TW202110923A - 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 DEG 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 a urethane resin composition and film.

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

As such a urethane resin composition, a urethane resin composition containing a main agent and a hardening agent has been proposed (for example, refer to Patent Document 1), wherein the main agent is made of one that does not have an aromatic ring. A polyol reacts with a polyisocyanate having an aromatic ring to produce an isocyanate group-terminated urethane prepolymer, and the urethane prepolymer is reacted with a branched diol. [Prior Technical Literature] [Patent Literature]

Patent Document 1 　 JP 2018-150421 A

[The problem to be solved by the invention]

However, in conventionally known resin compositions, there are cases in which it is not possible to sufficiently satisfy the compatibility of flexibility, scratch resistance, and solvent resistance. The present invention has been completed in view of the foregoing, and its subject is to have flexibility, scratch resistance, and solvent resistance at the same time. [Means to solve the problem]

In the past, in order to improve the scratch resistance, there have been many attempts to increase the hardness of the resin molded body. However, in the case of increasing the hardness of the resin molded body, the hardness of the resin itself also has an upper limit. On the other hand, once the resin is broken, the shape does not recover, so scratches are left. As a result, the scratch resistance cannot be sufficiently improved. situation. The inventors of the present invention have a concept contrary to this conventional attempt to increase the hardness of the resin, and have conceived that while suppressing the hardness of the resin molded body, increasing the deformation recovery rate, and thereby improving the smoothness of the resin molded body surface.

Then, it was found that the use of polycarbonate diol which is liquid at 25°C as the polyol component improves the flexibility of the soft segment, and that after adding a specific slippery imparting agent for imparting lubricity, it becomes Soft resin, but because the surface smoothness improvement effect and the stress dispersion effect caused by the flexibility are multiplied, no scratches are left on the resin surface, and the result can be a combination of flexibility and scratch resistance. Resin molded body. It was further discovered that the solvent resistance problem can be solved by using polycarbonate diol, and the present invention was completed.

The resin composition of the present invention includes a main agent (i), a hardener (ii), and a slippery imparting agent (iii), wherein the main agent (i) includes a polymer (A), and the polymer (A) is a multi-component The reaction product of alcohol (a) or polyol (a) and polyisocyanate (b), and has a hydroxyl group, the polyol (a) includes a polycarbonate polyol (a1) that is liquid at 25°C, and the curing The agent (ii) contains a polyisocyanate compound (d), and the aforementioned slippage 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. ] [Effects of the invention]

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

[Pattern for implementing the invention]

The resin composition of the present invention includes a main agent (i) and a hardener (ii). In the present invention, the main agent (i) and the hardening agent (ii) may each contain components other than those directly involved in the formation of hardened products (for example, polymers, compounds with hardening effect, etc.), or the main agent ( The composition of i) and the composition of the hardener (ii).

The aforementioned main agent (i) includes 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 aforementioned polymer (A) is a reaction product of polyol (a) or polyol (a) and polyisocyanate (b), and has a hydroxyl group.

The said polyol (a) contains the polycarbonate polyol (a1) which is liquid at 25 degreeC (Hereinafter, it may be referred to as "liquid polycarbonate polyol (a1).").

The aforementioned liquid polycarbonate polyol (a1) includes, for example, an esterification reaction product of a carbonate ester and a polyvalent alcohol, and a reaction product of a polyvalent alcohol and phosgene, which are liquid at 25°C .

Regarding the aforementioned carbonates, one kind or two or more kinds can be used, and examples include aliphatic carbonates, alicyclic carbonates (hereinafter, an alicyclic structure may be referred to as "alicyclic"), aromatics Carbonic acid ester (Hereinafter, the aromatic structure may be collectively referred to as "aromatic"). As for aliphatic carbonates, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, ethyl n-butyl carbonate, ethyl isobutyl carbonate can be cited Saturated aliphatic carbonates; ethylene carbonate, trimethylene carbonate, 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, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3 carbonate -Unsaturated aliphatic carbonates such as pentylene and 2,4-pentylene carbonate. Examples of aromatic carbonates include diphenyl carbonate, dibenzyl carbonate, and the like.

Regarding the aforementioned polyvalent alcohols, one kind or two or more kinds can be used, for example, ethylene glycol, propylene glycol, butylene glycol, pentanediol, 3-methyl-1,5-pentanediol, and hexamethylene glycol. Alcohol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol and other linear or branched diols; 1,4-cyclohexanedimethanol, hydrogenated bis Alicyclic diols such as phenol A; trimethylolmethane, trimethylolpropane, ditrimethylolpropane, neopentylerythritol, dineopentylerythritol and other trifunctional or higher polyols, etc.

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

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

The number average molecular weight of the aforementioned 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 1,800 or less, and still more preferably 1,500 the following.

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

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

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

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

Regarding the aforementioned polyester polyol, one kind or two or more kinds can be used, for example, polyester polyols obtained by reacting low-molecular-weight polyols and polycarboxylic acids; ε-caprolactone, etc. Polyester polyol obtained by the ring-opening polymerization reaction of the cyclic ester compound; polyester polyol obtained by copolymerizing the same.

Regarding the low molecular weight polyols used in the production of the aforementioned polyester polyols, 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-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octane Glycol, 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-ethyl-1,3-hexanediol, 2-methyl Aliphatic polyols with a molecular weight of 50 to 300, such as trimethylolpropane, ditrimethylolpropane, trimethylolpropane, neopentyl erythritol, etc.; Polyols with alicyclic structures such as hexanedimethanol and hydrogenated bisphenol A; polyols with aromatic structures such as bisphenol A and bisphenol F, etc.

Regarding the aforementioned polycarboxylic acid, one kind or two or more kinds can be used, for example, aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, dodecane dicarboxylic acid, etc.; 1,4- Alicyclic polycarboxylic acids such as cyclohexanedicarboxylic acid and cyclohexanetricarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, etc.; these acid anhydrides or Ester and so on.

Regarding the aforementioned polyether polyol, one or two or more types can be used. For example, one or two or more types of compounds having two or more active hydrogen atoms are used as the initiator and alkylene oxide is added. Compounds formed by polymerization, etc. As for the aforementioned compound having two or more active hydrogen atoms, for example, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, Neopentyl glycol, glycerin, diglycerin, trimethylolethane, trimethylolpropane, water, hexanetriol, etc. Moreover, as for the aforementioned alkylene oxide, for example, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and the like can be cited.

Examples of polycarbonate polyols other than the aforementioned liquid polycarbonate polyol (a1) include solid polycarbonate polyols at 25°C and the like.

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, and still more preferably 700 or more, preferably 10,000 or less, more preferably 5,000 or less, still more preferably 4,000 or less.

Regarding the aforementioned low-molecular-weight polyols, one kind or two or more kinds can be used, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3 -Propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, new Pentylene glycol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonane Alcohol, 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-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol , Glycerol, trimethylolpropane, ditrimethylolpropane, trimethylolpropane, neopentylerythritol and other aliphatic polyols with a molecular weight of 50 to 300; cyclohexane dimethanol, hydrogenated bisphenol A Polyols with alicyclic structures such as bisphenol A and bisphenol F, etc.; polyols with aromatic structure such as bisphenol A and bisphenol F.

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

Regarding the aforementioned polyisocyanate (b), one kind or two or more kinds can be used, including aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, etc., preferably aliphatic or alicyclic polyisocyanate is used . Regarding the aforementioned aliphatic or alicyclic polyisocyanate, one kind or two or more kinds can be used. For example, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate can be used. Isocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentyl diisocyanate, 1,3-cyclohexyl diisocyanate, 1,4-cyclohexyl diisocyanate, 1,3-bis(isocyanate Methyl)cyclohexane, 1,4-bis(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, etc. In addition, an allophanate modified body of the aforementioned aliphatic or alicyclic polyisocyanate, an isocyanurate modified body, etc. can be used. Among them, the allophanate modified body or the isocyanurate modified body of aliphatic or alicyclic polyisocyanate is preferred, and the isotricyanurate modified body of aliphatic or alicyclic polyisocyanate is more preferred. The polycyanate modified body is more preferably an isocyanurate modified body of aliphatic polyisocyanate.

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, and still more preferably 1.0 or more, preferably 1.3 or less, more preferably 1.2 or less, and still more preferably 1.1 or less.

The polymer (A) may be directly the polyol (a), or it may be produced by reacting the polyol (a) and the polyisocyanate (b).

啉等之含氮化合物；或者四丁氧基鈦、二丁基氧化錫、二月桂酸二丁基錫、2-乙基己酸錫、環烷酸鋅、環烷酸鈷、2-乙基己酸鋅、硫乙醇酸鉬、乙酸鉀、硬脂酸鋅、辛酸錫、二月桂酸二丁基錫、二新癸酸二辛基錫等之有機金屬化合物；或者氯化鐵、氯化鋅等之無機化合物等。When the polyol (a) and the polyisocyanate (b) are reacted, a urethane catalyst may coexist as needed. Regarding the aforementioned carbamate catalyst, one or more than two can be used, for example, triethylamine, tributylamine, benzyldibutylamine, triethylenediamine, N-methyl

Nitrogen-containing compounds such as morphine; or titanium tetrabutoxide, dibutyltin oxide, dibutyltin dilaurate, tin 2-ethylhexanoate, zinc naphthenate, cobalt naphthenate, 2-ethylhexanoic acid Organometallic compounds such as zinc, molybdenum thioglycolate, potassium acetate, zinc stearate, tin octoate, dibutyltin dilaurate, dioctyltin dineodecanoate, etc.; or inorganic compounds such as iron chloride and zinc chloride Wait.

烷等之醚溶劑；乙酸乙酯、乙酸丁酯等之酯溶劑；乙腈等之腈溶劑；二甲基甲醯胺、N-甲基吡咯啶酮等之醯胺溶劑等。During the aforementioned reaction, a reaction solvent may coexist. Regarding the aforementioned reaction solvent, one or more than two types can be used, for example, aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and acetone ; Tetrahydrofuran, two

Ether solvents such as alkane; ester solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone.

In the aforementioned reaction, the reaction temperature can be carried out at 50 to 90°C, and the reaction time can be carried out at 2 to 24 hours, for example. The reaction pressure may be any of normal pressure, increased pressure, and reduced pressure. The reactive gas environment can be an inert gas environment such as nitrogen, argon, etc., or can be a dry air environment, airtight conditions, and other conditions that do not mix in moisture.

The hydroxyl equivalent of the aforementioned polymer (A) is preferably 400 g/eq. or more, more preferably 450 g/eq. or more, preferably 4000 g/eq. or less, and more preferably 3000 g/eq. or less.

The aforementioned hardener (ii) contains a polyisocyanate compound (d). The aforementioned polyisocyanate compound (d) has two or more isocyanate groups. Regarding the aforementioned polyisocyanate compound (d), one kind or two or more kinds can be used. For example, as for the diisocyanate compound having two isocyanate groups, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, Diisocyanates with alicyclic structure such as isophorone diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, stubborn diisocyanate, tetramethyl stubborn diisocyanate, etc. ; For the polyisocyanate compound having 3 or more isocyanate groups, the isocyanurate body of diisocyanate, the trimethylolpropane adduct of diisocyanate, etc. are mentioned, and the isotrimerization of diisocyanate is preferred Cyanate ester. The aforementioned diisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate, and alicyclic diisocyanates such as isophorone diisocyanate.

Among them, the aforementioned 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 in the polyisocyanate compound (d), more preferably 80% by mass or more, and still more preferably 90% by mass or more, the upper limit It is 100% by mass.

The content of the aforementioned curing agent (ii) is less than 50% by mass in the urethane resin composition (in the components forming the aforementioned urethane resin composition), preferably 40% by mass or less, and more It is preferably 30% by mass or less, more preferably 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) and the isocyanate group of the polyisocyanate compound (d) contained in the curing agent (ii) is preferably 0.8 or more, more preferably 0.9 or more, preferably 1.5 or less, more preferably 1.2 or less.

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

[式(1)中，R¹ 、R² 各自獨立地表示甲基或羥基。n表示1~3,000之整數。]

[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 said slippery imparting agent (iii) should just be contained in the said urethane resin composition, and the mixing order of the said main agent (i) and the said hardening agent (ii) is not specifically limited.

In 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 still more preferably 6 to 2,200.

The molecular weight of the aforementioned 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, and still more preferably 110,000 or less.

The molecular weight of the compound (B) can be calculated based on the kinematic viscosity of the compound (B) at 25° C. using the formula of A.J. Barry.

The compound (B) may be directly mixed with the main agent (i) and the curing agent (ii), or may be dispersed in a dispersion medium such as water before mixing.

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

烷等之醚溶劑；乙酸乙酯、乙酸丁酯等之酯溶劑；乙腈等之腈溶劑；二甲基甲醯胺、N-甲基吡咯啶酮等之醯胺溶劑等。The aforementioned resin composition may contain an organic solvent (C) in the aforementioned main agent (i) or the aforementioned curing agent (ii) (preferably in the aforementioned main agent (i)). Regarding the aforementioned organic solvent (C), one kind or two or more kinds can be used, for example, aromatic hydrocarbon solvents such as toluene and xylene; acetone, methyl ethyl ketone, cyclohexanone, acetone, etc. Ketone solvent; tetrahydrofuran, two

Ether solvents such as alkane; ester solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone.

The content of the organic solvent (C) is preferably 30% by mass or more in the urethane resin composition, more preferably 40% by mass or more, still more preferably 50% by mass or more, and preferably 80 % By mass or less, 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 slipping agent (iii). As for the aforementioned other additives (D), adhesion imparting agents, leveling agents, catalysts, plasticizers, stabilizers, fillers, pigments, dyes, flame retardants, etc. can be listed, which can also be combined with the aforementioned main agents (i) A part or all of the hardener (iii) and the slippery imparting agent (iii) are premixed.

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

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

A thin film formed by applying the aforementioned urethane resin composition to a substrate and curing it to form a cured coating film is also included in the technical scope of the present invention. As for the aforementioned substrate, there is no particular limitation, and it can be used: wood; polyester resin, epoxy resin, polyamide resin, acrylic resin, polyolefin resin, polycarbonate resin, polyurethane resin, ABS Synthetic or natural resins such as resin, polyvinyl chloride resin, polystyrene resin, phenolic resin, melamine resin, urea resin, alkyd resin, etc.; aluminum, iron, copper, zinc, iron alloy, aluminum alloy, copper alloy, zinc alloy, etc. The metal; glass; ceramics and other substrates. With regard to the method of applying the aforementioned urethane resin composition to an article, dip coating, spin coating, flow coating, spray coating, roll coating, gravure roll coating, and air coating can be suitably used. Knife coating method, blade coating method, wire knife coating method, knife coating method, reverse coating method, transfer roll coating method, micro gravure coating method, kiss coating method, casting coating method, slot orifice coating method, Calender coating method, die coating method and other methods.

The thickness of the aforementioned 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, and still more preferably 50 μm or less.

The aforementioned urethane resin composition can be suitably used in, for example, automobiles, auto parts, home appliances, mobile phones, industrial products, medical products, optical components, robotics products, packaging materials, OA equipment, sporting goods, etc. article. [Example]

Hereinafter, the present invention will be explained in more detail by enumerating examples. However, the present invention is not limited by the following examples. Of course, it can also be appropriately modified and implemented within the scope that can conform to the purpose of the foregoing and the following. Within the technical scope of the present invention.

[Modulation example 1] Add 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.) into a nitrogen-replaced container equipped with a thermometer, a nitrogen introduction tube, and a stirrer. Stir. Next, 8 parts by mass of isocyanurate body (BURNOCK DN-902S) of hexamethylene diisocyanate and 0.01 parts by mass of dioctyltin versatate were added. After raising the internal temperature to 60°C while paying attention to the exotherm, the mixture was stirred for 3 hours while maintaining the temperature to obtain the main agent (A-1) of the prepolymer (A-1) containing a hydroxyl group and having an equivalent weight of 1954 and having a hydroxyl group at the molecular end ( i-1).

[Modulation example 2~6] Except that the type and amount of polyol and the type and amount of polyisocyanate were changed as described in Table 1, the same procedure as in Preparation Example 1 was carried out to obtain a prepolymer (A-2) containing the hydroxyl equivalent weight shown in Table 1. )~(A-6)'s main agent (i-2)~(i-6).

[Table 1] Modulation example 1 2 3 4 5 6 Prepolymer name (A-1) (A-2) (A-3) (A-4) (A-5) (A-6) Polyol PTMG2000 100 G3452 100 UH-200 100 T5652 100 T5651 100 UM-90 100 Polyisocyanate DN-902S 8 Hydroxyl equivalent (g/eq.) 1954 1011 500 453 1064 1011

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

[Example 1] Mix the main agent (i) 100 parts by mass and hardener (ii) (BURNOCK DN-902S) 5.3 parts by mass of the hardener (isocyanurate body of hexamethylene diisocyanate (BURNOCK DN-902S)) so that the NCO/OH ratio=1.10, Furthermore, a slippery imparting agent (iii) 0.5 parts by mass of WACKER AK-1000 (dimethyl polysiloxane oil) and 1.5 parts by mass of a leveling agent (SILCLEAN 3700, manufactured by BYK Japan) were mixed to obtain a thermosetting polyurethane Ester resin composition (1).

[Examples 2 to 8, Comparative Examples 1 to 5] Except that the main agent (i), curing agent (ii), and slipperiness imparting agent (iii) were changed as shown in Table 2 or Table 3, the same procedure as in Example 1 was carried out to obtain a thermosetting urethane resin Compositions (1)~(8), comparative compositions (1)~(7).

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

[Evaluation method of 100% modulus and elongation] Using a knife coater, the thermosetting urethane resin composition obtained in the examples and comparative examples was coated on a PET film so that the solid content film thickness became 30 microns, and dried at 70°C for 2 minutes. Furthermore, it dried at 110 degreeC for 2 minutes, and produced the polyurethane resin film. Next, the polyurethane resin film was cut into strip test pieces with a width of 5 mm and a length of 50 mm. Using a tensile testing machine, the distance between the chucks was 40 mm, the tensile speed was 10 mm/sec, and the temperature was 23°C. Next, a tensile test was performed, and the stress at the time of 100% elongation was set as the 100% modulus, and the elongation at break was set as the elongation.

[Evaluation method of hysteresis loss at 100% elongation recovery] Using a tensile testing machine, the chuck distance is 40mm, the tensile speed is 10mm/sec, and the temperature is 23°C. The tensile test is carried out, and the polyurethane resin film is obtained from the same procedure as above. After the cut strip test piece is stretched 100%, it is restored to the distance between the chucks 40mm at a stretching speed of 10mm/sec. At this time, from the integral value of the graph of the applied load and the amount of deformation, the heat loss ratio is calculated from the difference between the heat applied to the test piece when it is stretched and the heat released by the test piece when it is pulled back Set as hysteresis loss.

[Method of evaluating slipperiness] Using a surface measuring device manufactured by Shinto Scientific Co., Ltd., a load of 200 g, a 10 mm stainless steel ball indenter, and a test speed of 120 cm/min were used to measure the friction resistance of the polyurethane film obtained in the same manner as described above. The measured stress was evaluated based on the following criteria. ○: Less than 2kN △: 2kN or more and less than 1000kN ×: Above 1000kN

[Evaluation method of solvent resistance] The appearance of the polyurethane resin film obtained in the same manner as above was confirmed when one drop of MEK was dropped vertically with a dropper and wiped off after 10 seconds. The part where the dripping was swollen and clearly confirmed visually was evaluated as ×, the case where it was slightly confirmed was evaluated as △, and the case where it was not confirmed at all was evaluated as ○.

[Method for evaluating scratch resistance of steel wool] RUBBING TESTER (manufactured by Taiping Chemical Industry Co., Ltd.) was used for evaluation. Specifically, steel wool (manufactured by Japan Steel Wool Co., Ltd., brand name BONSTAR, product code No. 0000) was used as the abrasion body, and the abrasion body was rubbed back and forth 500 times 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 based on the following evaluation criteria. ○: No scratches are generated on the surface of the film. ×: Streak scratches are seen on the surface of the film.

[Table 2] Example 1 2 3 4 5 6 7 8 Composition (parts by mass) Main agent (i) (i-1) 100 100 100 100 (i-2) 100 (i-3) 100 (i-5) 100 100 Hardener (ii) Polyisocyanate DN-902S 5.3 5.3 5.3 5.3 9.8 19.8 9.3 5.7 HDI 1.7 Slippery imparting agent (iii) AK1000 0.5 0.5 0.5 0.5 0.5 AK10000 0.5 AK100000 0.5 C800 0.5 additive Leveling agent 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Evaluation results 100%M(MPa) 3.2 3.2 3.2 3.2 2.6 4.7 2.9 2.0 100% hysteresis loss (%) 0.2 0.2 0.2 0.2 0.9 0.2 1.6 7.6 Elongation (%) 136 136 136 136 235 107 290 390 Slippery ○ ○ ○ ○ ○ ○ ○ ○ Solvent resistance ○ ○ ○ ○ ○ ○ ○ ○ SW scratch resistance 500 times ○ ○ ○ ○ ○ ○ ○ ○

[table 3] Comparative example 1 2 3 4 5 Composition (parts by mass) Main agent (i) (i-1) 100 100 100 (i-4) 100 (i-6) 100 Hardener (ii) Polyisocyanate DN-902S 5.3 5.3 5.3 21.9 9.8 Slippery imparting agent (iii) AK1000 0.5 0.5 KF53 0.5 BYK-333 0.5 additive Leveling agent 3.0 3.0 3.0 3.0 3.0 Evaluation results 100%M(MPa) 3.2 3.2 3.2 4.1 2.0 100% hysteresis loss (%) 0.2 0.2 0.2 43.0 1.0 Elongation (%) 136 136 136 165 350 Slippery △ △ △ ○ ○ Solvent resistance ○ ○ ○ ○ X SW scratch resistance 500 times X X X X ○

In Tables 2 and 3, HDI means hexamethylene diisocyanate, AK1000 means dimethyl polysiloxane oil (AK1000, manufactured by Asahi Kasei Wacker Polysiloxane Co., Ltd.), and AK10000 means dimethyl polysiloxane oil (AK10000, Asahi Kasei WACKER Polysiloxane Co., Ltd. AK100000 means dimethyl polysiloxane oil (AK100000, Asahi Kasei WACKER Polysiloxane Co., Ltd.), C800 means polysiloxane emulsion (C800, Asahi Kasei WACKER Polysiloxane Co., Ltd.) Co., Ltd.), KF53 means methyl phenyl polysiloxane oil (KF-53, Shin-Etsu Silicone Co., Ltd.), BYK-333 means polyether modified polydimethylsiloxane (BYK-333, BYK ･Japan Co., Ltd. system).

Examples 1 to 8 are examples of the present invention, which can combine flexibility, scratch resistance, and solvent resistance. Comparative Examples 1 to 3 are examples that do not include the slipperiness imparting agent (iii), and the scratch resistance is insufficient. Comparative Examples 4 and 5 are examples in which the polycarbonate polyol which is liquid at 25°C is not used as the polymer, and the scratch resistance is insufficient, and the solvent resistance is insufficient.

no.

no.

no.

Claims (7)

A urethane resin composition comprising a main agent (i), a hardener (ii), and a slippery imparting agent (iii), wherein the main agent (i) includes a polymer (A), and the polymer (A) is a reaction product of polyol (a) or polyol (a) and polyisocyanate (b), and has a hydroxyl group, and this polyol (a) contains a polycarbonate polyol ( a1), the hardener (ii) contains a polyisocyanate compound (d), and 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 of 1 to 3,000]. The urethane resin composition of claim 1, wherein the polyisocyanate (b) contains an isocyanate compound having 3 or more isocyanate groups. The urethane resin composition of claim 1 or 2, wherein the polyisocyanate compound (d) contains an isocyanate compound having 3 or more isocyanate groups. A coating agent comprising the urethane resin composition according to any one of claims 1 to 3. A cured product, which is a cured product of the urethane resin composition of any one of claims 1 to 3 or a coating agent of claim 4. 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. An article having a hardened coating film as in Claim 5.