JP2019143133A - Urethane resin composition and coated article - Google Patents

Abstract

To provide a urethane resin composition that ensures excellent adhesion to various base materials including a resin base material showing poorly wetting properties, such as polypropylene, and can impart wetting resistant properties to the surface of a base material coated therewith, regardless of the type of the base material.SOLUTION: The present invention provides a urethane resin composition that is a reaction product of a compound having a specific structure (A), a polyisocyanate compound (B), and a compound having a specific structure (C), and a coating obtained from the same.SELECTED DRAWING: None

Description

  The present invention relates to a urethane resin composition, a coating film containing the urethane resin composition, and a coated article having a coating film containing the urethane resin composition.

  Conventionally, resin base materials such as polypropylene have been widely used industrially. For example, resin base materials are often used in automobiles, electrical appliances such as washing machines and refrigerators, and electronic devices such as smartphones and personal computers. This is because the resin base material is lighter and cheaper than metal materials and has the advantage of being easily molded and processed. There are also applications specific to resin substrates such as films. For example, films made of polyethylene terephthalate are widely used as substrates for release films used in the production process of food packaging materials and electronic materials.

  Generally, it is known that the surface of a resin base material is hard to get wet compared to a metal base material. The difficulty of wetting of the surface of the resin base material (hereinafter referred to as “hard wetting”) causes defects such as repellency when applying adhesives and paints, for example, and this makes it impossible to obtain a uniform coated surface. Is not desirable. In addition, it is known that a substrate exhibiting poor wettability generally exhibits poor adhesion, and in the case of an adhesive, adhesion failure is caused, and in the case of a paint, it is a cause of serious defects such as coating film peeling. Therefore, it is not desirable.

  As a method for improving wettability, a composition change or surface modification of a resin base material or a composition change of a material to be applied has been performed.

  As a composition change of a polypropylene base material, for example, a method of reacting polypropylene with an unsaturated carboxylic acid and an aromatic vinyl monomer has been reported (Patent Document 1), but sufficient improvement in wettability has been achieved. There was a problem that the reaction yield was not sufficient.

  As a surface modification method, for example, corona treatment has been conventionally known and has already been put into practical use (Non-patent Document 1). However, since a large-scale device is required, a large amount of capital investment is required and it is difficult to set optimum conditions, so it is not necessarily versatile, and it is a method for cleaving molecular chains. Therefore, there was a problem such as concern about a decrease in mechanical strength.

  As a composition change of the material to be applied, for example, a primer coating composition containing an aqueous polyolefin resin, an aqueous epoxy resin, and an aqueous polyurethane resin has been reported (Patent Document 2). Since the weight average molecular weight of the aqueous polyolefin resin is as high as 50,000 to 200,000, it is difficult to use it in a solvent system from the viewpoint of compatibility with the solvent and other resins. There was a limited problem. In the case of an aqueous dispersion, an additive such as an emulsifier is required. However, by adding the additive, for example, appearance failure such as whitening that occurs during a water resistance test, or the additive bleeds out to the coating surface. There was a problem.

  On the other hand, it is also widely known that desirable effects such as an antifouling function can be obtained when the surface of the base material exhibits poor wettability. For this reason, methods for imparting poor wettability to the substrate surface have been actively studied.

  As a method for imparting poor wettability, for example, a method using a coating composition containing an acrylic copolymer having an alkoxysilyl group, dimethylpolysiloxane having a hydroxy group at both ends, and a metal catalyst has been reported. (Patent Document 3). However, silicon-containing materials such as alkoxysilyl groups and dimethylpolysiloxane have low adhesion to the substrate, and adhere to substrates that have many hydroxyl groups that can react with these silicon compounds, such as glass. There was a limit to the application of.

  As described above, although a resin composition capable of sufficiently adhering to a substrate exhibiting poor wettability is strongly desired, its method has been limited.

  Also, regardless of the type of base material, a method for imparting poor wettability to the surface of the base material has been strongly desired, but has not been sufficiently solved.

JP 2009-13230 A JP 2017-132902 A Japanese Patent Laid-Open No. 2018-2927

Journal of the Japan Rubber Association 1997 70 333

  The present invention provides good adhesion to resin base materials such as polypropylene, and urethane that can impart wettability to the surface of the applied base material regardless of the type of the base material. It aims at providing a resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that a urethane resin composition which is a reaction product of two specific types of polyol compounds and polyisocyanate compounds is a resin base material including polypropylene. As a result, it was found that good adhesion can be obtained, and that the wettability can be imparted to the surface of the coated substrate regardless of the type of the substrate, and the present invention has been completed.

  That is, the present invention includes the following embodiments.

  It is a reaction product of a compound (A) represented by the following general formula (1), a polyisocyanate compound (B), and a compound (C) represented by the following general formula (2).

[In general formula (1), R represents a hydrocarbon group having 2 to 10,000 carbon atoms (wherein the hydrocarbon group may be linear or branched, and may be cyclic when the number of carbon atoms is 3 or more, It may be a saturated hydrocarbon or an unsaturated hydrocarbon). ]
The polyisocyanate compound (B) is preferably a polyisocyanate compound having two isocyanate groups in one molecule.

  [In the general formula (2), X represents a hydrocarbon group having 1 to 30 carbon atoms (wherein the hydrocarbon group may be a straight chain or a branched chain, and if it has 3 or more carbon atoms, it may be cyclic or saturated carbonization) Y may be hydrogen or unsaturated hydrocarbon), Y represents any one selected from the group consisting of a single bond, an ether group, a carbonyl group, an ester group, an amino group and an amide group, and Z represents a carbon number of 1 to 50 hydrocarbon groups, structures in which some or all of the carbon atoms of the hydrocarbon groups are substituted with heteroatoms, and structures in which some or all of the hydrogen atoms of the hydrocarbon groups are substituted with heteroatoms and / or functional groups (Herein, the hydrocarbon group may be a straight chain or a branched chain, and when the number of carbon atoms is 3 or more, it may be cyclic, saturated hydrocarbon, or unsaturated hydrocarbon). Represents one. ]

  In the urethane resin composition of the present invention, the compound (A) represented by the general formula (1) (hereinafter also referred to as the compound (A) or simply (A)) is present on two or more different carbons in the molecule. It preferably has one hydroxyl group and has 10 to 5,000 carbon atoms.

  In the urethane resin composition of the present invention, the compound (C) represented by the general formula (2) (hereinafter also referred to as the compound (C) or simply (C)) is preferably a monoglyceride.

  The number average molecular weight of the urethane resin composition of the present invention is preferably 3,000 to 500,000.

  In addition, the wettability in this invention is the wettability with respect to water unless there is particular notice.

  According to the present invention, good adhesion to a resin substrate exhibiting poor wettability, such as polypropylene, can be obtained, and it is difficult to wet the coated substrate surface regardless of the type of the substrate. The urethane resin composition which can provide is obtained.

  The urethane resin composition of the present invention is a reaction product of a compound (A) represented by the following general formula (1), a polyisocyanate compound (B), and a compound (C) represented by the following general formula (2). It is characterized by being.

[In general formula (1), R represents a hydrocarbon group having 2 to 10,000 carbon atoms (wherein the hydrocarbon group may be linear or branched, and may be cyclic when the number of carbon atoms is 3 or more, It may be a saturated hydrocarbon or an unsaturated hydrocarbon). ]

[In the general formula (2), X represents a hydrocarbon group having 1 to 30 carbon atoms (wherein the hydrocarbon group may be a straight chain or a branched chain, and if it has 3 or more carbon atoms, it may be cyclic or saturated carbonization) Y may be hydrogen or unsaturated hydrocarbon), Y represents any one selected from the group consisting of a single bond, an ether group, a carbonyl group, an ester group, an amino group and an amide group, and Z represents a carbon number of 1 to 50 hydrocarbon groups, structures in which some or all of the carbon atoms of the hydrocarbon groups are substituted with heteroatoms, and structures in which some or all of the hydrogen atoms of the hydrocarbon groups are substituted with heteroatoms and / or functional groups (Here, the hydrocarbon group may be linear or branched, and may be cyclic when it has 3 or more carbon atoms, and may be saturated or unsaturated hydrocarbon). Represents. ].

  The compound (A) of the present invention is not particularly limited, but examples thereof include glycols having 2 to 100 carbon atoms, polyol polyolefins having an unsaturated skeleton such as polybutadiene, polyisoprene, and polystyrene, polyethylene, Examples thereof include polyol polyolefins having a saturated skeleton such as polypropylene, hydrogenated polybutadiene, polybutene, and hydrogenated polyisoprene. Among these, from the viewpoint of adhesion, the carbon number is preferably 10 to 5,000, more preferably 30 to 1,000, and most preferably 70 to 250. Moreover, it is preferable to have one hydroxyl group on two or more different carbons in the molecule, and from the viewpoint of resin polymerizability, it is preferable to have a hydroxyl group at the molecular end. As such a compound (A), polyol polyolefins are preferable, and polyol polyolefins having an unsaturated skeleton are preferable.

  The polyisocyanate compound (B) of the present invention is not particularly limited. For example, diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, 2,4-toluene diisocyanate, 2,6- Isocyanates having an aromatic skeleton such as toluene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, 1,4-tetramethylxylylene diisocyanate, hexamethylene diisocyanate, Isophorone diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, hydrogenated diphenylmethane-2,4'-diisocyanate, hydrogenated xylylene diisocyanate, 2,2,4 Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isocyanates, and the like with an aliphatic skeleton such as norbornene diisocyanate. These may be monomeric or multimeric, and may be allophanate-modified or biuret-modified. Among these, diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate are preferable from the viewpoints of surface hardness and mechanical strength, and light resistance viewpoint Therefore, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane-4,4′-diisocyanate, and hydrogenated diphenylmethane-2,4′-diisocyanate are preferable. These may be used alone or in combination of two or more.

  Although it does not specifically limit as said compound (C) of this invention, Carbon number of X is 1-30, It is preferable that it is 1-15, It is more preferable that it is 2-10, 2 Most preferred is ~ 5. Y is any one selected from the group consisting of a single bond, an ether bond, a carbonyl group, an ester group, an amino group, and an amide group, and from the viewpoint of bond stability, a single bond, an ether bond, an ester group, It is preferably any one selected from the group consisting of amino groups, more preferably an ester group or an amino group, and most preferably an ester group. Z has 1 to 50 carbon atoms, preferably 1 to 28, more preferably 2 to 25, and most preferably 5 to 22. The element that substitutes carbon of Z is preferably oxygen and / or silicon from the viewpoint of wettability, and the element that substitutes hydrogen of Z is preferably fluorine from the viewpoint of wettability.

  The compound (C) is preferably monoglyceride.

  The hydroxyl group equivalent ratio of the compound (A) to the compound (C) is preferably from 0.010 to 99 as (C) / (A), more preferably from 0.050 to 20, and most preferably from 0.070 to 15. If the equivalent ratio is less than 0.010, the physical properties derived from (C) may not be sufficiently obtained, and if the equivalent ratio exceeds 99, the physical properties derived from (A) may not be sufficiently obtained. is there.

  The equivalent ratio of the total amount of hydroxyl groups (A) and (C) to the isocyanate group of the polyisocyanate (B) is preferably 0.70 to 1.3, preferably 0.8 to 1.2, as isocyanate group / hydroxyl group. Is more preferable, and 0.9 to 1.1 is most preferable. If the equivalent ratio is less than 0.70, it is difficult to obtain a sufficient molecular weight, so that the drying property may be insufficient. If the equivalent ratio exceeds 1.3, the molecular weight may be too large. There is a concern that the liquidity is insufficient.

  The number average molecular weight of the urethane resin composition that is the reaction product of (A), (C), and (B) is preferably 3,000 to 500,000, more preferably 3,000 to 250,000, and 3,000 to 100,000 is most preferred.

  In addition to compound (A), polyisocyanate (B), and compound (C), the urethane resin composition of the present invention may optionally contain other components as long as the object of the present invention is not impaired. good. Examples of other components include, but are not limited to, solvents, catalysts, antifoaming agents, leveling agents, organic thickeners, antioxidants, light stabilizers, adhesion improvers, mold release agents, reinforcing materials, and softening agents. Agents, colorants, flame retardants, antistatic agents, wetting and dispersing agents and the like.

  Examples of the solvent include, but are not limited to, aromatic hydrocarbon solvents such as toluene, ethylbenzene, trimethylbenzene, and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, and cyclohexane, acetone, methyl ethyl ketone, and methyl. Ketone solvents such as isobutyl ketone and cyclohexanone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl diglycol, ethyl diglycol and butyl Glycol ether solvents such as diglycol and propylene glycol monomethyl ether, ethyl acetate, butyl acetate, propylene glycol monomethyl ether Ester solvents such as teracetate, amide solvents such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, ethers such as diethyl ether and tetrahydrofuran, water, etc. Is mentioned. These may be used alone or in combination of two or more.

  When the urethane resin composition of the present invention contains a solvent, the content may be selected depending on the coating method and the desired film thickness of the urethane resin coating, and is not particularly limited, but is 100 parts by mass of the urethane resin composition. On the other hand, it is preferably 1.0 to 10,000 parts by mass, more preferably 40 to 3,200 parts by mass, and most preferably 150 to 2,000 parts by mass. If the content is less than 1.0 part by mass, the viscosity of the urethane resin composition may be increased and coating may be difficult. If the content exceeds 10,000 parts by mass, the thickness of the urethane resin coating film becomes thin. There is a risk that a sufficient film thickness cannot be obtained.

  The catalyst is not particularly limited, and examples thereof include organic metal compounds such as dibutyltin diacetate, dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof. These may be used alone or in combination of two or more.

  When the urethane resin composition of the present invention contains a catalyst, the content may be selected depending on the reactivity of the polyisocyanate compound to be used, and is not particularly limited, but is 0.0010 with respect to 100 parts by mass of the urethane resin composition. It is preferable that it is -1.0 mass part, It is more preferable that it is 0.0050-0.50 mass part, It is most preferable that it is 0.010-0.10 mass part. If the content is less than 0.0010 parts by mass, a sufficient catalytic effect may not be obtained, and if it exceeds 1.0 parts by mass, the economy may be deteriorated.

  The leveling agent is not particularly limited. For example, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, silicon surfactants, nonionic surfactants, fluorine surfactants, acrylic surfactants, etc. Is mentioned. These may be used alone or in combination of two or more.

  When the urethane resin composition of the present invention contains a leveling agent, the content is not particularly limited, but is preferably 0.0010 to 25 parts by mass with respect to 100 parts by mass of the urethane resin composition. It is more preferably 010 to 12 parts by mass, and most preferably 0.050 to 6.0 parts by mass. If the content is less than 0.0010 parts by mass, the leveling property may be insufficient, and if it exceeds 25 parts by mass, the adhesion of the urethane resin coating film may be insufficient.

  The coating film obtained from the urethane resin composition of the present invention has good adhesion to various substrates including a substrate exhibiting poor wettability to water. Articles having a film exhibit poor wettability. The difficulty wettability of the present invention is based on the contact angle of water with respect to the polypropylene base material, and the contact angle is preferably larger than this, more preferably 100 degrees or more.

  The article having the coating film can be suitably used for vehicle-related parts, electronic materials, structural materials, building materials, furniture, decorative sheets, sports equipment, stationery, and the like.

  The material of the base material is not particularly limited. For example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin), nylon 6, nylon 66, aramid, acrylic, polyethylene Resin such as terephthalate and polybutylene terephthalate, composite material composed of the resin base material and glass fiber, thermosetting resin such as epoxy resin, or composite material of thermoplastic resin such as polyphenylene sulfide and carbon fiber (CFRP, CFRTP), aluminum, aluminum alloy, magnesium, stainless steel, tinplate, electrogalvanized steel sheet, chrome plated steel sheet, and the like, and glass. These base materials may be used alone, or may be used as a composite material in which two or more kinds are used together or mixed.

  In addition, examples of the hardly wettable substrate in the present invention include resins having a contact angle with water at 25 ° C. of 70 ° or more. Examples of such a resin include polyolefin, and among these, polyethylene and polypropylene are preferable.

  The urethane resin coating film is formed from the urethane resin composition of the present invention. A method of forming a urethane resin coating film using the urethane resin composition of the present invention is not particularly limited, and a method of drying after applying the urethane resin composition of the present invention to at least one surface of the substrate, etc. Is mentioned.

  The method for applying the urethane resin composition of the present invention is not particularly limited. For example, the applicator method, bar coating method, spin coating method, spray coating method, dip coating method, nozzle coating method, gravure coating method, reverse roll Coating method, die coating method, air doctor coating method, blade coating method, rod coating method, curtain coating method, knife coating method, transfer roll coating method, squeeze coating method, impregnation coating method, kiss coating method, calendar coating method, extrusion coating method Etc.

  Although the drying temperature at the time of making it dry is not specifically limited, It is preferable that it is 0-300 degreeC, It is more preferable that it is 20-150 degreeC, It is most preferable that it is 60-120 degreeC. When the drying temperature is less than 0 ° C., when the solvent is included, the residue may become a problem. When the drying temperature exceeds 300 ° C., the urethane resin coating film may be thermally decomposed. The drying time is not particularly limited, but is preferably 5 seconds to 10 days, and more preferably 20 to 6,000 seconds. If the drying time is less than 5 seconds, drying may be poor. If it exceeds 10 days, the time required for the process becomes long, which is not preferable from the viewpoint of productivity.

  Although the thickness of a urethane resin coating film is not specifically limited, It is preferable that it is 0.050-300 micrometers, and it is more preferable that it is 0.10-200 micrometers. When the thickness is less than 0.050 μm, the wettability of the urethane resin coating film may be insufficient, and when it exceeds 300 μm, the adhesion of the urethane resin coating film may be insufficient.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. Unless otherwise specified,% notation is based on mass.

(Example 1)
Production of urethane resin compositions, preparation of test pieces and evaluation of physical properties of coating films were performed by the following methods. The results are shown in Table 1.

<Manufacture of urethane resin composition>
In a 2 L four-necked separable flask equipped with a stirrer, thermometer, heating device, and reflux tube, 150.0 g of hydroxyl-terminated polybutadiene 1, 2.9 g of behenic acid monoglyceride, diphenylmethane-4,4′-diisocyanate ( Hereinafter, it is referred to as MDI (trade name: Millionate MT, isocyanate group content 31.3%, manufactured by Tosoh Corporation) 17.2 g, dioctyltin dilaurate 0.094 g, and butyl acetate 1530 g, respectively, after charging at room temperature. The interior of the flask was purged with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 2 hours, stirring uniformly on 80 degreeC conditions. About the obtained urethane resin composition, the number average molecular weight and the viscosity were measured with the following method.

<Measurement of number average molecular weight>
It was determined by gel permeation chromatography (GPC). The conditions are as follows. A high-speed GPC device (HLC-8220 manufactured by Tosoh Corp.) as the device and G3000H-XL, G2500H-XL, G2000H-XL and G1000H-XL (all manufactured by Tosoh Corp.) connected in series in the order described. Was used as the mobile phase and the mobile phase speed was 1.00 mL / min. The column temperature was 40 ° C., the detector was a differential refractometer, and the molecular weight was determined as the molecular weight in terms of polystyrene. As a sample solution, a 0.50% concentration THF solution was prepared and used.

<Measurement of viscosity>
Based on JIS7117-2, it measured using the B type viscometer (Bismetron VS-A1 by the Shibaura system company).

<Creation of specimen>
The obtained urethane resin composition was applied to a polypropylene base material (Kobe Poly Sheet PP manufactured by Hitachi Chemical Co., Ltd.) using an applicator, allowed to stand at room temperature for 5 minutes, and then heated at 80 ° C. using a hot air dryer. A test piece having a coating film with a dry film thickness of 20 μm was prepared by drying for 30 minutes. A test piece was prepared in the same manner for a polyethylene substrate (manufactured by Partec).

<Evaluation of physical properties of coating film>
Evaluation was performed by the following method using the obtained test piece.

1. Drying property Drying property was confirmed based on JIS-5600-1-1 and evaluated in three stages according to the following criteria.
○: The center of the paint surface is firmly pinched between the thumb and forefinger, and the paint surface does not have a dent due to fingerprints. △: The center of the paint surface is gently rubbed with the fingertip, and no mark is left on the paint surface. : Touching the center of the paint surface lightly with your fingertip and having tack.

2. Adhesiveness About the test piece whose dryness evaluation was (circle), the mandrel test was done based on JIS5600-5-1, and the adhesiveness of the coating film with respect to the base material immediately after test piece preparation was confirmed. The test was performed using a mandrel tester (model 266 manufactured by Eriksen) under the condition that the diameter of the mandrel was 32 mm. The coating film after the test was visually confirmed and evaluated in two stages according to the following criteria.
○: No peeling of coating film ×: Peeling of coating film

3. Wetability For a test piece having a dryness evaluation of ◯, 2.0 μL of pure water was dropped on the coating film surface of the test piece, and a contact angle measuring device (automatic contact angle meter DMo-601 manufactured by Kyowa Interface Chemical Co., Ltd.) was used. The contact angle was measured. For a polypropylene base material that is relatively difficult to wet among the base materials used for the preparation of the test piece, the value when the water contact angle was measured by the same method was 93 degrees. A contact angle exceeding the contact angle in the case of a polypropylene base material can be said to exhibit good wettability.

(Example 2)
A 2 L four-necked separable flask equipped with a stirrer, thermometer, heating device, reflux tube, 150.0 g of hydroxyl-terminated polybutadiene 1, 1.5 g of caprylic acid monoglyceride, 17.2 g of MDI, dioctyl dilaurate 0.094 g of tin and 1520 g of butyl acetate were respectively charged at room temperature, and then the atmosphere in the flask was replaced with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 2 hours, stirring uniformly on 80 degreeC conditions. About the obtained urethane resin composition, the number average molecular weight and the viscosity were measured in the same manner as in Example 1. Using the obtained urethane resin composition, the test piece was prepared and the physical properties of the coating film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
In a 2 L four-necked separable flask equipped with a stirrer, thermometer, heating device and reflux tube, 130.0 g of hydroxyl-terminated polybutadiene 2, 5.5 g of behenic acid monoglyceride, 32.6 g of MDI, dioctyl dilaurate After 0.18 g of tin and 1515 g of butyl acetate were charged at room temperature, the inside of the flask was purged with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 2 hours, stirring uniformly on 80 degreeC conditions. About the obtained urethane resin composition, the number average molecular weight and the viscosity were measured in the same manner as in Example 1. Using the obtained urethane resin composition, the test piece was prepared and the physical properties of the coating film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
130.0 g of hydroxyl-terminated polybutadiene 2, 2.9 g of caprylic acid monoglyceride, 32.6 g of MDI, dioctyl dilaurate in a 2 L four-necked separable flask equipped with a stirrer, thermometer, heating device and reflux tube After 0.18 g of tin and 1490 g of butyl acetate were charged at room temperature, the inside of the flask was purged with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 2 hours, stirring uniformly on 80 degreeC conditions. About the obtained urethane resin composition, the number average molecular weight and the viscosity were measured in the same manner as in Example 1. Using the obtained urethane resin composition, the test piece was prepared and the physical properties of the coating film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)
A 2 L four-necked separable flask equipped with a stirrer, thermometer, heating device, and reflux tube was charged with 150.0 g of hydroxyl-terminated hydrogenated polyisoprene, 1.7 g of behenic acid monoglyceride, 19.2 g of MDI, and dilaurin. After 0.11 g of dioctyltin acid and 1539 g of cyclohexanone were charged at room temperature, the inside of the flask was purged with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 2 hours, stirring uniformly on 80 degreeC conditions. About the obtained urethane resin composition, the number average molecular weight and the viscosity were measured in the same manner as in Example 1. Using the obtained urethane resin composition, the test piece was prepared and the physical properties of the coating film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
In a 2 L four-necked separable flask equipped with a stirrer, thermometer, heating device, and reflux tube, 150.0 g of hydroxyl-terminated polybutadiene 1, 15.5 g of MDI, 0.084 g of dioctyltin dilaurate, butyl acetate Were charged at room temperature, and then the inside of the flask was purged with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 2 hours, stirring uniformly on 80 degreeC conditions. About the obtained urethane resin composition, the number average molecular weight and the viscosity were measured in the same manner as in Example 1. Using the obtained urethane resin composition, the test piece was prepared and the physical properties of the coating film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
A 2 L four-necked separable flask equipped with a stirrer, thermometer, heating device, and reflux tube was charged with 110.0 g of monoglyceride behenate, 65.0 g of MDI, 0.36 g of dioctyltin dilaurate, and butyl acetate. After charging 1570 g at room temperature, the flask was purged with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 2 hours, stirring uniformly on 80 degreeC conditions. About the obtained urethane resin composition, the number average molecular weight and the viscosity were measured in the same manner as in Example 1. Using the obtained urethane resin composition, the test piece was prepared and the physical properties of the coating film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
In a 2 L four-necked separable flask equipped with a stirrer, thermometer, heating device, and reflux tube, 150.0 g of hydroxyl-terminated polybutadiene 1, 0.43 g of ethylene glycol, 15.5 g of MDI, dioctyltin dilaurate 0.094 g and 1500 g of butyl acetate were charged at room temperature, and the inside of the flask was purged with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 2 hours, stirring uniformly on 80 degreeC conditions. About the obtained urethane resin composition, the number average molecular weight and the viscosity were measured in the same manner as in Example 1. Using the obtained urethane resin composition, the test piece was prepared and the coating film properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 4)
In a 2 L four-necked separable flask equipped with a stirrer, thermometer, heating device, and reflux tube, 150.0 g of hydroxyl-terminated hydrogenated polyisoprene, 17.3 g of MDI, 0.10 g of dioctyltin dilaurate, After 1510 g of cyclohexanone was charged at room temperature, the inside of the flask was purged with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 2 hours, stirring uniformly on 80 degreeC conditions. About the obtained urethane resin composition, the number average molecular weight and the viscosity were measured in the same manner as in Example 1. Using the obtained urethane resin composition, the test piece was prepared and the physical properties of the coating film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

-Hydroxyl-terminated polybutadiene 1: Trade name Poly bd R-45HT, number average molecular weight 2,800, hydroxyl group content 0.84 mol / kg, manufactured by Idemitsu Kosan Co., Ltd.-Hydroxyl terminal polybutadiene 2: Trade name Poly bd R-15HT, number average molecular weight 1,200, hydroxyl group content 1.84 mol / kg, manufactured by Idemitsu Kosan Co., Ltd., hydroxyl-terminated hydrogenated polyisoprene: Trade name EPOL, number average molecular weight 2,500, hydroxyl group content 0.94 mol / kg, manufactured by Idemitsu Kosan Co., Ltd., behenic acid Monoglyceride: Trade name Riquemar B-100, manufactured by Riken Vitamin Co., Caprylic acid monoglyceride: Trade name Riquemar M-100, manufactured by Riken Vitamin Co., ethylene glycol: Tokyo Chemical Industry Co., Ltd., reagent grade octyl tin dilaurate: manufactured by Kishida Chemical・ Butyl acetate: Gordo ・ Cyclohexanone: Go Dorchester Corporation.

  As is apparent from Table 1, according to the urethane resin composition of the present invention, sufficient adhesion to the resin base material is exhibited, including the polypropylene resin base material exhibiting high resistance to wettability, and the coating film surface is difficult. A coating composition capable of imparting wettability can be obtained.

Claims (11)

The following general formula (1):
[In general formula (1), R represents a hydrocarbon group having 2 to 10,000 carbon atoms (wherein the hydrocarbon group may be linear or branched, and may be cyclic when the number of carbon atoms is 3 or more, It may be a saturated hydrocarbon or an unsaturated hydrocarbon). ]
Compound (A) represented by
Polyisocyanate compound (B) and the following general formula (2):
[In the general formula (2), X represents a hydrocarbon group having 1 to 30 carbon atoms (wherein the hydrocarbon group may be a straight chain or a branched chain, and if it has 3 or more carbon atoms, it may be cyclic or saturated carbonization) Y may be hydrogen or unsaturated hydrocarbon), Y represents any one selected from the group consisting of a single bond, an ether group, a carbonyl group, an ester group, an amino group and an amide group, and Z represents a carbon number of 1 to 50 hydrocarbon groups, structures in which some or all of the carbon atoms of the hydrocarbon groups are substituted with heteroatoms, and structures in which some or all of the hydrogen atoms of the hydrocarbon groups are substituted with heteroatoms and / or functional groups (Herein, the hydrocarbon group may be a straight chain or a branched chain, and when the number of carbon atoms is 3 or more, it may be cyclic, saturated hydrocarbon, or unsaturated hydrocarbon). Represents one. ]
A compound (C) represented by:
A urethane resin composition characterized by being a reaction product of The compound (A) represented by the general formula (1) is a polyol polyolefin having 2 to 10,000 carbon atoms each having one hydroxyl group on two or more different carbons in the molecule. The urethane resin composition according to claim 1. The urethane resin composition according to claim 1 or 2, wherein the polyisocyanate compound (B) is a polyisocyanate compound having two isocyanate groups in one molecule. The urethane resin composition according to any one of claims 1 to 3, wherein the compound (C) represented by the general formula (2) is a monoglyceride. The urethane resin composition according to claim 1, wherein the number average molecular weight is 3,000 to 500,000. The coating composition containing the urethane resin composition in any one of Claims 1 thru | or 5. A coating film formed from the coating composition according to claim 6. The coating film according to claim 7, wherein the contact angle of water is 100 degrees or more. An article having the coating film according to claim 7 or 8. The article | item whose base material of the article | item of Claim 9 is resin. An article wherein the resin of claim 10 is a polyolefin.