WO2023243513A1

WO2023243513A1 - Urethane resin, adhesive, article, and method for producing article

Info

Publication number: WO2023243513A1
Application number: PCT/JP2023/021168
Authority: WO
Inventors: 慶彦白木
Original assignee: 東ソー株式会社
Priority date: 2022-06-15
Filing date: 2023-06-07
Publication date: 2023-12-21

Abstract

This urethane resin: is formed from a polyurethane containing a hydrogenated polyolefin polyol as the polyol unit; has a urethane group concentration of 0.80 to 1.10 mol/kg; and has a weight-average molecular weight of 12,300 to 42,000.

Description

Urethane resin, adhesive, article and article manufacturing method

The present invention relates to urethane resins, adhesives, articles, and methods for producing articles.

Base materials containing polyolefins such as polypropylene (hereinafter referred to as "polyolefin base materials") are widely used industrially. Polyolefin base materials have the advantage of being lighter and cheaper than metal materials, and are easier to mold and process.

It is known that the surface of polyolefin substrates is less wettable than that of metal substrates. Difficulty in wetting the surface is a factor that causes defects such as repellency when applying adhesives or paints, for example. Furthermore, a substrate whose surface is difficult to wet generally exhibits poor adhesion and is prone to poor adhesion and peeling of the coating film. For this reason, studies have been conducted to improve the adhesion between the base material and adhesives or paints by changing the composition of the base material, modifying the surface, or the like.

For example, Patent Document 1 describes a modified polyolefin in which properties such as adhesiveness are improved by melt-kneading a radical polymerization initiator, an unsaturated carboxylic acid monomer, and an aromatic vinyl monomer to a polyolefin resin. A method for obtaining a based resin composition is described.

Japanese Patent Application Publication No. 2009-13230

However, the method of changing the composition of the base material as described in Patent Document 1 has problems in terms of practicality and cost. Furthermore, the method of improving adhesion by surface modification of the base material (for example, corona treatment) also has the problem of requiring large-scale equipment and a large amount of capital investment. Therefore, there is a need to develop a method for improving the adhesion between polyolefin substrates and adhesives or paints without changing the composition of the substrate or modifying the surface of the substrate.

Therefore, some aspects of the present invention are to provide a urethane resin that can form a urethane resin layer that firmly adheres to a polyolefin base material, regardless of whether or not the surface of the polyolefin base material has been modified. With the goal. Another aspect of the present invention is to provide an adhesive containing the above urethane resin. Yet another aspect of the present invention is to provide an article including a polyolefin base material and a urethane resin layer formed using the above-mentioned urethane resin. Yet another aspect of the present invention is to provide a method for manufacturing the above article.

Some aspects of the present invention provide [1] to [23] shown below.

[1]
Consisting of polyurethane containing hydrogenated polyolefin polyol as a polyol unit,
The urethane group concentration is 0.80 to 1.10 mol/kg,
A urethane resin having a weight average molecular weight of 12,300 to 42,000.

[2]
The urethane resin according to [1], wherein the hydrogenated polyolefin polyol contains at least one selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyfarnesene polyol.

[3]
The hydrogenated polyolefin polyol includes a hydrogenated polybutadiene polyol,
The urethane resin according to [1] or [2], wherein the molar ratio of the 1,2-adduct to the 1,4-adduct in the hydrogenated polybutadiene polyol is from 20:80 to 90:10.

[4]
The urethane resin according to any one of [1] to [3], wherein the hydrogenated polyolefin polyol has an iodine value of 50 g/100 g or less.

[5]
The urethane resin according to any one of [1] to [4], wherein the hydrogenated polyolefin polyol has a hydroxyl group content of 0.50 to 2.00 mol/kg.

[6]
The urethane resin according to any one of [1] to [5], wherein the content of polyol units is 75.0 to 99.9% by mass based on the total mass of the polyurethane.

[7]
The urethane resin according to any one of [1] to [6], which is a mixture of two or more polyurethanes that differ in at least one of urethane group concentration and weight average molecular weight.

[8]
A polyurethane (A1) having a weight average molecular weight of 12,300 or more and less than 20,000;
The urethane resin according to [7], which is a mixture containing at least a polyurethane (A2) having a weight average molecular weight of 24,000 to 42,000.

[9]
The urethane resin according to [8], wherein the content of the polyurethane (A1) is 25% by mass or more based on the total mass of the urethane resin.

[10]
polyurethane (A3) having a weight average molecular weight of 12,300 to 32,000;
The urethane resin according to [7], which is a mixture containing at least polyurethane (A4) having a weight average molecular weight of more than 42,000 and 100,000 or less.

[11]
The urethane resin according to [10], wherein the content of the polyurethane (A3) is 50% by mass or more based on the total mass of the urethane resin.

[12]
polyurethane (A5) having a urethane group concentration of 0.80 to 1.02 mol/kg;
The urethane resin according to [7], which is a mixture containing at least a polyurethane (A6) having a urethane group concentration of more than 1.10 mol/kg and 3.00 mol/kg or less.

[13]
The urethane resin according to [12], wherein the content of the polyurethane (A5) is 50% by mass or more based on the total mass of the urethane resin.

[14]
The urethane resin according to any one of [1] to [13], wherein the urethane resin has a molecular weight distribution index of 2.5 to 6.0.

[15]
The urethane resin according to any one of [1] to [14], wherein the urethane resin has a surface energy of 23 mJ/m ² or less.

[16]
An adhesive comprising the urethane resin according to any one of [1] to [15].

[17]
The adhesive according to [16], which is for a polyolefin base material.

[18]
comprising a base material and a urethane resin layer adhered to one surface of the base material,
An article, wherein the urethane resin layer is formed of the urethane resin according to any one of [1] to [15] or a composition containing the urethane resin.

[19]
The article according to [18], wherein the urethane resin layer has a surface energy of 23 mJ/m ² or less.

[20]
The article according to [18] or [19], wherein the base material is a polyolefin base material.

[21]
A method for manufacturing an article comprising a base material and a urethane resin layer adhered to one surface of the base material, the method comprising:
Step (a) of arranging the urethane resin layer containing the urethane resin according to any one of [1] to [15] on the base material;
A method for manufacturing an article, comprising a step (b) of heating the base material and the urethane resin layer to bond the base material and the urethane resin layer.

[22]
The method for producing an article according to [21], wherein the base material is a polyolefin base material.

[23]
The method for producing an article according to [22], wherein the heating temperature in step (b) is 70 to 130°C.

According to some aspects of the present invention, there is provided a urethane resin that can form a urethane resin layer that firmly adheres to a polyolefin base material, regardless of whether or not the surface of the polyolefin base material has been modified. Can be done. According to another aspect of the present invention, an adhesive containing the above urethane resin can be provided. According to yet another aspect of the present invention, it is possible to provide an article including a polyolefin base material and a urethane resin layer formed using the above-mentioned urethane resin. According to yet another aspect of the present invention, a method for manufacturing the above article can be provided.

Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.

In this specification, a numerical range indicated using "-" indicates a range that includes the numerical values written before and after "-" as the minimum and maximum values, respectively. Furthermore, unless specifically specified, the units of numerical values written before and after "~" are the same. Further, in the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with the value shown in the Examples. Moreover, the upper limit values and lower limit values described individually can be combined arbitrarily. Further, the materials exemplified below may be used alone or in combination of two or more, unless otherwise specified. When a plurality of substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.

<Urethane resin and urethane resin composition>
The urethane resin composition is a composition containing a urethane resin. The urethane resin is made of polyurethane, which is a reaction product of a urethane resin-forming raw material containing a polyol compound and a polyisocyanate compound (for example, a reaction product obtained by reacting a polyol compound and a polyisocyanate compound in the presence of a catalyst). , contains at least a polyol unit and a polyisocyanate unit. Of the two types of structural units formed by the reaction (polymerization) of a polyol compound and a polyisocyanate compound, the structural unit derived from the polyol compound is a polyol unit, and the structural unit derived from a polyisocyanate compound is a polyisocyanate unit. The urethane resin may be made of one type of polyurethane, or may be a mixture of two or more types of polyurethane. Here, the mixture of two or more types of polyurethanes includes not only mixtures of polyurethanes having different constituent units (for example, polyol units and polyisocyanate units), but also mixtures of polyurethanes having different at least one of urethane group concentration and weight average molecular weight. It will be done.

The urethane resin (hereinafter, in some cases, referred to as "urethane resin (A)") according to one embodiment includes a hydrogenated polyolefin polyol as a polyol unit. More specifically, the urethane resin (A) is a resin made of polyurethane (hereinafter referred to as "polyurethane (A)") containing a hydrogenated polyolefin polyol as a polyol unit.

The urethane group concentration of the urethane resin (A) is 0.80 to 1.10 mol/kg, and the weight average molecular weight of the urethane resin (A) is 12,300 to 42,000. Here, the urethane group concentration of the urethane resin means the number of moles of urethane groups (-NHCOO-) contained per 1 kg of urethane resin. The same applies to the urethane group concentration of polyurethane, which means the number of moles of urethane groups (-NHCOO-) contained per 1 kg of polyurethane. Moreover, the urethane group concentration and weight average molecular weight of the urethane resin (A) mean the urethane group concentration and weight average molecular weight of the entire urethane resin (A). That is, when the urethane resin (A) is composed of a single polyurethane (A), the urethane group concentration and weight average molecular weight of the urethane resin (A) are as follows: When the urethane resin (A) is a mixture of two or more types of polyurethanes (A), it means the urethane group concentration and weight average molecular weight of the mixture. The urethane group concentration and weight average molecular weight of the mixture may be weighted average values based on the blending ratio of the urethane group concentration and weight average molecular weight of each polyurethane contained in the mixture.

The urethane resin composition according to one embodiment contains the urethane resin (urethane resin (A)) of the above embodiment. The urethane resin composition may optionally contain components other than the urethane resin (A) (hereinafter referred to as "other components") within a range that does not impair the object of the present invention.

According to the urethane resin and urethane resin composition of the above embodiments, it is possible to form a urethane resin layer that firmly adheres to the polyolefin base material, regardless of whether or not the surface of the polyolefin base material has been modified. Therefore, the urethane resin and urethane resin composition of the above embodiments are suitably used for adhesives for polyolefin base materials, paints for polyolefin base materials, and the like. In addition, the polyolefin base material here is a base material containing at least polyolefin and having a coated surface made of polyolefin. Examples of polyolefins include polyethylene, polypropylene, ethylene propylene rubber, ethylene propylene diene rubber, and the urethane resin and urethane resin composition of the above embodiments exhibit particularly strong adhesion to polyethylene and polypropylene. .

Although it is not clear why the urethane resin and urethane resin composition of the above embodiments can form a urethane resin layer that firmly adheres to a polyolefin base material, the present inventors speculate as follows. There is.

First, since the urethane resin (A) has a weight average molecular weight of 12,300 to 42,000, it has the property of being easily fluidized by heating. In addition, since the urethane resin (A) contains a hydrogenated polyolefin polyol as a polyol unit, it has a low polar part (a polyolefin part derived from a hydrogenated polyolefin polyol) and a high polar part (urethane bond), Since the urethane group concentration is 0.80 to 1.10 mol/kg, the concentration of the above-mentioned low polarity sites and high polarity sites is well balanced, and when fluidized (for example, melted) by heating, the polyolefin base material (especially It is thought that it has the property of easily penetrating into non-crystalline parts). When the urethane resin or urethane resin composition of the above embodiment is made to flow by heating and applied onto a polyolefin base material, the urethane resin (A) has the above properties, so that the surface of the polyolefin base material (adhesive to the polyolefin base material) It is presumed that a bonding region where the polyolefin in the polyolefin base material and the urethane resin (A) are mixed is formed at the interface with the agent layer, thereby firmly adhering the polyolefin base material and the urethane resin layer.

By the way, polyolefin base materials generally have low heat resistance and are prone to problems such as deterioration due to heat treatment at high temperatures (for example, 140° C. or higher). On the other hand, since the urethane resin (A) has a weight average molecular weight of 12,300 to 42,000, the urethane resin and urethane resin composition of the above embodiments have sufficient fluidity even at low temperatures (for example, 130° C. or lower). Tend. Therefore, according to the urethane resin and urethane resin composition of the above embodiments, it is possible to form a urethane resin layer that firmly adheres to the polyolefin base material without performing heat treatment at high temperatures. Also from this point of view, the urethane resin and urethane resin composition of the above embodiments can be said to be suitable for adhesives for polyolefin base materials and paints for polyolefin base materials.

Hereinafter, other components that may be included in the urethane resin (A) and the urethane resin composition will be explained.

(Urethane resin (A))
The urethane resin (A) contains a hydrogenated polyolefin polyol as a polyol unit. More specifically, the urethane resin (A) is a resin made of polyurethane (polyurethane (A)) containing a hydrogenated polyolefin polyol as a polyol unit.

A polyolefin polyol is a compound having multiple hydroxyl groups in the main chain or side chain of a polyolefin, and a hydrogenated polyolefin polyol is a hydrogenated product obtained by hydrogenating the polyolefin polyol. The urethane resin (A) may contain one or more types of hydrogenated polyolefin polyols as polyol units. Similarly, the number of hydrogenated polyolefin polyols contained as polyol units in the polyurethane (A) may be one or more types.

The hydrogenated polyolefin polyol may be one in which all of the double bonds in the polyolefin polyol are hydrogenated, or may be one in which the double bonds in the polyolefin polyol are partially hydrogenated. That is, the polyolefin polyol may have a double bond in its molecular structure. The double bond content in the hydrogenated polyolefin polyol can be confirmed using the iodine value as an index.

The iodine value of the hydrogenated polyolefin polyol is preferably 50 g/100 g or less, and 25 g/100 g or less, from the viewpoint of further improving the adhesive strength of the urethane resin (A) to the base material (especially the polyolefin base material). is more preferable, and even more preferably 15 g/100 g or less. The iodine value of the hydrogenated polyolefin polyol may be 10 g/100 g or less. The lower limit of the iodine value of the hydrogenated polyolefin polyol is 0 g/100 g. The iodine value of the hydrogenated polyolefin polyol may be 5 g/100 g or more. The above iodine value can be measured in accordance with the JIS standard (JIS K0070).

From the viewpoint of polymerizability with polyisocyanate, the hydrogenated polyolefin polyol preferably has a hydroxyl group at the molecular end (for example, at the end of the main chain). The hydroxyl group content in the hydrogenated polyolefin polyol is preferably 0.50 mol/kg or more, and 0.83 mol/kg from the viewpoint of further improving the adhesive strength of the urethane resin (A) to the base material (especially the polyolefin base material). It is more preferable that it is 1.10 mol/kg or more, and even more preferable that it is 1.10 mol/kg or more. The hydroxyl group content in the hydrogenated polyolefin polyol is preferably 2.00 mol/kg or less, and 1.50 mol/kg or less, from the viewpoint of further improving the adhesive strength of the urethane resin (A) to the base material (especially the polyolefin base material). It is more preferably at most 1.30 mol/kg, and even more preferably at most 1.30 mol/kg. From these viewpoints, the hydroxyl group content in the hydrogenated polyolefin polyol may be, for example, 0.50 to 2.00 mol/kg, 0.83 to 1.50 mol/kg, or 1.10 to 1.30 mol/kg. . The hydroxyl group content in the hydrogenated polyolefin polyol can be measured in accordance with JIS K-1557-1.

The number average molecular weight of the hydrogenated polyolefin polyol is preferably 1000 or more, more preferably 1300 or more, from the viewpoint of further improving the adhesive strength of the urethane resin (A) to the base material (especially the polyolefin base material). , more preferably 1500 or more. The number average molecular weight of the hydrogenated polyolefin polyol is preferably 4000 or less, more preferably 2400 or less, from the viewpoint of further improving the adhesive strength of the urethane resin (A) to the base material (especially polyolefin base material). , more preferably 1800 or less. From these viewpoints, the number average molecular weight of the hydrogenated polyolefin polyol may be, for example, 1000 to 4000, 1300 to 2400, or 1500 to 1800. The number average molecular weight of the hydrogenated polyolefin polyol is a polystyrene equivalent value measured using gel permeation chromatography (GPC).

Specific examples of hydrogenated polyolefin polyols include hydrogenated polybutadiene polyol, hydrogenated polyfarnesene polyol, hydrogenated polyisoprene polyol, and the like. From the viewpoint that the urethane resin (A) is easily compatible with a solvent, it is preferable that the hydrogenated polyolefin polyol contains at least one member selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyfarnesene polyol. More preferably, it contains polybutadiene polyol.

The hydrogenated polybutadiene polyol may contain only one of a 1,2-adduct and a 1,4-adduct, or may contain both of these. Here, the 1,2-adduct is a structural unit obtained by 1,2-addition of butadiene (including those with hydrogenated double bonds) derived from butadiene (1 and 2-positions). The 1,4-adduct refers to a structural unit derived from butadiene (including those in which the double bond is hydrogenated). Refers to a structural unit obtained by 4-addition (one in which the 1st and 4th positions are bonded to another structural unit).

The molar ratio of the 1,2-adduct to the 1,4-adduct in the hydrogenated polyolefin polyol (number of moles of 1,2-adduct: number of moles of 1,4-adduct) is determined by the urethane resin (A ) is easily compatible with the polyolefin base material, preferably from 20:80 to 90:10, more preferably from 65:35 to 90:10, even more preferably from 80:20 to 90:10, and from 80:20 to 85:15 is particularly preferred.

The polyurethane (A) may contain structural units (polyol units) derived from polyol compounds other than hydrogenated polyolefin polyols. For example, the polyurethane (A) may contain a polyol compound generally known as a chain extender as a polyol unit.

Examples of polyol compounds other than hydrogenated polyolefin polyols include polyether polyols such as polyethylene glycols, polypropylene glycols, and polybutylene glycols; caprylic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, stearic acid monoglyceride, and behenic acid. Monoglycerides such as monoglyceride; glycols having side chains such as 2-methyl-1,3-propanediol and 3-methyl-1,5-pentanediol; and the like. These may be used alone or in combination of two or more.

The content of structural units derived from polyol compounds other than the hydrogenated polyolefin polyol may be, for example, 0 to 20% by mass based on the total mass of all polyol units contained in the urethane resin (A). That is, the content of polyol units derived from hydrogenated polyolefin polyols in all polyol units contained in the urethane resin (A) may be 80 to 100% by mass. In this case, if the content of polyol units derived from hydrogenated polyolefin polyol in all polyol units is 80% by mass or more, the urethane resin (A) will more easily penetrate into the polyolefin base material, and the urethane resin (A) The adhesive strength to the base material tends to be further improved. From the viewpoint of easily obtaining similar effects, the content of polyol units derived from hydrogenated polyolefin polyols in all polyol units may be 90% by mass or more or 95% by mass or more.

The content of polyol units in the urethane resin (A) is determined from the viewpoint of further improving the adhesive strength of the urethane resin (A) to the base material (especially the polyolefin base material). It is preferably 75.0% by mass or more, more preferably 80.0% by mass or more, and even more preferably 85.0% by mass or more, based on the total mass of A). The content of polyol units in the urethane resin (A) is determined from the viewpoint of further improving the adhesive strength of the urethane resin (A) to the base material (especially the polyolefin base material). It is preferably 99.9% by mass or less, more preferably 95.0% by mass or less, and even more preferably 90.0% by mass, based on the total mass of A). From these viewpoints, the content of polyol units in the urethane resin (A) is, for example, 75.0 to 99.9 based on the total mass of the urethane resin (A) (that is, the total mass of the polyurethane (A)). % by weight, 80.0-95.0% by weight or 85.0-91.0% by weight.

The polyisocyanate compound contained in the urethane resin (A) as a polyisocyanate unit (that is, the polyisocyanate compound contained in the polyurethane (A) as a polyisocyanate unit) may be an aromatic polyisocyanate or a non-aromatic polyisocyanate. It may also be modified products thereof (for example, allophanate modified products, biuret modified products, etc.). The polyisocyanate compound contained in the urethane resin (A) as a polyisocyanate unit may be one type or multiple types. Similarly, the polyisocyanate compound contained in the polyurethane (A) as a polyisocyanate unit may be one type or multiple types.

Aromatic polyisocyanate is a polyisocyanate having an aromatic skeleton. Examples of aromatic polyisocyanates include diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, and toridine diisocyanate. , xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, 1,4-tetramethylxylylene diisocyanate and the like.

A non-aromatic polyisocyanate is a polyisocyanate that does not have an aromatic skeleton (for example, a polyisocyanate that has an aliphatic skeleton). Examples of the non-aromatic polyisocyanate include 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, norbornene diisocyanate, and the like.

The polyisocyanate compound preferably contains an aromatic polyisocyanate from the viewpoint of easily obtaining a urethane resin layer having excellent mechanical strength, such as diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 2, More preferably, at least one selected from the group consisting of 4-toluene diisocyanate and 2,6-toluene diisocyanate is included. The amount of aromatic polyisocyanate in all polyisocyanate compounds (that is, the content of polyisocyanateol units derived from aromatic polyisocyanate in all polyisocyanate units contained in the urethane resin (A)) is determined by the amount of urethane having excellent mechanical strength. From the viewpoint of making it easier to obtain a resin layer, the content may be 80 to 100% by mass, 90 to 100% by mass, or 95 to 100% by mass. From the same point of view, the total amount of diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate in all polyisocyanate compounds is 80 to 100 mass. %, 90-100% by weight or 95-100% by weight, and the amount of diphenylmethane-4,4'-diisocyanate in the total polyisocyanate compound is 80-100% by weight, 90-100% by weight or 95-100% by weight. It may be 100% by mass.

The polyisocyanate compound is composed of hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, and hydrogenated diphenylmethane-2,4'-diisocyanate from the viewpoint of easily obtaining a urethane resin layer with excellent light resistance. It may contain at least one selected from the group.

The isocyanate group content in the polyisocyanate compound is preferably 1.7 mol/kg or more, and 2.4 mol/kg or more, from the viewpoint of further improving the adhesive strength of the urethane resin (A) to the base material (especially polyolefin base material). It is more preferably at least 4.0 mol/kg, and even more preferably at least 4.0 mol/kg. The isocyanate group content in the polyisocyanate compound is preferably 12.0 mol/kg or less, and 11.0 mol/kg or less, from the viewpoint of further improving the adhesive strength of the urethane resin (A) to the base material (especially polyolefin base material). The amount is more preferably at most 8.0 mol/kg, and even more preferably at most 8.0 mol/kg. From these viewpoints, the isocyanate group content in the polyisocyanate compound may be, for example, 1.7 to 12.0 mol/kg, 2.4 to 11.0 mol/kg, or 4.0 to 8.0 mol/kg. . The isocyanate group content in the polyisocyanate compound can be measured in accordance with JIS K1603-1.

The urethane resin (A) may further contain structural units other than polyol units and isocyanate units within a range that does not impair the purpose of the present invention.

The urethane group concentration of the urethane resin (A) is 0.80 mol/kg or more, and from the viewpoint of further improving the adhesive strength of the urethane resin (A) to the base material (especially polyolefin base material), the urethane group concentration is 0.85 mol/kg or more. It is preferable that it is, and it is more preferable that it is 0.90 mol/kg or more. The urethane group concentration of the urethane resin (A) is 1.10 mol/kg or less, and from the viewpoint of further improving the adhesive strength of the urethane resin (A) to the base material (especially polyolefin base material), the urethane group concentration is 1.06 mol/kg or less. It is preferable that it is, and it is more preferable that it is 0.95 mol/kg or less. From these viewpoints, the urethane group concentration of the urethane resin (A) may be, for example, 0.80 to 1.06 mol/kg or 0.80 to 0.95 mol/kg, and 0.85 to 1.10 mol/kg. kg or 0.90 to 1.10 mol/kg. The urethane group concentration of the urethane resin (A) can be measured by the method described in Examples.

The urethane resin (A) may have a hydroxyl group. The hydroxyl group concentration (hydroxyl group content) of the urethane resin (A) may be, for example, 0.0010 to 0.32 mol/kg, 0.0060 to 0.30 mol/kg, or 0.010 to 0.29 mol/kg. There may be.

The urethane resin (A) may have an isocyanate group, but the isocyanate group concentration (isocyanate group content) of the urethane resin (A) should be 0 to 0.20 mol/kg from the viewpoint of storage stability. is preferable, 0 to 0.10 mol/kg is more preferable, and even more preferably 0 to 0.050 mol/kg. The isocyanate group concentration of the urethane resin (A) may be 0 mol/kg.

The weight average molecular weight of the urethane resin (A) is 42,000 or less, preferably 37,000 or less, and more preferably 25,000 or less. As the weight average molecular weight of the urethane resin (A) is lower, a urethane resin layer that firmly adheres to the polyolefin base material can be formed at a lower heat treatment temperature. The weight average molecular weight of the urethane resin (A) is 12,300 or more, and may be 12,500 or more or 13,000 or more. When the weight average molecular weight of the urethane resin (A) is appropriately large, deformation of the urethane resin layer is suppressed, and peeling of the urethane resin layer from the base material becomes difficult to occur. From these viewpoints, the weight average molecular weight of the urethane resin (A) may be, for example, 12,300 to 42,000, 12,500 to 37,000, or 13,000 to 25,000. The weight average molecular weight of the urethane resin (A) can be measured by the method described in Examples.

The molecular weight distribution index (weight average molecular weight/number average molecular weight) of the urethane resin (A) is 2.5 or more from the viewpoint of further improving the adhesive strength of the urethane resin (A) to a base material (especially a polyolefin base material). It is preferably 2.8 or more, more preferably 3.0 or more. The molecular weight distribution index of the urethane resin (A) is preferably 6.0 or less, and 5.5 or less, from the viewpoint of further improving the adhesive strength of the urethane resin (A) to the base material (especially polyolefin base material). It is more preferable that it is, and even more preferably that it is 5.0 or less. From these viewpoints, the molecular weight distribution index of the urethane resin (A) may be, for example, 2.5 to 6.0.

The surface energy of the urethane resin (A) is preferably 23 mJ/m ² or less (for example, 15 to 23 mJ/m ² ). The urethane resin (A) having such surface energy has the property of easily wetting and spreading on the base material. ) is likely to be formed, and the polyolefin base material and the urethane resin layer are more likely to be bonded more firmly. From the viewpoint of making it easier to obtain such effects, the surface energy of the urethane resin (A) may be 22 mJ/m ² or less. Here, the surface energy of the urethane resin (A) is determined by forming a film made of the urethane resin (A) and measuring the surface energy of the film by the method described in Examples. Specifically, the above film is produced by preparing a cyclohexane solution of urethane resin (A) at a concentration of 10% by mass, applying the solution to a polyethylene base material using an applicator method so that the dry film thickness is approximately 20 μm, and then It is formed by heating at 80° C. for 4 hours under reduced pressure in a vacuum dryer (drying to remove the solvent in the coating film and heat aging to smooth the film surface). Although the physical structure of the surface of the film may affect the surface energy, the above method allows the formation of a film with a smooth surface, minimizing the influence of the physical structure of the surface of the film and improving the urethane resin. (A) The surface energy of the object itself can be determined. The surface energy of the urethane resin (A) is determined by setting the urethane group concentration of the urethane resin (A) to 0.80 to 1.10 mol/kg, and setting the weight average molecular weight of the urethane resin (A) to 12,300 to 42,000. It can be adjusted depending on the type of hydrogenated polyolefin polyol, etc. For example, when the urethane group concentration is relatively high, the surface energy tends to be high.

The glass transition temperature of the urethane resin (A) may be −10° C. or lower, −20° C. or lower, or −28° C. or lower from the viewpoint of easily obtaining good tackiness. The glass transition temperature of the urethane resin (A) may be, for example, -10 to -80°C, -20 to -70°C, or -28 to -65°C. The glass transition temperature of the urethane resin (A) can be measured in accordance with JIS K6240.

The urethane resin (A) can be obtained by reacting a urethane resin-forming raw material containing at least a hydrogenated polyolefin polyol and a polyisocyanate compound. Specifically, for example, by heating a polyol compound containing a hydrogenated polyolefin polyol and a polyisocyanate compound while mixing them in the presence of a catalyst (urethanization catalyst) and a solvent (reaction solvent), the polyol compound and the polyisocyanate compound are heated. A urethane resin (A) consisting of polyurethane (A) which is a reaction product with a polyisocyanate compound can be obtained. Here, the urethane resin-forming raw material is an aggregate of compounds contained in the structural units of polyurethane (urethane resin), which is a reaction product. Therefore, the catalyst and solvent are not included in the urethane resin forming raw materials.

The content of the polyol compound and polyisocyanate compound in the urethane resin-forming raw material (i.e., the blending amount of the polyol compound and polyisocyanate compound) is determined by, for example, the total number of moles of hydroxyl groups (M _OH ) in the polyol compound and the amount of the polyisocyanate compound. The amount may be such that the ratio (M _NCO /M _OH ) to _the total number of moles of isocyanate groups therein (M NCO ) is 0.74 to 0.98. When the above ratio (M _NCO /M _OH ) is 0.74 or more, the molecular weight of the urethane resin (A) does not become too small, and the mechanical strength of the urethane resin layer formed using the urethane resin (A) increases. There is a tendency to improve. When the above ratio (M _NCO /M _OH ) is 0.98 or less, the molecular weight of the urethane resin (A) does not become too large, and the urethane resin (A) tends to more easily penetrate into the polyolefin base material. . From these viewpoints, the ratio (M _NCO /M _OH ) may be 0.75 or more or 0.78 or more, or 0.97 or less or 0.95 or less.

The content of hydrogenated polyolefin polyol and polyisocyanate compound in the urethane resin-forming raw material (that is, the blending amount of hydrogenated polyolefin polyol and polyisocyanate compound) is determined by the total number of moles of hydroxyl groups in hydrogenated polyolefin polyol (M _OH ') The ratio of the total number of moles of isocyanate groups in the polyisocyanate compound (M _NCO ) to the ratio (M _NCO /M _OH ') may be from 0.74 to 0.98. When the above (M _NCO /M _OH ') is 0.74 or more, the molecular weight of the urethane resin (A) does not become too small, and the mechanical strength of the urethane resin layer formed using the urethane resin (A) increases. There is a tendency to improve. When the above ratio (M _NCO /M _OH ') is 0.98 or less, the molecular weight of the urethane resin (A) does not become too large, and the urethane resin (A) tends to more easily penetrate into the polyolefin base material. be. From these viewpoints, the ratio (M _NCO /M _OH ') may be 0.75 or more or 0.78 or more, or 0.97 or less or 0.95 or less.

Examples of the catalyst 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 alone or in combination of two or more.

The amount of the catalyst may be selected depending on the reactivity of the polyisocyanate compound used. The amount of the catalyst blended is preferably 0.00010 parts by mass or more and 25 parts by mass or less, and 0.0010 parts by mass or more and 6.0 parts by mass or less, for example, per 1 part by mass of the urethane resin-forming raw material. is more preferable, and even more preferably 0.010 parts by mass or more and 1.0 parts by mass or less. When the amount of the catalyst blended is 0.00010 parts by mass or more per 1 part by mass of the urethane resin-forming raw material, a sufficient catalytic effect is more likely to be obtained. It is more preferable in terms of economy that the amount of the catalyst blended is 25 parts by mass or less per 1 part by mass of the urethane resin-forming raw material.

Examples of solvents include aromatic hydrocarbon solvents such as toluene, ethylbenzene, trimethylbenzene, and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, and cyclohexane; and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvent: Alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol; Methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl diglycol, ethyl diglycol, butyl diglycol, propylene glycol monomethyl ether, etc. glycol ether solvents; ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate; N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. Examples include amide solvents; ether solvents such as diethyl ether and tetrahydrofuran; water; and the like. These may be used alone or in combination of two or more.

The blending amount of the solvent is not particularly limited, and may be, for example, 1.0 parts by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of the urethane resin-forming raw material.

The urethane resin (A) may consist of one type of polyurethane (A), or two or more types of polyurethane (A) with different types of constituent units (polyol units, polyisocyanate units, etc.), urethane group concentration, weight average molecular weight, etc. ) may be a mixture. In particular, when the urethane resin (A) is a mixture of two or more polyurethanes (A) that differ in at least one of urethane group concentration and weight average molecular weight, the adhesion of the urethane resin layer to the polyolefin base material (especially polyethylene base material) tends to improve.

In one embodiment, the urethane resin (A) is a mixture containing at least a polyurethane (A1) having a weight average molecular weight of 12,300 or more and less than 20,000, and a polyurethane (A2) having a weight average molecular weight of 24,000 to 42,000. good. In this case, the adhesion of the urethane resin layer to the polyolefin base material tends to be further improved. Note that both polyurethanes (A1) and (A2) are polyurethanes containing hydrogenated polyolefin polyols as polyol units.

Polyurethane (A1) contributes to improving the heat fluidity of the urethane resin composition. From the viewpoint of being able to form a urethane resin layer that firmly adheres to the polyolefin base material at a lower heat treatment temperature, even if the weight average molecular weight of the polyurethane (A1) is 19,000 or less or 18,000 or less, good. The weight average molecular weight of the polyurethane (A1) may be 14,000 or more, 16,000 or more, or 17,000 or more from the viewpoint of more easily suppressing the occurrence of delamination due to deformation of the urethane resin layer.

Polyurethane (A2) contributes to improving the mechanical strength of the urethane resin layer. From the viewpoint of more easily suppressing the occurrence of delamination due to deformation of the urethane resin layer, the weight average molecular weight of the polyurethane (A2) may be 29,000 or more, 30,000 or more, or 31,000 or more. The weight average molecular weight of the polyurethane (A2) is 37,000 or less, 35,000 or less, 33,000 or less, 28,000 or less, or 26,000 or less, from the viewpoint of obtaining well-balanced properties of both the polyurethane (A1) and polyurethane (A2) resins. Good too. From the above viewpoint, the weight average molecular weight of the polyurethane (A2) may be from 24,000 to 28,000, or from 29,000 to 35,000.

The difference between the weight average molecular weight of polyurethane (A1) and the weight average molecular weight of polyurethane (A2) ([weight average molecular weight of polyurethane (A2)] - [weight average molecular weight of polyurethane (A1)]) is the difference between polyurethane (A1) and polyurethane (A2). From the viewpoint of obtaining well-balanced properties of both resins (A2), it is preferably from 5,000 to 15,000. The above difference may be 7000 or more or 9000 or more, or 13000 or less or 10000 or less.

The characteristics of polyurethane (A1) and polyurethane (A2) other than the weight average molecular weight are not particularly limited as long as the above urethane resin (A) can be obtained. The characteristics of polyurethane (A1) and polyurethane (A2) other than the weight average molecular weight may be the same as those of the urethane resin (A). For example, the urethane group concentration of polyurethane (A1) and polyurethane (A2) may be 0.80 to 1.10 mol/kg.

The content of polyurethane (A1) is determined by the total mass of urethane resin (A) (for example, the content of polyurethane (A1) and the content of polyurethane Based on the total content of A2), it is preferably 25% by mass or more, and may be 50% by mass or more, 70% by mass or more, or 85% by mass or more. From the same viewpoint, the content of polyurethane (A2) should be 75% by mass or less based on the total mass of the urethane resin (A) (for example, the sum of the content of polyurethane (A1) and the content of polyurethane (A2)). is preferable, and may be 50% by mass or less, 30% by mass or less, or 15% by mass or less.

The content of polyurethane (A1) is 95% by mass or less, 90% by mass or less, 80% by mass based on the total mass of urethane resin (A) (for example, the sum of the content of polyurethane (A1) and the content of polyurethane (A2)). % or less or 70% by mass or less. Similarly, the content of polyurethane (A2) is 5% by mass or more, 10% by mass or more based on the total mass of urethane resin (A) (for example, the sum of the content of polyurethane (A1) and the content of polyurethane (A2)). , 20% by mass or more, or 30% by mass or more.

When the urethane resin composition contains urethane resins other than urethane resin (A) as other components, the total mass of the urethane resins contained in the urethane resin composition (the content of urethane resin (A) and the amount of urethane resins other than urethane resin (A)) The content of polyurethane (A1) and the content of polyurethane (A2) based on the total content of urethane resins may be within the above ranges.

When the weight average molecular weight of polyurethane (A2) is 24,000 to 28,000, the content of polyurethane (A1) is the total mass of the urethane resin (A) (for example, the sum of the content of polyurethane (A1) and the content of polyurethane (A2)). The amount is preferably 25 to 90% by weight, more preferably 50 to 70% by weight.

When the weight average molecular weight of the polyurethane (A2) is 29,000 to 35,000, the content of the polyurethane (A1) is the total mass of the urethane resin (A) (for example, the sum of the content of polyurethane (A1) and the content of polyurethane (A2)). The amount is preferably 25 to 90% by weight, more preferably 70 to 80% by weight.

In another embodiment, the urethane resin (A) is a mixture containing at least a polyurethane (A3) having a weight average molecular weight of 12,300 to 32,000 and a polyurethane (A4) having a weight average molecular weight of more than 42,000 and 100,000 or less. It's good. Note that both polyurethanes (A3) and (A4) are polyurethanes containing hydrogenated polyolefin polyols as polyol units.

Polyurethane (A3) contributes to improving the heat fluidity of the urethane resin composition. From the viewpoint of being able to form a urethane resin layer that firmly adheres to the polyolefin base material at a lower heat treatment temperature, the weight average molecular weight of the polyurethane (A3) may be 28,000 or less or 24,000 or less. good. The weight average molecular weight of the polyurethane (A3) may be 14,000 or more, 16,000 or more, or 17,000 or more from the viewpoint of more easily suppressing the occurrence of delamination due to deformation of the urethane resin layer.

The weight average molecular weight of the polyurethane (A3) may be 12,300 or more and less than 20,000. That is, the polyurethane (A3) may be the above polyurethane (A1). In this case, the properties of both the polyurethane (A3) and polyurethane (A4) resins can be easily obtained in a well-balanced manner.

Polyurethane (A4) contributes to improving the mechanical strength of the urethane resin layer. From the viewpoint of more easily suppressing the occurrence of delamination due to deformation of the urethane resin layer, the weight average molecular weight of the polyurethane (A4) may be 50,000 or more or 55,000 or more. The weight average molecular weight of the polyurethane (A4) may be 80,000 or less, 70,000 or less, or 60,000 or less from the viewpoint of easily ensuring heat fluidity of the urethane resin composition.

The characteristics of polyurethane (A3) and polyurethane (A4) other than the weight average molecular weight are not particularly limited as long as the above urethane resin (A) can be obtained. The characteristics of the polyurethane (A3) and the polyurethane (A4) other than the weight average molecular weight may be the same as the characteristics of the urethane resin (A). For example, the urethane group concentration of polyurethane (A3) and polyurethane (A4) may be 0.80 to 1.10 mol/kg. The urethane group concentration of polyurethane (A4) may be greater than 1.10 mol/kg. When the urethane group concentration of polyurethane (A4) is greater than 1.10 mol/kg, it becomes easier to suppress the occurrence of layer peeling due to deformation of the urethane resin layer. The urethane group concentration of the polyurethane (A4) is preferably less than 1.30 mol/kg from the viewpoint of improving the adhesiveness of the urethane resin layer to the polyolefin base material.

The content of polyurethane (A3) is preferably 50% by mass or more, based on the total mass of the urethane resin (A) (for example, the sum of the content of polyurethane (A3) and the content of polyurethane (A4)), and is preferably 75% by mass. % or more, and even more preferably 90% by mass or more. From the same perspective, the content of polyurethane (A4) should be 50% by mass or less based on the total mass of the urethane resin (A) (for example, the sum of the content of polyurethane (A3) and the content of polyurethane (A4)). is preferable, and may be 25% by mass or less or 10% by mass or less.

The content of polyurethane (A3) is 95% by mass or less, 90% by mass or less, or 80% by mass based on the total mass of urethane resin (A) (for example, the sum of the content of polyurethane (A3) and the content of polyurethane (A4)). % or less. Similarly, the content of polyurethane (A4) is 5% by mass or more, 10% by mass or more based on the total mass of urethane resin (A) (for example, the sum of the content of polyurethane (A3) and the content of polyurethane (A4)). Or it may be 20% by mass or more.

When the urethane resin composition contains urethane resins other than urethane resin (A) as other components, the total mass of the urethane resins contained in the urethane resin composition (the content of urethane resin (A) and the amount of urethane resins other than urethane resin (A)) The content of polyurethane (A3) and the content of polyurethane (A4) based on the total content of urethane resins may be within the above ranges.

In another embodiment, the urethane resin (A) includes polyurethane (A5) having a urethane group concentration of 0.80 to 1.02 mol/kg, and polyurethane (A5) having a urethane group concentration of 1.10 mol/kg to more than 3.00 mol/kg. It may be a mixture containing at least the following polyurethane (A6). Note that both polyurethanes (A5) and (A6) are polyurethanes containing hydrogenated polyolefin polyols as polyol units.

Polyurethane (A5) contributes to improving the adhesion of the urethane resin composition to a base material (especially a polyolefin base material). From the viewpoint of being able to form a urethane resin layer that adheres more firmly to the polyolefin base material, the urethane group concentration of polyurethane (A5) is 0.85 mol/kg or more or 0.90 mol/kg or more. The amount may be 1.00 mol/kg or less or 0.98 mol/kg or less.

Polyurethane (A6) contributes to improving the mechanical strength of the urethane resin layer. From the viewpoint of more easily suppressing the occurrence of delamination due to deformation of the urethane resin layer, the urethane group concentration of the polyurethane (A6) may be 1.20 mol/kg or more or 1.30 mol/kg or more. The urethane group concentration of the polyurethane (A6) may be 2.50 mol/kg or less or 2.00 mol/kg or less from the viewpoint of improving the adhesiveness of the urethane resin layer to the polyolefin base material.

The characteristics of polyurethane (A5) and polyurethane (A6) other than the urethane group concentration are not particularly limited as long as the above urethane resin (A) can be obtained. The characteristics of polyurethane (A5) and polyurethane (A6) other than the urethane group concentration may be the same as those of the urethane resin (A). For example, the weight average molecular weight of polyurethane (A5) and polyurethane (A6) may be 12,300 to 42,000.

The weight average molecular weight of the polyurethane (A5) may be 12,300 or more and less than 20,000. That is, the polyurethane (A5) may be the above polyurethane (A1). In this case, the properties of both the polyurethane (A5) and polyurethane (A6) resins can be easily obtained in a well-balanced manner.

The weight average molecular weight of the polyurethane (A6) may be more than 42,000 and not more than 100,000. That is, polyurethane (A6) may be polyurethane (A4). However, if the urethane group concentration of polyurethane (A6) is 1.30 mol/kg or more, the weight average molecular weight of polyurethane (A6) must be 42,000 or less in order to improve the adhesion of the urethane resin layer to the polyolefin base material. is preferred.

The content of polyurethane (A5) is preferably 50% by mass or more, based on the total mass of the urethane resin (A) (for example, the sum of the content of polyurethane (A5) and the content of polyurethane (A6)), and is preferably 75% by mass. % or more, and even more preferably 90% by mass or more. From the same point of view, the content of polyurethane (A6) should be 50% by mass or less based on the total mass of the urethane resin (A) (for example, the sum of the content of polyurethane (A5) and the content of polyurethane (A6)). is preferable, and may be 25% by mass or less or 10% by mass or less.

The content of polyurethane (A5) is 95% by mass or less, 90% by mass or less, or 80% by mass based on the total mass of urethane resin (A) (for example, the sum of the content of polyurethane (A5) and the content of polyurethane (A6)). % or less. Similarly, the content of polyurethane (A6) is 5% by mass or more, 10% by mass or more based on the total mass of urethane resin (A) (for example, the sum of the content of polyurethane (A5) and the content of polyurethane (A6)). Or it may be 20% by mass or more.

When the urethane resin composition contains urethane resins other than urethane resin (A) as other components, the total mass of the urethane resins contained in the urethane resin composition (the content of urethane resin (A) and the amount of urethane resins other than urethane resin (A)) The content of polyurethane (A5) and the content of polyurethane (A6) based on the total content of urethane resins may be within the above ranges.

The urethane resin (A), which is a mixture of two or more polyurethanes (A), can be obtained by, for example, producing a mixture of two or more polyurethanes (A) by reacting a urethane resin-forming raw material containing at least a hydrogenated polyolefin polyol and a polyisocyanate compound. Easily prepared by separately synthesizing polyurethanes (for example, two or more of polyurethanes (A1) to (A6)) and then mixing the two or more obtained polyurethanes or a composition containing the polyurethanes. It is possible.

The content of the urethane resin (A) in the urethane resin composition varies depending on the application, but from the viewpoint of further improving the adhesion of the urethane resin layer to the polyolefin base material, the content of the urethane resin (A) is 1 based on the total solid content of the urethane resin composition. The content is preferably .0% by mass or more, more preferably 5.0% by mass or more, and even more preferably 10.0% by mass or more. The content of the urethane resin (A) may be 80.0% by mass or more, 85.0% by mass or more, or 90.0% by mass or more based on the total solid content of the urethane resin composition. The content of the urethane resin (A) in the urethane resin composition may be 100% by mass or less, 90.0% by mass or less, or 80.0% by mass or less, based on the total solid content of the urethane resin composition. There may be. In addition, in this specification, solid content means components other than the solvent (solvent).

(other ingredients)
Other components include, for example, a solvent, a catalyst, an antifoaming agent, a leveling agent, an organic thickener, an antioxidant, a light stabilizer, an adhesion improver, a mold release agent, a reinforcing material, a softener, a colorant, Additives include flame retardants, antistatic agents, wetting and dispersing agents, and the like. Other components may be urethane resin-forming raw materials such as polyol compounds and polyisocyanate compounds, and may also be components used in the synthesis of urethane resins, such as the above-mentioned urethanization catalyst and reaction solvent. The other component may be a urethane resin other than the urethane resin (A), that is, a urethane resin made of polyurethane that does not contain a hydrogenated polyolefin polyol as a polyol unit.

When the urethane resin composition further contains a urethane resin other than the urethane resin (A), the content of the urethane resin (A) is determined from the viewpoint of making it easier to obtain the above-mentioned effects of the urethane resin (A). Based on the total mass of urethane resins contained in (the sum of the content of urethane resin (A) and the content of urethane resins other than urethane resin (A)), it is preferably 80% by mass or more and less than 100% by mass, and 85% by mass or more. It is more preferably at least 90% by mass and less than 100% by mass, and even more preferably at least 90% by mass and less than 100% by mass.

When the urethane resin composition further contains a urethane resin other than the urethane resin (A), the total mass of the urethane resin contained in the urethane resin composition is 1.0 mass based on the total solid content of the urethane resin composition. % or more, 5.0 mass% or more, 10.0 mass% or more, 80.0 mass% or more, 85.0 mass% or more, or 90.0 mass% or more, and 100 mass% or less, 90.0 mass% or more It may be less than or equal to 80.0% by weight, and may be from 1.0 to 100% by weight.

The surface energy of the urethane resin composition is preferably 23 mJ/m ² or less (for example, 15 to 23 mJ/m ² ) from the viewpoint of facilitating stronger adhesion between the polyolefin base material and the urethane resin layer. From the same viewpoint, the surface energy of the urethane resin composition may be 22 mJ/m ² or less. Here, the surface energy of the urethane resin composition is the surface energy of the composition after removing the solvent when the urethane resin composition contains a solvent. The surface energy is determined by measuring the surface energy using the method described in Examples. Specifically, the above film is produced by preparing a cyclohexane solution of a urethane resin composition with a concentration of 10% by mass, applying the solution to a polyethylene base material using an applicator method so that the dry film thickness is approximately 20 μm, and then applying the solution under reduced pressure. It is formed by heating at 80° C. for 4 hours under reduced pressure in a dryer (drying to remove the solvent in the coating film and heat aging to smooth the film surface). Although the physical structure of the surface of the film may affect the surface energy, the above method allows the formation of a film with a smooth surface, minimizing the influence of the physical structure of the surface of the film and improving the urethane resin. The surface energy of the composition can be determined. The surface energy of the urethane resin composition can be determined by using a urethane resin (A) with a surface energy of 23 mJ/ ^m2 or less, and by adjusting the amount of the urethane resin (A) (for example, by adjusting the solid content of the urethane resin composition). It can be easily adjusted by setting the amount to 10% by mass or more based on the total amount.

<Adhesive>
The adhesive according to one embodiment contains the urethane resin (urethane resin (A)) of the above embodiment, and optionally contains the other components mentioned above. That is, the adhesive according to one embodiment may contain the urethane resin composition of the above embodiment or a dried product thereof, or may be the urethane resin composition of the above embodiment or a dried product thereof itself. More specifically, when the urethane resin composition of the above embodiment does not contain a solvent, the adhesive contains the urethane resin composition of the above embodiment (for example, the urethane resin composition itself of the above embodiment). obtain. When the urethane resin composition of the above embodiment contains a solvent, the adhesive includes the urethane resin composition of the above embodiment or a dried product thereof (for example, the urethane resin composition of the above embodiment or a dried product itself) It can be. Note that in this specification, the term "adhesive" refers to a material that is applied to two or more adherends to bond them together.

The above adhesive can firmly adhere even to polyolefin base materials that have not been surface modified, and is therefore suitably used for polyolefin base materials.

The adhesive may be liquid or solid. The liquid adhesive is, for example, a coating liquid for forming an adhesive layer. The adhesive, which is a coating liquid, may contain a solvent for the purpose of adjusting viscosity and the like. Examples of the solvent include the compounds exemplified above as reaction solvents for the synthesis of the urethane resin (A).

The content of the solvent may be selected in consideration of the coating method of the coating liquid, the desired thickness of the adhesive layer, etc. The content of the solvent in the coating solution (adhesive) is preferably 1.0 to 10,000 parts by mass, and 40 to 3,200 parts by mass, for example, based on 100 parts by mass of the solid content in the coating solution (adhesive). It is more preferable that the amount is 150 to 2000 parts by mass. When the content of the solvent is 1.0 parts by mass or more based on 100 parts by mass of solids in the coating liquid (adhesive), the viscosity of the adhesive is reduced and coating becomes easier. When the content of the solvent is 10,000 parts by mass or less per 100 parts by mass of solids in the coating liquid (adhesive), the thickness of the formed coating film (adhesive layer) will not become too thin and a sufficient film will be obtained. Easy to obtain thickness.

The coating liquid (adhesive) preferably contains a leveling agent from the viewpoint of making it easier to obtain a smooth adhesive layer. Examples of the leveling agent include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, silicone surfactants, nonionic surfactants, fluorine surfactants, and acrylic surfactants. These may be used alone or in combination of two or more. The content of the leveling agent is not particularly limited, but may be, for example, 0.0010 to 25 parts by mass based on 100 parts by mass of solid content in the coating liquid (adhesive).

As mentioned above, since the adhesive can be the above-mentioned urethane resin composition or its dried product itself, the content of each component contained in the adhesive is exemplified as the content of the same component contained in the above-mentioned urethane resin composition. It may be the same as the range specified. For example, the content of the urethane resin (A) in the adhesive is 1.0% by mass or more based on the total solid content of the adhesive, from the viewpoint of further improving the adhesion of the urethane resin layer to the polyolefin base material. It is preferably 5.0% by mass or more, more preferably 10.0% by mass or more, 80.0% by mass or more, 85.0% by mass or more, or 90.0% by mass or more. It may be. Further, the content of the urethane resin (A) in the adhesive may be 100% by mass or less, 90.0% by mass or less, or 80.0% by mass or less, based on the total solid content of the adhesive. Good too.

<Articles and their manufacturing methods>
An article according to one embodiment includes a base material and a urethane resin layer adhered to one surface of the base material.

The material constituting the base material is not particularly limited, and includes, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin), nylon 6, nylon 66, aramid, acrylic, It may be a resin such as polyethylene terephthalate or polybutylene terephthalate, it may be a metal such as aluminum, aluminum alloy, magnesium, stainless steel, tinplate, electrogalvanized steel sheet, chrome plated steel sheet, or it may be glass. The base material may contain one kind of these, or two or more kinds. The base material may contain two or more of these materials as a composite material. For example, the base material may be formed of a composite material made of the above resin and glass fiber, etc., or a composite material of a thermosetting resin such as an epoxy resin or a thermoplastic resin such as polyphenylene sulfide, and carbon fiber. (CFRP (Carbon Fiber Reinforced Plastics) or CFRTP (Carbon Fiber Reinforced Thermo plastics)) may be formed. Among these, plastic base materials are preferred because they are easy to mold after painting and have high versatility, and polyolefin base materials (e.g. polyethylene, polypropylene, etc.) are preferred because they are lightweight and inexpensive. A base material having a coated surface made of ethylene propylene rubber, ethylene propylene diene rubber, etc. is more preferable. Among the polyolefin base materials, base materials containing polyethylene and/or polypropylene are more preferred. The base material may be a base material whose surface has been modified by corona treatment or the like. The surface energy of the surface of the base material that adheres to the urethane resin layer may be, for example, 23 to 60 mJ/m ² . The surface energy of the above-mentioned base material can be measured by the method described in Examples.

The shape of the base material is not particularly limited, and may be flat (for example, film-like, sheet-like) or may have a curved surface.

The urethane resin layer is formed of the urethane resin or urethane resin composition of the above embodiment. Therefore, the urethane resin layer firmly adheres to the base material even when the base material is a polyolefin base material whose surface has not been modified. In such articles, a bonding region is formed at the interface between the base material (polyolefin base material) and the urethane resin layer, where the polyolefin in the base material and the urethane resin (A) in the urethane resin layer are mixed. It's fine.

The thickness of the urethane resin layer is not particularly limited, but is preferably 0.05 to 300 μm, more preferably 0.1 to 200 μm, and even more preferably 5 to 100 μm. When the thickness of the urethane resin layer is 0.05 μm or more, the urethane resin layer tends to have even better adhesive properties. When the thickness of the urethane resin layer is 300 μm or less, the time required for drying can be further reduced and even better productivity can be obtained.

The surface energy of the urethane resin layer may be smaller than the surface energy of the surface of the base material that adheres to the urethane resin layer, and may be, for example, 23 mJ/m ² or less, 22 mJ/m ² or less, or 20 mJ/m ² or less. When the base material is a polyolefin base material and the surface energy of the urethane resin layer is 23 mJ/ ^m2 or less, a bonding area where the polyolefin and urethane resin (A) in the base material are mixed is likely to be formed, The polyolefin base material and the urethane resin layer are more likely to be bonded more firmly. The surface energy of the urethane resin layer may be, for example, 15 to 23 mJ/m ² . The surface energy of the urethane resin layer can be adjusted by using a urethane resin (A) or a urethane resin composition having a surface energy of 23 mJ/m ² or less, as well as by changing the thickness of the layer, the type of base material, etc. The surface energy of the urethane resin layer can be measured by the method described in Examples. Furthermore, since it is practically difficult to measure the surface energy of the surface of the urethane resin layer that adheres to the base material after the article is manufactured, the surface energy of the surface of the urethane resin layer that is opposite to the base material is measured. .

The urethane resin layer may be, for example, an adhesive layer that adheres the base material (first base material) and another base material (second base material), and may be a coating material that coats the surface of the base material. It may also be a membrane. When the urethane resin layer is an adhesive layer, another base material (second base material) is bonded to the surface of the urethane resin layer opposite to the base material (first base material). Good too. That is, the article includes a first base material, a second base material, and a bond between the first base material and the second base material. It may also include an adhesive layer.

Examples of the material constituting the other base material (second base material) include the materials exemplified as the materials constituting the base material (first base material). The other base material (second base material) may be a base material whose surface has been modified by corona treatment or the like. Further, the other base material (second base material) may be a base material having a resin coating. The resin coating film may be formed of a resin that has an affinity with another base material (second base material). The resin coating film may be formed from the urethane resin composition of the above embodiment. Examples of the resin that forms the resin coating include urethane resin, epoxy resin, and acrylic resin. Among these, in consideration of affinity with the adhesive layer, the resin constituting the resin coating is preferably a urethane resin. The urethane resin preferably contains the urethane resin (A) of the above embodiment, and more preferably contains a mixture of polyurethane (A1) and polyurethane (A2). The urethane resin may include a mixture of polyurethane (A3) and polyurethane (A4) of the above embodiment, or a mixture of polyurethane (A5) and polyurethane (A6) of the above embodiment.

The above article includes, for example, the step (a) of arranging a urethane resin layer containing the urethane resin of the above embodiment on a first base material, heating the first base material and the urethane resin layer; a step (b) of adhering the first base material and the urethane resin layer, or in addition to the above steps (a) and (b), adhering the urethane resin layer to the first base material; It can be manufactured by a method including the step (c) of adhering a second base material to the surface opposite to the surface.

In step (a), the urethane resin layer may be disposed on the base material, for example, by applying a coating liquid (e.g., adhesive) containing a urethane resin onto one surface of the base material. When the coating liquid contains a solvent, the urethane resin layer may be formed by applying the coating liquid onto the substrate and then drying the resulting coating film. The coating liquid containing the urethane resin may be a coating liquid containing the urethane resin composition of the above embodiment. That is, step (a) may be a step of arranging a urethane resin layer containing a urethane resin composition or a dried product thereof on the first base material.

The method of applying the coating liquid is not particularly limited, and examples include an 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, and air coating method. Examples include a doctor coat method, a blade coat method, a rod coat method, a curtain coat method, a knife coat method, a transfer roll coat method, a squeeze coat method, an impregnation coat method, a kiss coat method, a calendar coat method, an extrusion coat method, and the like.

The drying temperature of the coating film is not particularly limited, but is preferably 300°C or lower, more preferably 150°C or lower, and even more preferably 130°C or lower. When the drying temperature is 300° C. or lower, damage to the base material and thermal decomposition of the urethane resin layer can be further suppressed. In particular, when the base material is a polyolefin base material, damage to the base material can be sufficiently reduced by setting the drying temperature to 130° C. or lower. The drying temperature of the coating film is preferably 50°C or higher, and may be 70°C or higher or 80°C or higher. When the drying temperature is 50° C. or higher, the amount of residual solvent can be further reduced. The drying time is not particularly limited, but is preferably from 5 seconds to 12 hours, more preferably from 20 seconds to 1 hour, and most preferably from 1 minute to 30 minutes. If the drying time is 5 seconds or more, 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 even better productivity.

In step (a), a coating liquid (e.g. adhesive) containing a urethane resin is applied onto a release film, etc. in advance to form a urethane resin layer, and then the urethane resin layer is applied onto one surface of the base material by laminating or the like. The urethane resin layer may be placed on the base material by pasting it on the base material.

The heating temperature (heat treatment temperature) in step (b) may be, for example, 70 to 300°C. When the heat treatment temperature is 70° C. or higher, poor adhesion can be further suppressed. When the heat treatment temperature is 300° C. or less, damage to the base material and thermal decomposition of the urethane resin layer can be further suppressed. The heating temperature in step (b) is preferably 70 to 130°C, more preferably 80 to 100°C when the base material is a polyolefin base material. Further, the heat treatment time is not particularly limited, but is 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 more, poor adhesion can be further suppressed. When the processing time is 12 hours or less, the time required for the process can be further reduced and even better productivity can be obtained.

The heating in step (b) may be heating for drying in step (a). That is, step (a) and step (b) may be overlapping steps. When carrying out step (a) and step (b) respectively, the heating temperature in step (b) may be higher than the drying temperature in step (a).

The adhesion between the second base material and the urethane resin layer in step (c) may be performed under the same heating conditions as in step (b). Further, step (b) and step (c) may be performed simultaneously. For example, after arranging a urethane resin layer and a second base material in this order on a first base material (for example, a polyolefin base material), by heating the obtained laminate, the first base material The adhesion with the urethane resin layer and the adhesion between the second base material and the urethane resin layer may be performed substantially simultaneously.

In step (c), the second base material may be bonded uncoated or may be bonded with the resin coating described above. The conditions for forming the resin coating (for example, the conditions for coating and drying) may be the same as the conditions for forming the urethane resin layer in step (a) above.

Hereinafter, the content of the present invention will be explained in more detail using Examples and Comparative Examples, but the present invention is not limited to the following Examples.

<Preparation of materials>
The materials shown below were prepared.
[Hydrogenated polyolefin polyol]
・Hydrogenated polybutadiene polyol 1: hydroxyl group-terminated hydrogenated polybutadiene (product name: GI-1000, manufactured by Nippon Soda Co., Ltd.), number average molecular weight = 1500, hydroxyl group content = 1.22 mol/kg, iodine value = 9.2 g/100 g, 1,2-adduct: 1,4-adduct = 85:15 (molar ratio)
・Hydrogenated polybutadiene polyol 2: hydroxyl group-terminated hydrogenated polybutadiene (product name: blend of GI-1000 and GI-2000, both manufactured by Nippon Soda Co., Ltd.), number average molecular weight = 1600, hydroxyl group content = 1.15 mol/kg, Iodine value = 10.0g/100g, 1,2-adduct:1,4-adduct = 85:15 (mole ratio)
・Hydrogenated polybutadiene polyol 3: hydroxyl group-terminated hydrogenated polybutadiene (product name: blend product of GI-1000 and GI-3000. Both manufactured by Nippon Soda Co., Ltd.), number average molecular weight = 1670, hydroxyl group content = 1.15 mol/kg, Iodine value = 9.7g/100g, 1,2-adduct:1,4-adduct = 85:15 (mole ratio)
・Hydrogenated polybutadiene polyol 4: hydroxyl group-terminated hydrogenated polybutadiene (product name: a blend of GI-1000 and GI-2000. Both manufactured by Nippon Soda Co., Ltd.), number average molecular weight = 1690, hydroxyl group content = 1.08 mol/kg, Iodine value = 10.7g/100g, 1,2-adduct:1,4-adduct = 85:15 (mole ratio)
・Hydrogenated polybutadiene polyol 5: hydroxyl group-terminated hydrogenated polybutadiene (product name: blend of GI-1000 and GI-3000, both manufactured by Nippon Soda Co., Ltd.), number average molecular weight = 1830, hydroxyl group content = 1.08 mol/kg, Iodine value = 10.1g/100g, 1,2-adduct:1,4-adduct = 85:15 (mole ratio)
・Hydrogenated polyfarnesene polyol 1: Hydroxy-terminated hydrogenated polyfarnesene (product name: KRASOL F3100), number average molecular weight = 2940, hydroxyl group content = 0.68 mol/kg, iodine value = 9.7 g/100 g
[Polyisocyanate]
・MDI: diphenylmethane-4,4'-diisocyanate (product name: Millionate MT, manufactured by Tosoh Corporation), isocyanate group content = 7.99 mol/kg
[Chain extender]
・MPD: 2-methyl-1,3-propanediol, manufactured by Tokyo Chemical Industry Co., Ltd. [catalyst]
・Dioctyltin dilaurate: Manufactured by Kishida Chemical Co., Ltd. [Solvent]
・Cyclohexanone: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

<Example 1>
(Preparation of urethane resin composition)
In a 2 L four-neck separable flask equipped with a stirrer, thermometer, heating device, and reflux tube, 150.0 g of hydrogenated polybutadiene polyol 1, 17.2 g of MDI, and a catalyst (dioctyltin dilaurate) were added. 0.137 g and 1506 g of a solvent (cyclohexanone) were each charged at room temperature. Next, the inside of the flask was replaced with nitrogen by blowing nitrogen gas into the flask. A urethane resin composition containing a urethane resin made of polyurethane (a1) (urethane resin (a1)) was obtained by reacting the mixture in the flask for 6 hours while stirring the mixture substantially uniformly at 80°C.

(Analysis of urethane resin)
The urethane resin composition obtained above is dried under reduced pressure and the solvent is distilled off to take out the urethane resin (a1), and the urethane group concentration, molecular weight, etc. of the urethane resin (a1) are determined by the method shown below. It was measured. The results are shown in Table 1. Note that the catalyst used in the reaction may remain in the urethane resin (a1) taken out by this method, but the amount of remaining catalyst is very small and is below the detection limit of the measurement method, so the following The measurement was performed assuming that there was no catalyst remaining.

[Measurement of isocyanate group content and urethane group concentration]
First, the content of isocyanate groups (NCO content) remaining in the urethane resin (a1) after the synthesis reaction was measured in accordance with JIS K1603-1. Next, the nitrogen content in the urethane resin (a1) was measured by elemental analysis. The urethane group concentration in the urethane resin (a1) was calculated from the residual amount of isocyanate obtained in the measurement and the results of elemental analysis.

[Measurement of hydroxyl group content]
The hydroxyl group content (OH content) remaining in the urethane resin (a1) was measured in accordance with JIS K1557-1.

[Measurement of molecular weight]
The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using gel permeation chromatography (GPC) under the following conditions, and the molecular weight distribution index (Mw/Mn) was determined. Note that the weight average molecular weight and number average molecular weight are molecular weights in terms of polystyrene.
[conditions]
・Equipment: High-speed GPC device (HLC-8320GPC manufactured by Tosoh Corporation)
・Column: One TSKgel guardcolumn α (6.0mm I.D. x 4cm) and two +α-M (67.8mm I.D. x 30cm) connected in series in this order (both manufactured by Tosoh Corporation) manufactured by).
・Mobile phase: cyclohexanone ・Mobile phase speed: 1.0 mL/min ・Column temperature: 40°C
・Detector: RI detector (polarity (+))
・Sample solution: cyclohexanone solution (concentration: 1mg/mL)
・Sample injection volume: 100μL

[Measurement of glass transition temperature]
The glass transition temperature (Tg) of the urethane resin (a1) was measured according to JIS K6240 using differential scanning calorimetry (DSC). The measurement was performed in a temperature range of -80°C to 200°C under a nitrogen atmosphere, and the temperature increase rate was 10°C/min. The gas flow rate was 50 mL/min. The sample used was one sealed in an Al pan.

(Measurement of surface energy)
First, the urethane resin composition obtained above was applied to a polyethylene base material (PE base material: Kobe Polysheet EL-N-AN manufactured by Hitachi Chemical Co., Ltd.) using an applicator, and left to stand for 5 minutes at room temperature. , and dried at 80° C. for 4 hours under reduced pressure using a vacuum dryer. As a result, a film (film thickness: 20 μm) consisting of a dried urethane resin composition (urethane resin (a1)) was formed on the PE base material.

Next, the contact angle of various probe liquids on the surface of the membrane was measured by a sessile drop method in accordance with JIS R3257. 2.0 μL of the probe liquid was dropped, and the contact angle was measured 1 second after dropping using a contact angle measuring device (Automatic Contact Angle Meter DMo-601 manufactured by Kyowa Kaimen Kagaku Co., Ltd.). Two types of probe liquids were used: pure water (72.8 mN/m, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and diiodomethane (50.8 mN/m, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). The contact angle was measured 10 times for each probe liquid, and the average value was taken as the measured value.

The surface energy of the film was calculated using the contact angle values of pure water and diiodomethane obtained above and Owens' theory (see Non-Patent Document 1), which is a known calculation method.

(Evaluation of adhesive physical properties)
[Preparation of PP test piece]
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, left to stand for 5 minutes at room temperature, and then heated with hot air. It was dried for 10 minutes at 80° C. using a drier to form an adhesive layer (thickness: 10 μm) containing a dried urethane resin composition on the PP base material. Next, a polyethylene terephthalate film (Toyobo Ester Film E5100 manufactured by Toyobo Co., Ltd.) was attached on the adhesive layer of the obtained laminate, and then heat treated at 80° C. for 10 minutes to obtain a polypropylene (PP) test piece. The surface energy of the coated surface of the PP base material evaluated by the same method as above was 35 mJ/m ² .

[Preparation of PE test piece]
A PE test piece was obtained in the same manner as the production of the PP test piece above, except that a polyethylene base material (PE base material: Kobe Polysheet EL-N-AN manufactured by Hitachi Chemical) was used instead of the polypropylene base material. . The surface energy of the coated surface of the PE base material evaluated by the same method as above was 39 mJ/m ² .

[Measurement of adhesive strength]
A 180 degree peel test was performed on each of the PP test piece and PE test piece obtained above in accordance with JIS K6854-2, and the adhesive strength of the adhesive layer to the PP base material and the PE base material was measured. For the test, an Autocom type testing machine (UTPS-Acs (S) manufactured by TSE) was used. The results are shown in Table 1.

<Examples 2 to 6, Comparative Examples 1 to 4>
Urethane resin compositions of Examples 2 to 6 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1, except that the amounts of each component were changed as shown in Table 1. The urethane resin compositions of Examples 2 to 6 and Comparative Examples 1 to 4 were urethane resins (urethane resins (a2) to (a6) consisting of polyurethanes (a2) to (a6) or polyurethanes (b1) to (b4), respectively. ) and urethane resins (b1) to (b4)). Next, in the same manner as in Example 1, urethane resins (a2) to (a6) and urethane resins (b1) to (b4) were respectively taken out from the obtained urethane resin composition, and urethane resins (a2) to (a6) And the urethane group concentration, molecular weight, etc. of the urethane resins (b1) to (b4) were measured. In addition, in the same manner as in Example 1, the surface energy of a film (film thickness 20 μm) made of a dried urethane resin composition (urethane resins (a2) to (a6) or urethane resins (b1) to (b4)) was The adhesive physical properties of the urethane resin composition were measured and evaluated. The results are shown in Table 1.

<Examples 7 to 10>
The procedure was carried out in the same manner as in Example 1, except that hydrogenated polybutadiene polyols 2 to 5 were used in place of hydrogenated polybutadiene polyol 1, and the amounts of each component were changed as shown in Table 2. Urethane resin compositions of Examples 7 to 10 were prepared. The urethane resin compositions of Examples 7 to 10 are urethane resin compositions containing urethane resins (urethane resins (a7) to (a10)) consisting of polyurethanes (a7) to (a10), respectively. Next, in the same manner as in Example 1, urethane resins (a7) to (a10) were each taken out from the obtained urethane resin composition, and the urethane group concentration, molecular weight, etc. of urethane resins (a7) to (a10) were measured. . In addition, in the same manner as in Example 1, the surface energy of a film (thickness: 20 μm) made of dried urethane resin compositions (urethane resins (a7) to (a10)) was measured, and the adhesion of the urethane resin composition was measured. The physical properties of the drug were evaluated. The results are shown in Table 2.

<Comparative example 5>
In a 2 L four-neck separable flask equipped with a stirrer, thermometer, heating device, and reflux tube, 150.0 g of hydrogenated polybutadiene polyol 1, 33.7 g of MDI, and a catalyst (dioctyltin dilaurate) were added. 0.281 g and 1735 g of a solvent (cyclohexanone) were each charged at room temperature. Next, the inside of the flask was replaced with nitrogen by blowing nitrogen gas into the flask. After reacting the mixture in the flask for 2 hours while stirring the mixture almost uniformly at 80°C, 8.74 g of MPD was added and the reaction was further carried out under the same conditions for 6 hours to form a urethane consisting of polyurethane (b5). A urethane resin composition containing a resin (urethane resin (b5)) was obtained. Next, in the same manner as in Example 1, urethane resin (b5) was taken out from the obtained urethane resin composition, and the urethane group concentration, molecular weight, etc. of urethane resin (b5) were measured. In addition, in the same manner as in Example 1, the surface energy of a film (thickness: 20 μm) made of a dried urethane resin composition (urethane resin (b5)) was measured, and the physical properties of the adhesive of the urethane resin composition were evaluated. did. The results are shown in Table 2.

<Comparative Examples 6-7>
Urethane resin compositions of Comparative Examples 6 and 7 were prepared in the same manner as Comparative Example 5, except that the amounts of each component were changed as shown in Table 2. The urethane resin compositions of Comparative Examples 6 and 7 are urethane resin compositions containing urethane resins (urethane resins (b6) and (b7)) consisting of polyurethanes (b6) and (b7), respectively. Next, in the same manner as in Example 1, urethane resins (b6) to (b7) were each taken out from the obtained urethane resin composition, and the urethane group concentration, molecular weight, etc. of urethane resins (b6) to (b7) were measured. . In addition, in the same manner as in Example 1, the surface energy of a film (thickness: 20 μm) made of dried urethane resin compositions (urethane resins (b6) to (b7)) was measured, and the adhesion of the urethane resin composition was measured. The physical properties of the drug were evaluated. The results are shown in Table 2.

<Examples 11 to 16>
A urethane resin composition containing the polyurethane (a3) obtained in Example 3 and a urethane resin composition containing the polyurethane (a9) obtained in Example 9 were mixed into a mixture of polyurethane (a3) and polyurethane (a9). The urethane resin (urethane resins (a11) to (a16)), which is a mixture of polyurethane (a3) and polyurethane (a9), can be made by mixing so that the ratio is the value shown in Table 3 (unit: parts by mass). Urethane resin compositions of Examples 11 to 16 containing each of the above were obtained. Further, in the same manner as in Example 1, urethane resins (a11) to (a16) were each taken out from the obtained urethane resin composition, and the urethane group concentration, molecular weight, etc. of the urethane resins (a11) to (a16) were measured. . Further, in the same manner as in Example 1, the adhesive physical properties of the urethane resin composition were evaluated. The results are shown in Table 3. In addition, the blending ratio of polyurethane (a3) and polyurethane (a9) is determined by calculating the amount of solid content obtained by drying the urethane resin composition under reduced pressure and distilling off the solvent, and the polyurethane content in the urethane resin composition. (Hereinafter, the same applies to Examples 17 to 26.)

<Examples 17 to 22>
A urethane resin composition containing the polyurethane (a3) obtained in Example 3 and a urethane resin composition containing the polyurethane (a10) obtained in Example 10 were mixed into a mixture of polyurethane (a3) and polyurethane (a10). By mixing the ratios to the values shown in Table 4 (unit: parts by mass), urethane resins (urethane resins (a17) to (a22)), which are mixtures of polyurethane (a3) and polyurethane (a10), can be made. Urethane resin compositions of Examples 17 to 22 containing each of the above were obtained. Further, in the same manner as in Example 1, urethane resins (a17) to (a22) were each taken out from the obtained urethane resin composition, and the urethane group concentration, molecular weight, etc. of the urethane resins (a17) to (a22) were measured. . Further, in the same manner as in Example 1, the adhesive physical properties of the urethane resin composition were evaluated. The results are shown in Table 4.

<Examples 23-24>
A urethane resin composition containing the polyurethane (a3) obtained in Example 3 and a urethane resin composition containing the polyurethane (b4) obtained in Comparative Example 4 were mixed into a mixture of polyurethane (a3) and polyurethane (b4). By mixing so that the ratio becomes the value shown in Table 5 (unit: parts by mass), urethane resin (urethane resin (a23) to (a24)), which is a mixture of polyurethane (a3) and polyurethane (b4), can be made. Urethane resin compositions of Examples 23 and 24 containing each of the above were obtained. Further, in the same manner as in Example 1, urethane resins (a23) to (a24) were each taken out from the obtained urethane resin composition, and the urethane group concentration, molecular weight, etc. of urethane resins (a23) to (a24) were measured. . Further, in the same manner as in Example 1, the adhesive physical properties of the urethane resin composition were evaluated. The results are shown in Table 5.

<Examples 25-26>
A urethane resin composition containing the polyurethane (a3) obtained in Example 3 and a urethane resin composition containing the polyurethane (b5) obtained in Comparative Example 5 were mixed into a mixture of polyurethane (a3) and polyurethane (b5). By mixing so that the ratio becomes the value shown in Table 5 (unit: parts by mass), urethane resin (urethane resin (a25) to (a26)), which is a mixture of polyurethane (a3) and polyurethane (b5), can be made. Urethane resin compositions of Examples 25 and 26 containing each of the above were obtained. Further, in the same manner as in Example 1, urethane resins (a25) to (a26) were each taken out from the obtained urethane resin composition, and the urethane group concentration, molecular weight, etc. of the urethane resins (a25) to (a26) were measured. . Further, in the same manner as in Example 1, the adhesive physical properties of the urethane resin composition were evaluated. The results are shown in Table 5.

<Example 27 and Comparative Example 8>
In the same manner as in Example 1, except that hydrogenated polyfarnesene polyol 1 was used instead of hydrogenated polybutadiene polyol 1, and the blending amount of each component was changed as shown in Table 6. Urethane resin compositions of Example 27 and Comparative Example 8 were prepared. The urethane resin compositions of Example 27 and Comparative Example 8 are urethane resin compositions containing urethane resins (urethane resins (a27) and (b8)) made of polyurethane (a27) and (b8), respectively. Next, in the same manner as in Example 1, urethane resins (a27) and (b8) were each taken out from the obtained urethane resin composition, and the urethane group concentration, molecular weight, etc. of urethane resins (a27) and (b8) were measured. . In addition, in the same manner as in Example 1, the surface energy of a film (thickness: 20 μm) made of a dried urethane resin composition (urethane resin (a27) or (b8)) was measured, and the adhesion of the urethane resin composition was measured. The physical properties of the drug were evaluated. The results are shown in Table 6.

Claims

Consisting of polyurethane containing hydrogenated polyolefin polyol as a polyol unit,
The urethane group concentration is 0.80 to 1.10 mol/kg,
A urethane resin having a weight average molecular weight of 12,300 to 42,000.
The urethane resin according to claim 1, wherein the hydrogenated polyolefin polyol contains at least one selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyfarnesene polyol.
The hydrogenated polyolefin polyol includes a hydrogenated polybutadiene polyol,
The urethane resin according to claim 1, wherein the molar ratio of the 1,2-adduct to the 1,4-adduct in the hydrogenated polybutadiene polyol is 20:80 to 90:10.
The urethane resin according to claim 1, wherein the hydrogenated polyolefin polyol has an iodine value of 50 g/100 g or less.
The urethane resin according to claim 1, wherein the hydrogenated polyolefin polyol has a hydroxyl group content of 0.50 to 2.00 mol/kg.
The urethane resin according to claim 1, wherein the content of polyol units is 75.0 to 99.9% by mass based on the total mass of the polyurethane.
The urethane resin according to claim 1, which is a mixture of two or more polyurethanes that differ in at least one of urethane group concentration and weight average molecular weight.
A polyurethane (A1) having a weight average molecular weight of 12,300 or more and less than 20,000;
The urethane resin according to claim 7, which is a mixture containing at least a polyurethane (A2) having a weight average molecular weight of 24,000 to 42,000.
The urethane resin according to claim 8, wherein the content of the polyurethane (A1) is 25% by mass or more based on the total mass of the urethane resin.
polyurethane (A3) having a weight average molecular weight of 12,300 to 32,000;
The urethane resin according to claim 7, which is a mixture comprising at least polyurethane (A4) having a weight average molecular weight of more than 42,000 and less than 100,000.
The urethane resin according to claim 10, wherein the content of the polyurethane (A3) is 50% by mass or more based on the total mass of the urethane resin.
Polyurethane (A5) having a urethane group concentration of 0.80 to 1.02 mol/kg;
The urethane resin according to claim 7, which is a mixture containing at least a polyurethane (A6) having a urethane group concentration of more than 1.10 mol/kg and 3.00 mol/kg or less.
The urethane resin according to claim 12, wherein the content of the polyurethane (A5) is 50% by mass or more based on the total mass of the urethane resin.
The urethane resin according to claim 1, wherein the urethane resin has a molecular weight distribution index of 2.5 to 6.0.
The urethane resin according to any one of claims 1 to 14, wherein the urethane resin has a surface energy of 23 mJ/m 2 or less.
An adhesive comprising the urethane resin according to any one of claims 1 to 14.
The adhesive according to claim 16, which is used for polyolefin substrates.
comprising a base material and a urethane resin layer adhered to one surface of the base material,
An article, wherein the urethane resin layer is formed of the urethane resin according to any one of claims 1 to 14 or a composition containing the urethane resin.
The article according to claim 18, wherein the urethane resin layer has a surface energy of 23 mJ/ m2 or less.
19. The article of claim 18, wherein the substrate is a polyolefin substrate.
A method for manufacturing an article comprising a base material and a urethane resin layer adhered to one surface of the base material, the method comprising:
Step (a) of arranging the urethane resin layer containing the urethane resin according to any one of claims 1 to 14 on a base material;
A method for manufacturing an article, comprising a step (b) of heating the base material and the urethane resin layer to bond the base material and the urethane resin layer.
The method for manufacturing an article according to claim 21, wherein the base material is a polyolefin base material.
The method for manufacturing an article according to claim 22, wherein the heating temperature in the step (b) is 70 to 130°C.