JP2012062387A - Urethane resin composition and molding obtained using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a urethane resin composition which can form a molding such as a film excellent in the low-temperature flexibility and dyeability, and is excellent in a dispersibility of various additives including a pigment.SOLUTION: The urethane resin composition contains urethane resin (C) obtained by reacting polyol (A) and polyisocyanate (B), wherein the polyol (A) contains a vinyl polymer (a1) having a vinyl polymer (a1') as a main chain that has two hydroxy groups in one terminal, and having a polyoxyethylene chain of number-average molecular weight of 200-800 in a side chain, and polyether polyol (a2).

Description

  The present invention relates to a urethane resin composition that can be used for various applications such as coating materials and adhesives, as well as molding materials such as films.

  Urethane resin compositions are conventionally used in various applications including molding materials such as films and sheets, adhesives, coating agents, and the like.

  Examples of the urethane resin composition include a substantially linear polymer of an ethylenically unsaturated monomer and a polymer having at least two groups having active hydrogen atoms locally at the end of the polymer. A composition containing a polyurethane resin having a terminal isocyanate group that reacts the union (A) and the polyisocyanate (B) as essential components is known (see, for example, Patent Document 1).

  However, for example, a urethane film used for a skin layer of a leather-like sheet or the like usually has a so-called low-temperature flexibility that hardly causes cracking or the like when subjected to a bending test in a temperature range of about −10 to 23 ° C. Among these, a film formed using the urethane resin composition described in the above-mentioned document 1 is not sufficient in terms of low-temperature flexibility, so that it may cause cracks or the like in a bending test in a low-temperature environment.

  Moreover, what was colored for the purpose of high designability etc. may be used for the urethane film used for the skin layer etc. of the said leather-like sheet | seat. Examples of the coloring method include, for example, a method of manufacturing a mixture of a urethane resin composition and a pigment and then forming the film into a film, or immersing a film formed using the urethane resin composition in a dye solution. The method of drying is mentioned.

  However, while there is a demand for a final product with a higher appearance and excellent design, the conventional urethane resin composition may not be able to uniformly disperse pigments, etc., and slight color unevenness may occur in the resulting film was there. In addition, even when a film produced in advance is immersed in a dye solution and dried, slight color unevenness occurs in the film, and high designability may not be imparted.

Japanese Patent Laid-Open No. 5-230166

  The problem to be solved by the present invention is to provide a urethane resin composition capable of forming a molded article such as a film having excellent low-temperature flexibility and dyeability and excellent dispersibility of various additives including pigments. It is to be.

  The inventors of the present invention have found that the problems of the present invention can be solved as a result of studies to solve the problems.

  That is, the present invention provides a vinyl polymer (a1) having a vinyl polymer (a1 ′) having two hydroxyl groups at one end as a main chain and a polyoxyethylene chain having a number average molecular weight of 200 to 800 in its side chain. And a polyol (A) containing a polyether polyol (a2) and a urethane resin (C) obtained by reacting a polyisocyanate (B). is there.

  Since the urethane resin composition of the present invention can form a molded article having excellent dispersibility of various additives including pigments and excellent low-temperature flexibility and dyeability, for example, a skin layer of a leather-like sheet It can also be used for various applications such as packaging films, optical films, antistatic films, antifogging films, coating agents, adhesives, and the like.

  The present invention includes a vinyl polymer (a1) having a main chain of a vinyl polymer (a1 ′) having two hydroxyl groups at one end and a polyoxyethylene chain having a number average molecular weight of 200 to 800 in its side chain; It is a urethane resin composition containing a urethane resin (C) obtained by reacting a polyol (A) containing a polyether polyol (a2) and a polyisocyanate (B).

  The urethane resin composition of the present invention may contain an organic solvent or an aqueous medium (F) as a solvent for the urethane resin (C), or may be solvent-free.

  The urethane resin (C) used in the present invention has a structure derived from the vinyl polymer (a1) as a side chain when the urethane resin is a main chain.

  Here, instead of the urethane resin (C), a urethane resin composition obtained by using a urethane resin having no vinyl polymer structure derived from the vinyl polymer (a1) in the side chain is a pigment or the like. It may not be sufficient in terms of dispersibility. Moreover, the dyeing | staining property of molded articles, such as a film obtained, may not be enough.

  Therefore, in order to impart excellent dispersibility and excellent dyeability such as pigments, it is important to use the urethane resin (C) having a structure derived from the vinyl polymer (a1) in the side chain. . The urethane resin (C) preferably contains 2% by mass to 50% by mass of the structure derived from the vinyl polymer (a1) with respect to the total amount of the urethane resin (C).

  The structure derived from the vinyl polymer (a1) that can form the side chain of the urethane resin (C) has a vinyl polymer (a1 ′) as the main chain, and a poly (ethylene) having a number average molecular weight of 200 to 800 in the side chain. It is a structure having an oxyethylene chain.

  Here, instead of the structure derived from the vinyl polymer (a1), when a urethane resin having a structure derived from a vinyl polymer having no polyoxyethylene chain having a number average molecular weight of 200 to 800 is used, In some cases, excellent dispersibility such as pigments and excellent dyeability cannot be imparted.

  Similarly, when the number average molecular weight of the polyoxyethylene chain is less than 200, it may not be possible to impart excellent dispersibility such as pigments and excellent dyeability.

  On the other hand, when the number average molecular weight of the polyoxyethylene chain exceeds 800, durability of the resulting film or film may be deteriorated or appearance may be deteriorated due to wrinkles.

  Therefore, the structure derived from the vinyl polymer (a1) preferably has a polyoxyethylene chain having a number average molecular weight of 300 to 700.

  Moreover, it is important that the urethane resin (C) has an ether structure in the main chain of the urethane resin (C).

  Here, instead of the urethane resin (C), a urethane resin composition using a urethane resin having no ether structure may not be able to form a molded article such as a film excellent in low-temperature flexibility.

  As the urethane resin (C), a resin having a weight average molecular weight in the range of 50,000 to 120,000 is used in order to impart excellent dispersibility and excellent dyeability such as pigments and excellent low-temperature flexibility. It is preferable.

  As said polyol (A) used for manufacture of the said urethane resin (C), as mentioned above, the vinyl polymer (a1 ') which has two hydroxyl groups in one terminal is made into a main chain, and the number average is carried out in the side chain. It is essential to use a polymer containing a vinyl polymer (a1) having a polyoxyethylene chain having a molecular weight of 200 to 800 and a polyether polyol (a2).

  Vinyl having a vinyl polymer (a1 ′) having two hydroxyl groups at one end used for production of the urethane resin (C) as a main chain and a polyoxyethylene chain having a number average molecular weight of 200 to 800 in its side chain As the polymer (a1), for example, a vinyl monomer containing a vinyl monomer (e) having a polyoxyethylene chain having a number average molecular weight of 200 to 800 in the presence of a chain transfer agent having two hydroxyl groups ( Those obtained by polymerizing E) can be used. Specifically, radical polymerization of the vinyl monomer (E) is carried out in the presence of a chain transfer agent (D) having two hydroxyl groups and a mercapto group, and the vinyl monomer starts from the mercapto group. What polymerized (E) is mentioned.

Since the obtained vinyl polymer (a1) has two hydroxyl groups derived from the chain transfer agent (D) at one end, the two hydroxyl groups and an isocyanate group contained in the polyisocyanate (B) described later are included. By reacting, a urethane bond can be formed.
The obtained vinyl polymer (a1) is a vinyl having two hydroxyl groups at one end formed by polymerization of the vinyl monomer (E) starting from the mercapto group of the chain transfer agent (D). When the polymer (a1 ′) is a main chain, a polyoxyethylene chain having a number average molecular weight of 200 to 800 is formed as a side chain.
The polyoxyethylene chain is preferably present in the range of 50% by mass to 95% by mass with respect to the total amount of the vinyl polymer (a1) in order to improve dispersibility and dyeability of pigments and the like.
The polyoxyethylene chain may be introduced into the vinyl polymer (a1) by using a vinyl monomer (e) having a polyoxyethylene chain having a number average molecular weight of 200 to 800 as the vinyl monomer. it can.

  The vinyl polymer (a1) has a number average molecular weight of 1000 to 8000 in order to facilitate viscosity control when reacting with the polyisocyanate (B) and improve the production efficiency of the urethane resin composition of the present invention. It is preferable to use what has this, and 2000-7000 are more preferable.

  In addition, the vinyl polymer (a1) has a vinyl polymer structure derived from the vinyl polymer (a1) in the side chain of the urethane resin (C), except for the two hydroxyl groups at one end. It is preferable that they have no other hydroxyl groups. Specifically, it is preferable not to use a hydroxyl group-containing vinyl monomer as the vinyl monomer (E) that can be used in the production of the vinyl polymer (a1).

  As a chain transfer agent that can be used for the production of the vinyl polymer (a1), it is preferable to use, for example, a chain transfer agent (D) having two hydroxyl groups and a mercapto group.

  Examples of the chain transfer agent (D) having two hydroxyl groups and a mercapto group include 3-mercapto-1,2-propanediol (thioglycerin), 1-mercapto-1,1-methanediol, and 1-mercapto. -1,1-ethanediol, 2-mercapto-1,3-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1 -Mercapto-2,3-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like can be used. Among them, it is preferable to use 3-mercapto-1,2-propanediol because it has less odor, is excellent in terms of workability and safety, and is versatile.

  Examples of the vinyl monomer (E) used in the production of the vinyl polymer (a1) include polyoxyethylene monomethyl ether (meth) acrylate and polyoxyethylene monoethyl ether (meth) acrylate. What contains the vinyl monomer (e) whose number average molecular weights of an oxyethylene chain are 200-800 can be used. Among these, the use of polyoxyethylene monomethyl ether (meth) acrylate improves the dispersibility of additives such as pigments and dyeability of the resulting film, and improves the production efficiency of the vinyl polymer (a1). Further, it is more preferable because good hydrophilicity can be imparted when the urethane resin (C) is stably dispersed in the aqueous medium (F).

  Moreover, as a vinyl monomer (E) used for manufacture of the said vinyl polymer (a1), in the range which does not impair the effect of this invention, other vinyl monomers other than the said vinyl monomer (e) The body can be used in combination.

  Examples of the other vinyl monomers include vinyl monomers having a polyoxyethylene chain number average molecular weight outside the range of 200 to 800, methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl. (Meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) ) Acrylates, dodecyl (meth) acrylates, stearyl (meth) acrylates, isobornyl (meth) acrylates, dicyclopentanyl (meth) acrylates, phenyl (meth) acrylates, benzyl (meth) acrylates and other (meth) acrylic esters (Meth) acrylic acid, (meth) acrylic acid β-carboxyethyl, 2- (meth) acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride Acid group-containing vinyl monomers such as itaconic anhydride; amide group-containing vinyl monomers such as (meth) acrylamide, N-monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide; N-methylol (Meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide; 2-aziridinylethyl (meth) acrylate; N, N-dimethyl Aminoethyl (meth) acrylate, N, N-dimethyl Tylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N- [2- (meth) [Acryloyloxyethyl] piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine, N- [2- (meth) acryloyloxyethyl] morpholine, 4- [N, N-dimethylamino] styrene, 4- [N , N-diethylamino] styrene, 2-vinylpyridine; N-methylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate; aminomethyl acrylate, aminoethyl acrylate, aminopropyl (meth) acrylate, amino -N-butyl (meta Nitrogen atom-containing vinyl monomers such as acrylate, butylvinylbenzylamine, vinylphenylamine and p-aminostyrene; Nitriles of unsaturated carboxylic acids such as (meth) acrylonitrile; 2,2,2-trifluoroethyl (meta ) Fluorine-containing vinyl monomers such as acrylate, 2,2,3,3-pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate; vinyl esters such as vinyl acetate, vinyl propionate and vinyl versatate Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether; vinyl compounds having an aromatic ring such as styrene, α-methyl styrene, divinyl styrene; isoprene, chloroprene, butadiene, ethylene , Tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone and the like can be used.

  The other vinyl monomer is preferably used in an amount of 10% by mass or less based on the total amount of the vinyl monomer (E) used for the production of the vinyl polymer (a1), and is 5% by mass or less. It is more preferable to use in the range.

  The polymerization reaction between the chain transfer agent (D) and the vinyl monomer (E) is performed, for example, under a solvent such as methyl ethyl ketone adjusted to a temperature of about 50 ° C. to 100 ° C., and the chain transfer agent (D) and the vinyl. It can proceed by supplying monomers (E) all at once or sequentially and radical polymerization. Thereby, the radical polymerization of the vinyl monomer (E) proceeds from the mercapto group or the like of the chain transfer agent (D), and the desired vinyl polymer (a1) can be produced. When the vinyl polymer (a1) is produced by the above method, a conventionally known polymerization initiator may be used as necessary.

  The vinyl polymer (a1) obtained by the above method is preferably used in the range of 20% by mass to 90% by mass with respect to the total amount of the polyol (A) used for the production of the urethane resin (C). When used in the range of 20% by mass to 60% by mass, a molded article such as a film excellent in low-temperature flexibility and dyeability can be formed, and a urethane resin composition excellent in dispersibility of pigments and the like is obtained. More preferable.

  Moreover, as a polyol (A) used for manufacture of the said urethane resin (C), polyether polyol (a2) is used with the said vinyl polymer (a1). The polyether polyol (a2) is used for introducing an ether structure into the urethane resin (C), and is important for imparting excellent low-temperature flexibility to a molded product such as a film obtained. .

  As the polyether polyol (a2), for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, Trimethylolethane, trimethylolpropane and the like can be used.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

  Specifically, as the polyether polyol (a2), at least one selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol, and a copolymer of ethylene oxide and tetrahydrofuran is used. Is preferable for imparting excellent low-temperature flexibility. Moreover, as said polyether polyol (a2), it is preferable to use the thing of the number average molecular weight of 800-5000.

  Moreover, as said polyol (A), the mass ratio [(a1) / (a2)] of the said vinyl polymer (a1) and the said polyether polyol (a2) contains in the range of 1/9-4/6. It is preferable to use those for improving the dispersibility of pigments and the like, and improving the dyeability and low-temperature flexibility of molded products such as films.

  As a polyol (A) used for manufacture of the said urethane resin (C), another polyol other than what was mentioned above can be used as needed.

  As other polyols, for example, polyester polyols, polycarbonate polyols, and the like can be used as long as the effects of the present invention are not impaired.

  Examples of the polyester polyol include a ring-opening polymerization reaction of a cyclic ester compound such as an aliphatic polyester polyol, an aromatic polyester polyol, or ε-caprolactone obtained by esterifying a low molecular weight polyol and a polycarboxylic acid. Polyesters, copolymerized polyesters thereof, and the like can be used.

  Examples of the low molecular weight polyol include ethylene glycol and propylene glycol.

  Examples of the polycarboxylic acid that can be used include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof.

  Moreover, as said polycarbonate polyol, what is obtained by making carbonate ester and a polyol react, for example, what is obtained by making phosgene, bisphenol A, etc. react can be used.

  As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

  Examples of the polyol capable of reacting with the carbonate ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-propa Diol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexane Relatively low molecular weight dihydroxy compounds such as dimethanol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, Polyester polyols such as hexamethylene adipate, polyhexamethylene succinate, and polycaprolactone can be used.

  When the urethane resin composition of the present invention uses an aqueous urethane resin composition in which the urethane resin (C) is dissolved or dispersed in the aqueous medium (F), the urethane resin (C) is hydrophilic. From the viewpoint of imparting, a hydrophilic group-containing polyol can be used as the other polyol.

  As the hydrophilic group-containing polyol, those having a hydrophilic group can be used. For example, an anionic group-containing polyol, a cationic group-containing polyol, and a nonionic group-containing polyol can be used. However, it is preferable to use an anionic group-containing polyol or a cationic group-containing polyol.

  As the anionic group-containing polyol, for example, a carboxyl group-containing polyol or a sulfonic acid group-containing polyol can be used.

  Examples of the carboxyl group-containing polyol include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 2,2′-dimethylolvaleric acid, and the like. Among them, it is preferable to use 2,2′-dimethylolpropionic acid. Moreover, the carboxyl group-containing polyester polyol obtained by making the said carboxyl group-containing polyol and various polycarboxylic acids react can also be used.

  Examples of the sulfonic acid group-containing polyol include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid, and salts thereof, and the low molecular weight polyol. Polyester polyol obtained by reacting can be used.

  The anionic groups are preferably partially or wholly neutralized with a basic compound or the like in order to exhibit good water dispersibility.

  Examples of basic compounds that can be used for neutralizing the anionic group include organic amines having a boiling point of 200 ° C. or higher, such as ammonia, triethylamine, morpholine, monoethanolamine, and diethylethanolamine, NaOH, KOH, and LiOH. A metal hydroxide containing etc. can be used. The basic compound is preferably used in the range of basic compound / anionic group = 0.5 to 3.0 (molar ratio) from the viewpoint of improving the water dispersion stability of the resulting coating agent. It is more preferable to use in the range which becomes 0.9-2.0 (molar ratio).

  Further, as the cationic group-containing polyol, for example, a tertiary amino group-containing polyol can be used. Specifically, N-methyl-diethanolamine, a compound having two epoxies in one molecule, and a secondary amine. A polyol obtained by reacting with can be used.

  It is preferable that a part or all of the cationic group is neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid and adipic acid.

  Further, the tertiary amino group as the cationic group is preferably partly or entirely quaternized. As the quaternizing agent, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like can be used, and dimethyl sulfate is preferably used.

  Further, as the nonionic group-containing polyol, polyalkylene glycol having a structural unit derived from ethylene oxide can be used.

  The hydrophilic group-containing polyol is preferably used in the range of 1% by mass to 45% by mass with respect to the total amount of the polyol (A).

  Examples of the polyisocyanate (B) used in the production of the urethane resin (C) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, Aromatic polyisocyanates such as tolylene diisocyanate, naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate or alicyclic Polyisos having structure It is possible to use the Aneto. Of these, 4,4'-diphenylmethane diisocyanate is preferably used.

  The urethane resin (C) is, for example, a polyol (A) containing the vinyl polymer (a1), the polyether polyol (a2), and, if necessary, other polyols in the absence of a solvent or in the presence of an organic solvent. ) And the polyisocyanate (B) can be reacted. Specifically, the reaction is preferably performed in the range of 20 ° C. to 120 ° C. for about 30 minutes to 24 hours.

  In the reaction of the polyol (A) and the polyisocyanate (B), for example, the equivalent ratio of the isocyanate group of the polyisocyanate (B) to the hydroxyl group of the polyol (A) is 0.8 to 2.5. Preferably, it is carried out in the range of 0.9 to 1.5.

  Examples of the organic solvent that can be used in producing the urethane resin (C) include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetate esters such as ethyl acetate and butyl acetate; acetonitrile Nitriles such as dimethylformamide and amides such as N-methylpyrrolidone can be used alone or in combination of two or more. The organic solvent may be used as a solvent for the urethane resin composition of the present invention.

  When the urethane resin (C) used in the present invention is produced, a chain extender is used as necessary for the purpose of further increasing the molecular weight and further improving the scratch resistance and the like. it can.

  As the chain extender, polyamine, other active hydrogen atom-containing compounds and the like can be used.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-. Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; Razide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5 5-Trimethylcyclohexane can be used, and ethylenediamine is preferably used.

  Examples of the other active hydrogen-containing compound include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and sucrose. , Glycols such as methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone , And water can be used alone or in combination of two or more thereof within a range in which the storage stability of the coating agent of the present invention is not lowered.

  The chain extender is preferably used, for example, in a range where the equivalent ratio of the amino group and excess isocyanate group of the polyamine is 1.9 or less (equivalent ratio), 0.3 to 1.0 (equivalent It is more preferable to use it in the range of the ratio.

  The urethane resin (C) obtained by the above method can be used as the urethane resin composition of the present invention by using it in combination with various additives as required without using a solvent.

  The urethane resin composition of the present invention preferably contains a solvent from the viewpoint of coating workability and the like, and as such a solvent, an organic solvent or an aqueous medium (F) can be used.

  As said organic solvent, methyl ethyl ketone etc. which were illustrated as what can be used when manufacturing the said urethane resin (C) can be used.

  The urethane resin composition containing the organic solvent as a solvent can be produced by mixing and stirring the urethane resin (C) produced by the above method and the organic solvent.

  When using the said organic solvent as a solvent, it is preferable that the non volatile matter of the urethane resin composition of this invention is the range of 10 mass%-50 mass%, and using it in the range of 20 mass%-40 mass%. preferable.

  Examples of the aqueous medium (F) include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; lactams such as N-methyl-2-pyrrolidone, and the like. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

  When the aqueous medium (F) is used as a solvent, the nonvolatile content of the urethane resin composition of the present invention is more preferably in the range of 10% by mass to 50% by mass, and in the range of 20% by mass to 50% by mass. It is preferable to use it.

  The urethane resin composition containing the aqueous medium (F) as a solvent is produced by, for example, producing a urethane resin (C) obtained by reacting a polyol (A) and a polyisocyanate (B), and then producing the urethane resin (C ) By neutralizing or quaternizing some or all of the hydrophilic groups, and then mixing with the aqueous medium (F) to disperse or dissolve the urethane resin (C) in the aqueous medium (F). can do.

  When mixing the urethane resin (C) and the aqueous medium (F), an emulsifier may be used as necessary. Moreover, you may use machines, such as a homogenizer, as needed.

  For example, a curing agent, a film forming aid, a filler, a thixotropic agent, a tackifier, a pigment, and the like are added to the urethane resin composition of the present invention as long as the purpose of the present invention is not impaired. be able to.

  As the curing agent, for example, an isocyanate-based crosslinking agent can be used. Specifically, tolylene diisocyanate, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, trimethylolpropane modified tolylene diisocyanate, and the like. Can be used.

  The film forming aid is not particularly limited, and examples thereof include anionic surfactants (such as dioctyl sulfosuccinate soda salt), hydrophobic nonionic surfactants (such as sorbitan monooleate), and silicone oil. It is done.

  Examples of the filler include metal oxides such as silicon, aluminum, titanium, zirconium, zinc, and tin and their hydrolysis condensates, carbonates (for example, calcium salts, calcium / magnesium salts, magnesium salts, etc.), Silicic acid, silicate (eg aluminum salt, magnesium salt, calcium salt etc.), hydroxide (eg aluminum salt, magnesium salt, calcium salt etc.), sulfate (eg barium salt, calcium salt, magnesium salt etc.), borate (For example, aluminum salt, zinc salt, calcium salt, etc.), titanate (for example, potassium salt, etc.) and the like.

  Examples of the thixotropy-imparting agent include fatty acid, fatty acid metal salt, fatty acid ester, paraffin, resin acid, surfactant, polyacrylic acid and the like surface-treated filler, polyvinyl chloride powder, hydrogenated castor oil, Fine powder silica, organic bentonite, sepiolite and the like can be mentioned.

  Although it does not specifically limit as said tackifier, For example, tackifiers, such as a rosin resin type, a terpene resin type, a phenol resin type, are mentioned.

As the pigment, known and commonly used inorganic pigments and organic pigments can be used.
As the inorganic pigment, for example, titanium oxide, antimony red, bengara, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite and the like can be used.

  Examples of the organic pigment include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, Organic pigments such as diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments can be used.

  Two or more kinds of these pigments can be used in combination. These pigments may be surface-treated and have a self-dispersing ability with respect to an aqueous medium.

  Furthermore, other additives include, for example, reaction accelerators (metal-based, metal salt-based, amine-based, etc.), stabilizers (ultraviolet absorbers, antioxidants, heat-resistant stabilizers, etc.), moisture removal agents (4- And various additives such as adsorbents (quick lime, slaked lime, zeolite, molecular sieves, etc.), adhesion-imparting agents, antifoaming agents, and leveling agents.

  The urethane resin composition of the present invention is, for example, a coating agent used for surface protection of various substrates, imparting design properties, imparting functionality such as solvent resistance, and an adhesive or film used for bonding various substrates. It is suitable as a molding material.

  Examples of the base material that can be coated with the coating agent to form a film or can be bonded include a glass base material, a metal base material, a plastic base material, a paper or wood base material, and a fibrous base material. . Moreover, it can also be used for the base material of porous body structures, such as a urethane foam.

  Examples of plastic base materials include polycarbonate base materials, polyester base materials, acrylonitrile-butadiene-styrene base materials, polyacryl base materials, polystyrene base materials, polyurethane base materials, epoxy resin base materials, polyvinyl chloride base materials, and polyamide base materials. A base material etc. can be used.

  As said metal base material, galvanized steel plates, such as a galvanized steel plate and an aluminum zinc alloy steel plate, an iron plate, an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate, a stainless steel plate etc. can be used, for example.

  The base material may be a planar material made of the above material or may have a curved portion, or may be a base material made of fibers such as a nonwoven fabric.

  Examples of the method for applying the coating agent or the like on the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.

  As a method of curing the urethane resin composition of the present invention and forming a molded article such as a film, for example, the urethane resin composition is applied to the surface of the same substrate as described above by the same method as described above, It can be produced by removing the solvent contained in the coating layer.

  The step of removing the solvent is preferably performed, for example, by leaving it at room temperature or leaving it at about 30 to 80 ° C.

  When dyeing molded articles such as films obtained above, azo dyes such as monoazo and disazo dyes, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline Dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, naphthalimide dyes, perinone dyes, phthalocyanine dyes, triallylmethane dyes, and the like can be used.

  As described above, the coating agent, adhesive, and molding material containing the urethane resin composition of the present invention are, for example, a surface coating of a substrate such as glass, a primer, and a surface coating of various plastic members of an electronic device, such as an automobile or a railway. Used for surface coating of light receiving surfaces of photovoltaic power generation devices such as photovoltaic power generation devices, surface coating of electronic components, wall materials, flooring, window glass, glasses, etc. It can be used for the production of moldings such as coating agents and their adhesives, skin layers and intermediate layers of leather-like sheets, packaging films, optical films, antistatic films, antifogging films and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

[Preparation Example 1] Preparation of vinyl polymer (a1-1) having a vinyl polymer having two hydroxyl groups at one end as a main chain and a polyoxyethylene chain having a number average molecular weight of 200 to 800 in its side chain 500 parts by mass of methyl ethyl ketone was charged into a four-necked flask equipped with a meter, a stirrer, a reflux condenser, and a nitrogen introduction tube, and then polyoxyethylene monomethyl ether methacrylate (polyoxyethylene chain number average molecular weight 500) in the reaction vessel. ) By supplying 485 parts by mass and 15 parts by mass of 3-mercapto-1,2-propanediol and reacting them, a vinyl polymer (a1-1) having two hydroxyl groups at one end with a number average molecular weight of 6000 is obtained. Obtained.

[Example 1]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 50 parts by mass of the vinyl polymer (a1-1) obtained in Preparation Example 1 and polyoxyethylene glycol (number average molecular weight 1500) ) 150 parts by mass, 15 parts by mass of 1,4-butanediol and 100 parts by mass of 4,4′-diphenylmethane diisocyanate were reacted for 4 hours in the presence of 300 parts by mass of methyl ethyl ketone as an organic solvent, and 200 parts by mass of methyl ethyl ketone as a diluting solvent. Part was added and the reaction continued further.

  When the weight average molecular weight of the reaction product reaches a range of 80000 to 120,000, the reaction is terminated by adding 3 parts by mass of methanol, and 175 parts by mass of methyl ethyl ketone is added as a diluent solvent, so that a nonvolatile resin containing urethane resin is contained. A urethane resin composition (X-1) having a content of 30% by mass was obtained.

[Example 2]
A non-volatile content of 30 mass in the same manner as in Example 1 except that 150 mass parts of polyoxypropylene glycol (number average molecular weight 1500) is used instead of 150 mass parts of the polyoxyethylene glycol (number average molecular weight 1500). % Urethane resin composition (X-2) was obtained.

[Example 3]
A method similar to Example 1 except that 150 parts by mass of a copolymer of ethylene oxide and tetrahydrofuran (number average molecular weight 1500) is used instead of 150 parts by mass of the polyoxyethylene glycol (number average molecular weight 1500). A urethane resin composition (X-3) having a nonvolatile content of 30% by mass was obtained.

[Example 4]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 275 parts by mass of the vinyl polymer (a1-1) obtained in Preparation Example 1 and polyoxyethylene glycol (number average molecular weight 1500) ) 138 parts by mass, 8 parts by mass of 1,4-butanediol and 110 parts by mass of 4,4′-diphenylmethane diisocyanate were reacted for 4 hours in the presence of 200 parts by mass of methyl ethyl ketone as an organic solvent, and 230 parts by mass of methyl ethyl ketone as a diluting solvent. Part was added and the reaction continued further.

  When the weight average molecular weight of the reaction product reaches the range of 6000 to 10,000, the reaction is terminated by adding 3 parts by mass of methanol, and further 200 parts by mass of methyl ethyl ketone is added as a diluent solvent, so that a nonvolatile resin containing urethane resin is contained. A urethane resin composition (X-4) of 30% by mass was obtained.

[Example 5]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 50 parts by mass of the vinyl polymer (a1-1) obtained in Preparation Example 1 and polyoxyethylene glycol (number average molecular weight 1500) ) 100 parts by mass, 50 parts by mass of polyoxytetramethylene glycol (number average molecular weight 1500), 15 parts by mass of 2,2-dimethylolpropionic acid and 100 parts by mass of 4,4′-diphenylmethane diisocyanate, methyl ethyl ketone as an organic solvent 300 The reaction was carried out for 4 hours in the presence of parts by mass, 200 parts by mass of methyl ethyl ketone was added as a dilution solvent, and the reaction was further continued.

  When the weight average molecular weight of the reactant reaches the range of 80,000 to 100,000, the reaction is terminated by adding 3 parts by mass of methanol, and further 175 parts by mass of methyl ethyl ketone is added as a diluting solvent, and an organic solvent solution of urethane resin Got.

  Next, 5 parts by mass of 48 mass% potassium hydroxide aqueous solution is added to the organic solvent solution of the urethane resin to neutralize part or all of the carboxyl groups of the polyurethane, and 700 parts by mass of water is further added to sufficiently An aqueous dispersion of urethane resin was obtained by stirring.

  Next, the urethane resin composition (X-5) having a nonvolatile content of 30% by mass was obtained by aging and removing the solvent from the urethane resin aqueous dispersion.

[Comparative Example 1]
Instead of using 150 parts by mass of a polyester polyol (number average molecular weight 1500) obtained by reacting adipic acid and 1,4-butanediol instead of 150 parts by mass of the polyoxyethylene glycol (number average molecular weight 1500). Obtained a comparative urethane resin composition (X′-1) having a nonvolatile content of 30% by mass in the same manner as in Example 1.

[Comparative Example 2]
Other than using 150 parts by mass of polycarbonate polyol (number average molecular weight 1500) obtained by reacting carbonate and 1,6-hexanediol instead of 150 parts by mass of the polyoxyethylene glycol (number average molecular weight 1500). Obtained a comparative urethane resin composition (X′-2) having a nonvolatile content of 30% by mass in the same manner as in Example 1.

[Comparative Example 3]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 200 parts by mass of the vinyl polymer (a1-1) obtained in Preparation Example 1 and 15 parts by mass of 1,4-butanediol and 45 parts by mass of 4,4′-diphenylmethane diisocyanate was reacted for 4 hours in the presence of 100 parts by mass of methyl ethyl ketone as an organic solvent, 70 parts by mass of methyl ethyl ketone was added as a diluting solvent, and the reaction was further continued.

  When the weight average molecular weight of the reaction product reaches the range of 50,000 to 80,000, the reaction is terminated by adding 3 parts by mass of methanol, and 100 parts by mass of methyl ethyl ketone is added as a diluent solvent, so that a nonvolatile resin containing urethane resin is contained. A comparative urethane resin composition (X′-3) of 30% by mass was obtained.

[Preparation Example 2] Preparation of vinyl polymer (Y-1) having a vinyl polymer having two hydroxyl groups at one end as a main chain and a polyoxyethylene chain having a number average molecular weight of 1000 on its side chain Thermometer, Into a four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, 450 parts by mass of methyl ethyl ketone was charged, and then polyoxyethylene monomethyl ether methacrylate (number average molecular weight of polyoxyethylene chain 1000) in the reaction vessel 400 By supplying 7 parts by mass of 7 parts by mass and 3-mercapto-1,2-propanediol, a vinyl polymer (Y-1) having two hydroxyl groups at one end with a number average molecular weight of 7000 was obtained. .

[Comparative Example 4]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 50 parts by mass of the vinyl polymer (Y-1) obtained in Preparation Example 2 and polyoxyethylene glycol (number average molecular weight 1500) ) 150 parts by mass, 15 parts by mass of 1,4-butanediol and 100 parts by mass of 4,4′-diphenylmethane diisocyanate were reacted for 4 hours in the presence of 300 parts by mass of methyl ethyl ketone as an organic solvent, and 200 parts by mass of methyl ethyl ketone as a diluting solvent. Part was added and the reaction continued further.

  When the weight average molecular weight of the reaction product reaches a range of 80000 to 120,000, the reaction is terminated by adding 3 parts by mass of methanol, and 175 parts by mass of methyl ethyl ketone is added as a diluent solvent, so that a nonvolatile resin containing urethane resin is contained. A comparative urethane resin composition (X′-4) having a content of 30% by mass was obtained.

[Preparation Example 3] Preparation of vinyl polymer (Y-2) having a vinyl polymer having two hydroxyl groups at one end as a main chain and a polyoxyethylene chain having a number average molecular weight of 2000 on its side chain, Thermometer, Into a four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, 450 parts by mass of methyl ethyl ketone was charged, and then polyoxyethylene monomethyl ether methacrylate (number average molecular weight of polyoxyethylene chain 2000) in the reaction vessel 400 By feeding 5 parts by mass and 5 parts by mass of 3-mercapto-1,2-propanediol, a vinyl polymer (Y-1) having two hydroxyl groups at one end with a number average molecular weight of 10,000 was obtained. .

[Comparative Example 5]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 50 parts by mass of the vinyl polymer (Y-2) obtained in Preparation Example 3 and polyoxyethylene glycol (number average molecular weight 1500) ) 150 parts by mass, 15 parts by mass of 1,4-butanediol and 100 parts by mass of 4,4′-diphenylmethane diisocyanate were reacted for 4 hours in the presence of 300 parts by mass of methyl ethyl ketone as an organic solvent, and 200 parts by mass of methyl ethyl ketone as a diluting solvent. The reaction was continued further.

  When the weight average molecular weight of the reactant reached the range of 80000 to 120,000, the reaction was terminated by adding 3 parts by mass of methanol, and 175 parts by mass of methyl ethyl ketone was further added as a diluent solvent, so that the nonvolatile resin containing urethane resin A comparative urethane resin composition (X′-5) of 30% by mass was obtained.

[Method for producing molded product (film)]
By applying the urethane resin compositions or comparative urethane resin compositions obtained in the examples and comparative examples onto a release paper, drying in a 90 ° C. environment for 30 minutes, and then removing the release paper A film having a thickness of 20 μm was prepared.

[Evaluation method of low-temperature flexibility]
Using a flexometer (manufactured by Toyo Seiki Co., Ltd.), the film obtained as described above was visually observed for the appearance of the film after being bent 500,000 times in a low temperature (−30 ° C.) environment. And evaluated according to the following evaluation criteria.

A: No cracks or wrinkles were observed, and the appearance was the same as the film before the bending test.
○: Although very slight wrinkles were observed, the appearance was almost the same as the film before the bending test.
Δ: Clear cracks could be confirmed.
X: The film broke due to cracks.

[Method for evaluating dispersibility of pigments, etc.]
5 parts by mass of a white pigment (Dillac White L, manufactured by DIC Corporation) is mixed with 100 parts by mass of the urethane resin compositions or comparative urethane resin compositions obtained in the above Examples and Comparative Examples, and the laboratory Stir and mix with a mixer.

  Subsequently, each mixture obtained above was applied onto a release paper, dried in an environment of 90 ° C. for 30 minutes, and then the release paper was removed to prepare a film having a thickness of 20 μm.

  Based on the presence or absence of uneven color on the film surface, the dispersibility of pigments and the like in the urethane resin composition was evaluated. The color unevenness of the film surface was evaluated by observing the film surface visually and based on the following criteria.

○: Uneven color was not confirmed at all, and the film surface was uniformly colored.
Δ: Although slight color unevenness could be confirmed in a very small part of the film, it was at a level of no practical problem.
X: Clear color unevenness over the entire film surface was confirmed.

[Dyeing evaluation method]
A film produced by the same method as described in [Method for producing molded product (film)] is immersed in a 1% by weight aqueous dye solution containing kayakalan Red (manufactured by Nippon Kayaku Co., Ltd.) for 5 minutes, and then Then, it was washed while overflowing water in a water bath at room temperature. This film was dried in an environment of 100 ° C. for 10 minutes to obtain a dyed film dyed red.

  The presence or absence of uneven color on the surface of the dyed film was visually observed and evaluated based on the following criteria.

○: Uneven color was not confirmed at all, and the entire dyed film surface was uniformly dyed.
Δ: Although slight color unevenness could be confirmed in a very small part of the dyed film, it was at a level of no practical problem.
X: Clear color unevenness over the entire surface of the dyed film was confirmed.

Claims (12)

A vinyl polymer (a1) having a polyoxyethylene chain having a number average molecular weight of 200 to 800 as a main chain, and a polyether polyol (a1 ′) having a vinyl polymer (a1 ′) having two hydroxyl groups at one end. A urethane resin composition comprising a urethane resin (C) obtained by reacting a polyol (A) containing a2) and a polyisocyanate (B). The urethane resin composition according to claim 1, wherein the vinyl polymer (a1) has a number average molecular weight of 2000 to 7000. The vinyl polymer (a1) is a chain transfer agent (D) having two hydroxyl groups and one mercapto group, and a vinyl monomer (e) having a polyoxyethylene chain having a number average molecular weight of 200 to 800 The urethane resin composition according to claim 1, which is obtained by reacting a vinyl monomer (E) containing The urethane resin composition according to claim 3, wherein the chain transfer agent (D) is 3-mercapto-1,2-propanediol. The urethane resin composition according to claim 3, wherein the vinyl monomer (e) having a polyoxyethylene chain having a number average molecular weight of 200 to 800 is polyoxyethylene monoalkyl ether (meth) acrylate. The urethane resin composition of Claim 1 whose mass ratio of the polyoxyethylene chain of the number average molecular weight 200-800 with respect to the whole quantity of the said vinyl polymer (a1) is 50 mass%-90 mass%. The urethane resin composition according to claim 1, wherein the polyether polyol (a2) has a number average molecular weight in the range of 800 to 5,000. The urethane resin composition according to claim 1, wherein a mass ratio [(a1) / (a2)] of the vinyl polymer (a1) and the polyether polyol (a2) is in a range of 1/9 to 4/6. object. The said polyether polyol (a2) contains 1 or more types chosen from the group which consists of a polyoxyethylene glycol, a polyoxypropylene glycol, and the copolymer of ethylene oxide and tetrahydrofuran. Urethane resin composition. Furthermore, the urethane resin composition of Claim 1 which contains an organic solvent. It is a urethane resin composition containing the said urethane resin (C) and an aqueous medium (F), Comprising: The said urethane resin (C) has a hydrophilic group, The urethane resin composition of Claim 1 . The molded product obtained using the urethane resin composition of any one of Claims 1-11.