JPH10110024A - Water-dispersible polyurethane resin composition, and adhesive and paint using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To sufficiently satisfy adhesion and adhesion to various base materials such as a polyolefin-containing aqueous polyurethane resin composition and all plastics including general-purpose polyolefins, An object of the present invention is to provide a water-based adhesive and a water-based paint having excellent durability. SOLUTION: In a water-dispersible polyurethane resin composition comprising an organic diisocyanate, an active hydrogen group-containing compound, a hydrophilic polar group and an active hydrogen group-containing compound, the active hydrogen group-containing compound has a hydroxyl group-containing poly (ethylene-butylene at both ends). A) a water-dispersible polyurethane resin composition comprising a copolymer, and an aqueous adhesive using the same;
The water-based paint exhibited good adhesion and adhesion to various substrates, and exhibited excellent stability over time and durability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-dispersible polyurethane resin composition using a specific hydroxyl group-containing polyolefin, and to a water-based adhesive and a water-based paint having good adhesion and adhesion to various materials, especially to polyolefin. About.

[0002]

2. Description of the Related Art In recent years, in the field of adhesives, paints, etc., organic solvents have been the mainstream, but from the viewpoints of air pollution prevention, regulations of the Fire Service Law, occupational hygiene, etc., water-based adhesives have been adopted. Is starting to be. This water-based adhesive, as a resin for paint,
There have been proposed polyester-based and polyether-based polyurethane resins containing a hydrophilic polar group such as a carboxylate. JP-A-5-117358 discloses an aqueous polyurethane resin composition obtained from a polyester diol having a hydroxyl group at both ends having a molecular weight of 15,000 to 10,000 and an isocyanate monomer having at least one isocyanate group. Have been. JP-A-4-68022 discloses an aqueous dispersion of a polyurethane resin obtained from a hydroxyl-containing polyalkylene oxide and a polyisocyanate. Furthermore, Japanese Patent Publication No. 5-86829 discloses an aqueous polyurethane resin-based adhesive containing a hydroxyl group-containing hydrogenated polybutadiene.

[0003]

SUMMARY OF THE INVENTION However, Japanese Patent Application Laid-Open No.
Conventional polyester-based water-based polyurethane resins such as the water-based polyurethane resin composition described in Japanese Patent No. 17358 are excellent in adhesion and adhesion to a so-called polar substrate such as polyethylene terephthalate and nylon, but are not suitable for non-polyolefins and the like. Adhesion to polar substrates was not satisfactory. JP-A-4-680
The aqueous dispersion of a polyurethane resin described in JP-A No. 22 is insufficient in water resistance, durability and mechanical strength because it is based on a polyether. In Japanese Patent Publication No. 5-86829,
An aqueous polyurethane-based adhesive using a hydroxyl group-containing hydrogenated polybutadiene with an improved number of functional groups and residual double bonds has been described, but this hydroxyl group-containing hydrogenated polybutadiene has an extremely high ratio of linear units and side chain units. Due to the bias, the crystallinity of the polyolefin portion becomes too large, and the adhesiveness to the obtained water-dispersible polyurethane,
It does not contribute to adhesion. Also, conventional hydroxyl group-containing polyolefins such as hydroxyl group-containing polybutadiene have a number of functional groups of more than 2, so that it is difficult to obtain the intended polyurethane resin itself, and also in the obtained resin, double bonds remain in the polybutadiene unit. Therefore, there was difficulty in weather resistance.

The present invention sufficiently satisfies adhesion and adhesion to various base materials such as a polyolefin-containing aqueous polyurethane resin composition and all plastics including general-purpose polyolefins, and has excellent durability and the like. It is an object to provide a water-based adhesive and a water-based paint.

[0005]

That is, the present invention provides the following (1) to (5). (1) an organic diisocyanate, an active hydrogen group-containing compound,
A water-dispersible polyurethane resin composition comprising a hydrophilic polar group and an active hydrogen group-containing compound, wherein the active hydrogen group-containing compound is a poly (ethylene-butylene) having hydroxyl groups at both ends.
A water-dispersible polyurethane-based resin composition comprising a copolymer.

(2) The ethylene / butylene molar ratio constituting the poly (ethylene-butylene) copolymer having hydroxyl groups at both ends described in (1) is 30/70 to 70/30, and the hydrophilic polarity An aqueous polyurethane resin composition, wherein the group is a carboxylate and / or sulfonate.

(3) The compound having a hydrophilic polar group and an active hydrogen group according to the above (1) and (2) has a number average molecular weight:
A water-dispersible polyurethane-based resin composition having a molecular weight of 500 to 10,000.

(4) An aqueous adhesive using the water-dispersible polyurethane resin composition according to any one of (1) to (3).

(5) An aqueous paint using the water-dispersible polyurethane resin composition according to any one of (1) to (3).

[0010]

DETAILED DESCRIPTION OF THE INVENTION The organic diisocyanate used in the present invention is hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated trimethyl xylylene diisocyanate. Isocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-trimethylhexaethylene-1,6-
Non-yellowing diisocyanate such as diisocyanate, 2,4,4-trimethylhexahexylene-1,6-diisocyanate, 2,4-tolylene diisocyanate, 2,6-
Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate,
There are yellowing diisocyanates such as 1,5-naphthylene diisocyanate and paraphenylene diisocyanate, and non-yellowing diisocyanates such as ortho-xylylene diisocyanate, meta-xylylene diisocyanate, para-xylylene diisocyanate and tetramethyl xylylene diisocyanate. These organic diisocyanates can be used alone or as a mixture. Furthermore, these adduct modified products, carbodiimide modified products, allophanate modified products, buret modified products, uretdione modified products, uretoimine modified products, and isocyanurate modified products can also be used.

The active hydrogen group-containing compound used in the present invention must contain a poly (ethylene-butylene) copolymer having hydroxyl groups at both ends. The content of the poly (ethylene-butylene) copolymer containing hydroxyl groups at both ends is preferably an amount introduced from 1 to 50% by weight, and particularly preferably an amount from 3 to 30% by weight when a polyurethane resin is used. When the amount of the poly (ethylene-butylene) copolymer containing hydroxyl groups at both ends is less than 1%, the adhesion to the polyolefin film becomes poor. If it exceeds 50% by weight, the adhesion to plastic films other than the polyolefin film will be poor.

The molar ratio of ethylene to butylene in the hydroxyl group-containing poly (ethylene-butylene) copolymer is 30/70 to 7
0/30, preferably 35/65 to 65/35
It is. If the molar ratio of ethylene to butylene is more than 30/70 or more than 70/30, the poly (ethylene-butylene) copolymer has high crystallinity and poor adhesion.

The poly (ethylene-butylene) copolymer having hydroxyl groups at both ends has a number average molecular weight of preferably from 500 to 10,000, particularly preferably from 1,000 to 9,000. If the number average molecular weight is less than 500, the adhesiveness and adhesion to a nonpolar substrate such as polyolefin will be poor. Also, 1
If it exceeds 000, the durability, adhesion and adhesion to polar substrates such as polyethylene terephthalate and nylon become poor.

The hydroxyl group-containing poly (ethylene-butylene) copolymer may be any of a random copolymer, a block copolymer and a graft copolymer, but a random copolymer is preferred. This is because the random copolymer has the lowest crystallinity, and as a result, adhesiveness and adhesiveness are easily developed.

As the poly (ethylene-butylene) copolymer having a hydroxyl group at both ends, specifically, there is, for example, Clayton Liquid HPVM-2202 manufactured by US Shell. The number average molecular weight of HPVM-2202 is 3,000-
4,000, ethylene / butylene molar ratio is 50/5
0, hydroxyl groups are present at both ends.

In the present invention, other active hydrogen group-containing compounds can be used, and roughly classified into a polymer polyol and a chain extender. Number average molecular weight 5
There are 00 to 10,000 polyester polyols, polyether polyols, polycarbonate polyols, polyether ester polyols and the like.

Examples of the polyester polyol include known phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, curtaconic acid, Azelaic acid, sebacic acid succinic acid, adipic acid, sebacic acid, azelaic acid, 1,4-
Cyclohexyldicarboxylic acid, α-hydromuconic acid,
polycarboxylic acids such as β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, β-diethylsuccinic acid, maleic acid, fumaric acid, hemimelitic acid, trimellitic acid, pyromellitic acid, and benzophenonetetracarboxylic acid Or one or more of anhydrides and the like, ethylene glycol,
Diethylene glycol, dipropylene glycol, 1,
2-propanediol, 1,3-propanediol,
1,2-butanediol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane-
1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, ethylene oxide and propylene oxide adducts of bisphenol A, low-molecular diols such as trimethylolpropane, glycerin, hexanetriol, and quadrol, low-molecular triols and the like Obtained from a dehydration condensation reaction with at least one of the following. Furthermore, ε
-Caprolactone, alkyl-substituted ε-caprolactone,
Lactone-based polyester polyols obtained from ring-opening polymerization of cyclic ester (so-called lactone) monomers such as δ-valerolactone and alkyl-substituted δ-valerolactone.

Examples of the polyether polyol include homopolymers and copolymers of epoxides such as ethylene oxide, propylene oxide, and tetrahydrofuran, and cyclic ethers.

As the polyetherester polyol, there is a copolyol obtained from the above-mentioned polyether polyol and the above-mentioned dicarboxylic acid.

As the polycarbonate polyol, one of the above-mentioned low molecular polyols of the polyester polyol source is used.
It can be obtained from a dealcoholation reaction, a glycol removal reaction, or a phenol reaction of any one or more kinds with a dialkyl carbonate, dialkylene carbonate, or diphenyl carbonate.

The above-mentioned polymer polyols include urea resins, acrylic resins, melamine resins, epoxy resins,
As long as it contains two or more active hydrogen groups, such as polyester resin and polyvinyl alcohol, it can be used as a high molecular polyol.

Examples of the chain extender include water having a molecular weight of 18 to 500, urea, low molecular polyol, low molecular polyamine and low molecular amino alcohol, and these may be used alone or in combination of two or more.

The low-molecular polyol as the chain extender includes the low-molecular polyol of the above-mentioned polyester polyol source.

As the low molecular weight polyamine, ethylenediamine, hexamethylenediamine, isophoronediamine,
Mensendiamine, 4,4'-diphenylmethanediamine, 4,4'-diaminodiphenylsulfone, metaxylenediamine, piperazine and the like, or a mixture of two or more thereof.

Examples of the amino alcohol include monoethanolamine, diethanolamine, N-methyldiethanolamine and N-phenyldipropanolamine.

The active hydrogen group-containing compound such as a polymer polyol or a chain extender has a functional group number of 2 to 3, and 2 is most preferable.

The hydrophilic polar group and the hydrophilic polar group of the active hydrogen group-containing compound used in the present invention are any of nonionic, anionic and cationic hydrophilic polar groups. Sources include nonionic hydrophilic polar groups such as poly (oxyethylene) ether, and-
COOM, (the M an alkali metal, an ammonium group, an organic amine) -SO ₃ M is anionic hydrophilic polar group, such as, hydrophilic polar group of cationic such as quaternary ammonium.

Examples of the compound having a nonionic hydrophilic polar group and an active hydrogen group include poly (oxyalkylene) ethers and polyoxyalkylene fatty acid esters containing one or more active hydrogen groups. Examples of the active hydrogen group-containing compound used as an initiator in the production of poly (oxyalkylene) ether include methanol, n-butanol, cyclohexanol, phenol, ethylene glycol, propylene glycol, aniline, trimethylolpropane, glycerin and the like. . Among these, in consideration of dispersion stability, it is preferable to use an alcohol having a smaller molecular weight such as methanol, ethanol, or ethylene glycol because the hydrophilicity becomes higher. In addition, examples of the fatty acid used for producing the polyoxyalkylene fatty acid ester include acetic acid, propionic acid, and butyric acid. Among these, in consideration of dispersion stability, it is preferable to use a lower fatty acid because it has higher hydrophilicity. The polyether chains present in the polyalkylene ether alcohol, polyoxyalkylene fatty acid ester, etc. are generally 3 to 90, particularly preferably 5 to 50, pure ethylene oxide chains and / or all alkylene oxide units. May be a mixed alkylene oxide chain containing at least 70% or more of ethylene oxide units.

The compound having an anionic hydrophilic polar group and an active hydrogen group comprises an organic acid having at least one active hydrogen group and a neutralizing agent. Organic acids having one or more active hydrogen groups include α-oxypropionic acid, oxysuccinic acid, dioxysuccinic acid, ε-oxypropane-1,
2,3-tricarboxylic acid, hydroxyacetic acid, α-hydroxybutyric acid, hydroxystearic acid, ricinoleic acid, ricinoleic acid, ricinostearolic acid, salicylic acid, mandelic acid, etc., oleic acid, ricinoleic acid, linoleic acid, etc. Hydroxy fatty acids obtained by hydroxylating saturated fatty acids, glutamine, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid, diamine-type amino acids such as diaminobenzenesulfonic acid, glycine, alanine, glutamic acid, taurine, aminocaproic acid, aminobenzoic acid, Monoamine-type amino acids such as aminoisophthalic acid and sulfamic acid, or 2,2-
Carboxylic acid-containing polyols such as dimethylolpropionic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid; adducts of iminodiacetic acid and glycidol;
Examples thereof include polyester polyols using hydroxysulfoisophthalic acid, polycaprolactone polyols using a carboxylic acid-containing polyol as an initiator, and transesterification products of a polyester polyol or a polycarbonate polyol with a carboxylic acid-containing polyol. Further, a half ester mixture or a half amide mixture containing a carboxyl group obtained by reacting a polyol or a polyamine such as the above-mentioned high molecular polyol or low molecular polyol with a polycarboxylic anhydride can also be used. In particular, when a polyol is added to a dianhydride such as pyromellitic anhydride, two carboxylic acids are generated, so that a hydrophilic polar group can be introduced into the molecular chain of the polyester polyol.
Other anionic hydrophilic groups include phosphoric acid and the like.

Examples of neutralizing agents include ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, Morpholine, N-methylmorpholine, 2-amino-2-ethyl-
Organic amines such as 1-propanol, alkali metals such as lithium, potassium and sodium, sodium hydroxide,
Inorganic alkalis such as potassium hydroxide may be mentioned. In order to improve the weather resistance and water resistance after drying, those having high volatility which easily dissociates by heat are preferable, and ammonia, trimethylamine and triethylamine are preferable. Further, these organic acids and neutralizing agents can be used alone or in combination of two or more.

The compound containing a cationic hydrophilic polar group and an active hydrogen group includes a tertiary amine containing at least one active hydrogen group capable of reacting with an isocyanate group, and an inorganic acid, an organic acid, and a quaternizing agent. Consists of what is selected. Examples of the tertiary amine include N-methyldiethanolamine, N-ethyldiethanolamine or an N-alkyldiethanolamine having an alkyl chain having a carbon number of more than 2, N-phenyldiethanolamine, N-phenyldipropanolamine, N-methyldiisopropanolamine, N,
N'-dihydroxyethylpiperazine, triethanolamine, trisisopropanolamine, N, N'-dimethylethanolamine, N-methyl-bis- (3-aminopropyl) -amine, N-methyl-bis- (2-aminopropyl ) -Amine and the like.

Examples of the inorganic and organic acids include hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid and sulfuric acid. As the quaternizing agent, dimethyl sulfate, benzyl chloride, bromoacetamide, chloroacetamide, or ethyl bromide,
And alkyl halides such as propyl bromide and butyl bromide. Other cationic hydrophilic polar group-containing compounds include primary amine salts, secondary amine salts, and tertiary amine salts.
And cationic compounds such as secondary amine salts and pyridinium salts.

Further, an amphoteric compound such as a reaction product of a tertiary amine-containing polyol and sulfobetaine can also be used.

Among the above-mentioned compounds containing a hydrophilic polar group and an active hydrogen group, preferred ones have a number average molecular weight of 500 to 10,000 in consideration of heat resistance, weather resistance, production method and the like.
0, polycaprolactone diol using dimethylolpropionic acid and / or dimethylolbutanoic acid, which is an anionic hydrophilic polar group-containing low molecular diol, a combination of polyesterdiol, polycarbonatediol and triethylamine as a neutralizing agent, And / or
Polyester polyols using 5-sodium sulfoisophthalic acid and polycarbonate-based polyols are preferred.

The anionic and cationic hydrophilic polar groups are finally present in the polyurethane resin in the form of a salt, but may be introduced into the resin after neutralization. The polar group may be introduced into the resin and then neutralized.

The amount of the nonionic hydrophilic polar group introduced is 0.1.
1 to 50% by weight, the introduction amount of the anionic and cationic hydrophilic polar groups is 0.1 to 1.0 mmol / g, and the preferable amount is 0.2 to 45% by weight for the nonionic type and the anionic and cationic types. In the cationic system, 0.2 to 0.8 mmol /
g. When the amount of the hydrophilic polar group introduced is less than the above lower limit, the polyurethane resin does not disperse well in water. If it exceeds the upper limit, the water resistance of the dried polyurethane resin is insufficient.

The polyurethane resin composition of the present invention includes:
A reaction terminator can be used if necessary. Examples of the reaction terminator include monoalcohols, monoamines, aminoalcohols, and mixtures thereof, and monoisocyanates can also be used.

Specific monoalcohols include methanol, ethanol, propanol, isopropanol,
2-ethylhexanol and the like. Monoamines include primary amines such as ethylamine, propylamine and butylamine, and secondary amines such as diethylamine and dibutylamine.
There are secondary amines. Examples of the amino alcohol include monoethanolamine and diethanolamine. Monoisocyanates include phenyl isocyanate and cyclohexyl isocyanate.

As a method for producing the polyurethane resin used in the present invention, a one-shot method in which the reaction is carried out in an atmosphere containing an excess of active hydrogen, or a method in which an active hydrogen compound and an organic diisocyanate are reacted in an excess of NCO groups to synthesize an NCO-terminated prepolymer. In advance, it can be synthesized by a known method such as a prepolymer method in which an active hydrogen compound is reacted. Also, after reacting the polyurethane resin in an organic solvent compatible with water, add water, and then remove the organic solvent or synthesize the resin without using a solvent and forcibly disperse or dissolve in water. Can also be obtained by the method

In the case of the one-shot method, active hydrogen / NCO
Is from 0.5 to less than 1, preferably from 0.8 to 1.
It is less than 1. When it is less than 0.5, the molecular weight of the polyurethane resin is too small, resulting in a lack of durability. In the case of one or more, gelation is likely to occur when synthesizing the resin.

In the case of the prepolymer method, the ratio of active hydrogen / NCO at the time of synthesizing the prepolymer is from 1.1 to 5.0, preferably from 1.5 to 4.0. If less than 1.1,
The molecular weight of the prepolymer is too large and it is difficult to proceed to the subsequent reaction steps. If it exceeds 5.0, the adhesiveness becomes poor.

When an organic solvent is used, usable organic solvents include aromatic solvents such as toluene, xylene, swazole (aromatic hydrocarbons manufactured by Cosmo Oil) and Solvesso (aromatic hydrocarbons manufactured by Exxon Chemical). , Acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as methanol, ethanol, isopropanol, esters such as ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, Examples thereof include glycol ether esters such as 3-methyl-3-methoxybutyl acetate and ethyl-3-ethoxypropionate, and ethers such as tetrahydrofuran and dioxane. The solvents may be used alone or in combination of two or more.

As a reaction catalyst for synthesizing an isocyanate group-terminated prepolymer or a polyurethane resin used in the present invention, a known urethanization catalyst can be used. Specific examples include organic metal compounds such as dioctyltin dilaurate, organic amines such as triethylenediamine, and salts thereof.

The number average molecular weight of the polyurethane resin thus obtained is preferably 5,000 or more, particularly preferably 10,000 or more. When the number average molecular weight of the polyurethane resin is less than 5,000, durability becomes poor.

The water-dispersible polyurethane resin composition of the present invention may be mixed with another aqueous resin such as an aqueous acrylic resin, polyvinyl alcohol, an aqueous polyester resin, an aqueous polyolefin resin, and a latex.

The water-based adhesive and the water-based paint of the present invention are blended with the water-dispersible polyurethane resin composition of the present invention, if necessary, with additives and auxiliaries commonly used in water-based adhesive systems or water-based paint systems. Obtained. For example, pigments, solvents, antiblocking agents, dispersion stabilizers, viscosity modifiers, leveling agents, antigelling agents, light stabilizers, antioxidants, UV absorbers, heat resistance improvers, inorganic and organic fillers, plastics Agents, lubricants, antistatic agents, reinforcing materials, catalysts and the like. The compounding method is obtained by a known method such as stirring and dispersion. If necessary, a curing agent such as Aquanate-100 (manufactured by Nippon Polyurethane Industry, water-dispersed polyisocyanate) may be blended immediately before use.

[0047]

As described above, according to the present invention, the adhesiveness and adhesion to various substrates such as polyolefin-containing aqueous polyurethane resin compositions and all plastics including general-purpose polyolefins can be sufficiently satisfied. It has become possible to provide a water-based adhesive and a water-based paint having excellent durability.

[0048]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Unless otherwise specified, "parts" and "%" in the examples mean "parts by weight" and "% by weight", respectively.

[Synthesis of Compound Containing Hydrophilic Polar Group and Active Hydrogen Group] Synthesis Example 1 268.0 parts of dimethylolpropionic acid was placed in a four-necked flask equipped with a stirrer, a thermometer, an Aline cooling tube, and a nitrogen gas inlet tube. , 732.0 parts of ε-caprolactone and 0.05 part of tetrabutyl titanate were charged and reacted at 200 ° C for 5 hours. The hydroxyl value of the obtained polyol A was 224.4 mgKOH / g, and the acid value was 112.2 mg.
KOH / g and number average molecular weight were 500.

Synthesis Example 2 In a reactor similar to Synthesis Example 1, dimethylolbutanoic acid was added
90 parts of a polycarbonate diol having a number average molecular weight of 3,000 obtained by dephenolation reaction of 4.0 parts of 1,6-hexanediol with diphenyl carbonate was 902.5%.
Parts, 2,3.5 parts of 1,6-hexanediol, 16
Warmed to 0 ° C. When the temperature reached 180 ° C., 0.05 parts of tetrabutyl titanate was charged and reacted for 6 hours. The hydroxyl value of the obtained polyol B is 56.1 m.
gKOH / g, acid value was 28.1 mgKOH / g, and number average molecular weight was 1,000.

Synthesis Example 3 In a reactor similar to that of Synthesis Example 1, 148.0 parts of dimethyl 5-sodium sulfoisophthalate and 542.9 parts of 1,6-hexanediol were charged, and a methanol removal reaction was performed at 180 ° C. I let it. Five hours after the start of the reaction, the distillation of methanol stopped, and 452.7 parts of adipic acid was added, followed by a further dehydration reaction at 180 ° C. After 5 hours from the addition of adipic acid, the distillation of water stopped. After adding 0.05 parts of tetrabutyl titanate, the temperature was raised to 200 ° C., and the pressure was gradually lowered to 0.5 Torr. Allowed to react for hours. The hydroxyl value of the obtained polyol C is 1
11.7 mg KOH / g, acid value 0.5 mg KOH / g
g, the sulfonate content was 0.5 mmol / g, and the number average molecular weight was 1,000.

Synthesis Example 4 In the same reactor as in Synthesis Example 1, 156.0 parts of dimethyl 5-potassium sulfoisophthalate, and the number average molecular weight obtained by the dephenolization reaction of 1,6-hexanediol and diphenyl carbonate. 789.0 parts of 3,000 polycarbonate diols and 8
7.0 parts and 0.05 parts of tetrabutyl titanate were charged, and a methanol removal reaction was performed at 180 ° C. for 4 hours under normal pressure. Thereafter, the pressure was gradually reduced to 0.5 mmHg, and the reaction was further performed at 180 ° C. for 2 hours. The hydroxyl value of the obtained sulfonate ester-containing polyol D was 56.1 mg.
In KOH / g, the sulfonate content is 0.5 mmol
/ G, number average molecular weight was 2,000. Table 1 shows the polyols A to D.

[0053]

[Table 1]

In Table 1, DMPA: dimethylolpropionic acid DMBA: dimethylolbutanoic acid DMIS: dimethyl 5-sodium sulfoisophthalate DMIP: dimethyl 5-potassium sulfoisophthalate ε-CL: ε-caprolactone HG-PCD: 1,6 -Polycarbonate having a hydroxyl group at both ends with a number average molecular weight of 3,000 obtained from hexanediol and diphenyl carbonate HG: 1,6-hexanediol AA: adipic acid TBT: tetrabutyl titanate

[Synthesis of Water-Dispersible Polyurethane Resin Composition] Example 1 Polyol A was placed in a four-necked flask equipped with a stirrer, a thermometer, an Aline cooling tube, and a nitrogen gas inlet tube.
Part, 184.3 parts of a poly (ethylene-butylene) copolymer having hydroxyl groups at both ends, obtained from 3-methyl-1,5-pentanediol and adipic acid, having a number average molecular weight of 3,000 and having hydroxyl groups at both ends. (HPVM-22
02, made by Shell) and 150 parts of acetone, and uniformly stirred. 48.4 parts of isophorone diisocyanate and 0.03 part of dibutyltin dilaurate as a urethanation catalyst were charged into this polyol solution,
The reaction was carried out at a temperature of 5 ° C. for 5 hours to obtain a urethane prepolymer solution containing both terminal isocyanate groups. After adding 150 parts of acetone and 9.3 parts of triethylamine to this prepolymer solution, 700 parts of water, 9.4 parts of isophoronediamine,
A mixed solution of 0.7 parts of monoethanolamine was added at a stretch to carry out elongation reaction and phase inversion, and reacted at 40 ° C. until the isocyanate group disappeared. Thereafter, deacetone was performed using an evaporator to obtain a water-dispersible polyurethane-based resin composition PU-1. The solid content of PU-1 is 30.9
%, The number average molecular weight was 49,000.

Example 2 In a reactor similar to that of Example 1, 140.1 of polyol B was added.
Parts, 93.4 parts of a polycarbonate having both ends hydroxyl groups having a number average molecular weight of 2,000 obtained from diphenyl carbonate and 1,6-hexanediol, 93.4 parts, HPVM-220
2, 16.8 parts, neopentyl glycol 4.9 parts,
300 parts of acetone was charged and uniformly stirred. 4 hydrogenated xylylene diisocyanate is added to this polyol solution.
2.6 parts and 0.03 part of dibutyltin dilaurate were charged and reacted at 50 ° C. until the isocyanate group disappeared. To this polymer solution was added 7.1 parts of triethylamine.
Added. Thereafter, 700 parts of water was added to perform phase inversion, and then deacetone was performed by an evaporator to obtain a water-dispersible polyurethane-based resin composition PU-2. PU-2
Has a solid content of 30.5% and a number average molecular weight of 25,000.
It was 0.

Example 3 In a reactor similar to that of Example 1, 158.6 of polyol C was added.
Parts, 28.6 parts of HPVM-2202, 15 parts of acetone
0 parts were charged and stirred uniformly. To this polyol solution, 85.2 parts of 4,4'-dicyclohexylmethane diisocyanate and 0.03 part of dibutyltin dilaurate were charged, and reacted at 50 ° C. for 5 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. To this prepolymer solution, 150 parts of acetone, 700 parts of water, 24.3 parts of isophorone diamine, and 3 parts of diethanolamine.
The mixed solution with 3 parts was added at a stretch to carry out elongation reaction and phase inversion, and reacted at 40 ° C. until the isocyanate group disappeared. After that, deacetone with an evaporator,
A water-dispersible polyurethane resin composition PU-3 was obtained. P
U-3 has a solid content of 30.0% and a number average molecular weight of 1
It was 9,000.

Example 4 In a reactor similar to that of Example 1, 168.6 of polyol D was added.
Parts, 56.2 parts of a polycarbonate having a hydroxyl group at both ends having a number average molecular weight of 2,000 obtained from diphenyl carbonate and 1,6-hexanediol, 56.2 parts, HPVM-220
2 in 20.2 parts and neopentyl glycol in 11.7 parts
Parts and 300 parts of acetone were charged and uniformly stirred. To this polyol solution, 41.1 parts of hydrogenated xylylene diisocyanate and 0.03 parts of dibutyltin dilaurate were charged and reacted at 50 ° C. until the isocyanate group disappeared. To this polymer solution, 700 parts of water was added to perform phase inversion, and then deacetone was performed by an evaporator to obtain a water-dispersible polyurethane-based resin composition PU-4. The solid content of PU-4 was 29.8%, and the number average molecular weight was 26,000.

Comparative Example 1 In a reactor similar to that in Example 1, 186.2 of polyol C was added.
And 150 parts of acetone, and uniformly stirred. 82. Isophorone diisocyanate was added to this polyol solution.
7 parts and 0.03 part of dibutyltin dilaurate were charged,
The reaction was carried out at 50 ° C. for 5 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. To this prepolymer solution, a mixed solution of 150 parts of acetone, 700 parts of water, 30.1 parts of isophoronediamine, and 1.1 parts of monoethanolamine was added all at once, and an elongation reaction and phase inversion were performed.
The reaction was carried out at 40 ° C. until the isocyanate groups disappeared. Thereafter, deacetone was performed using an evaporator to obtain a water-dispersible polyurethane-based resin composition PU-5. PU
The solid content of −5 is 30.0%, the number average molecular weight is 32,
000.

Comparative Example 2 In a reactor similar to that in Example 1, 21-end polyesters having hydroxyl groups at both ends and having a number average molecular weight of 3,000 obtained from 3-methyl-1,5-pentanediol and adipic acid were added.
9.6 parts, 19.6 parts of dimethylolpropionic acid and 150 parts of acetone were charged and uniformly stirred. 48.7 parts of isophorone diisocyanate and 0.03 part of dibutyltin dilaurate were charged into this polyol solution,
For 5 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. After adding 150 parts of acetone and 14.8 parts of triethylamine to this prepolymer solution, 700 parts of water and 11.1 parts of isophoronediamine were added.
A mixed solution of 2 parts and 0.9 parts of monoethanolamine was added all at once, and an elongation reaction and a phase inversion were carried out at 40 ° C. until the isocyanate group disappeared. Thereafter, deacetone was performed using an evaporator to obtain a water-dispersible polyurethane-based resin composition PU-6. The solid content of PU-6 is 3
1.5%, number average molecular weight was 40,000.

Comparative Example 3 In a reactor similar to that in Example 1, 45.8 of polyol A was added.
Part, 3-methyl-1,5-pentanediol and 183.2 parts of a polyester having a hydroxyl group at both ends having a number average molecular weight of 3,000 obtained from adipic acid, hydrogenated polybutadiene having a hydroxyl group at both ends (trade name: Polytail) HA,
Mitsubishi Chemical, linear unit / side chain unit = 10/9
12.2 parts of 0) and 150 parts of acetone were charged and uniformly stirred. 48.8 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate were added to this polyol solution.
03 parts were charged and reacted at 50 ° C. for 5 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. 150 parts of acetone and 70 parts of water were added to this prepolymer solution.
0 parts, a mixed solution of 9.3 parts of triethylamine, 9.3 parts of isophoronediamine and 0.7 part of monoethanolamine are added all at once, and an elongation reaction and phase inversion are carried out until the isocyanate groups disappear at 40 ° C. Reacted. Thereafter, evaporator deacetone was performed to obtain an aqueous polyurethane-based resin composition PU-7. The solid content of PU-7 is 30.
6%, the number average molecular weight was 49,000.

Comparative Example 4 Polyol A was placed in a reactor similar to that of Synthesis Example 1 at 45.degree.
One part, 180.2 parts of a polyester having both ends hydroxyl groups having a number average molecular weight of 3,000 obtained from 3-methyl-1,5-pentanediol and adipic acid, 180.2 parts, a hydrogenated polybutadiene having both ends hydroxyl groups (trade name: Polytail H,
Mitsubishi Chemical, linear unit / side chain unit = 80/2
1) and 150 parts of acetone were charged and stirred, but polytail H aggregated. Then, the temperature was increased to 50 ° C., but the polytail H was not dispersed, and the synthesis was abandoned. Table 2 shows Examples 1 to 4 and Table 3 shows Comparative Examples 1 to 4.

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[Table 2]

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[Table 3]

In Tables 2 and 3, 3-MPA: number average molecular weight of 3,000 obtained from 3-methyl-1,5-pentanediol and adipic acid
Hydroxyl-containing polyester PCD-2000: number average molecular weight 2,000 obtained from 1,6-hexanediol and diphenyl carbonate
Hydroxyl-terminated polycarbonate IPDI: isophorone diisocyanate H ₆ XDI: hydrogenated xylylene diisocyanate H ₁₂ MDI: 4,4′-dicyclohexylmethane diisocyanate DBTDL: dibutyltin dilaurate TEA: triethylamine IPDA: isophorone diamine NPG: neopentyl glycol MEA: Monoethanolamine DEA: Diethanolamine DMPA: Dimethylolpropionic acid

[Preparation of Adhesive] Example 5 PU-1 was prepared with the following composition. Aqueous polyurethane resin composition 50 parts Aquanate-100 3 parts (Aquanate-100: Nippon Polyurethane Industry, water-dispersible polyisocyanate)

Examples 6-8, Comparative Examples 5-7 Adhesives were prepared using PU-2-7 instead of PU-1.

[Adhesion Test] The prepared adhesive was applied to a bar coater No. At 6, coating was performed on both sides with the following combinations of films so that the coating amount was 2 g / m ² on a dry basis. (1) Corona treated CPP film / Corona treated CPP film (2) Corona treated PET film / Corona treated PET film (3) Corona treated PET film / Corona treated CPP film (4) Corona treated CPP film / Corona treated nylon film Adhesive Is applied to the adherend, and after taking an open time of 80 ° C. × 5 seconds, immediately bonding, and after bonding, 50 ° C.
It was left still for 24 hours. Then, it is cut to a width of 15 mm, a tensile speed: 50 mm / min, and a measurement atmosphere: 2
A T-type peel test was performed at 5 ° C. × 50% RH. Table 4 shows the results of the adhesion test.

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[Table 4]

In Table 4, CPP: unstretched polypropylene PET: polyethylene terephthalate Measurement unit: gf / 15 mm Film material breakage occurs in the CPP film

[Formation of Coating Film] Example 9 100 parts of PU-1 and 8 parts of N-methyl-pyrrolidone were blended to prepare a clear paint. Using this paint,
Dry coating film on polypropylene plate with bar coater 30-40
After being coated so as to have a μ, it was dried at 80 ° C. for 20 minutes, and left at room temperature for 5 hours.

Examples 9 to 12 and Comparative Examples 8 to 10 Instead of PU-1, PU-2 to 7 were used in the proportions shown in Tables 5 and 6 to prepare clear coatings. These paints were applied in the same manner as in Example 5.

The adhesion and flexibility of the coating films in Examples 7 to 9 and Comparative Examples 3 and 4 were evaluated. Adhesion is JIS K
It measured according to the crosscut tape method of -5400. Flexibility was evaluated by a hot and cold repetition test. Crosscut tape method: Cut 100mm squares into 100 squares using a cutter knife with a cutter guide using a cutter guide, then press with a cellophane tape on top of it, then peel off instantaneously and peel off the coating I saw 10: No peeling of the coating film is observed. 8: Peeling of the coating film is 0 to 5%. 6: Peeling of the coating film is 5 to 15%. 4: Peeling of the coating film is 15 to 35%. 35 to 65% 0: The peeling of the coating film was 65% or more. The hot and cold repetition method; The coating film appearance after 10 cycles of the coating film at -20 ° C for 1 hour and 50 ° C for 1 hour was evaluated. ：: No abnormality such as clouding, whitening, cracking, and peeling was observed in the coating film. ×: An abnormality was observed in the coating film. Tables 5 show evaluations of the coating films in Examples 7 to 9 and Comparative Examples 3 and 4.

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[Table 5]

Claims (5)

[Claims] 1. A water-dispersible polyurethane resin composition comprising an organic diisocyanate, an active hydrogen group-containing compound, a hydrophilic polar group and an active hydrogen group-containing compound, wherein the active hydrogen group-containing compound has a hydroxyl group-containing poly (ethylene- A water-dispersible polyurethane resin composition comprising a (butylene) copolymer. 2. An ethylene / poly (ethylene-butylene) copolymer having hydroxyl groups at both ends according to claim 1.
An aqueous polyurethane resin composition, wherein the molar ratio of butylene is 30/70 to 70/30, and the hydrophilic polar group is a carboxylate and / or sulfonate. 3. The compound having a hydrophilic polar group and an active hydrogen group according to claim 1, which has a number average molecular weight of 500-1.
A water-dispersible polyurethane resin composition having a molecular weight of 000. 4. An aqueous adhesive comprising the water-dispersible polyurethane resin composition according to claim 1. 5. An aqueous coating comprising the water-dispersible polyurethane resin composition according to claim 1.