JP2000143971A - Aqueous polyurethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous polyurethane resin composition suitable for a coating material or an adhesive above all for agricultural film or wall decorations and excellent in adhesion, weather resistance and antifog property. SOLUTION: When an aqueous polyurethane resin composition is prepared by dispersing an aqueous polyurethane resin produced from a polyester polyol and a polyisocyanate into water in an emulsified state, 1,2-hydroxystearic acid or/and 1,2-hydroxystearyl alcohol are used as essential constitutional components of the polyester polyol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water-based polyurethane resin composition, more particularly, a 12-urethane resin composition which can be particularly suitably used as a coating agent and / or an adhesive for plastic products such as agricultural films and wall coverings. The present invention relates to an aqueous polyurethane resin composition having excellent adhesion obtained from a polyester polyol having hydroxystearic acid and / or 12-hydroxystearyl alcohol as essential components and a polyisocyanate.

[0002]

2. Description of the Related Art In recent years, house cultivation and tunnel cultivation using agricultural films have been actively performed. In such cultivation, when the agricultural film is stretched and used, there is a drawback that clouding occurs due to the attachment of water droplets on the inside, which adversely affects the growth of the crop. In order to prevent this, a method such as applying or kneading a drip-proof agent on the inner wall has been adopted, but the drip-proof agent flows out and usually 1
The effect deteriorates in about a year, and it becomes necessary to re-apply, and during this time, there is a problem that agricultural work cannot be performed.

As a method for improving the durability, a method of applying a water-based polyurethane resin to the surface of a film to form a coating film has been proposed, but not only has the disadvantage of poor adhesion, but also has a disadvantage. The drip-proof effect is also insufficient,
This problem had to be solved as well.

[0004] Even when used as wallpaper, there are problems such as adhesiveness, fading or coloring by light, and it is essential to solve these problems.

[0005] For this reason, attempts have been made to improve the adhesion to an object to be coated by changing the composition of the aqueous polyurethane resin.

For example, Japanese Unexamined Patent Publication (Kokai) No. 62-246,972 discloses that a neutral or basic extender is blended with an aqueous polyurethane resin having a higher degree of branching using a trifunctional or higher functional polyol and / or a polyamine compound. But the improvement effect of this method is insufficient,
It was not practically satisfactory. In addition, Japanese Unexamined Patent Publication
No. 269723 discloses that, as a polyisocyanate compound, an aromatic polyisocyanate compound having high reactivity with water and a low reactivity with water are used in order to improve the properties of the water-based polyurethane resin having an increased degree of branching. It has been proposed to use an aliphatic or alicyclic polyisocyanate compound in combination, but while the strength of the coating film is increased,
There is a drawback that the flexibility is reduced, which is not satisfactory in practical use.

JP-A-7-298791 proposes to use an aqueous acrylic-modified urethane resin coating layer containing colloidal silica particles on one side of a synthetic resin film, but it is practically satisfactory. I couldn't do it. Further, Japanese Patent Application Laid-Open No. Hei 10-17689 proposes to use a coating film containing a polyurethane resin and a specific acrylic resin, but has a drawback that the production is troublesome and is not practically satisfactory. Did not.

Accordingly, an object of the present invention is to provide a water-based polyurethane resin excellent in adhesion, weather resistance and anti-fog properties, which can be suitably used as a coating agent or an adhesive especially for agricultural films or wall coverings. It is to provide a composition.

[0009]

The present inventors have conducted various studies and found that 12-hydroxystearic acid and / or
It has been found that the above object can be achieved by using an aqueous polyurethane resin composition containing a polyester polyol having 12-hydroxystearyl alcohol as an essential component and a polyisocyanate as essential components.

[0010] The present invention has been made based on the above findings, and is directed to 12-hydroxystearic acid and / or 12-hydroxystearic acid.
The present invention provides an aqueous polyurethane resin composition in which an aqueous polyurethane resin produced from a polyester polyol containing hydroxystearyl alcohol as an essential component and a polyisocyanate is emulsified and dispersed in water.

[0011] The present invention also relates to the present invention, wherein the polyester polyol comprises 12-hydroxystearic acid and a polyol having a di- or trifunctional hydrocarbon having 2 to 40 carbon atoms as an essential component, and if necessary, a polycarboxylic acid. To provide an aqueous polyurethane resin composition which is a polyester polyol derived by the above method.

[0012] The present invention also relates to the above-mentioned polyester polyol, wherein the above-mentioned polyester polyol contains, as essential components, 12-hydroxystearyl alcohol and polycarboxylic acid, and if necessary, other polyols having di- or tri-functional hydrocarbons having 2 to 40 carbon atoms. And a water-based polyurethane resin composition which is a polyester polyol derived from the above.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the aqueous polyurethane resin composition of the present invention will be described in detail.

The aqueous polyurethane resin composition of the present invention can be produced by a well-known method. For example, (1) a polyester polyol having 12-hydroxystearic acid and / or 12-hydroxystearyl alcohol as an essential component and a polyisocyanate are chained. A method in which a urethanation reaction is carried out in a solvent inert to the reaction together with an extender and having a high affinity for water to form a prepolymer, and the prepolymer is dispersed in water in the presence of an emulsifier, if necessary; In the method of (1), a polyol having a carboxyl group or a sulfonic acid group in a molecule or a polyol having a basic group in a molecule as a part of a chain extender is a solvent inert to a reaction and having high affinity for water. In the urethanization reaction to form a prepolymer, and then neutralize the prepolymer with a neutralizing agent The method and the like to the prepolymer imparting of dispersibility dispersed in water. In the methods (1) and (2), the chain extender can be used at any stage, and a method of simultaneously performing dispersion and chain extension can also be adopted.

Among these methods, in particular, the above (2)
This method is preferred because it does not require the use of an emulsifier, which not only simplifies the process but also eliminates the risk of adverse effects due to the emulsifier remaining in the coating film.

The polyester polyol containing 12-hydroxystearic acid which is used as one of the constituent components of the polyester polyol according to the present invention contains 12-hydroxystearic acid as an essential component and has 2 to 3 functional carbon atoms having 2 to 40 carbon atoms. It is preferable to use a polyol having a hydrocarbon and, if necessary, a polyester polyol derived from a polycarboxylic acid by a usual esterification reaction.

The polyester polyol containing 12-hydroxystearyl alcohol used as one of the constituent components of the polyester polyol according to the present invention comprises:
A polyester polyol derived from 12-hydroxystearyl alcohol as an essential component, a polycarboxylic acid and, if necessary, another polyol having a di- or tri-functional hydrocarbon having 2 to 40 carbon atoms by a normal esterification reaction. Preferably, there is.

The average molecular weight of the polyester polyol is usually 200 or more, preferably 200 to 10,000,
Particularly preferably, it is 300 to 5000. When the average molecular weight is less than 200, flexibility may be poor and adhesion to plastic may be reduced. When the average molecular weight is more than 10,000, viscosity becomes high, handling becomes difficult, and strength and solvent resistance are lowered. It tends to decrease.

In the above polyester polyol, 1
The content of 2-hydroxystearic acid (12-hydroxystearic acid residue) and / or 12-hydroxystearyl alcohol (12-hydroxystearyl alcohol residue) is preferably at least 10% by weight, more preferably at least 40% by weight. However, if necessary, one or several other polyols and polycarboxylic acids can be used in a range of less than 90% by weight.

Here, the content of 12-hydroxystearic acid and / or 12-hydroxystearyl alcohol is one of the constituent components of the polyester polyol.
If the amount is less than 0% by weight, the physical properties of the obtained aqueous polyurethane resin composition are undesirably reduced.

Examples of the above-mentioned polyol having a bifunctional or trifunctional hydrocarbon having 2 to 40 carbon atoms used for producing the above polyester polyol include ethylene glycol, diethylene glycol, triethylene glycol and 1,2-propylene glycol. , 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,
Examples thereof include low-molecular-weight polyols such as 4-butylene glycol, 3-methylpentanediol, 1,6-hexanediol, hexamethylene glycol, hydrogenated bisphenol A, and ethylene oxide and / or propylene oxide adducts of bisphenol A.

Examples of the polycarboxylic acid used to obtain the polyester polyol include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, and the like.
Isophthalic acid, terephthalic acid, trimetic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid,
And polycarboxylic acids such as hexahydrophthalic acid.

In addition to the above polyols, polyether polyols such as polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, and polytetramethylene glycol, the low molecular weight polyols and succinic acid, glutaric acid, adipic acid, sebacic acid, Polyols such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, endmethylenetetrahydrophthalic acid, polybasic acids such as hexatetrophthalic acid or condensates with carbonic acid, such as polyester polyols, polycarbonate polyols and polycaprolactone, are required Can be used together in the production of the aqueous polyurethane resin depending on the above.

Examples of the polyisocyanate used for producing the aqueous polyurethane resin include aliphatic, alicyclic and aromatic polyisocyanates, and specifically, 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, 1,4-cyclohexylene diisocyanate, 4, 4-dicyclohexylmethane diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1,5-naphthalenediisocyanate, isophorone diisocyanate and the like.

The above polyisocyanate is preferably used in an amount of 0.8 to 3 times, more preferably 1 to 2 times the total of the above-mentioned polyol, polyol having a carboxyl group or a sulfonic acid group and active hydrogen of a chain extender. Used to be equivalent. If the used amount of the isocyanate is less than 0.8 equivalent, excess polyol etc. will remain, and if it is more than 3 equivalent, a large amount of urea bond will be generated when water is added. In any case, the characteristics may be deteriorated.

As the chain extender used for producing the aqueous polyurethane resin composition of the present invention, a commonly used chain extender, for example, having an average molecular weight of 2
Low molecular weight polyol compounds and low molecular weight polyamine compounds of less than 00 are mentioned.

As the low molecular weight polyol compound,
The low-molecular-weight polyol used in the production of the polyester polyol and the low-molecular-weight polyol compound having a carboxyl group, a sulfonic acid group, or a basic group in the molecule are exemplified. Low molecular weight polyol compound having a carboxyl group or a sulfonic acid group in the molecule, for example,
2,2-dimethylolpropionic acid, 2,2-methylolbutyric acid, 2,2-dimethylolvaleric acid, 1,4-butanediol-2-sulfonic acid and the like can be used. Examples of the polyol having a basic group in the molecule include N-methyldiethanolamine, butyldiethanolamine, triethanolamine, and triisopropanolamine. In particular, it is preferable to use a polyol having a carboxyl group since an aqueous polyurethane resin having excellent dispersibility can be obtained. In particular, as described above, when preparing a self-emulsifying aqueous polyurethane resin composition by dispersing a prepolymer imparted with self-emulsifying dispersibility in water, an ion center is used as a part or all of the chain extender. It is preferable to use a low-molecular-weight polyol compound or alkanolamine compound having a carboxyl group or a sulfonic acid group in the molecule, which has the function of (1). In this case, the low molecular weight polyol compound or alkanolamine compound having a carboxyl group or a sulfonic acid group in the molecule is preferably 0.5 to 50% by weight, more preferably 0.5 to 50% by weight, based on all the reaction components constituting the aqueous polyurethane resin. Preferably, 1 to 30% by weight is used.
When the amount is less than 5% by weight, the self-emulsifying property becomes insufficient. When the amount exceeds 50% by weight, physical properties such as elongation may be reduced. Further, a trifunctional or higher functional polyol can be used as a part of the chain extender. For example, trimethylolpropane, glycerin, pentaerythritol, ditrimethylolpropane and the like can be mentioned.

When a low-molecular-weight polyol compound having a carboxyl group or a sulfonic acid group in the molecule is used, the prepolymer is neutralized with a neutralizing agent during or after the production to make it self-emulsifying. Examples of the neutralizing agent include organic amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, and triethanolamine; and inorganic amines such as sodium hydroxide, potassium hydroxide, and ammonia. Bases are used, and they are used in an amount sufficient to neutralize carboxyl groups or sulfonic groups.

When a polyol having basicity in the molecule is used, examples of the neutralizing agent include carboxylic acids such as formic acid, acetic acid and succinic acid, organic sulfonic acids such as paratoluenesulfonic acid, hydrochloric acid and phosphoric acid. Quaternizing agents such as inorganic acids, dialkyl sulfates, and alkyl halides;
These are used in an amount sufficient to neutralize amino groups.

The low molecular weight polyamine compound used as the chain extender includes, for example, ethylenediamine, propylenediamine, hexamethylenediamine, trelindiamine, xylylenediamine, diaminodiphenylamine, diaminocyclohexylmethane,
Piperazine, 2-methylpiperazine, isophoronediamine, melamine, succinic dihydrazide, adipic dihydrazide, phthalic dihydrazide, and triamine or higher polyamines such as melamine, diethyltriamine, triethylenetetramine, tri (aminimethyl) propane and the like. can give. The amount of the chain extender other than the low-molecular-weight polyol compound having a carboxyl group or a sulfonic acid group in the molecule is preferably 0.5% with respect to all components necessary for producing the intended aqueous polyurethane resin. -10% by weight.

Examples of the solvent which is inert to the above-mentioned reaction and has high affinity for water used for producing the above-mentioned aqueous polyurethane resin include, for example, acetone, methyl ethyl ketone, dioxane, tetrohydrofuran, N-methyl- 2-pyrrolidone and the like can be mentioned. These solvents are generally used in an amount of 10 to 100% by weight based on the total amount of the raw materials used for producing the prepolymer.

As described above, it is well known to produce an aqueous polyurethane resin from these raw materials, and it is possible to appropriately change the order in which these raw materials are charged, or to charge them separately.

The water-based polyurethane resin thus obtained is emulsified and dispersed in water to prepare the water-based polyurethane resin composition of the present invention. The aqueous polyurethane resin composition of the present invention is usually prepared so that the resin solid content is preferably 1 to 90% by weight, more preferably 5 to 80% by weight. When the resin solid content is less than 5% by weight, a long time is required for drying because of containing a large amount of water,
If it exceeds 80% by weight, the viscosity tends to be high and handling tends to be difficult. In addition, the resin of "resin solid content" here means an aqueous polyurethane resin and other aqueous resins that can be added as needed.

The water-based polyurethane resin composition of the present invention may further contain another water-based resin composition, if necessary. Specific examples include a water-based acrylic resin composition, a water-based epoxy resin composition, a water-based vinyl acetate resin composition, and the like. The ratio (weight ratio) of the water-based polyurethane resin composition of the present invention to another water-based resin composition is not particularly limited, but is usually 3: 7 to 10: 0.

The aqueous polyurethane resin composition of the present invention may contain an inorganic colloid sol such as colloidal silica or colloidal alumina, an antifogging agent, a colorant,
Conventional additives such as waxes, preservatives, defoamers, plasticizers, fillers, solvents, film-forming aids, dispersants, thickeners, and fragrances can also be added.

The colloidal silica that can be used in the present invention preferably has an average particle diameter in the range of 5 to 200 nm. If the average particle diameter is out of this range, the effects of the present invention may not be sufficiently exerted. There is. Further, the content of the aqueous polyurethane resin and the colloidal silica is preferably an amount in which the weight ratio of the aqueous polyurethane resin (solid content): colloidal silica is 1: 0.01 to 1: 5. If the weight ratio is out of the range, the effect of the present invention may not be sufficiently exhibited.

The water-based polyurethane resin composition of the present invention may contain, if necessary, a phenolic antioxidant, an organic phosphorus antioxidant such as an organic phosphite, a thioether antioxidant, an ultraviolet absorber, a hindered amine. A system light stabilizer and the like can be added.

Examples of phenolic antioxidants include:
Stearyl-β- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, stearyl-β- (3
-Tert-butyl-4hydroxy-5-methylphenyl) propionate, 1,6-hexamethylenebis [β-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [β-
(3-tert-butyl-4hydroxy-5-methylphenyl)
Propionate], 3,9-bis [1,1-dimethyl-
2- (β-3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxyethyl] -2,4
8,10-tetraoxaspio [5.5] undecane,
1,3,5-tris [β- (3,5-di-tert-butyl-4
(Hydroxyphenyl) propionyloxyethyl] isocinurate, tetrakis [methylene-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,6-di-tert-butyl-p-cresol,
2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-
6-tert-butylphenol), 2,2′-ethylidenebis (4,6-ditertbutylphenol), 2,2′-ethylidenebis (4-secbutyl-6-tertbutylphenol), bis [3 3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, 4,4'-butylidenebis (6-tert-butyl-m
-Cresol), 4,4'-thiobis (6-tert-butyl-m-cresol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,
1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene,
1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate,
3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and the like.

These phenolic antioxidants are preferably used in an amount of 0.001 to 5 parts by weight, more preferably 0.05 to 5 parts by weight, per 100 parts by weight of the aqueous polyurethane resin composition of the present invention.
Used to be 3 parts by weight.

As the organic phosphorus antioxidant, for example, tris (nonylphenyl) phosphite, tris (mono,
Di-mixed nonylphenyl) phosphite, tris (2,4
- di-tert-butylphenyl) phosphite, tetra (C ₁₂
~ C ₁₅ mixed alkyl) bisphenol A diphosphite, tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2
-Methyl-5-tert-butyl-4-hydroxyphenyl)
Butanetriphosphite, distearylpentaerythritol diphosphite), bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertbutyl-4-methylphenyl) pentaerythritoldiphosphite Phosphite, bis (2,4-di-α
-Cumylphenyl) pentaerythritol phosphite, 2,2'-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite , Tetrakis (2,4-di-tert-butylphenyl)
Biphenylenediphosphonite and the like.

These organophosphorus antioxidants are preferably used in an amount of 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, per 100 parts by weight of the aqueous polyurethane resin composition of the present invention.
Used to be parts by weight.

Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl-, dimyristyl-, distearyl-thiodipropionate, and alkyl (C = 8) such as pentaerythritol tetra (dodecylthiopropionate). -18) Esters of thiopropionic acid.

These thioether-based antioxidants are preferably used in an amount of 0.001 to 10 parts by weight, more preferably 0.01 to 100 parts by weight, based on 100 parts by weight of the aqueous polyurethane resin composition of the present invention.
It is used so as to be 0.5 to 5 parts by weight.

As the ultraviolet absorber, for example, 2,4-
2-hydroxybenzophenones such as dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); (2 ′ 2 -Hydroxy-5'-
Methylphenyl) benzotriazole, (2 ′ 2-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5-ditert-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-
Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'
-Dicumylphenyl) benzotriazole, 2,2'-
2- (2'hydroxyphenyl) such as methylenebis (4-tert-octyl-6-benzotriazolyl) phenol
Benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3 ′, 5′-di-tert-butyl-4′-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4
Benzoates such as hydroxybenzoate; 2,
4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) 1,3,5-triazine, 2,4-bis-
(2,4-dimethylphenyl) -6- (2-hydroxy-4-octoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-
Hexyloxy) triazines such as 1,3,5-triazine; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β , Β-diphenylacrylate, methyl-2-cyano-3-methyl-3- (p
Cyanoacrylates such as (-methoxyphenyl) acrylate.

These UV absorbers are preferably used in an amount of 0.1 part by weight in 100 parts by weight of the aqueous polyurethane resin composition of the present invention.
It is used in an amount of from 0.05 to 10 parts by weight, more preferably from 0.01 to 5 parts by weight.

Examples of hindered amine light stabilizers include, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6, -pentamethyl-
4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis (2,2,
6,6-tetramethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrakis (1,2,2, 6,6, -pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) -1, 2,
3,4-butanetetracarboxylate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) ) -2-Butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1-
(2-hydroxyethyl) -2,2,6,6-tetramethyl-4 piperidinol / diethyl succinate polycondensate,
1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate,
1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,6-
And bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate.

These hindered amine light stabilizers include:
Depending on the type and application of the resin to be added, 100 parts by weight of the aqueous polyurethane resin composition of the present invention, preferably 0.0
It is used in an amount of from 0.01 to 5 parts by weight, more preferably from 0.05 to 3 parts by weight.

The aqueous polyurethane resin composition of the present invention obtained as described above can form a polyurethane film excellent in adhesion, corrosion resistance, and various mechanical properties only by drying at room temperature.

The aqueous polyurethane resin composition of the present invention comprises:
Due to having the above properties, fibers, knits, wovens, non-wovens,
It can be used as an impregnating agent for wood, paper, leather, metal, glass, plastic products and the like, a coating agent, a paint, an adhesive, a vehicle for ink, a sizing agent, and the like.

Among these, the water-based polyurethane resin composition of the present invention is particularly excellent in adhesion to plastic products. The plastic products using the water-based polyurethane resin composition of the present invention are synthetic resins, for example, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, polybutene-1, poly-3-methyl. Α-olefin homopolymers and copolymers such as pentene, poly-4-methylpentene, ethylene-vinyl acetate copolymer, ethylene-propylene random and block copolymers; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene , Chlorinated polypropylene, polyvinylidene fluoride, rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-acrylate copolymer, vinyl chloride-cyclohexylmaleimide copolymer, etc. Halogen resin; amorphous or syndio Polystyrenes, styrene and / or syndiotactic polystyrene,
Copolymers of styrene and / or α-methylstyrene with other monomers (eg, maleic anhydride, acrylonitrile, methyl methacrylate, butadiene, phenylmaleimide, etc.) (eg, HiPS resin, AS resin, ABS resin, MBS) Resin, heat resistant ABS resin, super heat resistant ABS resin)
Styrene resins such as polyethylene terephthalate, polybutylene terephthalate, and polycaprolactone; linear polyesters such as polycaprolactam and polyhexamethylene adipamide; linear or branched aromatic polycarbonates; polyvinyl formal and polyvinyl Polyvinyl acetal such as butyral; polyoxymethylene; polymethyl methacrylate; acrylic resin; polyphenylene oxide; polyphenylene sulfide, polyether ether ketone; petroleum resin; cumarone resin; indene resin; polyurethane; And mixtures thereof. Also, a mixture of an elastomer such as an ethylene-propylene copolymer elastomer, an ethylene-propylene-ethylidene norbornene copolymer elastomer, and the above-mentioned thermoplastic resin may be used.

Further, since the water-based polyurethane resin composition of the present invention has a feature of being particularly excellent in adhesion to polyolefin among the above-mentioned plastics, it can be used for automobiles, agricultural poly, building materials, information recording-related equipment, It is suitable for use as a coating agent and / or adhesive for plastic products such as polyolefin materials such as food packaging materials. In particular, it is suitable when the plastic product is an agricultural film or wall covering.

[0052]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

[Synthesis of Polyester Polyol] Excessive amounts of the polyol component, carboxy alcohol component and polycarboxylic acid component are dehydrated and condensed at 220 to 240 ° C. by a conventional method, and then the excess polyol component is distilled off under reduced pressure. A polyester polyol having a hydroxyl group at a terminal was produced. Tables 1 and 2 below show the polyol component, carboxy alcohol component and polycarboxylic acid component used, the average molecular weight (number average), oxidation (AV) and hydroxyl value (OH) of the obtained polyester polyol.
V). The polyester polyols obtained in Production Examples 1 to 6 were used for producing the aqueous polyurethane resin composition of the present invention (Examples 1 to 6). Nos. 7 to 8 were used for producing the aqueous polyurethane resin compositions of Comparative Examples 1 to 4.

[0054]

[Table 1]

[0055]

[Table 2]

[Production of Aqueous Polyurethane Resin Composition] Aqueous polyurethane resin compositions of the following Examples 1 to 6 and Comparative Examples 1 to 4 were produced. Tables 3 and 4 below show the reaction components, ion centers, emulsification type and property values (solid content of resin,
(Viscosity, pH).

Example 1 Polyester polyol no. 222, hexamethylene diisocyanate (HDI) 78 parts, dimethylolpropionic acid 22 parts, N-methyl-2-pyrrolidone 8
Three parts were placed in a reaction vessel and reacted while maintaining the temperature at 80 to 100 ° C. to produce a prepolymer.

Next, 17.8 parts of triethylamine was added to neutralize the mixture, 8.3 parts of hexamethylenediamine was added, and a crosslinking reaction was carried out at 35 ° C. or less while adding water. To 33.1% resin solids.
% Of an aqueous polyurethane resin composition was produced.

Example 2 Polyester polyol no. 140 parts, 151 parts of hydrogenated meta-xylylene diisocyanate (H6XDI),
25 parts of 1,4-butanediol, 20 parts of dimethylolpropionic acid, and 80 parts of N-methyl-2-pyrrolidone were placed in a reaction vessel and reacted while keeping the temperature at 80 to 100 ° C. to produce a prepolymer.

Next, 17 parts of triethylamine was added to neutralize the mixture, and 538 parts of water was added to the mixture to give a resin solid content of 34.6%.
Was produced.

Example 3 Polyester polyol no. 3, 200 parts of isophorone diisocyanate (IPDI) and 90 parts of methyl ethyl ketone were placed in a reaction vessel, mixed well at 75 ° C., and 20 parts of dimethylolpropionic acid was added.
The reaction was performed at 70 ° C. for 12 hours. After neutralizing by adding 60 parts of 5% aqueous ammonia, 5 parts of ethylenediamine was added, methyl ethyl ketone was distilled off under reduced pressure, and 535 parts of water were added to produce an aqueous polyurethane resin composition having a resin solid content of 31.5%.

Example 4 Polyester polyol no. 235 parts, 82 parts of hydrogenated diphenylmethane diisocyanate (H12MDI), 58 parts of methyl ethyl ketone, 3 parts of 1,4-butanediol, and 17 parts of N-methyldiethanolamine are placed in a reaction vessel and reacted while keeping the temperature at 80 ° C to 100 ° C.
A prepolymer was produced.

Next, 10 parts of acetic acid was added for neutralization, and then methyl ethyl ketone was distilled off under reduced pressure, and 592 parts of water was added to produce an aqueous polyurethane resin composition having a resin solid content of 33.8%.

Example 5 Polyester polyol no. 5, 166 parts, isophorone diisocyanate (IPDI) 108 parts, 1,4-
Butanediol 5 parts, N-methyldiethanolamine 2
5 parts and 75 parts of N-methyl 2-pyrrolidone were placed in a reaction vessel and reacted while maintaining the temperature at 80 to 100 ° C. to produce a prepolymer.

Next, after neutralizing by adding 15 parts of acetic acid,
605 parts of water was added to produce an aqueous polyurethane resin composition having a resin solid content of 30.5%.

Example 6 Polyester polyol no. 6, 181 parts, isophorone diisocyanate (IPDI) 117 parts, 1,4-
Butanediol 5 parts, N-methyldiethanolamine 3
Parts, dimethylolpropionic acid 11 parts, N-methyl 2-
Put 81 parts of pyrrolidone in a reaction vessel,
To produce a prepolymer.

Next, 9 parts of triethylamine was added to neutralize the mixture, and 589 parts of water was added by the end of the reaction to produce an aqueous polyurethane resin composition having a resin solid content of 32.0%.

Comparative Example 1 Polyester polyol no. 7 in 200 parts, hexamethylene diisocyanate (HDI) 81.6 parts, dimethylolpropionic acid 20 parts, N-methyl 2-pyrrolidone 75 parts in a reaction vessel and react while keeping at 80-100 ° C to produce a prepolymer. did.

Then, 16 parts of triethylamine was added for neutralization, and 7.5 parts of hexamethylenediamine was added.
A crosslinking reaction was carried out at 35 ° C. or lower while adding water, and 553 parts of water was added by the end of the reaction to produce an aqueous polyurethane resin composition having a resin solid content of 32.4%.

Comparative Example 2 Polyester polyol no. 8 in 200 parts, hydrogenated meta-xylylene diisocyanate (H6XDI) 78.2
Parts, 20 parts of dimethylolpropionic acid, 58 parts of methyl ethyl ketone, 15 parts of 1,4-butanediol, and 90 parts of N-methyl-2-pyrrolidone in a reaction vessel.
The reaction was carried out while maintaining the temperature at 100 ° C. to produce a prepolymer.

Next, 17.8 parts of triethylamine was added to neutralize the mixture, and 592 parts of water was added to the mixture to obtain a resin solid content of 31.7.
% Of an aqueous polyurethane resin composition was produced.

Comparative Example 3 Polyester polyol no. 8 in 200 parts, hydrogenated diphenyl diisocyanate (H12MDI) 109 parts, methyl ethyl ketone 50 parts, 1,4-butanediol 2.
5 parts of N-methyldiethanolamine and 15 parts of N-methyldiethanolamine were placed in a reaction vessel and reacted at 80 to 100 ° C. to produce a prepolymer.

Next, 9 parts of acetic acid was added for neutralization, and then methyl ethyl ketone was distilled off under reduced pressure, and 503.5 parts of water was added to produce an aqueous polyurethane resin composition having a resin solid content of 36.7%.

Comparative Example 4 Polyester polyol no. 7, 216 parts, isophorone diisocyanate (IPDI) 124 parts, 1,4-
6.4 parts of butanediol, 4.4 parts of N-methyldiethanolamine, 14 parts of dimethylolpropionic acid, and 97.2 parts of N-methyl-2-pyrrolidone are placed in a reaction vessel, and 8
The reaction was carried out while maintaining the temperature at 0 to 100 ° C to produce a prepolymer.

Next, 10.8 parts of triethylamine was added to neutralize the mixture, and 702 parts of water was added by the end of the reaction to produce an aqueous polyurethane resin composition having a resin solid content of 31.1%.

[0076]

[Table 3]

[0077]

[Table 4]

Use Example 1 An aqueous polyurethane resin composition using a polyester polyol as a raw material and having a resin solid content of 20 shown in Tables 3 and 4 above was used.
%, And applied to a polyethylene terephthalate (PET) film and a corona-discharge treated polypropylene (PP) film, and after drying, JIS
The adhesion of the coating film was evaluated according to K5400. The results are shown in Table 5 below.

[0079]

[Table 5]

Use Example 2 Next, a mixture of an aqueous polyurethane resin composition and colloidal silica having the following composition was applied to one surface of polyethylene terephthalate having a thickness of 0.165 mm using a gravure coater (gravure roll: 160 mesh). An agricultural drip-proof film having a coating film formed by drying was prepared, and its performance was evaluated according to the following criteria (1) to (3). The results are shown in Tables 6 and 7 below.

[Blending] Aqueous polyurethane resin composition 50 parts by weight as solid content Colloidal silica 50 parts by weight as solid content [Adelite AT-30A, trade name, manufactured by Asahi Denka Kogyo Co., Ltd., average particle size 15 nm, water dispersion]

(1) Transparency The haze value was measured using a haze meter manufactured by Suga Test Instruments and evaluated. （(Good): 0 to 3%, Δ (somewhat poor): more than 3% to 5
%, X (poor): more than 5% (2) Adhesion Peeling test with cellophane tape ○: not peeling, △: partial peeling, ×: full peeling (3) Initial drip-proof and drip-proof durability Water temperature 40 ° C, 30 ° tilt on a water tank with an outside temperature of 5-10 ° C
, And the initial drip-proof property and drip-proof durability were evaluated according to the following criteria. Initial drip-proof property: 流 れ る: flows without adhesion of water droplets in less than 30 minutes after expansion, Δ: flows without adhesion of water droplets in 30 to 60 minutes after expansion, x: does not adhere to water droplets in more than 60 minutes after expansion and within 90 minutes Flowing, drip-proof durability; ○: The entire surface of the film flows without water droplets attached, Δ: Approximately 50% of the film flows without water droplets attached,
×: Water droplets adhere to almost the entire surface of the film

[0083]

[Table 6]

[0084]

[Table 7]

Use Example 3 0.1 m by the inflation process with the following composition:
An m-thick film was produced.

[Blending] Parts by weight Low density polyethylene (0.923 g / cm ² , MFR = 2.0) 100 Tris (2,4-di-tert-butylphenyl) phosphite 0.2 2-hydroxybenzophenone 0.1 Methylene bis amide 0.2 DHT-4A 0.2

Next, a mixture of the aqueous polyurethane resin composition and colloidal silica was applied to one surface of the polyethylene film in the same manner as in Use Example 2 using a 130-mesh gravure recorder to form a coating film having a thickness of 2 μm.
The film obtained here was exposed outdoors (Urawa City, Saitama Prefecture) with the coated surface outside, and the surface condition of the sample after 6 months and 12 months was observed. In the evaluation, the occurrence of dirt and scratches was visually evaluated and evaluated on a scale of 10 (weather resistance). 1 represents a state that hardly differs from that before exposure, and a state in which deterioration progresses as the numerical value increases. Represent. In addition, the light transmittance of the original film (at the start) and the film after 6 months was measured according to JIS K 7105.

Further, in order to confirm the adhesion between the film and the coating layer, a cellotape was rubbed with a finger on the coated surface of the unexposed film and 6 months after the exposure, and then strongly peeled off. As for the evaluation criteria, ○ indicates that the coating layer was completely left, △ indicates that the coating layer was partially peeled, and x indicates that the coating layer was almost completely stripped. Further, an anti-fogging test was performed using the unexposed film. The test method is as follows. A test film is placed on the inclined surface of the frame for cloudy observation surrounded by a wooden board on all sides, with the coating surface inside, a test film is placed on a water tank prepared at a water temperature of about 40 ° C., and a room temperature of 25 ° C. is applied.
Leave for a time. Then, while keeping the water bath at 40 ° C., the room temperature was lowered to 5 ° C., and after 1 hour, the occurrence of fogging on the inner surface of the film (the surface facing the water tank) was visually confirmed. ×
(Cloudy), △ (slightly cloudy) and ○ (no cloudy)
Was evaluated in three stages. The results are shown in Tables 8 and 9 below.
To

[0089]

[Table 8]

[0090]

[Table 9]

Use Example 4 An aqueous polyurethane resin composition using a polyester polyol as a raw material and having a resin solid content of 20 shown in Tables 3 and 4 was used.
%, And coated between a polypropylene sheet / plywood having a thickness of 0.1 mm, thermocompression bonded at 90 ° C., cured for 1 week at room temperature, and immersed in normal conditions and hot water at 60 ° C. for 48 hours (resistance to water). The peel strength of hot water) was measured. The results are shown in Table 10 below.

[0092]

[Table 10]

From the results in the above tables, it can be seen that, in the aqueous polyurethane resin composition, an aqueous polyurethane resin composition produced from a polyester polyol not containing 12-hydroxystearic acid and / or 12-hydroxystearyl alcohol as an essential component ( In the case of Comparative Example), the adhesion to the film was extremely poor, and was not practically satisfactory. On the other hand, an aqueous polyurethane resin composition (Example) obtained from a polyester polyol having 12-hydroxystearic acid and / or 12-hydroxystearyl alcohol as an essential component and a polyisocyanate has an effect on PET and PP. It was confirmed that it had excellent adhesion.

Further, from the result of the case where the aqueous polyurethane resin composition containing colloidal silica was applied to the agricultural drip-proof film, it was found that 12-hydroxystearic acid and / or 12-hydroxystearyl alcohol was not an essential component. In the case of the comparative example, the adhesive strength and the antifogging property were inferior, and were not practically satisfactory. On the other hand, 12
An aqueous polyurethane resin composition (Example) obtained from a polyester polyol having polyhydroxyistearic acid and / or 12-hydroxystearyl alcohol as essential components and a polyisocyanate has excellent adhesive strength and antifogging property. I was able to confirm that.

Furthermore, the peel adhesion strength of the polyolefin sheet / plywood was inferior in the case of the comparative example in which 12-hydroxystearic acid and / or 12-hydroxystearyl alcohol was not an essential component, Practically unsatisfactory. On the other hand, 12-hydroxystearic acid or / and 1
Aqueous polyurethane resin composition obtained from polyester polyol containing 2-hydroxystearyl alcohol as an essential component and polyisocyanate (Example)
Was confirmed to have excellent peel adhesion strength.

[0096]

The water-based polyurethane resin composition of the present invention can provide a coating film having excellent adhesion, weather resistance, anti-fogging property and peeling adhesive strength.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C09J 175/06 C09J 175/06 4J040 F term (reference) 2B024 DB01 2B029 EB02 EC03 EC16 EC19 EC20 4J002 CK031 FD040 FD050 FD070 GA01 GH02 GJ01 GL01 HA07 4J034 BA03 DA01 DB04 DB05 DB07 DC02 DC12 DC35 DC37 DC43 DF01 DF15 DF16 DF24 HA01 HA02 HA07 HC03 HC12 HC16 HC17 HC22 HC46 HC52 HC54 HC61 HC64 HC71 HC73 JA41 JA42 LA08 QB10 QC05 RA01 RA08 RA10 RA10 RA10 RA10 RA10 PB05 PC08 4J040 EF111 JA03 LA06 LA07 MB03 NA01 NA12

Claims (5)

[Claims] 1. A method according to claim 1, wherein
And a water-based polyurethane resin composition in which a water-based polyurethane resin produced from a polyester polyol containing 12-hydroxystearyl alcohol as an essential component and a polyisocyanate is emulsified and dispersed in water. 2. The method according to claim 1, wherein the polyester polyol is 12-
A hydroxystearic acid and a polyol having a bifunctional to trifunctional hydrocarbon having 2 to 40 carbon atoms as essential components;
The aqueous polyurethane resin composition according to claim 1, which is a polyester polyol derived from a polycarboxylic acid as required. 3. The method according to claim 1, wherein the polyester polyol is 12-
The aqueous polyurethane according to claim 1, which is a polyester polyol derived from hydroxystearyl alcohol and a polycarboxylic acid as essential components, and optionally other polyols having 2 to 3 functional hydrocarbons having 2 to 40 carbon atoms. Resin composition. 4. The aqueous polyurethane resin composition according to claim 1, which is used as a coating agent and / or an adhesive for plastic products. 5. The aqueous polyurethane resin composition according to claim 4, wherein the plastic product is an agricultural film or wall covering.