JP5202068B2 - Aqueous polyurethane resin composition, one-component adhesive and laminate using the same, and method for producing aqueous polyurethane resin composition - Google Patents

Description

  The present invention relates to an aqueous polyurethane resin composition, a one-component adhesive and laminate using the same, and a method for producing an aqueous polyurethane resin composition.

  In general, when manufacturing laminates by laminating various substrates such as rubber, metal, paper, fiber, wood, glass, polyvinyl chloride, polyolefin, etc. Adhesives containing dissolved resins have been used a lot.

  And when manufacturing a laminated body, after apply | coating the adhesive agent containing the resin melt | dissolved in the organic solvent on the base material, for example, this is dried and the organic solvent is volatilized, Then, it bonds together with a base material. Many dry lamination methods are used.

  In addition, as an adhesive containing an organic solvent-based resin, mainly from a polyurethane resin main agent having an active hydrogen having reactivity with an isocyanate group, such as a hydroxyl group or an amide group, and a polyisocyanate-based curing agent. There are two-component adhesives or one-component adhesives containing polyurethane resin.

  Such a two-component adhesive has a long time (that is, open time) until it loses its adhesiveness after being applied to a base material, and it can be used for adhesiveness at a low temperature of about 30 to 60 ° C. There is an advantage that it is excellent, and bonding with various base materials can be easily performed. In addition, since the main component polyurethane resin and the polyisocyanate curing agent react to increase the molecular weight, a laminate having excellent durability such as hydrolysis resistance and heat creep resistance can be obtained. However, since the main agent and the curing agent are mixed, the pot life of the adhesive bath is short, and there is a problem that a great amount of labor such as management of the production environment and the adhesive bath is required.

  On the other hand, the pot life of an adhesive bath like a two-pack adhesive does not substantially exist for a one-pack type adhesive, and management of the manufacturing environment, the adhesive bath, etc. is easy, but the open time is short, There is a drawback that durability such as hydrolysis resistance and heat creep resistance is inferior. The open time greatly depends on the temperature of the adhesive application surface after drying and tends to be relatively long at a high temperature, but tends to be short at a low temperature of about 30 to 60 ° C. In addition, there is a problem that a great deal of labor is required such as management of the drying temperature and the temperature of the adhesive application surface. Further, in order to impart adhesiveness to the polyurethane resin, polyester polyol is often used as the main raw material of the polyurethane resin, and in order to further increase the open time, the structure of the polyurethane resin is made as linear as possible. As a result, the polyurethane resin becomes susceptible to the influence of water and moisture, and is easily hydrolyzed, so that the quality of the laminate is deteriorated.

  In addition, these adhesives use dimethylformamide, toluene, methyl ethyl ketone, etc. as organic solvents, so many of them are highly flammable and highly toxic. There were problems with environmental pollution such as water quality. In addition, although the process of collect | recovering these organic solvents is also performed, there existed a problem that large disposal cost and labor were applied. In addition, the laminate obtained using an adhesive containing a resin dissolved in an organic solvent may leave an organic solvent inside the laminate, and the recent sick house syndrome, chemical hypersensitivity, skin damage, etc. The impact on the human body is also a problem.

  In order to solve these problems, studies have been made to shift from an adhesive containing a polyurethane resin dissolved in an organic solvent to an adhesive containing an aqueous polyurethane resin.

  As water-based polyurethane resins, hydrophilicity is imparted by introducing polyoxyethylene repeating units into the resin skeleton using dispersions in which polyurethane resins are forcibly dispersed using surfactants or polyether polyols such as polyethylene glycol. The former has a problem that the quality of the laminate is deteriorated because the surfactant bleeds with time, and the latter has a problem that the heat creep resistance and water resistance are insufficient. there were.

  Also, for example, in JP-A-6-31024 (Patent Document 1), a polyurethane resin excellent in water solubility or water dispersibility was obtained by ring-opening addition polymerization of lactones using dihydroxycarboxylic acid as an initiator. A polyurethane resin having a carboxyl group concentration of 10 or more, comprising a lactone-based polyester polyol, an organic diisocyanate, and a chain extender is disclosed. However, the polyurethane resin as described in Patent Document 1 is a resin having a weak cohesion because a carboxyl group is introduced into the soft segment, and the open time is slightly longer when used as an adhesive. It was insufficient in terms of durability such as adhesiveness at a low temperature of about ˜60 ° C., heat creep resistance, and water resistance.

  Furthermore, JP-A-2005-272775 (Patent Document 2) describes a method for producing an aqueous one-component urethane resin adhesive excellent in heat resistance and water resistance without using a two-component type combined with a crosslinking agent. When the carboxyl group-containing polyurethane resin is dissolved in a solvent, neutralized with a basic compound, and immediately before adding water or when water is dispersed in the polyurethane resin solution by adding water, aliphatic A method is disclosed in which a crosslinking agent such as an epoxy resin or a polyisocyanate adduct is dispersed and crosslinking is carried out in emulsion particles. However, the aqueous one-component urethane resin adhesive described in Patent Document 2 has a short open time and an adhesive property at a low temperature of about 30 to 60 ° C., although durability such as hydrolysis resistance is improved. There was a problem in that it was insufficient and it was difficult to stably manufacture the product.

As described above, the conventional adhesive containing a water-based polyurethane resin has not yet achieved a high level of compatibility with durability such as long open time and heat-resistant creep resistance and hydrolysis resistance, Furthermore, the adhesiveness at a low temperature of about 30 to 60 ° C. was insufficient. And the laminated body manufactured using such a conventional adhesive is not only adhesive strength but also heat resistant creep resistance and hydrolysis resistance than those obtained using an adhesive containing an organic solvent-based polyurethane resin. There was a problem that it was inferior also in durability, such as property.
JP-A-6-313024 JP 2005-272775 A

  The present invention has been made in view of the above-mentioned problems of the prior art, and is an aqueous polyurethane resin composition containing as little or no organic solvent as possible, and has a long open time and adhesiveness, particularly 30 to 60 ° C. Water-based polyurethane resin composition capable of obtaining a laminate having excellent adhesiveness even at a low temperature and having excellent adhesive strength, hydrolysis resistance, and heat-resistant creep resistance, and one-component adhesive using the same It aims at providing the manufacturing method of an agent and a laminated body, and its water-based polyurethane resin composition.

As a result of intensive studies to achieve the above object, the present inventor has developed an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate with a polyfunctional compound containing a polyol having a sulfone group and / or a sulfonate group. Japanese products
(i) an aqueous polyurethane resin composition obtained by carrying out a chain extension reaction using a polyamine aqueous solution of a specific concentration and simultaneously dispersing in water without causing a chain extension reaction; or
(ii) An aqueous polyurethane resin composition obtained by subjecting a chain extension reaction using a chain extender to a chain extension reaction using a polyamine aqueous solution of a specific concentration and simultaneously dispersing in water,
The inventors have found that the open time is long and that excellent adhesiveness, hydrolysis resistance and heat creep resistance are exhibited, and the present invention has been completed.

That is, one-component adhesive agent of the present invention, the polyisocyanate (A), a polyol having a sulfonic group and / or sulfonate groups (B ₁₎ a polyol other than the polyol having a sulfonic group and / or sulfonate group (B ₂ ) And / or a chain extender (B ₃ ) and a neutralized isocyanate group-terminated prepolymer obtained by reacting the polyfunctional compound (B) so as to satisfy the condition represented by the following formula (1): A chain extension reaction using a 0.05 to 3.0% by mass aqueous solution of polyamine (C) having two or more amino groups and / or imino groups so as to satisfy the condition represented by the following formula (2) are those obtained by simultaneously dispersed in water when is, a sulfonic group and / or polyols having a sulfonate group (B ₁₎ a polyester polyol of a lactone-based Those containing a first aqueous polyurethane resin composition is Le.
100/80 ≦ a / b ≦ 100/50 (1)
100/100 ≦ a / (b + c) ≦ 100/97 (2)
(In the formulas (1) and (2), a represents the number of isocyanate groups (NCO) contained in the polyisocyanate (A), and b represents a hydroxyl group (OH) contained in the polyfunctional compound (B). C represents the total number of amino groups (NH ₂ ) and imino groups (NH) contained in the polyamine (C).

In addition, the one-component adhesive of the present invention includes a polyisocyanate (A) having a polyol (B ₁ ) having a sulfone group and / or a sulfonate group and a polyol other than a polyol having a sulfone group and / or a sulfonate group (B _2). ) And / or a chain extender (B ₃ ) and a neutralized isocyanate group-terminated prepolymer obtained by reacting the polyfunctional compound (B) so as to satisfy the condition represented by the following formula (1): Is subjected to a chain extension reaction using the second chain extender (D) so as to satisfy the condition represented by the following formula (3), and then a polyamine having two or more amino groups and / or imino groups ( C) using a 0.05 to 3.0% by mass aqueous solution of C) and being subjected to a chain extension reaction so as to satisfy the condition represented by the following formula (4) and simultaneously dispersing in water, Are those polyols having a down and / or sulphonate groups (B ₁₎ contains a second aqueous polyurethane resin composition is a polyester polyol lactone.
100/80 ≦ a / b ≦ 100/50 (1)
100/95 ≦ a / (b + d) ≦ 100/80 (3)
100/100 ≦ a / (b + c + d) ≦ 100/97 (4)
(In the formulas (1), (3) and (4), a represents the number of isocyanate groups (NCO) contained in the polyisocyanate (A), and b represents hydroxyl contained in the polyfunctional compound (B). Represents the number of groups (OH), c represents the total number of amino groups (NH ₂ ) and imino groups (NH) contained in the polyamine (C), and d represents the amino group contained in the second chain extender (D). Represents the total number of groups (NH ₂ ) and imino groups (NH)).

First and second aqueous polyurethane resin composition according to the present invention (hereinafter, collectively referred to as "aqueous polyurethane resin composition of the present invention") Oite, the sulfone group in the polyurethane resin in the aqueous polyurethane resin composition And it is preferable that content of a sulfonate group is 0.3-3.0 mass% with respect to the mass of this polyurethane resin.

Product Sotai of the present invention is obtained by using a one-component adhesive agent of the present invention.

  According to the present invention, it is an aqueous polyurethane resin composition that contains as little or no organic solvent as possible, and has a long open time, adhesiveness, particularly excellent adhesiveness even at a low temperature of about 30 to 60 ° C., In addition, it is possible to provide an aqueous polyurethane resin composition, a one-pack type adhesive, and a laminate using the same, which can obtain a laminate excellent in adhesive strength, hydrolysis resistance and heat-resistant creep resistance. It becomes.

  Further, according to the aqueous polyurethane resin composition of the present invention, the organic solvent is contained as much as possible or not at all. Therefore, problems such as air pollution and water pollution due to the organic solvent, recovery work of the organic solvent, improvement of the working environment, and further volatilization. It becomes possible to take measures against the volatile organic compound (VOC). Furthermore, in the aqueous polyurethane resin composition of the present invention, since it can be used as a one-component adhesive that does not require an isocyanate curing agent, the problem of pot life like a two-component adhesive can be solved. it can.

  Further, the aqueous polyurethane resin composition of the present invention has a characteristic that the open time is long, and has excellent adhesiveness not only at a high temperature (about 70 to 100 ° C.) but also at a low temperature (about 30 to 60 ° C.). Therefore, it is possible to reduce labor such as the drying temperature for manufacturing the product stably and the temperature control of the adhesive application surface. Furthermore, according to the water-based polyurethane resin composition of the present invention, since it is excellent in durability such as water resistance and heat-resistant creep resistance, damage due to heat at the time of producing a laminate can be suppressed, and it is particularly useful as an adhesive. Therefore, it is possible to obtain a laminate that is stable in terms of quality, particularly durability such as adhesive strength, hydrolysis resistance, and heat resistance creep resistance.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  First, the 1st and 2nd water-based polyurethane resin composition of this invention, and those manufacturing methods are demonstrated.

That is, the first aqueous polyurethane resin composition of the present invention comprises a polyisocyanate (A) with a polyol (B ₁ ) having a sulfone group and / or sulfonate group, another polyol (B ₂ ), and / or a chain extender. A polyfunctional compound (B) containing (B ₃ ) is represented by the following formula (1):
100/80 ≦ a / b ≦ 100/50 (1)
0.05 to 3.0 mass of polyamine (C) having two or more amino groups and / or imino groups, a neutralized isocyanate group-terminated prepolymer obtained by reacting so as to satisfy the condition represented by % Aqueous solution and the following formula (2):
100/100 ≦ a / (b + c) ≦ 100/97 (2)
(In the formulas (1) and (2), a represents the number of isocyanate groups (NCO) contained in the polyisocyanate (A), and b represents a hydroxyl group (OH) contained in the polyfunctional compound (B). C represents the total number of amino groups (NH ₂ ) and imino groups (NH) contained in the polyamine (C).
The chain elongation reaction is performed so as to satisfy the condition represented by the formula (1) and at the same time dispersed in water.

Moreover, the manufacturing method of the 1st water-based polyurethane resin composition of this invention,
A polyfunctional compound (B) containing a polyol (B ₁ ) having a sulfone group and / or a sulfonate group and another polyol (B ₂ ) and / or a chain extender (B ₃ ) in the polyisocyanate (A) A step of obtaining a neutralized isocyanate group-terminated prepolymer by reacting so as to satisfy the condition represented by the formula (1), and an isocyanate group-terminated prepolymer neutralized product with an amino group and / or an imino group. Aqueous polyurethane by using a 0.05 to 3.0% by weight aqueous solution of polyamine (C) having two or more, chain-extending reaction so as to satisfy the condition represented by the formula (2), and simultaneously dispersing in water. Obtaining a resin composition;
It is a method including.

The second aqueous polyurethane resin composition of the present invention comprises a polyisocyanate (A), a polyol (B ₁ ) having a sulfone group and / or a sulfonate group, another polyol (B ₂ ), and / or a chain extender (B ₃ ) and a polyfunctional compound (B) containing the following formula (1):
100/80 ≦ a / b ≦ 100/50 (1)
The neutralized isocyanate group-terminated prepolymer obtained by reacting so as to satisfy the condition represented by the following formula (3) using the second chain extender (D):
100/95 ≦ a / (b + d) ≦ 100/80 (3)
After the chain elongation reaction so as to satisfy the condition represented by the following formula, a 0.05 to 3.0 mass% aqueous solution of polyamine (C) having two or more amino groups and / or imino groups is used. 4):
100/100 ≦ a / (b + c + d) ≦ 100/97 (4)
(In the formulas (1), (3) and (4), a represents the number of isocyanate groups (NCO) contained in the polyisocyanate (A), and b represents hydroxyl contained in the polyfunctional compound (B). Represents the number of groups (OH), c represents the total number of amino groups (NH ₂ ) and imino groups (NH) contained in the polyamine (C), and d represents the amino group contained in the second chain extender (D). Represents the total number of groups (NH ₂ ) and imino groups (NH).)
The chain elongation reaction is performed so as to satisfy the condition represented by the formula (1) and at the same time dispersed in water.

In addition, the method for producing the second aqueous polyurethane resin composition of the present invention,
A polyfunctional compound (B) containing a polyol (B ₁ ) having a sulfone group and / or a sulfonate group and another polyol (B ₂ ) and / or a chain extender (B ₃ ) in the polyisocyanate (A) A step of obtaining a neutralized isocyanate group-terminated prepolymer by reacting so as to satisfy the condition represented by the mathematical formula (1), and a second chain extender (D ) Using a polyamine (C) having two or more amino groups and / or imino groups after the chain extension reaction so as to satisfy the condition represented by the formula (3) using A step of obtaining a water-based polyurethane resin composition by using a mass% aqueous solution, causing a chain extension reaction so as to satisfy the condition represented by the mathematical formula (4) and simultaneously dispersing in water;
It is a method including.

  Although it does not specifically limit as polyisocyanate (A) concerning this invention, The aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate which have two or more isocyanate groups in 1 molecule can be used. . Examples of such polyisocyanate (A) include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate Aliphatic polyisocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and the like. Among these, aliphatic polyisocyanate and alicyclic polyisocyanate are preferable from the viewpoint that the obtained polyurethane resin is non-yellowing, and hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, and 1,3. -Bis (isocyanatomethyl) cyclohexane is particularly preferred. In addition, these polyisocyanates can be used individually by 1 type, or can also be used in combination of 2 or more type.

The polyfunctional compound (B) according to the present invention includes a polyol (B ₁ ) having a sulfone group and / or a sulfonate group, another polyol (B ₂ ), and / or a chain extender (B ₃ ).

The polyol (B ₁ ) having a sulfone group (—SO ₃ H) and / or a sulfonate group (—SO ₃ ^— ) according to the present invention can be obtained from a conventionally known method. For example, (i) dihydroxylsulfone A method of addition polymerization of ethylene oxide and / or propylene oxide to acid, (ii) a method of ring-opening addition polymerization of lactones to dihydroxysulfonic acid, and (iii) dihydroxysulfonic acid and polycarboxylic acids, if necessary. A method of performing a condensation reaction by adding a monohydric alcohol, (iv) a method of transesterifying a dicarboxylic acid having a sulfone group with a polyhydric alcohol, and (v) a method of ring-opening addition polymerization of the transesterified product and a lactone. .

As the dihydroxysulfonic acid used as a raw material for such a polyol (B ₁ ), a known compound can be appropriately used. For example, N, N-bis (2-hydroxyethyl) -2-aminoethylsulfonic acid 1,3-dimethylol-propanesulfonic acid, 1,3-dimethylol-butanesulfonic acid, 1,3-dimethylol-pentanesulfonic acid, 1-methylol-1-hydroxypropanesulfonic acid, 2,3-dihydroxybutanesulfonic acid And salts thereof (alkali metal salts, alkaline earth metal salts, etc.).

  In addition, the dicarboxylic acid having a sulfone group is not particularly limited, and examples thereof include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- [4-sulfophenoxy] isophthalic acid, and salts thereof (alkali Metal salts, alkaline earth metal salts).

  Furthermore, as the lactones used in the ring-opening addition polymerization, known compounds can be used as appropriate, and examples thereof include ε-caprolactone, γ-butyrolactone, and δ-valerolactone.

  In addition, as polycarboxylic acids used in the condensation reaction, known compounds can be used as appropriate, for example, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dimer acid, maleic acid, fumaric acid, etc. Alicyclic dicarboxylic acids such as aliphatic dicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and anhydrides and ester-forming derivatives thereof may be mentioned.

  Furthermore, as polyhydric alcohols that can be used in the condensation reaction and transesterification reaction, known compounds can be used as appropriate, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4- Aliphatic diols such as butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, 3-methyl-1,5-pentanediol Alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; and polyhydric (trivalent or higher) alcohols such as glycerin, trimethylolpropane and pentaerythritol.

In the present invention, the polyol (B ₁ ) having such a sulfone group and / or sulfonate group is dihydroxysulfonic acid and ethylene oxide and / or propylene from the viewpoint of suppressing the hydrolyzability of the resulting aqueous polyurethane resin. It is preferable to use a polyether polyol obtained by addition polymerization of oxide, and a lactone-based polyester polyol obtained by ring-opening addition polymerization of lactones to dihydroxysulfonic acid. In particular, in addition to the hydrolysis resistance of the polyurethane resin, it has better adhesion. In order to achieve this, it is preferable to use the lactone polyester polyol. Incidentally, it is preferable that the number average molecular weight of 300 to 3,000 of such polyols _{(B 1),} and more preferably 500 to 2,000.

The other polyol (B ₂ ) according to the present invention may be any polyol other than the polyol (B ₁ ) having the sulfone group and / or sulfonate group, and is not particularly limited. Examples of such other polyol (B ₂ ) include polyester polyol, polycarbonate polyol, and polyether polyol.

  Examples of such polyester polyols include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, and polybutylene. Sebacate diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene) adipate diol, polycondensate of 1,6-hexanediol and dimer acid, 1,6-hexanediol and adipic acid Examples thereof include a copolycondensate of dimer acid, a polycondensate of nonanediol and dimer acid, and a copolycondensate of ethylene glycol, adipic acid and dimer acid.

  Examples of such a polycarbonate polyol include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, and poly-1,4-cyclohexanedimethylene carbonate diol.

  Further, such polyether polyols include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol homopolymer, block copolymer, random copolymer, ethylene oxide and propylene oxide, ethylene oxide and butylene oxide random copolymer. A polymer and a block copolymer are mentioned. Furthermore, as such a polyether polyol, a polyether ester polyol having an ether bond and an ester bond can also be used.

Incidentally, these other polyols (B ₂₎ may be used singly, or may be used in combination of two or more. Further, it is preferable that the number average molecular weight of these other polyols _{(B 2)} is 500 to 5,000.

Examples of the chain extender (B ₃ ) according to the present invention include compounds having two or more hydrogen atoms that can react with an isocyanate group. Further, as such a chain extender (B ₃ ), it is preferable to use one having a molecular weight of 300 or less. Examples of such a chain extender (B ₃ ) include low ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, sorbitol and the like. Molecular weight polyhydric alcohol; low molecular weight polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine, triethylenetetramine and the like. One of these chain extenders (B ₃ ) can be used alone, or two or more thereof can be used in combination.

Moreover, as such a chain extender (B ₃ ), dihydroxysulfonic acid, 3,4-diaminobutanesulfonic acid exemplified as a raw material of the polyol (B ₁ ) having the sulfone group and / or sulfonate group, It has a sulfone group and / or a sulfonate group such as 6-diamino-2-toluenesulfonic acid, 2,4-diaminobenzenesulfonic acid, N- (2-aminoethyl) -2-aminoethylsulfonic acid and salts thereof. Compound; 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid and these A compound having a carboxyl group and / or a carboxylate group, such as a salt, may also be contacted with the resulting aqueous polyurethane resin composition. It can also be used within a range that does not affect the wearability, open time and hydrolysis resistance.

The polyamine (C) according to the present invention has two or more amino groups and / or imino groups. Such polyamine (C) is not particularly limited. For example, ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, hydrazine, 2-methylpiperazine, isophoronediamine, norbornanediamine, diamino Diamines such as diphenylmethane, tolylenediamine, xylylenediamine; polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, tris (2-aminoethyl) amine; diprimary amines and monocarboxylic acids Amidoamines derived from water-soluble amine derivatives such as monoketimines of diprimary amines; oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide Glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, 1,1'-ethylenehydrazine, 1,1'-trimethylenehydrazine, 1,1 '-(1,4 -Butylene) hydrazine derivatives such as dihydrazine. These polyamines (C) can be used individually by 1 type, or can also be used in combination of 2 or more type.

  As the second chain extender (D) according to the present invention (second aqueous polyurethane resin composition), polyamines similar to those exemplified as the polyamine (C) can be used.

  The first aqueous polyurethane resin composition of the present invention is an isocyanate group-terminated prepolymer obtained by reacting the aforementioned polyisocyanate (A) with the aforementioned polyfunctional compound (B) so as to satisfy specific conditions. The neutralized product is obtained by using a 0.05 to 3.0% by mass aqueous solution of the above-mentioned polyamine (C) and subjecting it to chain extension reaction so as to satisfy specific conditions and simultaneously dispersing it in water.

  In addition, the second aqueous polyurethane resin composition of the present invention has an isocyanate group terminal obtained by reacting the polyfunctional compound (B) with the polyisocyanate (A) so as to satisfy a specific condition. The neutralized prepolymer is subjected to a chain extension reaction using the second chain extender (D) described above so as to satisfy a specific condition, and then 0.05 to 3.0 of the polyamine (C) described above. It can be obtained by using a mass% aqueous solution and subjecting it to chain extension reaction so as to satisfy specific conditions and simultaneously dispersing in water.

In order to produce the first and second aqueous polyurethane resin compositions of the present invention, first, the polyfunctional compound (B) is added to the polyisocyanate (A) in the following formula (1):
100/80 ≦ a / b ≦ 100/50 (1)
To obtain a neutralized isocyanate group-terminated prepolymer. Here, a represents the number of isocyanate groups (NCO) contained in the polyisocyanate (A), and b represents the number of hydroxyl groups (OH) contained in the polyfunctional compound (B). When the value of a / b is less than 100/80, the resulting polyurethane resin has low cohesiveness. Therefore, when used as an adhesive, the open time becomes long, but adhesion, hydrolysis resistance, and heat resistant creep are increased. Durability such as property is reduced. On the other hand, if it exceeds 100/50, the resulting polyurethane resin has high cohesiveness, so that when used as an adhesive, the open time is shortened, and further, the adhesiveness at low temperatures is lowered.

  Furthermore, in the present invention, from the viewpoint of the balance of cohesiveness of the obtained polyurethane resin, the value of a / b is more preferably 100/75 or more and 100/60 or less.

The “isocyanate group-terminated prepolymer neutralized product” according to the present invention is a sulfone group of the polyfunctional compound (B) to be reacted with the polyisocyanate (A), specifically the sulfone group and / or sulfonate. A sulfonate group is obtained by neutralizing a sulfone group derived from a polyol (B ₁ ) having a group or a chain extender (B ₃ ). Further, such a neutralization reaction may be performed before, during or after the production of the prepolymer.

  Furthermore, the neutralizing agent used for the neutralization reaction is not particularly limited, but examples thereof include non-volatile bases such as sodium hydroxide and potassium hydroxide, trimethylamine, triethylamine, dimethylethanolamine, diisopropylaminoethanol, triethanolamine and the like. A volatile base such as ammonia, and these can be used alone or in combination of two or more. As such a neutralizing agent, a non-volatile base such as sodium hydroxide or potassium hydroxide is particularly preferable in order to improve the hydrolysis resistance of the polyurethane resin.

  Further, the method of reacting the polyfunctional compound (B) with the polyisocyanate (A) is not particularly limited. For example, a conventionally known one-stage so-called one-shot method, a multi-stage isocyanate polyaddition reaction method, etc. Can be adopted. Moreover, it is preferable that such reaction temperature is 40-150 degreeC. Furthermore, when performing the reaction, a reaction catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, N-methylmorpholine can be added as necessary. . Such a reaction can also be performed without a solvent, and an organic solvent that does not react with an isocyanate group can be added during or after the reaction. As such an organic solvent, for example, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone and the like can be used.

In order to produce the second aqueous polyurethane resin composition of the present invention, the neutralized isocyanate group-terminated prepolymer obtained as described above is used with the second chain extender (D). The following formula (3):
100/95 ≦ a / (b + d) ≦ 100/80 (3)
The chain extension reaction is carried out so as to satisfy the condition represented by (hereinafter, this chain extension reaction is referred to as “preliminary chain extension reaction”). In Formula (3), a represents the number of isocyanate groups (NCO) contained in the polyisocyanate (A), and b represents the number of hydroxyl groups (OH) contained in the polyfunctional compound (B). D represents the total number of amino groups (NH ₂ ) and imino groups (NH) contained in the second chain extender (D).

  When the value of a / (b + d) is within the above range, durability of the resulting aqueous polyurethane resin composition, particularly heat resistant creep resistance, is further improved. When the value of a / (b + d) is less than 100/95, since the bond (urea bond) with the amino group and / or imino group of the second chain extender (D) increases, an aqueous polyurethane resin composition And the subsequent chain extension reaction and aqueous dispersion with an aqueous solution of polyamine (C) become insufficient. On the other hand, when the value of a / (b + d) exceeds 100/80, further improvement in heat-resistant creep resistance due to the preliminary chain extension reaction is not observed.

  The temperature at which such a preliminary chain extension reaction is performed is preferably in the range of 30 to 60 ° C, and more preferably in the range of 40 to 50 ° C. When the reaction temperature is lower than the lower limit, the reaction proceeds, but the speed is slow and the reaction efficiency tends to deteriorate. On the other hand, when the upper limit is exceeded, the exotherm during the reaction becomes remarkably high, and the control is suppressed. Therefore, industrial production tends to be difficult. Moreover, it is preferable that it is about 10 to 60 minutes, and, as for the time which performs a preliminary | backup chain extension reaction, it is more preferable that it is about 15 to 30 minutes.

  Further, such a preliminary chain extension reaction can be performed without a solvent, but an organic solvent that does not react with an isocyanate group can be added. As such an organic solvent, for example, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, and N-methylpyrrolidone can be used.

In order to produce the second aqueous polyurethane resin composition of the present invention, the neutralized isocyanate group-terminated prepolymer was then subjected to preliminary chain extension reaction as described above, and then the polyamine (C). 0.05-3.0 mass% aqueous solution is used, following numerical formula (4):
100/100 ≦ a / (b + c + d) ≦ 100/97 (4)
A chain extension reaction is performed so as to satisfy the condition represented by

Moreover, in order to manufacture the 1st water-based polyurethane resin composition of this invention, 0.05-3 of the said polyamine (C) is made, without making the said isocyanate group terminal prepolymer neutralized product carry out preliminary chain extension reaction. Using a 0.0 mass% aqueous solution, the following formula (2):
100/100 ≦ a / (b + c) ≦ 100/97 (2)
A chain extension reaction is performed so as to satisfy the condition represented by

In Formulas (2) and (4), a represents the number of isocyanate groups (NCO) contained in the polyisocyanate (A), and b represents a hydroxyl group (N) contained in the polyfunctional compound (B). OH) represents the number of amino groups (NH ₂ ) and imino groups (NH) contained in the polyamine (C), and d represents the amino group contained in the second chain extender (D). This represents the total number of (NH ₂ ) and imino groups (NH).

  In the aqueous polyurethane resin composition of the present invention, the isocyanate group-terminated prepolymer neutralized product is subjected to a preliminary chain extension reaction, if necessary, and then a specific amount of polyamine (satisfying the condition represented by the above formula) ( It is necessary to carry out a chain extension reaction and simultaneously disperse in water using an aqueous polyamine solution containing C) and prepared to a specific concentration, that is, 0.05 to 3.0% by mass. This makes it possible to obtain a laminate having a long open time when used as an adhesive, good adhesion in a wide temperature range, and excellent durability such as adhesion strength, hydrolysis resistance and heat creep resistance. It becomes possible.

  The isocyanate group-terminated prepolymer neutralized product is subjected to a preliminary chain extension reaction as necessary, and then the a / (b + c) or a / (b + c + d) value is 100/100 using only the polyamine (C). When it is attempted to disperse in water after a chain extension reaction of ˜100 / 97, the viscosity of the reaction product increases instantaneously after the addition of polyamine (C) and eventually solidifies. It is difficult to use as.

  Further, the neutralized product of the isocyanate group-terminated prepolymer was subjected to a preliminary chain extension reaction as necessary, and then dispersed (emulsified) in water, and then subjected to a chain extension reaction with the polyamine (C). In such a case, when the water is dispersed, the free isocyanate group of the neutralized isocyanate group-terminated prepolymer reacts with water as a solvent, and the chain elongation reaction is not efficiently performed. Therefore, although the open time of the obtained water-based polyurethane resin composition becomes long, durability, such as adhesiveness, hydrolysis resistance, and heat-resistant creep resistance, will be remarkably inferior. In addition, when the disappearance of free isocyanate groups during water dispersion is significant, the amino group and / or imino group contained in the polyamine (C) may not sufficiently react and remain in the system, resulting in an aqueous solution obtained. There are also concerns about the problems of thermal discoloration and photodiscoloration of the polyurethane resin composition, and problems of lowering durability such as hydrolysis resistance and heat resistance creep resistance.

  In the present invention, when the value of a / (b + c) or a / (b + c + d) is less than 100/100, there is no effect on open time, adhesiveness, and heat-resistant creep property, but unreacted polyamine (C) is in the system. In the water-based polyurethane resin composition thus obtained, problems such as thermal discoloration and photodiscoloration and a decrease in hydrolysis resistance are likely to occur. On the other hand, when the value of a / (b + c) or a / (b + c + d) exceeds 100/97, the remaining free isocyanate groups react excessively with water as a solvent, so that high molecular weight cannot be achieved efficiently. Although the open time becomes long, durability such as adhesiveness, hydrolysis resistance, and heat-resistant creep resistance of the obtained laminate is insufficient. Furthermore, in the present invention, from the viewpoint of a balance between open time, adhesiveness and durability when used as an adhesive, the value of a / (b + c) or a / (b + c + d) is 100/100 or more and 100 / 99 or less is more preferable.

  In the present invention, as described above, the polyamine concentration of the aqueous polyamine solution for allowing the isocyanate group-terminated prepolymer neutralized product to undergo a chain extension reaction and simultaneously disperse in water is 0.05 to 3.0% by mass. When the polyamine concentration is less than 0.05% by mass, the amount of water as a solvent increases, and free isocyanate groups disappear due to the reaction with water before reacting with the polyamine. Therefore, although the open time of the obtained water-based polyurethane resin composition becomes long, durability, such as the adhesiveness of the obtained laminated body, hydrolysis resistance, and heat-resistant creep resistance, falls. On the other hand, when the polyamine concentration exceeds 3.0% by mass, the chain elongation reaction by the polyamine (C) proceeds instantaneously and the viscosity in the system increases, so that water dispersion cannot be stably performed. In addition, in this invention, it is more preferable to use the polyamine aqueous solution which prepared polyamine density | concentration to 0.1-1.5 mass% in the quantity which satisfy | fills said Numerical formula (2) or (4).

  There is no particular limitation on the method of causing the isocyanate group-terminated prepolymer neutralized product to undergo chain extension reaction and simultaneously dispersing in water. (I) The polyamine aqueous solution is added to the isocyanate group-terminated prepolymer neutralized product in a lump. (Ii) a method in which the polyamine aqueous solution is dividedly added to the neutralized isocyanate group-terminated prepolymer; (iii) a method in which the polyamine aqueous solution is dropped into the neutralized isocyanate group-terminated prepolymer; iv) Any of the methods of dropping the neutralized isocyanate group-terminated prepolymer into the polyamine aqueous solution can be employed.

  The reaction temperature at which the chain extension reaction and the water dispersion step are performed is preferably in the range of 20 to 80 ° C, and more preferably in the range of 40 to 60 ° C. When the reaction temperature is less than 20 ° C., the viscosity of the isocyanate group-terminated prepolymer neutralized product becomes high. Therefore, it takes time from the addition of the polyamine aqueous solution to homogenization, and stable water dispersion and chain extension reaction are performed. It tends to be difficult. On the other hand, if the reaction temperature exceeds 80 ° C., the free isocyanate group may disappear with water before reacting with the polyamine. As a result, the open time becomes longer, but the adhesion of the resulting laminate is increased. In addition, durability such as hydrolysis resistance and heat resistance creep resistance tends to decrease.

  In addition, the chain extension reaction and the water dispersion step can be performed without a solvent, but the isocyanate group-terminated prepolymer neutralized product and the polyamine aqueous solution are efficiently uniformized within a range not impairing the effects of the present invention. For this purpose, a water-soluble organic solvent can be mixed in advance with the polyamine aqueous solution. As such an organic solvent, for example, methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, dimethylformamide, and N-methylpyrrolidone can be used. Moreover, after carrying out water dispersion simultaneously with chain | strand extension reaction, water can also be added and redispersed.

  The method of causing the isocyanate group-terminated prepolymer neutralized product to undergo chain extension reaction and water dispersion using the polyamine aqueous solution is not particularly limited, but can be dispersed using, for example, a homomixer, a homogenizer, a disper, or the like. .

  Furthermore, it is preferable to carry out such a chain extension reaction and water dispersion step until the free isocyanate group of the isocyanate group-terminated prepolymer neutralized product is 0.3% by mass or less based on the polyurethane resin. It is more preferable to carry out until it becomes mass% or less. If the free isocyanate group is left over 0.3% by mass, the high molecular weight by the chain extension reaction becomes insufficient, resulting in insufficient adhesion, and durability such as heat-resistant creep resistance and hydrolysis resistance. Tend to be insufficient.

  In the aqueous polyurethane resin composition of the present invention, the sulfone group and / or sulfonate group-containing polyurethane resin obtained by the chain extension reaction has a content of sulfone group and sulfonate group of 0. 0 relative to the mass of the polyurethane resin. It is preferable that it is 3-3.0 mass%, and it is more preferable that it is 0.5-2.0 mass%. If the content is less than 0.3% by mass, the dispersion stability in water tends to be insufficient, and the stability of quality may be affected. On the other hand, when the content exceeds 3.0% by mass, the open time when the resulting aqueous polyurethane resin composition is used as an adhesive tends to be short, and adhesion at low temperatures and water resistance are reduced. Durability such as decomposability and heat-resistant creep tends to decrease.

  When an organic solvent is used in producing the aqueous polyurethane resin composition of the present invention, it is preferable to remove the organic solvent by, for example, a method such as vacuum distillation after being dispersed in water. When removing the organic solvent, a surfactant such as a higher fatty acid salt, a resin acid salt, a long-chain fatty alcohol sulfate ester salt, a higher alkyl sulfonate, an alkyl aryl sulfonic acid is used as necessary to maintain the emulsified form. Anionic surfactants such as salts, sulfonated castor oil and sulfosuccinic acid esters; nonionic surfactants such as long-chain fatty alcohols or ethylene oxide adducts of phenols can be used.

  The aqueous polyurethane resin composition of the present invention contains as little or no organic solvent as possible. Therefore, even when the aqueous polyurethane resin composition of the present invention contains an organic solvent, the content of the organic solvent is preferably 0.5% by mass or less based on the mass of the aqueous polyurethane resin composition. More preferably, it is 0.1 mass% or less.

  The aqueous polyurethane resin composition obtained as described above can be used for various uses such as adhesives, pressure-sensitive adhesives, coating primer agents, coating anchor agents, and the like, and in particular, a one-component type for producing a laminate. It can be suitably used as an adhesive.

  In addition, the aqueous polyurethane resin composition of the present invention can be used as it is for each application such as a one-component adhesive, but if necessary, the following known additive components conventionally used can be added to the present invention. You may use together in the range which does not affect the effect of invention.

  For example, in order to improve the durability of the resulting adhesive layer, a conventionally known crosslinking agent may be used in combination as necessary. Examples of such crosslinking agents include polyepoxy crosslinking agents, water-dispersed carbodiimide crosslinking agents, water-soluble oxazoline crosslinking agents, and water-dispersed polyisocyanate crosslinking agents. Among these, heat-resistant creep resistance And a polyepoxy crosslinking agent and a water-dispersed polyisocyanate crosslinking agent are preferable from the viewpoint of improving hydrolysis resistance, and a polyepoxy crosslinking agent is preferable from the viewpoint of pot life.

  Examples of such polyepoxy-based crosslinking agents include resorcin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and adipic acid diacid. Diepoxy compounds such as glycidyl ester and o-phthalic acid diglycidyl ester; sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc. Trivalent or higher epoxy compounds; epoxy cresol novolac resin, modified bisphenol A Epoxy resin. Among these, from the viewpoint that durability such as hydrolysis resistance can be remarkably improved without impairing the open time and adhesiveness of the obtained aqueous polyurethane resin composition, a trivalent or higher epoxy compound is preferably used. In particular, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether are preferable. In order to enhance the reaction activity of these polyepoxy crosslinking agents, various known amine catalysts such as triethylenediamine, tetramethylethylenediamine, pyridine and hexamethylenetetramine can be used in combination.

  Such a cross-linking agent mixing method comprises: (i) a method in which a cross-linking agent is added to the neutralized isocyanate group-terminated prepolymer and then dispersed in water with the polyamine aqueous solution simultaneously with a chain extension reaction; (ii) the isocyanate group Any method of adding a crosslinking agent after the terminal prepolymer neutralized product is water-dispersed simultaneously with the chain extension reaction with the polyamine aqueous solution may be used.

  In addition, in order to improve the processing suitability and adhesiveness of a one-part adhesive, thickeners such as associative thickeners and polycarboxylic acid thickeners as necessary; fluorine-based and acetylene glycol-based Various surfactants; anti-repellent agents for solvents such as n-methylpyrrolidone and propylene glycol monomethyl ether acetate; tackifiers such as rosin resins, rosin ester resins, terpene resins, terpene phenol resins, coumarone resins; antioxidants; Various stabilizers such as a light-resistant stabilizer and an ultraviolet absorber; antifoaming agents such as mineral oils and silicones, plasticizers; and colorants such as pigments may be added.

  Further, other aqueous dispersions, for example, emulsions of vinyl acetate, ethylene vinyl acetate, acrylic, acrylic styrene, etc .; styrene / butadiene, acrylonitrile / butadiene, acrylic, as long as the effects of the present invention are not impaired. -Latex such as butadiene; ionomer such as polyethylene and polyolefin; polyurethane, polyester, polyamide, epoxy resin and the like may be mixed.

  Next, the one-component adhesive and laminate of the present invention will be described. That is, the one-component adhesive of the present invention contains the above-described aqueous polyurethane resin composition of the present invention. In addition, by laminating various substrates using the one-component adhesive of the present invention, it is possible to produce the laminate of the present invention having excellent durability such as adhesive strength, heat-resistant creep resistance, and hydrolysis resistance. it can.

  The one-part adhesive of the present invention may be composed of only the aqueous polyurethane resin composition of the present invention described above, but contains the above-mentioned known additive components that have been conventionally used as necessary. Also good. When such an additive component is contained, the content of the aqueous polyurethane resin composition is preferably about 90% by mass or more, and about 90 to 99% by mass with respect to the mass of the one-component adhesive. Is more preferable.

  Although it does not restrict | limit especially as a kind of laminated body of this invention, For example, a plate-shaped laminated body, a sheet-like laminated body, and a leather-like laminated body can be provided. The substrate of the laminate is not particularly limited, but has a thickness such as metal, synthetic rubber, wood or glass; polyvinyl chloride or polyolefin plastic film, metal foil, paper, metal foil coated with plastic film, Film-like materials such as paper, plastic films deposited by aluminum or silica; resin layers made of known synthetic leather raw materials such as polyurethane resins, and base materials for leather-like laminates such as various woven fabrics, knitted fabrics, and nonwoven fabrics It is done.

The one-component adhesive of the present invention can be used by being applied to at least one of the substrates to be bonded together, and the coating amount is 10 to 300 g / m ^{2 in} mass per unit area of the polyurethane resin. The amount is preferably 50 to 150 g / m ² . If the coating amount is less than 10 g / m ² , the adhesive strength of the resulting laminate tends to decrease. On the other hand, if it exceeds 300 g / m ² , the drying time (water evaporation time) of the adhesive becomes longer, which is economically preferable. Absent.

  In addition, as a method of applying such a one-component adhesive, a conventionally known method can be appropriately employed. For example, coating such as roll coating, gravure coating, knife coating, reverse coating, kiss coating, etc .; spray And a method using a brush or the like.

  Further, the method of laminating the substrates using the one-component adhesive of the present invention is not particularly limited, and any of wet lamination method and dry lamination method may be used. In view of the above, the dry lamination method is more preferable.

  In such a wet laminating method, after applying an adhesive to a substrate, the other substrate is bonded. In the dry laminating method, an adhesive is applied to a substrate and then dried, and the other substrate is bonded. The drying conditions are not particularly limited, but for example, a time of 20 minutes or less at a temperature of 30 to 150 ° C. by a conventionally known dryer such as a hot air dryer, an infrared irradiation dryer, a microwave irradiation dryer, or a wet heat dryer. It is preferable to dry with.

Moreover, when bonding a base material, thermocompression bonding can be performed as needed. The thermocompression bonding conditions are preferably a pressure bonding temperature of room temperature to 150 ° C., a pressure bonding time of 20 minutes or less, and a pressure bonding pressure of 0.1 to 400 kg / cm ² . Further, the substrate may be bonded while thermocompression bonding, or may be thermocompression bonded after bonding the substrate.

  The laminate of the present invention thus obtained is used for interior materials for vehicles such as automobiles, daily necessaries such as shoes and wallets, furniture such as chairs and textile products such as clothing, building materials, vacuum It is applied to various uses such as molded products and packaging materials.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. The open time, adhesiveness, normal adhesiveness, hydrolysis resistance, and heat resistant creep resistance of the adhesive were evaluated or measured by the following methods.

(I) Open time of adhesive The adhesive is applied to a soft polyvinyl chloride film (Takafuji Kasei Co., Ltd., “Tough Neal SG482-2”, width 50 mm × length 100 mm × thickness 2 mm) using a brush. It apply | coated so that the mass per unit area might be 100 g / m < ² >, and it put into the hot-air dryer for 5 minutes at 60 degreeC, and made it the test piece. Immediately after drying, the sample is allowed to stand at 20 ° C., and the adhesive layers of the test pieces are bonded to each other every one minute, and then bonded with a hot press machine at 30 ° C. for 10 seconds under the condition of 40 N / cm ² until no adhesion occurs. Was measured. It means that the longer the time from drying to no adhesion, the longer the open time.

(Ii) Adhesive The adhesive is applied to a soft polyvinyl chloride film (Takafuji Kasei Co., Ltd., “Tough Neel SG482-2”, width 50 mm × length 100 mm × thickness 2 mm) using a brush per unit area of polyurethane resin. The mass was applied to 100 g / m ² and dried in a hot air dryer at 60 ° C. for 5 minutes. After drying and standing at 20 ° C. and curing for 1 minute, the adhesive layer surfaces were bonded together, and pressure bonded for 10 seconds at a temperature of 40, 60, and 80 ° C. under a pressure condition of 40 N / cm ² , respectively. A laminate was obtained.

  The obtained laminate was adjusted to a size of 20 mm wide × 100 mm long, and the strength of 180 degree peeling was measured with an autograph (AUTO GRAPH AG-IS, manufactured by Shimadzu Corporation) at a pulling speed of 100 mm / min. .

  Higher peel strength means better adhesion. In particular, the higher the peel strength of the laminate obtained when the temperature during hot pressing is lower, the better the low-temperature adhesiveness.

(Iii) Normal adhesive The unit area of the polyurethane resin on the soft polyvinyl chloride film (Takafuji Kasei Co., Ltd., “Tough Neal SG482-2”, width 50 mm × length 100 mm × thickness 2 mm) using a brush. It apply | coated so that the mass per hit might be 100 g / m < ² >, It put into the hot air dryer for 5 minutes at 60 degreeC, and was dried. Immediately after drying, the adhesive layers are bonded to each other, pressure bonded for 10 seconds at a temperature of 60 ° C. and a pressure of 40 N / cm ² with a hot press machine, and then cured for one day at a temperature of 20 ° C. and a humidity of 65% RH. Got the body.

  The obtained laminate was adjusted to a size of 20 mm wide × 100 mm long, and the strength of 180 degree peeling was measured with an autograph (AUTO GRAPH AG-IS, manufactured by Shimadzu Corporation) at a pulling speed of 100 mm / min. .

(Iv) Hydrolysis resistance A laminate of a soft polyvinyl chloride film was obtained in the same manner as in the above (iii) evaluation method for normal adhesion. This laminate was cut into a size of 20 mm wide × 100 mm long to obtain a test piece.

  The strength of 180 ° peeling was measured for the obtained test piece with an autograph (AUTO GRAPH AG-IS, manufactured by Shimadzu Corp.) at a pulling rate of 100 mm / min, and the strength was defined as initial adhesive strength. Moreover, after putting the said test piece into the thermo-hygrostat (Platinus PR-1SP, the product made by Tabai Espec Co., Ltd.) adjusted to a temperature of 70 ° C. and a humidity of 95% RH, and left for 1 week and 2 weeks, respectively, Cured for 1 day at ℃ and humidity of 65% RH, measured with 180 degree peeling strength at 100mm / min with autograph (AUTO GRAPH AG-IS, manufactured by Shimadzu Corporation) It was set as the later adhesive strength.

And the adhesive strength retention was computed based on following formula (5) from the initial stage adhesive strength obtained in this way, and the adhesive strength after a hydrolysis test. The higher the adhesive strength retention, the better the hydrolysis resistance.
Adhesive strength retention rate (%)
= {(Adhesive strength after hydrolyzability test) / (Initial adhesive strength)} × 100 (5).

Adhesive strength retention (%) = (Adhesive strength after hydrolyzability test) × 100 / (initial adhesive strength)
(V) Heat resistance creep resistance It evaluated according to the method described in the peeling test piece of JISK6833 (1994) 8.2.2. That is, the adhesive was applied to a soft polyvinyl chloride film (Takafuji Kasei Co., Ltd., “Tough Neal SG482-2”) using a brush so that the mass per unit area of the polyurethane resin was 100 g / m ² , It put into the hot-air dryer for 5 minutes at 60 degreeC, and was dried. Immediately after drying, the adhesive layers are bonded to each other, pressure bonded for 10 seconds at a temperature of 60 ° C. and a pressure of 40 N / cm ² with a hot press machine, and then cured for one day at a temperature of 20 ° C. and a humidity of 65% RH. Got the body.

  The obtained laminate was cut into a size of 20 mm wide × 150 mm long, suspended by a weight of 1 kg, and placed in a hot air dryer under an atmosphere of 70 ° C. After 30 minutes, the distance at which the laminate was peeled off Was measured. The smaller the peeled distance, the better the heat resistant creep resistance.

(Adjustment Example 1: Production of lactone-based polyester polyol having a sulfonate group)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, under a nitrogen stream, 302 g of dimethyl 5-sulfosodium isophthalate, 180 g of 1,4-butanediol and dibutyltin oxide as a catalyst Was transesterified at a reaction temperature of 190 to 200 ° C. until the acid value became 1 mgKOH / g or less for about 4 hours. Next, after cooling to 100 ° C., 518 g of ε-caprolactone was charged and reacted at a reaction temperature of 160 ° C. for about 8 hours to obtain a lactone polyester polyol having a sulfonate group. The obtained polyester polyol had a hydroxyl value of 104.5 mgKOH / g and an acid value of 0.5 mgKOH / g.

(Adjustment Example 2: Production of a lactone-based polyester polyol having a carboxyl group)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 148 g of 2,2-dimethylolbutanoic acid, 852 g of ε-caprolactone and dibutyltin oxide as a catalyst were added in an amount of 0. 02 g was charged and reacted at a reaction temperature of 160 ° C. for about 7 hours to obtain a lactone polyester polyol having a carboxyl group. The obtained polyester polyol had a hydroxyl value of 112.2 mgKOH / g and an acid value of 55.7 mgKOH / g.

<Production of aqueous polyurethane resin composition>
Example 1
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 306.6 g of polybutylene adipate diol (number average molecular weight 2000) and the sulfonate group obtained in Preparation Example 1 were added under a nitrogen stream. After adding 43.0 g of polyester polyol and 44.0 g of acetone and mixing them uniformly, 46.4 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. It was made to react for time, and the acetone solution of the isocyanate group terminal prepolymer neutralized material whose content of free isocyanate group is 1.6 mass% with respect to solid content was obtained. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product is cooled to 50 ° C., 220.0 g of acetone is added and mixed uniformly, and then an aqueous polyamine solution in which 5.0 g of ethylenediamine and 601.5 g of ion-exchanged water are mixed. (Polyamine concentration 0.82% by mass) was gradually added dropwise at 40 to 50 ° C., and water dispersion was performed simultaneously with the chain extension reaction. Here, the value of a / (b + c) was 100/100.

  Next, after aging this reaction solution for about 2 hours, the solvent was removed under reduced pressure at 30 ° C. for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 1.0% by mass. The obtained composition was a very stable emulsion without separation and sedimentation with time.

(Example 2)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 296.8 g of polybutylene adipate diol (number average molecular weight 2000) under a nitrogen stream was added to the sulfonate group obtained in Preparation Example 1. 41.8 g of polyester polyol having, 1.3 g of 1,4-butanediol and 44.0 g of acetone were added and mixed uniformly, then 32.0 g of isophorone diisocyanate and 24.2 g of hexamethylene diisocyanate were added, and then dibutyltin dilaurate 0.1 g was added, the temperature was raised to 80 ° C., and the mixture was reacted for about 7 hours, and the isocyanate group-terminated prepolymer neutralized product having a free isocyanate group content of 1.7% by mass relative to the solid content A solution was obtained. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product is cooled to 50 ° C., 220.0 g of acetone is added and mixed uniformly, and then an aqueous polyamine solution in which 5.2 g of ethylenediamine and 601.8 g of ion-exchanged water are mixed ( Polyamine concentration 0.85% by mass) was gradually added dropwise at 40 to 50 ° C., and water dispersion was performed simultaneously with the chain extension reaction. Here, the value of a / (b + c) was 100/100.

  Next, after aging this reaction solution for about 2 hours, the solvent was removed under reduced pressure at 30 ° C. for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 1.0% by mass. The obtained composition was a very stable emulsion without separation and sedimentation with time.

(Example 3)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 296.6 g of polybutylene adipate diol (number average molecular weight 2000) under a nitrogen stream, and the sulfonate group obtained in Preparation Example 1 were added. 42.1 g of polyester polyol and 44.0 g of acetone were added and mixed uniformly, then 57.3 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, the temperature was raised to 80 ° C., and about 4 It was made to react for time, and the acetone solution of the isocyanate group terminal prepolymer neutralized product whose content of a free isocyanate group is 2.9 mass% with respect to solid content was obtained. In addition, the value of a / b at the time of prepolymer manufacture was 100/55.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product was cooled to 50 ° C., 220.0 g of acetone was added and mixed uniformly, and then an aqueous polyamine solution in which 9.2 g of ethylenediamine and 1074.0 g of ion-exchanged water were mixed ( Polyamine concentration 0.85% by mass) was gradually added dropwise at 40 to 50 ° C., and water dispersion was performed simultaneously with the chain extension reaction. Here, the value of a / (b + c) was 100/100.

  Next, this reaction solution was aged for about 2 hours, and then desolvated and dehydrated at 30 ° C. under reduced pressure for about 5 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 1.0% by mass. The obtained composition was a very stable emulsion without separation and sedimentation with time.

Example 4
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 309.1 g of polybutylene adipatediol (number average molecular weight 2000) and the sulfonate group obtained in Preparation Example 1 were added under a nitrogen stream. 43.2 g of polyester polyol and 44.0 g of acetone were added and mixed uniformly, then 43.6 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. The reaction was carried out for a time to obtain an acetone solution of a neutralized isocyanate group-terminated prepolymer having a free isocyanate group content of 1.2% by mass based on the solid content. In addition, the value of a / b at the time of prepolymer manufacture was 100/75.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product was cooled to 50 ° C., 220.0 g of acetone was added and mixed uniformly, and then an aqueous polyamine solution in which 3.9 g of ethylenediamine and 599.9 g of ion-exchanged water were mixed ( Polyamine concentration 0.65% by mass) was gradually added dropwise at 40 to 50 ° C., and water dispersion was performed simultaneously with the chain extension reaction. Here, the value of a / (b + c) was 100/100.

  Next, after aging this reaction solution for about 2 hours, the solvent was removed under reduced pressure at 30 ° C. for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 1.0% by mass. The obtained composition was a very stable emulsion without separation and sedimentation with time.

(Example 5)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 306.6 g of polybutylene adipate diol (number average molecular weight 2000) and the sulfonate group obtained in Preparation Example 1 were added under a nitrogen stream. After adding 43.0 g of polyester polyol and 44.0 g of acetone and mixing them uniformly, 46.4 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. It was made to react for time, and the acetone solution of the isocyanate group terminal prepolymer neutralized material whose content of free isocyanate group is 1.6 mass% with respect to solid content was obtained. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product is cooled to 50 ° C., 220.0 g of acetone is added and mixed uniformly, and then an aqueous polyamine solution in which 4.5 g of ethylenediamine and 600.7 g of ion-exchanged water are mixed ( Polyamine concentration 0.74% by mass) was gradually added dropwise at 40 to 50 ° C., and water dispersion was performed simultaneously with the chain extension reaction. Here, the value of a / (b + c) was 100/97.

  Next, after aging this reaction solution for about 2 hours, the solvent was removed under reduced pressure at 30 ° C. for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 1.0% by mass. The obtained composition was a very stable emulsion without separation and sedimentation with time.

(Example 6)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 238.9 g of polybutylene adipate diol (number average molecular weight 2000) was added to the sulfonate group obtained in Preparation Example 1 under a nitrogen stream. After adding 105.0 g of polyester polyol and 44.0 g of acetone and mixing uniformly, 52.1 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. It was made to react for time, and the acetone solution of the isocyanate group terminal prepolymer neutralized product whose content of a free isocyanate group is 1.8 mass% with respect to solid content was obtained. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product is cooled to 50 ° C., 220.0 g of acetone is added and mixed uniformly, and then an aqueous polyamine solution in which 5.6 g of ethylenediamine and 602.4 g of ion-exchanged water are mixed ( Polyamine concentration 0.92% by mass) was gradually added dropwise at 40 to 50 ° C., and water dispersion was performed simultaneously with the chain extension reaction. Here, the value of a / (b + c) was 100/100.

  Next, after aging this reaction solution for about 2 hours, the solvent was removed under reduced pressure at 30 ° C. for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 2.5% by mass. The obtained composition was a very stable emulsion without separation and sedimentation with time.

(Example 7)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 330.3 g of polybutylene adipate diol (number average molecular weight 2000) under a nitrogen stream, and the sulfonate group obtained in Preparation Example 1 were added. After adding 21.3 g of polyester polyol and 44.0 g of acetone and mixing them uniformly, 44.4 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. It was made to react for time, and the acetone solution of the isocyanate group terminal prepolymer neutralized product whose content of a free isocyanate group is 1.5 mass% with respect to solid content was obtained. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product is cooled to 50 ° C., 220.0 g of acetone is added and mixed uniformly, and then an aqueous polyamine solution in which 4.8 g of ethylenediamine and 601.1 g of ion-exchanged water are mixed ( Polyamine concentration 0.79% by mass) was gradually added dropwise at 40 to 50 ° C., and water dispersion was performed simultaneously with the chain extension reaction. Here, the value of a / (b + c) was 100/100.

  Next, after aging this reaction solution for about 2 hours, the solvent was removed under reduced pressure at 30 ° C. for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 0.5% by mass. The obtained composition was a very stable emulsion without separation and sedimentation with time.

(Example 8)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 306.6 g of polybutylene adipate diol (number average molecular weight 2000) and the sulfonate group obtained in Preparation Example 1 were added under a nitrogen stream. After adding 43.0 g of polyester polyol and 44.0 g of acetone and mixing them uniformly, 46.4 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. The reaction was carried out for a time to obtain an acetone solution of a neutralized isocyanate group-terminated prepolymer having a free isocyanate group content of 1.6% by weight based on the solid content. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of this isocyanate group-terminated prepolymer neutralized product was cooled to 50 ° C., 220.0 g of acetone was added and mixed uniformly, and then an aqueous polyamine solution in which 5.0 g of ethylenediamine and 160.7 g of ion-exchanged water were mixed ( A polyamine concentration of 3.00% by mass) was gradually added dropwise at 40 to 50 ° C. to homogenize, and 440.8 g of ion-exchanged water was gradually added dropwise to carry out water dispersion simultaneously with the chain extension reaction. Here, the value of a / (b + c) was 100/100.

  Next, the reaction solution was aged for about 2 hours, and then the solvent was removed under reduced pressure at 30 ° C. for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 1.0% by mass. The obtained composition was a very stable emulsion without separation and sedimentation with time.

Example 9
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 306.6 g of polybutylene adipate diol (number average molecular weight 2000) and the sulfonate group obtained in Preparation Example 1 were added under a nitrogen stream. After adding 43.0 g of polyester polyol and 44.0 g of acetone and mixing them uniformly, 46.4 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. It was made to react for time, and the acetone solution of the isocyanate group terminal prepolymer neutralized material whose content of free isocyanate group is 1.6 mass% with respect to solid content was obtained. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product is cooled to 50 ° C., and 220.0 g of acetone and 20.0 g of sorbitol polyglycidyl ether (“Denacol EX-614B”, manufactured by Nagase ChemteX Corporation) are added uniformly. Then, a polyamine aqueous solution (polyamine concentration 0.82% by mass) in which 5.0 g of ethylenediamine and 601.5 g of ion-exchanged water are mixed is gradually added dropwise at 40 to 50 ° C. Dispersion was performed. Here, the value of a / (b + c) was 100/100.

  Next, after aging the reaction solution for about 2 hours, the solvent was removed at 30 ° C. under reduced pressure for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 1.0% by mass. Moreover, the compounding quantity of the said sorbitol polyglycidyl ether was 5.0 mass parts with respect to 100 mass parts of said polyurethane resins. The resulting composition was a very stable emulsion without separation and sedimentation over time.

(Example 10)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 306.6 g of polybutylene adipate diol (number average molecular weight 2000) and the sulfonate group obtained in Preparation Example 1 were added under a nitrogen stream. After adding 43.0 g of polyester polyol and 44.0 g of acetone and mixing them uniformly, 46.4 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. It was made to react for time, and the acetone solution of the isocyanate group terminal prepolymer neutralized material whose content of free isocyanate group is 1.6 mass% with respect to solid content was obtained. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product is cooled to 50 ° C., 220.0 g of acetone is uniformly mixed, 3.3 g of ethylenediamine is added, and the reaction is extended at 40-50 ° C. for about 1 hour. (Preliminary chain extension reaction). Here, the value of a / (b + d) was 100/90.

  Next, 20.0 g of sorbitol polyglycidyl ether (“Denacol EX-614B”, manufactured by Nagase ChemteX Corporation) was added to this reaction solution and mixed uniformly, and then 1.7 g of ethylenediamine and 601.5 g of ion-exchanged water were used. A polyamine aqueous solution (polyamine concentration of 0.28% by mass) was gradually added dropwise at 40 to 50 ° C., and water dispersion was performed simultaneously with the chain extension reaction. Here, the value of a / (b + c + d) was 100/100.

  Next, after aging this reaction solution for about 2 hours, the solvent was removed under reduced pressure at 30 ° C. for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 1.0% by mass. Moreover, the compounding quantity of the said sorbitol polyglycidyl ether was 5.0 mass parts with respect to 100 mass parts of said polyurethane resins. The resulting composition was a very stable emulsion without separation and sedimentation over time.

(Comparative Example 1)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 306.6 g of polybutylene adipate diol (number average molecular weight 2000) and the sulfonate group obtained in Preparation Example 1 were added under a nitrogen stream. After adding 43.0 g of polyester polyol and 44.0 g of acetone and mixing them uniformly, 46.4 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. It was made to react for time, and the acetone solution of the isocyanate group terminal prepolymer neutralized material whose content of free isocyanate group is 1.6 mass% with respect to solid content was obtained. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product is cooled to 50 ° C., 220.0 g of acetone is added and mixed uniformly, and further cooled to 30 ° C. or less, and 601.5 g of ion-exchanged water is added. The solution was gradually added dropwise and dispersed in water. After water dispersion, 5.0 g of ethylenediamine was added, and a chain extension reaction was performed for about 2 hours. Here, the value of a / (b + c) was 100/100.

  Next, the solvent was removed from the reaction solution under reduced pressure at 30 ° C. for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 1.0% by mass. The obtained composition was a very stable emulsion without separation and sedimentation with time.

(Comparative Example 2)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 306.6 g of polybutylene adipate diol (number average molecular weight 2000) and the sulfonate group obtained in Preparation Example 1 were added under a nitrogen stream. After adding 43.0 g of polyester polyol and 44.0 g of acetone and mixing them uniformly, 46.4 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. It was made to react for time, and the acetone solution of the isocyanate group terminal prepolymer neutralized material whose content of free isocyanate group is 1.6 mass% with respect to solid content was obtained. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product was cooled to 50 ° C., and 220.0 g of acetone was added and mixed uniformly. Then, 5.0 g of ethylenediamine was added, and the viscosity immediately increased and the reaction started. Solidified in 3 minutes. The solidified product could not be dispersed in water and was abandoned. Here, the value of a / (b + c) was 100/100.

(Comparative Example 3)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 306.6 g of polybutylene adipate diol (number average molecular weight 2000) and the sulfonate group obtained in Preparation Example 1 were added under a nitrogen stream. After adding 43.0 g of polyester polyol and 44.0 g of acetone and mixing them uniformly, 46.4 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. It was made to react for time, and the acetone solution of the isocyanate group terminal prepolymer neutralized material whose content of free isocyanate group is 1.6 mass% with respect to solid content was obtained. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product is cooled to 50 ° C., 220.0 g of acetone is added and mixed uniformly, and then 594.0 g of ion-exchanged water is gradually added dropwise, and the mixture is dispersed while being dispersed in water. Water extension reaction was performed for 2 hours.

  Next, the solvent was removed from the reaction solution under reduced pressure at 30 ° C. for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 1.0% by mass. The obtained composition was a very stable emulsion without separation and sedimentation with time.

(Comparative Example 4)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 256.2 g of polybutylene adipate diol (number average molecular weight 2000) was added to the carboxyl group obtained in Preparation Example 2 under a nitrogen stream. 88.0 g of polyester polyol and 44.0 g of acetone were added and mixed uniformly, then 51.9 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. An acetone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 1.8% by mass with respect to the solid content was obtained by reacting for a period of time. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product is cooled to 50 ° C., 220.0 g of acetone and 8.9 g of triethylamine are added and mixed uniformly, and further cooled to 30 ° C. or less to perform ion exchange. 602.3 g of water was gradually added dropwise and dispersed in water. After water dispersion, 5.6 g of ethylenediamine was added to the reaction solution, and a chain extension reaction was performed for about 2 hours. Here, the value of a / (b + c) was 100/100.

  Next, the reaction solution was desolvated for about 2 hours at 30 ° C. under reduced pressure to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of carboxyl groups and carboxylate groups in the polyurethane resin was 1.0% by mass. The obtained composition was a very stable emulsion without separation and sedimentation with time.

(Comparative Example 5)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 256.2 g of polybutylene adipate diol (number average molecular weight 2000) was added to the carboxyl group obtained in Preparation Example 2 under a nitrogen stream. 88.0 g of polyester polyol and 44.0 g of acetone were added and mixed uniformly, then 51.9 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. An acetone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 1.8% by mass with respect to the solid content was obtained by reacting for a period of time. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product was cooled to 50 ° C., 220.0 g of acetone and 8.9 g of triethylamine were uniformly mixed, and then 5.6 g of ethylenediamine and 602.3 g of ion-exchanged water were mixed. A polyamine aqueous solution (polyamine concentration 0.91% by mass) was gradually added dropwise at 40 to 50 ° C., and water dispersion was performed simultaneously with the chain extension reaction. Here, the value of a / (b + c) was 100/100.

  Next, after aging this reaction solution for about 2 hours, the solvent was removed under reduced pressure at 30 ° C. for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of carboxyl groups and carboxylate groups in the polyurethane resin was 1.0% by mass. The obtained composition was a very stable emulsion without separation and sedimentation with time.

(Comparative Example 6)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 256.2 g of polybutylene adipate diol (number average molecular weight 2000) was added to the carboxyl group obtained in Preparation Example 2 under a nitrogen stream. 88.0 g of polyester polyol and 44.0 g of acetone were added and mixed uniformly, then 51.9 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. An acetone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 1.8% by mass with respect to the solid content was obtained by reacting for a period of time. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product was cooled to 50 ° C., and 220.0 g of acetone and 8.9 g of triethylamine were uniformly mixed. Then, sorbitol polyglycidyl ether (“Denacol EX-614B”, 20.0 g (manufactured by Nagase ChemteX Corporation) was added and mixed uniformly. Next, an aqueous polyamine solution (polyamine concentration 0.91% by mass) obtained by mixing 5.6 g of ethylenediamine and 602.3 g of ion-exchanged water was gradually added dropwise to the reaction solution at 40 to 50 ° C. Dispersed. Here, the value of a / (b + c) was 100/100.

  Next, after aging this reaction solution for about 2 hours, the solvent was removed under reduced pressure at 30 ° C. for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of carboxyl groups and carboxylate groups in the polyurethane resin was 1.0% by mass. Moreover, the compounding quantity of the said sorbitol polyglycidyl ether was 5.0 mass parts with respect to 100 mass parts of said polyurethane resins. The resulting composition showed a tendency to thicken over time.

(Comparative Example 7)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 256.2 g of polybutylene adipate diol (number average molecular weight 2000) was added to the carboxyl group obtained in Preparation Example 2 under a nitrogen stream. 88.0 g of polyester polyol and 44.0 g of acetone were added and mixed uniformly, then 51.9 g of hexamethylene diisocyanate was added, then 0.1 g of dibutyltin dilaurate was added, and the temperature was raised to 80 ° C. An acetone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 1.8% by mass with respect to the solid content was obtained by reacting for a period of time. In addition, the value of a / b at the time of prepolymer manufacture was 100/70.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product was cooled to 50 ° C., and 220.0 g of acetone and 8.9 g of triethylamine were uniformly mixed. Then, 5.6 g of ethylenediamine and 602.3 g of ion-exchanged water were added. The mixed polyamine aqueous solution (polyamine concentration of 0.91% by mass) was gradually added dropwise at 40 to 50 ° C., and dispersed in water simultaneously with the chain extension reaction. Here, the value of a / (b + c) was 100/100.

  Next, after aging this reaction solution for about 2 hours, 20.0 g of sorbitol polyglycidyl ether ("Denacol EX-614B", manufactured by Nagase ChemteX Corporation) was added and mixed uniformly, and at 30 ° C under reduced pressure. Solvent removal was performed for about 2 hours to obtain an aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of carboxyl groups and carboxylate groups in the polyurethane resin was 1.0% by mass. Moreover, the compounding quantity of the said sorbitol polyglycidyl ether was 5.0 mass parts with respect to 100 mass parts of said polyurethane resins. The resulting composition showed a tendency to thicken over time.

(Comparative Example 8)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 301.8 g of polybutylene adipate diol (number average molecular weight 2000) under a nitrogen stream was added to the sulfonate group obtained in Preparation Example 1. 42.7 g of polyester polyol and 44.2 g of acetone are added and mixed uniformly, then 53.4 g of hexamethylene diisocyanate is added, the temperature is raised to 80 ° C., and the mixture is allowed to react for about 4 hours to obtain free isocyanate based on the solid content. An acetone solution of a neutralized isocyanate group-terminated prepolymer having a group content of 2.4% by mass was obtained. In addition, the value of a / b at the time of prepolymer manufacture was 100/60.

  The acetone solution of the isocyanate group-terminated prepolymer neutralized product is cooled to 30 ° C., 221.0 g of acetone and 13.3 g of diethanolamine are added, and the free isocyanate group content is 0.2% by mass or less at 40 to 50 ° C. After approximately 2 hours of chain extension reaction, 616.7 g of ion-exchanged water was gradually added to emulsify and disperse the sulfonate group-containing polyurethane resin, and after aging for about 2 hours, at 30 ° C. under reduced pressure. Solvent removal was performed for about 2 hours to obtain a hydroxyl group-containing aqueous polyurethane resin composition having a solid content of 40% by mass. In this composition, the content of sulfone groups and sulfonate groups in the polyurethane resin was 1.0% by mass, and the content of hydroxyl groups was 1.0% by mass. The resulting composition was very stable without separation and gelation over time.

  Using this water-based polyurethane resin composition as a main component of a two-component adhesive, an isocyanate curing agent (manufactured by Sumitomo Bayer Urethane Co., Ltd., “Baihijoule 3100”, NCO content 18% by mass), NCO / OH = 80 / It was mixed so that it might be 100 and used as a two-component adhesive. The pot life of this adhesive was 4 hours at a room temperature of 25 ° C.

<Evaluation of adhesive>
Tables 1 and 2 show associative thickeners ("Biserizer AP-2", manufactured by Sanyo Chemical Co., Ltd.) in the aqueous polyurethane resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 7. It added by the compounding quantity, it adjusted so that it might become a viscosity of 3000-5000 mPa * s, and the laminated body (test piece) was produced using the obtained liquid preparation as an adhesive agent. Moreover, the laminated body (test piece) was produced using the two-component adhesive obtained in Comparative Example 8. And the open time, low temperature adhesiveness, normal state adhesiveness, hydrolysis resistance, and heat resistant creep property were evaluated by the method as described above. The obtained evaluation results are shown in Tables 3 and 4. Moreover, the manufacturing conditions of the polyurethane resin composition in Examples 1-10 and Comparative Examples 1-8 are shown in Table 1 and Table 2.

  As is clear from the results described in Tables 1 to 4, when the one-part adhesive of the present invention comprising the aqueous polyurethane resin composition of the present invention (Examples 1 to 10) was used, It was confirmed that the adhesiveness was excellent. Further, in this case, it was confirmed that the obtained laminate had high peel strength and excellent adhesiveness, and also had good durability such as hydrolysis resistance and heat-resistant creep resistance. In addition, since all the laminates produced under a wide range of temperature conditions (40 ° C. to 80 ° C.) have high peel strength, it is confirmed that the aqueous polyurethane resin composition of the present invention has excellent adhesiveness in a wide temperature range. It was done.

  Further, since the aqueous polyurethane resin composition of the present invention does not substantially contain an organic solvent, it is different from an adhesive using an organic solvent-based polyurethane resin used in Comparative Example 8, and is originally obtained at the time of manufacturing a laminate. There was also no organic solvent odor from the resulting laminate. As a matter of course, since it is a one-pack type adhesive, there was no pot life of the adhesive bath.

  In contrast, when the isocyanate group-terminated prepolymer neutralized product was subjected to a chain extension reaction after emulsified and dispersed in water (Comparative Example 1), the hot time was high (80 ° C.), although the open time was long. Even if it was the produced laminated body, even if it was the laminated body produced on the conditions of low temperature (40-60 degreeC), peeling strength was remarkably inferior and it was confirmed that adhesiveness is unsatisfactory. In this case, the normal adhesion, hydrolysis resistance, and heat creep resistance were also extremely poor.

  In addition, when a chain extension reaction was performed on the neutralized isocyanate group-terminated prepolymer using the polyamine (C) itself so that a / (b + c) was 100/100 (Comparative Example 2), As a result, the aqueous polyurethane resin composition could not be prepared.

  Furthermore, when the isocyanate group-terminated prepolymer neutralized product was only dispersed in water and the chain extension reaction with the aqueous solution of polyamine (C) was not performed (Comparative Example 3), the open time was long, but adhesion Property, hydrolysis resistance, and heat creep resistance were poor.

Further, in a case of using the polyol having a carboxyl group instead of a polyol having a sulfonic group and / or sulfonate groups according to the present invention (B _1), and the neutralized prepolymer having a terminal isocyanate group was emulsified and dispersed in water When the chain elongation reaction is performed later with the polyamine (C) itself (Comparative Example 4), although the open time is long, the peel strength is low even in a laminate produced under hot press conditions at a high temperature (80 ° C.), The laminate produced under the low temperature (40 to 60 ° C.) condition had a marked decrease in peel strength. In this case, the normal adhesiveness, hydrolysis resistance, and heat creep resistance were also extremely poor. When this isocyanate group-terminated prepolymer neutralized product was subjected to a chain extension reaction with an aqueous solution of polyamine (C) and simultaneously dispersed in water (Comparative Example 5), the open time was long and produced under a wide range of press temperature conditions. The laminate obtained had a high peel strength and good normal adhesion, but the hydrolysis resistance was extremely poor. In this case, the heat resistance creep resistance was also poor.

  Furthermore, when a polyepoxy crosslinking agent is added to an isocyanate group-terminated prepolymer neutralized product obtained by using a polyol having a carboxyl group, followed by a chain extension reaction with an aqueous solution of polyamine (C) and simultaneously water dispersion. In the case of (Comparative Example 6) or in the case where a chain elongation reaction was performed with an aqueous solution of polyamine (C) and simultaneously dispersed in water, and then a polyepoxy compound was added (Comparative Example 7), the open time was shortened. In these cases, the laminate produced under hot press conditions of high temperature (80 ° C.) was able to withstand practical use although the peel strength was slightly low, but was produced under conditions of low temperature (40-60 ° C.). The resulting laminate had poor peel strength. Moreover, in these cases, it was confirmed that the obtained aqueous polyurethane resin also had a problem in terms of stable quality because the viscosity increased with time.

  In Comparative Example 8 using a two-component adhesive, the pot life was as short as 4 hours, and it was confirmed that there was a problem in terms of stable quality.

  As described above, according to the present invention, the water-based polyurethane resin contains as little or no organic solvent as possible and has a long open time, and has excellent adhesiveness, particularly even at a low temperature of about 30 to 60 ° C. It is possible to provide an aqueous polyurethane resin composition that has a laminate having excellent durability such as adhesive strength, hydrolysis resistance, and heat-resistant creep.

Therefore, by using the aqueous polyurethane resin composition of the present invention as a one-pack type adhesive, it becomes possible to stably produce a laminate product, and it is possible to provide a laminate excellent in quality and quality.

Claims (4)

Polyisocyanate (A), a polyol (B ₁ ) having a sulfone group and / or sulfonate group, a polyol (B ₂ ) other than a polyol having a sulfone group and / or a sulfonate group, and / or a chain extender (B ₃ ) An isocyanate group-terminated prepolymer neutralized product obtained by reacting a polyfunctional compound (B) containing a compound so as to satisfy the condition represented by the following formula (1), two amino groups and / or imino groups Using a 0.05 to 3.0% by mass aqueous solution of polyamine (C) having the above, the chain elongation reaction is carried out so as to satisfy the condition represented by the following formula (2), and at the same time, it is obtained by dispersing in water. There, a sulfonic group and / or polyols having a sulfonate group (B ₁₎ is Ah Ru water polyurethane resin in a polyester polyol lactone One-component adhesive agent characterized in that it contains.
100/80 ≦ a / b ≦ 100/50 (1)
100/100 ≦ a / (b + c) ≦ 100/97 (2)
(In the formulas (1) and (2), a represents the number of isocyanate groups (NCO) contained in the polyisocyanate (A), and b represents a hydroxyl group (OH) contained in the polyfunctional compound (B). C represents the total number of amino groups (NH ₂ ) and imino groups (NH) contained in the polyamine (C). Polyisocyanate (A), a polyol (B ₁ ) having a sulfone group and / or sulfonate group, a polyol (B ₂ ) other than a polyol having a sulfone group and / or a sulfonate group, and / or a chain extender (B ₃ ) An isocyanate group-terminated prepolymer neutralized product obtained by reacting a polyfunctional compound (B) containing a polyfunctional compound (B) so as to satisfy the condition represented by the following mathematical formula (1), a second chain extender (D) After the chain elongation reaction is performed so as to satisfy the condition represented by the following formula (3), 0.05 to 3.0% by mass of the polyamine (C) having two or more amino groups and / or imino groups It is obtained by using an aqueous solution and carrying out a chain extension reaction so as to satisfy the condition represented by the following formula (4) and simultaneously dispersing in water, and the sulfonate group and / or sulfonate group One-component adhesive agent characterized in that the polyol (B ₁₎ contains Oh Ru water polyurethane resin composition polyester polyol lactone with.
100/80 ≦ a / b ≦ 100/50 (1)
100/95 ≦ a / (b + d) ≦ 100/80 (3)
100/100 ≦ a / (b + c + d) ≦ 100/97 (4)
(In the formulas (1), (3) and (4), a represents the number of isocyanate groups (NCO) contained in the polyisocyanate (A), and b represents hydroxyl contained in the polyfunctional compound (B). Represents the number of groups (OH), c represents the total number of amino groups (NH ₂ ) and imino groups (NH) contained in the polyamine (C), and d represents the amino group contained in the second chain extender (D). Represents the total number of groups (NH ₂ ) and imino groups (NH).) The content of the sulfone group and the sulfonate group in the polyurethane resin in the aqueous polyurethane resin composition is 0.3 to 3.0% by mass with respect to the mass of the polyurethane resin. The one-component adhesive described. A laminate obtained by using the one-component adhesive according to any one of claims 1 to 3 .