JPH09302220A - Aqueous polyurethane resin composition and adhesive - Google Patents

Abstract

(57) Abstract: [PROBLEMS] To provide a one-component water-based polyurethane resin adhesive having excellent heat-resistant adhesion without heat treatment or the like at the time of adhesion. A polyester polyol composed of a carboxylic acid component and a glycol component, an isocyanate compound, an active hydrogen group-containing compound having a side chain of 2 to 10 carbon atoms, and having 6 to 20 carbon atoms in total. The present invention relates to an aqueous polyurethane resin composition in which a hydrophilic group-containing polyurethane resin obtained by reacting with a chain extender is dispersed in an aqueous medium.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyvinyl chloride (hereinafter referred to as PVC) base material, particularly a PV containing a plasticizer.
The present invention relates to an aqueous polyurethane resin composition having excellent adhesion to C substrate and excellent heat resistant adhesion.

[0002]

BACKGROUND OF THE INVENTION Aqueous polyurethane resins are used alone or in a mixture with other aqueous resins in the adhesive processing field. For example, for adhesion of PVC sheet and various wooden boards, for the purpose of improving heat resistance adhesion to a PVC substrate,
A water-based polyurethane resin is blended with a vinyl acetate emulsion or an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) emulsion for use.

Further, these compounds may be used as a one-pack type adhesive without using a cross-linking agent, but under the present circumstances, epoxy or aziridine is used for the purpose of improving the heat resistance at higher temperatures. It is used as a two-component adhesive in combination with the cross-linking agent.

However, in the two-component type adhesive which uses these cross-linking agents in combination, although the heat-resistant adhesive property is imparted by the cross-linking, there is a problem that the workability is poor because of the two-component type, and the processing such as temperature There is a problem that the crosslinking rate changes depending on the conditions.

Generally, as a method of improving the heat resistance of the aqueous polyurethane resin, there is a method of improving the cohesive force of the polyurethane resin. For example, it is known that the heat resistance is improved by increasing the content of the hard segment. Has been.

However, although these water-based polyurethane resins having a high hard segment content have high heat resistance as a polyurethane resin, they are wet-laminated at room temperature without any heat treatment step in the adhesion processing with the PVC substrate. In the processing of decorative plywood, etc., there is a problem that the adhesiveness to a PVC substrate containing a plasticizer is extremely poor, and these polyurethane resin adhesives cannot sufficiently impart heat resistant adhesiveness.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous polyurethane resin composition which overcomes the above-mentioned drawbacks found in conventional aqueous polyurethane resins for adhesion processing of PVC substrates,
That is, it is an object of the present invention to provide an aqueous polyurethane resin composition that can be used in a one-pack type that does not require the use of a cross-linking agent and that exhibits heat-resistant adhesiveness even in wet laminating processing particularly at room temperature.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a chain extender containing a side chain having 2 to 10 carbon atoms and containing an active hydrogen group having 6 to 20 carbon atoms as a whole. The inventors have found that the above problems can be solved by using a compound, and have completed the present invention.

That is, the present invention comprises a hydrophilic group-containing polyurethane resin obtained by reacting a polyester polyol composed of a carboxylic acid component and a glycol component, an isocyanate compound and a chain extender in an aqueous medium. In the aqueous polyurethane resin composition, an active hydrogen group-containing compound having a side chain having 2 to 10 carbon atoms and having 6 to 20 carbon atoms in total is used as a chain extender. To provide a composition, preferably having a side chain of 2 to 10 carbon atoms,
An aqueous polyurethane resin composition in which the active hydrogen-containing compound of the active hydrogen group-containing compound having 6 to 20 carbon atoms is glycol, and the hydrophilic group is preferably a carboxylate group. It is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The chain extender of the present invention has 2 to 1 carbon atoms.
Examples of the active hydrogen group-containing compound having a side chain of 0 and a total carbon number of 6 to 20 include glycol and diamine described below.

Examples of glycols are 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-pentyl-2-propyl-1,3-propane. Diol, 2-butyl-2-
Hexyl-1,3-propanediol, 2-ethyl-
1,3-hexanediol etc. can be mentioned.

Examples of diamines are N-hexylpropanediamine, N-heptylpropanediamine,
N-octylpropanediamine, N-ethylhexamethylenediamine, N, N'-diethylhexamethylenediamine, N, N'-bis (1,1-dimethylethyl)-
1,2-ethanediamine, N- (1-methylethyl)-
1,3-propanediamine and the like can be mentioned.

The above-mentioned glycol is preferable as the active hydrogen-containing compound, and 2-butyl-2-ethyl-1,3-propanediol is particularly preferable among the glycols.

In contrast to these active hydrogen group-containing compounds, when an active hydrogen group-containing compound having a side chain with 1 carbon atom is used, the resulting polyurethane resin has too strong cohesive force, and therefore PVC adhesion at low temperatures Is reduced, the carbon number is 1
When an active hydrogen group-containing compound having one or more side chains is used, the cohesive force of the resulting polyurethane resin is too low and the heat resistance is low. In either case, the heat resistant adhesiveness is low.

Even if the number of carbon atoms in the side chain is 2 to 10, if the number of carbon atoms in the entire molecule is 5 or less, the cohesive force of the resulting polyurethane resin is too strong, resulting in poor PVC adhesion at low temperatures. On the other hand, when the total number of carbon atoms in the molecule is 21 or more, the cohesive force of the resulting polyurethane resin is too low and the heat resistance is low. In either case, the heat resistant adhesion is low.

Further, the amount of the active hydrogen group-containing compound contained in the polyurethane resin is not particularly limited, but it is 0.2 to
20% by weight is suitable. When the amount of the active hydrogen group-containing compound is less than 0.2% by weight, the cohesive force of the resin is too strong, so that the PVC adhesion at low temperature decreases, and when it is more than 20% by weight, the cohesive force of the resin is weak. Since it is too much, the heat-resistant adhesiveness is lowered in any case. A more preferable amount is 0.5 to 15
% By weight.

Examples of the isocyanate compound used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate and 4,4'-diphenylmethane diisocyanate. ,
2,4'-diphenylmethane diisocyanate, 2,
2'-diphenylmethane diisocyanate, 3,3'-
Dimethyl-4,4'-biphenylene diisocyanate,
3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate , 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,
4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,
4'-dicyclohexylmethane diisocyanate, 3,
3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate and the like can be mentioned, and they can be used alone or in combination.

The amount of the isocyanate compound contained in the polyurethane resin is not particularly limited, but is 10 to 50% by weight.
Is appropriate. 50% by weight of isocyanate compound
If the amount is larger, the cohesive force of the resin is too strong, resulting in a marked decrease in PVC adhesion at low temperatures. Conversely, if it is less than 10% by weight, the cohesive force of the resulting polyurethane resin is too weak and the heat resistance is also reduced. In any case, the heat-resistant adhesiveness is lowered. A more preferable amount is 20 to 40% by weight.

As the polyester polyol composed of a carboxylic acid component and a glycol component used in the present invention, ethylene glycol, propylene glycol,
1,3-propanediol, 1,4-butanediol,
1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6,000), Dipropylene glycol, tripropylene glycol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-pentyl-2-
Propyl-1,3-propanediol, 2-butyl-2
-Hexyl-1,3-propanediol, 2-ethyl-
Glycol components such as 1,3-hexanediol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts, and succinic acid. ,
Adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,
4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and these dicarboxylic acids An anhydride or an ester-forming derivative of a polyester; Other examples include polyesters obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone and copolymerized polyesters thereof.

The average molecular weight of these polyester polyols is 500 to 5,000, preferably 800 to 5,000.
Those in the range of 2,000 are used. The aqueous polyurethane resin of the present invention is a polyurethane resin containing a polyester polyol as a main component, but other polyol components may be used in combination within the range not impairing the features of the present invention. Examples of such other polyol component include polyether polyol, polycarbonate polyol, polyacetal polyol, polyacrylate polyol, polyesteramide polyol, polythioether polyol and the like.

Examples of the raw material used for introducing a hydrophilic group into the polyurethane resin of the present invention include, for example, a salt of carboxylic acid and a salt of sulfonic acid having at least one active hydrogen atom in the molecule. A compound having a functional group of any of a carboxylic acid group and a sulfonic acid group, which is basically ionic, or a group having at least one or more active hydrogen atom in the molecule and comprising an ethylene oxide repeating unit. , A nonionic compound containing a group composed of a repeating unit of ethylene oxide and a repeating unit of other alkylene oxide.

Examples of the hydrophilic group-containing compound include 2-oxyethanesulfonic acid, phenolsulfonic acid,
Sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-
4,6-disulfonic acid, 2,4-diaminotoluene-5
-Sulfonic acid-containing compounds such as sulfonic acid and derivatives thereof or polyester polyols obtained by copolymerizing these; 2,2-dimethylolpropionic acid, 2,2-
Dimethylol butyric acid, 2,2-dimethylol valeric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3,4-
Carboxylic acid-containing compounds such as diaminobenzoic acid and derivatives thereof or polyester polyols obtained by copolymerizing these; at least 30% by weight or more of repeating units of ethylene oxide, and at least 1 in the polymer.
Molecular weight 300 to 20,000 containing one or more active hydrogens
0, polyoxyethylene glycol or polyoxyethylene-polyoxypropylene copolymer glycol, polyoxyethylene-polyoxybutylene copolymer glycol, polyoxyethylene-polyoxyalkylene copolymer glycol or nonionics such as monoalkyl ethers thereof Examples of the group-containing compound include polyester polyether polyols obtained by copolymerizing these compounds, and these are used alone or in combination.

Among these hydrophilic groups, anionic groups consisting of carboxylic acid salts are particularly preferable. Examples of the neutralizing agent that can be used in the production of the aqueous polyurethane resin of the present invention include non-volatile bases such as sodium hydroxide and potassium hydroxide; trimethylamine, triethylamine,
Examples include tertiary amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine, and volatile bases such as ammonia. The time for neutralizing the acid group may be before the urethanization reaction of the carboxylic acid group-containing active hydrogen-containing compound, during the urethanization reaction, or after the urethanization reaction.

As the chain extender, the above-mentioned carbon number 2 of the present invention can be used.
In addition to the active hydrogen-containing compound having a side chain of 10 to 10 and the total number of carbon atoms of 6 to 20, other active hydrogen-containing compound can be used in combination. Examples of this compound include glycol components used as raw materials for polyester polyols; glycerin, trimethylolethane,
Polyhydroxy compounds such as trimethylolpropane, sorbitol, pentaerythritol; ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,
5-dimethylpiperazine, isophoronediamine, 4,
4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine,
Diamines such as 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine and aminohexylpropanolamine; diethylenetriamine, Examples thereof include polyamines such as dipropylenetriamine and triethylenetetramine; hydrazines; polyamine compounds such as acid hydrazides, which may be used alone or in combination.

In order to impart the heat resistant adhesiveness of the present invention,
Among these chain extenders, it is preferable to use a polyamine compound in combination to obtain a polyurethane urea. As the method for producing the aqueous polyurethane resin composition of the present invention, any well-known method may be used. For example, the following method can be used.

Polyester polyol, hydrophilic group-containing compound, active hydrogen-containing compound containing a specific branched chain,
And other chain extender, if necessary, in an organic solvent solution or organic solvent dispersion of a hydrophilic group-containing polyurethane resin or polyurethane urea resin obtained by reacting with a polyisocyanate compound, and if necessary, a neutralizing agent A method in which an aqueous solution containing is mixed and, if necessary, the solvent is removed.

Polyester polyol, hydrophilic group-containing compound, active hydrogen-containing compound containing a specific branched chain,
And, if necessary, other chain extender, hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting with a polyisocyanate compound, mixed with an aqueous solution containing a neutralizing agent, or prepolymer in advance A method of obtaining an aqueous polyurethaneurea resin by adding a neutralizing agent therein, mixing with water, dispersing in water, reacting with a polyamine compound, and further removing the solvent as necessary.

Polyester polyol, hydrophilic group-containing compound, active hydrogen-containing compound containing a specific branched chain,
And, if necessary, other chain extender, a hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting with a polyisocyanate compound, is mixed with an aqueous solution containing a neutralizing agent and a polyamine compound, or A method in which a neutralizing agent is added to the prepolymer in advance, the mixture is mixed with an aqueous solution containing a polyamine compound, and then the solvent is removed if necessary to obtain an aqueous polyurethane urea resin.

The above-mentioned polyurethane resin or urethane prepolymer containing terminal isocyanate groups is produced by a conventionally known method. For example, in the production of a polyurethane resin, the polyisocyanate compound and the active hydrogen-containing compound have an equivalent ratio of isocyanate groups to active hydrogen groups of 1.
1: 1 to 0.8: 1, preferably 1.05: 1 to 0.9:
It is obtained by reacting at a ratio of 1. Further, in the case of a urethane prepolymer containing a terminal isocyanate group, the polyisocyanate compound and the active hydrogen active hydrogen-containing compound excluding the polyamine compound have an equivalent ratio of the isocyanate group and the active hydrogen group of 1.1: 1 to 3: 1, preferably 1.2: 1 to 2:
It is obtained by reacting at a ratio of 1. The reaction temperature in this case is usually 20 to 120 ° C, preferably 30 to 100 ° C.

These reactions are usually carried out using an organic solvent for the purpose of controlling the reaction of the reaction system or reducing the viscosity, but it can also be carried out without a solvent. The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; acetic acid esters such as ethyl acetate and butyl acetate; dimethylformamide. , N-methylpyrrolidone, and other amides. When such an organic solvent is removed by distillation from the finally obtained aqueous polyurethane resin, it is preferable to use an organic solvent having a relatively low boiling point, which is easily removed by distillation. Even when it is necessary to use an organic solvent having a boiling point of 100 ° C. or higher, it is preferable to keep the amount used to the minimum necessary.

When preparing an aqueous adhesive based on the aqueous polyurethane resin composition of the present invention, various additives can be used in combination. Examples of additives include tackifying resins such as rosin emulsion, terpene resin emulsion, and petroleum resin emulsion; various urethane-based and alkali-thickening type thickeners; organic solvents such as toluene and xylene; carbon black, clay, talc, Fillers such as silica, mica, calcium carbonate, and aluminum hydroxide; additives such as silica sol and alumina sol; film forming aids such as alkylene glycol derivatives; silane coupling agents; surfactants; leveling agents; antioxidants; Foaming agent; Anti-settling agent;
Thickeners; plasticizers; pigments, dyes; flame retardants; lubricants and the like.

The water-based adhesive of the present invention may optionally contain other water dispersion. Examples of such an aqueous dispersion include vinyl acetate-based, ethylene-vinyl acetate-based, acrylic-based, acrylic styrene-based emulsions; styrene-butadiene-based, acrylonitrile-butadiene-based, acrylic-butadiene-based latexes; polyethylene-based, Examples include polyolefin-based ionomers; polyurethane, polyester, polyamide, epoxy-based water dispersions and the like.

The water-based polyurethane resin composition and the water-based adhesive composition of the present invention can be used as a one-pack type which gives excellent heat-resistant adhesion without using a crosslinking agent as in the conventional products, but A cross-linking agent can be used to impart a high level of durability such as heat resistance, solvent resistance, water resistance, moist heat resistance, and weather resistance.

Examples of the crosslinking agent include epoxy resins, melamine resins, isocyanate compounds, aziridine compounds, polycarbodiimide compounds, polyoxazoline compounds and the like.

The substrate to which the aqueous polyurethane resin composition and the aqueous adhesive composition of the present invention are applied is PV.
Various plastics such as C, nylon, polyester, ABS and polyurethane, olefin base materials such as PE, PP and TPO, textile products, synthetic leather products, or aluminum,
Examples thereof include metals such as copper, iron and stainless steel, paper, wood, wood boards such as MDF, plywood, glass and the like, and are particularly useful as an adhesive for a PVC substrate containing a plasticizer.

The water-based polyurethane resin composition and water-based adhesive composition of the present invention can be used by blending the above-mentioned additives and the like to adjust to a predetermined concentration and viscosity, and then using a roll coater, knife coater, spray or the like. After applying to the adherend, a method of laminating with the adherend in a wet state can be mentioned. In addition to this, after applying the resin composition or the adhesive composition to the adherend, It is also possible to use a method of once drying and heat-sealing the adherend with heating.

[0037]

EXAMPLES In order to more specifically describe the present invention,
Examples will be described below, but the present invention is not limited to these examples. In the examples, "part" means "part by weight".

Example 1 An average molecular weight of 2, in a reactor equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube.
100 parts of 1,4-butanediol / adipic acid polyester polyol of 100 is added under reduced pressure to 120 to 13
After dehydration at 0 ° C, the mixture was cooled to 40 ° C and 55 parts of 2-butyl-2-ethyl-1,3-propanediol,
116 parts of 2,4-tolylene diisocyanate and 158 parts of methyl ethyl ketone were added and the mixture was subjected to a boiling point reaction for 2 hours while introducing nitrogen gas, then cooled to 60 ° C., and 1,4-butanediol / 2,2 having an average molecular weight of 2,000. 166 parts of dimethylolpropionic acid / adipic acid polyester polyol (acid value: 39.1, hydroxyl value: 43.3) were added and reacted at 60 ° C. for 2 hours to obtain a solvent solution of a terminal isocyanate prepolymer. Next, piperazine 16
Parts and 12 parts of triethylamine were added to 579 parts of ion-exchanged water, and a solvent solution of the homopolymer was gradually added thereto while stirring at high speed with a homomixer to prepare an aqueous polyurethane resin composition. Furthermore, methyl ethyl ketone was removed under azeotropic distillation to obtain an aqueous polyurethane resin composition a. The characteristic values of this resin are shown in Table 1. Then, a nonionic thickener is mixed with this resin to give a viscosity of 25,000 mPas.
Table 1 shows the results of evaluation of the heat-resistant adhesiveness of the sample with s by the heat-resistant creep test.

(Example 2) An average molecular weight of 2, in a reactor equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube.
100 parts of 1,6-hexanediol / neopentyl glycol / adipic acid polyester polyol of 000 are dehydrated at 120 to 130 ° C. under reduced pressure and then cooled to 40 ° C., and 2-butyl-2-ethyl-1 , 3-
After 9 parts of propanediol, 45 parts of 2,4-tolylene diisocyanate and 87 parts of methyl ethyl ketone were added and the mixture was subjected to a boiling point reaction for 2 hours while introducing nitrogen gas, it was cooled to 60 ° C. and 8 parts of 2,2-dimethylolpropionic acid. Was added and reacted at 70 ° C. for 2 hours to obtain a solvent solution of a terminal isocyanate prepolymer. Next, an aqueous polyurethane resin composition was prepared by adding 8 parts of piperazine and 6 parts of triethylamine to 276 parts of ion-exchanged water and gradually adding a solvent solution of the homopolymer thereto while stirring the mixture at high speed with a homomixer. Furthermore, methyl ethyl ketone was removed under azeotropy to obtain an aqueous polyurethane resin composition b. The characteristic values of this resin are shown in Table 1. Next, Table 1 shows the results of evaluating the heat resistant adhesiveness of this resin mixed with a nonionic thickening agent to have a viscosity of 30,000 mPa · s by a heat creep resistance test.

Example 3 Ebadic EP-as an ethylene-vinyl acetate copolymer emulsion (EVA)
11 [solid content 52.5-54.0%; manufactured by Dainippon Ink and Chemicals, Inc.] 50 parts by weight neutralized with 5.6% ammonia water and 50 parts by weight of the aqueous polyurethane resin composition a were mixed. , A nonionic thickener is mixed to obtain a viscosity of 30,000
Table 2 shows the results obtained by evaluating the heat-resistant adhesiveness of the resin having 0 mPa · s by the heat-resistant creep resistance test.

(Example 4) With respect to the aqueous polyurethane resin composition b, as in Example 3, EVA was mixed and thickened to have a viscosity of 34,000 mPas, and the heat resistance and adhesion were evaluated by the heat creep test. Is shown in Table 2.

(Comparative Example 1) An aqueous polyurethane resin composition c was obtained from the following raw materials in the same manner as in Example 1. The characteristic values of this resin are shown in Table 1. Similarly, Table 2 shows the results of evaluating the heat-resistant adhesiveness of the resin having a viscosity of 24,000 mPa · s by the heat-resistant creep resistance test.

Neopentyl glycol 34 parts 2,4-Tolylene diisocyanate 106 parts 1,4-Butanediol / adipic acid polyester polyol (average molecular weight 2,000) 100 parts 1,4-butanediol / 2,2-di Methylol propionic acid / adipic acid polyester polyol (average molecular weight 2,000, acid value: 39.1, hydroxyl value: 43.3) 152 parts Piperazine 14 parts Triethylamine 11 parts Methylethylketone 140 parts Ion-exchanged water 534 parts (Comparative Example 2) ) From the following raw materials in the same manner as in Example 2,
An aqueous polyurethane resin composition d was obtained. The characteristic values of this resin are shown in Table 1. Similarly, Table 2 shows the results of evaluation of the heat-resistant adhesiveness of the resin having a viscosity of 28,000 mPa · s by increasing its viscosity by a heat-resistant creep test.

1,4-butanediol 4 parts 2,4-tolylene diisocyanate 43 parts 1,4-butanediol / neopentyl glycol / adipic acid polyester polyol (average molecular weight 2,000) 100 parts 2,2-di Methylol propionic acid 7 parts Piperazine 8 parts Triethylamine 6 parts Methyl ethyl ketone 84 parts Ion-exchanged water 266 parts (Comparative Example 3) For the aqueous polyurethane resin composition c, EVA was mixed and thickened in the same manner as in Example 3 to obtain a viscosity of 30,000.
Table 2 shows the results obtained by evaluating the heat-resistant adhesiveness of the resin having 0 mPa · s by the heat-resistant creep resistance test.

(Comparative Example 4) With respect to the aqueous polyurethane resin composition d, as in Example 3, EVA was mixed and thickened to have a viscosity of 31,000 mPas, and the heat resistance and adhesion were evaluated by a heat resistance creep resistance test. The results are shown in Table 2.

<Performance Evaluation> The heat-resistant creep resistance test was conducted as follows. 1. A water-based polyurethane resin or a mixture of water-based polyurethane resin and EVA thickened with a rubber roller on a 300 × 150 mm board per solid content 2.
Apply 5 g and immediately stack PVC sheets on top
The product was pressed at cm ² for 20 minutes, left at room temperature for 1 week, cut into 150 × 25 mm, put in a constant temperature bath at 80 ° C. and left at a load of 500 g in the 180 ° direction for 24 hours, and the peeling distance was measured. .

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

EFFECT OF THE INVENTION The water-based polyurethane resin composition of the present invention can obtain excellent heat-resistant adhesiveness without heat treatment during adhesion.

Claims (8)

[Claims] 1. An aqueous polyurethane resin obtained by dispersing a hydrophilic group-containing polyurethane resin obtained by reacting a polyester polyol composed of a carboxylic acid component and a glycol component, an isocyanate compound and a chain extender in an aqueous medium. In the composition, the chain extender has 2 to 2 carbon atoms.
An aqueous polyurethane resin composition comprising an active hydrogen group-containing compound having 10 side chains and having a total carbon number of 6 to 20. 2. The active hydrogen-containing compound of the active hydrogen-containing compound having a side chain of 2 to 10 carbon atoms and having a total carbon number of 6 to 20 is glycol. The aqueous polyurethane resin composition described. 3. Glycol is 2-butyl-2-ethyl-
The aqueous polyurethane resin composition according to claim 2, which is 1,3-propanediol. 4. The aqueous polyurethane resin composition according to any one of claims 1 to 3, wherein the hydrophilic group is a carboxylate group. 5. The aqueous polyurethane resin composition according to any one of claims 1 to 4, wherein the isocyanate compound is used in an amount of 20 to 40% by weight based on the solid content of the aqueous polyurethane resin. 6. An active hydrogen-containing compound having a side chain of 2 to 10 carbon atoms and having 6 to 20 carbon atoms in total is used in an amount of 0.2 to 20% by weight based on the solid content of the aqueous polyurethane resin. The aqueous polyurethane resin composition according to any one of claims 1 to 5, wherein 7. The aqueous polyurethane resin composition according to any one of claims 1 to 6, wherein the polyurethane of the aqueous polyurethane resin composition is polyurethane urea. 8. An adhesive comprising the aqueous polyurethane resin composition according to claim 1.