification, divinyl 28 weight %, the terpolymer of vinylbenzene 69.7 weight %, resinous principle 50 weight %) 100 weight parts, with the carboxy-modified polyvinyl alcohol polymer of the random copolymerization of the methylene-succinic acid modification (polymerization degree 1700,2 moles of % of modification amount, 98 moles of % of saponification deg) 15% aqueous solution, 100 weight parts, with N with following formula (2) expression as the 4 officials energy epoxy compounds that contains the tertiary amine groups nitrogen-atoms, N, N ', N '-four glycidyl group-m-xylene diamine (aerochemistry Co., Ltd. of Mitsubishi system, trade(brand)name: TETRAD-X) 10 weight parts are modulated into water-resistant adhesive composition for wood through stirring.
In the described water-resistant adhesive composition for wood, resinous principle 100 weight parts with respect to described carboxy-modified styrene butadiene synthetic latex resin is contained contain 30 weight parts with described carboxy-modified polyvinyl alcohol polymer by the resinous principle that contains in this aqueous solution.In addition, with respect to resinous principle 100 weight parts that contained in the host that the aqueous solution constituted by described carboxy-modified styrene butadiene synthetic latex resin and described carboxy-modified polyvinyl alcohol polymer, contain the N of 15 weight parts, N, N ', N '-four glycidyl group-m-xylene diamine.
Figure C20048002701200131
Then, it is overlapping successively to be that thickness that the sal material of 5～8 weight % constitutes is respectively 3 veneers of 0.7mm, 1.7mm, 0.7mm by water ratio, is coated with 330g/m on the two sides of bonding plane 2The water-resistant adhesive composition for wood that obtains in the present embodiment of (two sides) amount.To eclipsed veneer in the manner described above, 20 ℃, sealing accumulation within 10 minutes, 20 ℃, under the colding pressing of 1MPa, kept 20 minutes, 110 ℃, under the hot pressing of 0.8MPa, kept 60 seconds, carry out the bonding glued board made from this, with this glued board as estimating the test board that adhesiveproperties is used.
Then, timber tensile shear bonding strength test method according to the tackiness agent of the K6851 of Japanese Industrial Standards (JIS) regulation, modulation has the test film of the shape and size of regulation, has measured the normality intensity of described test film, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling under 6000N/ minute load velocity conditions.Described normality intensity is that described test film is measured under the condition of measuring 20 ℃ of room temps and got.In addition, described water-fast intensity is described test film to be soaked after 7 days take out in 20 ℃ water, and under moistening state, measuring that 20 ℃ of room temps are measured down.And described heat-resisting water intensity is that described test film is soaked in 60 ℃ warm water in the water that is immersed in 20 ℃ after 3 hours up to turning cold, take out, under moistening state, measuring that 20 ℃ of room temps are measured down.In addition, the anti-intensity of boiling repeatedly is above-mentioned test film to be soaked take out after 4 hours and 60 ℃ air drying 20 hours in boiling water, in boiling water, soaked 4 hours afterwards, be immersed in again in 20 ℃ the water up to turning cold, take out, under moistening state, measuring that 20 ℃ of room temps are measured down.
The measurement result of bonding strength (MPa) is shown in Table 1.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Embodiment 2
In the present embodiment, except the carboxy-modified styrene butadiene synthetic latex resin that replaces using among the embodiment 1, use with the acrylic acid modified carboxy-modified styrene butadiene synthetic latex resin (terpolymer of vinylformic acid 5 weight %, divinyl 31 weight %, vinylbenzene 64 weight %, resinous principle 50 weight %) in addition, modulated water-resistant adhesive composition for wood with embodiment 1 identically.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 1.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Embodiment 3
In the present embodiment, except the carboxy-modified styrene butadiene synthetic latex resin that replaces using among the embodiment 1, used with the acrylic acid modified carboxy-modified styrene butadiene synthetic latex resin (terpolymer of vinylformic acid 10 weight %, divinyl 31 weight %, vinylbenzene 59 weight %, resinous principle 50 weight %) in addition, modulated water-resistant adhesive composition for wood with embodiment 1 identically.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 1.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Embodiment 4
In the present embodiment, except the carboxy-modified styrene butadiene synthetic latex resin that replaces using among the embodiment 1, use has changed the carboxy-modified styrene butadiene synthetic latex resin (terpolymer of methylene-succinic acid 0.3 weight %, divinyl 32 weight %, vinylbenzene 67.7 weight % of the modification amount of methylene-succinic acid, resinous principle 50 weight %) in addition, modulated water-resistant adhesive composition for wood with embodiment 1 identically.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 1.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Embodiment 5
In the present embodiment, except the carboxy-modified styrene butadiene synthetic latex resin that replaces using among the embodiment 1, used the acrylic latex resin (terpolymer of methacrylic acid 1 weight %, methyl methacrylate 54 weight %, butyl acrylate 45 weight % with the methacrylic acid modification, resinous principle 50 weight %) in addition, modulated water-resistant adhesive composition for wood with embodiment 1 identically.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 1.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Embodiment 6
In the present embodiment, add with embodiment 1 identical carboxy-modified styrene butadiene synthetic latex resin 100 weight parts and with 15% aqueous solution, 2 weight parts of the carboxy-modified polyvinyl alcohol polymer of the random copolymerization of toxilic acid modification (polymerization degree 1700,2 moles of % of modification amount, 98 moles of % of saponification deg) and with embodiment 1 in identical N, N, N ', N '-four glycidyl group-m-xylene diamine 5 weight parts is modulated to water-resistant adhesive composition for wood through stirring.
In the described water-resistant adhesive composition for wood, resinous principle 100 weight parts with respect to described carboxy-modified styrene butadiene synthetic latex resin is contained contain 0.6 weight part with described carboxy-modified polyvinyl alcohol polymer by the resinous principle that contains in this aqueous solution.In addition, with respect to resinous principle 100 weight parts that contained in the host that the aqueous solution constituted by described carboxy-modified styrene butadiene synthetic latex resin and described carboxy-modified polyvinyl alcohol polymer, contain the N of 10 weight parts, N, N ', N '-four glycidyl group-m-xylene diamine.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 1.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Table 1
Normality intensity Water-fast intensity Heat-resisting water intensity The anti-intensity repeatedly of boiling
Embodiment 1 1.17(100) 1.63(100) 1.45(100) 1.37(100)
Embodiment 2 1.80(100) 1.51(100) 1.53(100) 1.11(100)
Embodiment 3 1.75(100) 1.69(100) 1.56(100) 1.19(100)
Embodiment 4 1.73(100) 1.40(100) 1.40(100) 1.37(100)
Embodiment 5 1.76(100) 1.69(100) 1.54(100) 1.04(100)
Embodiment 6 1.67(100) 1.83(100) 1.77(100) 1.63(100)
As shown in Table 1, use the water-resistant adhesive composition for wood of embodiment 1～6, not only about its normality intensity, about its water-fast intensity, heat-resisting water intensity, the anti-intensity of boiling repeatedly also can obtain good adhesiveproperties, in the water-resistant adhesive composition for wood of described embodiment 1～6, with respect to resinous principle 100 weight parts that carboxy-modified latex resin contained, contained resinous principle in the aqueous solution of carboxy-modified polyvinyl alcohol polymer by this polymkeric substance is contained 0.6～30 weight part, in addition, with respect to resinous principle 100 weight parts that contained in the host that the aqueous solution constituted by described carboxy-modified latex resin and described carboxy-modified polyvinyl alcohol polymer, the N that contains 10～15 weight parts, N, N ', N '-four glycidyl group-m-xylene diamine.
Embodiment 7
In the present embodiment, except the 4 functional group's epoxy compoundss that replace using among the embodiment 1 with tertiary amine groups nitrogen-atoms, and used with 1 of following formula (3) expression, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene (aerochemistry Co., Ltd. of Mitsubishi system, trade(brand)name: TETRAD-C) in addition, modulated water-resistant adhesive composition for wood with embodiment 1 identically.
Figure C20048002701200171
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 2.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Comparative example 1
In this comparative example, except the 4 functional group's epoxy compoundss that replace using among the embodiment 1 with tertiary amine groups nitrogen-atoms, and Resins, epoxy (rising sun electrochemical industry Co., Ltd. system, the trade(brand)name: ア デ カ レ ジ Application E P-4100), modulated adhesive compound of bisphenol-A diglycidyl ether type have been used with embodiment 1 identically.
Then, the adhesive compound that obtains, make test board with embodiment 1 in using this comparative example, bonding bad (gas leak phenomenon) appearred in the result, can't obtain test board identically.Show the result in the table 2.
Comparative example 2
In this comparative example, except the 4 functional group's epoxy compoundss that replace using among the embodiment 1 with tertiary amine groups nitrogen-atoms, and used Resins, epoxy (Toto Kasei KK's system of 4 functional group's poly epihydric alcohol amine types of expression in the following formula (4), trade(brand)name: EPO TOHTO YH-434), modulated adhesive compound with embodiment 1 identically.
Figure C20048002701200181
Then, the adhesive compound that obtains, make test board with embodiment 1 in using this comparative example, bonding bad (gas leak phenomenon) appearred in the result, can't obtain test board identically.Show the result in the table 2.
Comparative example 3
In this comparative example, except the 4 functional group's epoxy compoundss that replace using among the embodiment 1 with tertiary amine groups nitrogen-atoms, and used Resins, epoxy (Na ガ セ ケ system テ Star Network Co., Ltd. system of glycerine polyglycidyl ether type, trade(brand)name: デ Na コ one Le EX-314), modulated adhesive compound with embodiment 1 identically.
Then, the adhesive compound that obtains, make test board with embodiment 1 in using this comparative example, bonding bad (gas leak phenomenon) appearred in the result, can't obtain test board identically.Show the result in the table 2.
Comparative example 4
In this comparative example, except the 4 functional group's epoxy compoundss that replace using among the embodiment 1 with tertiary amine groups nitrogen-atoms, and used Resins, epoxy (Toto Kasei KK's system of Bisphenol F diglycidyl ether-type, trade(brand)name: EPO TOHTO YDF-170), modulated adhesive compound with embodiment 1 identically.
Then, the adhesive compound that obtains, make test board with embodiment 1 in using this comparative example, bonding bad (gas leak phenomenon) appearred in the result, can't obtain test board identically.Show the result in the table 2.
Table 2
Normality intensity Water-fast intensity Heat-resisting water intensity The anti-intensity repeatedly of boiling
Embodiment 7 1.70(100) 1.57(100) 1.42(100) 1.00(100)
Comparative example 1 0(0) 0(0) 0(0) 0(0)
Comparative example 2 0(0) 0(0) 0(0) 0(0)
Comparative example 3 0(0) 0(0) 0(0) 0(0)
Comparative example 4 0(0) 0(0) 0(0) 0(0)
As shown in Table 2, the 4 functional group's epoxy compoundss that replace use among the embodiment 1 with tertiary amine groups nitrogen-atoms, and used 1, two (the N of 3-, N-diglycidyl amino methyl) water-resistant adhesive composition for wood of the embodiment 7 of hexanaphthene is identical with the water-resistant adhesive composition for wood of embodiment 1-6, not only about its normality intensity, and, also can obtain good adhesiveproperties about its water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling.
Relative therewith, use be different from 4 functional group's epoxy compoundss with tertiary amine groups nitrogen-atoms epoxy compounds comparative example 1,3,4 adhesive compound, use in the adhesive compound of comparative example 2 of the 4 functional group's epoxy compoundss do not belong to general formula (1) with tertiary amine groups nitrogen-atoms, can not obtain adhesiveproperties fully.
Embodiment 8
In the present embodiment, identical carboxy-modified styrene butadiene synthetic latex resin 100 weight parts among interpolation and the embodiment 1, with the carboxy-modified polyvinyl alcohol polymer of the random copolymerization (polymerization degree 1700 with the toxilic acid modification, 2 moles of % of modification amount, 98 moles of % of saponification deg) 15% aqueous solution, 50 weight parts, with with embodiment 1 in identical N, N, N ', N '-four glycidyl group-m-xylene diamine 1.5 weight parts, advance-go on foot lime carbonate (Japan Off ア イ Application ケ ミ カ Le Co., Ltd. system of adding as weighting agent, trade(brand)name: 100 weight parts ホ ワ イ ト Application P-30), modulated water-resistant adhesive composition for wood through stirring.
In the described water-resistant adhesive composition for wood, resinous principle 100 weight parts that contained with respect to described carboxy-modified styrene butadiene synthetic latex resin, by the resinous principle that contains in its aqueous solution, the described carboxy-modified polyvinyl alcohol polymer that contains 15 weight parts also contains lime carbonate 200 weight parts.In addition, with respect to resinous principle 100 weight parts that contained in the host that the aqueous solution constituted by described carboxy-modified styrene butadiene synthetic latex resin and described carboxy-modified polyvinyl alcohol polymer, contain the N of 2.6 weight parts, N, N ', N '-four glycidyl group-m-xylene diamine.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 3.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Embodiment 9
In the present embodiment, except N, N, N ', the use level of N '-four glycidyl group-m-xylene diamine is set at beyond 60 weight parts, has modulated water-resistant adhesive composition for wood with embodiment 7 identically.
In the described water-resistant adhesive composition for wood, resinous principle 100 weight parts that contained with respect to described carboxy-modified styrene butadiene synthetic latex resin, contain the described carboxy-modified polyvinyl alcohol polymer of 15 weight parts by the resinous principle that contains in its aqueous solution, also contain lime carbonate 200 weight parts.In addition, with respect to resinous principle 100 weight parts that contained in the host that the aqueous solution constituted by described carboxy-modified styrene butadiene synthetic latex resin and described carboxy-modified polyvinyl alcohol polymer, contain the N of 104 weight parts, N, N ', N '-four glycidyl group-m-xylene diamine.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 3.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Table 3
Normality intensity Water-fast intensity Heat-resisting water intensity The anti-intensity repeatedly of boiling
Embodiment 8 1.65(100) 1.28(100) 1.29(100) 1.02(100)
Embodiment 9 1.45(100) 1.30(100) 1.49(100) 1.02(100)
As shown in Table 3, when using the water-resistant adhesive composition for wood of embodiment 8,9, identical with the water-resistant adhesive composition for wood of embodiment 1-6, not only about its normality intensity, and, also can obtain good adhesiveproperties about its water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling.Described embodiment 8, in 9 the water-resistant adhesive composition for wood, resinous principle 100 weight parts with respect to carboxy-modified latex resin, the resinous principle that contains in the aqueous solution by its polymkeric substance, the carboxy-modified polyvinyl alcohol polymer that contains 15 weight parts with the toxilic acid modification, also contain lime carbonate 200 weight parts, and with respect to resinous principle 100 weight parts that contained in the host that the aqueous solution constituted by described carboxy-modified latex resin and described carboxy-modified polyvinyl alcohol polymer, the N that contains 1.5～104 weight parts, N, N ', N '-four glycidyl group-m-xylene diamine.
Embodiment 10
In the present embodiment, identical carboxy-modified styrene butadiene synthetic latex resin 100 weight parts among interpolation and the embodiment 1, with the carboxy-modified polyvinyl alcohol polymer of the random copolymerization (polymerization degree 1700 with the toxilic acid modification, 2 moles of % of modification amount, 98 moles of % of saponification deg) 15% aqueous solution, 40 weight parts, with with embodiment 1 in identical N, N, N ', N '-four glycidyl group-m-xylene diamine 8 weight parts, further add lime carbonate (Japan Off ア イ Application ケ ミ カ Le Co., Ltd. system as weighting agent, trade(brand)name: 50 weight parts ホ ワ イ ト Application P-30), modulated water-resistant adhesive composition for wood through stirring.
In the described water-resistant adhesive composition for wood, resinous principle 100 weight parts that contained with respect to described carboxy-modified styrene butadiene synthetic latex resin, the described carboxy-modified polyvinyl alcohol polymer that contains 12 weight parts by the resinous principle that contains in its aqueous solution, also contain N, N, N ', N '-four glycidyl group-m-xylene diamine 16 weight parts and lime carbonate 100 weight parts.In addition, with respect to resinous principle 100 weight parts that contained in the host that the aqueous solution constituted by described carboxy-modified styrene butadiene synthetic latex resin and described carboxy-modified polyvinyl alcohol polymer, N, N, N ', the use level of N '-four glycidyl group-m-xylene diamine is 14 weight parts.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 4.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Embodiment 11
In the present embodiment, except the carboxy-modified polyvinyl alcohol polymer of random copolymerization that replaces using among the embodiment 10, and use changed toxilic acid modification amount the carboxy-modified polyvinyl alcohol polymer of random copolymerization (polymerization degree 1700,0.2 mole of % of modification amount, 98 moles of % of saponification deg) in addition, modulated water-resistant adhesive composition for wood with embodiment 10 identically.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 4.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Embodiment 12
In the present embodiment, except the carboxy-modified polyvinyl alcohol polymer of random copolymerization that replaces using among the embodiment 10, and use changed toxilic acid modification amount the carboxy-modified polyvinyl alcohol polymer of random copolymerization (polymerization degree 1700,4.0 moles of % of modification amount, 98 moles of % of saponification deg) in addition, modulated water-resistant adhesive composition for wood with embodiment 10 identically.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 4.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Embodiment 13
In the present embodiment, except the carboxy-modified polyvinyl alcohol polymer of random copolymerization that replaces using among the embodiment 10, and use changed toxilic acid modification amount the carboxy-modified polyvinyl alcohol polymer of random copolymerization (polymerization degree 1700,10 moles of % of modification amount, 98 moles of % of saponification deg) in addition, modulated water-resistant adhesive composition for wood with embodiment 10 identically.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 4.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Embodiment 14
In the present embodiment, except the carboxy-modified polyvinyl alcohol polymer of random copolymerization that replaces using among the embodiment 10, and used with the carboxy-modified polyvinyl alcohol polymer of random copolymerization (polymerization degree 400,1.0 moles of % of modification amount, 75 moles of % of saponification deg) of methylene-succinic acid modification in addition, modulated water-resistant adhesive composition for wood with embodiment 10 identically.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 4.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Embodiment 15
In the present embodiment, identical carboxy-modified styrene butadiene synthetic latex resin 100 weight parts among interpolation and the embodiment 10, with identical 15% aqueous solution, 400 weight parts of using the carboxy-modified polyvinyl alcohol polymer of random copolymerization of toxilic acid modification among the embodiment 10, with with embodiment 10 in identical N, N, N ', N '-four glycidyl group-m-xylene diamine 44 weight parts, further add lime carbonate (Japan Off ア イ Application ケ ミ カ Le Co., Ltd. system as weighting agent, trade(brand)name: 100 weight parts ホ ワ イ ト Application P-30), modulated water-resistant adhesive composition for wood through stirring.
In the described water-resistant adhesive composition for wood, resinous principle 100 weight parts that contained with respect to described carboxy-modified styrene butadiene synthetic latex resin, contain the described carboxy-modified polyvinyl alcohol polymer of 120 weight parts by the resinous principle that contains in its aqueous solution, also contain lime carbonate 200 weight parts.In addition, with respect to resinous principle 100 weight parts that contained in the host that the aqueous solution constituted by described carboxy-modified styrene butadiene synthetic latex resin and described carboxy-modified polyvinyl alcohol polymer, contain 40 weight part N, N, N ', N '-four glycidyl group-m-xylene diamine.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 4.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Embodiment 16
In the present embodiment, add with embodiment 10 in identical carboxy-modified styrene butadiene synthetic latex resin 100 weight parts, with embodiment 10 in the identical carboxy-modified polyvinyl alcohol polymer of random copolymerization with the toxilic acid modification 15% aqueous solution, 100 weight parts and with embodiment 10 in identical N, N, N ', N '-four glycidyl group-m-xylene diamine 10 weight parts, further add as weighting agent with embodiment 15 in identical lime carbonate 250 weight parts that use, modulated water-resistant adhesive composition for wood through stirring.
In the described water-resistant adhesive composition for wood, resinous principle 100 weight parts that contained with respect to described carboxy-modified styrene butadiene synthetic latex resin, contain the described carboxy-modified polyvinyl alcohol polymer of 30 weight parts by the resinous principle that contains in its aqueous solution, also contain lime carbonate 500 weight parts.In addition, with respect to resinous principle 100 weight parts that contained in the host that the aqueous solution constituted by described carboxy-modified styrene butadiene synthetic latex resin and described carboxy-modified polyvinyl alcohol polymer, contain 15 weight part N, N, N ', N '-four glycidyl group-m-xylene diamine.
Then, the water-resistant adhesive composition for wood that in using present embodiment, obtains, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
The measurement result of bonding strength (MPa) is shown in Table 4.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Table 4
Normality intensity Water-fast intensity Heat-resisting water intensity The anti-intensity repeatedly of boiling
Embodiment 10 1.43(100) 1.78(100) 1.71(100) 1.19(100)
Embodiment 11 1.63(100) 1.57(100) 1.65(100) 1.24(100)
Embodiment 12 1.53(100) 1.62(100) 1.54(100) 1.46(100)
Embodiment 13 1.66(100) 1.62(100) 1.64(100) 1.62(100)
Embodiment 14 1.68(100) 1.80(100) 1.87(100) 1.56(100)
Embodiment 15 1.65(100) 1.55(100) 1.50(100) 1.45(90)
Embodiment 16 1.46(100) 1.33(100) 1.31(100) 1.06(100)
As shown in Table 4, when using the water-resistant adhesive composition for wood of embodiment 10～16, identical with the water-resistant adhesive composition for wood of embodiment 1-6, not only about its normality intensity, and, also can obtain good adhesiveproperties about its water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling.In the water-resistant adhesive composition for wood of described embodiment 10～16, resinous principle 100 weight parts with respect to carboxy-modified latex resin, the polymerization degree that the resinous principle that contains in the aqueous solution by its polymkeric substance contains 12～120 weight parts is 400～1700 scope, the modification amount is the scope of 0.2～10 mole of %, saponification deg is the carboxy-modified polyvinyl alcohol polymer of 75～98 moles of % scopes, and the lime carbonate that contains 100～500 weight parts, and with respect to resinous principle 100 weight parts that contained in the host that the aqueous solution constituted by described carboxy-modified latex resin and described carboxy-modified polyvinyl alcohol polymer, the N that contains 14～40 weight parts, N, N ', N '-four glycidyl group-m-xylene diamine.
Embodiment 17
In the present embodiment, modulate in the same manner behind the water-resistant adhesive composition for wood its this adhesive compound that has obtained having kept respectively under 35 ℃ of temperature 5 minutes, 3 hours, 8 hours except using with embodiment 1, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
Measurement result through the bonding strength (MPa) of the described water-resistant adhesive composition for wood after 5 minutes after will beginning respectively to modulate is shown in Table 5; To be shown in Table 6 through the measurement result of the bonding strength (MPa) of the described water-resistant adhesive composition for wood after 3 hours; To be shown in Table 7 through the measurement result of the bonding strength (MPa) of the described water-resistant adhesive composition for wood after 8 hours.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Comparative example 5
In this comparative example, at first in not using carboxy-modified styrene butadiene synthetic latex (Asahi Kasei Corporation, trade(brand)name: DL-612, resinous principle 48%) 60 weight parts, add 15% aqueous solution, 100 weight parts and lime carbonate (Japan Off ァ イ Application ケ ミ カ Le Co., Ltd. system, the trade(brand)name: 30 weight parts ホ ワ イ ト Application P-30) of not using carboxy-modified polyvinyl alcohol polymer (the Network ラ レ of Co., Ltd. system, trade(brand)name: PVA-217, the polymerization degree 1700,88 moles of % of saponification deg), fully mix, modulated the host of adhesive compound.Then the polymethylene polyphenyl base polymeric polyisocyanate that in being heated to 35 ℃ described host 100 weight parts, adds to be heated to 35 ℃ in advance as linking agent (Sumitomo バ イ エ Le Co., Ltd., trade(brand)name: 10 weight parts ス ミ ジ ユ one Le 44V-20), modulated adhesive compound through stirring.
Then, take by weighing when beginning to modulate meter and under 35 ℃ of temperature, kept the adhesive compound that obtains this comparative example of 5 minutes, 3 hours, 8 hours respectively, the thickness that constitutes at the sal material that by water ratio is 5～8% is on the veneer of 1.7mm, use the hand roller of band rubber, with 330g/m 2The glue spread on (two sides) is coated with equably, judges coating.The adhesive compound that obtains in this comparative example after modulation beginning, has been spent 150 minutes gelation will have been taken place, and after the modulation beginning, has passed through 3 hours adhesive compound and the adhesive compound that passed through 8 hours can not be coated with at all.
Then, except using the adhesive compound that in this comparative example, to obtain after described modulation, keeping under 35 ℃ of temperature 5 minutes the adhesive compound, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
To modulate the measurement result that beginning the time rises through the bonding strength (MPa) of the described adhesive compound after 5 minutes respectively is shown in Table 5; To be shown in Table 6 through the measurement result of the bonding strength (MPa) of the described adhesive compound after 3 hours; To be shown in Table 7 through the measurement result of the bonding strength (MPa) of the described adhesive compound after 8 hours.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Comparative example 6
In this comparative example, at first mix iso-butylene-maleic anhydride-polymer maleimides (the Network ラ レ of Co., Ltd. system, trade(brand)name: イ ソ バ Application 304, iso-butylene: maleic anhydride: maleimide=1: 0.5: 0.5 (mol ratio)) 50 weight parts, 25% ammoniacal liquor, 20 weight parts, pure water 75 weight parts, stirred 2 hours down at 80～95 ℃, modulated iso-butylene-maleic anhydride-polymer maleimides aqueous solution.Then described iso-butylene-maleic anhydride-polymer maleimides aqueous solution is cooled to 40～50 ℃, add carboxy-modified styrene butadiene synthetic latex (Japanese ゼ オ Application Co., Ltd. system, trade(brand)name: NipolLX430, resinous principle 49%) 140 weight parts and lime carbonate (Japan Off ア イ Application ケ ミ カ Le Co., Ltd. system, trade(brand)name: 140 weight parts ホ ワ イ ト Application P-30), fully mix the host of modulation adhesive compound.
Then, in being heated to 35 ℃ described host 100 weight parts, add the Resins, epoxy that the linking agent be heated to 35 ℃ in advance is a glycerine polyglycidyl ether type (Na ガ セ ケ system テ Star Network Co., Ltd., trade(brand)name: 5 weight parts デ Na コ one Le EX-314), modulated adhesive compound through stirring.
Then, take by weighing the adhesive compound that obtains through in this comparative example after under 35 ℃ of temperature, keeping 5 minutes, 3 hours, 8 hours respectively after the described modulation, judge coating identically with comparative example 5.The adhesive compound that obtains in this comparative example has been spent 60 minutes gelation will have been taken place after described modulation, can not be coated with through the adhesive compound after 3 hours with through the adhesive compound after 8 hours from described when modulation at all.
Then, except using the adhesive compound that in this comparative example, to obtain after described modulation, keeping under 35 ℃ of temperature 5 minutes the adhesive compound, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
To modulate the measurement result that beginning the time rises through the bonding strength (MPa) of the described adhesive compound after 5 minutes respectively is shown in Table 5; To be shown in Table 6 through the measurement result of the bonding strength (MPa) of the described adhesive compound after 3 hours; To be shown in Table 7 through the measurement result of the bonding strength (MPa) of the described adhesive compound after 8 hours.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Comparative example 7
In this comparative example, at first mix iso-butylene-maleic anhydride polymkeric substance (the Network ラ レ of Co., Ltd. system, trade(brand)name: イ ソ バ Application 06, iso-butylene: maleic anhydride=1: 1 (mol ratio)) 50 weight parts, sodium hydroxide 20 weight parts, pure water 85 weight parts, stirred 2 hours down at 80～95 ℃, modulated iso-butylene-maleic anhydride aqueous solutions of polymers.Then described iso-butylene-maleic anhydride aqueous solutions of polymers is cooled to 40～50 ℃, add carboxy-modified styrene butadiene synthetic latex (Japanese ゼ オ Application Co., Ltd. system, trade(brand)name: NipolLX430, resinous principle 49%) 150 weight parts, white lime 70 weight parts and pure water 60 weight parts afterwards, fully mix the host of modulation adhesive compound.
Then, in being heated to 35 ℃ described host 100 weight parts, add the linking agent glycerine polyglycidyl ether type be heated to 35 ℃ in advance Resins, epoxy (Na ガ セ ケ system テ Star Network Co., Ltd., trade(brand)name: 5 weight parts デ Na コ one Le EX-314), modulated adhesive compound through stirring.
Then, take by weighing the adhesive compound that obtains through in this comparative example after under 35 ℃ of temperature, keeping 5 minutes, 3 hours, 8 hours respectively after the described modulation, judge coating identically with comparative example 5.The adhesive compound that obtains in this comparative example has been spent 120 minutes gelation will have been taken place after described modulation, can not be coated with through the adhesive compound after 3 hours with through the adhesive compound after 8 hours from described modulation at all.
Then, except using the adhesive compound that in this comparative example, to obtain after described modulation, keeping under 35 ℃ of temperature 5 minutes the adhesive compound, make test board with embodiment 1 identically, and measured the normality intensity of this test board, water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling identically with embodiment 1.
To modulate respectively and begin meter and be shown in Table 5 through the measurement result of the bonding strength (MPa) of the described adhesive compound after 5 minutes; To be shown in Table 6 through the measurement result of the bonding strength (MPa) of the described adhesive compound after 3 hours; To be shown in Table 7 through the measurement result of the bonding strength (MPa) of the described adhesive compound after 8 hours.In addition, the area that ruptures in the xylem percentage with respect to the area of bonding plane is shown in the bracket as material fracture rate (%).
Table 5
Normality intensity Water-fast intensity Heat-resisting water intensity The anti-intensity repeatedly of boiling
Embodiment 17 1.75(100) 1.75(100) 1.69(100) 1.22(100)
Comparative example 5 1.76(100) 1.34(100) 1.45(100) 1.35(100)
Comparative example 6 1.29(100) 1.22(100) 1.22(100) 1.01(98)
Comparative example 7 0.84(90) 0.68(43) 0.77(93) 0.74(23)
Table 6
Normality intensity Water-fast intensity Heat-resisting water intensity The anti-intensity repeatedly of boiling
Embodiment 17 1.63(100) 1.71(100) 1.61(100) 1.27(100)
Comparative example 5 0(0) 0(0) 0(0) 0(0)
Comparative example 6 0(0) 0(0) 0(0) 0(0)
Comparative example 7 0(0) 0(0) 0(0) 0(0)
Table 7
Normality intensity Water-fast intensity Heat-resisting water intensity The anti-intensity repeatedly of boiling
Embodiment 17 1.69(100) 1.61(100) 1.53(100) 1.50(100)
Comparative example 5 0(0) 0(0) 0(0) 0(0)
Comparative example 6 0(0) 0(0) 0(0) 0(0)
Comparative example 7 0(0) 0(0) 0(0) 0(0)
By table 5～7 as can be known, use has been added N in the host that the aqueous solution constituted by described carboxy-modified latex resin and described carboxy-modified polyvinyl alcohol polymer, N, N ', during the water-resistant adhesive composition for wood of the embodiment 17 of N '-four glycidyl group-m-xylene diamine, serviceable time is long, coating is good and not only about its normality intensity, and about its water-fast intensity, heat-resisting water intensity, the anti-intensity repeatedly of boiling, also can obtain good adhesiveproperties.
On the contrary, contain not adhesive compound with the comparative example 5 of carboxy-modified latex resin, the aqueous solution of not using carboxy-modified polyvinyl alcohol polymer and isocyanate ester compound, contain the aqueous solution of iso-butylene-maleic anhydride-amide polymer or iso-butylene-maleic anhydride polymkeric substance and do not use carboxy-modified latex resin and the adhesive compound of the comparative example of the Resins, epoxy of glycerine polyglycidyl ether type 6,7 in, its serviceable time is shorter.
Embodiment 18
In the present embodiment, keeping making test board with embodiment 1 this adhesive compound of 5 minutes under 35 ℃ of temperature except using to modulate in the same manner behind the water-resistant adhesive composition for wood with embodiment 1 identically.
Then, described test board is cut into the size of 9cm * 28cm, it is as test film, overlapping with 2 these test films, on both sides, be coated with the 5g pure water respectively equably, wrap in afterwards in the plastics, under 40 ℃, the atmosphere of 90% relative humidity, placed 14 days.Through after the described processing, with the naked eye relatively pass through the test film of described processing and untreated test film, judge through whether variable color of the test film after the described processing.Show the result in the table 8.
Comparative example 8
In this comparative example, keeping having made test board with embodiment 1 this adhesive compound of 5 minutes under 35 ℃ of temperature except use to modulate behind the adhesive compound identically with comparative example 6 identically.
Then, the test board that in using this comparative example, obtains, judge whether variable color of test film with embodiment 18 identically.Show the result in the table 8.
Comparative example 9
In this comparative example, at first with synthetic identically host 100 weight parts of comparative example 6 in add linking agent N, N, N ', N '-four glycidyl group-m-xylene diamine 3 weight parts has modulated adhesive compound through stirring.Then, after modulation, under 35 ℃ of temperature, kept 5 minutes.Except the adhesive compound that uses such acquisition, made test board with embodiment 1 identically.
Then, in using this comparative example, obtain the ground test board, judge whether variable color of test film identically with embodiment 18.Show the result in the table 8.
Comparative example 10
In this comparative example, keeping having made test board with embodiment 1 this adhesive compound of 5 minutes under 35 ℃ of temperature except use to modulate after the adhesive compound identically with comparative example 7 identically.
Then, in using this comparative example, obtain the ground test board, judge whether variable color of test film identically with embodiment 18.Show the result in the table 8.
Comparative example 11
In this comparative example, at first with synthetic identically host 100 weight parts of comparative example 7 in add linking agent N, N, N ', N '-four glycidyl group-m-xylene diamine 3 weight parts has modulated adhesive compound through stirring.Then, after modulation, under 35 ℃ of temperature, kept 5 minutes.Except the adhesive compound that uses such acquisition, made test board with embodiment 1 identically.
Then, in using this comparative example, obtain the ground test board, judge whether variable color of test film identically with embodiment 18.Show the result in the table 8.
Comparative example 12
In this comparative example, at first with embodiment 1 in 15% aqueous solution, 50 weight parts of the identical carboxy-modified polyvinyl alcohol polymer that uses, add the acrylic acid series latex (Nippon Shokubai Kagaku Kogyo Co., Ltd's system, the trade(brand)name: CK-200) 50 weight parts and lime carbonate (Japan Off ア イ Application ケ ミ カ Le Co., Ltd. system, trade(brand)name: 60 weight parts ホ ワ イ ト Application P-30) that contain amino with active hydrogen, fully mix the host of modulation adhesive compound.
Then, in being heated to 35 ℃ described host 100 weight parts, add the N that is heated to 35 ℃ in advance, N, N ', N '-four glycidyl group-m-xylene diamine 6.6 weight parts has modulated adhesive compound through stirring.Then, after modulation, under 35 ℃ of temperature, kept 5 minutes.Except the adhesive compound that uses such acquisition, made test board with embodiment 1 identically.
Then, in using this comparative example, obtain the ground test board, judge whether variable color of test film identically with embodiment 18.Show the result in the table 8.
Table 8
Whether variable color
Embodiment 18 ○
Comparative example 8 ×
Comparative example 9 ×
Comparative example 10 ×
Comparative example 11 ×
Comparative example 12 ×
Zero ... there is not variable color
* ... confirm variable color
As shown in Table 8, added N in the host that the aqueous solution constituted of use by described carboxy-modified latex resin and described carboxy-modified polyvinyl alcohol polymer, N, N ', the bonding timber of water-resistant adhesive composition for wood of the embodiment 18 of N '-four glycidyl group-m-xylene diamine does not have variable color.
On the contrary, the aqueous solution that just contains iso-butylene-maleic anhydride-amide polymer, do not use carboxy-modified latex resin, the adhesive compound of the comparative example 8 of glycerine polyglycidyl ether type Resins, epoxy, the aqueous solution that contains iso-butylene-maleic anhydride-amide polymer, do not use carboxy-modified latex resin, N, N, N ', the adhesive compound of the comparative example 9 of N '-four glycidyl group-m-xylene diamine, the aqueous solution that contains iso-butylene-maleic anhydride polymkeric substance, do not use carboxy-modified latex resin, the adhesive compound of the comparative example 10 of glycerine polyglycidyl ether type Resins, epoxy, the aqueous solution that contains iso-butylene-maleic anhydride polymkeric substance, do not use carboxy-modified latex resin, N, N, N ', the adhesive compound of the comparative example 11 of N '-four glycidyl group-m-xylene diamine, the aqueous solution that contains carboxy-modified polyvinyl alcohol polymer, the acrylic emulsion and the N that contain amino with active hydrogen, N, N ', the adhesive compound of the comparative example 12 of N '-four glycidyl group-m-xylene diamine has used the bonding timber of these adhesive compounds that variable color has all taken place.
Water-resistant adhesive composition for wood of the present invention is suitable for the manufacturing of wood fibre board, furniture, bar, tool movement and other carpenter works such as glued board, LVL, thin paneling type decorative sheet, composite material, fiber laminate, is particularly suitable for the secondary processing that glued board sticks with glue agent and glued board and sticks with glue agent.
Water-resistant adhesive composition for wood of the present invention can also be applicable to that corrugated cardboard, paper, cloth, metal, glass, wolline plate, plastic plate (comprising vinylchloride resin plate, ABS plate, FRP plate, polystyrene resin plate etc.), inorganic board (comprising mineral fibreboard, plasterboard, calcium silicate boards etc. such as asbestos plate), cement are in material outside the inorganic board timber such as (comprising asbestos plate, cement pulpboard, concrete slab etc.) bonding except timber such as described wood fibre board, carpenter work.For the material beyond the described timber, the water-resistant adhesive composition for wood of present embodiment not only go for bonding between the commaterial and also go for not bonding, timber between the same material and described each material between bonding in.
In addition, water-resistant adhesive composition for wood of the present invention can also be as being coated with application composition or coating composition.

Claims (6)

1. water-resistant adhesive composition for wood, comprising:
(A) by do not comprise contain the aminoacrylic acid emulsion or contain amino water-borne acrylic resin, intramolecularly has the host that the aqueous solution of the carboxy-modified polyvinyl alcohol polymer that the carboxy-modified aqueous emulsifying resin of carboxyl or carboxy-modified latex resin that intramolecularly has carboxyl and intramolecularly have carboxyl constitutes, and
(B) as 4 functional group's epoxy compoundss with tertiary amine groups nitrogen-atoms, contain N with what general formula (1) was represented, the compound of N-2-glycidyl amino,
Figure C2004800270120002C1
In the formula, D represents to be selected from a kind of divalent group in phenylene that ring type alkylidene group, phenylene, the alkyl of straight or branched alkylidene group, the carbonatoms 3～12 of carbonatoms 1～12 replace, the phenylene that halogen replaces.
2. water-resistant adhesive composition for wood according to claim 1, in wherein said carboxy-modified aqueous emulsifying resin or the described carboxy-modified latex resin, its carboxy-modified amount is the scope of 0.1～20 weight %.
3. water-resistant adhesive composition for wood according to claim 1, the carboxy-modified amount of wherein said carboxy-modified polyvinyl alcohol polymer are 0.1～10 mole of %, and the polymerization degree is 100～6000 scope.
4. water-resistant adhesive composition for wood according to claim 1, wherein with respect to resinous principle 100 weight parts contained in described carboxy-modified aqueous emulsifying resin or the carboxy-modified latex resin, with contained resinous principle in the aqueous solution of this carboxy-modified polyvinyl alcohol polymer in this polymkeric substance, contain 0.2～270 weight part.
5. water-resistant adhesive composition for wood according to claim 1 wherein with respect to resinous principle 100 weight parts that contain in the described host, contains the described N of containing of 3～150 weight parts, the compound of N-2-glycidyl amino.
6. water-resistant adhesive composition for wood according to claim 1 wherein with respect to resinous principle 100 weight parts contained in described carboxy-modified aqueous emulsifying resin or the carboxy-modified latex resin, contains the weighting agent of 0～700 weight part.
CNB2004800270128A 2003-09-19 2004-09-15 Water-resistant adhesive composition for wood Expired - Fee Related CN100419036C (en)

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JPH04328185A (en) * 1991-04-26 1992-11-17 Ooshika Shinko Kk Aqueous adhesive composition
JPH04328184A (en) * 1991-04-26 1992-11-17 Ooshika Shinko Kk Aqueous adhesive composition

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JPH04328185A (en) * 1991-04-26 1992-11-17 Ooshika Shinko Kk Aqueous adhesive composition
JPH04328184A (en) * 1991-04-26 1992-11-17 Ooshika Shinko Kk Aqueous adhesive composition

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