WO2020213747A1 - Urethane resin composition and film - Google Patents

Abstract

The problem addressed by the present invention is to balance flexibility, scratch resistance, and solvent resistance. The urethane resin composition of the present invention contains a base resin (i), a curing agent (ii), and a lubricant (iii) and is characterized in that the base resin (i) includes a polymer (A), the polymer (A) is a polyol (a) or the reaction product of a polyol (a) and a polyisocyanate (b) and has a hydroxyl group, the polyol (a) includes a polycarbonate polyol (a1) that is liquid at 25°C, the curing agent (ii) includes a polyisocyanate compound (d), and the lubricant (iii) includes a compound (B) represented by formula (1). [In formula (1), R¹ and R² each independently represent a methyl group or a hydroxyl group. n represents an integer of 1-3,000.]

Description

Urethane resin composition and film

The present invention relates to urethane resin compositions and films.
The present application claims priority based on Japanese Patent Application No. 2019-080002 filed in Japan on April 19, 2019, the contents of which are incorporated herein by reference.

Urethane resin compositions have excellent flexibility, elasticity, etc., and are used in various applications such as automobile parts, home appliance parts, packaging materials, leather-like sheets, and printing rolls.

As such a urethane resin composition, a polyol having no aromatic ring and a polyisocyanate having an aromatic ring are reacted to produce a urethane prepolymer having an isocyanate group terminal, and the urethane prepolymer is reacted with a branched diol to form a main agent. A urethane resin composition containing a curing agent has been proposed (see, for example, Patent Document 1).

JP-A-2018-150421

However, with the conventionally known resin compositions, there are cases where the compatibility of flexibility, scratch resistance, and solvent resistance is not sufficiently satisfied. The present invention has been made in view of the above circumstances, and an object of the present invention is to achieve both flexibility, scratch resistance, and solvent resistance.

Conventionally, many attempts have been made to increase the hardness of the resin molded product in order to improve the scratch resistance. However, when the hardness of the resin molded product is increased, the hardness of the resin itself has an upper limit, but once the resin is destroyed, the shape is not restored and scratches remain, and as a result, the scratch resistance is sufficiently improved. Sometimes I couldn't. The present inventors have decided to improve the deformation recovery rate while suppressing the hardness of the resin molded product, and further to improve the smoothness of the surface of the resin molded product, in the opposite idea to the conventional attempt to increase the resin hardness. I was inspired.

Therefore, when a polycarbonate diol liquid at 25 ° C. was used as a polyol component to improve the flexibility of the soft segment and a specific slipper imparting agent was added to impart slipperiness, a flexible resin was obtained. Despite this, the synergistic effect of improving the slipperiness of the surface and the effect of stress dispersion brought about by the flexibility leave no scratches on the resin surface, and as a result, resin molding that can achieve both flexibility and scratch resistance. I found that I could get a body. Furthermore, they have found that the problem of solvent resistance can be solved by using a polycarbonate diol, and have completed the present invention.

The resin composition of the present invention contains a main agent (i), a curing agent (ii), and a slipper-imparting agent (iii), and the main agent (i) contains a polymer (A). The polymer (A) is a polyol (a) or a reaction product of the polyol (a) and a polyisocyanate (b), which has a hydroxyl group, and the polyol (a) is a liquid polycarbonate at 25 ° C. The compound (B) containing the polyol (a1), the curing agent (ii) containing the polyisocyanate compound (d), and the slipper-imparting agent (iii) represented by the following formula (1). )including.

 

[In formula (1), R ¹ and R ² each independently represent a methyl group or a hydroxyl group. n represents an integer from 1 to 3,000. ]

The resin composition of the present invention can have both flexibility, scratch resistance, and solvent resistance.

The resin composition of the present invention contains a main agent (i) and a curing agent (ii). In the present invention, the main agent (i) and the curing agent (ii) may each contain components other than the components directly involved in the formation of the cured product (for example, polymers, compounds having a curing action, etc.), and the main agent (i) The composition of i) and the composition of the curing agent (ii) may be used.

The main agent (i) contains a polymer (A) and a compound (B) represented by the following formula (1).

 

[In formula (1), R ¹ and R ² each independently represent a methyl group or a hydroxyl group. n represents an integer from 1 to 3,000. ]

The polymer (A) is a polyol (a) or a reaction product of the polyol (a) and the polyisocyanate (b), and has a hydroxyl group.

The polyol (a) contains a polycarbonate polyol (a1) that is liquid at 25 ° C. (hereinafter, may be referred to as "liquid polycarbonate polyol (a1)").

Examples of the liquid polycarbonate polyol (a1) include an esterification reaction product of a carbonic acid ester and a polyhydric alcohol, and a reaction product of a polyhydric alcohol and a phosgene, which is liquid at 25 ° C.

As the carbonic acid ester, one kind or two or more kinds can be used, for example, an aliphatic carbonate, an alicyclic carbonate (hereinafter, including an alicyclic structure may be referred to as an "alicyclic"). Examples include aromatic carbonates (hereinafter, the inclusion of aromatic structures may be collectively referred to as "aromatic"). Examples of the aliphatic carbonate include saturated aliphatic carbonates such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, ethyl-n-butyl carbonate and ethylisobutyl carbonate; ethylene carbonate, trimethylene carbonate, etc. Tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1, Examples thereof include unsaturated aliphatic carbonates such as 4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate and 2,4-pentylene carbonate. Examples of the aromatic carbonate include diphenyl carbonate and dibenzyl carbonate.

As the polyhydric alcohol, one kind or two or more kinds can be used, for example, ethylene glycol, propylene glycol, butanediol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, diethylene glycol, di. Linear or branched diols such as propylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol, hydrogenated bisphenol A; trimethylolmethane , Trimethylol propane, ditrimethylol propane, pentaerythritol, dipentaerythritol and other trifunctional or higher functional polyols.

The liquid polycarbonate polyol may be liquid at 25 ° C., may be an amorphous or crystalline polycarbonate polyol, and is preferably an amorphous polycarbonate polyol. The number of hydroxyl groups contained in the liquid polycarbonate polyol is preferably 2.

The viscosity of the liquid polycarbonate polyol is preferably 10,000 mPa · s or less, more preferably 7,000 mPa · s or less, still more preferably 5,000 mPa · s or less, for example 100 mPa · s, at room temperature (25 ° C.). As mentioned above, it is preferably 500 mPa · s or more.

The number average molecular weight of the liquid polycarbonate polyol is preferably more than 500, more preferably 600 or more, still more preferably 700 or more, preferably less than 2,000, more preferably 1800 or less, still more preferably 1,500. It is as follows.

In the present specification, the number average molecular weight and the weight average molecular weight represent conversion values obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

The glass transition temperature of the liquid polycarbonate polyol is preferably −100 ° C. or higher, more preferably −90 ° C. or higher, further preferably −80 ° C. or higher, particularly preferably −75 ° C. or higher, and preferably −5 ° C. or lower. It is more preferably −15 ° C. or lower, further preferably −25 ° C. or lower, and particularly preferably −35 ° C. or lower.

The content of the liquid polycarbonate polyol is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and the upper limit is 100% by mass in the polyol (a).

The polyol (a) may contain other polyols (a2) in addition to the polycarbonate polyol (a1) which is liquid at 25 ° C. Examples of the other polyol (a2) include polyester polyols, polyether polyols, polycarbonate polyols other than the liquid polycarbonate polyol (a1), low molecular weight polyols, and the like.

As the polyester polyol, one kind or two or more kinds can be used. For example, a polyester polyol obtained by reacting a low molecular weight polyol with a polycarboxylic acid; a cyclic ester compound such as ε-caprolactone is ring-opened. Polyester polyols obtained by polymerization reaction; polyester polyols obtained by copolymerizing these compounds and the like can be mentioned.

As the low molecular weight polyol used for producing the polyester polyol, one kind or two or more kinds can be used, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1 , 3-Propanediol, Dipropylene glycol, Tripropylene glycol, 1,2-Butandiol, 1,3-Butandiol, 1,4-Butandiol, 2,3-Butandiol, 1,5-Pentanediol, Neo Pentyl glycol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Diol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl- The molecular weight of 1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, glycerin, trimethylolpropane, ditrimethylolpropane, trimethylolpropane, pentaerythritol, etc. is 50. Examples thereof include aliphatic polyols having a temperature of 300 or more; polyols having an alicyclic structure such as cyclohexanedimethanol and hydrogenated bisphenol A; polyols having an aromatic structure such as bisphenol A and bisphenol F.

As the polycarboxylic acid, one kind or two or more kinds can be used, for example, an aliphatic polycarboxylic acid such as succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid; 1,4-cyclohexanedicarboxylic acid, cyclohexane. Alicyclic polycarboxylic acids such as tricarboxylic acids; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; anhydrides or esterified products thereof.

As the polyether polyol, one kind or two or more kinds can be used. For example, a compound obtained by addition polymerization of an alkylene oxide using one kind or two or more kinds of compounds having two or more active hydrogen atoms as an initiator. And so on. Examples of the compound having two or more active hydrogen atoms include propylene glycol, trimethylolglycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, and di. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, water and hexanetriol. Examples of the alkylene oxide include propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

Examples of the polycarbonate polyol other than the liquid polycarbonate polyol (a1) include a polycarbonate polyol that is solid at 25 ° C.

The number average molecular weight of the polyester polyol, the polyether polyol, and the polycarbonate polyol other than the polycarbonate polyol (a1) is preferably more than 300, more preferably 500 or more, still more preferably 700 or more, and preferably 10,000 or less. , More preferably 5,000 or less, still more preferably 4,000 or less.

As the low molecular weight polyol, one kind or two or more kinds can be used, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene. Glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,5-hexane Diol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol , 1,12-Dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2 An aliphatic polyol having a molecular weight of 50 or more and 300 or less, such as -ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, glycerin, trimethylolpropane, ditrimethylolpropane, trimethylolpropane, and pentaerythritol. Examples include polyols having an alicyclic structure such as cyclohexanedimethanol and hydrogenated bisphenol A; polyols having an aromatic structure such as bisphenol A and bisphenol F.

The content of the other polyol is, for example, 30% by mass or less, 20% by mass or less, 10% by mass or less, and the lower limit is 0% by mass in the polyol (a).

As the polyisocyanate (b), one kind or two or more kinds can be used, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aliphatic or alicyclic polyisocyanates. It is preferable to use it. As the aliphatic or alicyclic polyisocyanate, one type or two or more types can be used, for example, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3. -Cyclopentylene diisocyanate, 1,3-cyclohexamethylene diisocyanate, 1,4-cycloheximethylene diisocyanate, 1,3-di (isocyanate methyl) cyclohexane, 1,4-di (isocyanate methyl) cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate and the like can be used. Further, an allophanate-modified product or an isocyanurate-modified product of the aliphatic or alicyclic polyisocyanate can be used. Among these, an allophanate modified or isocyanurate modified product of an aliphatic or alicyclic polyisocyanate is preferable, an isocyanurate modified product of an aliphatic or alicyclic polyisocyanate is more preferable, and an isocyanurate modified product of an aliphatic polyisocyanate is more preferable. Is even more preferable.

The molar ratio (NCO / OH) of the isocyanate group contained in the polyisocyanate (b) to the hydroxyl group contained in the polyol (a) is preferably 0.8 or more, more preferably 0.9 or more, still more preferably 0.9 or more. It is 1.0 or more, preferably 1.3 or less, more preferably 1.2 or less, and further preferably 1.1 or less.

The polymer (A) may be the polyol (a) as it is, or may be produced by reacting the polyol (a) with the polyisocyanate (b).

When reacting the polyol (a) and the polyisocyanate (b), a urethanization catalyst may coexist, if necessary. As the urethanization catalyst, one kind or two or more kinds can be used, and for example, a nitrogen-containing compound such as triethylamine, tributylamine, benzyldibutylamine, triethylenediamine, N-methylmorpholin; or titanium tetrabutoxide, dibutyltin oxide. , Dibutyltin dilaurate, tin 2-ethylcaproate, zinc naphthenate, cobalt naphthenate, zinc 2-ethylcaproate, molybdenum glycolate, potassium acetate, zinc stearate, tin octylate, dibutyltin dilaurate, dioctyltin dineodecanate, etc. Organic metal compounds; or inorganic compounds such as iron chloride and zinc chloride.

A reaction solvent may coexist during the reaction. As the reaction solvent, one kind or two or more kinds can be used, for example, an aromatic hydrocarbon solvent such as toluene and xylene; a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone and acetylacetone; and an ether solvent such as tetrahydrofuran and dioxane. ; Ester solvent such as ethyl acetate and butyl acetate; nitrile solvent such as acetonitrile; amide solvent such as dimethylformamide and N-methylpyrrolidone.

At the time of the reaction, the reaction temperature can be, for example, 50 to 90 ° C., and the reaction time can be, for example, 2 to 24 hours. The reaction pressure may be normal pressure, pressurization, or depressurization. The reaction atmosphere may be an inert gas atmosphere such as nitrogen or argon, or may be a dry air atmosphere, a closed condition, or other conditions where water is not mixed.

The hydroxyl group equivalent of the polymer (A) is preferably 400 g / eq. As mentioned above, more preferably 450 g / eq. The above is preferable, and 4000 g / eq. Hereinafter, more preferably 3000 g / eq. It is as follows.

The curing agent (ii) contains a polyisocyanate compound (d). The polyisocyanate compound (d) has two or more isocyanate groups. As the polyisocyanate compound (d), one kind or two or more kinds can be used. For example, as the diisocyanate compound having two isocyanate groups, an alicyclic structure such as cyclohexanediisocyanate, dicyclohexylmethanediisocyanate, isophoronediisocyanate or the like can be used. Diisocyanates having: Hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, aliphatic diisocyanates such as tetramethylxylylene diisocyanate, and examples of the polyisocyanate compound having three or more isocyanate groups include isocyanurates of diisocyanates and diisocyanates. Examples thereof include a trimethylolpropane adduct compound, and an isocyanurate compound of diisocyanate is preferable. Examples of the diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate and alicyclic diisocyanates such as isophorone diisocyanate.

Among them, the polyisocyanate compound (d) preferably contains a polyisocyanate compound having three or more isocyanate groups. The content of the polyisocyanate compound having 3 or more isocyanate groups is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more in the polyisocyanate compound (d). The upper limit is 100% by mass.

The content of the curing agent (ii) is less than 50% by mass, preferably 40% by mass or less, and more preferably 30% by mass or less in the urethane resin composition (in the components forming the urethane resin composition). More preferably, it is 20% by mass or less, and the lower limit is, for example, 0.1% by mass.

The molar ratio (NCO / OH) of the hydroxyl group of the polymer (A) contained in the main agent (i) to the isocyanate group of the polyisocyanate compound (d) contained in the curing agent (ii) is preferably 0.8. As mentioned above, it is more preferably 0.9 or more, preferably 1.5 or less, and more preferably 1.2 or less.

The slippery imparting agent (iii) contains a compound (B) represented by the following formula (1).

[In formula (1), R ¹ and R ² each independently represent a methyl group or a hydroxyl group. n represents an integer from 1 to 3,000. ]

The slippery imparting agent (iii) may be contained in the urethane resin composition, and the mixing order of the main agent (i) and the curing agent (ii) is not particularly limited.

In the formula (1), R ¹ and R ² are preferably methyl groups from the viewpoint of scratch resistance. n is preferably 1 to 3,000, more preferably 5 to 2,500, and even more preferably 6 to 2,200.

The molecular weight of the compound (B) is, for example, 500 or more, more preferably 1,000 or more, still more preferably 5,000 or more, preferably 150,000 or less, more preferably 120,000 or less, still more preferably. It is 110,000 or less.

The molecular weight of the compound (B) is based on the kinematic viscosity of the compound (B) at 25 ° C. J. It can be obtained by Barry's formula.

The compound (B) may be mixed with the main agent (i) and the curing agent (ii) as it is, or may be mixed after being dispersed in a dispersion medium such as water in advance.

The content of the compound (B) is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, based on 100 parts by mass of the total of the main agent (i) and the curing agent (ii). It is more preferably 0.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.

The resin composition may contain an organic solvent (C) in the main agent (i) or the curing agent (ii) (preferably in the main agent (i)). As the organic solvent (C), one kind or two or more kinds can be used, for example, aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and acetylacetone; tetrahydrofuran, dioxane and the like. Ether solvent; ester solvent such as ethyl acetate and butyl acetate; nitrile solvent such as acetonitrile; amide solvent such as dimethylformamide and N-methylpyrrolidone.

The content of the organic solvent (C) is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and preferably 80% by mass or less in the urethane resin composition. It is more preferably 70% by mass or less, still more preferably 65% by mass or less.

The urethane resin composition may contain other additives (D) in addition to the main agent (i), the curing agent (ii), and the slipper-imparting agent (iii). Examples of the other additive (D) include a tackifier, a leveling agent, a catalyst, a plasticizer, a stabilizer, a filler, a pigment, a dye, a flame retardant, and the like, and these include the main agent (i) and curing. It may be premixed with a part or all of the agent (iii) and the slip-imparting agent (iii).

When the other additive (D) is contained, the content thereof is, for example, 30% by mass or less, 10% by mass or less, 5% by mass or less, and the lower limit is 0% by mass, based on the total amount of the urethane resin composition. is there.

The cured product of the present invention can be obtained by mixing and curing the main agent (i), the curing agent (ii), and the slipper-imparting agent (iii). The curing temperature can be, for example, 40 to 250 ° C., and the curing time can be, for example, about 1 to 1,000 seconds. A drying step may be provided in advance before the curing, or a secondary curing step may be provided after the curing. The secondary curing temperature can be, for example, 40 to 100 ° C., and the secondary curing time can be, for example, 1 to 24 hours.

A film obtained by applying the urethane resin composition to a base material and curing it to form a cured coating film is also included in the technical scope of the present invention. The base material is not particularly limited, and wood; polyester resin, epoxy resin, polyamide resin, acrylic resin, polyolefin resin, polycarbonate resin, polyurethane resin, ABS resin, polyvinyl chloride resin, polystyrene resin, phenol resin, melamine resin. , Urea resin, alkyd resin and other synthetic or natural resins; metals such as aluminum, iron, copper, zinc, iron alloys, aluminum alloys, copper alloys and zinc alloys; glass; base materials such as ceramics can be used. Examples of the method of applying the urethane resin composition to an article include a dip coating method, a spin coating method, a flow coating method, a spray coating method, a roll coating method, a gravure roll coating method, an air doctor coating method, a blade coating method, and a wire. Doctor coat method, knife coat method, reverse coat method, transferor coat method, microgravure coat method, kiss coat method, cast coat method, slot orifice coat method, calendar coat method, die coat method and the like can be appropriately adopted. ..

The thickness of the cured coating film is, for example, 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, preferably 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less.

The urethane resin composition can be suitably used for articles such as automobiles, automobile parts, home appliances, mobile phones, industrial supplies, medical supplies, optical members, robot supplies, packaging materials, OA equipment, and sports equipment.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can be adapted to the gist of the above and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention.

[Preparation Example 1]
100 parts by mass of methyl ethyl ketone and 100 parts by mass of polycarbonate diol (Duranol T-5652, manufactured by Asahi Kasei Co., Ltd.) were placed in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer and stirred. Then, 8 parts by mass of an isocyanurate form of hexamethylene diisocyanate (Bernock DN-902S) and 0.01 part by mass of dioctyl tin versate were added. After raising the internal temperature to 60 ° C. while paying attention to heat generation, the mixture is stirred for 3 hours while maintaining the temperature, and the main agent (i) containing a prepolymer (A-1) having a hydroxyl group at the molecular end having a hydroxyl group equivalent weight of 1954. -1) was obtained.

[Preparation Examples 2 to 6]
Prepolymers (A-2) to equivalent weights of hydroxyl groups shown in Table 1 in the same manner as in Preparation Example 1 except that the type and amount of polyol and the type and amount of polyisocyanate were changed as shown in Table 1. Main agents (i-2) to (i-6) containing (A-6) were obtained.

 

In Table 1, PTMG2000 represents polyoxytetramethylene glycol (PTMG2000, molecular weight 2,000, manufactured by Mitsubishi Chemical Corporation), and G3452 represents a polycarbonate polyol (G3452, number average molecular weight 2,000, manufactured by Asahi Kasei Co., Ltd.). UH-200 represents a polycarbonate polyol (UH-200, average molecular weight 2,000, manufactured by Ube Industries, Ltd.), and T5652 represents a polycarbonate polyol (T5652, number average molecular weight 2,000, manufactured by Asahi Kasei Co., Ltd.). T5651 represents a polycarbonate polyol (T5651, number average molecular weight 1,000, manufactured by Asahi Kasei Co., Ltd.), and UM-90 represents a polycarbonate polyol (UM-90, number average molecular weight 900, manufactured by Ube Industries, Ltd.), DN-902S. Represents an isocyanurate form of hexamethylene diisocyanate (Bernock DN-902S, manufactured by DIC Co., Ltd.).

[Example 1]
100 parts by mass of the main agent (i) and 5.3 parts by mass of the curing agent (ii) (isocyanurate form of hexamethylene diisocyanate (Bernock DN-902S)) were mixed so that the NCO / OH ratio was 1.10, and the mixture was further slipped. A thermosetting urethane resin composition by mixing 0.5 parts by mass of a sex-imparting agent (iii) Wacker AK-1000 (dimethylpolysiloxane oil) and 1.5 parts by mass of a leveling agent (Silclean 3700, manufactured by Big Chemie Japan). I got the thing (1).

[Examples 2 to 8, Comparative Examples 1 to 5]
The thermosetting urethane resin composition (1) is the same as in Example 1 except that the main agent (i), the curing agent (ii), and the slippering agent (iii) are changed as shown in Table 2 or Table 3. )-(8), comparative compositions (1)-(7) were obtained.

The obtained urethane resin composition and comparative composition were evaluated by the following methods.

[Evaluation method of 100% modulus and elongation]
The thermosetting urethane resin compositions obtained in Examples and Comparative Examples were applied onto a PET film with a knife coater so that the solid content film thickness was 30 microns, and at 70 ° C. for 2 minutes, and further at 110 ° C. for 2 minutes. It was dried to prepare a polyurethane resin film. Next, a test piece of a polyurethane resin film having a width of 5 mm and a length of 50 mm was cut out into strips, and a tensile test was conducted using a tensile tester in an environment with a chuck distance of 40 mm, a tensile speed of 10 mm / sec, and a temperature of 23 ° C. The stress at 100% elongation is 100% modulus, and the elongation at break is elongation.

[Evaluation method of hysteresis loss at 100% elongation recovery]
A strip-shaped test piece cut out from the polyurethane resin film obtained in the same manner as above was subjected to a tensile test using a tensile tester in an environment with a chuck distance of 40 mm, a tensile speed of 10 mm / sec, and a temperature of 23 ° C. Immediately after 100% stretching, the film was returned to a chuck distance of 40 mm at a tensile speed of 10 mm / sec. At that time, the loss ratio of the amount of heat obtained from the difference between the amount of heat given when the test piece was pulled and the amount of heat released when the test piece was pulled back from the integrated value of the graph of the applied load and the amount of deformation was defined as the hysteresis loss.

[Evaluation method of slipperiness]
The frictional resistance of the polyurethane film obtained in the same manner as above was measured using a surface measuring instrument manufactured by Shinto Kagaku Co., Ltd. at a load of 200 g, a 10 mm stainless steel ball indenter, and a test speed of 120 cm / min.
The measured stress was evaluated according to the following criteria.
◯: Less than 2 kN Δ: 2 kN or more and less than 1000 kN ×: 1000 kN or more

[Evaluation method of solvent resistance]
A drop of MEK was dropped on the polyurethane resin film obtained in the same manner as above with a dropper, and a change in appearance was confirmed when the film was wiped off after 10 seconds. When the hanging part was swollen and could be clearly confirmed visually, it was evaluated as x, when it was slightly confirmed, it was evaluated as Δ, and when it could not be confirmed at all, it was evaluated as ○.

[Evaluation method of steel wool scratch resistance]
Evaluation was performed using RUBBING TESTER (manufactured by Taihei Rika Kogyo Co., Ltd.).
Specifically, steel wool (manufactured by Nippon Steel Wool Co., Ltd., trade name BONSTAR, product number No. 0000) was used as the wear body, and the wear body was rubbed 500 times back and forth on the surface of the coating film under the condition of a load of 500 g. .. The state of the coating film surface after rubbing was visually evaluated according to the following evaluation criteria.
◯: There were no scratches on the film surface.
X: Streaks were observed on the surface of the film.

 

 

In Tables 2 and 3, HDI represents hexamethylene diisocyanate, AK1000 represents dimethyl silicone oil (AK1000, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), and AK10000 represents dimethyl silicone oil (AK10000, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.). AK100,000 represents dimethyl silicone oil (AK100,000, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), C800 represents a silicone emulsion (C800, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), and KF53 represents methylphenyl silicone oil (KF-). 53, manufactured by Shin-Etsu Silicone Co., Ltd.), BYK-333 represents polyether-modified polydimethylsiloxane (BYK-333, manufactured by Big Chemie Japan Co., Ltd.).

Examples 1 to 8 are examples of the present invention, and were able to achieve both flexibility, scratch resistance, and solvent resistance. Comparative Examples 1 to 3 were examples in which the slipper-imparting agent (iii) was not contained, and the scratch resistance was insufficient. Comparative Examples 4 and 5 are examples in which a polycarbonate polyol that is liquid at 25 ° C. is not used as the polymer, and the scratch resistance is insufficient or the solvent resistance is insufficient.

Claims (7)

1. It contains a main agent (i), a curing agent (ii), and a slippering agent (iii).
   The main agent (i) contains the polymer (A), and the main agent (i) contains the polymer (A).
   The polymer (A) is a polyol (a) or a reaction product of the polyol (a) and a polyisocyanate (b) and has a hydroxyl group.
   The polyol (a) contains a polycarbonate polyol (a1) that is liquid at 25 ° C.
   The curing agent (ii) contains the polyisocyanate compound (d) and contains.
   A urethane resin composition in which the slippery imparting agent (iii) contains a compound (B) represented by the following formula (1).
   

   

   [In formula (1), R ¹ and R ² each independently represent a methyl group or a hydroxyl group. n represents an integer from 1 to 3,000. ]
2. The urethane resin composition according to claim 1, wherein the polyisocyanate (b) contains an isocyanate compound having three or more isocyanate groups.
3. The urethane resin composition according to claim 1 or 2, wherein the polyisocyanate compound (d) contains an isocyanate compound having three or more isocyanate groups.
4. A coating agent containing the urethane resin composition according to any one of claims 1 to 3.
5. The urethane resin composition according to any one of claims 1 to 3 or the cured product of the coating agent according to claim 4.
6. A film having a base material and a cured coating film of the urethane resin composition according to any one of claims 1 to 3 or the coating agent according to claim 4.
7. An article having the cured coating film according to claim 6.