JP6772441B2 - UV-resistant polyurethane composition, coating material using the composition - Google Patents

Description

Electronic device parts such as mobile phones and communication tablets, home appliance parts. The present invention relates to a UV-resistant polyurethane composition useful for daily necessities and automobile members, particularly plastic members, a molded body 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 type and combination of each component. In particular, molded bodies and coating materials using such resins are widely used in electronic device parts, furniture / home appliances, daily necessities, and automobile parts. However, when such a molded product or coating material is used in contact with the human body for a long period of time, the sebum component contained in sweat, oleic acid contained in skin protective cream, or a sunscreen (for example, cream, lotion, etc.) ), The surface of the molded product or coating agent deteriorates or becomes sticky due to the ultraviolet absorber component or the like, and there is a problem that it cannot withstand long-term use.

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

However, the curable compositions described in these patent documents have not been satisfactory in terms of resistance to UV absorbers contained in sunscreens.

That is, although polyurethane-based resin coating materials have been improved in durability against oil components such as oleic acid and beef tallow, they are resistant to UV absorbers contained in cosmetics and sunscreens (creams, lotions, etc.). The resistance is often insufficient, and the adhesion of the ultraviolet absorber may cause deterioration of the appearance of the surface of the molded body. Therefore, there is a demand for a plastic paint that is resistant to ultraviolet absorbers.

JP-A-2007-112986 Japanese Unexamined Patent Publication No. 2008-063395 Japanese Unexamined Patent Publication No. 2008-075048 Japanese Unexamined Patent Publication No. 2008-303284

The present invention has been made based on the above circumstances, and an object of the present invention is a polyurethane composition having excellent durability against ultraviolet absorbers contained in cosmetics, sunscreens, etc. (hereinafter, "ultraviolet resistant absorber"). The present invention is to provide a "polyurethane composition"), a coating material and a coating film using the composition.

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

[1] A UV-resistant polyurethane composition containing a polyisocyanate (A), an aminoalcohol (B), and a polyol (C) as monomer units, a hydroxyl-terminated prepolymer having an isocyanurate ring structure, and a curing agent. ..

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

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

[4] The UV-resistant polyurethane composition according to any one of [1] to [3] above, wherein the isocyanurate ring structure of the hydroxyl-terminated prepolymer is derived from a trimer of isophorone diisocyanate. ..

[5] The ultraviolet absorber-resistant polyurethane composition according to any one of the above [1] to [4], wherein the hydroxyl-terminated prepolymer has an average number of hydroxyl groups of 2.0 to 11.0.

[6] The UV-resistant polyurethane according to any one of [1] to [5] above, wherein the component of the polyol (C) in the UV-resistant polyurethane composition is less than 50%. Composition.

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

[8] The ultraviolet-resistant polyurethane composition according to any one of [1] to [6] above, wherein an adduct of hexamethylene diisocyanate is used as the curing agent.

[9]
A coating material comprising the ultraviolet absorber-resistant polyurethane composition according to any one of the above [1] to [8].

[10]
A coating film comprising the ultraviolet absorber-resistant polyurethane composition according to any one of the above [1] to [8].

The UV-resistant polyurethane composition of the present invention has excellent durability against UV absorbers contained in cosmetics, sunscreens, etc. Therefore, for example, by using this as a coating material for plastic members, cosmetics and sunscreens can be used. Durability against the ultraviolet absorber contained in the above can be imparted to the member. Further, the ultraviolet absorber-resistant polyurethane composition of the present invention has excellent adhesion to a plastic base material such as ABS and PET.

Hereinafter, the present invention will be described in detail.

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

Here, the ultraviolet absorber used as an index of the ultraviolet absorber property mentioned in the effect of the present invention will be described. UV absorbers include para-aminobenzoic acid, cinnamic acid, benzophenone, salicylic acid, benzoyltriazole, other aromatic UV absorbers, and mixtures of one or more of these. By shifting to a molded body or a polyurethane-based coating material, phenomena such as deterioration of the appearance of the surface of the molded body and stickiness can be seen. As sunscreens having a particularly strong tendency, those containing 3% by mass or more of salicylic acid-based ultraviolet absorbers, those containing 2% by mass or more of benzophenone-based ultraviolet absorbers, and those containing both of them are known. ing.

As shown in Examples described later, the ultraviolet absorber-resistant polyurethane composition of the present invention has at least 2-hydroxy-4-methoxybenzophenone, -2-ethylhexyl salicylate, and salicylic acid-3,3 among these ultraviolet absorbers. , 5-trimethylcyclohexyl, -2-ethylhexyl 3,3-diphenyl-2-cyanoacrylate, 2-ethylhexyl-4-methoxycinnamate, and 4-tert-butylbenzoyl (4-methoxybenzoyl) excellent against methane Shows durability.

Next, the hydroxyl-terminated prepolymer composition used in the ultraviolet-resistant polyurethane composition of the present invention will be described.

The hydroxyl-terminated prepolymer of the present invention is obtained by reacting polyisocyanate (A) with aminoalcohol (B) polyol (C). The isocyanurate ring structure of the hydroxyl-terminated prepolymer may be derived from polyisocyanate (A), aminoalcohol (B), polyol (C), and is not particularly limited. However, it is preferable to use a polyisocyanate having an isocyanurate ring structure because of its easy availability.

The isocyanate source of the polyisocyanate (A) is not particularly limited, and examples thereof include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and aromatic aliphatic diisocyanates. Of these, aliphatic diisocyanates or alicyclic diisocyanates are preferable from the viewpoint of coating film weather resistance and ultraviolet absorber resistance, and alicyclic diisocyanates are preferable from the viewpoint of solvent solubility and dryness.

<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. Etc., and a mixture thereof can also be used.

<Alicyclic diisocyanate>
Specific examples of the alicyclic diisocyanate include isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornan diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate. A mixture of these can also be used. Among these alicyclic diisocyanates, isophorone diisocyanate (hereinafter referred to as "IPDI") is particularly preferable from the viewpoint of ultraviolet absorber resistance and productivity.

<Aromatic diisocyanate>
Specific examples of the aromatic diisocyanate include 2,4-tolylene diisocyanis, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 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-phenylenediisocyanide, p-phenylenediisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate Etc., and a mixture thereof can also be used.

<Aromatic aliphatic diisocyanate>
Specific examples of the aromatic aliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene, ω, ω. '-Diisocyanato-1,4-diethylbenzene and the like can be mentioned, and mixtures thereof can also be used.

Further, as long as the gist of the present invention is not deviated, for example, the above-mentioned aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, aromatic aliphatic diisocyanate, or isocyanurate group-containing polyisocyanate and uretdione made from these diisocyanates are used. Group-containing polyisocyanates, uretdione and isocyanurate group-containing polyisocyanates, urethane group-containing polyisocyanates, allophanate group-containing polyisocyanates, bullet group-containing polyisocyanates, uretoimine group-containing polyisocyanates and the like can also be used in combination.

<Amino alcohol>
The amino alcohol (B) is not particularly limited as long as it is a compound having an amino group and a hydroxyl group, but from the viewpoint of reaction control during synthesis of the hydroxyl group-terminated prepolymer, for example, it is first in one molecule. Those having one secondary amino group or a secondary amino group and one to three hydroxyl groups are preferable.

Specific examples of such amino alcohol (B) include, for example, 2-aminoethanol, 2- (methylamino) ethanol, 2-amino-2-methyl-1-propanol, 1-amino-2-propanol, 2-. 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-hydroxyisobutylamide, 2-hydroxypropionamide, 2-amino-4-methyl-1-pentanol, 3-amino-1-propanol, 5-amino-1-pen Tanol, 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-piperidin methanol, 3-piperidin methanol, 4-piperidin methanol, 3-hydroxypiperidin, 4-hydroxypiperidin, 2-piperidinethanol, 4-piperidinethanol , 2-Pyrrolidinemethanol, 2- (4-piperidyl) -2-propanol, 4-hydroxy-2,2,6,6-tetramethylpiperidin, nortropin, 1- [2- (2-hydroxyethoxy) ethyl] piperazine , 1-piperazin ethanol, 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.

The polyol (C) is not particularly limited, and examples thereof include polycarbonate polyols, polycaprolactone polyols, polyester polyols, polyether polyols, polyolefin polyols, acrylic polyols, silicone polyols, castor oil-based polyols, and fluorine-based polyols. It can be used alone or in combination of two or more. The molecular weight of the polyol (C) is preferably a number average molecular weight of 250 to 50,000, and more preferably 300 to 4,000. If the number average molecular weight is less than the lower limit, the adhesion to the plastic substrate may be lowered, and if it exceeds the upper limit, the solvent solubility may be lowered, which is not preferable.

Further, the polyol (C) preferably has an active hydrogen group number (average number of functional groups) of 1.9 or more in one molecule. If the number of active hydrogen groups is less than 1.9, the ultraviolet absorber properties and mechanical properties may deteriorate.

<Polycarbonate polyol>
Specific examples of the polycarbonate polyol include 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-dimethylolheptan, diethylene glycol, dipropylene glycol , Neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, One or more low-molecular-weight polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, diphenyl carbonate, dinaphthyl carbonate, Examples thereof include those obtained from a dealcoholization reaction or a dephenolization reaction with diaryl carbonates such as dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, and tetrahydronaphthyl carbonate. Further, from the viewpoint of imparting abrasion resistance, scratch resistance, and olein acidity, a polycarbonate polyol composed of 1,6-hexanediol and diethyl carbonate can be preferably used.

<Polycaprolactone Polyester>
Specific examples of the polycaprolactone polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptan, diethylene glycol, Dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis (β-hydroxyethyl) benzene, xylyl A product obtained by ring-opening and adding one or both of ε-caprolactone and alkyl-substituted ε-caprolactone using one or more low-molecular-weight polyols such as lenglycol, glycerin, trimethylolpropane, and pentaerythritol as an initiator. Can be used.

<Polyester polyol>
Specific examples of polyester polyols include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, glutaconic acid, and azeline. Acids, 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 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-dimethylolheptan, diethylene glycol , Dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis (β-hydroxyethyl) benzene, Examples thereof include those obtained by a compaction reaction with one or more of low molecular weight polyols having a molecular weight of 500 or less, such as xylylene glycol, glycerin, trimethylolpropane, and pentaerythritol. Further, a polyester-amide polyol obtained by substituting a small molecule polyamine such as hexamethylenediamine, isophorone diamine, or monoethanolamine or a low molecular weight amino alcohol as a part of the low molecular weight polyol can also be used.

<Polyether polyol>
Specific examples of polyether polyols 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-Nonandiol, 3-Methyl-1,5-Pentanediol, 3,3-Dimethylol heptane, Diethylene glycol, Dipropylene Glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, penta Two or more active hydrogen groups such as low molecular weight polyols such as erythritol, or low molecular weight polyamines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, and xylylenediamine, preferably 2-3. Polyether polyol obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc., or alkyl glycidyl ethers such as methyl glycidyl ether, phenyl glycidyl ether, etc. Examples thereof include polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as arylglycidyl ethers and tetrahydrofuran.

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

<Acrylic polyol>
Examples of the acrylic polyol include an acrylic acid ester and / or a methacrylic acid ester [hereinafter referred to as (meth) acrylic acid ester], and an acrylic acid hydroxy compound having at least one hydroxyl group in the molecule which can be a reaction point and / or. Acrylic monomer copolymerized with a hydroxymethacrylic acid compound (hereinafter referred to as (meth) acrylic acid hydroxy compound] and a polymerization initiator using heat energy, light energy such as ultraviolet rays or electron beams, etc. can be mentioned. ..
<(Meta) acrylic acid ester>
Specific examples of the (meth) acrylic acid ester include alkyl esters having 1 to 20 carbon atoms. Specific examples of such (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate. (Meta) such as hexyl (meth) acrylate, -2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate. Acrylic acid alkyl ester; ester of (meth) acrylic acid with alicyclic alcohol such as cyclohexyl (meth) acrylate; (meth) acrylic acid aryl ester such as phenyl (meth) acrylic acid, benzyl (meth) acrylic acid Can be mentioned. Such (meth) acrylic acid ester may be used alone or in combination of two or more kinds.

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

<Silicone polyol>
Specific examples of the silicone polyol include 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. Examples thereof include polysiloxanes such as α and ω-dihydroxypolydiphenylsiloxane.

<Castor oil-based polyol>
Specific examples of castor oil-based polyols include linear or branched polyester polyols obtained by reacting castor oil fatty acids with polyols. Further, dehydrated castor oil, partially dehydrated partially dehydrated castor oil, and hydrogenated castor oil can also be used.

<Fluorine-based polyol>
Specific examples of the fluorine-based polyol are linear or branched polyols obtained by a copolymerization reaction containing a fluorine-containing monomer and a monomer having a hydroxy group as essential components. Here, the fluorine-containing monomer is preferably a fluoroolefin, for example, tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoromethyltrifluoroethylene. Can be mentioned. Examples of the monomer having a hydroxyl group include 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 vinyl hydroxyalkyl crotonates. Hydroxy group-containing carboxylic acid vinyl such as, or a monomer having a hydroxyl group such as an allyl ester can be mentioned.

Next, a general method for producing a hydroxyl-terminated prepolymer constituting the ultraviolet-resistant polyurethane composition of the present invention will be described. The method for producing the hydroxyl-terminated prepolymer is not limited to this.

<Manufacturing method of hydroxyl-terminated prepolymer>
In the presence or absence of an organic solvent, the polyisocyanate (A) and the polyol (C) are urethanized to obtain an isocyanate group-terminated isocyanate modified product. The isocyanate group-terminated isocyanate modified product and the amino alcohol (B) are charged in an amount such that the molar ratio (R) of the isocyanate group to the amino group is preferably 0.7 to 1.3 with R = isocyanate group / amino group. A hydroxyl group-terminated prepolymer is produced by subjecting it to a urea conversion reaction, preferably at 80 ° C. or lower.

Further, in a series of manufacturing steps, it is preferable to proceed the reaction under a nitrogen gas or a dry air stream in order to suppress the reaction between the isocyanate group and the water content.

The reaction temperature of the urea conversion 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. When the reaction temperature is set to 80 ° C. or lower, the hydroxyl group derived from the aminoalcohol (B) reacted with the polyisocyanate (A) and the remaining isocyanate group cause a urethanization reaction to form aggregates and insolubilize the entire system. Can be suppressed.

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

<Organic solvent used in manufacturing>
Specific examples of such an organic solvent include aliphatic hydrocarbons such as octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, ketones such as methylethyl ketone, methylisobutylketone and cyclohexanone, ethyl acetate, and the like. Esters such as butyl acetate and isobutyl acetate, glycol ether esters such as ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate and ethyl-3-ethoxy propionate, and dioxane. Halogenized hydrocarbons such as ethers, methylene iodide and monochlorobenzene, polar aproton solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide and hexamethylphosphonylamide, and thirds such as diacetone alcohol. Examples include grade alcohols. These solvents can be used alone or in combination of two or more.

Further, alcohols such as ethanol and isopropanol can also be used as long as the performance does not deteriorate.

The average number of hydroxyl group functional groups of the hydroxyl-terminated prepolymer in the present invention is not particularly limited, but is preferably 2.0 to 11.0 from the viewpoint of ultraviolet absorber resistance, and 3.0 to 9. It is more preferably 0.

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

Examples of the curing agent include polyisocyanates, and from the viewpoint of weather resistance of the coating film, aliphatic polyisocyanates or alicyclic polyisocyanates, and polyisocyanates in combination thereof are preferable. As the curing agent, an adduct body in which hexamethylene diisocyanate (hereinafter referred to as “HDI”) is partially urethane-modified is particularly preferable from the viewpoint of compatibility with the hydroxyl-terminated prepolymer and the organic solvent.

Further, the curing agent is, for example, the above-mentioned aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, aromatic aliphatic diisocyanate, or isocyanurate obtained from these diisocyanates as a raw material, as long as the gist of the present invention is not deviated. Group-containing polyisocyanate, uretdione group-containing polyisocyanate, uretdione group and isocyanurate group-containing polyisocyanate, urethane group-containing polyisocyanate, allophanate group-containing polyisocyanate, bullet group-containing polyisocyanate, uretoimine group-containing polyisocyanate, etc. Two or more types can be used in combination.

The UV-resistant polyurethane composition of the present invention may be filled with, for example, an antioxidant, a UV absorber, a pigment, a dye, a solvent, a flame retardant, a hydrolysis inhibitor, a lubricant, a plasticizer, and a filler, if necessary. Additives such as materials, antistatic agents, dispersants, catalysts, storage stabilizers, surfactants and leveling agents can be appropriately added.

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

The ultraviolet absorber-resistant polyurethane composition of the present invention is used, for example, as an electronic device member such as a communication tablet, a furniture / home appliance member, a molded product such as daily necessities, an automobile member, or a coating material.

The molded body includes, for example, a member, a structure, a film, and a sheet, and is molded by a known technique such as casting or coating.

When the ultraviolet absorber-resistant polyurethane composition of the present invention is used as a coating material, for example, the above-mentioned resin composition for a coating material containing a hydroxyl-terminated prepolymer, the above-mentioned curing agent, and, if necessary, the above-mentioned curing agent After mixing the above additives and stirring uniformly, a coating film is formed on the substrate by known techniques such as spray coating, knife coating, wire bar coating, doctor blade coating, reverse roll coating, and calendar coating. To do.

Examples of the above-mentioned 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, 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, polyether ether ketone resin, polyphenylene sulfide resin , NBR resin, chloroprene resin, SBR resin, SEBS resin, olefin resin such as polyethylene and polypropylene, and the like.

In order to improve the adhesiveness of these base materials, the surface of the base material can be treated in advance by corona discharge treatment, frame treatment, ultraviolet irradiation treatment, ozone treatment, primer treatment, solvent treatment and the like.

The amount of the coating material applied is not particularly limited, but it is preferable to apply the coating material so that the dry film thickness is 20 μm or more, for example. By setting the film thickness to 20 μm or more, the ultraviolet absorber property of the coating material can be improved.

Next, when the ultraviolet-resistant polyurethane composition of the present invention is used as a paint compounding solution, the coating solution is a molar of a hydroxyl group of a hydroxyl-terminated prepolymer and an isocyanate group of a polyisocyanate used as a curing agent. The ratio (R) is preferably R = isocyanate group / hydroxyl group and R = 0.4 to 2.5, and more preferably R = 0.7 to 1.5. It is preferable to do so. The organic solvent used for dilution is not particularly limited, but can be used alone or in combination of two or more of the above <organic solvents used for production>.

Examples of the present invention will be described below, but the present invention is not construed as being limited to these examples.

<Synthesis of hydroxyl-terminated prepolymer>
<Manufacturing example 1>
IPDI isocyanurate (manufactured by Ebonic, trade name: VESTANAT T1890 / 100, NCO content 17.) As polyisocyanate (A) in a 4-necked flask with a capacity of 1 liter equipped with a stirrer, a thermometer, a heating device, and a distillation tower. 236 g of 3% by mass, hereinafter referred to as "IPDI isocyanurate"), 47 g of isophorone diisocyanate (hereinafter referred to as "IPDI"), and 500 g of methyl ethyl ketone (hereinafter referred to as "MEK") were charged, and these were charged at 25 ° C. A polyisocyanate solution was prepared by bubbling with nitrogen gas while stirring uniformly with. 75 g of polyol 1 (1,6-hexanediol-based polycarbonate polyol, number average molecular weight 1,000, number of functional groups 2) was charged into this polyisocyanate solution as polyol (C), and a urethanization reaction was carried out at 70 ° C. under a nitrogen stream. This was carried out to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution was cooled to room temperature, and 142 g of 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Kasei Co., Ltd.) was gradually charged as aminoalcohol (B) at 60 ° C. under a nitrogen stream. The reaction was carried out while maintaining the following to obtain a hydroxyl-terminated prepolymer solution PC-1. The hydroxyl value of this prepolymer was 134 KOHmg / g, and the average number of hydroxyl groups was 6.0.

<Manufacturing example 2>
A 1-liter capacity four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 225 g of IPDI isocyanurate, 45 g of IPDI, and 500 g of MEK as polyisocyanate (A), and these were charged at 25 ° C. A polyisocyanate solution was prepared by bubbling with nitrogen gas while stirring uniformly with. 100 g of polyol 1 as polyol (C) was charged into this polyisocyanate solution, and a urethanization reaction was carried out at 70 ° C. under a nitrogen stream to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution is cooled to room temperature, and 130 g of 2-amino-2-ethyl-1,3-propanediol as aminoalcohol (B) is gradually charged and reacted while maintaining 60 ° C. or lower under a nitrogen stream. As a result, a hydroxyl-terminated prepolymer solution PC-2 was obtained. The hydroxyl value of this prepolymer was 122 KOHmg / g, and the average number of hydroxyl groups was 6.1.

<Manufacturing example 3>
205 g of IPDI isocyanurate, 41 g of IPDI, and 500 g of MEK were charged as polyisocyanate (A) into a 4-necked flask having a capacity of 1 liter equipped with a stirrer, a thermometer, a heating device, and a distillation column, and these were charged at 25 ° C. A polyisocyanate solution was prepared by bubbling with nitrogen gas while stirring uniformly with. 150 g of polyol 1 as polyol (C) was charged into this polyisocyanate solution, and a urethanization reaction was carried out at 70 ° C. under a nitrogen stream to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution is cooled to room temperature, and 104 g of 2-amino-2-ethyl-1,3-propanediol as aminoalcohol (B) is gradually charged and reacted while maintaining 60 ° C. or lower under a nitrogen stream. As a result, a hydroxyl-terminated prepolymer solution PC-3 was obtained. The hydroxyl value of this prepolymer was 98 KOHmg / g, and the average number of hydroxyl groups was 6.6.

<Manufacturing example 4>
199 g of IPDI isocyanurate, 40 g of IPDI, and 500 g of MEK were charged as polyisocyanate (A) into a 4-necked flask having a capacity of 1 liter equipped with a stirrer, a thermometer, a heating device, and a distillation column, and these were charged at 25 ° C. A polyisocyanate solution was prepared by bubbling with nitrogen gas while stirring uniformly with. To this polyisocyanate solution, 50 g of polyol 1 and 100 g of polyol 2 (1,6-hexanediol-based polycarbonate polyol, number average molecular weight 2,000, number of functional groups 2) were charged as polyol (C), and the temperature was 70 ° C. under a nitrogen stream. The urethanization reaction was carried out in 1 to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution is cooled to room temperature, and 111 g of 2-amino-2-ethyl-1,3-propanediol as aminoalcohol (B) is gradually charged and reacted while maintaining 60 ° C. or lower under a nitrogen stream. As a result, a hydroxyl-terminated prepolymer solution PC-4 was obtained. The hydroxyl value of this prepolymer was 105 KOHmg / g, and the average number of hydroxyl groups was 6.2.

<Manufacturing example 5>
207 g of IPDI isocyanurate, 42 g of IPDI, and 500 g of MEK were charged as polyisocyanate (A) into a 4-necked flask having a capacity of 1 liter equipped with a stirrer, a thermometer, a heating device, and a distillation column, and these were charged at 25 ° C. A polyisocyanate solution was prepared by bubbling with nitrogen gas while stirring uniformly with. 125 g of polyol 2 as polyol (C) was charged into this polyisocyanate solution, and a urethanization reaction was carried out at 70 ° C. under a nitrogen stream to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution is cooled to room temperature, and 120 g of 2-amino-2-ethyl-1,3-propanediol as aminoalcohol (B) is gradually charged and reacted while maintaining 60 ° C. or lower under a nitrogen stream. As a result, a hydroxyl-terminated prepolymer solution PC-5 was obtained. The hydroxyl value of this prepolymer was 123 KOHmg / g, and the average number of hydroxyl groups was 6.0.

<Manufacturing example 6>
A 1-liter capacity four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 263 g of IPDI isocyanurate, 53 g of IPDI, and 500 g of MEK as polyisocyanate (A), and these were charged at 25 ° C. A polyisocyanate solution was prepared by bubbling with nitrogen gas while stirring uniformly with. 5 g of polyol 2 as polyol (C) was charged into this polyisocyanate solution, and a urethanization reaction was carried out at 70 ° C. under a nitrogen stream to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution is cooled to room temperature, and 179 g of 2-amino-2-ethyl-1,3-propanediol as aminoalcohol (B) is gradually charged and reacted while maintaining 60 ° C. or lower under a nitrogen stream. As a result, a hydroxyl-terminated prepolymer solution PC-6 was obtained. The hydroxyl value of this prepolymer was 168 KOHmg / g, and the average number of hydroxyl groups was 5.7.

<Manufacturing example 7>
A 1-liter capacity four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 225 g of IPDI isocyanurate, 45 g of IPDI, and 500 g of MEK as polyisocyanate (A), and these were charged at 25 ° C. A polyisocyanate solution was prepared by bubbling with nitrogen gas while stirring uniformly with. To this polyisocyanate solution, 100 g of polyol 3 (1,4-butanediol / adipic acid-based polyester polyol, number average molecular weight 1,000, number of functional groups 2) was charged as polyol (C), and urethane was charged at 70 ° C. under a nitrogen stream. The chemical reaction was carried out to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution is cooled to room temperature, and 130 g of 2-amino-2-ethyl-1,3-propanediol as aminoalcohol (B) is gradually charged and reacted while maintaining 60 ° C. or lower under a nitrogen stream. As a result, a hydroxyl-terminated prepolymer solution PC-7 was obtained. The hydroxyl value of this prepolymer was 122 KOHmg / g, and the average number of hydroxyl groups was 6.1.

<Manufacturing example 8>
A 1-liter capacity four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 225 g of IPDI isocyanurate, 45 g of IPDI, and 500 g of MEK as polyisocyanate (A), and these were charged at 25 ° C. A polyisocyanate solution was prepared by bubbling with nitrogen gas while stirring uniformly with. 100 g of polyol 4 (polycaprolactone polyol, number average molecular weight 1,000, number of functional groups 2) was charged into this polyisocyanate solution as polyol (C), and a urethanization reaction was carried out at 70 ° C. under a nitrogen stream to carry out an isocyanate-modified solution. Got The obtained polyisocyanate modified solution is cooled to room temperature, and 130 g of 2-amino-2-ethyl-1,3-propanediol as aminoalcohol (B) is gradually charged and reacted while maintaining 60 ° C. or lower under a nitrogen stream. As a result, a hydroxyl-terminated prepolymer solution PC-8 was obtained. The hydroxyl value of this prepolymer was 122 KOHmg / g, and the average number of hydroxyl groups was 6.1.

<Manufacturing example 9>
A 1-liter capacity four-necked flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 234 g of IPDI isocyanurate, 47 g of IPDI, and 500 g of MEK as polyisocyanate (A), and these were charged at 25 ° C. A polyisocyanate solution was prepared by bubbling with nitrogen gas while stirring uniformly with. 100 g of polyol 1 as polyol (C) was charged into this polyisocyanate solution, and a urethanization reaction was carried out at 70 ° C. under a nitrogen stream to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution is cooled to room temperature, and 119 g of diethanolamine (manufactured by Kishida Chemical Co., Ltd.) is gradually charged as aminoalcohol (B) and reacted while maintaining 60 ° C. or lower under a nitrogen stream to cause a hydroxyl-terminated prepolymer. Solution PC-9 was obtained. The hydroxyl value of this prepolymer was 128 KOHmg / g, and the average number of hydroxyl groups was 6.1.

<Manufacturing example 10>
223 g of IPDI isocyanurate, 44 g of IPDI, and 500 g of MEK were charged as polyisocyanate (A) into a 4-necked flask having a capacity of 1 liter equipped with a stirrer, a thermometer, a heating device, and a distillation column, and these were charged at 25 ° C. A polyisocyanate solution was prepared by bubbling with nitrogen gas while stirring uniformly with. 125 g of polyol 1 as polyol (C) was charged into this polyisocyanate solution, and a urethanization reaction was carried out at 70 ° C. under a nitrogen stream to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution is cooled to room temperature, and 108 g of diethanolamine (manufactured by Kishida Chemical Co., Ltd.) is gradually charged as aminoalcohol (B) and reacted while maintaining 60 ° C. or lower under a nitrogen stream to cause a hydroxyl-terminated prepolymer. Solution PC-10 was obtained. The hydroxyl value of this prepolymer was 115 KOHmg / g, and the average number of hydroxyl groups was 6.3.

<Manufacturing example 11>
In a 4-necked flask with a capacity of 1 liter equipped with a stirrer, a thermometer, a heating device, and a distillation column, 212 g of IPDI isocyanurate, 42 g of IPDI, and 500 g of MEK were charged as polyisocyanate (A), and these were charged at 25 ° C. A polyisocyanate solution was prepared by bubbling with nitrogen gas while stirring uniformly with. 150 g of polyol 1 as polyol (C) was charged into this polyisocyanate solution, and a urethanization reaction was carried out at 70 ° C. under a nitrogen stream to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution is cooled to room temperature, and 96 g of diethanolamine (manufactured by Kishida Chemical Co., Ltd.) is gradually charged as aminoalcohol (B) and reacted while maintaining 60 ° C. or lower under a nitrogen stream to cause a hydroxyl-terminated prepolymer. Solution PC-11 was obtained. The hydroxyl value of this prepolymer was 102 KOHmg / g, and the average number of hydroxyl groups was 6.6.

<Manufacturing example 12>
190 g of IPDI isocyanurate, 38 g of IPDI, and 500 g of MEK were charged as polyisocyanate (A) into a 4-necked flask having a capacity of 1 liter equipped with a stirrer, a thermometer, a heating device, and a distillation column, and these were charged at 25 ° C. A polyisocyanate solution was prepared by bubbling with nitrogen gas while stirring uniformly with. 200 g of polyol 1 as polyol (C) was charged into this polyisocyanate solution, and a urethanization reaction was carried out at 70 ° C. under a nitrogen stream to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution is cooled to room temperature, and 72 g of diethanolamine (manufactured by Kishida Chemical Co., Ltd.) is gradually charged as aminoalcohol (B) and reacted while maintaining 60 ° C. or lower under a nitrogen stream to cause a hydroxyl-terminated prepolymer. Solution PC-12 was obtained. The hydroxyl value of this prepolymer was 77 KOHmg / g, and the average number of hydroxyl groups was 7.5.

<Manufacturing example 13>
In a 4-necked flask with a capacity of 1 liter equipped with a stirrer, a thermometer, a heating device, and a distillation column, 206 g of HDI allophanate (manufactured by Toso Co., Ltd., Coronate 2770, NCO content 19.4%) was added as polyisocyanate (A). , IPDI (41 g) and MEK (500 g) were charged, and these were bubbling with nitrogen gas while uniformly stirring at 25 ° C. to prepare a polyisocyanate solution. 125 g of polyol 1 as polyol (C) was charged into this polyisocyanate solution, and a urethanization reaction was carried out at 70 ° C. under a nitrogen stream to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution is cooled to room temperature, and 128 g of 2-amino-2-ethyl-1,3-propanediol as aminoalcohol (B) is gradually charged and reacted while maintaining 60 ° C. or lower under a nitrogen stream. As a result, a hydroxyl-terminated prepolymer solution PC-13 was obtained. The hydroxyl value of this prepolymer was 111 KOHmg / g, and the average number of hydroxyl groups was 4.

<Manufacturing example 14>
285 g of HDI Adduct (manufactured by Tosoh Corporation, Coronate HL, NCO content 12.7%) as polyisocyanate (A) in a 4-necked flask with a capacity of 1 liter equipped with a stirrer, thermometer, heating device, and distillation column. , IPDI (43 g), MEK (250 g), and diacetone alcohol (DAA) (179 g) were charged, and these were bubbling with nitrogen gas while uniformly stirring at 25 ° C. to prepare a polyisocyanate solution. 125 g of polyol 1 as polyol (C) was charged into this polyisocyanate solution, and a urethanization reaction was carried out at 70 ° C. under a nitrogen stream to obtain an isocyanate-modified solution. The obtained polyisocyanate modified solution is cooled to room temperature, and 118 g of 2-amino-2-ethyl-1,3-propanediol as aminoalcohol (B) is gradually charged and reacted while maintaining 60 ° C. or lower under a nitrogen stream. As a result, a hydroxyl-terminated prepolymer solution PC-14 was obtained. The hydroxyl value of this prepolymer was 112 KOHmg / g, and the average number of hydroxyl groups was 6.4.

Tables 1 and 2 show the blending amounts and properties of the raw materials used for the hydroxyl-terminated prepolymers of PC-1 to PC-14.

<Preparation of coating material>
The hydroxyl group-terminated prepolymers of PC-1 to PC-14, the hydroxyl groups of acrylic polyols and polycarbonate diols, and polyisocyanates (HDI Adduct, manufactured by Toso Co., Ltd., trade name: coronate HL, NCO content 12.7% by mass, solid) The molar ratio of (75% by mass) with the isocyanate group is 1.0 by R = isocyanate group / hydroxyl group, and MEK or MEK is added so that the total solid content is 45% by mass. A coating mixture was prepared by diluting with a mixed solvent of DAA. This was applied to a polyethylene terephthalate plate (manufactured by PALTEK Corporation) 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 polyol shown in Comparative Example 3 is Acrydic A-801 manufactured by DIC Corporation (hydroxyl value 50 KOHmg / g, solid content 50% by mass), and the polycarbonate diol shown in Comparative Example 4 is Nipponporan 970 manufactured by Tosoh Corporation (hydroxyl value). 224 KOH mg / g).

Tables 3 to 4 show the composition of each compounding solution and various physical properties of the obtained coating material.

The abbreviations used in Tables 3 and 4 are as follows.
(1) Compound a: 2-Hydroxy-4-methoxybenzophenone (2) Compound b: 2-ethylhexyl salicylate (3) Compound c: Salicylic acid 3,3,5-trimethylcyclohexyl (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% diluted solution of glycerin) ..

The evaluation results shown in Tables 3 and 4 are based on the following evaluation methods.

<UV absorber resistance>
0.02 g of the following compounds (1) to (5) was added dropwise to the coating film, left at 80 ° C. for 1 hour, and then the droplets were wiped off to visually evaluate the appearance. Since compound (6) is a solid, it was dissolved in glycerin so as to be 3%, 0.02 g of the solution was added dropwise to the coating film, left at 80 ° C. for 1 hour, the droplets were wiped off, and the appearance was visually evaluated. ..
<Compound>
(1) 2-Hydroxy-4-methoxybenzophenone (2) 2-ethylhexyl salicylate (3) 3,3,5-trimethylcyclohexyl salicylic acid (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 coating film (evaluation: A)
-The coating film has slight chemical marks (evaluation: B)
-The coating film is significantly swollen and the gloss is changed (evaluation: C).
-The coating film is dissolved (evaluation: D).

<Go board tape peeling test>
The adhesion of the coating film was evaluated according to the checkered tape peeling test of JIS K-5600-8-5-2. The numerical value in the table means the number of squares remaining without peeling out of 100 squares.

As shown in Tables 3 and 4, it was found that the coating materials according to Examples 1 to 6 and 9 to 12 were excellent in ultraviolet absorber resistance and also in adhesion to a plastic base material. .. On the other hand, the coating materials of Comparative Examples 1 to 4 were inferior in ultraviolet absorber resistance.

Claims (6)

It is characterized by using a hydroxyl group-terminated prepolymer which is a reaction product of polyisocyanate (A), aminoalcohol (B) and polyol (C) and has an isocyanurate ring structure, and an adduct of hexamethylene diisocyanate as a curing agent. The ultraviolet absorber polyurethane composition to be used, wherein the amino alcohol (B) has one primary amino group or a secondary amino group, and the polyol (C) is a polycarbonate polyol. A characteristic UV-resistant polyurethane composition. The ultraviolet absorber-resistant polyurethane composition according to claim 1 , wherein the isocyanurate ring structure of the hydroxyl-terminated prepolymer is derived from a trimer of isophorone diisocyanate. The ultraviolet absorber-resistant polyurethane composition according to claim 1 or 2 , wherein the hydroxyl-terminated prepolymer has an average number of hydroxyl groups in the range of 2.0 to 11.0. The ultraviolet-absorbing polyurethane composition according to any one of claims 1 to 3 , wherein the component derived from the polyol (C) in the ultraviolet-absorbing polyurethane composition is less than 50% by mass . .. A coating material comprising the ultraviolet absorber-resistant polyurethane composition according to any one of claims 1 to 4 . A coating film comprising the ultraviolet absorber-resistant polyurethane composition according to any one of claims 1 to 4 .