JP2017122169A - Ultraviolet absorber resistant polyurethane urea resin composition, and molded body and coating material using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet absorber resistant polyurethane urea resin composition usable in a molded body and a coating material which achieve both liquid resistance and durability against an ultraviolet absorber contained in cosmetics or the like, and are excellent in various characteristics such as abrasion resistance, scratch resistance, oleic acid resistance, water resistance, stain resistance and weather resistance.SOLUTION: By using an ultraviolet absorber resistant polyurethane urea resin composition, which contains a reaction product of at least polyol (A), polyisocyanate (B), a molecular weight regulator (C) and diamine (D), and a silicone-free bubble-breaking polymer (E), as a coating material of a molded body and a member, liquid resistance and durability against an ultraviolet absorber can be imparted, which can suppress foaming in a molding process.SELECTED DRAWING: None

Description

  The present invention relates to a UV-absorbing polyurethane urea resin composition useful for electronic device members such as communication tablets, clothing, furniture / household appliance members, daily goods, and automobile members, and a molded article using the composition, and The coating material.

  Polyurethane urea resin is excellent in various physical properties such as wear resistance, flexibility, flexibility, flexibility, processability, adhesion, chemical resistance, etc., and is also suitable for various processing methods. , Widely used as resin components such as coating materials, inks, adhesives and paints for clothing, furniture / household appliances, household goods, construction / civil engineering, and automotive parts, or as various molded products such as films and sheets .

  These polyurethane urea resins are generally obtained by reacting a polyol component, a polyisocyanate component, and further a chain extender component, and polyurethane urea resins having various performances are provided depending on the type and combination of each component. Has been. In particular, since molded products and coating materials using such resins can impart a moist feel and other tactile functions, they are used in electronic equipment members, clothing, furniture / home appliances, daily goods, and automobile parts. It is used for many purposes. However, when used in contact with the human body for a long period of time, the sebum component contained in sweat, the oleic acid contained in the skin protection cream, the UV absorber component, etc. may cause deterioration of the surface of the molded product and stickiness. However, it may not be able to withstand long-term use.

In such a background, development of a polyurethane-based resin exhibiting oil resistance against oleic acid, which is a main component of sebum components, is being promoted.
As a polyurethane resin excellent in oleic acid resistance, a polyisocyanate compound, a polycarbonate diol using 1,5-pentanediol and 1,6-hexanediol in any composition ratio, and a polysiloxane as an essential component A curable composition having a soft touch feeling and excellent oleic acid resistance has been proposed (for example, see Patent Documents 1 to 4).

  In addition, it has a polycarbonate diol composed of 2-methyl-1,3-propanediol or 3-methyl-1,5-pentanediol, water resistance composed of a diisocyanate compound, and oil resistance against oleic acid and beef tallow, etc. A coating agent composition having excellent elastic strength and adhesion to members has been proposed (see, for example, Patent Document 5 and Patent Document 6).

  However, conventional molded products and coating materials have been improved in oil resistance against oil components such as oleic acid and beef tallow, but liquid resistance and durability against UV absorbers contained in cosmetics and the like It is often insufficient, and it is presumed that the phenomenon of appearance deterioration or stickiness of the surface of the molded product occurs due to the adhesion of the ultraviolet absorber. In the molding process, foaming of the coating agent composition sometimes becomes a problem.

JP 2007-112986 A JP 2008-063395 A JP 2008-075048 A JP 2008-303284 A JP 2008-037993 A Japanese Patent Laying-Open No. 2005-206674

  This invention is made | formed based on the above situations, The objective is the reaction production | generation of a polyol (A), a polyisocyanate (B), a molecular weight modifier (C), and a diamine (D). By using a composition in which a silicone-free foam-breaking polymer (E) is added to the product as a coating material for molded articles and members, both liquid resistance and durability against UV absorbers contained in cosmetics and the like are achieved. In addition, it has excellent properties such as abrasion resistance, scratch resistance, oleic acid resistance, water resistance, stain resistance, and weather resistance, and is an anti-UV absorbent polyurethane urea resin that is excellent in suppressing foaming of the resin composition during the molding process. It is providing a composition, a molded object using the composition, and a coating material.

  That is, the present invention includes the following embodiments.

[1] Polyurethane urea containing a reaction product of polyol (A), polyisocyanate (B), molecular weight modifier (C), and diamine (D), and a silicone-free foam-breaking polymer (E) A resin composition comprising:
The urea group concentration in the polyurethane urea resin composition is 0.4-1 mmol / g,
The urethane group concentration is 1 mmol / g or less, and the urethane group concentration ratio obtained by the following formula 1 is 40 to 70% by mass.
UV-absorbing polyurethane urea resin composition characterized in that

Urethane group concentration ratio = urethane group concentration x 100 / (urethane group concentration + urea group concentration)
(Equation 1)

  [2] The polyisocyanate (B) is an alicyclic diisocyanate, and the molecular weight modifier (C) is at least one selected from the group consisting of C1-C20 end-capped alcohols and end-capped amines. The UV-absorbing polyurethane urea resin composition as described in [1] above.

  [3] The UV-absorbing polyurethane urea resin composition according to [1] or [2] above has a number average molecular weight based on gel permeation chromatography (GPC) of 30,000 to 100,000. A UV-absorbing polyurethane urea resin composition having a molecular weight distribution of 300,000 or more and an area ratio of 20% or less.

  [4] With respect to the reaction product of the polyol (A), the polyisocyanate (B), the molecular weight modifier (C), and the diamine (D), the silicone-free foam-breaking polymer (E) is 0. The ultraviolet absorber-resistant polyurethane urea resin composition according to any one of [1] to [3] above, which is contained in an amount of 001 to 3.0% by mass.

  [5] A molded article using the ultraviolet ray-resistant polyurethane urea resin composition according to any one of [1] to [4].

  [6] A coating material using the ultraviolet absorbent anti-resisting polyurethane urea resin composition according to any one of [1] to [4].

  [7] A curable composition comprising the ultraviolet ray-resistant polyurethane urea resin composition according to any one of [1] to [4] above and a curing agent.

  By using the UV-absorbing polyurethane urea resin composition of the present invention as a coating material for moldings and members, it is possible to achieve both liquid resistance and durability against UV absorbers contained in cosmetics that could not be achieved in the past. In addition, various properties such as abrasion resistance, scratch resistance, oleic acid resistance, water resistance, stain resistance, and weather resistance can be imparted, and foaming can be suppressed during the molding process. Furthermore, favorable adhesive performance can be provided by mix | blending a hardening | curing agent with a UV absorber resistant polyurethane urea resin composition.

  The UV-absorbing polyurethane urea resin composition of the present invention comprises a reaction product of polyol (A), polyisocyanate (B), molecular weight modifier (C), and diamine (D), and no silicone. A polyurethane urea resin composition containing a foam-breaking polymer (E), wherein the urea group concentration in the resin composition is 0.4 to 1 mmol / g, the urethane group concentration is 1 mmol / g or less, and The urethane group concentration ratio calculated | required by the said Numerical formula 1 is 40-70 mass%, It is characterized by the above-mentioned.

  Here, the ultraviolet absorbent used for the index of the ultraviolet absorbent resistance mentioned in the effect of the present invention will be described in detail. As ultraviolet absorbers, paraaminobenzoic acid type, cinnamic acid type, benzophenone type, salicylic acid type, benzoyltriazole type, other aromatic ultraviolet absorbers mainly contained in cosmetics, etc., and a mixture comprising one or more of these Is mentioned. If the molded product or coating material does not have UV-absorbing properties, it is estimated that the UV absorber will migrate to the molded product or coating material, resulting in deterioration of the appearance of the molded product surface or stickiness. The

<Paraaminobenzoic acid type>
Specific examples of the paraaminobenzoic acid system include, for example, paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl-p-aminobenzoate, isoamyl-p-dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, and the like. It is done.

<Cinnamic acid type>
Specific examples of the cinnamic acid type include, for example, 2-ethoxyethyl-p-methoxycinnamate, ethylhexyl-p-methoxycinnamate, diisopropylmethylcinnamate, diisopropylethylcinnamate, isopropylmethoxycinnamate, 2-ethylhexyl-4. -Methoxycinnamate and the like.

<Benzophenone series>
Specific examples of the benzophenone series include 2-hydroxy-4-methoxybenzophenone, 5-sulfonic acid-2-hydroxy-4-methoxybenzophenone, trihydrad-5-sulfonic acid-2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, 2,2′-hydroxy-4,4′-dimethoxybenzophenone, 2,2′-hydroxy-4,4′-dimethoxy-5,5′-sodium benzophenone disulfonate, 2,2′-4 , 4′-tetrahydroxymenzophenone, sodium hydroxymethoxybenzophenone sulfonate, and the like.

<Salicylic acid type>
Specific examples of salicylic acid series include dipropylene glycol salicylate, 2-ethylhexyl salicylate, 3,3,5-trimethylcyclohexyl salicylate, octyl salicylate, homomenthyl salicylate and the like.

<Benzoyltriazole series>
Specific examples of the benzoyltriazole series include 2- (2-hydroxy-5-methoxypropyl) -benzotriazole, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (3-tert -Butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5- tert-octylphenyl) -2H-benzotriazole and the like.

<Other aromatic UV absorbers>
Specific examples of other aromatic ultraviolet absorbers include, for example, 4-tert-butyl-4′-methoxybenzoylmethane, 4-tert-butylbenzoyl (4-methoxybenzoyl) methane, 3,3-diphenyl-2- Examples include 2-ethylhexyl cyanoacrylate.

  Among these UV absorbers, in particular, ethyl paraaminobenzoate, 2-ethylhexyl-4-methoxycinnamate, 2-hydroxy-4-methoxybenzophenone, 2-ethylhexyl salicylate, salicylic acid-3,3,5-trimethylcyclohexyl 4-tert-butylbenzoyl (4-methoxybenzoyl) methane and 2,3-diethyl-2-cyanoacrylate-2-ethylhexyl can be a significant hindrance to the UV-absorbing property of molded articles and coating materials.

  Further, the polyol (A) used in the present invention is not particularly limited as long as it has the above-mentioned performance. For example, polycarbonate polyol, polycaprolactone polyol, polyester polyol, polyether polyol, polyolefin polyol, An acrylic polyol, a silicone polyol, a castor oil-based polyol, a fluorine-based polyol, and the like can be mentioned. Among these, one or two or more kinds can be used in combination.

  The molecular weight of the polyol (A) is preferably a number average molecular weight of 500 to 50,000, and more preferably 1,000 to 4,000. When the number average molecular weight is less than 500, the UV-absorbing property may be deteriorated. When the number average molecular weight exceeds the upper limit, the heat resistance may be deteriorated.

  The polyol (A) preferably has an active hydrogen group number per molecule, that is, an average functional group number of hydroxyl groups that are active hydrogen groups of the polyol, of 1.9 to 4.0. When the number of active hydrogen groups is less than the lower limit, the wear resistance and mechanical properties may be reduced. Moreover, when exceeding an upper limit, there exists a possibility that a softness | flexibility and ultraviolet absorber resistance may fall.

<Polycarbonate polyol>
Specific examples of the polycarbonate polyol include ethylene glycol, 1,2-propanediol, 1,3 in which R in the following general formula (1) is a divalent C 2-20 aliphatic or alicyclic hydrocarbon. -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, dimer Acid diol, bisphenol A ethylene oxide and propylene oxide adducts, bis β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol and other low molecular polyols, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, and alkylene carbonates such as ethylene carbonate and propylene carbonate , Diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, tetrahydronaphthyl carbonate and the like obtained from dealcoholization reaction and dephenol reaction. . Further, 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, diethylene glycol Propylene 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, Glyce Using one or more of low molecular polyols such as ethylene, trimethylolpropane, pentaerythritol, etc. as initiators, and those obtained by ring-opening addition of either or both of ε-caprolactone and alkyl-substituted ε-caprolactone Can do.

<Polyester polyol>
Specific examples of the polyester polyol 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, and azelaic acid. , Sebacic acid, 1,4-cyclohexyl dicarboxylic 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 acids or anhydrides thereof, 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, , 9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-di 1 of low molecular weight polyols having a molecular weight of 500 or less such as methanol, dimer acid diol, ethylene oxide and propylene oxide adducts of bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like. The thing obtained from a polycondensation reaction with more than a kind can be mentioned. In addition, a polyester-amide polyol obtained by replacing a part of the low molecular polyol with a low molecular polyamine such as hexamethylene diamine, isophorone diamine or 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, diethylene glycol Propylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, Such as pentaerythritol Molecular polyols or compounds having 2 or more, preferably 2 to 3 active hydrogen groups such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine and other low molecular weight polyamines As initiators, polyether polyols 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, aryl glycidyl ethers such as phenyl glycidyl ether And polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as 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 acrylic acid ester and / or methacrylic acid ester (hereinafter referred to as (meth) acrylic acid ester), acrylic acid hydroxy compound and / or methacrylic acid having at least one hydroxyl group in the molecule that can be a reaction point. Examples thereof include those obtained by copolymerizing an acrylic monomer using a thermal compound, a light energy such as an ultraviolet ray or an electron beam, and the like with a hydroxy compound (hereinafter referred to as a (meth) acrylic acid hydroxy compound) and a polymerization initiator.

<(Meth) acrylic acid ester>
Specific examples of (meth) acrylic acid esters include alkyl esters having 1 to 20 carbon atoms. Specific examples of such (meth) acrylate esters 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 Acrylic acid alkyl ester; (meth) acrylic acid ester such as cyclohexyl (meth) acrylate with cycloaliphatic alcohol; (meth) acrylic acid aryl ester such as phenyl (meth) acrylate and benzyl (meth) acrylate Can be mentioned. Such (meth) acrylic acid ester can mention what was individual or combined 2 or more types.

<(Meth) acrylic acid hydroxy compound>
Specific examples of the (meth) acrylic acid hydroxy compound have at least one hydroxyl group in the molecule that can be a reaction point with the polyisocyanate (B), specifically, 2-hydroxyethyl acrylate, Acrylic acid hydroxy compounds such as 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxy-2,2-dimethylpropyl acrylate, and pentaerythritol triacrylate are listed. Moreover, methacrylic acid hydroxy compounds, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethylpropyl methacrylate, and pentaerythritol trimethacrylate, are mentioned. These acrylic acid hydroxy compounds and methacrylic acid hydroxy compounds can be used singly 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, α, ω-dihydroxypolydimethylsiloxane having at least one terminal hydroxyl group in the molecule, α And polysiloxanes such as ω-dihydroxypolydiphenylsiloxane.

<Castor oil-based polyol>
Specific examples of the castor oil-based polyol include linear or branched polyester polyols obtained by a reaction between a castor oil fatty acid and a polyol. Dehydrated castor oil, partially dehydrated castor oil partially dehydrated, and hydrogenated castor oil added with hydrogen can also be used.

<Fluorine-based polyol>
A specific example of the fluorine-based polyol is 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 fluorine-containing monomer is preferably a fluoroolefin, such as tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoromethyltrifluoroethylene, etc. Is 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 hydroxyalkyl vinyl crotonates. And a monomer having a hydroxyl group, such as a hydroxyl group-containing vinyl carboxylate or allyl ester.

  In addition, from the viewpoint of durability, weather resistance, flexibility, etc., a polyol obtained by transesterifying the polycarbonate polyol, the polycaprolactone polyol and an aliphatic glycol is also suitable for the polyol (A). Can be used. The optimum ratio of polycarbonate polyol and aliphatic glycol to polycaprolactone polyol [(polycarbonate polyol + aliphatic glycol) / polycaprolactone polyol] is preferably 99/1 to 60/40 by mass ratio. The copolymer polyols thus obtained can enhance the performance such as durability, weather resistance and flexibility as compared with the case where each is used alone or as a mixture.

<Aliphatic glycol>
Examples of the aliphatic glycol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane. Diol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, etc. be able to.

<Method for producing copolymer polyol>
A known technique can be used as a method for producing the copolymer polyol. In general, polycarbonate polyol, polycaprolactone polyol, and aliphatic glycol are blended and dissolved at 60 ° C. until uniform while bubbling nitrogen gas. Thereafter, the ester exchange reaction is performed at 190 ° C. until the target molecular weight is reached.

  Next, the polyisocyanate (B) used in the UV-absorbing polyurethane urea resin composition of the present invention will be described in detail.

  The polyisocyanate (B) of the present invention is preferably an alicyclic diisocyanate from the viewpoint of resistance to ultraviolet absorbers.

<Alicyclic diisocyanate>
Specific examples of such alicyclic diisocyanates include isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethylxylene diisocyanate, and the like. it can. Among these alicyclic diisocyanates, isophorone diisocyanate is particularly preferable from the viewpoint of UV-absorbing property and productivity.

  In addition, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, isocyanurate group-containing polyisocyanate, uretdione group-containing polyisocyanate, uretdione obtained from these polyisocyanates as long as performance does not deteriorate Group and isocyanurate group-containing polyisocyanate, urethane group-containing polyisocyanate, allophanate group-containing polyisocyanate, burette group-containing polyisocyanate, uretoimine group-containing polyisocyanate and the like can be used in combination.

<Aromatic diisocyanate>
Specific examples of the aromatic diisocyanate include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate mixture, 4,4′-diphenylmethane diisocyanate. 2,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate / 4,4′-diphenylmethane diisocyanate mixture, 4,4′-diphenylether 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 Isocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, can be mentioned 3,3'-dimethoxy-4,4'-diisocyanate.

<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, trioxyethylene diisocyanate and the like. Can be mentioned.

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

  Next, the molecular weight modifier (C) used in the UV-absorbing polyurethane urea resin composition of the present invention will be described in detail.

  The molecular weight modifier (C) of the present invention is preferably selected from at least one type of end-capped alcohol and / or end-capped amine having 1 to 20 carbon atoms. By adjusting the molecular weight, it is possible to enhance the UV absorber resistance.

<End-blocking alcohol>
Specific examples of the end-capped alcohol are monoalcohols having 1 to 20 carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol, 1-tridecanol, 2- Tridecanol, 2-octyldodecanol, 1-pentadecanol, 2-pentadecanol, cyclopentadecanol, palmityl alcohol, stearyl alcohol, cyclopentanol, cyclohexanol, methylcyclohexanol, trimethylcyclohexanol, etc. It can gel alone, or two or more may be used in combination. Among these, from the viewpoint of compatibility, 2-propanol having a side chain, 2-butanol, isobutanol, 2-pentanol, isoamyl alcohol, 2-hexanol, 2-ethyl-1-hexanol, 3, 3, Monoalcohols such as 5-trimethyl-1-hexanol, 2-tridecanol, 2-octyldodecanol, and 2-pentadecanol are preferable because they can provide good UV-absorbing property, and 2-ethyl-1-hexanol is more preferable. preferable.

<End-capped amine>
Specific examples of the end-capped amine are compounds having one functional group of primary amine and secondary amine, such as ethylamine, morpholine, propylamine, butylamine, isobutylamine, tert-butylamine, pentylamine. , Cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, aniline, o-fluoroaniline, m-fluoroaniline, p-fluoroaniline, o -Anisidine, m-anisidine, p-anisidine, o-toluidine, m-toluidine, p-toluidine, 2-naphthylamine, 2-aminobiphenyl, 4-aminobiphenyl, dimethylamine, dibutylamine, Ethylamine, monoethanolamine, diethanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nt-butylethanolamine, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, homopiperazine, N-methylhomopiperazine, 2,6-dimethylpiperazine, N-methylpiperazine, N-ethylpiperazine, N-ethoxycarbonylpiperazine, N-benzylpiperazine, 2,6-dimethylmorpholine, piperidine, 2,6-dimethylpiperidine, 3,3-dimethylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, 4-piperidone ethylene ketal, pyrrolidine, 2,5-dimethylpyrrolidine N- (3-aminopropyl) diethanol Min, N-cyclohexylethanolamine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 3-pyrrolidinol, indoline, iminobenzyl, thiazoline, N-methylcyclohexylamine, pyrrole, 2-methylpyrrole, 2,4-dimethylpyrrole , 2,5-dimethylpyrrole, nitropyrrole, 2-acetylpyrrole, chlorinated pyrrole, brominated pyrrole, iodinated pyrrole, 3-pyrroline, pyrazole, imidazole, 2-pyrazoline, purine, indole, carbazole, N-methylaniline , N-ethylaniline, N-methylbenzylamine, N-methylphenethylamine, diphenylamine and the like, and can be used alone or in combination of two or more. Among these, ethylamine, morpholine, monoethanolamine, propylamine, dibutylamine, diethylamine, diethanolamine, N-methylethanolamine, and N-ethylethanolamine are preferable because they can impart good UV-absorbing property.

Next, the diamine (D) used for the formation of the urea group of the UV-absorbing polyurethane-resin resin composition of the present invention will be described in detail.
As diamine (D) of this invention, it is preferable to use an alicyclic diamine from a viewpoint of ultraviolet-ray absorber resistance.

<Alicyclic diamine>
Examples of such alicyclic diamines include isophorone diamine, cyclohexane diamine, norbornane diamine, hydrogenated tolylene diamine, hydrogenated xylene diamine, and hydrogenated tetramethyl xylene diamine. Among these diamines, isophorone diamine is particularly preferable from the viewpoint of imparting excellent ultraviolet ray resistance.

  In addition, ethylenediamine, butylenediamine, hexamethylenediamine, diphenylmethanediamine, tolylenediamine, xylylenediamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, Di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 2-hydroxy-1,3-propanediamine and the like can be used in combination.

  Next, the silicone-free foam-breaking polymer (E) used for suppressing foaming of the resin composition in the molding process will be described in detail.

  In the present invention, the silicone-free foam-breaking polymer (E) is added to the reaction product of the polyol (A), the polyisocyanate (B), the molecular weight modifier (C), and the diamine (D). To use.

  Examples of the silicone-free foam-breaking polymer (E) of the present invention include BYK-A505 (manufactured by BYK), BYK-A525 (manufactured by BYK), BYK-A535 (manufactured by BYK) and the like. Among these, BYK-A535 is preferable because a good bubble breaking effect can be obtained in the present invention.

  In the present invention, the silicone-free foam-breaking polymer (E) is a reaction product of the polyol (A), the polyisocyanate (B), the molecular weight modifier (C), and the diamine (D). It is preferable to contain 0.001-3.0 mass%, and it is more preferable to contain 0.005-2.5 mass%.

  Furthermore, a silicone-free leveling agent having a defoaming effect or the like can be used in combination with the silicone-free foam-breaking polymer (E). In the present invention, a better foam breaking effect can be obtained by using the silicone-free foam-breaking polymer (E) and the silicone-free leveling agent in combination.

  Examples of leveling agents that do not contain silicone include polyflow no. 75 (manufactured by Kyoeisha Chemical Co., Ltd.), Polyflow No. 77 (manufactured by Kyoeisha Chemical Co., Ltd.), Polyflow No. 90 (manufactured by Kyoeisha Chemical Co., Ltd.), Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), BYK-361N (manufactured by BYK), BYK-356 (manufactured by BYK), disparon OX-77EF (manufactured by Enomoto Kasei Co., Ltd.), disparon 1927 (manufactured by Enomoto Kasei Co., Ltd.) and the like. it can.

  When the silicone-free foam-breaking polymer (E) and the silicone-free leveling agent are used in combination, the silicone-free foam-breaking polymer (E) and the silicone-free leveling agent are added to the resin solids before addition. The silicone-free foam-breaking polymer (E) is preferably used in a combination of 0.001 to 3.0% by mass, the silicone-free leveling agent and the like in the range of 0.05 to 3.0% by mass, More preferably, the silicone-free foam-breaking polymer (E) is used in combination in the range of 0.002 to 2.0% by mass, and the silicone-free leveling agent and the like in the range of 0.1 to 2.0% by mass.

  Next, a general method for producing the ultraviolet ray resistant polyurethane urea resin composition of the present invention will be described. Moreover, the manufacturing method of a UV absorber resistant polyurethane urea resin composition is not restricted to this.

<Method for producing UV-absorbing polyurethane urea resin composition>
First step: A polyol (A) and a polyisocyanate (B) are charged in an excess amount of an isocyanate group, and urethanized in the presence or absence of an organic solvent, preferably at 20 to 100 ° C. To produce isocyanate group-terminated prepolymer I.
Second step: Isocyanate group-terminated prepolymer I and molecular weight modifier (C) are preferably reacted at 20 to 100 ° C. to produce isocyanate group-terminated prepolymer II.
Third step: The isocyanate group-terminated prepolymer II, the diamine (D) and, if necessary, the molecular weight modifier (C) are preferably subjected to a urea reaction at 20 to 60 ° C.
Moreover, in a series of manufacturing processes, in order to suppress the reaction between isocyanate groups and moisture, the reaction is preferably allowed to proceed under a nitrogen gas or a dry air stream.

<First step: step of producing isocyanate group-terminated prepolymer I>
As the “amount of excess isocyanate group” in the first step, for example, the molar ratio between the isocyanate group of the organic diisocyanate (B) and the hydroxyl group of the polyol (A) is R = isocyanate group / It is preferable to charge so that it may become 1.5-3.0 in a hydroxyl group, and it is still more preferable to charge so that it may become R = 1.8-2.7. When the isocyanate group is less than the lower limit, a large number of urethane groups are introduced into the resin skeleton, which may cause a decrease in UV-absorbing property. When the isocyanate group exceeds the upper limit, a urea compound is generated, which may cause turbidity or formation of aggregates, which is not preferable.

  Moreover, 20-120 degreeC is preferable and, as for the reaction temperature of urethanation reaction, 50-100 degreeC is more preferable. The urethanization reaction proceeds even without a catalyst, but a known urethanization reaction catalyst can be used to accelerate the reaction.

<Urethaneization reaction catalyst>
Specific examples of catalysts that can be used in the urethanization reaction include, for example, organic metal compounds such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof. Can do.

  The reaction time of the urethanization reaction varies depending on the presence or absence of the catalyst, the type, and the temperature, but is generally within 10 hours, preferably 1 to 5 hours is sufficient. In addition, problems such as coloring may occur as the reaction time increases.

  In addition, as the organic solvent used for the production of the UV-absorbing polyurethane urea resin composition, a solvent that does not affect the reaction in the presence of the organic solvent is appropriately selected.

<Organic solvent used for production>
Specific examples of the organic solvent include aliphatic hydrocarbons such as octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethyl acetate, propyl acetate, and butyl acetate. , Esters such as isobutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, glycol ether esters such as 3-methyl-3-methoxybutyl acetate and ethyl-3-ethoxypropionate, ethers such as dioxane Halogenated hydrocarbons such as methylene iodide and monochlorobenzene, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphonilamide, etc. Such as sexual aprotic solvents. These solvents can be used alone or in combination of two or more.

<Second step: Step of producing isocyanate group-terminated prepolymer II>
In the second step, it is preferable to produce the isocyanate group-terminated prepolymer II by reacting the molecular weight modifier (C) with the isocyanate group-terminated prepolymer I obtained in the first step.
Moreover, unless the said performance falls, molecular weight regulator (C) can also be used at a 3rd process. Here, the modification amount of the molecular weight modifier (C) is preferably modified by 1 to 3 mol% with respect to the isocyanate group of the polyisocyanate (B). When the amount of modification is less than the lower limit, there is a risk of deteriorating the UV-absorbing property. Moreover, when exceeding an upper limit, there exists a possibility of causing a heat resistant fall.

<Third step: Step of urea-forming isocyanate group-terminated prepolymer II>
In the third step, a urea reaction is carried out with the mixture of the isocyanate group-terminated prepolymer II and the diamine (D) or the diamine (D) and the molecular weight modifier (C) produced in the second step, and the number average molecular weight is 60, 000-100,000 UV-absorbing polyurethane urea resin compositions of the present invention can be obtained. In addition, the molar ratio of the diamine (D) and the molecular weight modifier (C) used in the second step or the third step is charged so that the diamine (D) / molecular weight modifier (C) = 10-20. It is preferable. When this molar ratio is less than 10, the mechanical properties may be deteriorated. Moreover, when it exceeds 20, there exists a possibility of causing the fall of heat resistant ultraviolet-ray absorber property.

  The number-average molecular weight of the ultraviolet ray resistant polyurethane urea resin composition thus obtained is preferably in the range of 30,000 to 100,000, and more preferably in the range of 35,000 to 90,000. If the number average molecular weight is less than 30,000, the heat resistance may be lowered, and if it exceeds 100,000, the ultraviolet absorbent resistance may be lowered. Further, the molecular weight distribution based on GPC is preferably such that the molecular weight of 300,000 or more is 20% or less in terms of area ratio, and if it exceeds the upper limit value, the UV-absorbing property may be lowered.

  The viscosity of the UV-absorbing polyurethane urea resin composition is not particularly limited, but is preferably 4,000 to 25,000 mPa · s at 25 ° C., more preferably 5,000 to 20, 000 mPa · s. If the viscosity exceeds the upper limit, the workability may be lowered.

  Moreover, in this invention, it becomes possible to improve adhesive performance by using a hardening | curing agent.

<Curing agent>
Specific examples of the curing agent include the above-mentioned aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, isocyanurate group-containing polyisocyanate obtained using these polyisocyanates as raw materials, uretdione group-containing polyisocyanate, Uretodione group and isocyanurate group-containing polyisocyanate, urethane group-containing polyisocyanate, allophanate group-containing polyisocyanate, burette group-containing polyisocyanate, uretoimine group-containing polyisocyanate and the like can be used.

  Among these, it is preferable to use an isocyanurate group-containing polyisocyanate of an aliphatic diisocyanate.

  The ultraviolet-resistant absorbent polyurethane urea resin composition obtained according to the present invention includes, for example, an antioxidant, an ultraviolet absorbent, a pigment, a dye, a solvent, a flame retardant, a hydrolysis inhibitor, and a lubricant as necessary. Additives such as plasticizers, fillers, antistatic agents, dispersants, catalysts, storage stabilizers, surfactants, and leveling agents can be appropriately blended.

  Next, a molded body using the UV-absorbing polyurethane urea resin composition of the present invention and a method for processing the coating material will be described.

  The UV-absorbing polyurethane urea resin composition of the present invention is used as a molded product and a coating material for electronic device members such as communication tablets, clothing, furniture / home appliance members, daily goods, and automobile members.

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

  As the coating material, the UV-absorbing polyurethane urea resin composition of the present invention is mixed with the above-mentioned crosslinking agents and additives as necessary, and after uniform stirring, spray coating, knife coating, wire bar It is a coating film formed on a substrate by a known technique such as coating, doctor blade coating, reverse roll coating, calendar coating, or the like.

<Base material>
Examples of the base material include stainless steel, phosphate-treated steel, zinc steel, iron, copper, aluminum, brass, glass, 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, chlorination Polyolefin resin, polyolefin resin, polyamide resin, polyether ether ketone resin, polyphenylene sulfide resin, NBR resin, chloroprene resin, SBR resin, SEBS resin, polyethylene, polypropylene Base materials molded from materials such as olefin resin such as polyethylene, polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyethylene resin, polypropylene resin, polystyrene resin, 6-nylon resin, 6,6-nylon resin And inorganic fibers such as organic fibers and glass wool mainly composed of at least one selected from acrylic resins, polyvinyl alcohol resins, cellulose, polylactic acid, cotton, and wool, and carbon fibers.

  In order to increase the adhesion of these substrates, the substrate surface can be previously subjected to treatment such as corona discharge treatment, flame treatment, ultraviolet irradiation treatment, and ozone treatment.

  Moreover, it is preferable to apply | coat so that it may become at least 40 g / m <2> or more as conversion amount of resin solid content as a coating material application amount. When it is less than the lower limit, there is a risk of lowering the ultraviolet absorber resistance, wear resistance, and scratch resistance.

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

<Synthesis of UV-absorbing polyurethane urea resin composition>
<Example 1>
In a four-liter flask having a capacity of 2 liters equipped with a stirrer, a thermometer, a heating device, and a distillation tower, 252 g of polyol 1, 350 g of N, N-dimethylformamide (hereinafter referred to as DMF), methyl ethyl ketone ( In the following, 350 g of MEK was charged, and nitrogen gas was bubbled while stirring uniformly at 45 ° C. to prepare a polymer polyol solution. To this polymer polyol solution, 13.5 g of hexamethylene diisocyanate (manufactured by Tosoh Corporation, NCO content: 49.9 mass%, hereinafter referred to as HDI) and isophorone diisocyanate (manufactured by Evonik Japan, NCO content: 37.5% by mass, hereinafter referred to as IPDI) was charged, and urethanation reaction was carried out at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 0.8% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 1.6 g of 2-tridecanol and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.8% by mass. 15.0 g of isophorone diamine (hereinafter referred to as IPDA) and 0.4 g of monoethanolamine (hereinafter referred to as MEA) are mixed in advance with the obtained isocyanate group-terminated urethane prepolymer II solution. An amine solution was added and a chain extension reaction was carried out at 40 ° C. for 4 hours to obtain a UV absorber-resistant polyurethane urea resin composition PU-1. The number-average molecular weight of the UV-absorbing polyurethane urea resin composition PU-1 was 85,000, the molecular weight of 300,000 or more in the molecular weight distribution was 10% by area, and the viscosity at 25 ° C. was 13,000 mPa · s. It was.

<GPC: Measurement of molecular weight>
(1) Measuring instrument: HLC-8220 (manufactured by Tosoh Corporation)
(2) Column: TSKgel (manufactured by Tosoh Corporation)
・ G3000H-XL
・ G2500H-XL
・ G2000H-XL, G1000H-XL
(3) Carrier: LiBr 0.1% -containing DMF (N, N-dimethylformamide)
(4) Detector: RI (refractive index) detector (5) Temperature: 40 ° C
(6) Flow rate: 1.000 ml / min
(7) Calibration curve: Standard polystyrene (manufactured by Tosoh Corporation)
F-80 (molecular weight: 7.06 × 105, molecular weight distribution: 1.05)
F-20 (molecular weight: 1.90 × 105, molecular weight distribution: 1.05)
F-10 (molecular weight: 9.64 × 104, molecular weight distribution: 1.01)
F-2 (molecular weight: 1.81 × 104, molecular weight distribution: 1.01)
F-1 (molecular weight: 1.02 × 104, molecular weight distribution: 1.02)
A-5000 (molecular weight: 5.97 × 103, molecular weight distribution: 1.02)
A-2500 (molecular weight: 2.63 × 103, molecular weight distribution: 1.05)
A-500 (molecular weight: 5.0 × 102, molecular weight distribution: 1.14)
(8) Sample solution concentration: 0.5% LiBr / DMF solution

<Example 2>
A two-liter four-necked flask equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 250 g of polyol 2, 350 g of DMF, and 350 g of MEK while stirring them uniformly at 45 ° C. Nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 5 g of HDI and 30 g of IPDI, and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 0.7% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 0.5 g of n-butanol, and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.7% by mass. The resulting isocyanate group-terminated urethane prepolymer II solution was added with an amine solution in which 14 g of IPDA and 0.5 g of MEA were mixed in advance, and subjected to chain extension reaction at 40 ° C. for 4 hours to absorb UV rays. An agent-based polyurethane urea resin composition PU-2 was obtained. The number average molecular weight of the UV-absorbing polyurethane urea resin composition PU-2 was 90,000, the molecular weight of 300,000 or more in the molecular weight distribution was 13% by area, and the viscosity at 25 ° C. was 14,000 mPa · s. It was.

<Example 3>
A 4-liter flask with a capacity of 2 liters equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 250 g of polyol 3, 350 g of DMF, and 350 g of MEK while stirring them uniformly at 45 ° C. Nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 5 g of HDI and 30 g of IPDI, and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 0.7% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 0.5 g of n-butanol, and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.7% by mass. The resulting isocyanate group-terminated urethane prepolymer II solution was added with an amine solution in which 14 g of IPDA and 0.5 g of MEA were mixed in advance, and subjected to chain extension reaction at 40 ° C. for 4 hours to absorb UV rays. An agent-based polyurethane urea resin composition PU-3 was obtained. The number average molecular weight of the UV-absorbing polyurethane urea resin composition PU-3 was 95,000, the molecular weight of 300,000 or more in the molecular weight distribution was 15% by area, and the viscosity at 25 ° C. was 18,000 mPa · s. It was.

<Example 4>
A two-liter four-necked flask equipped with a stirrer, thermometer, heating device, and distillation tower is charged with 236 g of polyol 4, 350 g of DMF, and 350 g of MEK while stirring them uniformly at 45 ° C. Nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 47 g of IPDI and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 0.8% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 1 g of 2-ethyl-1-hexanol and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.8% by mass. By adding an amine solution prepared by previously mixing 15.5 g of IPDA and 0.5 g of morpholine to the resulting isocyanate group-terminated urethane prepolymer II solution, the chain extension reaction was carried out at 40 ° C. for 4 hours. UV-absorbing polyurethane urea resin composition PU-4 was obtained. The number average molecular weight of the UV-absorbing polyurethane urea resin composition PU-4 was 85,000, the molecular weight of 300,000 or more in the molecular weight distribution was 10% by area, and the viscosity at 25 ° C. was 13,000 mPa · s. It was.

<Example 5>
A two-liter four-necked flask equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 233 g of polyol 5, 350 g of DMF, and 350 g of MEK while stirring them uniformly at 45 ° C. Nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 50 g of IPDI and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 0.9% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 1 g of 2-ethyl-1-hexanol and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.9% by mass. The resulting isocyanate group-terminated urethane prepolymer II solution was added with an amine solution prepared by previously mixing 16 g of IPDA and 0.5 g of morpholine, and allowed to undergo chain extension reaction at 40 ° C. for 4 hours, thereby preventing UV absorption. An agent-based polyurethane urea resin composition PU-5 was obtained. The number average molecular weight of the UV-absorbing polyurethane urea resin composition PU-5 was 80,000, the molecular weight of 300,000 or more in the molecular weight distribution was 9% by area, and the viscosity at 25 ° C. was 11,000 mPa · s. It was.

<Example 6>
A two-liter four-necked flask equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 236 g of polyol 5, 350 g of DMF, and 350 g of MEK while stirring them uniformly at 45 ° C. Nitrogen gas was bubbled to prepare a polymer polyol solution. 2,4′-diphenylmethane diisocyanate / 4,4′-diphenylmethane diisocyanate mixture (trade name: Millionate NM, NCO content: 33.6% by mass, hereinafter referred to as MDI). ) Was added and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 0.7% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 1 g of 2-ethyl-1-hexanol and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.6% by mass. By adding an amine solution in which 13.5 g of IPDA and 0.5 g of MEA were mixed in advance to the obtained isocyanate group-terminated urethane prepolymer II solution, a chain extension reaction was performed at 40 ° C. for 4 hours. An ultraviolet absorbent polyurethane urea resin composition PU-6 was obtained. The number average molecular weight of the UV-absorbing polyurethane urea resin composition PU-6 was 89,000, the molecular weight of 300,000 or more in the molecular weight distribution was 13% by area, and the viscosity at 25 ° C. was 25,000 mPa · s. It was.

<Example 7>
A 2 liter four-necked flask equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 231.5 g of polyol 4, 350 g of DMF, and 350 g of MEK, and these were uniformly stirred at 45 ° C. Then, nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 53 g of hydrogenated diphenylmethane diisocyanate (manufactured by Bayer, NCO content: 32.0% by mass, hereinafter referred to as hydrogenated MDI), and urethanized at 75 ° C. for 3 hours in a nitrogen stream. By making it react, the isocyanate group terminal urethane prepolymer I solution was obtained. The NCO content of this prepolymer was 0.7% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 1 g of 2-ethyl-1-hexanol and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.7% by mass. The resulting isocyanate group-terminated urethane prepolymer II solution was added with an amine solution in which 14 g of IPDA and 0.5 g of morpholine were mixed in advance, and subjected to chain extension reaction at 40 ° C. for 4 hours, thereby preventing UV absorption. An adhesive polyurethane urea resin composition PU-7 was obtained. The number-average molecular weight of the UV-absorbing polyurethane urea resin composition PU-7 was 84,000, the molecular weight of 300,000 or more in the molecular weight distribution was 11% by area, and the viscosity at 25 ° C. was 20,000 mPa · s. It was.

<Example 8>
A two-liter four-necked flask equipped with a stirrer, thermometer, heating device, and distillation tower is charged with 216 g of polyol 6, 350 g of DMF, and 350 g of MEK, while stirring them uniformly at 45 ° C. Nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 15 g of HDI and 50 g of IPDI, and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 1.5% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 0.3 g of methanol and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 1.4% by mass. The resulting isocyanate group-terminated urethane prepolymer II solution was added with an amine solution prepared by mixing 15 g of IPDA and 0.9 g of morpholine in advance, and allowed to undergo chain extension reaction at 40 ° C. for 4 hours, thereby preventing UV absorption. A base polyurethane urea resin composition PU-8 was obtained. The number average molecular weight of the UV-absorbing polyurethane urea resin composition PU-8 was 80,000, the molecular weight of 300,000 or more in the molecular weight distribution was 8% in area ratio, and the viscosity at 25 ° C. was 20,000 mPa · s. It was.

<Example 9>
A two-liter four-necked flask equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 153 g of polyol 2, 85 g of polyol 7, 350 g of DMF, and 350 g of MEK, and these were placed at 45 ° C. The polymer polyol solution was prepared by nitrogen gas bubbling with uniform stirring. This polymer polyol solution was charged with 48.5 g of IPDI and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 0.7% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 0.5 g of n-butanol, and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.7% by mass. By adding an amine solution in which 12.5 g of IPDA and 0.5 g of morpholine were mixed in advance to the resulting isocyanate group-terminated urethane prepolymer II solution, a chain extension reaction was performed at 40 ° C. for 4 hours. An ultraviolet absorbent polyurethane urea resin composition PU-9 was obtained. The number average molecular weight of the UV-absorbing polyurethane urea resin composition PU-9 was 78,000, the molecular weight of 300,000 or more in the molecular weight distribution was 8% by area ratio, and the viscosity at 25 ° C. was 10,000 mPa · s. It was.

<Example 10>
A 2-liter four-necked flask equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 226 g of polyol 4, 350 g of DMF, and 350 g of MEK while stirring them uniformly at 45 ° C. Nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 52.2 g of IPDI and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 1.1% by mass.
Addition of 21.3 g of IPDA and 0.5 g of morpholine in advance to this isocyanate group-terminated urethane prepolymer I solution, followed by chain extension reaction at 40 ° C. for 4 hours, prevents UV absorption A solid polyurethane urea resin composition PU-10 was obtained. The number average molecular weight of the UV-absorbing polyurethane urea resin composition PU-10 was 130,000, the molecular weight of 300,000 or more in the molecular weight distribution was 25% by area, and the viscosity at 25 ° C. was 35,000 mPa · s. It was.

<Example 11>
A four-necked flask with a capacity of 2 liters equipped with a stirrer, thermometer, heating device and distillation tower is charged with 324 g of polyol 5, 300 g of DMF, and 300 g of MEK while stirring them uniformly at 45 ° C. Nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 60 g of IPDI and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 0.9% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 1 g of 2-ethyl-1-hexanol and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.6% by mass. To the obtained isocyanate group-terminated urethane prepolymer II solution, an amine solution prepared by previously mixing 11 g of IPDA and 4 g of MEA is added, and subjected to a chain extension reaction at 40 ° C. for 4 hours. -Based polyurethane urea resin composition PU-11 was obtained. The number average molecular weight of the UV-absorbing polyurethane urea resin composition PU-11 was 40,000, the molecular weight of 300,000 or more in the molecular weight distribution was 5% by area, and the viscosity at 25 ° C. was 6,000 mPa · s. It was.

<Comparative Example 1>
A four-necked flask with a capacity of 2 liters equipped with a stirrer, a thermometer, a heating device and a distillation tower was charged with 148 g of polyol 6, 350 g of DMF and 350 g of MEK while stirring them uniformly at 45 ° C. Nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 62 g of MDI and 55 g of IPDI, and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 3.5% by mass.
35 g of 1,4-butanediol was added to this isocyanate group-terminated urethane prepolymer I solution, and a chain extension reaction was carried out at 75 ° C. under a nitrogen stream to obtain a polyurethane resin composition PU-12. The number average molecular weight of the polyurethane resin composition PU-12 was 85,000, the molecular weight of 300,000 or more in the molecular weight distribution was 11% by area ratio, and the viscosity at 25 ° C. was 10,000 mPa · s.

<Comparative example 2>
A 2-liter four-necked flask equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 260 g of polyol 1, 350 g of DMF, and 350 g of MEK, and nitrogen was stirred uniformly at 45 ° C. A solution of a polymer polyol was prepared by gas bubbling. This polymer polyol solution was charged with 13 g of MDI and 17 g of IPDI, and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 0.5% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 0.5 g of n-butanol, and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.5% by mass. A polyurethane urea resin is obtained by adding an amine solution prepared by previously mixing 9 g of IPDA and 0.5 g of MEA to the resulting isocyanate group-terminated urethane prepolymer II solution and subjecting it to chain extension reaction at 40 ° C. for 4 hours. Composition PU-13 was obtained. The number average molecular weight of the polyurethane urea resin composition PU-13 was 75,000, the molecular weight of 300,000 or more in the molecular weight distribution was 8% by area, and the viscosity at 25 ° C. was 15,000 mPa · s.

<Comparative Example 3>
A 2 liter four-necked flask equipped with a stirrer, thermometer, heating device and distillation tower was charged with 196.5 g of polyol 2, 350 g of DMF and 350 g of MEK, and these were uniformly stirred at 45 ° C. Then, nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 65 g of IPDI and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 2.0% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 1.5 g of 2-ethyl-1-hexanol and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. It was. The NCO content of this prepolymer was 1.9% by mass. A polyurethane urea resin composition is prepared by adding an amine solution prepared by previously mixing 36 g of IPDA and 1 g of MEA to the resulting isocyanate group-terminated urethane prepolymer II solution and subjecting it to chain extension reaction at 40 ° C. for 4 hours. PU-14 was obtained. The number average molecular weight of polyurethane urea resin composition PU-14 was 90,000, the molecular weight of 300,000 or more in the molecular weight distribution was 12% by area ratio, and the viscosity at 25 ° C. was 30,000 mPa · s.

<Comparative example 4>
A four-necked flask with a capacity of 2 liters equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 239 g of polyol 6, 350 g of DMF, and 350 g of MEK while stirring them uniformly at 45 ° C. Nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 22 g of MDI and 29 g of IPDI, and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 0.5% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 0.9 g of n-butanol and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.5% by mass. The resulting isocyanate group-terminated urethane prepolymer II solution was added with an amine solution in which 8.4 g of IPDA and 0.7 g of MEA were mixed in advance, and subjected to chain extension reaction at 40 ° C. for 4 hours to form polyurethane. Urea resin composition PU-15 was obtained. The number average molecular weight of polyurethane urea resin composition PU-15 was 60,000, the molecular weight of 300,000 or more in the molecular weight distribution was 6% by area ratio, and the viscosity at 25 ° C. was 4,000 mPa · s.

<Comparative Example 5>
A 2-liter four-necked flask equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 194 g of polyol 7, 350 g of DMF, and 350 g of MEK, and nitrogen was stirred uniformly at 45 ° C. A solution of a polymer polyol was prepared by gas bubbling. This polymer polyol solution was charged with 31.5 g of HDI and 43 g of IPDI, and urethanated at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 1.6% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 1 g of 2-ethyl-1-hexanol and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 1.6% by mass. The resulting isocyanate group-terminated urethane prepolymer II solution was added with an amine solution prepared by mixing 30.0 g of IPDA and 0.5 g of MEA in advance, and subjected to a chain extension reaction at 40 ° C. for 4 hours to produce polyurethane. Urea resin composition PU-16 was obtained. The number average molecular weight of the polyurethane urea resin composition PU-16 was 95,000, the molecular weight of 300,000 or more in the molecular weight distribution was 15% by area ratio, and the viscosity at 25 ° C. was 34,000 mPa · s.

<Comparative Example 6>
A two-liter four-necked flask equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 233 g of polyol 5, 350 g of DMF, and 350 g of MEK while stirring them uniformly at 45 ° C. Nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 50 g of IPDI and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 0.9% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 1 g of 2-ethyl-1-hexanol and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.9% by mass. The resulting isocyanate group-terminated urethane prepolymer II solution was added with an amine solution prepared by previously mixing 16 g of IPDA and 0.5 g of morpholine, and allowed to undergo chain extension reaction at 40 ° C. for 4 hours, thereby preventing UV absorption. A base polyurethane urea resin composition PU-17 was obtained. The number average molecular weight of the UV-absorbing polyurethane urea resin composition PU-17 was 80,000, the molecular weight of 300,000 or more in the molecular weight distribution was 9% by area, and the viscosity at 25 ° C. was 11,000 mPa · s. It was.

<Comparative Example 7>
A two-liter four-necked flask equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 233 g of polyol 5, 350 g of DMF, and 350 g of MEK while stirring them uniformly at 45 ° C. Nitrogen gas was bubbled to prepare a polymer polyol solution. This polymer polyol solution was charged with 50 g of IPDI and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer I solution. The NCO content of this prepolymer was 0.9% by mass.
This isocyanate group-terminated urethane prepolymer I solution was charged with 1 g of 2-ethyl-1-hexanol and subjected to a urethanization reaction at 75 ° C. for 3 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer II solution. The NCO content of this prepolymer was 0.9% by mass. The resulting isocyanate group-terminated urethane prepolymer II solution was added with an amine solution prepared by previously mixing 16 g of IPDA and 0.5 g of morpholine, and allowed to undergo chain extension reaction at 40 ° C. for 4 hours, thereby preventing UV absorption. A base polyurethane urea resin composition PU-18 was obtained. The number average molecular weight of the UV-absorbing polyurethane urea resin composition PU-18 was 80,000, the molecular weight of 300,000 or more in the molecular weight distribution was 9% by area, and the viscosity at 25 ° C. was 11,000 mPa · s. It was.

  Next, the silicone-free foam-breaking polymer (E) and, if necessary, the silicone-free leveling agent and the like were blended in each of the obtained compositions as shown in Tables 1 and 2. In Tables 1 and 2, a component that suppresses foaming, such as a silicone-free foam-breaking polymer (E), is referred to as a foam inhibitor.

  Tables 1 and 2 show the blending amounts and properties of the raw materials used for each of the PU-1 to PU-18 resin compositions.

Abbreviations used in Examples, Comparative Examples, Table 1 and Table 2 are as follows.
(1) MDI: 2,4′-diphenylmethane diisocyanate / 4,4′-diphenylmethane diisocyanate mixture (manufactured by Tosoh Corporation, trade name: Millionate NM, NCO content: 33.6% by mass)
(2) HDI: hexamethylene diisocyanate (Tosoh Corporation, NCO content: 49.9% by mass)
(3) IPDI: Isophorone diisocyanate (Evonik Japan, NCO content: 37.8% by mass)
(4) Hydrogenated MDI: hydrogenated diphenylmethane diisocyanate (manufactured by Bayer, NCO content: 32.0% by mass)
(5) Polyol 1: 1,6 hexanediol polycarbonate polyol, number average molecular weight 4,000, average number of functional groups 2
(6) Polyol 2: 1,6 hexanediol polycarbonate polyol, number average molecular weight 3,000, average functional group number 2
(7) Polyol 3: 1,4 butanediol / adipic acid polyester polyol, number average molecular weight 3,000, average number of functional groups 2
(8) Polyol 4: 1,6 hexanediol polycarbonate polyol, number average molecular weight 2,000, average functional group number 2
(9) Polyol 5: 1,6 hexanediol-based polycarbonate polyol (number average molecular weight 2,000) / polycaprolactone polyol (number average molecular weight 2,000) = copolymer polyol having a mass ratio of 7/3, number average molecular weight 2,000 , Average functional group number 2
(10) Polyol 6: 1,6 hexanediol-based polycarbonate polyol, number average molecular weight 1,500, average functional group number 2
(11) Polyol 7: 1,6 hexanediol polycarbonate polyol, number average molecular weight 1,000, average functional group number 2
(12) MEA: Monoethanolamine (13) IPDA: Isophoronediamine (14) DMF: N, N-dimethylformamide (15) MEK: Methyl ethyl ketone (16) Foaming inhibitor 1: Silicone-free foam-breaking polymer (BYK) Product name: BYK-A535)
(17) Foaming inhibitor 2: Acrylic polymer (Kyoeisha Chemical Co., Ltd., trade name: Polyflow No. 90)
(18) Silicone: Silicone-containing foam inhibitor (manufactured by BYK, trade name: BYK-067A)
(19) Urethane group concentration ratio: Urethane group concentration × 100 / (urethane group concentration + urea group concentration)

<Production of coating material>
Each resin composition of the obtained PU-1 to PU-18 was dried to a thickness of 50 μm on one side of a 25 μm-thick biaxially stretched polyethylene terephthalate film (Ester film E5100, manufactured by Toyobo Co., Ltd.). The coating material was produced by applying with a bar coater and drying at 120 ° C. for 10 minutes.

  Tables 3 to 4 show various physical properties of the obtained coating material.

Abbreviations used in Table 3 and Table 4 are as follows.
(1) Compound a: 2-hydroxy-4-methoxybenzophenone (2) Compound b: Salicylic acid-2-ethylhexyl (3) Compound c: Salicylic acid-3,3,5-trimethylcyclohexyl (4) Compound d: 4-tert -Butylbenzoyl (4-methoxybenzoyl) methane (5) Compound e: 3,3-diphenyl-2-cyanoacrylate-2-ethylhexyl As shown in Tables 3 and 4, according to Examples 1 to 11 It has been found that the coating material is excellent in various properties such as ultraviolet absorber resistance, oleic acid resistance, water resistance, stain resistance, weather resistance, and foam suppression. On the other hand, the coating materials of Comparative Examples 1 to 7 were inferior in UV-absorbing agent resistance, heat resistance, and foam suppression properties.

(1) Evaluation test 1:
<Abrasion resistance>
In accordance with JIS L1096, the wearability was measured with a Taber abrasion tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) using a load of 1 kg, a disk rotation speed of 60 rpm × 500 rotations, and a wear wheel H-22.
<Evaluation criteria>
・ Coating film is peeled off or most of it is worn (Evaluation: X)
・ Part of the coating film is worn (evaluation: △)
・ No change in appearance (evaluation: ○)

(2) Evaluation test 2:
<Oleic acid resistance>
10 g / m 2 of oleic acid was applied to the coating film and allowed to stand at 80 ° C. for 24 hours, and then the wiping appearance was visually evaluated.
<Evaluation criteria>
・ A part of coating film to most part dissolved (Evaluation: X)
· Most of the coating film has wrinkles (evaluation: △)
・ Slightly wrinkled coating film (Evaluation: ○)
・ No change in coating film (evaluation: ◎)

(3) Evaluation test 3:
<Ultraviolet absorber resistance>
The following compound was adjusted to 3% with glycerin on the coating film, the adjustment solution was applied at 10 g / m 2, and allowed to stand at 80 ° C. for 24 hours, and then the wiping appearance was visually evaluated.
<Compound>
(1) 2-hydroxy-4-methoxybenzophenone (2) salicylic acid-2-ethylhexyl (3) salicylic acid-3,3,5-trimethylcyclohexyl (4) 4-tert-butylbenzoyl (4-methoxybenzoyl) methane (5 ) 3,3-Diphenyl-2-cyanoacrylate-2-ethylhexyl <Evaluation criteria>
・ Part to most of the coating film dissolved (Evaluation: X)
· Most of the coating film has wrinkles (evaluation: △)
・ Slightly wrinkled coating film (Evaluation: ○)
・ No change in coating film (evaluation: ◎)

(4) Evaluation test 4:
<Tensile properties>
The resin composition of PU-1 to PU-15 is casted to a thickness of 100 μm on the release paper, left at room temperature for 30 minutes, then in a dryer at 60 ° C. for 2 hours, at 120 ° C. for 2 hours. A test piece was prepared by performing heat treatment for 7 hours, followed by curing for 7 days in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The obtained test piece was measured for tensile properties according to JIS K6251.
Test apparatus: Tensilon UTA-500 (manufactured by A & D)
・ Measurement conditions: 25 ° C. × 50% RH
Head speed: 200mm / min Dumbbell: No. 4

(5) Evaluation test 5:
<Heat resistance>
Test pieces prepared for tensile measurement were processed under the following conditions, and the tensile properties of evaluation test 5 were evaluated.
・ Processing device: Blast constant temperature dryer DRK633DA (manufactured by Advantech)
・ Processing conditions: 120 ° C., air circulation system ・ Processing time: 500 hours

(6) Evaluation test 6
<Hydrolysis resistance>
Test pieces prepared for tensile measurement were processed under the following conditions, and the tensile properties of evaluation test 5 were evaluated.
・ Processing equipment: constant temperature and humidity chamber SH-220 (manufactured by Espec)
・ Processing conditions: 80 ° C. × 95% RH
・ Test time: 500 hours

(7) Evaluation test 7
<Weather resistance>
Test pieces prepared for tensile measurement were processed under the following conditions, and the tensile properties of evaluation test 5 were evaluated.
・ Processing equipment: QUV (manufactured by Q-LAB)
・ Lamp: EL-313
・ Illuminance: 0.59 w / m2
・ Λmax: 313 nm
1 cycle: 12 hours [UV irradiation: 8 hours (temperature 70 ° C.), condensation: 4 hours (temperature 50 ° C.)]
・ Processing time: 720 hours

(8) Evaluation test 8
<Foam suppression>
100 g of the resin composition of PU-1 to PU-18 was taken in a 300 ml transparent container, stirred with a stirrer, and the time for which the bubbles completely disappeared while standing still was measured.
・ Agitator: Three-one motor G600 (manufactured by Shinto Kagaku)
-Stirring conditions: 600 rpm x 1 minute-Measuring conditions: 25 ° C x 50% RH
<Evaluation criteria>
-Time to eliminate bubbles: 3 hours or more (evaluation: x)
-Time to eliminate bubbles: within 3 hours (Evaluation: △)
・ Blowing time: Within 2 hours (Evaluation: ○)
-Time to eliminate bubbles: within 1 hour (Evaluation: ◎)

(9) Evaluation test 9
<Adhesiveness>
Cast a resin composition of PU-1 to PU-18 to a thickness of 70 μm on a PP film subjected to corona discharge treatment with a thickness of 50 μm, and bond it to a woven fabric, at 120 ° C. in a dryer. A heat treatment was performed for 5 minutes, followed by curing for 7 days in an environment of a temperature of 23 ° C. and a relative humidity of 50%, thereby preparing a test piece. The obtained test piece was measured according to JIS K6854-2 for peel adhesive strength.
Test apparatus: Tensilon UTA-500 (manufactured by A & D)
・ Measurement conditions: 25 ° C. × 50% RH
・ Head speed: 200mm / min <Evaluation criteria>
-PP film material destruction: ○
・ Weaving material destruction: ○
・ Peeling due to resin layer failure: △
・ Interface peeling: ×

Claims (7)

A polyurethane urea resin composition comprising a reaction product of a polyol (A), a polyisocyanate (B), a molecular weight modifier (C), and a diamine (D), and a silicone-free foam-breaking polymer (E) Because
The urea group concentration in the polyurethane urea resin composition is 0.4-1 mmol / g,
The urethane group concentration is 1 mmol / g or less, and the urethane group concentration ratio obtained by the following formula 1 is 40 to 70% by mass.
An anti-ultraviolet absorbent polyurethane urea resin composition characterized by that.

Urethane group concentration ratio = urethane group concentration x 100 / (urethane group concentration + urea group concentration)
(Equation 1) The polyisocyanate (B) is an alicyclic diisocyanate, and the molecular weight modifier (C) is at least one selected from the group consisting of C1-C20 end-capped alcohols and end-capped amines. The ultraviolet-ray-absorbing polyurethane urea resin composition according to claim 1. The UV-absorbing polyurethane urea resin composition according to claim 1 or 2 has a number average molecular weight based on gel permeation chromatography (GPC) of 30,000 to 100,000, and 300 in a molecular weight distribution. A UV-absorbing polyurethane urea resin composition having a molecular weight of 1,000 or more and an area ratio of 20% or less. With respect to the reaction product of the polyol (A), the polyisocyanate (B), the molecular weight modifier (C), and the diamine (D), the silicone-free foamable polymer (E) is 0.001 to 3. The ultraviolet-ray-absorbing polyurethane urea resin composition according to any one of claims 1 to 3, which is contained in an amount of 0.0 mass%. A molded article comprising the ultraviolet-absorbing polyurethane urea resin composition according to any one of claims 1 to 4. A coating material comprising the ultraviolet-absorbing polyurethane urea resin composition according to any one of claims 1 to 4. A curable composition comprising the ultraviolet-absorbing polyurethane urea resin composition according to any one of claims 1 to 4 and a curing agent.