JP2018070871A - Aqueous adhesive composition for woody material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesion aid for an aqueous adhesive for woody material, which is used for an aqueous adhesive composition, having excellent adhesive strength and water resistance.SOLUTION: An adhesion aid for an aqueous adhesive for woody material contains epoxy-modified polyamine containing polyepoxide and polyamine as constituent monomers; an aqueous adhesive composition for woody material contains the adhesion aid for an aqueous adhesive for woody material (Aα), at least one crosslinker selected from the group consisting of phenolic resin, urea resin, melamine resin, and urea melamine resin, and water.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous adhesive composition for a wood material. More specifically, the present invention relates to a water-based adhesive composition for a wood material having excellent adhesiveness.

A general adhesive for woody materials, which is a reaction product of phenol, melamine, urea, and formalin, is insufficient in strength and water resistance of a molded product.
As an adhesive for improving the strength of the woody material, a combination of an amino adhesive and a phenol resin has been proposed (for example, Patent Document 1).
In addition, a combination of a resin obtained by reacting melamine and / or urea with formalin and hexamethylenetetramine has been proposed as an adhesive having fast curing properties (for example, Patent Document 2).

JP-A-10-151608 JP-A-11-217552

However, in the techniques of Patent Documents 1 and 2, although the strength has been improved to some extent, further improvement in strength is required.
An object of the present invention is to solve the above-mentioned problems and to provide an adhesive aid for a water-based adhesive for a woody material for an aqueous adhesive composition excellent in adhesive strength and water resistance.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention is an adhesion aid (Aα) for a water-based adhesive for wood materials, which contains an epoxy-modified polyamine (A) containing polyepoxide (a1) and polyamine (a2) as constituent monomers.

The adhesion aid (Aα) for water-based adhesive for woody material of the present invention has the following effects.
(1) The water-based adhesive composition for a wood material is imparted with excellent adhesion to the wood material.
(2) Excellent strength (bending strength, impact resistance) after curing.
(3) Excellent water resistance after curing.

<Epoxy-modified polyamine (A)>
The epoxy-modified polyamine (A) in the present invention contains a polyepoxide (a1) and a polyamine (a2) described later as constituent monomers [hereinafter sometimes abbreviated as constituent units]. A reaction product having (a1) and (a2) as constituent monomers is preferred, and a reaction product of (a1) and (a2) is more preferred.

  The polyepoxide (a1) has at least two epoxy groups in the molecule, and includes an aromatic ring-containing polyepoxide (a11), an aliphatic polyepoxide (a12), an alicyclic ring-containing polyepoxide (a13), and a heterocyclic ring-containing polyepoxide ( a14) and the like.

  Examples of the aromatic ring-containing polyepoxide (a11) include divalent to 10-valent or higher polyglycidyl ethers of polyhydric phenol (a111), aromatic ring-containing polyglycidylamine (a112), and other aromatic ring-containing polyepoxides (a113). And mixtures thereof.

The polyhydric phenol constituting the polyglycidyl ether (a111) of the polyhydric phenol is divalent to 10-valent or higher, having 6 or more carbon atoms (hereinafter sometimes abbreviated as C) and a number average molecular weight [hereinafter Mn Abbreviated. The measurement is based on a gel permeation chromatography (GPC) method under the conditions described below. ] 10,000 or less polyhydric phenols (bisphenol A, -F, -B, -AD and -S, halogenated bisphenol A, pyrogallol, phenol novolac, cresol novolac, etc.), and their polyglycidyl ethers Bisphenol A type polyglycidyl ether (polyglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol or more of epichlorohydrin), bisphenol F type polyglycidyl ether, bisphenol S type polyglycidyl ether, phenol novolac type poly Examples thereof include glycidyl ether and cresol novolac type polyglycidyl ether.
Examples of other divalent to 10-valent or higher polyglycidyl ethers include polyglycidyl ethers of polyphenols obtained by the condensation reaction of phenol and glioxal, glutaraldehyde or formaldehyde, and polyphenols obtained by the condensation reaction of resorcin and acetone. Examples thereof include polyglycidyl ether.

  Examples of the aromatic ring-containing amine constituting the aromatic ring-containing polyglycidylamine (a112) include C6-30 aromatic ring-containing monovalent to tetravalent or higher aromatic ring-containing polyamines (aniline, 1,3- and / or Or 1,4-phenylenediamine, 2,4- and / or 2,6-tolylenediamine, and the like. Examples of the polyglycidylamine include diglycidylamine [N, N-diglycidylaniline and the like], Tetraglycidyl or higher polyglycidylamine [1,3- and / or 1,4-phenylenetetraglycidylamine, 2,4- and / or 2,6-tolylenetetraglycidylamine, 4,4′-diphenylmethanetetra Glycidylamine, m- and / or p-xylylenetetraglycidylamine, α, α, α ′ α'- tetramethylxylylene tetraglycidyl amine] and the like.

  Furthermore, other aromatic ring-containing polyepoxides (a113) include diglycidyl urethane compounds obtained by addition reaction of tolylene diisocyanate (hereinafter abbreviated as TDI) or diphenylmethane diisocyanate (hereinafter abbreviated as MDI) and glycidol, TDI or Addition of glycidyl group-containing polyurethane (pre) polymer obtained by reacting glycidol and polyol with MDI, addition of alkylene oxide of bisphenol A (hereinafter abbreviated as AO) [ethylene oxide (hereinafter abbreviated as EO) or propylene oxide (hereinafter abbreviated as PO)] The diglycidyl ether of a thing is mentioned.

  Examples of the aliphatic polyepoxide (a12) include 2- to 8-valent polyglycidyl ethers of aliphatic polyhydric alcohols (a121), polyglycidyl esters of aliphatic polycarboxylic acids (a122) and aliphatic polyglycidylamines (a123) and These mixtures are mentioned.

  Examples of the polyhydric alcohol constituting the polyglycidyl ether (a121) of the aliphatic polyhydric alcohol include C2 or more and Mn 1,000 or less [ethylene glycol, propylene glycol, tetramethylene glycol, polyethylene glycol, polypropylene glycol, triglyceride. Methylolpropane, glycerin, pentaerythritol, sorbitol (hereinafter abbreviated as EG, PG, TMG, PEG, PPG, TMP, GR, PE, SO, etc.), and the like. As their polyglycidyl ether, diglycidyl ether [ EG diglycidyl ether, PG diglycidyl ether, TMG diglycidyl ether, PEG (Mn 100 to 1,000) diglycidyl ether, PPG (Mn 100 to 1,500) diglycidyl ether Ter, etc.], triglycidyl ether [TMP triglycidyl ether and GR triglycidyl ether, etc.], tetravalent or higher polyglycidyl ether [PE tetraglycidyl ether, SO polyglycidyl ether, SO polyglycidyl ether, diPE polyglycidyl ether, poly (Polymerization degree 2-20) GR polyglycidyl ether etc.] etc. are mentioned.

Examples of the aliphatic polycarboxylic acid constituting the polyglycidyl ester (a122) of the aliphatic polycarboxylic acid include divalent to hexavalent C4-24 aliphatic polycarboxylic acids [succinic acid, adipic acid, sebacic acid, azelaic acid, Butanetetracarboxylic acid, (meth) acrylic acid, etc.], and polyglycidyl esters thereof include diglycidyl esters [diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate, diglycidyl azelate, etc.], tetraglycidyl esters [ Butanetetracarboxylic acid tetraglycidyl etc.] and unsaturated carboxylic acid glycidyl ester [(meth) acrylic acid glycidyl ester etc.].
Examples of the polyglycidyl ester of the aliphatic polycarboxylic acid include polymers and copolymers of glycidyl esters of unsaturated carboxylic acids such as (meth) acrylic acid glycidyl ester.
Examples of the aliphatic polyglycidylamine (a123) include polyglycidylamines having 2 to 6 and C2-24 aliphatic amines, such as tetraglycidylamine of ethylenediamine.

  Examples of the alicyclic ring-containing polyepoxide (a13) include polyepoxides having 2 to 6 valences and C6 to 36 alicyclic ring-containing compounds, and alicyclic ring-containing unsaturated hydrocarbon polyepoxides having 2 to 6 C6 to 24 per molecule. Polyepoxides of hydrocarbons having one or more double bonds [vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, etc.], polyepoxides of alicyclic ethers and alicyclic esters [bis (2,3- Epoxycyclopentyl) ether, EG bisepoxydicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6- Methylcyclohexylmethyl) adipate, etc.], aroma Nuclear hydrogenation product of containing polyepoxides are also included.

  Examples of the heterocyclic ring-containing polyepoxide (a14) include divalent to hexavalent C5-30, such as trisglycidylmelamine.

  Among the polyepoxides (a1), from the viewpoints of adhesion and water resistance, the aromatic ring-containing polyepoxide (a11) is preferred, the polyglycidyl ether (a111) of polyhydric phenol is more preferred, and the bisphenol A type is particularly preferred. Polyglycidyl ether.

  Examples of the polyamine (a2) include the following (a21) to (a24) and a mixture of two or more thereof.

(A21) Aliphatic poly (2-7 valent) amine C2 or more and Mn500 or less, for example, C2-10 alkylene diamine (ethylenediamine, propylenediamine, etc.), polyalkylene (C2-10) poly (trivalent-6 valent) Or more) amines [diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.], and their alkyl (C1-4) or hydroxyalkyl (C2-4) substituents such as dialkyl (C1-3) aminopropylamine , Trimethylhexamethylenediamine, aminoethylethanolamine;

(A22) Alicyclic ring-containing poly (2 to 3 valent) amines having C4-15, such as 1,3-diaminocyclohexane, isophoronediamine;

(A23) Heterocycle-containing poly (2 to 3 valent) amines of C4-15, such as piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine;

(A24) Aromatic ring-containing polyamines C8-15, such as xylylenediamine, tetrachloro-p-xylylenediamine, diaminodiphenylmethane.

  Among the polyamines (a2), from the viewpoints of adhesiveness and water resistance, (a21) and (a22) are preferable, polyalkylene polyamines are more preferable, and diethylenetriamine is particularly preferable.

The epoxy-modified polyamine (A) can be obtained, for example, by reacting (a1) and (a2) by a known method.
The total of the primary amino group and the secondary amino group in (A) is preferably 1 to 20 mol / kg, more preferably 2 to 10 mol / kg, from the viewpoints of adhesiveness and water resistance.

The GPC measurement conditions for Mn and weight average molecular weight (Mw) in the present invention are as follows.
<GPC measurement conditions>
[1] Apparatus: Gel permeation chromatograph
“HLC-8120GPC”, manufactured by Tosoh Corporation [2] Column: “TSKgel G6000PWxl”, “TSKgel”
G3000PWxl "[both manufactured by Tosoh Corporation] are connected in series.
[3] Eluent: 0.5% by weight of lithium bromide dissolved in N, N-dimethylformamide
What was solved.
[4] Reference material: polystyrene [5] Injection conditions: sample concentration 0.25% by weight, column temperature 40 ° C.

<Adhesion aid for water-based adhesive for woody materials (Aα)>
The adhesion assistant (Aα) for water-based adhesive for woody materials of the present invention contains the polyepoxy-modified polyamine (A). Based on the weight of the (Aα), the weight of the (A) is preferably 10 to 80% by weight, more preferably 20 to 70% by weight.
Examples of the form of (Aα) include an aqueous medium solution and an aqueous medium dispersion as it is (A). Moreover, this (A (alpha)) may contain the below-mentioned additive (E). The (Aα) is suitably used for the wood material adhesive composition (X) described later.

<Crosslinking agent (B)>
Examples of the crosslinking agent (B) in the present invention include at least one selected from the group consisting of a phenol resin (B1), a urea resin (B2), a melamine resin (B3), and a urea melamine resin (B4).
Of the above (B), from the viewpoint of adhesive strength, it is preferable that (B1) is contained in an amount of 50% by weight or more, and (B1) is more preferable.

Phenolic resin (B1):
The phenol resin (B1) is, for example, a reaction product of phenol, cresol, xylenol, resorcinol (preferably phenol) and formaldehyde.
The (B1) is preferably a resol-type phenol resin, and the average number of aromatic rings of (B1) is preferably 1 to 4, more preferably 1.5 to 3.

Urea resin (B2):
The urea resin (B2) is, for example, a reaction product of urea and formaldehyde.

Melamine resin (B3):
The melamine resin (B3) is, for example, a reaction product of melamine and formaldehyde.

Urea melamine resin (B4):
The urea melamine resin (B4) is a reaction product of urea, melamine and formaldehyde, for example.

The cross-linking agent (B) preferably has a methylol group. In that case, the methylol group concentration in (B) is preferably 2 to 25 mol / kg, more preferably from the viewpoint of adhesive strength and industrial balance. The amount is 4 to 18 mol / kg, particularly preferably 6 to 16 mol / kg.
The methylol group concentration can be measured by a known method, ¹ H-NMR (nuclear magnetic resonance method), ¹³ C-NMR.
Further, Mn (number average molecular weight) of (B) is preferably 90 to 1,000, more preferably 120 to 800, particularly preferably 150 to 600, from the viewpoint of adhesive strength and industrial balance.
The solubility of B in 100 g of water (25 ° C.) is preferably 5 g or more, more preferably 15 g or more, and particularly preferably 25 g or more from the viewpoint of handling the aqueous adhesive composition (X) described later.

[Water-based adhesive composition for woody material (X)]
The aqueous adhesive composition for woody material (X) of the present invention contains the adhesive aid for water-based adhesive for woody material (Aα), the crosslinking agent (B), and water.
In addition, (X) may be an epoxy-modified polyamine (A) and a crosslinking agent (B), which may be an aqueous medium solution or an aqueous dispersion, respectively. (X) is preferably an aqueous medium solution (Aα0) of (A), an aqueous dispersion (B00) and / or an aqueous medium solution (B0) of (B), from an industrial and adhesive viewpoint. And containing.
Here, the aqueous dispersion refers to a dispersion of the particles (A) or (B) in an aqueous medium, and includes an emulsion.
The aqueous medium includes water and a mixture of water containing water as a main component (50% by weight or more) and an organic solvent described later. As the aqueous medium, water is preferred.

Examples of the organic solvent include those having 1 to 8 carbon atoms [may be abbreviated as C], for example, alcohol (methanol, isopropanol, etc.), ketone (acetone, methylmethylketone, etc.), ether (ethylene glycol monomethyl ether, diethylene ether). Propylene glycol monomethyl ether, etc.), tetrahydrofuran, dioxane, and ethyl acetate.
Among the above organic solvents, preferred are alcohols and ethers, and more preferred are ethylene glycol monomethyl ether and isopropyl alcohol.

In the aqueous adhesive composition (X) of the present invention, the weight ratio [(A) / (B)] of (A) to (B) is preferably 0.2 from the viewpoint of impact resistance and adhesive strength. /99.8 to 15/85, more preferably 0.5 / 99.5 to 12/88, and particularly preferably 1/99 to 10/90.
The total weight of (A) and (B) based on the weight of (X) is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, from the industrial and adhesive viewpoints. .

<Curing accelerator (C)>
The aqueous adhesive composition (X) of the present invention may contain a curing accelerator (C) in order to improve adhesiveness and curability.
The curing accelerator (C) includes ammonium salt, dimethylaminoethanol, alkyl (C1-4) imidazole, 1,8-diazabicyclo [5.4.0] -7-undecene (salt), 1,5-diazabicyclo. [4.3.0] -5-Nonene (salt) and the like. Examples of the ammonium salt include ammonium chloride, ammonium sulfate, and ammonium phosphate.
Of the curing accelerators (C), dimethylaminoethanol and ammonium salts are preferable from the viewpoint of adhesion and water resistance, and ammonium sulfate is more preferable.

  The amount of (C) in the aqueous adhesive composition (X) is preferably 0.1 to 10% by weight, more preferably 0.3 to 0.3%, based on the total weight of the (A) and (B). 5% by weight.

<Additive (E)>
In the aqueous adhesive composition (X) of the present invention, an adhesive improver, a filler, an antiseptic, a heat stabilizer, a weathering stabilizer, a colorant, a thickening agent are necessary as long as the effects of the present invention are not impaired. One or more additives (E) selected from the group consisting of an agent, a leveling agent, an antifoaming agent, a viscoelasticity adjusting agent, and a dynamic surface tension adjusting agent can be contained.
The (E) can be added at any stage of the production process (X).
The total content of the additive (E) is preferably 30% or less, more preferably 0.01 to 20%, particularly preferably 0.1 to 10 based on the total weight of (X) after the addition of the additive. %.

Examples of the adhesion improver (E0) include alkylene (C2-3) oxide adducts (E01) [polyethylene glycol and the like] of monovalent alcohols and alkylene oxide adducts (E02) of monovalent alcohols. [PO of ethylene glycol monobutyl ether, 2-mole adduct, etc.]. Examples of the alkylene oxide include ethylene oxide (EO) and propylene oxide.
The weight ratio [EO / PO] of (E01) and (E02) is preferably 50/50 to 100/0, more preferably 70/30 to 100/0. The Mn of (E01) and (E02) is preferably 200 to 1,000, more preferably 300 to 700.
The content of (E0) is, for example, 10% or less, preferably 0.01 to 3%, based on the total weight of (X) after the additive is added.

Examples of the filler (E1) include sodium carbonate and silica.
The content of (E1) is, for example, 10% or less, preferably 0.01 to 3%, based on the total weight of (X) after addition of the additive.

Examples of the preservative (E2) include methyl paraben and ethyl paraben.
The content of (E2) is, for example, 10% or less, preferably 0.01 to 3%, based on the total weight of (X) after addition of the additive.

Examples of the heat resistance stabilizer (E3) include tris (2,4-di-t-butylphenyl) phosphate, dioctadecyl-3,3′-thiodipropionate, and the like.
The content of (E3) is, for example, 10% or less, preferably 0.01 to 3%, based on the total weight of (X) after addition of the additive.

As the weather resistance stabilizer (E4), ultraviolet absorbers such as salicylic acid compounds (phenyl salicylate, p-tert-butylphenyl salicylate, etc.), benzophenones (2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, etc.), Benzotriazole compounds [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, etc.], cyanoacrylate compounds (2-ethylhexyl- 2-cyano-3,3′-diphenyl acrylate, etc.); light stabilizers such as hindered amines [octylated diphenylamine, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate, etc.] It is done.
The content of (E4) is, for example, 10% or less, preferably 0.1 to 3%, based on the total weight of (X) after the additive is added.

Colorants (E5) include pigments and dyes. Among pigments, inorganic pigments include titanium oxide, talc, zinc phosphate, carbon black, chromium oxide, ferrite, etc .; organic pigments include azo pigments (azo lake, monoazo, disazo, chelate azo, etc.), polycyclic And formula pigments (benzimidazolone, phthalocyanine, quinacridone, dioxazine, isoindolinone, thioindigo, perylene, quinophthalone, anthraquinone, etc.).
Examples of the dye include nigrosine and aniline.
The content of (E5) is, for example, 50% or less, preferably 1 to 30%, based on the total weight of the epoxy emulsion (X) after addition of the additive.

Examples of the thickener (E6) include montmorillonite and colloidal alumina.
The content of (E6) is, for example, 10% or less, preferably 0.01 to 5%, based on the total weight of (X) after addition of the additive.

As a leveling agent (E7), Mn is preferably 100 to 1,000, polyolefin resin [polyethylene, polypropylene, etc.], olefin- (meth) acrylic acid copolymer [ethylene- (meth) acrylic acid copolymer, etc. ], Polyvinylpyrrolidone, etc. are mentioned.
The content of (E7) is, for example, 6% or less, preferably 0.01 to 3%, based on the total weight of (X) after addition of the additive.

Examples of the antifoaming agent (E8) include mineral oil defoaming agents and silicone oil defoaming agents.
The content of (E9) is, for example, 6% or less, preferably 0.01 to 3%, based on the total weight of (X) after addition of the additive.

As the viscoelasticity adjusting agent (E9), a polymer type (Mn 10,000-500,000, for example, polycarboxylic acid, polysulfonic acid, polyether-modified carboxylic acid, polyether), association type (Mn 10,000-500). 1,000, for example, urethane-modified polyether).
The content of (E9) is, for example, 10% or less, preferably 0.01 to 5%, based on the total weight of (X) after addition of the additive.

Examples of the dynamic surface tension adjusting agent (E10) include acetylene glycol and fluorine-containing compound silicone-containing compounds. The dynamic surface tension adjusting agent has a function of reducing the surface tension.
The content of (E10) is, for example, 20% or less, preferably 0.01 to 10%, based on the total weight of (X) after the addition of the additive.

<Wood material>
The aqueous adhesive composition (X) for woody materials of the present invention can be suitably used as an adhesive for woody materials (wood, wood chips, wood flour, etc.). In particular, the wood material is excellent in adhesiveness (adhesiveness, water resistance), and is particularly suitable as a bonding agent for particleboard.
The woody material of the present invention is obtained by bonding a woody material through a cured product of the aqueous adhesive composition (X).

  The curing conditions are preferably from 100 to 200 ° C., more preferably from 120 to 180 ° C. from the viewpoint of adhesiveness and industry, and from the same viewpoint, preferably from 1 to 60 minutes, more preferably from 3 to 3 minutes. A cured product can be formed in a curing time of 30 minutes, particularly preferably 5 to 10 minutes.

   EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the examples, “part” means “part by weight” and “%” other than mol% means “% by weight”.

<< Adhesion aid for water-based adhesive for wood materials (Aα) >>
<Example 1>
In a separable colben equipped with a thermometer, a stirrer and a reflux condenser, 150.1 parts of diethylenetriamine and 75.0 parts of ethylene glycol monomethyl ether were charged and stirred at 50 ° C. for 1 hour.
Next, 249.9 parts of bisphenol diglycidyl ether type epoxy resin [manufactured by Shell Chemical Company, Epicoat 828] was added dropwise over 1 hour, followed by reaction at 50 ° C. for 1 hour. After cooling to 30 ° C., 75.0 parts of isopropyl alcohol and 450.0 parts of ion-exchanged water are charged, and stirred for 1 hour, for an aqueous adhesive for woody material containing epoxy-modified polyamine (A-1). Adhesion aid (Aα-1) [aqueous medium solution, (A) content 40%] was obtained.
In addition, the sum total of the primary amino group and secondary amino group of (A-1) was 10.9 mol / kg.

<Example 2>
A separable colben equipped with a thermometer, a stirrer, and a reflux condenser was charged with 77.00 parts of diethylenetriamine and 67.0 parts of ethylene glycol monomethyl ether, and stirred at 50 ° C. for 1 hour.
Next, 323.0 parts of bisphenol diglycidyl ether type epoxy resin [manufactured by Shell Chemical Company, Epicoat 1001] was added dropwise over 1 hour, and reacted at 50 ° C. for 1 hour. After cooling to 30 ° C., 41.5 parts of a 2 mol PO adduct of ethylene glycol monobutyl ether, 41.5 parts of polyethylene glycol [Mn400] and 450.0 parts of ion-exchanged water were added and stirred for 1 hour. Adhesion aid (Aα-2) [aqueous medium solution, content of (A) 40%] for water-based adhesive for woody material containing epoxy-modified polyamine (A-2) was obtained.
In addition, the sum total of the primary amino group and secondary amino group of (A-2) was 5.6 mol / kg.

<Example 3>
A separable colben equipped with a thermometer, a stirrer, and a reflux condenser was charged with 183.9 parts of triethylenetetramine and 75.0 parts of ethylene glycol monomethyl ether, and stirred at 50 ° C. for 1 hour.
Next, 216.1 parts of bisphenol diglycidyl ether type epoxy resin [manufactured by Shell Chemical Company, Epicoat 828] was added dropwise over 1 hour, followed by reaction at 50 ° C. for 1 hour. After cooling to 30 ° C., 75.0 parts of isopropyl alcohol and 450.0 parts of ion-exchanged water are added and stirred for 1 hour, for an aqueous adhesive for woody material containing epoxy-modified polyamine (A-3) Adhesion aid (Aα-3) [aqueous medium solution, (A) content 40%] was obtained.
In addition, the sum total of the primary amino group and secondary amino group of (A-3) was 12.6 mol / kg.

<Example 4>
In a separable flask equipped with a dropping funnel for monomer dispersion, a dropping funnel for initiator solution, a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 369.4 parts of ion-exchanged water, Aqualon KH-1025 [interface] Activator, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] 1.6 parts (solid content: 0.4 part) and 4.0 parts of sodium hydrogen carbonate were charged. The mixture was stirred while blowing nitrogen, and the temperature was raised to 70 ° C.
Next, 201.3 parts of ion-exchanged water, 8.0 parts of surfactant [Eleminol CLS-20, manufactured by Sanyo Chemical Industries, Ltd.], 48.8 parts of methyl methacrylate, 174.0 parts of styrene, , 60.0 parts of glycidyl methacrylate, 113.2 parts of butyl acrylate, and 4.0 parts of 1-dodecanethiol were prepared, and after the monomer dispersion was prepared and stirred, charged into the dropping funnel for monomer dispersion, Of this, 30.5 parts was added to the separable flask.
Next, an initiator solution consisting of 0.9 parts of ammonium persulfate and 8.1 parts of ion-exchanged water, a reducing agent solution consisting of 0.2 parts of sodium thiosulfate pentahydrate and 6.6 parts of ion-exchanged water. Were added to the dropping funnel for the initiator solution and the dropping funnel for the reducing agent solution, respectively, added to the separable flask in order, the polymerization was started, and the remaining temperature was maintained at 70 ± 2 ° C. The monomer dispersion was added dropwise at a constant rate over 3 hours. Thereafter, stirring was continued for 90 minutes at the same temperature, followed by cooling to room temperature, charging 201.8 parts of tetraethylenepentamine and 302.7 parts of ion-exchanged water, and stirring for 1 hour, whereby an epoxy-modified polyamine (A-4 ) Containing an adhesive aid (Aα-4) [aqueous dispersion, median particle size: 0.2 μm, content of (A) 40%].
In addition, the sum total of the primary amino group and secondary amino group of (A-4) was 8.9 mol / kg, and Mn of (A-4) was 9,000.

<Example 5>
A separable colben equipped with a thermometer, a stirrer, and a reflux condenser was charged with 184.8 parts of tridiethylenetetraamine and 66.7 parts of ethylene glycol monomethyl ether, and stirred at 50 ° C. for 1 hour.
Next, 215.2 parts of bisphenol diglycidyl ether type epoxy resin [manufactured by Shell Chemical Company, Epicoat 807] was added dropwise over 1 hour, and reacted at 50 ° C. for 1 hour. After cooling to 30 ° C,
Charge 17.5 parts of ion-exchanged water and stir for 1 hour, charge 66.7 parts of isopropyl alcohol and 421.9 parts of ion-exchanged water, stir for 1 hour, and contain epoxy-modified polyamine (A-0). As a result, an adhesion aid (Aα-5) [aqueous medium solution, content of (A) 40%] for an aqueous adhesive for wood materials was obtained.
In addition, the sum total of the primary amino group and secondary amino group of (A-5) was 9.5 mol / kg.

<Comparative Example 1>
40 parts of triethanolamine (ratio A-1) and 60 parts of water are charged in a container and mixed to form an adhesion aid for water-based adhesive for wood materials (ratio Aα-1) [aqueous solution, containing (A) 40%] was obtained.

<< Crosslinking agent (B) >>
<Production Example 1>
A reaction vessel was charged with 100 parts of phenol and 250 parts of a 30% formaldehyde aqueous solution and stirred at 25 ° C.
8.0 parts of 50% aqueous sodium hydroxide solution was added to the reaction vessel, stirred at 65 ° C. for 3 hours, cooled to room temperature, and further 89.5 parts of ion-exchanged water was added to the crosslinking agent (B-1). An aqueous solution (B0-1) [content of (B) 40%] was obtained.
The methylol group concentration of (B-1) was 9 mol / kg.

<Production Example 2>
A reaction vessel was charged with 100 parts of urea and 243.0 parts of a 37% aqueous formaldehyde solution and stirred at 25 ° C.
In another container, 136.3 parts of ion-exchanged water and 3.0 parts of sodium hydroxide were charged to prepare an aqueous sodium hydroxide solution.
The total amount of this sodium hydroxide solution was added to the reaction vessel, stirred at 90 ° C. for 1 hour, then cooled to room temperature, and an aqueous solution (B0-2) of the crosslinking agent (B-2) [content of (B) 40 %].
The methylol group concentration of (B-2) was 21 mol / kg.

<Production Example 3>
A reaction vessel was charged with 124.0 parts of melamine, 200.0 parts of a 37% aqueous formaldehyde solution, and 14.0 parts of methanol and stirred at 25 ° C.
In another container, 166.0 parts of ion-exchanged water and 3.0 parts of sodium hydroxide were charged to prepare an aqueous sodium hydroxide solution.
The total amount of this sodium hydroxide solution was added to the reaction vessel, stirred at 90 ° C. for 2 hours, then cooled to room temperature, and an aqueous solution (B0-3) of the crosslinking agent (B-3) [content of (B) 40 %].
The methylol group concentration of (B-3) was 15 mol / kg.

<Production Example 4>
A reaction vessel was charged with 50 parts of urea, 62.0 parts of melamine, 220 parts of a 37% formaldehyde aqueous solution, and 14.0 parts of methanol and stirred at 25 ° C.
In a separate container, 144 parts of ion-exchanged water and 3.0 parts of sodium hydroxide were charged to prepare an aqueous sodium hydroxide solution.
The total amount of this sodium hydroxide solution was added to the reaction vessel and stirred at 90 ° C. for 1 hour, then cooled to room temperature, and an aqueous solution (B0-4) of the crosslinking agent (B-4) [content of (B) 40 %].
The methylol group concentration of (B-4) was 18 mol / kg.

<Examples 11 to 27, Comparative Example 11>
According to the blending composition (part) in Table 1, each container was blended and mixed to obtain an aqueous adhesive composition (X) for woody materials. Using the obtained aqueous adhesive composition (X), a particle board was produced in the following manner and evaluated by [Evaluation Method] described later. The results are shown in Table 1.

<1> Preparation of particle board 100 parts of particle board Lawan chip [weight average particle diameter: 1.5 mm] dried for 6 hours with a circulating dryer at 130 ° C. is returned to room temperature, and the aqueous adhesive composition (X) 25.0 parts and ion-exchanged water 5.0 parts. This mixture was hot-pressed at 180 ° C. and 30 kgf / cm ² for 1.5 minutes to prepare a particle board having a specific gravity of 0.7 and a thickness of 3 mm.

<2> Evaluation method (2-1) Bending strength of particle board (evaluation of adhesiveness)
The bending strength of the particle board was measured according to the test method of JIS A5908. The details of the test method are shown.
The manufactured particle board was cut into 20 mm × 200 mm, and the bending strength was measured at a speed of 10 mm / min using an autograph [“AGS-500D” manufactured by Shimadzu Corporation].

(2-2) Wet strength test of particle board when wet (evaluation of water resistance)
The water resistance test of the particle board is based on the test method of JIS A5908, and the bending strength is measured at a speed of 10 mm / min by using an autograph [“AGS-500D” manufactured by Shimadzu Corporation] in a wet state. did.

(2-3) Impact resistance (impact resistance) of particle board
The impact resistance test of the particle board was performed according to ASTM D6610.
The manufactured particle board was cut into 12.7 mm × 127 mm, and the Charpy impact strength was measured.

In addition, the hardening accelerator (C) in Table 1 is as follows.
Curing accelerator (C-1): Dimethylaminoethanol curing accelerator (C-2): 1,5-diazabicyclo [4.3.0] -5-nonene curing accelerator (C-3): Ammonium chloride

  From the results of Table 1, the adhesion aid (Aα) for the water-based adhesive for wood materials according to the present invention has superior adhesion to the wood material to the water-based adhesive composition for wood materials (X) as compared with the comparative one. Gives sex. Moreover, it turns out that the wooden material adhere | attached with hardened | cured material is excellent in intensity | strength (bending strength) and water resistance.

  Since the water-based adhesive composition for wood materials of the present invention is excellent in adhesiveness and water resistance, it is useful as an adhesive for various wood materials. In particular, it can be suitably used as an adhesive for bonding wood boards and particle boards.

Claims (8)

  An adhesion aid (Aα) for a water-based adhesive for woody materials, comprising an epoxy-modified polyamine (A) containing polyepoxide (a1) and polyamine (a2) as constituent monomers.   The adhesion assistant for an aqueous adhesive for woody materials according to claim 1, wherein the total of the primary amino group and the secondary amino group of (A) is 1 to 20 mol / kg.   3. The water-based adhesive for woody materials according to claim 1 or 2, wherein (A) comprises a polyepoxide (a1) and an aliphatic polyamine (a21) and / or an alicyclic polyamine (a22) as constituent monomers. Adhesive aid.   Adhesion aid (Aα) for aqueous adhesive for woody materials according to any one of claims 1 to 3, phenol resin (B1), urea resin (B2), melamine resin (B3), and urea melamine resin (B4) An aqueous adhesive composition for woody material (X) comprising at least one crosslinking agent (B) selected from the group consisting of: and water.   The aqueous adhesive composition for woody materials according to claim 4, wherein the methylol group concentration of (B) is 2 to 25 mol / kg.   The water-based adhesive composition for a woody material according to claim 4 or 5, wherein the weight ratio [(A) / (B)] of (A) to (B) is 0.2 / 99.8 to 15/85. object.   Furthermore, ammonium salt, dimethylaminoethanol, alkyl (C1-4) imidazole, 1,8-diazabicyclo [5.4.0] -7-undecene (salt) and 1,5-diazabicyclo [4.3.0]. ] The water-based adhesive composition for woody materials according to any one of claims 1 to 6, comprising at least one curing accelerator (C) selected from the group consisting of -5-nonene (salt).   A wood material to which a wood material is bonded via a cured product of the water-based adhesive composition for wood material (X) according to any one of claims 4 to 7.