JP7576903B2 - Polyurethane urea resin composition and coating agent - Google Patents

Description

The present invention relates to a polyurethane urea resin composition having high heat resistance, a coating agent using the composition, and uses thereof.

Traditionally, polyurethane resins have been widely used as resin components in coating materials, inks, adhesives, paints, and other materials for electronic equipment parts, clothing, furniture and home appliances, daily necessities, construction and civil engineering, and automotive parts, as well as in various molded products such as films and sheets, due to their excellent physical properties such as abrasion resistance, flexibility, flexibility, processability, adhesiveness, and chemical resistance, and their suitability for various processing methods.

Such polyurethane resins are also used in synthetic leather, and because their appearance and texture are similar to natural leather, they are widely used in the fields of clothing, bags, sacks, footwear, etc. For example, it has been proposed to use polyurethane obtained from 4,4'-diphenylmethane diisocyanate (hereinafter also referred to as MDI), polyether, and 4,4'-diaminodiphenylmethane as a leather sheet material (see Patent Document 1). Also, in order to improve the solubility of polyurethane resin in solvents and to reduce the viscosity of the resin solution to improve workability, a urethane resin composition containing an isomer other than 4,4'-diphenylmethane diisocyanate has been proposed (see Patent Document 2).

However, it was insufficient in terms of workability during processing, shape stability when the molded product was exposed to a high-temperature environment, and weather resistance.

Special Publication No. 4-80141 Japanese Patent Application Publication No. 10-8383

The present invention was made in consideration of the above-mentioned background art, and its purpose is to provide a resin composition that has a high softening temperature, excellent weather resistance, and good handling properties.

As a result of intensive research into solving the above problems, the inventors discovered that the above problems could be solved by a polyurethane urea resin composition using a specific polycarbonate diol and a specific polyisocyanate, and thus completed the present invention.

That is, the present invention includes the following embodiments:

[1] A polyurethane urea resin composition obtained from polyol (A), polyisocyanate (B), diamine (C), and monoamine (M), characterized in that polyol (A) contains polycarbonate diol (a1) having a number average molecular weight of 2200 to 6000, polyisocyanate (B) contains alicyclic diisocyanate (b1), and the polyurethane urea resin composition has a number average molecular weight of 30,000 to 90,000.

[2] The polyurethane urea resin composition according to the above [1], characterized in that the polyol (A) contains the polycarbonate diol (a1) and a chain extender (a2), and the chain extender (a2) is a diol having 2 to 8 carbon atoms.

[3] The polyurethane urea resin composition according to [1] or [2] above, characterized in that the alicyclic diisocyanate (b1) contains dicyclohexylmethane-4,4'-diisocyanate and isophorone diisocyanate.

[4] The polyurethane urea resin composition according to any one of [1] to [3] above, characterized in that the diamine (C) contains an alicyclic diamine.

[5] A polyurethane urea resin composition according to any one of [1] to [4] above, having a softening temperature of 150°C or higher.

[6] A coating agent containing the polyurethane urea resin composition described in any one of [1] to [5] above.

[7] The coating agent according to 6 above, characterized in that the polyurethane urea resin composition is used in a one-component system.

[8] A coating film obtained from the coating agent described in [6] or [7] above.

[9] A molded article using the coating agent described in [6] or [7] above.

[10] A method for producing a polyurethane urea resin composition obtained by reacting an isocyanate-terminated prepolymer (P) obtained from a polyol (A) and a polyisocyanate (B) with a diamine (C) and a monoamine (M), characterized in that the polyol (A) contains a polycarbonate diol (a1) having a number average molecular weight of 2200 to 6000, the polyisocyanate (B) contains an alicyclic diisocyanate (b1), and the number average molecular weight of the polyurethane urea resin composition is 30,000 to 90,000.

In the present invention, the softening temperature is an index of the heat resistance of the resulting resin composition, and the higher the softening temperature, the higher the heat resistance.

According to the present invention, it is possible to obtain a polyurethane urea resin composition that has a high softening temperature, excellent weather resistance, and good handling properties.

The polyurethane urea resin composition of the present invention is characterized in that it is a polyurethane urea resin composition obtained from polyol (A), polyisocyanate (B), diamine (C), and monoamine (M).

The polyol (A) of the present invention contains a polycarbonate diol (a1) having a number average molecular weight of 2,200 to 6,000.

Polycarbonate diol (a1) can be obtained by reacting carbonates such as dialkyl carbonates (e.g., dimethyl carbonate, diethyl carbonate), alkylene carbonates (e.g., ethylene carbonate, propylene carbonate), diaryl carbonates (e.g., diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, tetrahydronaphthyl carbonate), and the like, with glycol.

The glycol is selected from the group of low molecular weight diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, and xylylene glycol. These may be used alone or in combination of two or more.

In the present invention, the polycarbonate diol (a1) is preferably an alkylene carbonate as a carbonate, and is preferably 1,6-hexanediol as a glycol, because it can increase the softening temperature of the resulting polyurethane urea resin and is easily available.

In the present invention, a copolymer polyol obtained by subjecting polycarbonate diol (a1) to an ester exchange reaction with polyester polyol (a3) can be used in place of polycarbonate diol (a1).

Examples of the polyester polyol (a3) include polyester polyols obtained from glycol and dicarboxylic acid components, and those obtained by ring-opening addition polymerization of cyclic ester compounds such as lactones using glycol as an initiator.

Examples of the glycols 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-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, and the like. Trimethylolpropane, glycerin, pentaerythritol, sorbitol, and the like can be used in combination.

Polyester polyols prepared by known condensation methods of these alcohols with dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, adipic acid, tartaric acid, pimelic acid, sebacic acid, phthalic acid, and terephthalic acid can be used.

Preferred lactones include, for example, β-propiolactone, β-butyrolactone, γ-butyrolactone, β-valerolactone, γ-valerolactone, δ-valerolactone, α-caprolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, 4-methylcaprolactone, γ-caprylolactone, ε-caprylolactone, and ε-palmitolactone. One or more of these may be used in combination. Among these, a ring-opening addition polymer of ε-caprolactone using ethylene glycol as an initiator is preferred from the standpoint of stability during polymerization and economic efficiency.

When using a copolymer polyol obtained by transesterifying polycarbonate diol (a1) and polyester polyol (a3), the mass ratio of polycarbonate diol (a1) to polyester polyol (a3) is preferably in the range of (a1)/(a3) = 95/5 to 50/50, more preferably in the range of (a1)/(a3) = 90/10 to 60/40.

By setting the mass ratio within these ranges, the balance between the cohesive strength of the polycarbonate diol, the urethane group concentration, and the polyester polyol content can improve both flexibility and adhesion to the substrate.

The number average molecular weight of the polycarbonate diol (a1) is in the range of 2200 to 6000, and in consideration of the high softening temperature characteristics, ease of synthesis, and ease of handling, the range of 2500 to 4000 is preferable, and the range of 2800 to 3500 is even more preferable. The number average molecular weight of the copolymer polyol obtained by the ester exchange reaction of the polycarbonate diol (a1) and the polyester polyol (a3) is also the same.

The polyisocyanate (B) in the present invention includes an alicyclic diisocyanate from the viewpoint of weather resistance. Examples of alicyclic diisocyanates include isophorone diisocyanate (hereinafter referred to as IPDI), cyclohexane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (hereinafter referred to as hydrogenated diphenylmethane diisocyanate or hydrogenated MDI), norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate. Among these alicyclic diisocyanates, IPDI and hydrogenated MDI are preferred, and it is particularly preferred to use the above two in combination from the viewpoints of flexibility, durability, and productivity.

When IPDI and hydrogenated MDI are used in combination, the mass ratio of IPDI to hydrogenated MDI is preferably in the range of 10/90 to 75/25, and more preferably in the range of 10/90 to 40/60.

In addition, aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, aromatic aliphatic diisocyanates, isocyanurate group-containing polyisocyanates obtained from these polyisocyanates as raw materials, uretdione group-containing polyisocyanates, uretdione group- and isocyanurate group-containing polyisocyanates, urethane group-containing polyisocyanates, allophanate group-containing polyisocyanates, biuret group-containing polyisocyanates, uretoimine group-containing polyisocyanates, etc. can be used in combination to the extent that performance is not reduced.

Examples of the diamine (C) of the present invention include alicyclic diamines such as isophoronediamine, cyclohexanediamine, norbornanediamine, hydrogenated tolylenediamine, hydrogenated xylenediamine, and hydrogenated tetramethylxylenediamine, and diamines other than alicyclic diamines such as ethylenediamine, butylenediamine, hexamethylenediamine, diphenylmethanediamine, tolylenediamine, xylylenediamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, and 2-hydroxy-1,3-propanediamine, which may be used alone or in combination of two or more.

Of these diamines, it is preferable to use alicyclic diamines, and it is more preferable to use isophorone diamine because of the balance between flexibility and durability.

The monoamine (M) of the present invention is not particularly limited, but examples thereof include ethylamine, morpholine, propylamine, dibutylamine, diethylamine, monoethanolamine, dibutylamine monoethanolamine, diethanolamine, N-methylethanolamine, N-ethylethanolamine, N-n-butylethanolamine, N-t-butylethanolamine, hydroxyethylpiperazine, N-(3-aminopropyl)diethanolamine, and N-cyclohexylethanolamine. Among these, monoethanolamine is preferred from the viewpoints of reactivity and molecular weight control.

In the present invention, a chain extender (a2) may be used as necessary. The chain extender is not particularly limited, but examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,4-bis(β-hydroxyethoxy)benzene, neopentyl glycol, methyloctanediol, 1,9-nonanediol, bisphenol, cyclohexanedimethanol, dimethylolheptane, and polypropylene glycol. Among these, diols having 2 to 8 carbon atoms are preferred, and 1,4-butanediol and 1,6-hexanediol are preferred from the perspective of the balance between durability and flexibility.

The molar ratio of polycarbonate diol (A) to chain extender (a2), (a2)/(A), is preferably 0.05 to 7, more preferably 0.1 to 5, and particularly preferably 0.2 to 4.

The polyurethane urea resin in the present invention has a number average molecular weight of 30,000 to 90,000, preferably 40,000 to 80,000. If the number average molecular weight is below the lower limit, the softening temperature of the resin composition may decrease. If the number average molecular weight exceeds the upper limit, the viscosity of the resin solution may increase, which may decrease the handleability.

Next, a general method for producing the polyurethane urea resin composition of the present invention will be described with reference to the following example.

First step: Polyol (A) and polyisocyanate (B) are charged so that there is an excess of isocyanate groups, and a urethane reaction is carried out in the presence or absence of an organic solvent to produce an isocyanate-terminated prepolymer (P).

Second step: The isocyanate-terminated prepolymer (P) is reacted with the diamine (C) and monoamine (M) to form a urea compound.

In addition, in the series of manufacturing processes, it is preferable to carry out the reaction under a nitrogen gas or dry air stream in order to suppress the reaction between the isocyanate group and moisture.

In the first step, "so that there is an excess of isocyanate groups" means that when the raw materials are charged, the molar ratio of the isocyanate groups of the polyisocyanate (B) to the hydroxyl groups of the polyol (A) is preferably 1.5 to 3.0, R = isocyanate groups/hydroxyl groups, and more preferably R = 1.8 to 2.7.

The reaction temperature for the urethane reaction is preferably 20 to 120°C, and more preferably 50 to 100°C. Although this urethane reaction will proceed without a catalyst, it is also possible to accelerate the reaction by using a known urethane reaction catalyst.

Catalysts that can be used in the urethane reaction include, for example, organometallic compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dioctyltin dilaurate, and organic amines such as triethylenediamine and triethylamine, and their salts.

The reaction time for the urethane reaction varies depending on the presence or absence of a catalyst, its type, and the temperature, but generally 10 hours or less, and preferably 1 to 5 hours, is sufficient. However, as the reaction time increases, problems such as discoloration may occur.

The organic solvent used in the production of the polyurethane urea resin composition is appropriately selected from those that do not affect the reaction in the presence of the organic solvent.

Examples of organic solvents include aliphatic hydrocarbons such as octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, 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-ethoxypropionate, ethers such as dioxane, halogenated hydrocarbons such as methylene iodide and monochlorobenzene, and polar aprotic solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and hexamethylphosphonylamide. These solvents can be used alone or in combination of two or more.

In the second step, the isocyanate-terminated prepolymer (P) produced in the first step is reacted with diamine (C) and monoamine (M) to form a urea at 20 to 60°C to obtain the polyurethane urea resin of the present invention.

When using the polyurethane urea resin composition of the present invention, it is preferable to use it in a one-component system that does not use a curing agent such as polyisocyanate, since it has a high softening temperature even without the use of a curing agent. The softening temperature can be increased by using a curing agent, but since there is a risk of losing flexibility, the amount used is preferably 10 parts by mass or less, more preferably 3 parts by mass or less, per 100 parts by mass of the polyurethane urea resin composition.

As the curing agent, for example, the above-mentioned aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, araliphatic diisocyanates, isocyanurate group-containing polyisocyanates obtained using these polyisocyanates as raw materials, uretdione group-containing polyisocyanates, uretdione group- and isocyanurate group-containing polyisocyanates, urethane group-containing polyisocyanates, allophanate group-containing polyisocyanates, biuret group-containing polyisocyanates, uretoimine group-containing polyisocyanates, etc. can be used.

The polyurethane urea resin composition obtained by the present invention can be appropriately blended with additives such as antioxidants, ultraviolet absorbers, pigments, dyes, solvents, flame retardants, hydrolysis inhibitors, lubricants, plasticizers, fillers, antistatic agents, dispersants, catalysts, storage stabilizers, surfactants, and leveling agents, as necessary.

The polyurethane urea resin composition of the present invention thus obtained can have a softening temperature of 150°C or higher. By achieving a softening temperature of 150°C or higher, the composition can maintain its shape and function under high temperature conditions, and can be more useful in electronic device components, furniture and home appliance components, daily necessities, automobile components, etc.

Next, we will explain the coating agent using the polyurethane urea resin composition of the present invention, and the coating film and molded article obtained from the coating agent.

The polyurethane urea resin composition of the present invention is suitable for use as a coating agent, coating film, or molded product for electronic device components such as communication tablets, synthetic leather for clothing, bags, pouches, footwear, etc., furniture and home appliance components, daily necessities, and automobile components.

The coating agent is a composition in which the polyurethane urea resin composition of the present invention is mixed with a solvent, additives, etc. as necessary, and can be suitably used, for example, as a paint, adhesive, etc.

The coating film is formed on a substrate by mixing a coating agent containing at least the polyurethane urea resin composition of the present invention with the above-mentioned crosslinking agent and additives as necessary, stirring the mixture uniformly, and then applying the mixture to a substrate by known techniques such as spray coating, knife coating, wire bar coating, doctor blade coating, reverse roll coating, and calendar coating.

Molded products include components, structures, films, and sheets, including those molded by known techniques such as casting and coating.

The substrates include stainless steel, phosphate-treated steel, galvanized 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, phenolic resin, melamine resin, polyacetal resin, chlorinated polyolefin resin, polyolefin resin, polyamide resin, polyether ether ketone Examples of such materials include substrates molded from materials such as olefin resins such as styrene resin, polyphenylene sulfide resin, NBR resin, chloroprene resin, SBR resin, SEBS resin, polyethylene, and polypropylene; organic fibers containing at least one main component selected from polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyethylene resin, polypropylene resin, polystyrene resin, 6-nylon resin, 6,6-nylon resin, acrylic resin, polyvinyl alcohol resin, cellulose, polylactic acid, cotton, and wool; inorganic fibers such as glass wool; and carbon fibers.

To improve adhesion, the surfaces of these substrates can be pretreated with corona discharge, flame treatment, ultraviolet light irradiation, ozone treatment, etc.

The following describes examples of the present invention, but the present invention is not limited to these examples.

[Synthesis of polyurethane urea resin composition]
[Example 1]
In a 2-liter four-neck flask equipped with a stirrer, a thermometer, a heating device, and a distillation column, 159 g of polycarbonate diol 1 (1,6-hexanediol-based polycarbonate polyol, number average molecular weight 3,000) and 700 g of N,N-dimethylformamide (hereinafter referred to as DMF) were charged, and these were uniformly stirred at 45°C while bubbling with nitrogen gas to prepare a polymer polyol solution. 14 g of isophorone diisocyanate (hereinafter referred to as IPDI) and 49 g of hydrogenated diphenylmethane diisocyanate (hereinafter referred to as hydrogenated MDI) were charged into this polymer polyol solution, and a urethane reaction was carried out at 75°C for 2 hours under a nitrogen gas flow to obtain an isocyanate group-terminated urethane prepolymer (P) solution. The NCO content of this prepolymer solution was 1.1% by mass.

An amine solution in which 20 g of isophorone diamine (hereinafter referred to as IPDA) and 2 g of monoethanolamine (hereinafter referred to as MEA) were mixed in advance was added to the obtained isocyanate group-terminated urethane prepolymer (P) solution, and a chain extension reaction was carried out at 40°C for 2 hours to obtain a polyurethane urea resin composition. The number average molecular weight of the obtained polyurethane urea resin composition measured by GPC was 75,000, and the viscosity at 25°C was 20,000 mPa·s.

[GPC: Molecular weight measurement conditions]
(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: THF (tetrahydrofuran)
(4) Detector: RI (refractive index) detector (5) Temperature: 40° C.
(6) Flow rate: 1.000ml/min
(7) Calibration curve: Standard polystyrene (manufactured by Tosoh Corporation)
・F-80 (molecular weight: 7.06×10 ⁵ , molecular weight distribution: 1.05)
・F-20 (molecular weight: 1.90×10 ⁵ , molecular weight distribution: 1.05)
・F-10 (molecular weight: 9.64×10 ⁴ , molecular weight distribution: 1.01)
・F-2 (molecular weight: 1.81×10 ⁴ , molecular weight distribution: 1.01)
・F-1 (molecular weight: 1.02×10 ⁴ , molecular weight distribution: 1.02)
・A-5000 (molecular weight: 5.97×10 ³ , molecular weight distribution: 1.02)
・A-2500 (molecular weight: 2.63×10 ³ , molecular weight distribution: 1.05)
・A-500 (molecular weight: 5.0×10 ² , molecular weight distribution: 1.14)
(8) Sample solution concentration: 0.5% THF solution.

[Synthesis of other polyurethane urea resin compositions]
The polyurethane urea resins of Examples 2 to 5 and Comparative Examples 1 to 3 were synthesized in the same manner as in the production of the polyurethane urea resin composition of Example 1, with the charging compositions of the respective raw materials (amounts blended on a mass basis) being as shown in Table 1.

[Preparation of film using polyurethane urea resin composition]
The obtained polyurethane urea resin composition was applied onto a release paper so as to give a dry film thickness of 60 μm, and after standing at room temperature for 20 minutes, it was heat-treated in a dryer at 60° C. for 20 minutes and then at 120° C. for 20 minutes, and then aged at 40° C. for 24 hours to obtain a film. The physical properties of this film were evaluated.

[Evaluation Test 1]
[Tensile properties]
The tensile properties of the obtained film were measured in accordance with JIS K6251. The results are shown in Tables 1 and 2.
Test equipment: Tensilon UTA-500 (manufactured by A&D Co., Ltd.)
Measurement conditions: 25°C x 50% RH
・Head speed: 200 mm/min・Dumbbell No. 4.

[Evaluation Test 2]
[Softening temperature]
A test piece was obtained from the obtained film using a dumbbell, and a 2 cm mark was drawn on the test piece, and the thickness at the center of the mark was measured. A weight of a predetermined weight was attached to one grip of the test piece, and the other grip was clamped with a double clip, and the test piece was hung in a dryer so that the clip was on the upper side. The temperature in the dryer was then increased, and the distance between the marks was observed. The temperature at which the distance between the marks reached 4 cm was read as the softening temperature. If this softening temperature was 150°C or higher, it could be said that the evaluation was good. The results are shown in Tables 1 and 2.
Processing equipment: constant temperature blower dryer DRK633DA (manufactured by Advantec)
Weight of weight: thickness of center of gauge line (μm) × 0.05g
・Dumbbell No. 2 (JIS K6251 compliant)
Heating rate: 5°C/min.

[Evaluation Test 3]
[Handling]
The handleability is considered to be good if the viscosity at 25° C. is 80,000 mPa·s or less.

[Evaluation Test 4]
[Weather resistance]
The obtained film was subjected to a weather resistance treatment under the following conditions, and the color number was measured.
<Weather resistance test>
Processing device: QUV (manufactured by Q-LAB)
・Lamp: EL-313
・Illuminance: 0.59w/ ^m2
・λmax: 313nm
1 cycle: 12 hours (UV irradiation: 8 hours (temperature 70°C), condensation: 4 hours (temperature 50°C)
Processing time: 300 hours <number of colors measured>
The weather-resistant film was measured for b* using a color difference meter (CR-310, manufactured by Konica Minolta, Inc.) A b* value of 1.0 or less can be considered to be good.

[Evaluation Test 5]
[Wear resistance]
According to JIS L1096, the abrasion resistance was measured using a Taber abrasion tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) with a load of 1 kg, a disk rotation speed of 60 rpm x 500 rotations, and an abrasion wheel H-22.
<Evaluation criteria>
・The coating film has peeled off or most of it has worn away (rating: ×)
・Part of the coating film is worn away (Rating: △)
・No change in appearance was observed (rating: ○)

The raw materials used in Tables 1 and 2 are as follows:
(1) IPDI: Isophorone diisocyanate (manufactured by Evonik)
(2) Hydrogenated MDI: Hydrogenated diphenylmethane diisocyanate (manufactured by Sumika Covestro Urethane Co., Ltd.)
(3) MDI-1: 2,2'-MDI+2,4'-MDI=1.8% by mass, 4,4'-MDI=98.2% by mass
(4) MDI-2: 2,2'-MDI+2,4'-MDI=93.0 mass%, 4,4'-MDI=7.0 mass%
*MDI: Diphenylmethane diisocyanate (manufactured by Tosoh Corporation)
(5) Polyol-1: 1,6 hexanediol-based polycarbonate polyol, number average molecular weight 3,000
(6) Polyol-2: 1,6 hexanediol-based polycarbonate polyol (number average molecular weight 3,000) / polycaprolactone polyol (number average molecular weight 3,000) = copolymer polyol with a mass ratio of 7/3, number average molecular weight 3,000
(7) Polyol-3: 1,6 hexanediol-based polycarbonate polyol, number average molecular weight 2,500
(8) Polyol-4: 1,6 hexanediol-based polycarbonate polyol, number average molecular weight 2,000
(9) 1,4-BG: 1,4-butanediol (manufactured by Mitsubishi Chemical Corporation)
(10) 1,6-HG: 1,6-hexanediol (manufactured by Ube Industries, Ltd.)
(11) IPDA: Isophoronediamine (manufactured by Evonik)
(12) DMF: N,N-dimethylformamide (manufactured by Mitsubishi Gas Chemical Company, Inc.)
(13) MEK: Methyl ethyl ketone (manufactured by Maruzen Oil Co., Ltd.)

Claims (10)

A polyurethane urea resin composition obtained from a polyol (A), a polyisocyanate (B), a diamine (C), and a monoamine (M),
The polyol (A) contains a polycarbonate diol (a1) having a number average molecular weight of 2,200 to 6,000;
The polyisocyanate (B) contains an alicyclic diisocyanate (b1),
The alicyclic diisocyanate (b1) includes dicyclohexylmethane-4,4'-diisocyanate and isophorone diisocyanate;
The polyurethane urea resin composition has a number average molecular weight of 30,000 to 90,000. The ratio of dicyclohexylmethane-4,4'-diisocyanate to isophorone diisocyanate is
Isophorone diisocyanate:dicyclohexylmethane-4,4'-diisocyanate=22.03:77.97-70.59:29.41
The polyurethane urea resin composition according to claim 1, The polyol (A) contains the polycarbonate diol (a1) and a chain extender (a2),
3. The polyurethane urea resin composition according to claim 1, wherein the chain extender (a2) is 1,4-butanediol or 1,6-hexanediol . The polyurethane urea resin composition according to any one of claims 1 to 3, having a softening temperature of 170°C or higher. 4. The polyurethane urea resin composition according to claim 1, which has a softening temperature of 180° C. or higher. A coating agent comprising the polyurethane urea resin composition according to any one of claims 1 to 5. The coating agent according to claim 6, characterized in that the polyurethane urea resin composition is used in a one-component system. A coating film obtained from the coating agent according to claim 6 or 7. A molded article using the coating agent according to claim 6 or 7. A method for producing a polyurethane urea resin composition obtained by reacting an isocyanate-terminated prepolymer (P) obtained from a polyol (A) and a polyisocyanate (B), with a diamine (C) and a monoamine (M), comprising the steps of:
The polyol (A) contains a polycarbonate diol (a1) having a number average molecular weight of 2,200 to 6,000;
The polyisocyanate (B) contains an alicyclic diisocyanate (b1),
The alicyclic diisocyanate (b1) includes dicyclohexylmethane-4,4'-diisocyanate and isophorone diisocyanate;
The polyurethane urea resin composition has a number average molecular weight of 30,000 to 90,000.