JP2022179350A - Urethane resin composition, adhesive composition, and method for producing article - Google Patents

Abstract

To provide a urethane resin composition that has high storage stability and can give a plastic substrate with an excellent adhesive property.SOLUTION: A urethane resin composition contains a product from the reaction between a polyol compound (A), a polyisocyanate compound (B), and an optional component, or a chain extender (C). The polyol compound (A) is at least one selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyfarnesene polyol. In the reaction product, the total content of the polyol compound (A) and the chain extender (C) is 75 mass% or more and 99.9 mass% or less.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a urethane resin composition, an adhesive composition, and a method for producing an article.

Plastic substrates are widely used industrially. For example, plastic base materials are widely used for automobile interior materials; electric appliances such as washing machines and refrigerators; electronic devices such as smartphones and personal computers; There are also uses specific to plastic substrates such as films. For example, films made of polyethylene terephthalate are widely used as food packaging materials, base materials for release films used in the manufacturing process of electronic materials, and the like.

It is generally known that the surface of a plastic base material is less wettable than that of a metal base material. The difficulty of wetting the surface of the plastic base material (hereinafter referred to as "difficult wettability") causes defects such as cissing when applying adhesives or paints, which makes it difficult to obtain a uniform coating surface. , undesirable. In addition, substrates exhibiting poor wettability are generally known to exhibit poor adhesion. Undesirable.

As a method for improving the adhesiveness of the plastic base material, there is a method of improving the wettability by changing the composition of the plastic base material, modifying the surface thereof, or the like. However, it requires a large equipment investment due to the need for large equipment, it is difficult to set optimal conditions, it requires a surface modification process, and it cuts the molecular chains on the surface of the plastic substrate. Therefore, there is a problem that there is a concern that the mechanical strength is lowered.

Therefore, Patent Document 1 discloses a hydrogenated polyisoprene skeleton urethane resin composition as an adhesive exhibiting good adhesion to polypropylene, which is an untreated plastic substrate exhibiting poor wettability and adhesion. ing.

JP 2020-66686 A

However, the urethane resin composition according to Patent Document 1 has low compatibility with solvents, and there is a problem that the resin solid content precipitates over time, and further improvement is required for industrial use.
Accordingly, one embodiment of the present invention is directed to providing a urethane resin composition, an adhesive composition, and an adhesive layer that are excellent in storage stability and exhibit good adhesion to plastic substrates. there is Other embodiments of the present invention are also directed to providing an article comprising the adhesive layer and a method of manufacturing the article.

That is, the present invention includes the embodiments shown below.
[1] a polyol compound (A);
a polyisocyanate compound (B);
containing a reaction product of an optional chain extender (C),
The polyol compound (A) is one or more selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyfarnesene polyol,
The urethane resin composition, wherein the total content of the polyol compound (A) and the chain extender (C) in the reaction product is 75% by mass or more and 99.9% by mass or less.
[2] The urethane resin composition according to [1], wherein the polyol compound (A) has a double bond content of 50 g/100 g or less as an iodine value.
[3] Described in [1] or [2], wherein the molar ratio of the 1,2-adduct and the 1,4-adduct in the hydrogenated polybutadiene polyol molecule is 20:80 or more and 85:15 or less. urethane resin composition.
[4] [1] or [2], wherein the molar ratio of the 1,4-adduct and the 3,4-adduct in the hydrogenated polyfarnesene polyol molecule is 80:20 or more and 50:50 or less; ] The urethane resin composition as described in .
[5] Any one of [1] to [4], wherein the polyol compound (A) is two or more selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyfarnesene polyol. urethane resin composition.
[6] The urethane resin composition according to any one of [1] to [5], which has a weight average molecular weight of 8,000 or more and 95,000 or less.
[7] An adhesive composition comprising the urethane resin composition according to any one of [1] to [6].
[8] An adhesive layer containing the adhesive composition according to [7].
[9] a substrate;
An article comprising the adhesive layer according to [8].
[10] The article according to [9], wherein the adhesive layer and the substrate have a heat-changeable portion at their adhesive interface.
[11] The article according to [9] or [10], wherein the substrate is plastic.
[12] The article according to [9] or [10], wherein the substrate is polyolefin.
[13] An article comprising the article according to any one of [9] to [12] and another substrate.
[14] The article according to [13], wherein the other substrate is a substrate having a resin coating film.
[15] A method for manufacturing the article according to any one of [9] to [14],
A method comprising heating the substrate and the adhesive layer.
[16] The method for producing an article according to [15], wherein the heating is at 70°C or higher and 300°C or lower.

According to one embodiment of the present invention, it is possible to provide a urethane resin composition, an adhesive composition, and an adhesive layer that are excellent in storage stability and exhibit good adhesion to plastic substrates. Further, according to another embodiment of the present invention, it is possible to provide an article provided with the adhesive layer and a method for manufacturing the article.

Exemplary embodiments for implementing aspects of the invention are described in further detail. However, the present invention is not limited to the following embodiments.

[Urethane resin composition]
A urethane resin composition according to one embodiment of the present invention is
a polyol compound (A);
a polyisocyanate compound (B);
containing a reaction product of an optional chain extender (C),
The polyol compound (A) is one or more selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyfarnesene polyol,
The total content of the polyol compound (A) and the chain extender (C) in the reaction product is 75% by mass or more and 99.9% by mass or less.

[[Polyol compound (A)]]
The polyol compound (A) is one or more selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyfarnesene polyol.
Although the polyol compound (A) is not particularly limited, it may partially have a double bond in its molecular structure. From the viewpoint of adhesion, the double bond content in the polyol compound (A) is preferably 50 g/100 g or less, more preferably 25 g/100 g or less, and 15 g/100 g or less as an iodine value. is most preferred and may be 10 g/100 g. The iodine value can be measured according to JIS (JIS K0070).

Hydrogenated polybutadiene polyols are not particularly limited, but include, for example, 1,2-adducts, 1,4-adducts, and those having both of these skeletons in one molecule. . In the case of having both skeletons, the molar ratio of the 1,2-adduct and the 1,4-adduct is preferably 20:80 or more and 85:15 or less, and 65:35 or more from the viewpoint of compatibility. 85:15 or less is more preferable, and 80:20 or more and 85:15 or less is most preferable. These may be used independently and may use 2 or more types together.

Hydrogenated polyfarnesene polyols are not particularly limited, but for example, 1,4-adducts, 3,4-adducts, and those having both of these skeletons in one molecule is mentioned. When both skeletons are present, the molar ratio of the 1,4-adduct and the 3,4-adduct is preferably 80:20 or more and 50:50 or less, and 70:30 or more, from the viewpoint of compatibility. 50:50 or less is more preferable, and 65:35 or more and 50:50 or less is most preferable. These may be used independently and may use 2 or more types together.

From the viewpoint of resin polymerizability, it is preferable to have a hydroxyl group at the molecular end.
Among these, from the viewpoint of compatibility and adhesion with solvents, additives, and other resins,
(1) Hydroxyl-terminated hydrogenated polybutadiene having an iodine value of 15 g/100 g or less and a molar ratio of 1,2-adduct and 1,4-adduct per molecule of 80:20 or more and 85:15 or less; or,
(2) a hydroxyl-terminated hydrogenated polyfarnesene having an iodine value of 15 g/100 g or less and a molar ratio of 1,4-adduct and 3,4-adduct per molecule of 65:35 or more and 50:50 or less;
is preferred,
(1′) Hydroxyl-terminated hydrogenated polybutadiene having an iodine value of 10 g/100 g or less and a molar ratio of 1,2-adduct and 1,4-adduct per molecule of 80:20 or more and 85:15 or less ,or,
(2′) Hydroxyl-terminated hydrogenated polyfarnesene having an iodine value of 10 g/100 g or less and a molar ratio of 1,4-adduct and 3,4-adduct per molecule of 65:35 or more and 50:50 or less ,
may be

From the viewpoint of adhesive strength, the polyol compound (A) is preferably two or more selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyfarnesene polyol.
The weight average molecular weight of the polyol compound (A) is such that the total content of the polyol compound (A) and the chain extender (C) in the reaction product is 75% by mass or more and 99.9% by mass or less. As far as possible, it is preferably 1,000 or more, more preferably 2,000 or more, and most preferably 3,000 or more. When the polyol compound (A) consists of two or more kinds, the weight average molecular weight of the polyol compound (A) means two or more kinds selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyfarnesene polyol. It means the weight average molecular weight of the mixture.

[[Polyisocyanate compound (B)]]
The polyisocyanate compound (B) is not particularly limited, but examples include diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 2,4-toluenediisocyanate, and 2,6-toluene. Isocyanates having an aromatic skeleton such as 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 isocyanates having an aliphatic skeleton such as diisocyanate, dimer acid diisocyanate, norbornene diisocyanate; and the like. These may be monomers or polymers, 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 preferred from the viewpoint of mechanical strength, and hexagonal Methylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate and hydrogenated diphenylmethane-2,4'-diisocyanate are preferred. These may be used independently and may use 2 or more types together.

[[chain extender (C)]]
The urethane resin composition may be a reaction product obtained by reacting the polyol compound (A), the polyisocyanate compound (B), and an optional chain extender (C).
Examples of the chain extender (C) include, but are not limited to, polyether polyols such as polyethylene glycols, polypropylene glycols, and polybutylene glycols; caprylic acid monoglyceride, capric acid monoglyceride, and lauric acid monoglyceride. monoglycerides such as monoglyceride stearate and monoglyceride behenate; glycols having side chains such as 2-methyl-1,3-propanediol and 3-methyl-1,5-pentanediol; polyols such as mentioned. These may be used independently and may use 2 or more types together.

[[Total content]]
Total content of the polyol compound (A) and the chain extender (C) in the reaction product of the polyol compound (A), the polyisocyanate compound (B), and the optional chain extender (C) The amount is preferably 75% by mass or more and 99.9% by mass or less, more preferably 78% by mass or more and 95% by mass or less, and most preferably 80% by mass or more and 90% by mass or less. If the content is less than 75% by mass or more than 99.9% by mass, there is a concern that the adhesiveness will be insufficient.

The weight average molecular weight of the urethane resin composition is preferably 8,000 or more and 95,000 or less, more preferably 10,000 or more and 50,000 or less, and preferably 14,000 or more and 35,000 or less. Most preferably, it may be 14,000 or more and 26,000 or less. Also when the urethane resin composition is a reaction product of the polyol compound (A), the polyisocyanate compound (B), and the chain extender (C), it is preferable that the molecular weight is the same.

In addition to the polyol compound (A), the polyisocyanate compound (B), and the optional chain extender (C), the urethane resin composition optionally contains other components within a range that does not impair the object of the present invention. may be Other components are not particularly limited, and examples include solvents, catalysts, antifoaming agents, leveling agents, organic thickeners, antioxidants, light stabilizers, adhesion improvers, release agents, reinforcing agents, and softening agents. agents, coloring agents, flame retardants, antistatic agents, wetting and dispersing agents, and the like.

The solvent is not particularly limited, and examples include aromatic hydrocarbon solvents such as toluene, ethylbenzene, trimethylbenzene, and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, and cyclohexane; acetone, methyl ethyl ketone, 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, butyl Glycol ether solvents such as diglycol and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethyl Amide solvents such as acetamide and N-methylpyrrolidone; ether solvents such as diethyl ether and tetrahydrofuran; water; These may be used independently and may use 2 or more types together.

When the urethane resin composition contains a solvent, the content thereof may be selected depending on the coating method and the thickness of the desired urethane resin coating film, and is not particularly limited. 0 parts by mass or more and 10,000 parts by mass or less, more preferably 40 parts by mass or more and 3,200 parts by mass or less, and most preferably 150 parts by mass or more and 2,000 parts by mass or less. . When the content of the solvent is 1.0 parts by mass or more, the viscosity of the urethane resin composition can be reduced, and coating becomes easier. When the content of the solvent is 10,000 parts by mass or less, the film thickness of the urethane resin coating film does not become too thin, and a sufficient film thickness can be easily obtained.

The catalyst is not particularly limited, and examples thereof include organometallic compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dioctyltin dilaurate; organic amines such as triethylenediamine and triethylamine; and salts thereof. These may be used independently and may use 2 or more types together.

When the urethane resin composition contains a catalyst, the content thereof may be selected according to the reactivity of the polyisocyanate compound used, and is not particularly limited, but is 0.00010 parts by mass or more with respect to 1 part by mass of the urethane resin composition. It is preferably 25 parts by mass or less, more preferably 0.0010 parts by mass or more and 6.0 parts by mass or less, and most preferably 0.010 parts by mass or more and 1.0 parts by mass or less. When the content is 0.00010 parts by mass or more, a sufficient catalytic effect is more likely to be obtained, and when the content is 25 parts by mass or less, it is more preferable in terms of economy.

The leveling agent is not particularly limited, and examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, silicone surfactants, nonionic surfactants, fluorine surfactants, acrylic surfactants, and the like. is mentioned. These may be used independently and may use 2 or more types together.

When the urethane resin composition contains a leveling agent, the content is not particularly limited, but is preferably 0.0010 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the urethane resin composition. It is more preferably 010 parts by mass or more and 12 parts by mass or less, and most preferably 0.050 parts by mass or more and 6 parts by mass or less. When the content is 0.0010 parts by mass or more, the leveling property becomes more sufficient, and when the content is 25 parts by mass or less, the adhesiveness of the urethane resin coating film tends to become more sufficient.

The coating film obtained from the urethane resin composition according to the present embodiment exhibits good adhesion to various substrates including plastic substrates exhibiting poor wettability.

[Adhesive composition, adhesive layer, article, method for producing article]
The urethane resin composition described above can be suitably used for an adhesive composition.
An adhesive composition according to one embodiment of the present invention contains the urethane resin composition.
Further, an adhesive layer according to one embodiment of the present invention contains the adhesive composition.
Furthermore, an article according to one embodiment of the present invention comprises the adhesive layer and a substrate. Here, it is preferable that the adhesive layer and the base material have a heat-changeable portion at their adhesive interface. A heat-changed portion is a portion that is changed by heating. In other words, the article according to this embodiment is formed by bonding the adhesive layer and the base material together by heating.

The material of the substrate is not particularly limited, and examples include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin), nylon 6, nylon 66, aramid, acrylic, polyethylene. Resins such as terephthalate and polybutylene terephthalate; composite materials composed of the plastic base material and glass fiber; composite materials of thermosetting resins such as epoxy resins or thermoplastic resins such as polyphenylene sulfide and carbon fibers (CFRP (Carbon Carbon Fiber Reinforced Thermo plastics); CFRTP (Carbon Fiber Reinforced Thermo plastics)), metals such as aluminum, aluminum alloys, magnesium, stainless steel, tin plate, electrogalvanized steel plate, chromium plated steel plate; These substrates may be used alone, or two or more of them may be used in combination or as a composite material in which they are mixed. Among these, plastic substrates are preferable because they are highly versatile substrates such as easy molding after coating, polyolefins are more preferable because they are lightweight and inexpensive, and polyethylene, polypropylene, and polystyrene are most preferable.

A method of manufacturing an article according to one embodiment of the present invention includes heating a substrate and an adhesive layer. Heating is preferably performed at a temperature of 70°C or higher and 300°C or lower.
The method for manufacturing an article according to this embodiment may further comprise forming an adhesive layer on the substrate.
The method of forming an adhesive layer using the adhesive composition and manufacturing an article is not particularly limited, and for example, a method of applying the adhesive composition to at least one surface of a substrate and then drying the adhesive composition. is mentioned.

The method of applying the adhesive composition is not particularly limited, and examples thereof include 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. be done.

Although the drying temperature is not particularly limited, it is preferably 50 to 300°C, more preferably 50 to 200°C, and most preferably 80 to 150°C. If the drying temperature is 50° C. or higher, the amount of residual solvent can be further reduced. When the drying temperature is 300° C. or lower, thermal decomposition of the adhesive layer can be further suppressed. The drying time is not particularly limited, but preferably 5 seconds to 12 hours, more preferably 20 seconds to 1 hour, and most preferably 1 minute to 30 minutes. When the drying time is 5 seconds or longer, poor drying can be further suppressed. When the drying time is 12 hours or less, the time required for the process can be further reduced, resulting in further excellent productivity.

The article may further comprise other substrates. Other substrates may be substrates having a resin coating.
That is, an article can be obtained by bonding a base material having an adhesive layer and another base material. At this time, the other base material may be used for adhesion without being coated, or the other base material may be coated with a resin having an affinity for the other base material and used for adhesion. When a resin having affinity with other substrates is applied, the resin composition is selected depending on the substrate and is not particularly limited, and examples thereof include urethane resins, epoxy resins and acrylic resins. Among others, considering affinity with the adhesive layer, the other base material is preferably a urethane resin. Moreover, the urethane resin applied to the other substrate may be the same as or different from the urethane resin composition according to one embodiment of the present invention. The conditions for applying the resin to the other substrate and drying it are preferably the same as the conditions for drying the urethane resin composition according to the embodiment of the present invention.

The temperature at which the base material having the urethane resin adhesive layer according to one embodiment of the present invention is bonded to another base material is not particularly limited, but is preferably 70 to 300°C, more preferably 100 to 250°C. and most preferably 130 to 200°C. When the treatment temperature is 70° C. or higher, poor adhesion can be further suppressed. When the temperature is 300°C or lower, thermal decomposition of the urethane resin coating film can be further suppressed. The treatment time is not particularly limited, but preferably 1 second to 12 hours, more preferably 10 seconds to 1 hour, and most preferably 10 seconds to 30 minutes. When the treatment time is 1 second or longer, poor adhesion can be further suppressed. When the treatment time is 12 hours or less, the time required for the process can be further reduced, resulting in further excellent productivity.

Although the thickness of the adhesive layer is not particularly limited, it is preferably 0.05 to 300 μm, more preferably 0.1 to 200 μm, and most preferably 5 to 100 μm. When the thickness is 0.05 µm or more, the adhesiveness of the adhesive layer is further excellent. When the thickness is 300 µm or less, the time required for drying can be further reduced, so the productivity is further improved.

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)
A urethane resin composition was produced, a test piece was prepared, a coating film physical property was evaluated, and a storage stability was evaluated by the following methods. Table 1 shows the results.

<Production of urethane resin composition>
150.0 g of hydroxyl-terminated hydrogenated polybutadiene 1 and diphenylmethane-4,4′-diisocyanate (hereinafter referred to as MDI) were placed in a 2 L four-necked separable flask equipped with a stirrer, thermometer, heating device and reflux tube. ), 0.281 g of dioctyltin dilaurate, and 1735 g of cyclohexanone were charged at room temperature, and then nitrogen gas was blown into the flask to replace the inside of the flask with nitrogen. After reacting these for 2 hours with uniform stirring under conditions of 80° C., 8.74 g of 2-methyl-1,3-propanediol was added, and the mixture was further reacted for 6 hours under the same conditions to obtain a urethane resin composition. got About the obtained urethane resin composition, the weight average molecular weight was measured by the following method.

<Measurement of weight average molecular weight>
Determined by gel permeation chromatography (GPC). The conditions are as follows. A high-speed GPC device (HLC-8320GPC manufactured by Tosoh Corporation) as an apparatus, one TSKgel guard column α (6.0 mm ID × 4 cm) as a column, two +α-M (67.8 mm ID × 30 cm), Those which were connected in series in the order described were used (both columns are manufactured by Tosoh Corporation). Cyclohexanone was used as the mobile phase with a mobile phase rate of 1.0 mL/min. The column temperature was set to 40° C., the detector was an RI detector (polarity (+)), and the molecular weight was obtained as polystyrene equivalent molecular weight. A sample solution was prepared using cyclohexanone so as to have a concentration of 1 mg/mL. The sample injection volume was 100 μL.

<Preparation of test piece>
First, the urethane resin composition obtained above was applied to a polypropylene base material (PP base material; Kobe Poly Sheet PP manufactured by Hitachi Chemical Co., Ltd.) using a bar coater and allowed to stand at room temperature for 5 minutes. It was dried at 80° C. for 5 minutes using a hot air dryer to obtain a polypropylene test piece having an adhesive layer with a dry film thickness of 10 μm. Next, after laminating a polyethylene terephthalate film (Toyobo Ester Film E5100 manufactured by Toyobo Co., Ltd.) on the adhesive layer, a test piece was obtained by heat-treating at 185° C. for 10 minutes. A test piece using a polyethylene base material (PE base material; Koube Poly Sheet EL-N-AN manufactured by Hitachi Chemical Co., Ltd.) was also prepared in a similar manner. However, the heat treatment temperature was changed to 140°C.

<Evaluation of adhesive properties>
A 180-degree peel test was performed on the test pieces obtained by laminating them in accordance with JISK6854-2 to evaluate the adhesive strength. The test was measured using an Autocom type testing machine (UTPS-Acs (S) manufactured by TSE Co., Ltd.).

<Evaluation of storage stability>
The urethane resin composition obtained above was allowed to stand at room temperature (20 to 25° C.) and stored. The appearance of the urethane resin composition after production was visually observed for a certain period of time to confirm the presence or absence of turbidity and phase separation (turbidity and phase separation occur due to precipitation of the urethane resin composition). The confirmation period was every 24 hours for 5 days after production, and thereafter every 7 days based on the date of production. Confirmation was carried out for 84 days. Storage stability was assessed based on the time to onset of turbidity and phase separation. Here, the best result is that turbidity and phase separation do not occur within the period.

(Example 2)
150.0 g of hydroxyl-terminated hydrogenated polybutadiene 1, 22.5 g of MDI, 0.137 g of dioctyltin dilaurate, and After charging 1554 g of cyclohexanone at room temperature, the inside of the flask was replaced with nitrogen gas by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 6 hours, stirring uniformly at 80 degreeC conditions. The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Example 3)
150.0 g of hydroxyl-terminated hydrogenated polybutadiene 1, 19.5 g of MDI, 0.137 g of dioctyltin dilaurate, and After charging 1527 g of cyclohexanone at room temperature, the inside of the flask was replaced with nitrogen gas by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 6 hours, stirring uniformly at 80 degreeC conditions. The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Example 4)
150.0 g of hydroxyl-terminated hydrogenated polybutadiene 1, 18.0 g of MDI, 0.137 g of dioctyltin dilaurate, and After charging 1513 g of cyclohexanone at room temperature, the inside of the flask was replaced with nitrogen by blowing in nitrogen gas. The urethane resin composition was obtained by making these react for 6 hours, stirring uniformly at 80 degreeC conditions. The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Example 5)
150.0 g of hydroxyl-terminated hydrogenated polyfarnesene, 16.4 g of MDI, 0.0759 g of dioctyltin dilaurate, and cyclohexanone were placed in a 2-liter four-neck separable flask equipped with a stirrer, thermometer, heating device, and reflux tube. 1498 g of each was charged at room temperature, and then the inside of the flask was replaced with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 6 hours, stirring uniformly at 80 degreeC conditions. The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Example 6)
120.7 g of hydroxyl-terminated hydrogenated polybutadiene 1, 29.3 g of hydroxyl-terminated hydrogenated polybutadiene 2, and 19.0 g of MDI were placed in a 2-liter four-necked separable flask equipped with a stirrer, a thermometer, a heating device, and a reflux tube. 7 g of dioctyltin dilaurate, 0.129 g of dioctyltin dilaurate, and 1529 g of cyclohexanone were added at room temperature, and then nitrogen gas was blown into the flask to replace the inside of the flask with nitrogen. The urethane resin composition was obtained by making these react for 6 hours, stirring uniformly at 80 degreeC conditions. The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Example 7)
93.4 g of hydroxyl-terminated hydrogenated polybutadiene 1, 56.6 g of hydroxyl-terminated hydrogenated polybutadiene 2, and 19.0 g of MDI were placed in a 2-liter four-necked separable flask equipped with a stirrer, thermometer, heating device, and reflux tube. After charging 8 g of dioctyltin dilaurate, 0.121 g of dioctyltin dilaurate, and 1530 g of cyclohexanone at room temperature, nitrogen gas was blown into the flask to replace the inside of the flask with nitrogen. The urethane resin composition was obtained by making these react for 6 hours, stirring uniformly at 80 degreeC conditions. The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Example 8)
134.2 g of hydroxyl-terminated hydrogenated polybutadiene 1, 15.9 g of hydroxyl-terminated hydrogenated polybutadiene 3, and 19.9 g of MDI were placed in a 2-liter four-necked separable flask equipped with a stirrer, thermometer, heating device, and reflux tube. 7 g of dioctyltin dilaurate, 0.129 g of dioctyltin dilaurate, and 1529 g of cyclohexanone were added at room temperature, and then nitrogen gas was blown into the flask to replace the inside of the flask with nitrogen. The urethane resin composition was obtained by making these react for 6 hours, stirring uniformly at 80 degreeC conditions. The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Example 9)
119.4 g of hydroxyl-terminated hydrogenated polybutadiene 1, 30.6 g of hydroxyl-terminated hydrogenated polybutadiene 3, and 19.0 g of MDI were placed in a 2-liter four-necked separable flask equipped with a stirrer, thermometer, heating device, and reflux tube. After charging 9 g of dioctyltin dilaurate, 0.121 g of dioctyltin dilaurate, and 1530 g of cyclohexanone at room temperature, nitrogen gas was blown into the flask to replace the inside of the flask with nitrogen. The urethane resin composition was obtained by making these react for 6 hours, stirring uniformly at 80 degreeC conditions. The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Comparative example 1)
110.0 g of hydroxyl-terminated hydrogenated polybutadiene 1, 45.2 g of MDI, 0.376 g of dioctyltin dilaurate, and After charging 1550 g of cyclohexanone at room temperature, the inside of the flask was replaced with nitrogen by blowing nitrogen gas. After reacting these for 2 hours with uniform stirring under conditions of 80° C., 16.7 g of 2-methyl-1,3-propanediol was added, and the mixture was further reacted for 6 hours under the same conditions to obtain a urethane resin composition. got The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Comparative example 2)
100.0 g of hydroxyl-terminated hydrogenated polybutadiene 1, 70.0 g of MDI, 0.583 g of dioctyltin dilaurate, and After charging 1803 g of cyclohexanone at room temperature, nitrogen gas was blown into the flask to replace the inside of the flask with nitrogen. After reacting these for 2 hours with uniform stirring under conditions of 80° C., 29.8 g of 2-methyl-1,3-propanediol was added, and the mixture was further reacted for 6 hours under the same conditions to obtain a urethane resin composition. got The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 3)
150.0 g of hydroxyl-terminated polybutadiene, 16.4 g of MDI, 0.0937 g of dioctyltin dilaurate, and 1498 g of cyclohexanone were placed in a 2-liter four-necked separable flask equipped with a stirrer, thermometer, heating device, and reflux tube. , and after charging at room temperature, the inside of the flask was replaced with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 6 hours, stirring uniformly at 80 degreeC conditions. The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 4)
150.0 g of hydroxyl-terminated polyfarnesene, 16.4 g of MDI, 0.0834 g of dioctyltin dilaurate, and 1498 g of cyclohexanone were placed in a 2-liter four-necked separable flask equipped with a stirrer, thermometer, heating device, and reflux tube. , and after charging at room temperature, the inside of the flask was replaced with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 6 hours, stirring uniformly at 80 degreeC conditions. The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 5)
150.0 g of hydroxyl-terminated hydrogenated polyisoprene, 16.4 g of MDI, 0.103 g of dioctyltin dilaurate, and 150.0 g of hydroxyl-terminated hydrogenated polyisoprene, 16.4 g of MDI, After charging 1499 g of cyclohexanone at room temperature, the inside of the flask was replaced with nitrogen by blowing in nitrogen gas. The urethane resin composition was obtained by making these react for 6 hours, stirring uniformly at 80 degreeC conditions. The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 6)
150.0 g of hydroxyl-terminated polyisoprene, 16.4 g of MDI, 0.0937 g of dioctyltin dilaurate, and cyclohexanone were placed in a 2-liter four-necked separable flask equipped with a stirrer, thermometer, heating device, and reflux tube. After charging 1498 g of each at room temperature, the inside of the flask was replaced with nitrogen by blowing nitrogen gas. The urethane resin composition was obtained by making these react for 6 hours, stirring uniformly at 80 degreeC conditions. The weight average molecular weight of the resulting urethane resin composition was measured in the same manner as in Example 1. Using the obtained urethane resin composition, a test piece was prepared and the physical properties of the adhesive and storage stability were evaluated in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 7)
A 10% hexane solution of hydrogenated polyisoprene liquid rubber (trade name Kuraprene LIR-290, weight average molecular weight 31,000, manufactured by Kuraray Co., Ltd.) was used instead of the urethane resin composition, and the test was performed in the same manner as in Example 1. Pieces were prepared, adhesive physical properties were evaluated, and storage stability was evaluated. Table 1 shows the results.

・Hydroxyl group-terminated hydrogenated polybutadiene 1: Product name GI-1000, number average molecular weight 1,500, hydroxyl group content 1.22 mol / kg, iodine value 9.2 g / 100 g, manufactured by Nippon Soda Co., Ltd. ・Hydroxyl group-terminated hydrogenated polybutadiene 2: Product Name GI-2000, number average molecular weight 2,000, hydroxyl group content 0.84 mol / kg, iodine value 13.3 g / 100 g, manufactured by Nippon Soda Co., Ltd., hydroxyl group-terminated hydrogenated polybutadiene 3: trade name GI-3000, number average molecular weight 3 , 100, hydroxyl group content 0.51 mol/kg, iodine value 13.8 g/100 g, manufactured by Nippon Soda Co., Ltd., hydroxyl-terminated hydrogenated polyfarnesene: trade name Krasol F3100, number average molecular weight 3,000, hydroxyl group content 0.68 mol/kg, Iodine value 9.7 g/100 g, manufactured by TOTAL ・Hydroxy group-terminated polybutadiene: trade name Poly bd R-45HT, number average molecular weight 2,800, hydroxyl group content 0.84 mol/kg, iodine value 633 g/100 g, manufactured by Idemitsu Kosan Co., Ltd. ・Hydroxyl-terminated polyfarnesene: trade name Krasol F3000, number average molecular weight 3,000, hydroxyl group content 0.75 mol/kg, iodine value 369 g/100 g, manufactured by TOTAL Hydroxyl-terminated hydrogenated polyisoprene: trade name EPOL, number average molecular weight 2, 500, hydroxyl group content 0.94 mol/kg, iodine value 7.9 g/100 g, manufactured by Idemitsu Kosan Co., Ltd., hydroxyl group-terminated polyisoprene: trade name Poly ip, number average molecular weight 2,500, hydroxyl group content 0.84 mol/kg, iodine value 350 g / 100 g, manufactured by Idemitsu Kosan Co., Ltd., diphenylmethane-4,4'-diisocyanate (MDI): trade name Millionate MT, isocyanate group content 31.3%, manufactured by Tosoh Corporation, 2-methyl-1,3-propanediol: Tokyo Manufactured by Kasei Kogyo Co., Ltd. ・Dioctyltin dilaurate: Manufactured by Kishida Chemical Co., Ltd. ・Cyclohexanone: Manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.

As is clear from Table 1, the urethane resin composition according to one embodiment of the present invention can impart sufficient adhesion to plastic substrates, including polypropylene substrates, which are polyolefins exhibiting poor adhesion. A urethane resin composition can be obtained.

Claims (16)

a polyol compound (A);
a polyisocyanate compound (B);
containing a reaction product of an optional chain extender (C),
The polyol compound (A) is one or more selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyfarnesene polyol,
The urethane resin composition, wherein the total content of the polyol compound (A) and the chain extender (C) in the reaction product is 75% by mass or more and 99.9% by mass or less. 2. The urethane resin composition according to claim 1, wherein the polyol compound (A) has a double bond content of 50 g/100 g or less as an iodine value. 3. The urethane resin composition according to claim 1, wherein the molar ratio of the 1,2-adduct and the 1,4-adduct in the hydrogenated polybutadiene polyol molecule is 20:80 or more and 85:15 or less. . The urethane according to claim 1 or 2, wherein the molar ratio of the 1,4-adduct and the 3,4-adduct in the hydrogenated polyfarnesene polyol molecule is 80:20 or more and 50:50 or less. Resin composition. The urethane resin composition according to claim 1 or 2, wherein the polyol compound (A) is two or more selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyfarnesene polyol. The urethane resin composition according to claim 1 or 2, having a weight average molecular weight of 8,000 or more and 95,000 or less. An adhesive composition comprising the urethane resin composition according to claim 1. An adhesive layer comprising the adhesive composition of claim 7 . a substrate;
and an adhesive layer according to claim 8 . 10. The article of claim 9, wherein the adhesive layer and the substrate have a heat sensitive zone at their adhesive interface. 10. The article of claim 9, wherein said substrate is plastic. 10. The article of claim 9, wherein said substrate is polyolefin. An article comprising the article of claim 9 and another substrate. 14. The article according to claim 13, wherein said other substrate is a substrate having a resin coating. A method of manufacturing an article according to claim 9,
A method comprising heating the substrate and the adhesive layer. 16. The method for manufacturing an article according to claim 15, wherein the heating is from 70[deg.]C to 300[deg.]C.