JP3493649B2 - Water-dispersible polyurethane resin composition, and adhesive and paint using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-dispersible polyurethane-based resin composition using a specific hydroxyl group-containing polyolefin and various materials, particularly an aqueous adhesive and an aqueous paint having good adhesion and adhesion to polyolefin. Regarding

[0002]

2. Description of the Related Art In recent years, organic solvents have been mainly used in the fields of adhesives, paints, etc., but water-based ones have been adopted from the viewpoints of preventing air pollution, regulations under the Fire Service Act, occupational hygiene, etc. Is being started. As this water-based adhesive, resin for paint,
It has been proposed to use a polyester-based or polyether-based polyurethane resin containing a hydrophilic polar group such as a carboxylate. Japanese Unexamined Patent Publication (Kokai) No. 5-117358 discloses an aqueous polyurethane resin composition obtained from a polyester diol having hydroxyl groups at both ends having a molecular weight of 15,000 to 10,000 and an isocyanate monomer having at least one isocyanate group. Has been done. Further, JP-A-4-68022 discloses an aqueous dispersion of a polyurethane resin obtained from a hydroxyl group-containing polyalkylene oxide and polyisocyanate. Further, Japanese Patent Publication No. 5-86829 discloses an aqueous polyurethane resin adhesive containing a hydrogenated polybutadiene having a hydroxyl group.

[0003]

However, JP-A-5-1 is used.
Conventional polyester-based water-based polyurethane resins, such as the water-based polyurethane resin composition described in Japanese Patent No. 17358, have good adhesiveness and adhesion to so-called polar base materials such as polyethylene terephthalate and nylon, but non-polyolefin such as polyolefin. Adhesion to polar substrates was unsatisfactory. Japanese Patent Laid-Open No. 4-680
Since the aqueous dispersion of polyurethane resin described in JP-A No. 22 is a polyether base, it has insufficient water resistance, durability and mechanical strength. Japanese Patent Publication No. 5-86829 discloses that
An aqueous polyurethane adhesive using a hydroxyl-containing hydrogenated polybutadiene with improved number of functional groups and residual double bonds is described, but this hydroxyl-containing hydrogenated polybutadiene has an extremely high ratio of linear units to side chain units. Since it is biased, the crystallinity of the polyolefin part becomes too large, and the adhesiveness to the resulting water-dispersible polyurethane,
It does not contribute to adhesion. In addition, since conventional hydroxyl group-containing polyolefins such as hydroxyl group-containing polybutadiene have a functional number of more than 2, it is difficult to obtain the target polyurethane resin itself, and the obtained resin also has a double bond remaining in the polybutadiene unit. Therefore, the weather resistance was difficult.

The present invention has sufficiently excellent adhesiveness and adhesiveness to various substrates such as polyolefin-containing waterborne polyurethane resin compositions and all-purpose plastics including general-purpose polyolefins, and has excellent durability. It is an object to provide an aqueous adhesive and an aqueous paint.

[0005]

That is, the present invention is shown in the following (1) to (5). (1) Organic diisocyanate, 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) containing hydroxyl groups at both ends
A water-dispersible polyurethane-based resin composition comprising a copolymer.

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

(3) The number average molecular weight of the hydrophilic polar group- and active hydrogen group-containing compound described in (1) and (2) above is
A water-dispersible polyurethane-based resin composition, which is 500 to 10,000.

(4) A water-based adhesive using the water-dispersible polyurethane resin composition described in (1) to (3) above.

(5) An aqueous paint using the water-dispersible polyurethane resin composition described in (1) to (3) above.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Organic diisocyanates used in the present invention include 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-trimethylhexahexylene-1,6-
Non-yellowing diisocyanates 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 yellowing resistant diisocyanates such as ortho-xylylene diisocyanate, meta-xylylene diisocyanate, para-xylylene diisocyanate and tetramethylxylylene diisocyanate. These organic diisocyanates may be used alone or as a mixture. Further, modified products such as 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 both-end hydroxyl group-containing poly (ethylene-butylene) copolymer is preferably 1 to 50% by weight of the polyurethane resin, and particularly preferably 3 to 30% by weight. When the introduction amount of the poly (ethylene-butylene) copolymer having hydroxyl groups at both ends is less than 1%, the adhesiveness to the polyolefin film becomes poor. If it exceeds 50% by weight, the adhesiveness to a plastic film other than the polyolefin film becomes poor.

The molar ratio of ethylene and butylene in the hydroxyl group-containing poly (ethylene-butylene) copolymer is 30/70 to 7
0/30, preferably 35 / 65-65 / 35
Is. When the molar ratio of ethylene to butylene is more than 30/70 and that of butylene is more than 70/30, the crystallinity of the poly (ethylene-butylene) copolymer becomes large and the adhesiveness becomes poor.

The number average molecular weight of the poly (ethylene-butylene) copolymer having hydroxyl groups at both ends is preferably 500 to 10,000, and particularly preferably 1,000 to 9,000. When the number average molecular weight is less than 500, the adhesiveness and adhesion to a non-polar substrate such as polyolefin becomes poor. Also, 1
If it exceeds 50,000, the durability and the adhesiveness and adhesion to polar substrates such as polyethylene terephthalate and nylon will be poor.

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

Specific examples of the poly (ethylene-butylene) copolymer containing hydroxyl groups at both ends include Kraton 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 they are roughly classified into polymer polyols and chain extenders. As a high molecular weight polyol, the number average molecular weight is 5
There are polyester polyols, polyether polyols, polycarbonate polyols, polyether ester polyols, and the like of 0 to 10,000.

As the polyester polyol, 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, hemimellitic acid, trimellitic acid, pyromellitic acid, and benzophenonetetracarboxylic acid Or, one or more kinds of anhydrides and 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, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, trimethylolpropane, glycerin, hexanetriol, quadrol, and other low-molecular diols, low-molecular triols, etc. Obtained by dehydration condensation reaction with one or more of Furthermore, ε
-Caprolactone, alkyl-substituted ε-caprolactone,
Examples include lactone polyester polyols obtained by 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 polyether ester polyol, there are copolyols obtained from the above-mentioned polyether polyols and the above-mentioned dicarboxylic acids.

As the polycarbonate polyol, one of the low molecular weight polyols derived from the polyester polyol source described above is used.
It is obtained from a dealcoholation reaction, a deglycolization reaction, or a dephenolation reaction of any one or more of dialkyl carbonate, dialkylene carbonate, and diphenyl carbonate.

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

The chain extender includes water having a molecular weight of 18 to 500, urea, low molecular weight polyols, low molecular weight polyamines and low molecular weight amino alcohols, and these may be used alone or in combination of two or more kinds.

As the low molecular weight polyol as the chain extender, there are the low molecular weight polyols of the above 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 amino alcohols include monoethanolamine, diethanolamine, N-methyldiethanolamine and N-phenyldipropanolamine.

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

The hydrophilic polar group used in the present invention and the hydrophilic polar group of the active hydrogen group-containing compound are nonionic, anionic or cationic hydrophilic polar groups. Sources include nonionic hydrophilic polar groups such as poly (oxyethylene) ether,
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 nonionic hydrophilic polar group- and active hydrogen group-containing compound 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 and glycerin. . Of 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 is 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. A mixed alkylene oxide chain containing at least 70% of ethylene oxide units may be used.

The anionic hydrophilic polar group- and active hydrogen group-containing compound comprises organic acids having at least one active hydrogen group and a neutralizing agent. Examples of the 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, ricinoelaidic acid, ricinostearolic acid, salicylic acid, mandelic acid, etc., oleic acid, ricinoleic acid, linoleic acid, etc. Hydroxy fatty acid obtained by hydroxylating saturated fatty acid, glutamine, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid, diamino acid 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, 5-
Examples thereof include a polyester polyol using hydroxysulfoisophthalic acid, a polycaprolactone polyol using a carboxylic acid-containing polyol as an initiator, a transesterification product of a polyester polyol or a polycarbonate polyol and a carboxylic acid-containing polyol. Further, it is also possible to use a half ester mixture or a half amide mixture containing a carboxyl group obtained by reacting a polyol such as a high molecular polyol or a low molecular polyol described above or a polyamine with a polycarboxylic acid anhydride. In particular, when a polyol is added to a dianhydride such as pyromellitic dianhydride, two carboxylic acids are produced, so that a hydrophilic polar group can be introduced into the molecular chain of the polyester polyol.
Examples of other anionic hydrophilic groups include phosphoric acid and the like.

As the neutralizing agent, 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,
Examples thereof include inorganic alkalis such as potassium hydroxide. In order to improve weather resistance and water resistance after drying, those having high volatility that easily dissociate by heat are preferable, and ammonia, trimethylamine and triethylamine are preferable. In addition, these organic acids and the neutralizing agent may be used alone or as a mixture of two or more kinds.

Examples of the cationic hydrophilic polar group- and active hydrogen group-containing compound include tertiary amines containing at least one active hydrogen group capable of reacting with an isocyanate group, inorganic acids, organic acids and quaternizing agents. Consisting of what is selected. As the tertiary amine, N-methyldiethanolamine, N-ethyldiethanolamine or 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,
Examples thereof include alkyl halides such as propyl bromide and butyl bromide. Further, as other cationic hydrophilic polar group-containing compounds, primary amine salts, secondary amine salts, tertiary amine salts, and
Examples include cationic compounds such as primary 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 hydrophilic polar group- and active hydrogen group-containing compounds, the preferable 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, a combination of polycaprolactone diol, polyester diol, polycarbonate diol and triethylamine as a neutralizing agent using dimethylolpropionic acid and / or dimethylolbutanoic acid, which is an anionic hydrophilic polar group-containing low molecular weight diol, And / or
Polyester polyols using 5-sodium sulfoisophthalic acid and polycarbonate-based polyols are preferred.

Although the anionic and cationic hydrophilic polar groups will eventually be present in the polyurethane resin in the form of salts, they may be neutralized and then introduced into the resin. The polar group may be introduced into the resin and then neutralized.

The amount of introduced nonionic hydrophilic polar group is 0.
1 to 50% by weight, the amount of anionic and cationic hydrophilic polar groups introduced is 0.1 to 1.0 mmol / g, and the preferred amount is 0.2 to 45% by weight for nonionic, anionic and In a cationic system, 0.2-0.8 mmol /
It is g. When the amount of the hydrophilic polar group introduced is less than the above lower limit, the polyurethane resin is not well dispersed in water. If the upper limit is exceeded, the water resistance of the polyurethane resin after drying will be insufficient.

The polyurethane resin composition of the present invention comprises
A reaction terminator can be used if necessary. Examples of the reaction terminator include monoalcohol, monoamine, aminoalcohol and the like, and a mixture thereof, and monoisocyanate 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 primary amines. Examples of amino alcohols include monoethanolamine and diethanolamine. Monoisocyanates include phenyl isocyanate and cyclohexyl isocyanate.

As the method for producing the polyurethane resin used in the present invention, the one-shot method in which the reaction is carried out in an atmosphere of excess active hydrogen, or the active hydrogen compound and the organic diisocyanate are reacted in excess of NCO groups to synthesize an NCO-terminated prepolymer. After that, it can be synthesized by a known method such as a prepolymer method of reacting an active hydrogen compound. In addition, after reacting the polyurethane resin in an organic solvent compatible with water, water is added and then the organic solvent is removed, or the resin is synthesized without using a solvent and forcedly dispersed or dissolved in water. Can also be obtained

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

In the case of the prepolymer method, the ratio of active hydrogen / NCO at the time of synthesizing the prepolymer is 1.1 to 5.0, preferably 1.5 to 4.0. If less than 1.1,
Since the molecular weight of the prepolymer becomes too large, it is difficult to proceed to the subsequent reaction step. 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, swazol (aromatic hydrocarbon produced by Cosmo Petroleum), Solvesso (aromatic hydrocarbon produced by Exxon Chemical Co., Ltd.) and the like. , Acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone system such as cyclohexanone, alcohol system such as methanol, ethanol, isopropanol, ester system such as ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, Examples thereof include glycol ether ester systems such as 3-methyl-3-methoxybutyl acetate and ethyl-3-ethoxypropionate, and ether systems such as tetrahydrofuran and dioxane. The solvent may be used alone or in combination of two or more.

As the reaction catalyst for synthesizing the isocyanate group-terminated prepolymer and the polyurethane resin used in the present invention, known urethanization catalysts 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, and particularly preferably 10,000 or more. When the number average molecular weight of the polyurethane resin is less than 5,000, the durability becomes poor.

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

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

[0047]

As described above, according to the present invention, sufficient adhesion and adhesion to various substrates such as polyolefin-containing waterborne polyurethane resin composition and all plastics including general-purpose polyolefin can be 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 specifically described below with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" in the examples mean "parts by weight" and "% by weight", respectively.

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

Synthetic Example 2 A reactor similar to Synthetic Example 1 was charged with 7 parts of dimethylolbutanoic acid.
90 parts of 4.0 parts of a polycarbonate diol having a number average molecular weight of 3,000 obtained by a dephenol reaction of 1,6-hexanediol and diphenyl carbonate was used.
Parts, 1,6-hexanediol 23.5 parts charge, 16
Warmed to 0 ° C. When the temperature reached 180 ° C, 0.05 part 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 A reactor similar to Synthesis Example 1 was charged with 148.0 parts of dimethyl 5-sodium sulfoisophthalate and 542.9 parts of 1,6-hexanediol, and a methanol removal reaction was conducted at 180 ° C. Let After 5 hours from the start of the reaction, the distillation of methanol stopped, so 452.7 parts of adipic acid was added, and dehydration reaction was further carried out at 180 ° C. Since the distillation of water stopped 5 hours after the addition of adipic acid, 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. Reacted for hours. The hydroxyl value of the obtained polyol C is 1
11.7 mgKOH / g, acid value 0.5 mgKOH /
g, the sulfonate content was 0.5 mmol / g, and the number average molecular weight was 1,000.

Synthesis Example 4 156.0 parts of dimethyl 5-potassium sulfoisophthalate was placed in the same reactor as in Synthesis Example 1, and the number average molecular weight obtained by the dephenol reaction of 1,6-hexanediol and diphenyl carbonate. 789.0 parts of 3,000 polycarbonate diols and 8 parts of 1,6-hexanediol
7.0 parts and 0.05 parts of tetrabutyl titanate were charged, and the methanol removal reaction was carried out at 180 ° C. for 4 hours under normal pressure. Then, 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 is 56.1 mg.
KOH / g, sulfonate content is 0.5 mmol
/ G, the number average molecular weight was 2,000. Polyols A to D are shown in Table 1.

[0053]

[Table 1]

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

[Synthesis of Water-Dispersible Polyurethane-Based Resin Composition] Example 1 Polyol A is 46.1 in a four-necked flask equipped with a stirrer, a thermometer, an Aren cooling tube, and a nitrogen gas introducing tube.
Part, 3-methyl-1,5-pentanediol and adipic acid, 184.3 parts of a polyester having a number average molecular weight of 3,000 and having hydroxyl groups at both ends, and a poly (ethylene-butylene) copolymer having hydroxyl groups at both ends (HPVM-22
No. 02, made by Shell) and 11.1 parts of acetone and 150 parts of acetone were added and stirred uniformly. This polyol solution was charged with 48.4 parts of isophorone diisocyanate and 0.03 part of dibutyltin dilaurate as a urethane-forming catalyst.
The reaction was carried out at 0 ° C for 5 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. 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 with 0.7 part of monoethanolamine was added all at once, an extension reaction and a phase inversion were performed, and the reaction was carried out at 40 ° C. until the isocyanate group disappeared. Then, acetone was removed with an evaporator to obtain a water-dispersible polyurethane resin composition PU-1. The solid content of PU-1 is 30.9.
%, And the number average molecular weight was 49,000.

Example 2 140.1 of polyol B was placed in the same reactor as in Example 1.
Parts, 93.4 parts of a polycarbonate having a number average molecular weight of 2,000 and having hydroxyl groups at both ends obtained from diphenyl carbonate and 1,6-hexanediol, HPVM-220
2 16.8 parts, neopentyl glycol 4.9 parts,
300 parts of acetone was charged and uniformly stirred. Add 4 parts hydrogenated xylylene diisocyanate to this polyol solution.
2.6 parts and 0.03 parts of dibutyltin dilaurate were charged and reacted at 50 ° C. until the isocyanate groups disappeared. To this polymer solution, triethylamine was added to 7.1.
Added some. Thereafter, 700 parts of water was added to carry out phase inversion, and then acetone was removed with an evaporator to obtain a water-dispersible polyurethane 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 The same reactor as in Example 1 was charged with 158.6 of polyol C.
Parts, 28.6 parts of HPVM-2202, 15 parts of acetone
0 part was charged and stirred uniformly. This polyol solution was charged with 85.2 parts of 4,4'-dicyclohexylmethane diisocyanate and 0.03 part of dibutyltin dilaurate 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 isophoronediamine, and diethanolamine3.
A mixed solution with 3 parts was added all at once to carry out extension reaction and phase inversion, and the reaction was carried out at 40 ° C. until the isocyanate group disappeared. After that, de-acetone is performed 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 number average molecular weight of 2,000 and having hydroxyl groups at both ends obtained from diphenyl carbonate and 1,6-hexanediol, HPVM-220
20.2 parts, neopentyl glycol 11.7
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 part of dibutyltin dilaurate were charged and reacted at 50 ° C. until the isocyanate groups disappeared. 700 parts of water was added to this polymer solution for phase inversion, and then acetone was removed by an evaporator to obtain a water-dispersible polyurethane resin composition PU-4. PU-4 had a solid content of 29.8% and a number average molecular weight of 26,000.

Comparative Example 1 Polyol C was added to a reactor similar to that used in Example 1 with 186.2.
Parts and 150 parts of acetone were charged and stirred uniformly. 82. Isophorone diisocyanate was added to this polyol solution.
Charge 7 parts and 0.03 parts of dibutyltin dilaurate,
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 to carry out an extension reaction and phase inversion,
The reaction was carried out at 40 ° C. until the isocyanate groups disappeared. Then, acetone was removed with an evaporator to obtain a water-dispersible polyurethane resin composition PU-5. PU
The solid content of -5 is 30.0%, the number average molecular weight is 32,
It was 000.

Comparative Example 2 In a reactor similar to that of Example 1, 21-hydroxyl-terminated polyester having a number average molecular weight of 3,000 and obtained from 3-methyl-1,5-pentanediol and adipic acid was used.
9.6 parts, 19.6 parts of dimethylol propionic acid, and 150 parts of acetone were charged and stirred uniformly. This polyol solution was charged with 48.7 parts of isophorone diisocyanate and 0.03 part of dibutyltin dilaurate and heated to 50 ° C.
Was reacted 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.
A mixed solution of 2 parts and 0.9 parts of monoethanolamine was added all at once, an extension reaction and a phase inversion were performed, and the reaction was carried out at 40 ° C. until the isocyanate group disappeared. Then, acetone was removed with an evaporator to obtain a water-dispersible polyurethane resin composition PU-6. The solid content of PU-6 is 3
1.5%, the number average molecular weight was 40,000.

Comparative Example 3 In a reactor similar to that used in Example 1, 45.8 of polyol A was added.
Parts, 183.2 parts of a polyester having a number average molecular weight of 3,000 and having hydroxyl groups at both ends obtained from 3-methyl-1,5-pentanediol and adipic acid, hydrogenated polybutadiene having a hydroxyl group at both ends (trade name: Polytere HA,
Mitsubishi Chemical, linear unit / side chain unit = 10/9
12.2 parts of 0) and 150 parts of acetone were charged and stirred uniformly. To this polyol solution was added 48.8 parts of isophorone diisocyanate and 0.
03 parts 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 and 70 parts of water were added.
A mixed solution of 0 part, 9.3 parts of triethylamine, 9.3 parts of isophoronediamine and 0.7 part of monoethanolamine was added all at once to carry out extension reaction and phase inversion until the isocyanate group disappeared at 40 ° C. It was made to react. Then, the evaporator was subjected to acetone removal to obtain an aqueous polyurethane resin composition PU-7. The solid content of PU-7 was 30.
6% and the number average molecular weight were 49,000.

Comparative Example 4 Polyol A was added to a reactor similar to that used in Synthesis Example 1 in an amount of 45.
10.2 parts, 180.2 parts of a polyester having a number average molecular weight of 3,000 and having hydroxyl groups at both ends obtained from 3-methyl-1,5-pentanediol and adipic acid, hydrogenated polybutadiene having a hydroxyl group at both ends (trade name: Polytail H,
Mitsubishi Chemical, straight chain unit / side chain unit = 80/2
0) was charged with 16.8 parts and 150 parts with acetone and stirred, but Polytail H aggregated. Therefore, the temperature was heated 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: 3-methyl-1,5-pentanediol and a number average molecular weight 3,000 obtained from adipic acid.
Polyester PCD-2000 containing hydroxyl groups at both ends of the compound: 1,6-hexanediol and diphenyl carbonate
Both end hydroxyl group-containing 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 formulation. Aqueous polyurethane-based resin composition 50 parts Aquanate-100 3 parts (Aquanate-100: manufactured by Nippon Polyurethane Industry Co., Ltd., water-dispersible polyisocyanate)

Examples 6 to 8 and Comparative Examples 5 to 7 PU-2 to 7 were used instead of PU-1 to prepare adhesives.

[Adhesion Test] The prepared adhesive was applied to a bar coater No. In No. 6, the both surfaces were coated with the following film combinations so that the coating amount was 2 g / m ² when dry. (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 an open time of 80 ° C x 5 seconds, it is immediately laminated and then 50 ° C after lamination.
It was allowed to stand under the condition of 24 hours. Then, cut into a width of 15 mm, pulling speed: 50 mm / min, measuring atmosphere: 2
A T-type peeling test was conducted at 5 ° C. × 50% RH. The results of the adhesion test are shown in Table 4.

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[Table 4]

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

[Preparation of coating film] Example 9 A clear paint was prepared by blending 100 parts of PU-1 and 8 parts of N-methyl-pyrrolidone. With this paint,
Dry coating on polypropylene plate with a bar coater 30-40
After coating so as to have a thickness of μ, the coating was dried at 80 ° C. for 20 minutes and then left at room temperature for 5 hours.

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

The adhesion and flexibility of the coating films of Examples 7 to 9 and Comparative Examples 3 and 4 were evaluated. Adhesion is JIS K
It measured according to the cross-cut tape method of -5400. The flexibility was evaluated by a hot and cold repeated test. Cross-cut tape method: Using a cutter guide to make a cut into 100 squares of 1 mm square with a cutter knife on the coating film, press it with cellophane tape from above, and then peel it off momentarily and the coating film peels off I saw. 10: No peeling of coating film 8: Peeling of coating film is 0 to 5% 6: Peeling of coating film is 5 to 15% 4: Peeling of coating film is 15 to 35% 2: Peeling of coating film 35 to 65% 0: Peeling of coating film is 65% or more by hot and cold repeating method; The coating film was evaluated for the appearance after 10 cycles of -20 ° C for 1 hour and 50 ° C for 1 hour. ◯: No abnormalities such as clouding, whitening, cracking, and peeling are observed in the coating film. X: Abnormalities in the coating film are observed. Examples 5 to 9 and Comparative Examples 3 and 4 show the evaluation of the coating film.

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[Table 5]

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-59-113016 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 18/00-18/87 C08L 75 / 04-75/16 C09D 175/04-175/16 C09J 175/04-175/16

Claims (5)

(57) [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 is poly (ethylene- Butylene) copolymer is contained, The water dispersible polyurethane type resin composition characterized by the above-mentioned. 2. Ethylene constituting the poly (ethylene-butylene) copolymer containing 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 a sulfonate. 3. The number average molecular weight of the hydrophilic polar group- and active hydrogen group-containing compound according to claim 1 or 2 is 500 to 1.
A water-dispersible polyurethane-based resin composition, which is 10,000. 4. A water-based adhesive using the water-dispersible polyurethane resin composition according to claim 1. 5. A water-based paint using the water-dispersible polyurethane resin composition according to claim 1.