JP6645208B2 - UV resistant polyurethane composition, coating material using the composition - Google Patents

Description

  Electronic device components such as mobile phones and communication tablets, and home appliance components. The present invention relates to a UV-resistant polyurethane composition useful for household goods and automobile parts, particularly plastic parts, a molded article using the composition, and a coating material.

  The polyurethane resin is obtained by reacting a polyisocyanate component and a polyol component, and polyurethane resins having various performances are provided depending on the types and combinations of the components. In particular, molded articles and coating materials using such resins are widely used for electronic device parts, furniture and home appliances, daily miscellaneous goods, and automobile parts. However, when such a molded article or a coating material is used in contact with the human body for a long time, oleic acid contained in sweat or oleic acid contained in a skin protective cream, or a sunscreen (eg, cream, lotion, etc.) ) Causes the deterioration of the surface of the molded article or the coating agent or the phenomenon of becoming tacky due to the ultraviolet absorbent component and the like, and there is a problem that it cannot withstand long-term use.

  Against this background, development of polyurethane resins that exhibit oil resistance to oleic acid, which is a main component of sebum components, has been promoted. Polyurethane resins having excellent oleic acid resistance include, as essential components, polycarbonate diol using a polyisocyanate compound, 1,5-pentanediol and 1,6-hexanediol at an arbitrary composition ratio, and polysiloxane. Curable compositions have been proposed (for example, see Patent Documents 1 to 4).

  However, the curable compositions described in these patent documents were not satisfactory with respect to the resistance to the ultraviolet absorber contained in the sunscreen.

  That is, although the durability of oil-based components such as oleic acid and beef tallow has been improved in conventional polyurethane resin coating materials, it has been found that such materials are not suitable for ultraviolet absorbers contained in cosmetics and sunscreens (creams, lotions, etc.). The resistance is often insufficient, and the appearance of the surface of the molded article may be deteriorated by the attachment of the ultraviolet absorbent. Therefore, there is a demand for a plastic paint resistant to an ultraviolet absorber.

JP 2007-112986 A JP 2008-063395 A JP 2008-075048 A JP 2008-303284 A

  The present invention has been made based on the above circumstances, and an object of the present invention is to provide a polyurethane composition (hereinafter, referred to as an “ultraviolet absorbent”) having excellent durability against an ultraviolet absorbent contained in cosmetics, sunscreens and the like. The present invention provides a coating material and a coating film using the composition.

  That is, the present invention includes the following embodiments [1] to [10].

  [1] A resistant resin containing a hydroxyl group-terminated prepolymer having an isocyanurate ring structure, which is a reaction product of a polyisocyanate (A), a monol (B), a polyol (C), and an amino alcohol (D), and a curing agent. Ultraviolet absorbent polyurethane composition.

  [2] The ultraviolet absorbent-resistant polyurethane composition according to the above [1], wherein the polyisocyanate (A) has an isocyanurate ring structure.

  [3] The polyurethane composition according to [1] or [2], wherein the isocyanate source of the polyisocyanate (A) is selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates. object.

  [4] The ultraviolet ray resistance according to any of [1] to [3], wherein the isocyanurate ring structure of the hydroxyl-terminated prepolymer having an isocyanurate ring structure is derived from a trimer of isophorone diisocyanate. Absorbent polyurethane composition.

  [5] The ultraviolet absorbent-resistant polyurethane composition according to any one of [1] to [4], wherein the hydroxyl-terminated prepolymer having an isocyanurate ring structure has an average number of functional groups of 2 to 11. object.

  [6] The method according to any one of [1] to [5] above, wherein the polyol (C) is contained in an amount of 1 to 50% by mass in a solid content of the hydroxyl-terminated prepolymer having an isocyanurate ring structure. UV-resistant polyurethane composition.

  [7] The ultraviolet ray absorption according to any of [1] to [6], wherein at least one selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates is used as a curing agent. Polyurethane composition.

  [8] The method according to any one of [1] to [6], wherein at least one selected from the group consisting of an isocyanurate of hexamethylene diisocyanate and an adduct of hexamethylene diisocyanate is used as the curing agent. UV-resistant polyurethane composition.

  [9] A coating material comprising the ultraviolet absorbent polyurethane composition according to any one of [1] to [8].

  [10] A coating film comprising the ultraviolet absorbent polyurethane composition according to any one of [1] to [8].

  Since the ultraviolet ray absorbent polyurethane composition of the present invention has excellent durability against ultraviolet ray absorbents contained in cosmetics and sunscreens, for example, by using this as a coating material for plastic members, cosmetics and sunscreens And the like, can impart durability to the ultraviolet absorber contained in the member. Furthermore, the hydroxyl-terminated prepolymer having an isocyanurate ring structure of the present invention is excellent in compatibility with a curing agent and adhesion to a plastic substrate such as ABS and PET.

  Hereinafter, the present invention will be described in detail.

  The ultraviolet absorbent polyurethane composition of the present invention is characterized by containing a hydroxyl group-terminated prepolymer having an isocyanurate ring structure and a curing agent.

  Here, the ultraviolet absorbent used as an index of the resistance to the ultraviolet absorbent mentioned in the effect of the present invention will be described. Examples of the ultraviolet absorber include paraaminobenzoic acid, cinnamic acid, benzophenone, salicylic acid, benzoyltriazole, other aromatic ultraviolet absorbers, and a mixture of one or more of these. By migrating to a molded article or a polyurethane-based coating material, phenomena such as deterioration of the appearance of the molded article and tackiness are observed. As sunscreen agents having a particularly strong tendency, those containing 3% by mass or more of a salicylic acid-based ultraviolet absorber, those containing 2% by mass or more of a benzophenone-based ultraviolet absorber, and those containing both of them are known. ing.

  As shown in Examples described later, the ultraviolet absorbent resistant polyurethane composition of the present invention comprises at least 2-hydroxy-4-methoxybenzophenone, 2-ethylhexyl salicylate, 3,3,5 salicylate among these ultraviolet absorbents. -Excellent durability against trimethylcyclohexyl, 2-ethylhexyl 3,3-diphenyl-2-cyanoacrylate, 2-ethylhexyl-4-methoxycinnamate, and 4-tert-butylbenzoyl (4-methoxybenzoyl) methane Is shown.

  Next, the hydroxyl-terminated prepolymer composition having an isocyanurate ring structure, which is used in the polyurethane composition resistant to ultraviolet light of the present invention, will be described.

  The hydroxyl-terminated prepolymer having an isocyanurate ring structure of the present invention is a reaction product of a polyisocyanate (A), a monol (B), a polyol (C), and an amino alcohol (D). The isocyanurate ring structure of the hydroxyl-terminated prepolymer having an isocyanurate ring structure may be derived from polyisocyanate (A), monool (B), polyol (C), or It may be derived from alcohol (D), and is not particularly limited, but it is preferable to use a polyisocyanate having an isocyanurate ring structure from the viewpoint of easy availability.

  The isocyanate source of the polyisocyanate (A) is not particularly limited, and examples thereof include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and araliphatic diisocyanates. Among these, aliphatic diisocyanates and alicyclic diisocyanates are preferred from the viewpoints of weather resistance of the coating film and ultraviolet absorber resistance, and alicyclic diisocyanates are preferred from the viewpoint of solvent solubility and drying properties.

<Aliphatic diisocyanate>
Specific examples of the aliphatic diisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, and trioxyethylene diisocyanate. And the like, and mixtures thereof can also be used.

<Alicyclic diisocyanate>
Specific examples of the alicyclic diisocyanate include, for example, isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethyl xylene diisocyanate, and the like. Mixtures of these can also be used. Among these alicyclic diisocyanates, isophorone diisocyanate (hereinafter, referred to as “IPDI”) is particularly preferable from the viewpoint of resistance to ultraviolet absorbers and productivity.

<Aromatic diisocyanate>
Specific examples of the aromatic diisocyanate include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethyl Carboxymethyl-4,4'-diisocyanate or the like can be cited, and may also be used a mixture thereof.

<Aromatic diisocyanate>
Specific examples of the araliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene, ω, ω′-. Examples thereof include diisocyanato-1,4-diethylbenzene and the like, and mixtures thereof can also be used.

  Further, within the scope of the present invention, for example, the above-mentioned aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, or isocyanurate group-containing polyisocyanate using these polyisocyanates as raw materials, A uretdione group-containing polyisocyanate, a uretdione group- and isocyanurate group-containing polyisocyanate, a urethane group-containing polyisocyanate, an allophanate group-containing polyisocyanate, a buret group-containing polyisocyanate, and a uretoimine group-containing polyisocyanate can also be used in combination.

<Monool>
The monol (B) is not particularly limited, but has a carbon number of 1 to 20 from the viewpoint of solvent solubility, curing agent compatibility, and ultraviolet absorber resistance of a hydroxyl group-terminated prepolymer having an isocyanurate ring structure. Alkyl alcohols are preferred.

  Specific examples of such a monol (B) include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol , 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2,2-dimethyl-1-propanol, 1-hexanol, 2-hexanol, 2-methyl-1-pentanol, 2-ethyl-2-butanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 1-nonanol, 2-nonanol, 3,5,5-trimethyl-1 -Hexanol, 1-decanol, isodecanol, 1-undecanol, 2-undecanol, 1-dodecano , 1-tridecanol, isotridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol, etc. Can be mentioned.

  Further, a hydroxyl-terminated compound that can react with isocyanate, such as benzyl alcohol, methoxypolyethylene glycol, or fluoroalcohols, may be used in combination without departing from the spirit of the present invention.

<Polyol>
The polyol (C) is not particularly limited and includes, for example, polycarbonate polyol, polycaprolactone polyol, polyester polyol, polyether polyol, polyolefin polyol, acrylic polyol, silicone polyol, castor oil-based polyol, and fluorine-based polyol. They can be used alone or in combination of two or more.

  As the molecular weight of the polyol (C), the number average molecular weight is preferably from 250 to 50,000, and more preferably from 300 to 4,000. If the number average molecular weight is less than the lower limit, the adhesion to the plastic substrate may decrease, and if it exceeds the upper limit, the solvent solubility may decrease.

  The polyol (C) preferably has an active hydrogen group number (average number of functional groups) in one molecule of 1.9 or more. If the number of active hydrogen groups is less than 1.9, the resistance to ultraviolet absorbers and mechanical properties may be reduced.

  The polyol (C) component is preferably contained in an amount of 1 to 50% by mass in the solid content of the hydroxyl-terminated prepolymer having an isocyanurate ring structure.

<Polycarbonate polyol>
Specific examples of the polycarbonate polyol include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol , Neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, ethylene oxide or propylene oxide adduct of bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, Glycerin, One or more low-molecular-weight polyhydric alcohols such as limethylolpropane and pentaerythritol, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; alkylene carbonates such as ethylene carbonate and propylene carbonate; diphenyl carbonate, dinaphthyl carbonate and dianthryl Examples thereof include those obtained from a dealcoholation reaction or a dephenolization reaction with a diaryl carbonate such as carbonate, diphenanthryl carbonate, diindanyl carbonate, and tetrahydronaphthyl carbonate. From the viewpoint of imparting abrasion resistance, scratch resistance and oleic acid resistance, a polycarbonate polyol composed of 1,6-hexanediol and diethyl carbonate can be suitably used.

<Polycaprolactone polyol>
Specific examples of the polycaprolactone polyol include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene Glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, ethylene oxide or propylene oxide adduct of bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol , Glycerin One or more of low molecular polyols such as trimethylolpropane and pentaerythritol can be used as an initiator, and one obtained by ring-opening addition of one or both of ε-caprolactone and alkyl-substituted ε-caprolactone can be used. .

<Polyester polyol>
Specific examples of polyester polyols include, for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaine Acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, β-diethylsuccinic acid, maleic acid, fumaric acid, etc. One or more kinds of dicarboxylic acids or anhydrides thereof, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butane Diol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol , 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4 -Low molecular weight polyols having a molecular weight of 500 or less such as dimethanol, dimer acid diol, ethylene oxide and propylene oxide adducts of bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, and pentaerythritol. And those obtained from a polycondensation reaction with at least one of the above. Further, a polyester-amide polyol obtained by replacing a part of the low-molecular polyol with a low-molecular polyamine such as hexamethylenediamine, isophoronediamine, monoethanolamine or a low-molecular amino alcohol can also be used.

<Polyether polyol>
Specific examples of the polyether polyol include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene Glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, penta Low content such as erythritol Starting compounds having two or more, preferably two to three active hydrogen groups such as polyols or low molecular weight polyamines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, etc. As an agent, polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, or alkyl glycidyl ethers such as methyl glycidyl ether, and aryl glycidyl ethers such as phenyl glycidyl ether And polyether polyols obtained by ring-opening polymerization of a cyclic ether monomer such as tetrahydrofuran.

<Polyolefin polyol>
Specific examples of the polyolefin polyol include, for example, polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.

<Acrylic polyol>
As the acrylic polyol, for example, an acrylic acid ester and / or a methacrylic acid ester (hereinafter referred to as (meth) acrylic acid ester) and a hydroxy compound having at least one hydroxyl group in a molecule which can be a reaction site and / or A methacrylic acid hydroxy compound (hereinafter referred to as (meth) acrylic acid hydroxy compound) and a polymerization initiator obtained by copolymerizing an acrylic monomer by using heat energy, light energy such as ultraviolet light or electron beam, or the like. .

<(Meth) acrylate>
Specific examples of (meth) acrylic acid esters include, for example, alkyl esters having 1 to 20 carbon atoms. Specific examples of such (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (Meth) such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate Alkyl acrylate; ester of (meth) acrylic acid with alicyclic alcohol such as cyclohexyl (meth) acrylate; aryl (meth) acrylate such as phenyl (meth) acrylate and benzyl (meth) acrylate Can be mentioned. Such (meth) acrylic acid esters can be used alone or in combination of two or more.

<Hydroxy (meth) acrylate compound>
Specific examples of the (meth) acrylic acid hydroxy compound include, for example, at least one hydroxyl group in a molecule that can be a reaction point with polyisocyanate, and specifically, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, Examples include hydroxy acrylate compounds such as hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxy-2,2-dimethylpropyl acrylate, and pentaerythritol triacrylate. In addition, hydroxy methacrylate compounds such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethylpropyl methacrylate, and pentaerythritol trimethacrylate are exemplified. These acrylic acid hydroxy compounds and methacrylic acid hydroxy compounds can be used alone or in combination of two or more.

<Silicone polyol>
Specific examples of the silicone polyol include, for example, a vinyl group-containing silicone compound obtained by polymerizing γ-methacryloxypropyltrimethoxysilane and the like, and α, ω-dihydroxypolydimethylsiloxane having at least one terminal hydroxyl group in the molecule, Polysiloxanes such as α, ω-dihydroxypolydiphenylsiloxane can be mentioned.

<Castor oil-based polyol>
Specific examples of the castor oil-based polyol include, for example, a linear or branched polyester polyol obtained by reacting a castor oil fatty acid with a polyol. Also, dehydrated castor oil, partially dehydrated castor oil partially dehydrated, and hydrogenated castor oil to which hydrogen has been added can be used.

<Fluorine-based polyol>
Specific examples of the fluorine-based polyol include, for example, a linear or branched polyol obtained by a copolymerization reaction using a fluorine-containing monomer and a monomer having a hydroxy group as essential components. Here, the fluorinated monomer is preferably a fluoroolefin, for example, tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoromethyltrifluoroethylene Is mentioned. Examples of the monomer having a hydroxyl group include, for example, hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and cyclohexanediol monovinyl ether; hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether; And a monomer having a hydroxyl group such as a hydroxyl group-containing vinyl carboxylate or allyl ester.

<Amino alcohol>
The amino alcohol (D) is not particularly limited as long as it is a compound having an amino group and a hydroxyl group. From the viewpoint of controlling the reaction at the time of synthesizing a hydroxyl-terminated prepolymer having an isocyanurate ring structure, for example, 1 Those having one primary amino group or secondary amino group and one to three hydroxyl groups in the molecule are preferred.

  Specific examples of such an amino alcohol (D) include, for example, 2-aminoethanol, 2- (methylamino) ethanol, 2-amino-2-methyl-1-propanol, 1-amino-2-propanol, -Amino-1-propanol, 1-amino-2-methyl-2-propanol, 2- (ethylamino) ethanol, 2- (tert-butylamino) ethanol, 2- (propylamino) ethanol, 2- (isopropylamino) ) Ethanol, 2-amino-1-butanol, 1-amino-2-butanol, 4- (methylamino) -1-butanol, 2-amino-3,3-dimethylbutanol, 2-amino-3-methyl-1 -Butanol, 2- (butylamino) ethanol, 2-hydroxyisobutyramide, 2-hydroxypropiona , 2-amino-4-methyl-1-pentanol, 3-amino-1-propanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 2-amino-3-hydroxypropionic acid, 3-amino-2,2-dimethyl-1-propanol, 4-amino-1-butanol, 8-amino-1-octanol, 10-amino-1-decanol, 2-isopropylamino-3-methyl-1-butanol , 12-amino-1-dodecanol, 2- (cyclohexylamino) ethanol, 2-aminocyclohexanol, 4-amino-2-methyl-1-butanol, 3- (methylamino) -1-propanol, 2-piperidinemethanol , 3-piperidinemethanol, 4-piperidinemethanol, 3-hydroxypiperidine, 4-hydroxy Peridine, 2-piperidineethanol, 4-piperidineethanol, 2-pyrrolidinemethanol, 2- (4-piperidyl) -2-propanol, 4-hydroxy-2,2,6,6-tetramethylpiperidine, nortropine, 1- [ 2- (2-hydroxyethoxy) ethyl] piperazine, 1-piperazineethanol, diethanolamine, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 3-amino-1 , 2-propanediol, 2-amino-2-ethyl-1,3-propanediol, diisopropanolamine, 2-[(hydroxymethyl) amino] ethanol, N- (3-aminopropyl) diethanolamine, 3-methylamino -1,2-propanediol, 3-tert-butylamino Examples thereof include -1,2-propanediol, tris (hydroxymethyl) aminomethane, and N- [tris (hydroxymethyl) methyl] glycine.

  Next, a general method for producing a hydroxyl-terminated prepolymer having an isocyanurate ring structure, which constitutes the polyurethane composition having ultraviolet absorbent resistance according to the present invention, will be described. The method for producing a hydroxyl-terminated prepolymer having an isocyanurate ring structure is not limited to this.

<Method for producing hydroxyl-terminated prepolymer having isocyanurate ring structure>
In the presence or absence of an organic solvent, the polyisocyanate (A), the monol (B), and the polyol (C) are preferably mixed with each other at a molar ratio (R) of isocyanate group to hydroxyl group, preferably R = isocyanate group / An amount of 1.5 to 50 in terms of hydroxyl groups is charged, and preferably a urethanization reaction is performed at 60 ° C. or higher to produce a modified polyisocyanate.

  The obtained polyisocyanate-modified product and amino alcohol (D) are mixed in such an amount that the molar ratio (R) of the isocyanate group to the amino group is preferably 0.7 to 1.3 as R = isocyanate group / amino group. And a urea reaction at 80 ° C. or less to produce a hydroxyl-terminated prepolymer having an isocyanurate ring structure.

  In a series of production steps, it is preferable to advance the reaction under a stream of nitrogen gas or dry air in order to suppress the reaction between the isocyanate group and moisture.

  The reaction temperature of the urea-forming reaction is preferably 80 ° C or lower, more preferably 60 ° C or lower. The lower limit of the reaction temperature is not particularly limited as long as the reaction solution does not solidify. By setting the reaction temperature to 80 ° C. or lower, hydroxyl groups derived from the amino alcohol (D) reacted with the polyisocyanate-modified product (reacted product of the polyisocyanate (A), the monool (B), and the polyol (C)) The remaining isocyanate groups can be prevented from undergoing a urethanization reaction to suppress generation of aggregates and insolubilization of the entire system.

  The hydroxyl-terminated prepolymer having an isocyanurate ring structure thus obtained preferably has 2 to 11 functional groups, more preferably 3 to 10 functional groups.

  The organic solvent used for producing the hydroxyl-terminated prepolymer having an isocyanurate ring structure is not particularly limited as long as it does not affect the reaction in the presence of the organic solvent.

<Organic solvent used in production>
Specific examples of such an organic solvent include, for example, aliphatic hydrocarbons such as octane, cyclohexane, alicyclic hydrocarbons such as methylcyclohexane, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, ethyl acetate, Esters such as butyl acetate and isobutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, glycol ether esters such as 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, and dioxane. Ethers, halogenated hydrocarbons such as methylene iodide and monochlorobenzene, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide Polar aprotic solvents, tertiary alcohols and diacetone alcohol and the like. These solvents can be used alone or in combination of two or more.

  In addition, alcohols such as ethanol and isopropanol can be used as long as the performance is not reduced.

  Next, the curing agent constituting the ultraviolet absorbent polyurethane composition of the present invention will be described.

  Examples of the curing agent include polyisocyanates, and aliphatic polyisocyanates or alicyclic polyisocyanates, and polyisocyanates obtained by combining them are preferable from the viewpoint of coating film weather resistance. As the curing agent, an isocyanurate form of hexamethylene diisocyanate (hereinafter, referred to as “HDI”) or HDI may be used from the viewpoint of compatibility with a hydroxyl group-terminated prepolymer having an isocyanurate ring structure and an organic solvent and weather resistance. Adducts partially modified with urethane are particularly preferred.

  Further, in the curing agent, for example, the above-mentioned aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, or uretdione obtained from these polyisocyanates as a raw material without departing from the spirit of the present invention. Group-containing polyisocyanate, uretdione group and isocyanurate group-containing polyisocyanate, urethane group-containing polyisocyanate, allophanate group-containing polyisocyanate, burette group-containing polyisocyanate, etc. alone or in combination of two or more. Can also be used.

  In the ultraviolet ray-resistant polyurethane composition of the present invention, if necessary, for example, an antioxidant, an ultraviolet ray absorbent, a pigment, a dye, a flame retardant, a hydrolysis inhibitor, a lubricant, a plasticizer, a filler, Additives such as an antistatic agent, a dispersant, a catalyst, a storage stabilizer, a surfactant, and a leveling agent can be appropriately compounded.

  Next, a method for processing a molded product and a coating material using the ultraviolet absorbent polyurethane composition of the present invention will be described.

  The ultraviolet absorbent resistant polyurethane composition of the present invention is used, for example, as a molded product of electronic device members such as communication tablets, furniture / home electric appliance members, household goods, automobile members and the like, or as a coating material.

  The molded article includes, for example, members, structures, films, and sheets, and is molded by a known technique such as casting or coating.

  When the ultraviolet absorbent polyurethane composition of the present invention is used as a coating material, for example, the resin composition for a coating material containing a hydroxyl-terminated prepolymer having an isocyanurate ring structure described above may be added to the curing agent described above. And, if necessary, mixing the above-mentioned additives, after uniform stirring, spray coating, knife coating, wire bar coating, doctor blade coating, reverse roll coating, calender coating, etc. A coating film is formed thereon.

  Examples of the base material include acrylic resin, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene phthalate resin, polystyrene resin, AS resin, ABS resin, polycarbonate-ABS resin, 6-nylon resin, and 6, 6-nylon resin, MXD6 nylon resin, polyvinyl chloride resin, polyvinyl alcohol resin, polyurethane resin, phenol resin, melamine resin, polyacetal resin, chlorinated polyolefin resin, polyolefin resin, polyamide resin, polyetheretherketone resin, polyphenylene sulfide resin , NBR resin, chloroprene resin, SBR resin, SEBS resin, polyethylene, and a substrate molded from a material such as olefin resin such as polypropylene. That.

  These substrates may be subjected to a corona discharge treatment, a flame treatment, an ultraviolet irradiation treatment, an ozone treatment, a primer treatment, a solvent treatment or the like in advance on the surface of the substrate in order to enhance the adhesiveness.

  The amount of the coating material to be applied is not particularly limited. For example, it is preferable to apply the coating material so that the dry film thickness becomes 20 μm or more. When the film thickness is 20 μm or more, the resistance of the coating material to ultraviolet absorbers can be improved.

  Next, when the ultraviolet ray-resistant polyurethane composition of the present invention is used as a coating composition, the coating composition includes a hydroxyl group of a hydroxyl-terminated prepolymer having an isocyanurate ring structure, and a polyisocyanate used as a curing agent. Is preferably blended such that R = isocyanate group / hydroxyl group and R = 0.4 to 2.5, and more preferably R = 0.7 to 1.0. It is preferable to mix them so as to be 5. The organic solvent used for dilution is not particularly limited, but may be used alone or in combination of two or more of the above <organic solvents used for production>.

  Hereinafter, examples of the present invention will be described, but the present invention should not be construed as being limited to these examples.

<Synthesis of hydroxyl-terminated prepolymer>
<Production Example 1>
As a polyisocyanate (A), IPDI isocyanurate (manufactured by Evonik, trade name: VESTANAT T1890 / 100, NCO content: 17) in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column. 245 g of 3 mass%, hereinafter referred to as “IPDI nullate”, 49 g of IPDI, and 500 g of methyl ethyl ketone (hereinafter, referred to as “MEK”) were charged, and nitrogen gas was bubbled while uniformly stirring at 25 ° C. A polyisocyanate solution was prepared. In this polyisocyanate solution, 10 g of methanol (manufactured by Kishida Chemical Co.) as a monol (B) and polyol 1 as a polyol (C) (1,6-hexanediol-based polycarbonate polyol, number average molecular weight 1,000, number of functional groups 2) 100 g of the mixture was charged, and a urethanization reaction was performed at 75 ° C. in a nitrogen stream to obtain a modified polyisocyanate. The obtained modified polyisocyanate was cooled to room temperature, 96 g of diethanolamine (manufactured by Kishida Chemical Co., Ltd.) was gradually charged as an amino alcohol (D), and a urea-forming reaction was carried out while maintaining the temperature at 60 ° C. or lower under a nitrogen stream to obtain a hydroxyl group. A terminal prepolymer solution PP-1 was obtained. The hydroxyl value of this prepolymer was 102 KOHmg / g.

<Production Example 2>
A one-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 236 g of IPDI-nurate, 47 g of IPDI, and 500 g of MEK as a polyisocyanate (A). The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. 10 g of 1-propanol (manufactured by Kishida Chemical Co.) as a monol (B) and 100 g of a polyol 1 as a polyol (C) were charged into this polyisocyanate solution, and a urethanization reaction was carried out at 75 ° C. in a nitrogen stream to carry out polyisocyanate modification. I got a body. The resulting polyisocyanate-modified solution was cooled to room temperature, 106 g of diethanolamine (manufactured by Kishida Chemical Co., Ltd.) was gradually charged as amino alcohol (D), and a urea-forming reaction was carried out while maintaining the temperature at 60 ° C. or lower under a nitrogen stream. A hydroxyl-terminated prepolymer solution PP-2 was obtained. The hydroxyl value of this prepolymer was 113 KOHmg / g.

<Production Example 3>
A one-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 236 g of IPDI-nurate, 47 g of IPDI, and 500 g of MEK as a polyisocyanate (A). The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. To this polyisocyanate solution, 10 g of isopropanol (manufactured by Kishida Chemical Co., Ltd.) as monool (B) and 100 g of polyol 1 as polyol (C) were charged, and a urethanization reaction was carried out at 75 ° C. under a nitrogen stream to obtain a modified polyisocyanate. Obtained. The resulting polyisocyanate-modified solution was cooled to room temperature, 106 g of diethanolamine (manufactured by Kishida Chemical Co., Ltd.) was gradually charged as amino alcohol (D), and a urea-forming reaction was carried out while maintaining the temperature at 60 ° C. or lower under a nitrogen stream. A hydroxyl-terminated prepolymer solution PP-3 was obtained. The hydroxyl value of this prepolymer was 113 KOHmg / g.

<Production Example 4>
A one-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 236 g of IPDI-nurate, 47 g of IPDI, and 500 g of MEK as a polyisocyanate (A). The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. 10 g of 1-butanol (manufactured by Kishida Chemical Co., Ltd.) as the monool (B) and 100 g of polyol 1 as the polyol (C) were charged into this polyisocyanate solution, and a urethanization reaction was carried out at 75 ° C. in a nitrogen stream to modify the polyisocyanate. I got a body. The resulting polyisocyanate-modified solution was cooled to room temperature, 109 g of diethanolamine (manufactured by Kishida Chemical Co., Ltd.) was gradually charged as amino alcohol (D), and a urea-forming reaction was carried out while maintaining the temperature at 60 ° C. or lower under a nitrogen stream. A hydroxyl group-terminated prepolymer solution PP-4 was obtained. The hydroxyl value of this prepolymer was 115 KOHmg / g.

<Production Example 5>
A 1-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 233 g of IPDI-nurate, 47 g of IPDI, and 500 g of MEK as a polyisocyanate (A). The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. 10 g of 1-pentanol (manufactured by Kishida Chemical Co., Ltd.) as the monol (B) and 100 g of the polyol 1 as the polyol (C) were charged into this polyisocyanate solution, and a urethane-forming reaction was carried out at 75 ° C. in a nitrogen stream to obtain a polyisocyanate. A modified product was obtained. The obtained polyisocyanate-modified solution was cooled to room temperature, 110 g of diethanolamine (manufactured by Kishida Chemical Co., Ltd.) was gradually charged as amino alcohol (D), and a urea-forming reaction was performed while maintaining the temperature at 60 ° C. or lower under a nitrogen stream. A hydroxyl group-terminated prepolymer solution PP-5 was obtained. The hydroxyl value of this prepolymer was 117 KOH mg / g.

<Production Example 6>
A 1-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 232 g of IPDI-nurate, 46 g of IPDI, and 500 g of MEK as a polyisocyanate (A). The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. 10 g of 1-hexanol (manufactured by Kishida Chemical Co., Ltd.) as a monol (B) and 100 g of a polyol 1 as a polyol (C) were charged into this polyisocyanate solution, and a urethane-forming reaction was carried out at 75 ° C. in a nitrogen stream to carry out polyisocyanate modification. I got a body. The resulting solution of the modified polyisocyanate was cooled to room temperature, 111 g of diethanolamine (manufactured by Kishida Chemical Co., Ltd.) was gradually charged as amino alcohol (D), and a urea-forming reaction was carried out while maintaining the temperature at 60 ° C. or lower under a nitrogen stream. A hydroxyl group-terminated prepolymer solution PP-6 was obtained. The hydroxyl value of this prepolymer was 118 KOH mg / g.

<Production Example 7>
A 1-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 231 g of IPDI nullate, 46 g of IPDI, and 500 g of MEK as a polyisocyanate (A), and these were charged at 25 ° C. The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. To this polyisocyanate solution, 10 g of 2-ethylhexanol (manufactured by KH Neochem) as a monol (B) and 100 g of a polyol 1 as a polyol (C) were charged, and a urethanization reaction was carried out at 75 ° C. in a nitrogen stream to obtain a polyisocyanate. A modified product was obtained. The resulting modified polyisocyanate solution was cooled to room temperature, 113 g of diethanolamine (manufactured by Kishida Chemical Co., Ltd.) was gradually charged as amino alcohol (D), and a urea-forming reaction was carried out under a nitrogen stream while maintaining the temperature at 60 ° C. or lower. A hydroxyl group-terminated prepolymer solution PP-7 was obtained. The hydroxyl value of this prepolymer was 120 KOHmg / g.

<Production Example 8>
A one-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 230 g of IPDI nullate, 46 g of IPDI, and 500 g of MEK as a polyisocyanate (A). The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. 10 g of isotridecanol (manufactured by KH Neochem) as a monol (B) and 100 g of a polyol 1 as a polyol (C) were charged into this polyisocyanate solution, and a urethanization reaction was carried out at 75 ° C. in a nitrogen stream to obtain a polyisocyanate. A modified product was obtained. The resulting polyisocyanate-modified solution was cooled to room temperature, 109 g of diethanolamine (manufactured by Kishida Chemical Co., Ltd.) was gradually charged as an amino alcohol (D), and a urea-forming reaction was carried out while maintaining the temperature at 60 ° C. or lower under a nitrogen stream. A hydroxyl-terminated prepolymer solution PP-8 was obtained. The hydroxyl value of this prepolymer was 122 KOH mg / g.

<Production Example 9>
In a 1-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column, 225 g of IPDI nullate, 45 g of IPDI, and 500 g of MEK were charged as polyisocyanate (A), and these were charged at 25 ° C. The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. To this polyisocyanate solution, 10 g of trifluoroethanol (manufactured by Tosoh F-Tech) and 100 g of polyol 1 as polyol (C) were charged as a monol (B), and a urethane-forming reaction was carried out at 75 ° C. in a nitrogen stream to carry out polyisocyanate modification. I got a body. The resulting solution of the modified polyisocyanate was cooled to room temperature, and 121 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was gradually charged as amino alcohol (D). The urea reaction was carried out while maintaining the temperature at 60 ° C. or lower to obtain a hydroxyl-terminated prepolymer solution PP-9. The hydroxyl value of this prepolymer was 113 KOHmg / g.

<Production Example 10>
A one-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 246 g of IPDI-nurate, 49 g of IPDI, and 500 g of MEK as a polyisocyanate (A). The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. 5 g of 1-propanol (manufactured by Kishida Chemical Co., Ltd.) as a monol (B) and 50 g of a polyol 1 as a polyol (C) were charged into this polyisocyanate solution, and a urethanation reaction was carried out at 75 ° C. under a nitrogen stream to modify the polyisocyanate. I got a body. The resulting polyisocyanate-modified solution was cooled to room temperature, and 149 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was gradually charged as amino alcohol (D), and the mixture was placed under a nitrogen stream. And a urea reaction while maintaining the temperature at 60 ° C. or lower to obtain a hydroxyl-terminated prepolymer solution PP-10. The hydroxyl value of this prepolymer was 140 KOHmg / g.

<Production Example 11>
A one-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 249 g of IPDI nullate, 50 g of IPDI, and 500 g of MEK as a polyisocyanate (A), and these were charged at 25 ° C. The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. 10 g of 1-propanol (manufactured by Kishida Chemical Co., Ltd.) as a monol (B) and 50 g of a polyol 1 as a polyol (C) were charged into this polyisocyanate solution, and a urethanization reaction was carried out at 75 ° C. in a nitrogen stream to modify the polyisocyanate. I got a body. The resulting solution of the modified polyisocyanate was cooled to room temperature, and 141 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually charged as an amino alcohol (D), and the solution was stirred under a nitrogen stream. And a urea reaction while maintaining the temperature at 60 ° C. or lower to obtain a hydroxyl-terminated prepolymer solution PP-11. The hydroxyl value of this prepolymer was 132 KOHmg / g.

<Production Example 12>
A 1-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 226 g of IPDI-nurate, 45 g of IPDI, and 500 g of MEK as a polyisocyanate (A). The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. 5 g of 1-propanol (manufactured by Kishida Chemical Co., Ltd.) as a monool (B) and 100 g of polyol 1 as a polyol (C) were charged into this polyisocyanate solution, and a urethanization reaction was carried out at 75 ° C. under a nitrogen stream to modify the polyisocyanate. I got a body. The resulting polyisocyanate-modified solution was cooled to room temperature, and 124 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was gradually charged as amino alcohol (D), and the solution was stirred under a nitrogen stream. And a urea reaction while maintaining the temperature at 60 ° C. or lower, to obtain a hydroxyl-terminated prepolymer solution PP-12. The hydroxyl value of this prepolymer was 116 KOHmg / g.

<Production Example 13>
A 1-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 229 g of IPDI-nurate, 46 g of IPDI, and 500 g of MEK as a polyisocyanate (A). The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. 10 g of 1-propanol (manufactured by Kishida Chemical Co.) as a monol (B) and 100 g of a polyol 1 as a polyol (C) were charged into this polyisocyanate solution, and a urethanization reaction was carried out at 75 ° C. in a nitrogen stream to carry out polyisocyanate modification. I got a body. The obtained polyisocyanate-modified solution was cooled to room temperature, and 115 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was gradually charged as amino alcohol (D), and the solution was stirred under a nitrogen stream. The urea-forming reaction was carried out while maintaining the temperature at 60 ° C. or lower to obtain a hydroxyl-terminated prepolymer solution PP-13. The hydroxyl value of this prepolymer was 108 KOHmg / g.

<Production Example 14>
A one-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 223 g of IPDI nullate, 44 g of IPDI, and 500 g of MEK as polyisocyanate (A), and these were charged at 25 ° C. The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. In this polyisocyanate solution, 10 g of 1-propanol (manufactured by Kishida Chemical Co., Ltd.) as monool (B) and polyol 2 (1,6-hexanediol-based polycarbonate polyol as polyol (C), number average molecular weight 2,000, number of functional groups) 100 g of 2) was charged, and a urethanization reaction was performed at 75 ° C. under a nitrogen stream to obtain a modified polyisocyanate. The resulting solution of the modified polyisocyanate was cooled to room temperature, and 123 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was gradually charged as amino alcohol (D), and the solution was stirred under a nitrogen stream. The urea-forming reaction was carried out while maintaining the temperature at 60 ° C. or lower to obtain a hydroxyl-terminated prepolymer solution PP-14. The hydroxyl value of this prepolymer was 117 KOH mg / g.

<Production Example 15>
A one-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 223 g of IPDI nullate, 45 g of IPDI, and 500 g of MEK as a polyisocyanate (A). The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. To this polyisocyanate solution, 10 g of 2-ethylhexanol (manufactured by KH Neochem) as a monol (B) and 100 g of a polyol 1 as a polyol (C) were charged, and a urethanization reaction was carried out at 75 ° C. in a nitrogen stream to obtain a polyisocyanate. A modified product was obtained. The obtained polyisocyanate-modified solution was cooled to room temperature, and 122 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually charged as an amino alcohol (D), and the solution was stirred under a nitrogen stream. The urea-forming reaction was carried out while maintaining the temperature at 60 ° C. or lower to obtain a hydroxyl-terminated prepolymer solution PP-15. The hydroxyl value of this prepolymer was 115 KOHmg / g.

<Production Example 16>
In a 1-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column, 217 g of IPDI nullate, 43 g of IPDI, and 500 g of MEK were charged as polyisocyanate (A), and these were charged at 25 ° C. The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. To this polyisocyanate solution, 10 g of 2-ethylhexanol (manufactured by KH Neochem) as a monol (B) and 100 g of a polyol 2 as a polyol (C) were charged. A modified product was obtained. The resulting modified polyisocyanate solution was cooled to room temperature, and 130 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was gradually charged as amino alcohol (D), and the solution was stirred under a nitrogen stream. The urea reaction was carried out while maintaining the temperature at 60 ° C. or lower to obtain a hydroxyl-terminated prepolymer solution PP-16. The hydroxyl value of this prepolymer was 122 KOH mg / g.

<Production Example 17>
A 1-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 229 g of IPDI-nurate, 46 g of IPDI, and 500 g of MEK as a polyisocyanate (A). The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. In this polyisocyanate solution, 10 g of 1-propanol (manufactured by Kishida Chemical Co., Ltd.) as a monol (B) and polyol 3 (1,4-butanediol / adipic acid-based polyester polyol as a polyol (C), a number average molecular weight of 1,000) And 100 g of the functional group 2), and a urethanization reaction was carried out at 75 ° C. in a nitrogen stream to obtain a modified polyisocyanate. The obtained polyisocyanate-modified solution was cooled to room temperature, and 115 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was gradually charged as amino alcohol (D), and the solution was stirred under a nitrogen stream. The urea reaction was carried out while maintaining the temperature at 60 ° C. or lower to obtain a hydroxyl-terminated prepolymer solution PP-17. The hydroxyl value of this prepolymer was 108 KOHmg / g.

<Production Example 18>
A 1-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 229 g of IPDI-nurate, 46 g of IPDI, and 500 g of MEK as a polyisocyanate (A). The mixture was bubbled with nitrogen gas while stirring uniformly to prepare a polyisocyanate solution. To this polyisocyanate solution, 10 g of 1-propanol (manufactured by Kishida Chemical Co.) as monool (B) and 100 g of polyol 4 (polycaprolactone polyol, number average molecular weight 1,000, number of functional groups 2) as polyol (C) were charged. The urethanization reaction was carried out at 75 ° C. under a nitrogen stream to obtain a modified polyisocyanate. The obtained polyisocyanate-modified solution was cooled to room temperature, and 115 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was gradually charged as amino alcohol (D), and the solution was stirred under a nitrogen stream. The urea-forming reaction was carried out while maintaining the temperature at 60 ° C. or lower to obtain a hydroxyl-terminated prepolymer solution PP-18. The hydroxyl value of this prepolymer was 108 KOHmg / g.

<Production Example 19>
HDI allophanate (manufactured by Tosoh Corporation, trade name: Coronate 2770, NCO content: 19.4% by mass) was placed in a four-neck flask having a capacity of 1 liter equipped with a stirrer, a thermometer, a heating device, and a distillation column. ), 36 g of IPDI and 500 g of MEK, and nitrogen gas bubbling was carried out at 25 ° C. while uniformly stirring to prepare a polyisocyanate solution. To this polyisocyanate solution, 10 g of 2-ethylhexanol (manufactured by KH Neochem) as a monol (B) and 100 g of a polyol 1 as a polyol (C) were charged, and a urethanization reaction was carried out at 75 ° C. in a nitrogen stream to obtain a polyisocyanate. A modified product was obtained. The resulting polyisocyanate-modified solution was cooled to room temperature, and 176 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was gradually charged as amino alcohol (D), and the mixture was stirred under a nitrogen stream. The urea reaction was carried out while maintaining the temperature at 60 ° C. or lower to obtain a hydroxyl-terminated prepolymer solution PP-19. The hydroxyl value of this prepolymer was 165 KOHmg / g.

<Production Example 20>
250 g of HDI adduct (manufactured by Tosoh Corporation, C-HL, NCO content: 12.7%) as a polyisocyanate (A) in a four-neck flask having a capacity of 1 liter equipped with a stirrer, a thermometer, a heating device, and a distillation column. , 50 g of IPDI, 181 g of MEK, and 256 g of diacetone alcohol (hereinafter, DAA) were charged, and nitrogen gas was bubbled while uniformly stirring at 25 ° C. to prepare a polyisocyanate solution. To this polyisocyanate solution, 10 g of 2-ethylhexanol (manufactured by KH Neochem) as a monol (B) and 100 g of a polyol 1 as a polyol (C) were charged, and a urethanization reaction was carried out at 75 ° C. in a nitrogen stream to obtain a polyisocyanate. A modified product was obtained. The resulting polyisocyanate-modified solution was cooled to room temperature, and 139 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was gradually charged as amino alcohol (D), and the mixture was placed under a nitrogen stream. The urea-forming reaction was carried out while maintaining the temperature at 60 ° C. or lower to obtain a hydroxyl-terminated prepolymer solution PP-20. The hydroxyl value of this prepolymer was 130 KOHmg / g.

  Tables 1 to 3 show the amounts and properties of the raw materials used for the hydroxyl-terminated prepolymers of PP-1 to PP-18 and PP-19 to PP-20.

<Preparation of coating material>
The obtained hydroxyl-terminated prepolymers of PP-1 to PP-20, hydroxyl groups of acrylic polyol and polycarbonate diol, and polyisocyanates (HDI adduct, manufactured by Tosoh Corporation, trade name: Coronate HL, NCO content of 12.7% by mass, solids) And a molar ratio of the isocyanate group to R = isocyanate group / hydroxyl group is 1.0, and MEK or MEK is added so that the total solid content is 45% by mass. The mixture was diluted with a mixed solvent of DAA to prepare a coating composition. This was applied to a polyethylene terephthalate plate (manufactured by Paltec) with an applicator so that the film thickness after drying was 30 μm, dried at 25 ° C. for 1 hour, and then cured at 80 ° C. for 10 hours to prepare a coating material. The acrylic polyols shown in Comparative Examples 3 and 7 were DIC Acridic A-801 (hydroxyl value 50 KOH mg / g, solid content 50% by mass), and the polycarbonate diols shown in Comparative Examples 4 and 8 were Nipporan 970 manufactured by Tosoh Corporation (hydroxyl value: 224 KOHmg / g).

  Tables 4 to 7 show the composition of each compound solution and various physical properties of the obtained coating material.

Abbreviations used in Tables 4 to 7 are as follows.
(1) Compound a: 2-hydroxy-4-methoxybenzophenone (2) Compound b: 2-ethylhexyl salicylate (3) Compound c: 3,3,5-trimethylcyclohexyl salicylate (4) Compound d: 3,3-diphenyl 2-Ethylhexyl 2-cyanoacrylate (5) Compound e: 2-ethylhexyl-4-methoxycinnamate (6) Compound f: 4-tert-butylbenzoyl (4-methoxybenzoyl) methane (3% glycerin dilution)

  The evaluation results shown in Tables 4 to 7 are based on the following evaluation methods.

<Film drying property>
The dried state of the coating film dried at 25 ° C. for 1 hour after application with an applicator was evaluated by finger touch <Evaluation criteria>
-No stickiness on the coating film (Evaluation: A)
・ The coating film has stickiness (Evaluation: B)

(2) Evaluation test 2:
<UV absorber resistance>
To the coating film, 0.02 g of the following compounds (1) to (5) were dropped, left at 80 ° C. for 1 hour, and the dropped material was wiped off, and the appearance was visually evaluated.
Since the compound (6) is a solid, it was dissolved in glycerin to a concentration of 3%, 0.02 g of the solution was dropped on the coating film, left at 80 ° C. for 1 hour, and the dropped material was wiped off, and the appearance was visually evaluated. .

<Compound>
(1) 2-hydroxy-4-methoxybenzophenone (2) 2-ethylhexyl salicylate (3) 3,3,5-trimethylcyclohexyl salicylate (4) 2-ethylhexyl 3,3-diphenyl-2-cyanoacrylate (5) 2-Ethylhexyl-4-methoxycinnamate (6) 4-tert-butylbenzoyl (4-methoxybenzoyl) methane <Evaluation criteria>
-No change in the coating film (Evaluation: A)
-A coating film with a slight chemical solution mark (Evaluation: B)
-Coating film with significant swelling and gloss change (Evaluation: C)
・ What caused dissolution of the coating film (Evaluation: D)

  As shown in Tables 4 to 7, it was found that the coating materials according to Examples 1 to 36 had excellent resistance to ultraviolet absorbers. On the other hand, the coating materials of Comparative Examples 1 to 8 were inferior in the resistance to ultraviolet absorbers.

Claims (9)

Look-containing polyisocyanate (A) and the hydroxyl-terminated prepolymer having an isocyanurate ring structure which is the reaction product of a mono-ol (B) and the polyol (C) and amino alcohols (D), a curing agent, a polyol ( (C) 1 to 50% by mass of the hydroxyl group-terminated prepolymer having an isocyanurate ring structure in a solid content of the ultraviolet absorbent-resistant polyurethane composition. The ultraviolet absorbent resistant polyurethane composition according to claim 1, wherein the polyisocyanate (A) has an isocyanurate ring structure. The ultraviolet absorbent resistant polyurethane composition according to claim 1 or 2, wherein the isocyanate source of the polyisocyanate (A) is selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates. The ultraviolet absorbent polyurethane according to any one of claims 1 to 3, wherein the isocyanurate ring structure of the hydroxyl-terminated prepolymer having an isocyanurate ring structure is derived from a trimer of isophorone diisocyanate. Composition. The ultraviolet absorbent resistant polyurethane composition according to any one of claims 1 to 4, wherein the hydroxyl group-terminated prepolymer having an isocyanurate ring structure has an average number of functional groups of 2 to 11. The ultraviolet absorbent polyurethane composition according to any one of claims 1 to 5 , wherein at least one selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates is used as a curing agent. . As a curing agent, anti-UV-absorbing agent according to any one of claims 1 to 5, characterized by using at least one selected from the group consisting of adducts of an isocyanurate form and hexamethylene diisocyanate of hexamethylene diisocyanate Polyurethane composition. A coating material comprising the ultraviolet absorbent polyurethane composition according to any one of claims 1 to 7 . A coating film comprising the ultraviolet absorbent polyurethane composition according to any one of claims 1 to 7 .