JP5107828B2 - Polyurethane, process for producing polyurethane, and product using polyurethane - Google Patents

Description

  The present invention relates to polyurethane, a method for producing polyurethane, and a product using polyurethane.

Polyurethane is a general term for polymer compounds containing a urethane bond (—NHCOO—) in the main chain. Polyurethane can be obtained, for example, by a polyaddition reaction (Scheme 1 below) between a polyol (active hydrogen compound) and a polyisocyanate compound (polyisocyanate). At this time, various polyurethanes can be produced by variously changing the raw materials and reaction conditions. For example, the physical properties of the polyurethane can be changed by changing the structure of the portion (R, R ′) other than the urethane bond and the polymerization degree n. Furthermore, for example, a foamed urethane foam can be produced by using reaction conditions in which a polymerization (polyaddition) reaction and a foaming reaction (decarboxylation) occur simultaneously. As described above, polyurethane has unique characteristics as compared with other polymers, and can have various characteristics. Therefore, its use is extremely wide.

  One important use of polyurethane is as a paint. In this case, an ultraviolet absorber may be added to the polyurethane paint for the purpose of preventing deterioration of the coating film due to light. However, when the ultraviolet absorber is simply mixed with the polyurethane paint, the ultraviolet absorber may be separated from the polyurethane. For example, if any solvent (for example, water) adheres to the coating film of the polyurethane paint, only the ultraviolet absorber may be extracted into the solvent. In addition, even if a polyurethane coating film is left to stand for a long time in a normal use state, the UV absorber may gradually precipitate on the surface of the coating film and be separated from the coating film. Sometimes called “bleed out”). Thus, if the ultraviolet absorber is separated from the polyurethane, the original purpose of preventing the deterioration of the polyurethane coating film due to light cannot be sufficiently achieved.

In order to solve such problems, attempts have been made to increase the compatibility with polyurethane resins by increasing the molecular weight of the ultraviolet absorber and to reduce separation. However, in this method, there is a possibility that separation between the polyurethane and the ultraviolet absorber cannot be sufficiently prevented. In view of this, an ultraviolet absorber having a reactive group is bonded to a polyurethane polymer chain and integrated with the polymer chain to prevent separation of the ultraviolet absorber (Patent Documents 1 and 2). In this case, a benzophenone ultraviolet absorber or a benzotriazole ultraviolet absorber excellent in reactivity with polyurethane is used.
Japanese Patent No. 3580832 JP-A-2005-206720

  However, the benzophenone ultraviolet absorber has a problem that the ultraviolet absorption performance is not sufficient. Some benzotriazole-based ultraviolet absorbers have been pointed out to be carcinogenic. Furthermore, even a benzotriazole-based ultraviolet absorber having no safety problem has a problem that it is very expensive and has a large cost burden in practice.

  Thus, both benzophenone-based and benzotriazole-based UV absorbers have practical problems when used in combination with polyurethane chains. However, ultraviolet absorbers other than these are difficult to bind and integrate with the polyurethane chain.

  Therefore, an object of the present invention is to provide a polyurethane in which a highly practical ultraviolet absorber is combined with a polyurethane chain and integrated. Furthermore, this invention also provides the manufacturing method of the polyurethane which can manufacture such a polyurethane efficiently, and the product using the said polyurethane.

前記化学式（ｉ）中、
Ｒ ^３ 〜Ｒ ^１６ は、それぞれ独立に、水素原子、水酸基、直鎖若しくは分枝アルキル基、直鎖若しくは分枝アルコキシ基、置換若しくは無置換フェニル基、または任意の置換基であり、
Ｕは、ポリウレタン鎖であり、Ｌは、任意の原子団であるか、または存在しない。

前記化学式（２）中、
Ｒ ^１７ は、水素原子、直鎖若しくは分枝アルキル基、飽和若しくは不飽和の直鎖若しくは分枝若しくは環状炭化水素基、または任意の原子団であり、
Ｒ ^１８ は、水素原子または保護基であり、
Ｌ ^２ およびＬ ^３ は、それぞれ独立に、直鎖若しくは分枝アルキレン基、飽和若しくは不飽和の直鎖若しくは分枝若しくは環状炭化水素基、または任意の原子団であるか、または存在しない。
In order to solve the above-described problems, the polyurethane of the present invention is represented by the following chemical formula (i), and a UV absorber as a triazine derivative is directly or indirectly via another atomic group in the polyurethane chain. A covalently bonded polyurethane,
A polyurethane obtained by reacting the following component (d) in addition to the following components (a) to (c) .

Component (a): Polyol
Component (b): Polyisocyanate compound
Component (c): Triazine derivative
Component (d): at least one selected from the group consisting of carboxylic acid diols represented by the following chemical formula (2), tautomers and stereoisomers thereof, and salts thereof

In the chemical formula (i),
R ^{3 to} R ¹⁶ are each independently a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a linear or branched alkoxy group, a substituted or unsubstituted phenyl group, or an arbitrary substituent,
U is a polyurethane chain and L is any atomic group or absent.

In the chemical formula (2),
R ¹⁷ is a hydrogen atom, a linear or branched alkyl group, a saturated or unsaturated linear or branched or cyclic hydrocarbon group, or any atomic group,
R ¹⁸ is a hydrogen atom or a protecting group,
L ² and L ³ are each independently a linear or branched alkylene group, a saturated or unsaturated linear or branched or cyclic hydrocarbon group, or any atomic group, or absent.

The method for producing the polyurethane of the present invention is a method for producing the polyurethane of the present invention,
(A) reacting said components (a) ~ (c)
and
(B) A process comprising the step of reacting the reaction product of the step (A) with the component (d) . As will be described later, the polyurethane of the present invention is not limited to this production method, and may be produced by any method .

  Furthermore, the product of the present invention includes the polyurethane of the present invention, and includes polyurethane foam, bedding, diapers, cushioning materials, heat insulating materials, structural materials, elastomers, industrial parts, rolls, packing, shoe soles, hoses, civil engineering supplies, and construction. Materials, waterproofing, rooftop waterproofing solvent, indoor flooring, waterproofing for joints, textiles, sportswear, underwear, rain gear, synthetic leather, artificial leather, shoes, clothing, paint, adhesive, automotive parts, woodworking supplies, It is a product used as a hard coat film or a laminated film.

  As a result of intensive studies, the present inventors have found that triazine derivatives are excellent in ultraviolet absorption performance, cost, safety, and the like, and can be combined and integrated with a polyurethane chain.

  That is, according to the present invention, it is possible to provide a polyurethane in which a highly practical ultraviolet absorber, which is a triazine derivative, is combined with a polyurethane chain and integrated. Furthermore, according to the production method of the present invention, it is possible to efficiently produce such a polyurethane of the present invention. Since the polyurethane of the present invention effectively prevents separation of the ultraviolet absorber, it has excellent performance such as light resistance and weather resistance, and can be used for various products as described above. Furthermore, the use of the polyurethane of the present invention is not limited to this, and may be used for any use.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.

  When various compounds used in the present invention have tautomers or stereoisomers (eg, geometric isomers, conformational isomers, optical isomers, etc.), unless otherwise specified, any isomers of the present invention Can be used. Further, when various compounds used in the present invention can form a salt, the salt can also be used in the present invention unless otherwise specified. The salt may be, for example, an acid addition salt or a base addition salt. The acid forming the acid addition salt may be an inorganic acid or an organic acid, and the base forming the base addition salt may be an inorganic base or an organic base. The inorganic acid is not particularly limited. For example, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypofluorite, hypochlorous acid, hypobromite, Hypoarousous acid, fluorinated acid, chlorous acid, bromic acid, iodic acid, fluoric acid, chloric acid, bromic acid, iodic acid, perfluoric acid, perchloric acid, perbromic acid, periodic acid, etc. Can be given. The organic acid is not particularly limited, and examples thereof include p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, p-bromobenzenesulfonic acid, carbonic acid, succinic acid, citric acid, benzoic acid, and acetic acid. The inorganic base is not particularly limited, and examples thereof include ammonium hydroxide, alkali metal hydroxides, alkaline earth metal hydroxides, carbonates and hydrogen carbonates, and more specifically, for example, Examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydroxide and calcium carbonate. The organic base is not particularly limited, and examples thereof include ethanolamine, triethylamine, and tris (hydroxymethyl) aminomethane. The method for producing these salts is not particularly limited, and for example, the salt can be produced by a method such as appropriately adding the acid or base as described above to the electron donor / acceptor linking molecule by a known method.

  In various compounds used in the present invention, when an isomer exists in a substituent or the like, any isomer may be used unless otherwise specified. For example, when the term “phenylene group” is simply used, it may be an o-phenylene group, an m-phenylene group, or a p-phenylene group. When simply referred to as “naphthyl group”, it may be a 1-naphthyl group or a 2-naphthyl group. In addition, when simply referred to as “butyl group”, it may be an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

  In the present invention, the “alkyl group” is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Groups and the like. The same applies to groups containing an alkyl group in the structure (alkylamino group, alkoxy group, etc.). Further, the perfluoroalkyl group is not particularly limited, but is derived from, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. The same applies to groups containing a perfluoroalkyl group in the structure (perfluoroalkylsulfonyl group, perfluoroacyl group, etc.). In the present invention, the acyl group is not particularly limited. For example, formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, cyclohexanoyl group, benzoyl group, ethoxycarbonyl The same applies to groups containing an acyl group in the structure (acyloxy group, alkanoyloxy group, etc.). In the present invention, the carbon number of the acyl group includes carbonyl carbon. For example, an alkanoyl group having 1 carbon atom (acyl group) refers to a formyl group. Furthermore, in the present invention, “halogen” refers to any halogen element, and examples thereof include fluorine, chlorine, bromine and iodine. In the organic compound used in the present invention, the “hetero atom” is an atom incorporated in the molecular skeleton of the organic compound and means an atom other than carbon and hydrogen. In the present invention, the “inert gas” refers to all gases having poor reactivity including noble gases, and includes, for example, nitrogen gas. The noble gas refers to a gas composed of any one of the six elements of group 18 elements of the periodic table: helium, neon, argon, krypton, xenon, and radon. The inert gas sometimes refers only to a rare gas in a narrow sense, but in the present invention, it refers to a broader concept as described above.

前記化学式（ｉ）中、
Ｒ^３〜Ｒ^１６は、それぞれ独立に、水素原子、水酸基、直鎖若しくは分枝アルキル基、直鎖若しくは分枝アルコキシ基、置換若しくは無置換フェニル基、または任意の置換基であり、
Ｕは、ポリウレタン鎖であり、Ｌは、任意の原子団であるか、または存在しない。なお、Ｒ^３〜Ｒ^１６は、例えば、前記化学式（１）と同じで良い。好ましいＲ^３〜Ｒ^１６は、化学式（１）について後述する通りである。

また、本発明のポリウレタンは、前述の成分（ａ）〜（ｃ）に加え、さらに下記成分（ｄ）を反応させて得られるポリウレタンである。

成分（ａ）：ポリオール
成分（ｂ）：ポリイソシアナト化合物
成分（ｃ）：トリアジン誘導体
成分（ｄ）：下記化学式（２）で表されるカルボン酸ジオール、その互変異性体および立体異性体、ならびにそれらの塩からなる群から選択される少なくとも一つ

前記化学式（２）中、
Ｒ ^１７ は、水素原子、直鎖若しくは分枝アルキル基、飽和若しくは不飽和の直鎖若しくは分枝若しくは環状炭化水素基、または任意の原子団であり、
Ｒ ^１８ は、水素原子または保護基であり、
Ｌ ^２ およびＬ ^３ は、それぞれ独立に、直鎖若しくは分枝アルキレン基、飽和若しくは不飽和の直鎖若しくは分枝若しくは環状炭化水素基、または任意の原子団であるか、または存在しない。
[1. Polyurethane]
As described above, the polyurethane of the present invention is a polyurethane in which an ultraviolet absorber, which is a triazine derivative, is covalently bonded to a polyurethane chain directly or indirectly through another atomic group. Polyurethane of the present invention, it expresses under Symbol Formula (i).

In the chemical formula (i),
R ^{3 to} R ¹⁶ are each independently a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a linear or branched alkoxy group, a substituted or unsubstituted phenyl group, or an arbitrary substituent,
U is a polyurethane chain and L is any atomic group or absent. R ^{3 to} R ¹⁶ may be the same as the chemical formula (1), for example. Desirable R ^{3 to} R ¹⁶ are as described later for the chemical formula (1).

Further, the polyurethane of the present invention, in addition to the aforementioned ingredients (a) ~ (c), Ru polyurethane der obtained by further reacting the following components (d).

Component (a): Polyol component (b): Polyisocyanate compound component (c): Triazine derivative
Component (d): at least one selected from the group consisting of carboxylic acid diols represented by the following chemical formula (2), tautomers and stereoisomers thereof, and salts thereof

In the chemical formula (2),
R ¹⁷ is a hydrogen atom, a linear or branched alkyl group, a saturated or unsaturated linear or branched or cyclic hydrocarbon group, or any atomic group,
R ¹⁸ is a hydrogen atom or a protecting group,
L ² and L ³ are each independently a linear or branched alkylene group, a saturated or unsaturated linear or branched or cyclic hydrocarbon group, or any atomic group, or absent.

[1-1. Component (a) (Polyol)]
The component (a) (polyol) is not particularly limited. For example, the polyol is a low molecular polyol, polyester polyol, polycarbonate polyol, polyether polyol, polyester polycarbonate polyol, polybutadiene polyol, silicone polyol, low molecular diol, polyester diol, polycarbonate diol, polyether diol, polyester polycarbonate diol, polybutadiene diol. And at least one selected from the group consisting of silicone diols is preferable, but polyols other than these may be used.

  Examples of the low molecular polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 2-butyl-2-ethyl-1,3-propane. Diol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol), 2-isopropyl-1,4-butanediol, 3-methyl-2 , 4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-1, 5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2 Ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octane Diols, aliphatic diols such as 1,9-nonanediol and 1,10-decanediol, cyclohexanedimethanol (for example, 1,4-cyclohexanedimethanol), cyclohexanediol (for example, 1,3-cyclohexanediol, 1,4- Cyclohexanediol), 2-bis (4-hydroxycyclohexyl) -propane and other alicyclic diols, trimethylolethane, trimethylolpropane, hexitols, pentitols, glycerin, polyglycerin, pentaerythritol, dipentaerythritol, tetra Methylolup Trivalent or more polyols of bread, and the like.

  Examples of the polyester polyol include esters of polyols such as the low-molecular polyol and polycarboxylic acids, ester-forming derivatives of polycarboxylic acids (esters, anhydrides, halides, etc.), lactones, hydroxycarboxylic acids, and the like. A compound. Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, and 2-methyladipine. Acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, aliphatic dicarboxylic acid (for example, hydrogenated dimer acid) Dimer acid etc.), aromatic dicarboxylic acid (eg phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid etc.), alicyclic dicarboxylic acid (eg cyclohexane dicarboxylic acid etc.), tricarboxylic acid (eg trimellitic acid, trimesic acid, Castor oil fatty acid trimer, etc.), tetracarboxylic acid (eg, pyromellitic acid), and the like. Examples of the ester-forming derivative of the polyvalent carboxylic acid include acid anhydrides, halides (chloride, bromide, etc.), esters (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, amyl). And lower aliphatic esters such as esters). Examples of the lactone include γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone. The hydroxycarboxylic acid may be, for example, a hydroxycarboxylic acid having a structure in which the lactone is ring-opened.

  Examples of the polyether polyol include an ethylene oxide adduct, a propylene oxide adduct, polytetramethylene glycol, and an oxide adduct of the low molecular polyol. Examples of the ethylene oxide adduct include diethylene glycol and triethylene glycol. Examples of the propylene oxide adduct include dipropylene glycol and tripropylene glycol. Examples of the oxide adduct of the low-molecular polyol include an ethylene oxide adduct, a propylene oxide adduct, ethylene oxide, and a propylene oxide adduct.

The polyol may be, for example, a diol containing two hydroxyl groups or may contain three or more hydroxyl groups, but a diol is preferred. The diol is more preferably at least one selected from the group consisting of, for example, a low molecular diol, a polyester diol, a polycarbonate diol, and a polyether diol. When the diol is represented by the chemical formula HO—R′—OH, R ′ is not particularly limited, and may be, for example, a hydrocarbon group or an atomic group containing a heteroatom such as oxygen or silicon. good. The hydrocarbon group may be saturated or unsaturated, may be linear or branched, may or may not contain a cyclic structure, and may or may not contain an aromatic group. . The hydrocarbon group is not particularly limited, and for example, a linear or branched alkylene group, a group having a cyclic structure, a group having aromaticity, and the like are preferable. As the group having a cyclic structure, for example, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group and the like are preferable. Or the group couple | bonded through the alkylene group etc. may be sufficient. As the group having aromaticity, for example, an o-phenylene group, an m-phenylene group, a p-phenylene group and the like are preferable, and two or more of these groups are bonded directly or via an alkylene group or the like. It may be. Although it does not restrict | limit especially as said low molecular diol, For example, each low molecular diol etc. which were illustrated in the above are mentioned, For example, only 1 type may be used or 2 or more types may be used together. The polycarbonate diol may be, for example, a polycarbonate diol represented by the following chemical formula (7).

In the chemical formula (7), L ¹⁰⁰ is arbitrary, and each L ¹⁰⁰ may be the same as or different from each other. The L ^100, for example, a hydrocarbon group is preferable. The hydrocarbon group may be saturated or unsaturated, may be linear or branched, may or may not contain a cyclic structure, and may or may not contain an aromatic group. . As the hydrocarbon group, a linear or branched alkylene group, a group having aromaticity, and the like are preferable. As the group having aromaticity, for example, an o-phenylene group, an m-phenylene group, a p-phenylene group and the like are preferable, and two or more of these groups are bonded directly or via an alkylene group or the like. It may be. In the chemical formula (7), the degree of polymerization n is not particularly limited, but is, for example, 1 to 30, preferably 3 to 7. The molecular weight of the polycarbonate diol represented by the chemical formula (7) is not particularly limited, but is, for example, 300 to 4000, preferably 500 to 1000. The relationship between the polymerization degree n and the molecular weight (Mw) is, for example, when the polycarbonate diol represented by the chemical formula (7) is a polycarbonate diol of 1,6-hexanediol (L ¹⁰⁰ = C ₆ H ₁₂ ), Mw = 262 when n = 1, Mw = 406 when n = 2, Mw = 550 when n = 3, Mw = 982 when n = 6, and Mw = 4006 when n = 27. The polyester diol may be, for example, a polyester diol represented by a structure in which a carbonate bond (—O—CO—O—) is changed to an ester bond (—O—CO—) in the chemical formula (7). . The polyether diol may be, for example, a polyether diol represented by a structure in which a carbonate bond (—O—CO—O—) is changed to an ether bond (—O—) in the chemical formula (7). . These polycarbonate diol, polyester diol, and polyether diol may have a structure obtained by polymerizing one kind or two or more kinds of the low-molecular polyol, for example. Although it does not restrict | limit especially as a low molecular polyol in this case, For example, each low molecular polyol illustrated above is mentioned. Among these, from the viewpoint of the strength of the polymer and the like, a linear alkylene diol having 2 to 10 carbon atoms is preferable, and 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol is more preferable, and 1,4-butanediol and 1,6-hexanediol are more preferable.

The polycarbonate diol represented by the chemical formula (7) is, for example, a polycarbonate diol represented by the following formula (8) (a polycarbonate diol of 2,2-dimethyl-1,3-propanediol) or a following formula (9 ) (Polycarbonate diol of 1,6-hexanediol) represented by

  Furthermore, as the polyol, in addition to the above-mentioned various polyols, for example, other polyols generally used in polyurethane synthesis can be preferably used. Moreover, as said component (a), only one type may be used among these various polyols, and multiple types may be used together as needed. In addition, although the molecular weight (Mw) of the said component (a) (polyol) is not restrict | limited in particular, For example, it is 300-4000, Preferably it is 500-1000.

[1-2. Component (b) (polyisocyanate compound)]
The component (b) (polyisocyanate compound) is not particularly limited. The polyisocyanate compound may be a diisocyanate compound containing two isocyanato groups, or may contain three or more isocyanato groups, but a diisocyanate compound is preferred. For example, a diisocyanate compound represented by the following chemical formula (10) can be used.

In the chemical formula (10), L ²⁰⁰ is arbitrary. L ²⁰⁰ is preferably, for example, a hydrocarbon group. The hydrocarbon group may be saturated or unsaturated, may be linear or branched, may or may not contain a cyclic structure, and may or may not contain an aromatic group. . The hydrocarbon group is preferably a linear or branched alkylene group, a group having a cyclic structure, or a group having aromaticity. As the group having a cyclic structure, for example, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group and the like are preferable. Or the group couple | bonded through the alkylene group etc. may be sufficient. As the group having aromaticity, for example, o-phenylene group, m-phenylene group, p-phenylene group and the like are preferable, and two or more of these groups are bonded directly or via an alkylene group or the like. It may be.

  The diisocyanate compound (diisocyanate) is not particularly limited, and aromatic diisocyanate, alicyclic diisocyanate, aliphatic diisocyanate and the like can be used as appropriate, but alicyclic isocyanate is preferable from the viewpoint of light resistance, strength, flexibility, and the like. . Examples of the aromatic diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, and 1,5-naphthylene diisocyanate. 3,3′-dimethyldiphenyl-4,4′-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate, and the like. Examples of the alicyclic diisocyanate include isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, trans-1,4-cyclohexyl diisocyanate, and norbornene diisocyanate. Examples of the aliphatic diisocyanate include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.

As the diisocyanate compound, for example, a diisocyanate compound represented by any one of the following formulas (11) to (14) is particularly preferable. A compound represented by the following formula (11), that is, 4,4′-diisocyanatodiphenylmethane is usually abbreviated as MDI. The compound represented by the following formula (12), that is, 4,4′-diisocyanatodicyclohexylmethane has a structure in which 12 hydrogen atoms are added to the benzene ring of MDI, and is therefore abbreviated as H12MDI or the like. There is. A compound represented by the following formula (13), that is, 1,6-diisocyanatohexane (hexylene diisocyanate) may be abbreviated as HDI or the like. A compound represented by the following formula (14), namely 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl = isocyanate (isophorone diisocyanate) may be abbreviated as IPDI or the like.

  Examples of the polyisocyanate compound having three or more isocyanato groups in one molecule include triphenylmethane triisocyanate, 1-methylbenzole-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, and the like. . Moreover, for example, isocyanurate trimers, biuret trimers, trimethylolpropane adducts of the diisocyanate compounds (diisocyanates) exemplified above are also included.

  As the component (b), in addition to the aforementioned MDI, H12MDI, HDI, IPDI, and other various polyisocyanate compounds exemplified above, for example, other diisocyanate compounds generally used in polyurethane synthesis are also preferable. Can be used. In addition, as said component (b), only one type may be used among the various polyisocyanate compounds mentioned above, and multiple types may be used together as needed. The polyisocyanate compound may be used in the form of a modified product such as carbodiimide modification, isocyanurate modification, biuret modification or the like, or may be used in the form of a blocked isocyanate blocked with various blocking agents.

前記化学式（１）中、
Ｌ^１は、直鎖若しくは分枝アルキレン基であるか、または存在せず、
Ｒ^１およびＲ^２は、それぞれ独立に、水素原子、または直鎖若しくは分枝状置換基であり、前記直鎖若しくは分枝状置換基は、主鎖中に、Ｃ、Ｎ、Ｏ、Ｓ、ＰおよびＳｉを含んでいても含んでいなくても良く、
Ｒ^３〜Ｒ^１６は、それぞれ独立に、水素原子、水酸基、直鎖若しくは分枝アルキル基、直鎖若しくは分枝アルコキシ基、置換若しくは無置換フェニル基、または任意の置換基である。 [1-3. Ingredient (c) (Ultraviolet Absorber)]
The component (c) (ultraviolet absorber) is a triazine derivative as described above. The triazine derivative is preferably at least one compound selected from the group consisting of triazine derivatives represented by the following chemical formula (1), tautomers and stereoisomers thereof, and salts thereof. Among the UV absorbers that are triazine derivatives, the triazine derivatives represented by the following chemical formula (1) are particularly excellent in UV absorption performance, cost, safety, etc., and are easily combined with a polyurethane chain, This is because it is highly practical.

In the chemical formula (1),
L ¹ is a linear or branched alkylene group or absent,
R ¹ and R ² are each independently a hydrogen atom or a linear or branched substituent, and the linear or branched substituent is C, N, O, S, It may or may not contain P and Si,
R ^{3 to} R ¹⁶ are each independently a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a linear or branched alkoxy group, a substituted or unsubstituted phenyl group, or an arbitrary substituent.

In the chemical formula (1), it is preferable that at least one of R ⁴ and R ⁶ is a hydroxyl group. In the chemical formula (1), it is preferable that at least one selected from the group consisting of R ⁷ , R ¹¹ , R ¹² and R ¹⁶ is a hydroxyl group. L ¹ is preferably a straight-chain or branched alkylene group having 1 to 18 carbon atoms, more preferably a straight-chain or molecular alkylene group having 1 to 12 carbon atoms, and 1 to 6 carbon atoms. A linear or branched alkylene group is more preferable, and L ¹ is particularly preferably a methylene group.

In the chemical formula (1), at least one of R ¹ and R ² is preferably a linear or branched alkyl group. Carbon number of the said linear or branched alkyl group is 1-18, for example, Preferably it is 1-12, More preferably, it is 1-6. For example, both of R ¹ and R ² may be the linear or branched alkyl group, one may be the linear or branched alkyl group, and the other may be a hydrogen atom. The linear or branched alkyl group is preferably a group having an oxygen atom (ether bond) instead of a methylene group (—CH ₂ —) in the chain.

In R < ³ > -R < ¹⁶ > in the said Chemical formula (1), carbon number of the said linear or branched alkyl group is 1-18, for example, Preferably it is 1-12, More preferably, it is 1-6. The same applies to the linear or branched alkoxy group. In R ^{3 to} R ¹⁶ , the linear or branched alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group. The linear or branched alkoxy group is particularly preferably a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group or tert-butoxy group.

前記化学式（３）中、Ｒ^１０００は、直鎖若しくは分枝アルキル基であり、Ｒ^３およびＲ^５〜Ｒ^１６は、前記化学式（１）と同じである。Ｒ^１０００において、前記直鎖若しくは分枝アルキル基の炭素数は、例えば１〜１８、好ましくは１〜１２、より好ましくは１〜６である。 The triazine derivative represented by the chemical formula (1) is preferably, for example, a triazine derivative represented by the following chemical formula (3), or a tautomer or stereoisomer thereof.

In the chemical formula (3), R ¹⁰⁰⁰ is a linear or branched alkyl group, and R ³ and R ^{5 to} R ¹⁶ are the same as those in the chemical formula (1). In ^R1000 , the linear or branched alkyl group has, for example, 1 to 18, preferably 1 to 12, and more preferably 1 to 6 carbon atoms.

In the chemical formula (3), R ³ and R ^{5 to} R ¹⁶ are preferably each independently a hydrogen atom or a linear or branched alkyl group. Carbon number of the said linear or branched alkyl group is 1-18, for example, Preferably it is 1-12, More preferably, it is 1-6, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl. A group, isobutyl group, sec-butyl group or tert-butyl group is particularly preferred.

Among the triazine derivatives represented by the chemical formula (1), particularly preferred triazine derivatives include, for example, triazine derivatives represented by the following formulas (4) to (6), and tautomers and stereoisomers thereof. Although it is at least one selected from the group which consists of, it is not limited to these.

  The triazine derivative represented by the chemical formula (4) or (5) can be purchased from Ciba Specialty Chemicals Co., Ltd. under the trade name Tinuvin 400, for example. However, the triazine derivative represented by the chemical formula (4) or (5) is not limited thereto, and may be obtained or synthesized by other methods. The triazine derivative represented by the chemical formula (6) can be purchased from Ciba Specialty Chemicals, Inc. under the trade name Tinuvin 405, for example. However, the triazine derivative represented by the chemical formula (6) is not limited thereto, and may be obtained or synthesized by other methods. Tinuvin is a registered trademark of Ciba Specialty Chemicals Co., Ltd.

前記化学式（２）中、
Ｒ^１７は、水素原子、直鎖若しくは分枝アルキル基、飽和若しくは不飽和の直鎖若しくは分枝若しくは環状炭化水素基、または任意の原子団であり、
Ｒ^１８は、水素原子または保護基であり、
Ｌ^２およびＬ^３は、それぞれ独立に、直鎖若しくは分枝アルキレン基、飽和若しくは不飽和の直鎖若しくは分枝若しくは環状炭化水素基、または任意の原子団であるか、または存在しない。
[1-4. Component (d) (carboxylic acid diol)]
In addition to the components (a) to (c), the polyurethane of the present invention further comprises a carboxylic acid diol represented by the following chemical formula (2), a tautomer and stereoisomer thereof, and a salt thereof. Ru polyurethane der obtained by reacting at least one (component (d)) is selected from.

In the chemical formula (2),
R ¹⁷ is a hydrogen atom, a linear or branched alkyl group, a saturated or unsaturated linear or branched or cyclic hydrocarbon group, or any atomic group,
R ¹⁸ is a hydrogen atom or a protecting group,
L ² and L ³ are each independently a linear or branched alkylene group, a saturated or unsaturated linear or branched or cyclic hydrocarbon group, or any atomic group, or absent.

In the chemical formula (2), R ¹⁸ may be a protective group, but is preferably a hydrogen atom because deprotection is not necessary. If the reactivity of the hydroxyl group added to L ² and L ³ is sufficiently high, the objective is to produce the polyurethane of the present invention even if the carboxyl group in the chemical formula (2) is not protected with a protecting group (R ¹⁸ ). Can be used in the reaction. From this viewpoint, in L ² , the linear or branched alkylene group has, for example, 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and a methylene group is particularly preferable. The same is true in L ^3. L ² and L ³ are particularly preferably both methylene groups. In R ¹⁷ , L ² and L ³ , the “saturated or unsaturated linear or branched or cyclic hydrocarbon group” has, for example, 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 carbon atoms. ~ 6. The cyclic hydrocarbon group may be an aromatic ring or a non-aromatic ring, and examples thereof include groups derived from benzene, naphthalene, cyclohexane and the like.

  The compound (carboxylic acid diol) represented by the chemical formula (2) is, for example, at least one selected from the group consisting of dimethylolpropionic acid (DMPA), dimethylolbutanoic acid (DMBA) dimethylolbutyric acid, and dimethylolvaleric acid. It is preferable that In addition to these, for example, other carboxylic acid diols generally used in polyurethane synthesis can also be preferably used. Moreover, only one type of compound (carboxylic acid diol) represented by the chemical formula (2) may be used, or two or more types may be used in combination as necessary.

In the case where the components (a) ~ (d) were reaction, it is how combine to form a polyurethane of the present invention, it is not necessarily clear. The component (c) can be considered as follows, for example. That is, the oxygen atom of the secondary hydroxyl group of the triazine derivative represented by the chemical formula (1) (the oxygen atom indicated by the symbol “α” and the arrow in the following chemical formula) is bonded to the polyurethane chain by condensation, polyaddition or the like. It is possible that Furthermore, when the triazine derivative represented by the formula (3), an oxygen atom (in the following chemical formula, an oxygen atom indicated by the symbol and arrows "β") that the added of R ¹⁰⁰⁰ R ¹⁰⁰⁰ from is eliminated, the oxygen It is also conceivable that the atoms are bonded to the polyurethane chain by condensation, polyaddition or the like. However, these are examples of presumable reaction mechanisms and structures, and the structure of the compound of the present invention is not limited by these considerations.

Further, the polyurethane of the present invention, for example, as described above, wherein the components (a) ~ (d) can be obtained by reaction. However, the production method of the polyurethane of the present invention is not limited at all, and may be produced by any production method. For example, as long as a polyurethane having the same structure as the polyurethane of the present invention can be obtained even by a production method using a raw material having a structure different from that of the components (a) to ( d ) , it may be produced by the method. Polyurethane is the polyurethane of the present invention.

[2. Method for producing polyurethane]
As described above, the method for producing the polyurethane of the present invention is not limited at all. For example, as described above, wherein the component (a) Ru can be reacted ~ (d) is to produce a polyurethane of the present invention. For example, when water is added to the reaction system for reaction, it is preferable to react the component (d) in addition to the components (a) to (c), which is excellent in reaction efficiency, polyurethane yield, and the like. The polyurethane production method of the present invention may be, for example, a method of synthesizing a polyurethane chain in one step (one-shot method). Alternatively, a method in which a polyol and a polyisocyanate compound are reacted in advance to synthesize an isocyanato group-terminated prepolymer, and a target polyurethane is obtained using a chain extender such as diamine (prepolymer method) may be used. In the one-shot method, for example, the following formula (I) is preferably satisfied. In the prepolymer method, for example, the following formula (II) is preferably satisfied, but this is not restrictive.

0.8 ≦ NCO / OH ≦ 1.0 (I)
1.2 ≦ NCO / OH ≦ 4.0 (II)

In the formula (I) and (II), the term "NCO" is the sum of the isocyanate group (-NCO) number in all components prior SL component (a) ~ (d), and "OH" is This is the total number of hydroxyl groups (—OH) in all the components (a) to ( d ) . In the prepolymer method, the lower limit value of NCO / OH is more preferably 1.5 or more, and the upper limit value is more preferably 2.0 or less.

  Moreover, when manufacturing the polyurethane of this invention, you may react, for example, dissolving each component in a solvent. Further, for example, the reaction may be performed using water, various organic solvents described later, or the like as a dispersion medium under conditions that do not substantially hinder the reaction. The type of the solvent and the dispersion medium can be appropriately selected with reference to a known polyurethane production method, for example, as described later. Further, these methods can be combined with any of the one-shot method and the prepolymer method described above.

  In the method for producing a polyurethane of the present invention, when the components (a) to (d) are reacted, for example, all of the components (a) to (d) may be reacted at a time. That is, in the step (A) in which the components (a) to (c) are reacted, the component (d) may be reacted together. However, according to the production method, the components (a) to (c) are reacted first (the step (A)), and the product is reacted later with the component (d) (the step (B)). The component (c) (triazine derivative) is more preferable because it is more easily bonded to the polyurethane chain. The reason for this is not necessarily clear, but is considered as follows, for example. That is, when the component (d) (carboxylic acid diol) is added simultaneously with the component (c) (triazine derivative), since the reactivity of the component (c) is low, only the carboxylic acid diol (component (d)) Reacts preferentially with the components (a) and (b), and the triazine derivative (component (c)) does not bind. On the other hand, when the components (a) to (c) are reacted in advance without adding the component (d), the triazine derivative (component (c)) can be efficiently bonded to the polyurethane chain. However, this consideration is an example of a presumable reaction mechanism and does not limit the present invention.

  It is not always clear what kind of reaction occurs in each of the steps (A) and (B), but it is considered as follows, for example. That is, in the step (A), the component (a) (polyol) and the component (b) (polyisocyanate compound) are polymerized to form a prepolymer chain having a short chain length. The component (c) (triazine derivative) is bonded. As a result, a prepolymer is produced in which the component (c) (triazine derivative) is bonded to the chain and integrated. Next, in the step (B), the prepolymer which is the product of the step (A) is copolymerized with the component (d) (carboxylic acid diol) to produce a polymer having a long chain length. In addition, as a product of the step (A), a reaction product of the component (b) and the component (c) (triazine derivative) (not reacted with the component (a) (polyol)) remained. In this case, it is considered that this reacts with the component (d) (carboxylic acid diol) and is incorporated into the chain of the polymer (polyurethane). However, these are examples of reaction mechanisms that may occur or can be estimated in the steps (A) and (B). The steps (A) and (B) and their products, and the present invention are not limited in any way by these descriptions.

  Hereinafter, the method for producing the polyurethane of the present invention will be described more specifically.

Production method of the present invention, prior to SL to step (A) and (B) other steps may be included as appropriate, it may not contain. In addition, for example, in the production method of the present invention, components other than the components (a) to (d) may or may not be appropriately used as the reactant. The component (a) (polyol) and the component (b) (polyisocyanate compound) are not particularly limited, and various compounds can be selected widely. Further, the amount of the component (c) (triazine derivative) incorporated in the polyurethane chain as an ultraviolet absorber is not particularly limited, and can be appropriately adjusted.

The production method of the present invention can be performed, for example, as follows. Various reaction conditions such as reaction temperature, reaction time, solvent, dispersion medium, concentration, and substance amount ratio are not limited to the following conditions. For example, the various reaction conditions can be appropriately changed with reference to a known polyurethane production method and the like. In the following, the production method mainly includes (A) a step of reacting the components (a) to (c) and (B) a step of reacting the reaction product of the step (A) with the component (d). will be described, but the method, prior Symbol reacted all at once the component in the step (a) (a) ~ ( d), etc. are omitted the step (B), it can be appropriately changed.

[2-1. Step (A)]
First, the step (A) is performed. Specifically, for example, it can be performed as follows.

  That is, first, the component (a) (polyol), the component (b) (polyisocyanate compound), and the component (c) (triazine derivative) are prepared. The substance amount (number of moles) of the component (a) (polyol) is not particularly limited and may be set as appropriate. In the case of the one-shot method, the amount of the component (a) (polyol) relative to 1 mol of the component (b) (polyisocyanate compound) is, for example, 1.00 to 1.25 mol based on the formula (I). There is, but is not limited to this. In the case of the prepolymer method, the amount of the component (a) (polyol) relative to 1 mol of the component (b) (polyisocyanate compound) is, for example, 0.25 to 0.84 mol based on the formula (II), Preferably it is 0.50-0.84 mol, More preferably, it is 0.50-0.64 mol, However, It is not limited to this. The substance amount (number of moles) of the component (c) (triazine derivative) is not particularly limited, and can be set as appropriate. For example, in the polyurethane (urethane resin) produced in the present invention, the content of the ultraviolet absorber, that is, the component (c) (triazine derivative) is, for example, 0.1 to 50.0%, preferably 0 in mass ratio. .4 to 20.0%, more preferably 1.0 to 10.0%, but not limited to this value. The component (c) (triazine derivative) can obtain a sufficient ultraviolet absorbing ability even in a relatively small amount, and is preferably 10.0% by mass or less in consideration of the influence on other physical properties of polyurethane. The amount of the component (c) (triazine derivative) relative to 1 mol of the component (b) (polyisocyanato compound) is not particularly limited and can be set as appropriate. The reaction component (raw material) is a substance of Examples described later, the NCO / OH is 1.5, the resin acid value of the polyurethane to be produced is 15, the content of the component (c) (triazine derivative) in the polyurethane Is calculated as the aforementioned numerical range, the amount of the component (c) (triazine derivative) relative to 1 mol of the component (b) (polyisocyanate compound) is, for example, 0.001 to 0.660 mol, preferably 0.005. It is -0.265 mol, More preferably, it is 0.013-0.125 mol. This numerical range also applies when the reaction component (raw material) is other than the substance of the example, when the NCO / OH is a numerical value other than 1.5, and when the resin acid value is a numerical value other than 15. It can be determined according to In the present invention, the unit of the resin acid value is mg-KOH / g unless otherwise specified. In the production method of the present invention, the ratio of the reaction components (the components (a) to (d) and other components) such as the raw material monomer is very high, for example, the properties of the raw material monomer ( It can be set as appropriate according to the use of the polyurethane to be produced and the like, and is not limited by the numerical range described in this specification.

  Next, the components (a) to (c) are reacted. At this time, if necessary, components other than the components (a) to (c), for example, a catalyst or the like may coexist as appropriate. The catalyst is not particularly limited, and examples thereof include DBTDL (dibutyltin dilaurate), other metal catalysts, and amine catalysts. The substance amount (number of moles) of the catalyst is not particularly limited and varies depending on the type of the catalyst. However, for example, 1 to 10,000 μmol, preferably 10 to 1000 μmol, relative to 1 mol of the component (b) (polyisocyanate compound). More preferably, it is 50-500 micromol.

The reaction may be performed, for example, without solvent, but is preferably performed using a solvent from the viewpoint of ease of reaction control. The solvent is not particularly limited, but from the viewpoints of solubility and reactivity of the components (a) to (c), for example, ketone, chain aliphatic hydrocarbon, cyclic aliphatic hydrocarbon, aromatic hydrocarbon , Ether, ester, amide, sulfoxide, alcohol and the like are preferable. Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 2-hexanone, cyclohexanone, and acetophenone. Examples of the chain aliphatic hydrocarbon include hexane, 2-methylpentane, heptane, octane and the like. Examples of the cyclic aliphatic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane. Examples of the aromatic hydrocarbon include benzene, xylene, toluene, ethylbenzene, and the like. Examples of the ether include diethyl ether, dibutyl ether, dioxane, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, and the like. Examples of the ester include ethyl acetate, propyl acetate, butyl acetate, methyl propionate, propylene glycol monomethyl ether acetate and the like. Examples of the amide include N-methylpyrrolidone and dimethylformamide. Examples of the sulfoxide include dimethyl sulfoxide. Examples of the alcohol include methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, hexanol, 2-methyl-1-pentanol and the like. These solvents may be used alone or in combination of two or more. In the production method of the present invention, when the total mass of all reaction components (including the components (a) to (d)) other than the solvent is A and the mass of the solvent is B, the following formula (III) is used. The reaction component content C (%) is not particularly limited, but is, for example, 10 to 100%, preferably 40 to 100%, and more preferably 70 to 100%. In addition, about alcohol, depending on reaction condition setting, it can also be used not as a solvent but as a reaction terminator, for example.

C = A / (A + B) × 100 (III)

  The temperature of the reaction is not particularly limited, and varies depending on the type of each reaction component (particularly, the component (b) (polyisocyanate compound)), but it is, for example, 40 to 180 ° C, preferably 60 to 150 ° C. Preferably it is 60-100 degreeC. The reaction time is not particularly limited, and may vary depending on the reaction temperature and the type of each reaction component (particularly, the component (b) (polyisocyanate compound)), for example, 1 to 12 hours, preferably 1 to 6 hours, more preferably 1.5 to 4 hours. The reaction is preferably carried out while thoroughly stirring the reaction system from the viewpoints of, for example, improving the reaction rate, uniformity of the reaction, and preventing reaction runaway. The reaction may be performed, for example, in the air, but may be performed in an inert gas such as nitrogen or argon from the viewpoint of preventing side reactions.

  The reaction tracking can be performed using, for example, GPC (gel filtration chromatography). The end of the step (A) may be appropriately determined and is not particularly limited. For example, when the raw material disappears or the peak fluctuation disappears in the analysis by GPC or the like, the reaction is terminated, and the next step (B) Can move on.

[2-2. Step (B)]
Next, the step (B) is performed. A specific method is not particularly limited. For example, without purifying the reaction mixture obtained in the step (A), that is, without removing the solvent or the like, the component (d) (carboxylic acid diol) is added and reacted as it is, (B) may be performed. Therefore, the solvent used in the step (B) may be the same as that in the step (A), for example. The amount of component (d) added is not particularly limited. The reaction component (raw material) is a substance of Examples described later, NCO / OH = 1.5, the weight ratio of the ultraviolet absorber (the component (c)) in the polyurethane resin is 4%, and the resin acid value is 0, for example. When calculated as -60 mg-KOH / g, preferably 5-30 mg-KOH / g, more preferably 10-30 mg-KOH / g, the amount of the component (d) added is the amount of the component ( b) For example, 0 to 0.53 mol, preferably 0.08 to 0.35 mol, and more preferably 0.15 to 0.35 mol with respect to 1 mol of the polyisocyanate compound used. When the reaction component (raw material) is other than the materials of the examples, the NCO / OH is a numerical value other than 1.5, and the resin acid value is a numerical value other than those described above, this numerical range is also followed. Can be determined. In this step, components other than the component (d) may or may not be added as necessary. Moreover, a solvent etc. may be added suitably as needed and it is not necessary to add. The reaction temperature and reaction time are not particularly limited, and are, for example, the same as the numerical range exemplified in the step (A). The reaction is preferably carried out while thoroughly stirring the reaction system from the viewpoints of, for example, improving reaction rate, uniformity of reaction, prevention of reaction runaway, and the like. The reaction may be performed, for example, in the air, but may be performed in an inert gas such as nitrogen or argon from the viewpoint of preventing side reactions. The reaction tracking can be performed using, for example, GPC (gel filtration chromatography). The step (B) may be appropriately determined at the end, and is not particularly limited. For example, when the raw material disappears or the peak fluctuation disappears in the analysis by GPC or the like, the reaction can be ended.

[2-3. Step (C): Chain Extension]
In the production method of the present invention, the product of the step (B) may be used as the polyurethane of the present invention. However, as described above, the production method of the present invention may appropriately include steps other than the steps (A) and (B). For example, the process (C) of making the product of the said process (B) react with a chain extender further may be included. A specific method is not particularly limited. For example, the chain extension step (C) may be performed as it is without adding the chain extender without purifying the reaction mixture obtained in the step (B), that is, without removing the solvent. Therefore, the solvent used in the step (C) may be the same as that in the step (B), for example. In the chain extension step (C), it is preferable to carry out the reaction by adding a dispersion medium such as water in addition to the solvent, but the reaction can also be carried out without adding the dispersion medium. When adding a dispersion medium, the addition amount is not particularly limited, but is, for example, 1.0 to 50.0 times the mass of the solvent, preferably 1.5 to 20.0 times, more preferably 2.0 to 10.0 times. The chain extender is not particularly limited, but for example, polyamine is preferable, and diamine or triamine is more preferable. Examples of the diamine include alkylene diamine, polyether diamine, alicyclic diamine, and aromatic diamine. Examples of the alkylene diamine include ethylene diamine (EDA) and propylene diamine (PDA). Examples of the polyether diamine include polyoxypropylene diamine and polyoxyethylene diamine. Examples of the alicyclic diamine include mensendiamine, isophoronediamine, norbornenediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, 3,9-bis ( 3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane and the like. Examples of the aromatic diamine include m-xylylenediamine, α- (m / p aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldiphenylmethane, dimethylthiotoluenediamine, Examples include diethyltoluenediamine and α, α′-bis (4-aminophenyl) -p-diisopropylbenzene. Examples of the diamine include hydrazine, dicarboxylic acid dihydrazide compounds, and the like. Examples of the triamine include dialkylene triamine. Examples of the dialkylenetriamine include diethylenetriamine and dipropylenetriamine. The addition amount of the chain extender is not particularly limited, but is, for example, 0.15 to 0.68 mol, preferably 0.1 to 0.1 mol of the component (b) (polyisocyanate compound) used in the step (A). 15 to 0.45 mol, more preferably 0.30 to 0.45 mol. This numerical range is applicable when the NCO / OH is, for example, 1.2 to 4.0, preferably 1.5 to 4.0, more preferably 1.5 to 2.0. Even when NCO / OH is in a numerical range other than this, the amount of the chain extender added can be determined accordingly. If necessary, components other than the chain extender may or may not be added as appropriate. For example, in this step, when water is added to emulsify and react, it is preferable to add a neutralizing agent in order to keep the pH of the system appropriately. The neutralizing agent is not particularly limited, and examples thereof include tertiary amine, ammonia, trimethylammonium hydroxide, metal hydroxide and the like. Examples of the tertiary amine include trialkylamine, N, N-dialkylalkanolamine, and trialkanolamine. Examples of the trialkylamine include trimethylamine, triethylamine (TEA), and tributylamine. Examples of the N, N-dialkylalkanolamine include N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-dipropylethanolamine, and 1-dimethylamino-2-methyl-2-propanol. Etc. Examples of the trialkanolamine include triethanolamine. Examples of the metal hydroxide include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. Among these neutralizing agents, tertiary amines are particularly preferable from the viewpoint of poor reactivity with isocyanato groups (—NCO). This is because if the reactivity with the isocyanato group (—NCO) is poor, chain elongation due to the reaction between the remaining isocyanato group (—NCO) and the hydroxyl group (—OH) is hardly inhibited. Although the addition amount of the neutralizing agent is not particularly limited, it is, for example, 10 to 100 mol%, preferably 30 to 100 mol%, more preferably 60 to the use amount (mol) of the component (d) (carboxylic acid diol). 100 mol%. Moreover, a solvent, a dispersion medium, etc. may be added suitably as needed and it is not necessary to add.

  The reaction temperature in the chain extension step (C) is not particularly limited and can be set as appropriate. The reaction temperature is, for example, 10 to 80 ° C., preferably 20 to 60 ° C., more preferably 25 to 40 ° C., although it depends on the types of reactants, particularly isocyanato compound (isocyanate) and chain extender. For example, if the temperature is too high at the end of the step (B), the neutralizing agent and the chain extender may be added and reacted after cooling to an appropriate temperature. The reaction time is not particularly limited and can be set as appropriate. The appropriate reaction time varies depending on the reaction temperature, and depends on the type of the reactant, particularly the isocyanato compound (isocyanate) and the chain extender. For example, 0.5 to 6 hours, preferably 0.5 to 3 hours, More preferably, it is 1-2 hours. The reaction is preferably carried out while thoroughly stirring the reaction system from the viewpoints of, for example, improving the reaction rate, uniformity of the reaction, and preventing reaction runaway. The reaction may be performed, for example, in the air, but may be performed in an inert gas such as nitrogen or argon from the viewpoint of preventing side reactions. The reaction tracking can be performed using, for example, GPC (gel filtration chromatography). The end of the step (C) may be appropriately determined and is not particularly limited. For example, when the raw material disappears or the peak fluctuation disappears in the analysis by GPC or the like, the reaction can be terminated.

  As described above, the polyurethane of the present invention can be produced. Furthermore, when this is used as, for example, a polyurethane paint, a thickener may be added to the reaction solution or emulsion after completion of the step (B) or (C) to obtain an appropriate viscosity, which may be used as a paint. Further, if necessary, wax, antifoaming agent or the like may be added as appropriate to form a paint. For example, when a polyurethane foam is used, a foaming agent may coexist in at least one of the reaction steps.

[3. Products using polyurethane]
The use of the polyurethane of the present invention is not particularly limited and may be used for any purpose, but is particularly suitable for use as a paint. This is because the polyurethane of the present invention effectively prevents separation of the ultraviolet absorber and is excellent in performance such as light resistance and weather resistance. The polyurethane of the present invention is suitable, for example, for various polyurethane paints shown in Table 1 below, and among these, particularly suitable for lacquer type paints. The descriptions in Table 1 below are partially modified with reference to the description in “Table 24 Classification of polyurethane paints by curing mode” on page 49 of “Summary of polyurethane raw material industry” 4th edition (Urethane Industry Association). is there. However, in this invention, the classification | category in following Table 1 is a mere illustration, and the coating material using the polyurethane of this invention is not limited to these. Moreover, the curing method and curing conditions in Table 1 below are merely examples, and are not limited to these. For example, a lacquer type paint may be cured with a reaction.

  Examples of paints include outdoor building paints, automotive paints, powder paints, clear top coatings, overprint protective coating layers for inkjet printing materials and sublimation transfer printing materials, adhesives used for LCD displays, and various printed materials. Examples include protective coatings, fiber treatment polymer chemicals, protective coatings for olefin cosmetics, protective coatings for window sticking, and the like. The polyurethane of the present invention is not limited to these, and may be used for any paint.

  Furthermore, the polyurethane of the present invention is not limited to paint, and may be used for any application. For example, when the polyurethane of the present invention is produced, it is possible to impart characteristics according to the application by appropriately adjusting the various reaction conditions. The polyurethane of the present invention is, for example, as described above, polyurethane foam, bedding, diapers, cushioning materials, heat insulating materials, structural materials, elastomers, industrial parts, rolls, packing, shoe soles, hoses, civil engineering products, building material products, waterproofing. Materials, roofing waterproofing solvent, indoor flooring, jointing waterproofing material, textile, sportswear, underwear, rain gear, synthetic leather, artificial leather, shoes, clothing, paint, adhesive, automotive parts, woodwork supplies, hard coat film, Or it can use for the product used as a laminated | multilayer film, and can also be used for arbitrary products or uses other than these.

  Examples of the present invention will be described below.

  In the following examples, PCD Mw1000 is a polycarbonate diol purchased from Nippon Polyurethane Industry Co., Ltd. (trade name NIPPOLAN 981). Its structure is as described in the chemical formula (9). “Mw1000” in the PCD Mw1000 indicates that the weight average molecular weight is about 1000. Tinuvin 400 and Tinuvin 405 (both trade names) were purchased from Ciba Specialty Chemicals Co., Ltd. The structure of the triazine derivative is as described above. A benzotriazole-based ultraviolet absorber (trade name RUVA-100) was purchased from Otsuka Chemical Co., Ltd. H12MDI (4,4'-diisocyanatodicyclohexylmethane) was purchased from Sumika Bayer Urethane Co., Ltd. (trade name Dismodule W). The structure of H12MDI is as described in the chemical formula (12). DBTDL (di-n-butyltin dilaurate) was purchased from Kanto Kasei Kogyo Co., Ltd. DMPA (dimethylolpropionic acid) was purchased from Kanto Kasei Kogyo Co., Ltd. EDA (ethylenediamine) was purchased from Kishida Chemical Co., Ltd. (first grade). NMP (N-methyl-2-pyrrolidone) was purchased from Mitsubishi Chemical Corporation. TEA (triethylamine) was purchased from Kishida Chemical Co., Ltd. (first grade). An antifoaming agent (trade name SN deformer 777) was purchased from San Nopco. In addition, unless otherwise specified, GPC is a Shimadzu Corporation instrument (Liquid feeding unit LC-6A for high speed liquid chromatograph Shimadzu UV spectrophotometer detector SPD-6A (measurement wavelength 254 nm)) Chromatopack C- 6R) and Shimadzu Corporation column (trade name: Shimadzu High Performance Liquid Chromatogram High Performance Packing Column Shim-pack GPC-802C, 801C) with THF as the mobile phase (tetrahydrofuran deer 1 purchased from Kanto Chemical Co., Inc.) Grade). The solid content (NV) in the solution was determined by weighing 1 g of the solution into a metal container having a width of 5 cm, a length of 5 cm, and a depth of 1 cm, placing it in a 200 ° C. oven for 10 minutes, air cooling, and weight before and after drying. I asked for it. Unless otherwise specified, the viscosities of B type viscometer and rotor No. 2 was measured at 25 ± 0.5 ° C. The average particle size was measured by “Dynamic Light Scattering Particle Size Distribution Measurement Device BL-550 (trade name)” manufactured by Horiba, Ltd. The average particle diameter indicates a median diameter unless otherwise specified.

[Example 1]
The polyurethane of the present invention was produced (synthesized) as follows.

Using the reactants listed in Table 2 below, the reaction steps (A) to (C) were performed to synthesize the polyurethane of the present invention.

  Steps (A) to (C) were performed as follows.

[Step (A)]
In a reactor equipped with a stirrer, a thermometer, a nitrogen vent tube, and a condenser tube, NMP (715.9 g), DBTDL (12.6 g) previously diluted to 1% by mass with NMP, PCD Mw1000 (860.0 g), Tinuvin 400 (64.7 g) and H12MDI (524.8 g) were added. The reaction system was heated to 85 ° C. while continuing the bubbling and stirring of nitrogen gas, and the reaction was continued at 85 ° C. while continuing the bubbling and stirring of nitrogen gas. The reaction was followed by GPC, and when the reaction was performed at 85 ° C. for 1.5 hours, the step (A) was completed.

[Step (B)]
After completion of the step (A), DMPA (56.3 g) was added to the reactor which was air-cooled with stirring and cooled to 50 ° C. The reaction system was heated to 85 ° C. again while continuing the aeration and stirring of nitrogen gas into the reaction system, and the reaction was continued at 85 ° C. while continuing the aeration and stirring of nitrogen gas. The reaction was monitored by GPC, and when the reaction was performed at 85 ° C. for 3 hours, the step (B) was completed.

[Step (C)]
After completion of the step (B), TEA (42.5 g) as a neutralizing agent was gradually added dropwise to the reactor cooled to 60 ° C. while stirring and air-cooled. While further stirring, ion-exchanged water (2819.3 g) preheated to 50 ° C. was gradually added to emulsify. Further, EDA (36.2 g) was gradually added dropwise to the reactor which was air-cooled with stirring and cooled to 40 ° C. Furthermore, the reaction was continued at 40 ° C. The reaction was followed by GPC, and when the reaction was conducted at 40 ° C. for 1 hour, the step (C) was completed. In this way, the polyurethane of the present invention could be produced. Furthermore, after the completion of the step (C), as a post-treatment, an antifoaming agent (7.7 g) diluted with water to 10% by mass in advance is added to the reactor and stirred for 5 minutes to obtain an emulsion containing the polyurethane of the present invention. Obtained. The emulsion was a slightly brownish cloudy liquid. The solid content (NV) in the emulsion was 29.7% (mass ratio), the viscosity was 15.0 mPa · s, and the average particle size of the polyurethane was 62.4 nm.

The tracking results of the reaction steps (A) to (C) by GPC are shown in Table 3 below and FIG. FIG. 1 is a GPC chromatogram of the reaction mixture. Table 3 is a table showing the peak area ratio and the like of each substance calculated from the chromatogram of FIG. In FIG. 1, (1) shows the chromatogram of the raw material mixture just before the start of the step (A). (2) shows a chromatogram of the reaction mixture immediately after completion of the step (A) and before addition of DMPA. (3) shows a chromatogram of the reaction mixture immediately after neutralization with TEA after the completion of the step (B). (4) shows a chromatogram of the reaction mixture immediately after completion of the step (C). The numbers in the figure are the retention times of each peak. “UVA monomer” indicates a peak presumed to be unreacted tinuvin 400 (ultraviolet absorber). “UVA + H12MDI” indicates a peak presumed to be a reaction product of Tinuvin 400 and H12MDI. A gentle peak with a retention time of about 29 minutes or less indicates a peak presumed to be polyurethane (a reaction product of tinuvin 400, H12MDI, and PCD, or a product of tinuvin 400, H12MDI, PCD, and DMPA). . In Table 3, in the column of “molecular structure (estimated)”, “UVA monomer” indicates unreacted tinuvin 400 (ultraviolet absorber). “UVA + H12MDI” indicates a reaction product of Tinuvin 400 and H12MDI. “UVA + 12MDI + PCD” indicates a reaction product of Tinuvin 400, H12MDI, and PCD, or a product of Tinuvin 400, H12MDI, PCD, and DMPA. “Retention time” indicates an approximate numerical value of GPC retention time assumed from each molecular structure. Each column of (1) to (4) corresponds to the chromatogram of (1) to (4) in FIG. 1, and the numerical value (%) in each column indicates the peak area ratio.

  As shown in Table 3 and FIG. 1, before the reaction, that is, before performing the step (A) (chromatogram (1)), the peak of the UVA monomer (tinuvin 400) which is a triazine derivative appeared strongly. After step (A) (chromatogram (2)), the UVA monomer peak disappeared completely. Furthermore, as the reaction proceeded after the step (B) (chromatogram (3)) and after the step (C) (chromatogram (4)), the polyurethane peak gradually increased. After the step (C) (chromatogram (4)), the peak of the reaction product (dimer) of Tinuvin 400 and H12MDI disappeared almost completely. Furthermore, as shown in FIG. 1, after the step (C) (chromatogram (4)), a short peak with a retention time of about 20 minutes increased. This suggests that the polyurethane to which Tinuvin 400 (ultraviolet absorber), which is a triazine derivative, is bonded is further polymerized by the action of the chain extender.

  As described above, according to this example, it was possible to efficiently produce a polyurethane in which an ultraviolet absorber as a triazine derivative was bonded to a chain using the production method of the present invention.

  In addition, the emulsion containing the polyurethane of the present invention obtained in this example was directly used as a polyurethane paint in the characteristic evaluation described later.

[Example 2]
A polyurethane was synthesized in the same manner as in Example 1 except that the same mass of tinuvin 405 was used instead of tinuvin 400 as a triazine derivative, and an emulsion containing the polyurethane of the present invention was obtained. This emulsion was a slightly brownish cloudy liquid, the solid content was 29.3% (mass ratio), the viscosity was 13.5 mPa · s, and the average particle size was 57.0 nm.

  In addition, the emulsion containing the polyurethane of the present invention obtained in this example was directly used as a polyurethane paint in the characteristic evaluation described later.

[Reference Example 1]
Polyurethane was synthesized in the same manner as in Example 1 except that RUVA-100 (trade name of Otsuka Chemical Co., Ltd.), which is a benzotriazole-based ultraviolet absorber, was used instead of the triazine derivative to obtain an emulsion containing polyurethane. This emulsion was a slightly brownish cloudy liquid, the solid content was 29.7% (mass ratio), the viscosity was 18.0 mPa · s, and the average particle size was 68.3 nm. This emulsion was directly used as a polyurethane paint in the characteristic evaluation described later.

[Comparative Example 1]
Polyurethane was synthesized in the same manner as in Example 1 or 2 except that tinuvin 400 or tinuvin 405 (ultraviolet absorber), which are triazine derivatives, was not used for synthesis, and an emulsion containing polyurethane was obtained. This emulsion was a cloudy white liquid, the solid content was 30.2% (mass ratio), the viscosity was 10.0 mPa · s, and the average particle size was 95.8 nm. This emulsion was directly used as a polyurethane paint in the characteristic evaluation described later.

[Comparative Example 2]
In step (C), polyurethane was synthesized in the same manner as in Comparative Example 1 except that NMP having the same mass was used instead of ion-exchanged water. Since no ion exchange water was added, the product was not an emulsion but a solution containing polyurethane. This solution was a slightly yellowish transparent liquid, the solid content was 20.1% (mass ratio), and the viscosity was 460.0 mPa · s. In addition, the reason why ion-exchanged water was not added is that, as will be described later, an ultraviolet absorbent that is hardly soluble in water is dissolved and used. This solution was directly used as a polyurethane paint in the characteristic evaluation described later.

In addition, in the polyurethane synthesis of Example 1, Example 2, Reference Example 1, Comparative Example 1 and Comparative Example 2, the mixing ratio of each reactant (raw material ratio) is almost the same, but is summarized in Table 4 below. I write.

The results of tracing the reactions of Example 1, Example 2 and Reference Example 1 with GPC are summarized in Table 5 below. The measurement method and the meaning of each item are the same as in Table 3 above. However, “UVA” indicates the ultraviolet absorber used in each synthesis. In Table 5 below, the data of Example 1 is the same data as in Table 3 above.

[Example 3]
Said components (a) to (d), ie DBTDL (12.6 g), PCD Mw1000 (component (a)), H12MDI (component (b)), Tinuvin 400 (component (c)), and DMPA (component (d) )) Was synthesized in the same manner as in Example 1 except that the reaction was carried out in one step without dividing it into the two steps (A) and (B).

  That is, first, in a reactor equipped with a stirrer, a thermometer, a nitrogen vent pipe, and a cooling pipe, NMP (715.9 g), DBTDL (12.6 g) previously diluted to 1% by mass with NMP, PCD Mw1000 (860) 0.0 g), Tinuvin 400 (64.7 g), H12MDI (524.8 g), DMPA (56.3 g) were added. The reaction system was heated to 85 ° C. while continuing the bubbling and stirring of nitrogen gas, and the reaction was continued at 85 ° C. while continuing the bubbling and stirring of nitrogen gas. The reaction was monitored by GPC, and when the reaction was performed at 85 ° C. for 3.0 hours, the reaction was once terminated.

  Thereafter, TEA (42.5 g) as a neutralizing agent was gradually added dropwise to the reactor which was air-cooled with stirring and cooled to 60 ° C. While further stirring, ion-exchanged water (2819.3 g) preheated to 50 ° C. was gradually added to emulsify. Further, EDA (36.2 g) was gradually added dropwise to the reactor which was air-cooled with stirring and cooled to 40 ° C. Furthermore, the reaction was continued at 40 ° C. The reaction was followed by GPC, and the reaction was terminated when reacted at 40 ° C. for 1 hour. In this way, the polyurethane of the present invention could be produced. Further, as a post-treatment, an antifoaming agent (7.7 g) diluted with water to 10% by mass in advance was added to the reactor and stirred for 5 minutes to obtain an emulsion containing the polyurethane of the present invention. This emulsion was a slightly yellowish cloudy liquid. The solid content (NV) in the emulsion was 29.7% (mass ratio), the viscosity was 10.0 mPa · s, and the average particle size of the polyurethane was 82.7 nm. This emulsion was directly used as a polyurethane paint in the characteristic evaluation described later.

[Example 4]
An emulsion containing the polyurethane of the present invention was obtained in the same manner as in Example 3 (in a one-step synthesis) except that tinuvin 405 was used instead of tinuvin 400. This emulsion was a slightly yellowish cloudy liquid. The solid content (NV) in the emulsion was 29.9% (mass ratio), the viscosity was 10.0 mPa · s, and the average particle size of the polyurethane was 71.7 nm. This emulsion was directly used as a polyurethane paint in the characteristic evaluation described later.

[Reference Example 2]
An emulsion containing polyurethane was obtained in the same manner as in Example 3 (in a one-step synthesis) except that the same mass of RUVA-100 (benzotriazole-based ultraviolet ray) was used in place of Tinuvin 400 (an ultraviolet absorber of a triazine derivative). The emulsion was a slightly brownish cloudy liquid. The solid content (NV) in the emulsion was 30.0% (mass ratio), the viscosity was 14.5 mPa · s, and the average particle size of the polyurethane was 58.3 nm. This emulsion was directly used as a polyurethane paint in the characteristic evaluation described later.

[Example 5]
Except for adding triethylamine (neutralizing agent) from the beginning, that is, NMP (715.9 g), DBTDL (12.6 g) previously diluted to 1% by mass with NMP, PCD Mw1000 (860.0 g), Tinuvin 400 ( 64.7 g), H12MDI (524.8 g), DMPA (56.3 g) and TEA (42.5 g) were added at the same time, and triethylamine was not added thereafter. An emulsion containing was obtained. The emulsion was a slightly brownish cloudy liquid. The solid content (NV) in the emulsion was 30.1% (mass ratio), the viscosity was 15.0 mPa · s, and the average particle size of the polyurethane was 65.4 nm. This emulsion was directly used as a polyurethane paint in the characteristic evaluation described later.

In addition, as a result of tracking the reaction by GPC, in Examples 3 to 5 in which the components (a) to (d) were reacted in one step, a triazine-based ultraviolet absorber (tinuvin 400 or 405) was introduced into the polymer chain. It has been confirmed that. The measuring method is the same as in the above-described Example 1, Example 2, and Reference Example 1. The results of tracing the reactions of Example 3, Example 4 and Reference Example 2 by GPC are summarized in Table 6 below. In Table 6 below, (1) shows the GPC measurement result of the raw material mixture (including the components (a) to (d)) just before the start of the reaction. (2) shows the GPC measurement result of the reaction mixture immediately after neutralization with TEA. (3) shows the GPC measurement result of the reaction mixture after completion of the reaction. The meanings of the other items are the same as those in Tables 3 and 5. However, “UVA” indicates the ultraviolet absorber used in each synthesis. As shown in the column of “UVA + 12MDI + PCD” in Table 6 below, in Example 3 and Example 4, as the reaction proceeds, a polyurethane in which a triazine derivative (ultraviolet absorber) is bonded to a polymer chain is obtained with a certain yield. It was. For Example 4, the chromatogram is shown in FIG. In FIG. 2, (1) shows the chromatogram of (1) in the following Table 6. (3) shows the chromatogram of (3) in Table 6 below. “UVA + 12MDI + PCD” indicates the peak of the product of Tinuvin 405, H12MDI, PCD and DMPA, ie the polyurethane of interest. The numbers in the figure are the retention times of each peak. The rest is the same as FIG. In Example 5 as well, GPC of the reaction mixture immediately before the start of the reaction and after the end of the reaction was measured, and it was confirmed that a polyurethane having a triazine derivative (ultraviolet absorber) bonded to the polymer chain was obtained. It was.

For the emulsions or solutions of Examples 1 to 5, Reference Examples 1 and 2 and Comparative Examples 1 and 2 synthesized as described above, the synthesis method, composition, characteristic value (physical property value) and appearance are summarized in Table 7 below. . In Table 7 below, vis (FC # 4) is measured at 25.0 ± 0.5 ° C. using a JIS (former) K5400 Ford Cup # 4, and the continuity of the sample. Indicates the number of seconds required for outflow. Vis (B type) is the viscosity measured with the above-mentioned B type viscometer. NV (solid content) and median (average particle size) are as described above. Moreover, UVA (4%) shows that it added so that the content rate of an ultraviolet absorber might be 4 parts (mass ratio) with respect to 100 parts of solid content other than an ultraviolet absorber. “DMPA AV = 15” indicates that the amount of DMPA added was adjusted so that the resin acid value of the polyurethane was 15 mg-KOH / g. “Index 1.50” indicates that the aforementioned NCO / OH value is 1.50.

[Comparative Example 3]
Adecanol UC-3140 (trade name of ADEKA Corporation), which is a benzotriazole-based ultraviolet absorber, was added to the emulsion obtained in Comparative Example 1 and dispersed therein to obtain an emulsion containing an ultraviolet absorber. The amount of Adecanol UC-3140 added was 30.2 g with respect to 1000 g of the emulsion obtained in Comparative Example 1. This emulsion was directly used as a polyurethane paint in the characteristic evaluation described later.

[Comparative Example 4]
To the solution obtained in Comparative Example 2, the tinuvin 400 which is a UV absorber of a triazine derivative was added and heated to 60 ° C. with stirring. The amount of tinuvin 400 added was 8.0 g with respect to 1000 g of the solution obtained in Comparative Example 2. The heating was continued as it was at 60 ° C., and the heating was continued for 30 minutes until the ultraviolet absorber (Tinuvin 400) was completely dissolved to obtain a solution containing the ultraviolet absorber. Although this solution was cooled to room temperature, precipitation and separation of the UV absorber did not occur. This solution was directly used as a polyurethane paint in the characteristic evaluation described later.

[Comparative Example 5]
To the solution obtained in Comparative Example 2, the tinuvin 405, which is an ultraviolet absorber of a triazine derivative, was added and heated to 60 ° C. with stirring. The amount of tinuvin 405 added was 8.0 g with respect to 1000 g of the solution obtained in Comparative Example 2. The heating was continued as it was at 60 ° C., and the heating was continued for 30 minutes until the ultraviolet absorber (Tinuvin 405) was completely dissolved to obtain a solution containing the ultraviolet absorber. Although this solution was cooled to room temperature, precipitation and separation of the UV absorber did not occur. This solution was directly used as a polyurethane paint in the characteristic evaluation described later.

[Reference Example 3]
The RUVA-100, which is a benzotriazole-based ultraviolet absorber, was added to the solution obtained in Comparative Example 2 and heated to 60 ° C. with stirring. The amount of RUVA-100 added was 8.0 g with respect to 1000 g of the solution obtained in Comparative Example 2. Heating was continued as it was at 60 ° C., and heating was continued for 30 minutes until the ultraviolet absorber (RUVA-100) was completely dissolved, thereby obtaining a solution containing the ultraviolet absorber. Although this solution was cooled to room temperature, precipitation and separation of the UV absorber did not occur. This solution was directly used as a polyurethane paint in the characteristic evaluation described later.

<Evaluation characteristics evaluation of polyurethane paint>
The polyurethane emulsions or solutions of Examples 1 to 5, Reference Examples 1 to 3 and Comparative Examples 1 to 5 synthesized as described above were actually used as polyurethane paints, and their characteristics were confirmed (evaluated). Specifically, each of the polyurethane paints is applied to a PET film having a film thickness of 25 μm (trade name Lumirror # QR32, manufactured by Toray Industries, Inc.) with a dry coating thickness of 100 mg / dm ² (10.0 g / m ² ). And dried at 150 ° C. for 2 minutes. The polyurethane paint-coated PET film was evaluated for general physical properties and accelerated weather resistance (including light resistance).

Test conditions (evaluation conditions) for general physical properties are as follows.

Pencil hardness According to JIS K 5600-5-4 (1999).
As the pencil, uni (trade name) manufactured by Mitsubishi Pencil Co., Ltd. was used.
Cross-cut adhesion According to JIS K 5600-5-6 (1999).
The film thickness was 10 μm and the cut interval was 1 mm.
Steel wool rubbing
Steel wool # 0000, load 100g, 1 reciprocation / second
The number of reciprocations until the polyurethane coating layer is peeled off
Was written.
Water resistance After immersing in warm water of 80 ° C. for 4 hours, the appearance was visually evaluated.
Severe water resistance After immersion in warm water at 70 ° C. for 100 hours, the appearance was visually evaluated.
EtOH resistance The appearance was visually evaluated after immersion in EtOH for 24 hours at room temperature.

The accelerated weather resistance test was performed according to a normal use method described in the manual of the product using a die plastic metal weather KU-R5 type (trade name) air-cooled freezer placed by Daipura Wintes Co., Ltd. The test conditions are as follows.

Test mode: Irradiation + Shower Light source: Metal halide lamp Filter: 295-780 nm KF-1 filter (including visible light)
Irradiation: 540 W / m ² (Iwasaki Luminometer), BPT 63 ° C., 50% RH
Shower: 1 minute shower every 1 hour of irradiation

The test results of the general physical properties are shown in Table 8 below. As shown in Table 8, the coating film formed with the polyurethane paint of the example exhibited performance comparable to that of the comparative and reference polyurethane paints in general physical properties. That is, the polyurethane of this example was able to bind the triazine derivative (ultraviolet absorber) to the chain without impairing its performance.

Further, the accelerated weather resistance test results are shown in Table 9 below. In the table, “L”, “a”, and “b” are chromaticities according to the L ^* a ^* b ^* color system (JIS Z 8729) before light irradiation or after light irradiation for 200 hours. The color difference is a color difference between before light irradiation and after 200 hours of light irradiation according to the L ^* a ^* b ^* color system (JIS Z 8729). “WS” in the appearance evaluation indicates a water spot (a phenomenon in which traces of water droplets remain on the coating film), and the appearance was evaluated so that the water spot was not generated.

  In Table 9, the visual evaluation is shown in four stages of “◯”, “◯ Δ”, “Δ”, and “X” in order from the better result. For example, an evaluation of “X” for the golden change indicates that the golden change is remarkable, and an evaluation of “X” for the gloss indicates that the gloss is almost lost. In addition, golden discoloration (yellowing) originates in discoloration of PET film. The cause of this golden change (yellowing) is not always clear, but it is considered that, for example, the polyurethane paint is altered by light irradiation and the UV absorption ability is lowered, and further, the PET film therebelow is altered by UV rays. .

  In Table 9, the practicality as a paint can be confirmed by referring to the color difference before and after the test, particularly ΔE. If ΔE is small, it means that there is little discoloration due to light irradiation and the practicality as a paint is sufficient.

  As can be seen from Table 9, Examples 1 to 5, which are polyurethane paints of the present invention, had a sufficiently small color difference before and after the test (that is, less discoloration) and sufficient practicality even after 200 hours of light irradiation. As described above, the polyurethanes of Examples 1 to 5 have a triazine derivative bonded to a chain as an ultraviolet absorber. On the other hand, in Comparative Examples 1 and 2 that did not contain an ultraviolet absorber, discoloration and alteration due to ultraviolet absorption occurred immediately and could not be put to practical use. In Comparative Examples 1 to 5, in which the triazine derivative was simply mixed or dispersed without bonding to the chain, it withstood short-time light irradiation, but after 200 hours of light irradiation, as shown in Table 9 A major discoloration and alteration has occurred. The same applies to Reference Example 3 in which a benzotriazole ultraviolet absorber (RUVA-100) is mixed.

  Furthermore, as can be seen from Table 9, the polyurethanes of Examples 1 to 5 are more resistant to weathering and light than those of Reference Examples 1 and 2 in which a benzotriazole ultraviolet absorber (RUVA-100) is bonded to the chain. However, the performance was superior to those of Reference Examples 1 and 2. That is, according to the present invention, a triazine derivative that is safe, inexpensive, and easy to handle can be used as an ultraviolet absorber, and an ultraviolet absorbing ability that is superior to an expensive and difficult-to-handle benzotriazole ultraviolet absorber can be imparted to polyurethane. did it.

  Further, according to visual observation, the test pieces of Examples 1 to 5 showed almost no uneven color even after 200 hours of light irradiation. On the other hand, the test pieces of Comparative Examples 1 to 5 and Reference Example 3 had severe color unevenness and significant discoloration. Further, in Reference Example 1 and Reference Example 2, considerable golden discoloration (yellowing) and uneven color occurred.

  As described above, according to the present invention, it is possible to provide a polyurethane in which a highly practical ultraviolet absorber represented by the chemical formula (1) is combined with a polyurethane chain and integrated. Furthermore, according to the production method of the present invention, it is possible to efficiently produce such a polyurethane of the present invention. The polyurethane of the present invention is excellent in performance such as light resistance and weather resistance since separation of the UV absorber is effectively prevented. The use of the polyurethane of the present invention is not particularly limited and may be used for any purpose, but is particularly suitable for use as a paint. Furthermore, the polyurethane of the present invention is not limited to paint, and may be used for any application. For example, the polyurethane of the present invention includes polyurethane foam, bedding, diapers, cushioning materials, heat insulating materials, structural materials, elastomers, industrial parts, rolls, packing, shoe soles, hoses, civil engineering supplies, building materials supplies, waterproof materials, and rooftop waterproofing. As solvent, indoor flooring, waterproofing materials for joints, textiles, sportswear, underwear, rain gear, synthetic leather, artificial leather, shoes, clothing, paint, adhesives, automotive parts, woodwork supplies, hard coat film, or laminated film It can be used for a product to be used, and can be used for any other products or applications.

FIG. 1 is a GPC chromatogram of a reaction mixture in an example of polyurethane production. FIG. 2 is a GPC chromatogram of the reaction mixture in another example of polyurethane production.

Claims (15)

The polyurethane represented by the following chemical formula (i) is a polyurethane in which an ultraviolet absorber as a triazine derivative is covalently bonded directly or indirectly through another atomic group to a polyurethane chain ,
A polyurethane obtained by reacting the following component (d) in addition to the following components (a) to (c).

Component (a): Polyol
Component (b): Polyisocyanate compound
Component (c): Triazine derivative
Component (d): at least one selected from the group consisting of carboxylic acid diols represented by the following chemical formula (2), tautomers and stereoisomers thereof, and salts thereof

In the chemical formula (i),
R ^{3 to} R ¹⁶ are each independently a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a linear or branched alkoxy group, a substituted or unsubstituted phenyl group, or an arbitrary substituent,
U is a polyurethane chain and L is any atomic group or absent.

In the chemical formula (2),
R ¹⁷ is a hydrogen atom, a linear or branched alkyl group, a saturated or unsaturated linear or branched or cyclic hydrocarbon group, or any atomic group,
R ¹⁸ is a hydrogen atom or a protecting group,
L ² and L ³ are each independently a linear or branched alkylene group, a saturated or unsaturated linear or branched or cyclic hydrocarbon group, or any atomic group, or absent. The polyurethane according to claim 1, wherein, in the chemical formula (2), L ² and L ³ are methylene groups, and R ¹⁸ is a hydrogen atom . The compound represented by the chemical formula (2) is at least one selected from the group consisting of dimethylolpropionic acid (DMPA), dimethylolbutanoic acid (DMBA) dimethylolbutyric acid, and dimethylolvaleric acid. 2. The polyurethane according to 2. The triazine derivative of the component (c) is at least one selected from the group consisting of triazine derivatives represented by the following chemical formula (1), tautomers and stereoisomers thereof, and salts thereof. The polyurethane according to any one of 1 to 3 .

In the chemical formula (1),
L ¹ is a linear or branched alkylene group or absent,
R ¹ and R ² are each independently a hydrogen atom or a linear or branched substituent, and the linear or branched substituent is C, N, O, S, It may or may not contain P and Si,
R ^{3 to} R ¹⁶ are each independently a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a linear or branched alkoxy group, a substituted or unsubstituted phenyl group, or an arbitrary substituent. The polyurethane according to claim 4, wherein L ¹ in the chemical formula (1) is a methylene group. In the chemical formula (1), at least one of R ¹ and R ² is a linear or branched alkyl group, or an oxygen atom (in place of a methylene group in the chain of the linear or branched alkyl group) The polyurethane according to claim 4 or 5, which is a group having an ether bond). The polyurethane according to any one of claims 1 to 6, wherein in the chemical formula (i) or (1), at least one of R ⁴ and R ⁶ is a hydroxyl group. The polyurethane according to any one of claims 1 to 7, wherein in the chemical formula (i) or (1), at least one selected from the group consisting of R ⁷ , R ¹¹ , R ¹² and R ¹⁶ is a hydroxyl group. The triazine derivative represented by the chemical formula (1) is a triazine derivative represented by the following chemical formula (3), or a tautomer or stereoisomer thereof, according to any one of claims 4 to 8. Polyurethane.

In the chemical formula (3), R ¹⁰⁰⁰ is a linear or branched alkyl group, and R ³ and R ^{5 to} R ¹⁶ are the same as those in the chemical formula (1). The polyurethane according to claim 9, wherein R ³ and R ^{5 to} R ¹⁶ are each independently a hydrogen atom or a linear or branched alkyl group. The triazine derivative represented by the chemical formula (1) is at least one selected from the group consisting of triazine derivatives represented by the following formulas (4) to (6), and tautomers and stereoisomers thereof. The polyurethane according to claim 4.

The polyol in the component (a) is a low molecular polyol, polyester polyol, polycarbonate polyol, polyether polyol, polyester polycarbonate polyol, polybutadiene polyol, silicone polyol, low molecular diol, polyester diol, polycarbonate diol, polyether diol, polyester polycarbonate diol. The polyurethane according to any one of claims 1 to 11, which is at least one selected from the group consisting of polybutadiene diol and silicone diol. A process for producing the polyurethane according to any one of claims 1 to 12,
(A) Step of reacting the components (a) to (c)
and
(B) A step of reacting the reaction product of the step (A) with the component (d).
Manufacturing method. A process for producing the polyurethane according to any one of claims 1 to 12,
The manufacturing method including the process of making the said component (d) react with the said components (a)-(c). A polyurethane foam, a bedding, a diaper, a cushioning material, a heat insulating material, a structural material, an elastomer, an industrial part, a roll, a packing, a shoe sole, a hose, a civil engineering article, comprising the polyurethane according to any one of claims 1 to 12. Building materials, waterproofing materials, roofing waterproofing solvent, indoor flooring, waterproofing materials for joints, textiles, sportswear, underwear, rain gear, synthetic leather, artificial leather, shoes, clothing, paints, adhesives, automotive parts, woodworking supplies Products used as hard coat films or laminated films.

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