WO2012121311A1 - Polyurethane compound, composition containing same, aqueous polyurethane dispersion composition, and substances resulting from curing same - Google Patents

Abstract

The present invention addresses the problem of providing: a novel polyurethane compound that, when cured, has a high elastic modulus and hardness; a composition containing said compound; an aqueous polyurethane dispersion composition; and substances resulting from curing said compositions. The present invention relates to a polyurethane compound obtained by reacting a (meth)acrylate compound (C) containing at least one hydroxyl group per molecule, a polyisocyanate compound (B), and a polycarbonate diol (A) that has one hydroxyl group on each end of the molecular chain and has a repeating unit represented by formula (1), at least.

Description

Polyurethane compound, composition containing the same, aqueous polyurethane dispersion composition and cured product thereof

The present invention relates to a polyurethane compound, a composition containing the polyurethane compound, a dispersion of the polyurethane compound, and a cured product thereof.

Polyurethane compounds are widely used, for example, for interior and exterior materials for aircraft and automobiles, exterior wall and floor materials for homes, parts for home appliances and electronic materials, or as raw materials for paints, coating agents, or adhesives. The above-mentioned coating films such as paints and coating agents not only produce a beautiful appearance, but also serve to protect the base material, so that hardness, strength, durability and the like are required. For this purpose, polyurethane compounds that give a harder coating are strongly desired.

For such a polyurethane compound as a raw material for a paint, a coating agent, or an adhesive, an active energy ray-curable resin is used from the viewpoint of workability and the like. In particular, acrylic-modified urethane resins are cured immediately upon irradiation with active energy rays, resulting in high processing speed and low total cost. Therefore, they can be used in various fields such as various coating agents such as hard coating agents, paints, and adhesives. It's being used.

Hard coating agents are required to have various functions such as weather resistance, abrasion resistance, heat resistance, and hydrolysis resistance, and are polycarbonate-based acrylic modified that is superior in functionality to polyester-based and polyether-based acrylic-modified urethane resins. Urethane resins are being considered. For example, since a polyester system has an ester bond, a hard coat agent produced using this has a disadvantage that it is inferior in hydrolysis resistance. A polyether system has an ether bond, so a hard coat agent produced using this has a weather resistance. There is a disadvantage that it is inferior in heat resistance and heat resistance. Patent Document 1 proposes a 1,6-hexanediol-type polycarbonate diol resin composition from the viewpoint of excellent wear resistance, adhesion, and weather resistance. However, there is a problem that the hardness which is one of the important functions of the hard coat agent is not yet sufficient.

JP 2002-348499 A

An object of the present invention is to provide a novel polyurethane compound, a composition containing the same, an aqueous polyurethane dispersion composition, and a cured product thereof, which give a cured product having a high elastic modulus and high hardness.

（式中、Ｚ^１及びＺ^２は、それぞれ独立に、炭素数１～１０の直鎖又は分岐鎖のアルカンジイル基を示す。）
　［２］ポリカーボネートジオール（Ａ）が、式（１）で表される繰り返し単位と、式（２）で表される繰り返し単位とを有しかつ分子鎖の両末端に水酸基を１個ずつ有するものである前記［１］に記載のポリウレタン化合物。

（式中、Ｚ^３は、置換基を有してもよい炭素数２～１０の直鎖若しくは分岐鎖のアルカンジイル基、置換基を有してもよい炭素数３～１０のシクロアルカンジイル基、又は置換基を有してもよい主鎖中に脂環構造を有する炭素数５～１０のアルカンジイル基のいずれかを示す。）
　［３］さらに酸性基含有ポリオール（Ｄ）を反応させて得られる前記［１］又は［２］に記載のポリウレタン化合物。
　［４］さらに鎖延長剤（Ｅ）を反応させて得られる前記［１］～［３］のいずれか一つに記載のポリウレタン化合物。
　［５］少なくとも、前記［１］～［４］のいずれか一つに記載のポリウレタン化合物が水系媒体中に分散されている水性ポリウレタン分散体。
　［６］少なくとも、前記［１］～［４］のいずれか一つに記載のポリウレタン化合物が有機溶媒中に分散又は溶解されているポリウレタン溶液。
　［７］前記［１］～［４］のいずれか一つに記載のポリウレタン化合物と、重合開始剤（Ｇ）と、必要に応じて重合性不飽和結合を有する化合物（Ｆ）とを含有するポリウレタン組成物。
　［８］前記［７］に記載のポリウレタン組成物を硬化させた硬化物。
　［９］少なくとも、前記［１］～［４］のいずれか一つに記載のポリウレタン化合物と、重合開始剤（Ｇ）と、必要に応じて重合性不飽和結合を有する化合物（Ｆ）とが水系媒体中に分散されている水性ポリウレタン分散体組成物。
　［１０］前記［９］に記載の水性ポリウレタン分散体組成物を塗布して乾燥させ、硬化させた硬化物。
　［１１］ポリカーボネートジオール（Ａ）とポリイソシアネート化合物（Ｂ）とを反応させて、末端にイソシアナト基を有するポリウレタンプレポリマーを得た後、前記ポリウレタンプレポリマーと分子内に１個以上の水酸基を有する（メタ）アクリレート化合物（Ｃ）とを反応させる前記［１］又は［２］に記載のポリウレタン化合物の製造方法。
　［１２］ポリカーボネートジオール（Ａ）とポリイソシアネート化合物（Ｂ）と酸性基含有ポリオール（Ｄ）とを反応させて、末端にイソシアナト基を有するポリウレタンプレポリマーを得た後、前記ポリウレタンプレポリマーと分子内に１個以上の水酸基を有する（メタ）アクリレート化合物（Ｃ）とを反応させる前記［３］に記載のポリウレタン化合物の製造方法。
　［１３］ポリカーボネートジオール（Ａ）とポリイソシアネート化合物（Ｂ）と必要に応じて酸性基含有ポリオール（Ｄ）とを反応させて、末端にイソシアナト基を有するポリウレタンプレポリマーを得た後、鎖延長剤（Ｅ）を反応させ、その後、分子内に１個以上の水酸基を有する（メタ）アクリレート化合物（Ｃ）と反応させる前記［４］に記載のポリウレタン化合物の製造方法。
　［１４］ポリカーボネートジオール（Ａ）とポリイソシアネート化合物（Ｂ）と酸性基含有ポリオール（Ｄ）とを反応させて、末端にイソシアナト基を有するポリウレタンプレポリマーを得た後、前記酸性基含有ポリオールに由来する酸性基を中和し、水系媒体中に分散させた後、必要に応じて鎖延長剤（Ｅ）と反応させ、その後、分子内に１個以上の水酸基を有する（メタ）アクリレート化合物（Ｃ）と反応させる前記［５］に記載の水性ポリウレタン分散体の製造方法。
　［１５］ポリカーボネートジオール（Ａ）とポリイソシアネート化合物（Ｂ）と必要に応じて酸性基含有ポリオール（Ｄ）とを有機溶媒中で反応させて、末端にイソシアナト基を有するポリウレタンプレポリマーを得た後、必要に応じて鎖延長剤（Ｅ）と反応させ、分子内に１個以上の水酸基を有する（メタ）アクリレート化合物（Ｃ）と反応させる前記［６］に記載のポリウレタン溶液の製造方法。 The present invention has been made to solve the above problems, and specifically has the following configuration.
[1] At least a polycarbonate diol (A) having a repeating unit represented by the following formula (1) and having one hydroxyl group at both ends of the molecular chain, a polyisocyanate compound (B), A polyurethane compound obtained by reacting a (meth) acrylate compound (C) having one or more hydroxyl groups.

(In the formula, Z ¹ and Z ² each independently represent a linear or branched alkanediyl group having 1 to 10 carbon atoms.)
[2] The polycarbonate diol (A) has a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2) and has one hydroxyl group at both ends of the molecular chain. The polyurethane compound according to [1] above.

(In the formula, Z ³ represents an optionally substituted linear or branched alkanediyl group having 2 to 10 carbon atoms, or an optionally substituted cycloalkanediyl group having 3 to 10 carbon atoms. Or an alkanediyl group having 5 to 10 carbon atoms having an alicyclic structure in the main chain which may have a substituent.
[3] The polyurethane compound according to [1] or [2] obtained by further reacting the acidic group-containing polyol (D).
[4] The polyurethane compound according to any one of [1] to [3] obtained by further reacting with a chain extender (E).
[5] An aqueous polyurethane dispersion in which at least the polyurethane compound according to any one of [1] to [4] is dispersed in an aqueous medium.
[6] A polyurethane solution in which at least the polyurethane compound according to any one of [1] to [4] is dispersed or dissolved in an organic solvent.
[7] The polyurethane compound according to any one of [1] to [4], a polymerization initiator (G), and a compound (F) having a polymerizable unsaturated bond as necessary. Polyurethane composition.
[8] A cured product obtained by curing the polyurethane composition according to [7].
[9] At least the polyurethane compound according to any one of [1] to [4], a polymerization initiator (G), and, if necessary, a compound (F) having a polymerizable unsaturated bond. An aqueous polyurethane dispersion composition dispersed in an aqueous medium.
[10] A cured product obtained by applying the aqueous polyurethane dispersion composition according to [9], drying and curing.
[11] After reacting the polycarbonate diol (A) with the polyisocyanate compound (B) to obtain a polyurethane prepolymer having an isocyanato group at the end, the polyurethane prepolymer and the molecule have one or more hydroxyl groups. The method for producing a polyurethane compound according to [1] or [2], wherein the (meth) acrylate compound (C) is reacted.
[12] After reacting the polycarbonate diol (A), the polyisocyanate compound (B) and the acidic group-containing polyol (D) to obtain a polyurethane prepolymer having an isocyanato group at the terminal, the polyurethane prepolymer and the intramolecular The method for producing a polyurethane compound according to the above [3], wherein the (meth) acrylate compound (C) having one or more hydroxyl groups is reacted.
[13] After the polycarbonate diol (A), the polyisocyanate compound (B) and, if necessary, the acidic group-containing polyol (D) are reacted to obtain a polyurethane prepolymer having an isocyanato group at the terminal, a chain extender The process for producing a polyurethane compound according to the above [4], wherein (E) is reacted and then reacted with a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule.
[14] After reacting the polycarbonate diol (A), the polyisocyanate compound (B), and the acidic group-containing polyol (D) to obtain a polyurethane prepolymer having an isocyanato group at the terminal, it is derived from the acidic group-containing polyol. The acidic group to be neutralized is dispersed in an aqueous medium, then reacted with a chain extender (E) as necessary, and then a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule. The method for producing an aqueous polyurethane dispersion according to the above [5].
[15] After reacting the polycarbonate diol (A), the polyisocyanate compound (B) and, if necessary, the acidic group-containing polyol (D) in an organic solvent to obtain a polyurethane prepolymer having an isocyanate group at the terminal The method for producing a polyurethane solution according to [6], wherein the polyurethane solution is reacted with a chain extender (E) as necessary and reacted with a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule.

The polyurethane compound of the present invention, a composition containing the same and a cured product thereof are excellent in elastic modulus and hardness, and are optimal in various fields requiring high hardness, such as metal, wood, paper, plastic, electric / electronic. -Suitable for use in many fields, such as coating agents in the automotive field, automobile interior and exterior, furniture, paints for floors and walls of building materials, various adhesives, inks, decorative films (especially hard coat layers for decorative films) be able to.

Hereinafter, the polyurethane compound of the present invention, a composition containing the same, and a cured product thereof will be described in detail.

(Polycarbonate diol (A))
The polycarbonate diol (A) according to the present invention has a repeating unit represented by the following formula (1).

In formula (1), Z ¹ and Z ² each independently represent a linear or branched alkanediyl group having 1 to 10 carbon atoms. Examples of the alkanediyl group represented by Z ¹ and Z ² include a methylene group, an ethylene group, a trimethylene group, a propane-1,2-diyl group, a tetramethylene group, a butane-1,3-diyl group, a pentamethylene group, and a hexamethylene group. Examples include a methylene group, a heptamethylene group, an octamethylene group, and a decamethylene group.

The alkanediyl group represented by Z ¹ and Z ² is a straight chain having 1 to 4 carbon atoms or the alkanediyl group represented by Z ¹ and Z ² from the viewpoint that the cured product obtained by curing the polymerizable composition containing the resulting polyurethane compound has a higher elastic modulus. Branched alkanediyl groups are more preferred. Examples of the linear or branched alkanediyl group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a propane-1,2-diyl group, a tetramethylene group, and a butane-1,3-diyl group. Groups.

The bond of Z ¹ and Z ^{2 to} the benzene ring is preferably a 1,4-bond (para form) or a 1,3-bond (meta form), and more preferably a 1,4-bond (para form).

The polycarbonate diol (A) according to the present invention has one hydroxyl group at both ends of the molecular chain. Therefore, the polycarbonate diol (A) according to the present invention is composed of only the repeating unit represented by the formula (1) and two hydroxyl groups at both ends of the molecular chain, for example, the following formula (3):

（式中、Ｚ^１及びＺ^２は前記と同じであり、ｎは繰り返し単位数を表す整数である。）
で表わされるポリカーボネートジオールであってもよいし、式（１）で表される繰り返し単位と、１種以上の他の繰り返し単位と、分子鎖の両末端の２個の水酸基で構成されるポリカーボネートジオール共重合体であってもよい。

(In the formula, Z ¹ and Z ² are the same as described above, and n is an integer representing the number of repeating units.)
Or a polycarbonate diol composed of a repeating unit represented by the formula (1), one or more other repeating units, and two hydroxyl groups at both ends of the molecular chain. A copolymer may also be used.

The ratio of the repeating unit represented by the formula (1) to other repeating units is preferably 1:99 to 99: 1, more preferably 30:70 to 99: 1, and 50:50 to 99: 1. Is more preferable, and 55:45 to 99: 1 is particularly preferable.

A polycarbonate diol particularly suitable as a polycarbonate diol represented by only the repeating unit represented by the formula (1) and two hydroxyl groups is represented by the following formula (3a).

（式中、ｎは繰り返し単位の数を表す整数である。）

(In the formula, n is an integer representing the number of repeating units.)

The number, content, number average molecular weight and the like of the repeating unit represented by the formula (1) of the polycarbonate diol (A) according to the present invention are from the viewpoint of mechanical performance, hydrolysis resistance, heat resistance, weather resistance, From the viewpoint of applicability in various fields, it is as follows.
The number of repeating units represented by the formula (1) is preferably 1 to 18, more preferably 2 to 13.
The number average molecular weight of the polycarbonate diol (A) according to the present invention is preferably 200 to 3,000, more preferably 300 to 2,000, and still more preferably 400 to 1,000. If the number average molecular weight is too high, the melting point becomes high and handling may be difficult. On the other hand, if the number average molecular weight is too low, the number of carbonate bonds decreases, and it may be difficult to express the properties as a polycarbonate diol.

The polycarbonate diol (A) according to the present invention can be produced by reacting an aromatic diol compound with carbonate ester, phosgene or the like by a known method such as a carbonate method or a phosgene method. Of these, the carbonate method is preferred.
As a carbonate method, the following manufacturing method A is mentioned preferably, for example.
In production method A, as shown in the following reaction formula, an aromatic dihydroxyl compound (4) and a carbonate ester (5) are subjected to a transesterification reaction in the presence or absence of a catalyst to give polycarbonate diol (3 ).

In the above formula relating to production method A, R ¹ and R ² represent a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, or together, alkanediyl having 2 to 4 carbon atoms Indicates a group. n represents the number of repeating units, and is preferably 1 to 18, more preferably 2 to 13.

In the above production method A, alcohols (R ¹ OH, R ² OH, etc.) derived from the carbonate ester (5) are by-produced during the transesterification reaction, and therefore it is preferable to proceed the reaction while extracting it by distillation or the like. . Moreover, in the said manufacturing method A, when using carbonate carbonates, such as ethylene carbonate, as carbonate ester (5), since glycols derived from alkylene carbonate are by-produced, it is preferable to advance reaction, extracting this by distillation etc. .
The details of the aromatic dihydroxyl compound (4), the carbonate ester (5), and the transesterification will be described later in [Production Method B].

The polycarbonate diol (A) according to the present invention is a polycarbonate diol composed of a repeating unit represented by the formula (1), one or more other repeating units, and two hydroxyl groups at both ends of the molecular chain. In the case of a polymer, the other repeating unit is not particularly limited as long as it has a carbonate structure. However, since the melting point and glass transition temperature of the obtained polyurethane compound can be lowered, the following formula (2 ) Is preferred.

In the formula, Z ³ is a linear or branched alkanediyl group having 2 to 10 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 10 carbon atoms which may have a substituent, Or an alkanediyl group having 5 to 10 carbon atoms having an alicyclic structure in the main chain which may have a substituent. Here, the “substituent” may be any group that does not participate in the subsequent urethanization reaction.

Examples of the linear or branched alkanediyl group having 2 to 10 carbon atoms represented by Z ³ include an ethylene group, a trimethylene group, a propane-1,2-diyl group, a tetramethylene group, and a butane-1,3-diyl group. , Pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, decamethylene group and the like.

Examples of the cycloalkanediyl group having 3 to 10 carbon atoms represented by Z ³ include cyclopropane-1,2-diyl group, cyclobutane-1,3-diyl group, cyclopentane-1,2-diyl group, cyclohexane-1 , 2-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,4-diyl group, cycloheptane-1,4-diyl group, cyclooctane-1,5-diyl group, cyclononane-1,5- A diyl group, a cyclodecane-1,6-diyl group, an adamantane-1,3-diyl group and the like can be mentioned.

Examples of the alkanediyl group having 5 to 10 carbon atoms having an alicyclic structure in the main chain represented by Z ³ include a cyclopropane-1,2-dimethylene group, a cyclobutane-1,3-dimethylene group, a cyclopentane-1, 2-dimethylene group, cyclopentane-1,3-dimethylene group, cyclohexane-1,2-dimethylene group, cyclohexane-1,3-dimethylene group, cyclohexane-1,4-dimethylene group, cyclohexane-1,2-diethylene group And cyclohexane-1,3-diethylene group, cyclohexane-1,4-diethylene group, cycloheptane-1,4-dimethylene group, cyclooctane-1,5-dimethylene group and the like.

Among the above, Z ³ is preferably a linear alkanediyl group having 3 to 6 carbon atoms or an alkanediyl group having 6 to 8 carbon atoms having an alicyclic structure in the main chain. Said Z ³ is in particular trimethylene group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, cyclohexane-1,3-dimethylene group, cyclohexane-1, It is preferably one or more selected from the group consisting of 4-dimethylene groups.

That is, the polycarbonate diol (A) according to the present invention is composed of a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), and two hydroxyl groups at both ends of the molecular chain. For example, the following formula (3 ′):

（式中、Ｚ^１、Ｚ^２及びＺ^３は前記と同じであり、ｎは繰り返し単位数を表す整数である。）
で表わされるランダム共重合のポリカーボネートジオール共重合体であってもよい。

(In the formula, Z ¹ , Z ² and Z ³ are the same as described above, and n is an integer representing the number of repeating units.)
The polycarbonate diol copolymer of the random copolymer represented by these may be sufficient.

In the polycarbonate diol copolymer, the molar ratio of [(repeating unit represented by formula (1)) / (repeating unit represented by formula (2))] is preferably 1/9 to 9/1, 5 to 5/1 is more preferable, and 1/3 to 3/1 is still more preferable.

The number of repeating units represented by the formulas (1) and (2) of the polycarbonate diol copolymer, the content, the number average molecular weight, etc. are from the viewpoint of mechanical performance, hydrolysis resistance, heat resistance, weather resistance, From the viewpoint of applicability in various fields, it is as follows.
The repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) may be block copolymerized or randomly copolymerized.
The number of repeating units represented by the formula (1) is preferably 1 to 20, more preferably 2 to 15, and the content of the repeating units is preferably 10 to 20 in the polycarbonate diol copolymer. 90 mol%, more preferably 25 to 75 mol%.
The number of the repeating unit represented by the formula (2) is preferably 1 to 30, more preferably 2 to 20, and the content of the repeating unit is preferably 10 to 10 in the polycarbonate diol copolymer. 90 mol%, more preferably 25 to 75 mol%.
The number average molecular weight of the polycarbonate diol copolymer according to the present invention is preferably 200 to 3,000, more preferably 300 to 2,000, and still more preferably 900 to 1,500.

Other preferable physical properties of the polycarbonate diol (A) according to the present invention are as follows.
The Hazen unit color number (APHA) defined in JIS K 1557 is preferably 200 or less, more preferably 100 or less, still more preferably 70 or less, and particularly preferably 1 to 60.
The hydroxyl value is preferably 35 to 600 mgKOH / g, more preferably 50 to 400 mgKOH / g, still more preferably 100 to 150 mgKOH / g, and particularly preferably 110 to 130 mgKOH / g.
The acid value is preferably 1 mgKOH / g or less, more preferably 0.1 mgKOH / g or less, and still more preferably 0.01 to 0.05 mgKOH / g.
The melting point is preferably −100 to + 250 ° C., more preferably −80 to + 200 ° C., still more preferably −20 to + 170 ° C., and particularly preferably 0 to 160 ° C.
The glass transition point is preferably −80 to + 50 ° C., more preferably −60 to + 20 ° C., and further preferably −55 to −20 ° C.
The viscosity is preferably 10 to 10,000 cp (75 ° C.), more preferably 50 to 5,000 cp (75 ° C.), and still more preferably 100 to 1,500 cp (75 ° C.).

Examples of the method for producing the polycarbonate diol copolymer include a method of reacting an aromatic diol compound, an aliphatic dihydroxyl compound, carbonate ester, phosgene, and the like by a known method such as a carbonate ester method or a phosgene method. Of these, the carbonate method is preferred.
As a carbonate method, the following manufacturing method B is mentioned preferably, for example.
In the production method B, as shown in the following reaction formula, an aromatic dihydroxyl compound (4), a carbonate ester (5) and an aliphatic dihydroxyl compound (6) are reacted in the presence or absence of a catalyst, In this method, a polycarbonate diol copolymer (3 ') is obtained by transesterification.

In addition, in the reaction formula of the following production method B, only when the structural unit derived from the aliphatic dihydroxyl compound (6) is present at the left end as the polycarbonate diol copolymer (3 ′) in order to simply describe the reaction formula. Is described. However, the terminal is not limited to a structural unit derived from the aliphatic dihydroxyl compound (6).

In the above formula relating to production method B, R ¹ , R ² , Z ³ and n are the same as described above.
In the above production method B, alcohols (R ¹ OH, R ² OH, etc.) derived from the carbonic ester (5) are by-produced during the transesterification reaction. Therefore, it is preferable to proceed the reaction while extracting this by distillation or the like. . Moreover, in the said manufacturing method B, when using carbonate carbonate, such as ethylene carbonate, as carbonate ester (5), since glycols derived from alkylene carbonate are by-produced, reaction can be advanced while extracting this by distillation etc. preferable.

The aromatic dihydroxyl compound used in the polycarbonate diol according to the present invention is represented by the following formula (4).

In the formula, Z ¹ and Z ² are the same as described above, and each independently represents a linear or branched alkanediyl group having 1 to 10 carbon atoms. Specific examples and preferred examples of the alkanediyl group are as described above, and a linear or branched alkanediyl group having 1 to 4 carbon atoms is preferable.
Z ¹ and Z ² are preferably 1,4-bond (para-form) or 1,3-bond (meta-form), and more preferably 1,4-bond (para-form).
Particularly preferred aromatic dihydroxyl compounds (a) include 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,4-benzenedipropanol, 1,4-benzenedibutanol, and 1,3-benzene. Dimethanol, 1,3-benzenediethanol, 1,3-benzenedipropanol, 1,3-benzenedibutanol, 4- (4-hydroxymethylphenyl) butanol, 3- [4- (2-hydroxyethyl) phenyl] Examples thereof include compounds having a linear or branched alkanediyl group having 1 to 4 carbon atoms such as propanol.

The carbonate ester (5) that can be used in the polycarbonate diol according to the present invention is not particularly limited, but it is desirable to appropriately select one that can efficiently extract by-product alcohols derived from the carbonate ester. Examples thereof include dialkyl carbonate, diaryl carbonate, and alkylene carbonate.
The dialkyl carbonate is preferably a dialkyl carbonate having an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include dimethyl carbonate and diethyl carbonate.
Examples of the diaryl carbonate include diphenyl carbonate.
The alkylene carbonate is preferably an alkylene carbonate having an alkanediyl group having 2 to 4 carbon atoms, and specific examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate and the like. Among these, from the viewpoint of easy extraction of by-product alcohols, dialkyl carbonate having an alkyl group having 1 to 4 carbon atoms is preferable, and dimethyl carbonate is particularly preferable.

The aliphatic dihydroxyl compound that can be used in the polycarbonate diol according to the present invention is represented by the following formula (6).

In the formula, Z ³ is the same as described above, and may have a linear or branched alkanediyl group having 2 to 10 carbon atoms, which may have a substituent, or may have 3 to 10 carbon atoms which may have a substituent. It represents either a cycloalkanediyl group or an alkanediyl group having 5 to 10 carbon atoms having an alicyclic structure in the main chain which may have a substituent.

Examples of alkanediols in which Z ³ is an alkanediyl group having 2 to 10 carbon atoms include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and the like.
Examples of the branched carbon chain of the alkanediyl group include 1,3-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,6-diol, neopentyl glycol, 2 -Methyl-1,8-octanediol and the like.

Examples of the cycloalkanediol in which Z ³ is a cycloalkanediyl group having 3 to 10 carbon atoms include cyclopropane-1,2-diol, cyclobutane-1,3-diol, cyclopentane-1,2-diol, cyclohexane- 1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cycloheptane-1,4-diol, cyclooctane-1,5-diol, cyclononane-1,5-diol, cyclodecane- Examples include 1,6-diol and adamantane-1,3-diol.

Examples of cycloalkanediol in which Z ³ is an alkanediyl group having 5 to 10 carbon atoms having an alicyclic structure in the main chain include cyclopropane-1,2-dimethanol, cyclobutane-1,3-dimethanol, cyclo Examples include pentane-1,3-dimethanol and 1,4-cyclohexanedimethanol.

Of these, alkanes having 4 to 8 carbon atoms, particularly 4 to 6 carbon atoms, such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and the like, are easy to handle and easy to obtain. Aliphatic diols having an alicyclic structure having 5 to 8 carbon atoms such as diol and 1,4-cyclohexanedimethanol are more preferred.

Examples of the catalyst used for the production of the polycarbonate diol according to the present invention include a catalyst (transesterification catalyst) used in a normal transesterification reaction. For example, preferred are alkali metal compounds, alkaline earth metal compounds, aluminum compounds, zinc compounds, manganese compounds, nickel compounds, antimony compounds, zirconium compounds, titanium compounds, and organic tin compounds.
Examples of alkali metal compounds include alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (lithium carbonate, sodium carbonate, potassium carbonate, etc.), and alkali metal carboxylates. (Lithium acetate, sodium acetate, potassium acetate, etc.), alkali metal alkoxides (lithium methoxide, sodium methoxide, potassium t-butoxide, etc.) and the like. Alkaline earth metal hydroxides include alkaline earth metal hydroxides. Products (magnesium hydroxide, etc.), alkaline earth metal alkoxides (magnesium methoxide, etc.) and the like.

Examples of the aluminum compound include aluminum compounds such as aluminum alkoxide (aluminum ethoxide, aluminum isopropoxide, aluminum sec-butoxide, etc.) and aluminum acetylacetonate.
Examples of the zinc compound include zinc carboxylates (such as zinc acetate) and zinc acetylacetonate. Examples of the manganese compounds include manganese carboxylates (such as manganese acetate) and manganese acetylacetonate. Examples of nickel compounds include nickel carboxylates (such as nickel acetate) and nickel acetylacetonate.
Examples of the antimony compound include antimony carboxylates (such as antimony acetate) and antimony alkoxide, and examples of the zirconium compound include zirconium alkoxide (zirconium propoxide, zirconium butoxide, etc.) and zirconium acetylacetonate.

Examples of the titanium compound include titanium alkoxide (titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, tetracyclohexyl titanate, tetrabenzyl titanate, etc.), titanium acylate (tributoxy titanium stearate, isopropoxy titanium stearate, etc.) , Titanium chelates (diisopropoxy titanium bisacetylacetonate, dihydroxy bis lactato titanium, etc.) and the like.
Examples of the organotin compound include dibutyltin oxide, dibutyltin diacetate, and dibutyltin dilaurate.
The carboxylic acid in each carboxylate is preferably a carboxylic acid having 2 to 30 carbon atoms, and more preferably a carboxylic acid having 2 to 18 carbon atoms. Each alkoxide is preferably an alkoxy group having 1 to 30 carbon atoms, and more preferably an alkoxy group having 2 to 18 carbon atoms.
In said catalyst, a titanium compound and an organotin compound are preferable, a titanium compound is more preferable, and a titanium alkoxide is still more preferable. Among the titanium alkoxides, titanium tetraethoxide, titanium tetrapropoxide, and titanium tetrabutoxide are more preferable, and titanium tetrabutoxide is particularly preferable.
In addition, said aromatic dihydroxyl compound (4), carbonate ester (5), aliphatic dihydroxyl compound (6), and a catalyst can be used individually by 1 type or in combination of 2 or more types.

The transesterification reaction in the method for producing a polycarbonate diol according to the present invention can be performed in the presence or absence of a catalyst, but it is preferably performed in the presence of a catalyst from the viewpoint of reaction efficiency.
The reaction temperature and reaction pressure in the transesterification reaction vary depending on the types of the carbonic acid ester (5) and the aliphatic dihydroxyl compound (6) to be used. In the case of production method A, aromatic dihydroxyl such as 1,4-benzenedimethanol In the case of compound (4) and production method B, it is preferable that the aromatic dihydroxyl compound (4) and the aliphatic dihydroxyl compound (6) are not substantially distilled off. The reaction temperature is preferably 90 to 230 ° C., and the reaction pressure is preferably reduced from normal pressure to 30 to 500 mmHg. The reaction can be performed in an atmosphere of air, carbon dioxide gas, or inert gas (nitrogen, argon, helium, etc.) or in an air stream, but is preferably performed in an inert gas atmosphere or in an air stream.
Further, in the case of production method A, the amount used in the case of using a catalyst is the production method with respect to the total charged amount of aromatic dihydroxyl compound (4) and carbonate ester (5) at the start of the reaction. In the case of B, 1 to 20,000 ppm based on the weight of the catalyst with respect to the total charged amount of the aromatic dihydroxyl compound (4), carbonate ester (5) and aliphatic dihydroxyl compound (6) at the start of the reaction. Is preferable, 10 to 5,000 ppm is more preferable, and 100 to 4,000 ppm is still more preferable.

Further, a catalyst of a high molecular weight polycarbonate diol obtained by reacting an aliphatic dihydroxyl compound (6) with a carbonate ester (5) and an aromatic dihydroxyl compound (4) such as 1,4-benzenedimethanol A polycarbonate diol copolymer can also be obtained by transesterification in the presence or absence of.
Further, a catalyst of a high molecular weight polycarbonate diol obtained by reacting an aromatic dihydroxyl compound (4) such as 1,4-benzenedimethanol with a carbonate ester (5), and an aliphatic dihydroxyl compound (6) A polycarbonate diol copolymer can also be obtained by transesterification in the presence or absence of.

The average molecular weight of the polycarbonate diol (A) according to the present invention is prepared by changing the reaction molar ratio of the aromatic dihydroxyl compound (4), the carbonate ester (5), and the aliphatic dihydroxyl compound (6) to be used. be able to.
When the average molecular weight of the produced polycarbonate diol or polycarbonate diol copolymer is smaller than the target average molecular weight, the aromatic dihydroxyl compound (4) and / or the aliphatic dihydroxyl compound (6) are further reduced under reduced pressure. On the contrary, when the average molecular weight is larger than the target average molecular weight, the aromatic dihydroxyl compound (4) and / or the aliphatic dihydroxyl compound (6) is added to cause further ester exchange reaction. A polycarbonate diol or a polycarbonate diol copolymer having a target average molecular weight can be obtained.
The constituent molar ratio of the repeating unit of the polycarbonate diol copolymer according to the present invention can be prepared by changing the molar ratio of the aromatic dihydroxyl compound (4) and the aliphatic dihydroxyl compound (6). .

(Polyisocyanate compound (B))
The polyisocyanate compound (B) that can be used in the present invention is not particularly limited. Specifically, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2, 6-tolylene diisocyanate, 4,4'-diphenylenemethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanate Natobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate P-isocyanatophenylsulfonyl isocyanate Aromatic diisocyanate compounds such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, Aliphatic poly, such as methyl 2,6-diisocyanatocaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2,6-diisocyanatocaproic acid 2-isocyanatoethyl Isocyanate compounds: isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexyl Diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, etc. Etc. These polyisocyanate compounds may be used individually by 1 type, and may use multiple types together.

The number of isocyanate groups per molecule of the polyisocyanate compound is usually two, but polyisocyanates having three or more isocyanato groups such as triphenylmethane triisocyanate can be used as long as the polyurethane compound in the present invention does not gel. Can be used.

Among the above polyisocyanate compounds, 4,4'-diphenylenemethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenation) from the viewpoint of controlling reactivity and imparting strength. MDI) is preferred.

((Meth) acrylate compound having hydroxyl group (C))
Although it does not restrict | limit especially as a (meth) acrylate compound (henceforth "(meth) acrylate compound (C)") which has one or more hydroxyl groups in a molecule | numerator which can be used by this invention, For example, ethylene glycol mono (Meth) acrylate, propylene glycol mono (meth) acrylate, butanediol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meta ) Acrylate, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate Monohydric alcohol mono (meth) acrylates such as polypropylene glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, ethoxylated neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate. (Meth) acrylate; trimethylolpropane mono (meth) acrylate, ethoxylated trimethylolpropane mono (meth) acrylate, propoxylated trimethylolpropane mono (meth) acrylate, tris (2-hydroxyethyl) isocyanurate mono (meth) acrylate, Glycerin mono (meth) acrylate, trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane di (meth) acrylate, propoxylation Mono (meth) acrylates and di (meth) acrylates of trivalent alcohols such as limethylolpropane di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, glycerin di (meth) acrylate, Mono and di (meth) acrylates in which some of the hydroxyl groups of these alcohols are modified with alkyl groups or ε-caprolactone; pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, ditrimethylolpropane mono (meth) acrylate , Pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, ditrimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaeri Polyfunctional (meth) acrylates of tetrahydric or higher alcohols such as lithol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate and the like, and hydroxyl groups of these alcohols Specific examples thereof include polyfunctional (meth) acrylates having hydroxyl groups partially modified with alkyl groups or ε-caprolactone. These (meth) acrylate compounds (C) may be used individually by 1 type, and may use multiple types together.

Among the above (meth) acrylate compounds (C), dihydric alcohols such as ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate and butanediol mono (meth) acrylate from the viewpoint of low viscosity and low cost. The mono (meth) acrylate is preferably ethylene glycol mono (meth) acrylate.

The polyurethane compound of the present invention is obtained by reacting a polycarbonate diol (A), a polyisocyanate compound (B), and a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule. Details of the reaction are as described later, but may be carried out according to a known method for producing a polyurethane compound. Also, for example, after reacting the polycarbonate diol (A) and the polyisocyanate compound (B) to obtain a polyurethane prepolymer having an isocyanato group at the terminal, one or more hydroxyl groups in the molecule are added to the polyurethane prepolymer. The polyurethane compound of the present invention may be produced by reacting the (meth) acrylate compound (C).

(Acid group-containing polyol (D))
In addition to the polycarbonate diol (A), the polyisocyanate compound (B), and the (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule, the polyurethane compound of the present invention includes an acidic group-containing polyol (D ) May be obtained.
The acidic group-containing polyol (D) is not particularly limited as long as it is a compound containing two or more hydroxyl groups and one or more acidic groups in one molecule. Examples of the acidic group include a carboxy group, a sulfonyl group, a phosphoric acid group, and a phenolic hydroxyl group.
Among the acidic group-containing polyols (D), a compound having two or more hydroxyl groups and one or more carboxy groups in one molecule is preferable, and a compound having two hydroxyl groups and one carboxy group in one molecule. Is more preferable.

Specific examples of the acidic group-containing polyol (D) include, for example, dimethylol alkanoic acid such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid, N, N-bishydroxyethylglycine, N , N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, acidic group-containing polyether polyol, acidic group-containing polyester polyol, and the like. Of these, dimethylolalkanoic acid is preferable from the viewpoint of availability, and in this case, the alkanoic acid preferably has 4 or less carbon atoms, and more preferably 2,2-dimethylolpropionic acid.
As for the said acidic group containing polyol (D), only 1 type may be used independently and 2 or more types may be used together.

The polyurethane compound of the present invention also includes a polycarbonate diol (A), a polyisocyanate compound (B), a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule, and an acidic group-containing polyol (D). Obtained by reacting with. Details of the reaction are as described later, but may be carried out according to a known method for producing a polyurethane compound. Further, for example, after reacting the polycarbonate diol (A), the polyisocyanate compound (B) and the acidic group-containing polyol (D) to obtain a polyurethane prepolymer having an isocyanate group at the terminal, the polyurethane prepolymer and the molecule The polyurethane compound of the present invention may be produced by reacting (meth) acrylate compound (C) having one or more hydroxyl groups therein.

(Chain extender (E))
The polyurethane compound of the present invention comprises a polycarbonate diol (A), a polyisocyanate compound (B), a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule, and an acidic group-containing polyol as an optional component. It may be obtained by reacting (D) with a chain extender (E).
Examples of the chain extender (E) include compounds having reactivity with isocyanato groups. For example, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl -Amines such as 3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, adipoylhydrazide, hydrazine, 2,5-dimethylpiperazine, diethylenetriamine, triethylenetetramine Compounds, diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, polyalkylene glycols typified by polyethylene glycol, water, etc., among which primary diamine compounds are preferred. And the like. These may be used alone or in combination of two or more.

The method for adding the chain extender (E) may be a one-shot method in which each raw material is reacted at once, or a prepolymer method in which it is reacted with a polyurethane prepolymer having an isocyanato group at the molecular end.
The polyurethane prepolymer is obtained by reacting a polycarbonate diol (A), a polyisocyanate compound (B), and an optional acidic group-containing polyol (D).
The polyurethane prepolymer comprises a polycarbonate diol (A), a polyisocyanate compound (B), an optional acidic group-containing polyol (D), and a (meth) acrylate having one or more hydroxyl groups in the molecule. What reacted with the compound (C) may be used. In this case, when the (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule has only one hydroxyl group in the molecule, it has one or more hydroxyl groups in the molecule (meta ) When a large amount of acrylate compound (C) is added, the isocyanate group of the polyurethane prepolymer is almost sealed with (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule. E) may not be allowed to react.

The amount of the chain extender (E) can be appropriately selected. When an aqueous polyurethane dispersion is produced by the prepolymer method, the number of moles of the group having reactivity with the isocyanate group in the chain extender other than water is not more than twice the number of moles of the isocyanate group in the polyurethane prepolymer. A chain extender can be added as follows. More preferably, the molar ratio of the polyurethane prepolymer to the chain extender is mixed at 1: 1 to 0.8: 1.

The polyurethane compound of the present invention can be produced by reacting a polycarbonate diol (A), a polyisocyanate compound (B), and a (meth) acrylate compound (C) containing at least one hydroxyl group. The reaction temperature is 0 to 150 ° C, preferably 20 to 100 ° C. In addition, this reaction may be performed in an inert gas atmosphere, in an air atmosphere, or in a mixed atmosphere of an inert gas and air, but when air is used, it is dried. It is preferred to use air.

As a ratio of the three components, the total number of moles of hydroxyl groups contained in the polycarbonate diol (A) and the (meth) acrylate compound (C) containing hydroxyl groups, and the number of moles of isocyanate groups contained in the polyisocyanate compound (B). The ratio (OH / NCO) is preferably a ratio of 100/100 to 110/100. By making the total number of moles of hydroxyl groups larger than the number of moles of isocyanato groups, the remaining unreacted isocyanate groups can be reduced.

Examples of the catalyst that can be used in the above reaction include a catalyst (urethanization catalyst) used in a normal urethanization reaction. Although not particularly limited, for example, organotin compounds such as dibutyltin diacetate and dibutyltin dilaurate; organotitanium compounds such as titanium tetraacetylacetonate and titanium diisopropoxybis (ethylacetoacetate); zirconium tetraacetylacetonate and zirconium di Specific examples include organic zirconium compounds such as butoxybis (ethylacetoacetate); tertiary amine compounds such as triethylamine. These urethanization catalysts may be used individually by 1 type, and may use multiple types together.
Of these catalysts, organotin compounds and organozirconium compounds are preferred, with dibutyltin dilaurate and zirconium tetraacetylacetonate being more preferred.
The addition amount of the urethanization catalyst is 0.00005% by weight to 0% based on the total weight of the polycarbonate diol (A), the polyisocyanate compound (B) and the (meth) acrylate compound (C) having a hydroxyl group to be used. 0.01% by weight is preferable, 0.0001% by weight to 0.005% by weight is more preferable, and 0.0003% by weight to 0.003% by weight is particularly preferable.

Moreover, in the said reaction, in order to suppress the polymerization reaction of a (meth) acrylate group during reaction, a polymerization inhibitor and antioxidant can be used. Specific examples include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, p-benzoquinone, and 2,5-dihydroxy-p-benzoquinone. These polymerization inhibitors and antioxidants may be used alone or in combination of two or more.
The addition amount of the polymerization inhibitor and the antioxidant is 0.00005 weight with respect to the total weight of the polycarbonate diol (A), the polyisocyanate compound (B), and the (meth) acrylate compound (C) having a hydroxyl group. % To 0.01% by weight, more preferably 0.0001% to 0.005% by weight, particularly preferably 0.0003% to 0.003% by weight.

Furthermore, by performing the said reaction in the organic solvent which does not have the active hydrogen group which reacts with an isocyanato group, the obtained reaction solution can be made into the polyurethane solution of this invention as it is. The organic solvent is not particularly limited, but for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl Ester solvents such as ether acetate, ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, benzene, toluene, Specific examples include aromatic solvents such as xylene and tetramethylbenzene. It is below. These organic solvents may be used individually by 1 type, and may use multiple types together.
The amount of the organic solvent used is such that the ratio of the total weight of the polycarbonate diol (A), the polyisocyanate compound (B) and the (meth) acrylate compound (C) to be used is 1/9 to 9 / A ratio of 1 is preferable, a ratio of 2/8 to 8/2 is more preferable, and a ratio of 3/7 to 7/3 is particularly preferable.

Alternatively, the isolated polyurethane compound can be dissolved or dispersed in an organic solvent to form a liquid or pasty polyurethane solution. In this case, the solid content concentration of the polyurethane compound is preferably 3 to 95% by weight. A liquid or pasty polyurethane solution can be used as an adhesive, a coating agent, or a paint. The organic solvent to be used is not particularly limited, but is the same as those listed as usable for the above-mentioned reaction.

(Polyurethane composition)
The polyurethane composition (curable resin composition) of the present invention is a compound (F) having a polymerizable unsaturated bond other than the polyurethane compound of the present invention, if necessary, the polyurethane compound of the present invention, a polymerization initiator (G). It is characterized by containing.

Examples of the polymerization initiator (G) used in the polyurethane composition of the present invention include commonly used photopolymerization initiators.
The photopolymerization initiator is not particularly limited. For example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p′-bisdiethylaminobenzophenone, benzoin ethyl ether Benzoin n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl-α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxy Cyclohexylphenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-2-methyl 1-phenylpropan-1-one, 2,4,6, -trimethylbenzophenone, 4-methylbenzophenone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy-1,2- And diphenylethanone. Preferred examples include 1-hydroxycyclohexyl phenyl ketone and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. These photoinitiators may be used individually by 1 type, and may use multiple types together.
The addition amount of the photopolymerization initiator is preferably 0.3% by weight to 10% by weight and more preferably 0.5% by weight to 5% by weight with respect to the weight of the polyurethane compound.

The compound (F) having a polymerizable unsaturated bond used in the polyurethane composition of the present invention is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid alkyl esters such as n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Monoesterified products of (meth) acrylic acid and dihydric alcohols having 2 to 8 carbon atoms such as 3-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, butanediol di (meth) acrylate, hexane Diol (meth) acrylate, D Xylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) Di (meth) acrylate such as acrylate, ethoxylated neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) Tri (meth) acrylates such as acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, glycerol tri (meth) acrylate, etc. Pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra Polyfunctional (meth) acrylates such as (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate, (Meth) acrylate in one molecule such as polyfunctional (meth) acrylate in which a part of these (meth) acrylate is substituted with alkyl group or ε-caprolactone The Royle group 3 to be 6 Available (meth) acrylate compounds, and the like specifically. These polymerizable compounds may be used individually by 1 type, and may use multiple types together.
The addition amount of the compound (F) having a polymerizable unsaturated bond is preferably 100 parts by weight or less with respect to 100 parts by weight of the polyurethane compound.

Furthermore, the polyurethane composition of the present invention includes a coloring pigment, an extender pigment, a bright pigment, a thickening agent, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, depending on the use and if necessary. Usual paint additives such as plasticizers, surface conditioners and anti-settling agents can be used. These paint additives may be used alone or in combination of two or more. Moreover, if these additives are well-known, they can be used without any limitation as long as the properties of the polyurethane composition and the cured product thereof are not impaired.

(Cured product)
The cured product of the present invention is prepared by adjusting the polyurethane composition to an appropriate viscosity with an organic solvent or the like, if necessary, and then ultraviolet rays, visible light, laser light, electron beams, X rays, γ rays, plasma, microwaves. It can be produced by polymerization and curing by irradiating energy rays such as. Alternatively, it can be produced by polymerization and curing by heat.

The solvent that can be used as the organic solvent is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Ester solvents such as dipropylene glycol monomethyl ether acetate; ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether; benzene Fragrance such as toluene, xylene, tetramethylbenzene Such as system solvent is exemplified specifically. These organic solvents may be used individually by 1 type, and may use multiple types together.

Examples of the material to be coated or the material to be coated when the cured product of the present invention is obtained as a coating or coating include metals, plastics, inorganic materials, wood, and resins such as ABS resin and polycarbonate resin.

(Aqueous polyurethane dispersion)
The polyurethane compound of the present invention can also be dispersed in an aqueous medium to form an aqueous polyurethane dispersion. In obtaining the aqueous polyurethane dispersion of the present invention, the polycarbonate diol (A), the polyisocyanate compound (B), the (meth) acrylate compound (C), and the aqueous medium are essential components, but acidic groups The contained polyol (D) and the chain extender (E) are optional components.

That is, in the aqueous polyurethane dispersion of the present invention, a polyurethane compound obtained by reacting a polycarbonate diol (A), a polyisocyanate compound (B), and a (meth) acrylate compound (C) is dispersed in an aqueous medium. An aqueous polyurethane dispersion; a polyurethane compound obtained by reacting a polycarbonate diol (A), a polyisocyanate compound (B), a (meth) acrylate compound (C), and an acidic group-containing polyol (D) is an aqueous medium. An aqueous polyurethane dispersion dispersed in a polyurethane compound obtained by reacting a polycarbonate diol (A), a polyisocyanate compound (B), a (meth) acrylate compound (C), and a chain extender (E) , Aqueous polyurethane dispersions dispersed in aqueous media; polycarbonate The polyurethane compound obtained by reacting the todiol (A), the polyisocyanate compound (B), the (meth) acrylate compound (C), the acidic group-containing polyol (D), and the chain extender (E) is an aqueous medium. An aqueous polyurethane dispersion dispersed therein can be mentioned.

For example, when the polyurethane compound of the present invention is obtained by reacting a polycarbonate diol (A), a polyisocyanate compound (B), a (meth) acrylate compound (C), and an acidic group-containing polyol (D), At least the polycarbonate diol (A), the polyisocyanate compound (B), the (meth) acrylate compound (C), and the acidic group-containing polyol (D) are reacted, and then the acidic group is neutralized with a base. By dispersing in an aqueous medium, an aqueous polyurethane dispersion can be obtained.
In the above-mentioned method for producing an aqueous polyurethane dispersion, the (meth) acrylate compound (C) may be reacted with the polyurethane prepolymer before the polyurethane prepolymer is dispersed in the aqueous medium, or the polyurethane together with the aqueous medium. You may make it react with a prepolymer, and after making it disperse | distribute in an aqueous medium, you may make it react with a polyurethane prepolymer.

For example, the polyurethane compound of the present invention is reacted with polycarbonate diol (A), polyisocyanate compound (B), (meth) acrylate compound (C), acidic group-containing polyol (D), and chain extender (E). When obtained by reacting the polycarbonate diol (A), the polyisocyanate compound (B) and the acidic group-containing polyol (D) to obtain a polyurethane prepolymer having an isocyanato group at the terminal, the acidic group The acidic group derived from the contained polyol is neutralized, dispersed in an aqueous medium, reacted with a chain extender (E), and then a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule. ).
In the method for producing an aqueous polyurethane dispersion, the (meth) acrylate compound (C) and the chain extender (E) may be reacted with the polyurethane prepolymer before the polyurethane prepolymer is dispersed in the aqueous medium. It may be reacted with the polyurethane prepolymer together with the aqueous medium, or may be reacted with the polyurethane prepolymer after being dispersed in the aqueous medium.

Examples of the base for neutralizing the acidic group include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine. And organic amines such as pyridine; inorganic alkalis such as sodium hydroxide and potassium hydroxide; ammonia and the like. Among these, organic amines are preferable, tertiary amines are more preferable, and triethylamine is most preferable. These may be used alone or in combination of two or more.

Examples of the aqueous medium include water and a mixed medium of water and a hydrophilic organic solvent. The aqueous medium is preferably used in such an amount that the proportion of the polyurethane resin in the aqueous polyurethane resin dispersion is 5 to 60% by weight, more preferably 20 to 50% by weight.

Examples of the water include clean water, ion-exchanged water, distilled water, and ultrapure water, but preferably ion-exchanged in consideration of availability and particle instability due to the influence of salt. Water is mentioned.
Examples of the hydrophilic organic solvent include ketones such as acetone and ethyl methyl ketone, esters, ethers such as tetrahydrofuran and N-methylmorpholine, and amides such as dimethylformamide, N-methylpyrrolidone and N-ethylpyrrolidone. And alcohols. These may be used alone or in combination of two or more.

(Aqueous polyurethane dispersion composition)
The aqueous polyurethane dispersion composition can be prepared by adding the compound (F) having the polymerizable unsaturated bond and the polymerization initiator (G) to the aqueous polyurethane dispersion of the present invention. For the above composition, pigments, dyes, thickeners, curing catalysts, UV absorbers, light stabilizers, antifoaming agents, plasticizers, surface conditioners, anti-settling agents and the like are used for ordinary paints as necessary. Additives can be contained alone or in combination of two or more.

Further, the aqueous polyurethane dispersion composition of the present invention can be applied to a substrate or a release material by a method such as bell coating, spray coating, roll coating, shower coating, or dip coating. By heating this at a temperature of 50 to 250 ° C. or leaving it at room temperature for a long time, it can be dried to obtain a cured product.

Next, the present invention will be specifically described with reference to examples and comparative examples.

The hydroxyl value of the polycarbonate diol was measured by a method based on JIS K 1577.
The acid value was measured according to JIS K 1557 method B. The moisture was measured by a coulometric titration method using a Karl Fischer moisture meter.

APHA measured the Hazen unit color number (APHA) as follows based on JIS K 1557 based on JIS K 1557.
(Standard solution adjustment)
A solution in which 1.245 g of potassium chloroplatinate, 1.000 g of cobalt chloride hexahydrate, 500 ml of water and 100 ml of hydrochloric acid were placed in a 1 liter measuring flask and completely dissolved, and then water was added up to the marked line was standardized. . This solution is APHA standard solution no. No. 500 and various standard solutions are No. Dilute 500 standard solution with water and adjust. For example, APHA standard solution No. 100 is No. 100. Dilute 20.0 ml of 500 standard solution with 80.0 ml of water.
(Measuring method)
It is a colorless, transparent, flat-bottomed glass tube with the same diameter and the same diameter with the same wall thickness of 23 mm, and a colorimetric tube with a marked line at the same height from the bottom so that the liquid volume is 100 ml. Insert the sample up to the marked line, taking care to avoid bubbles. Next, a suitable APHA standard solution was placed on a white plate and compared from above, and a standard solution having a concentration closest to the sample was obtained. The number of the standard solution was designated as APHA.

The conversion rate of the isocyanate group at the time of synthesizing the polyurethane compound was calculated from the isocyanate group content measured by a method according to JIS K 1603.

The solid content concentration of the polyurethane compound solution was calculated from the weight loss before and after drying after the polyurethane compound solution was dried at 140 ° C. for 3 hours. The viscosity was measured with an E-type viscometer.

An ultraviolet curing device (manufactured by Sen Special Light Source, HM15001C-4, lamp: SE-1500M) was used for curing the polyurethane compound.
The hardness of the cured product was measured by measuring the amplitude decay time with a pen drum type hardness tester (manufactured by BYK-Gardner GmbH, a pen drum hardness tester) by placing a coating film sample made of a glass plate on a sample stage. The longer the amplitude decay time, the greater the hardness.

The elastic modulus, tensile strength, and elongation at break of the cured product were measured by a method in accordance with JIS K 7311 by forming a film sample from a polystyrene resin plate into a film. The measurement conditions were a measurement temperature of 23 ° C., a humidity of 50%, and a tensile speed of 100 mm / min.

The abrasion of the cured product was determined by setting a coating film sample made of a polycarbonate resin plate on a sample stage, and using a taper abrasion tester (manufactured by TOYOSEIKI, HS), rotating speed: 60 rpm, load: 500 g, worn wheel: H- 18 was used to measure the weight loss of the coating. The smaller the weight loss, the better the wear resistance.

[Example 1]
(1) Synthesis of Polycarbonate Diol Into a 500 ml glass round bottom flask equipped with a rectifying tower, a stirrer, a thermometer, and a nitrogen introduction tube, 199.3 g (2.21 mol) of dimethyl carbonate and 1,4-benzenedimethanol 65 .2 g (0.47 mol), 1,6-hexanediol 167.2 g (1.41 mol), and titanium tetrabutoxide 0.03 g were charged while distilling off a mixture of methanol and dimethyl carbonate under normal pressure and stirring. The transesterification reaction was carried out for 6 hours. During this time, the reaction temperature was gradually raised from 95 ° C. to 200 ° C., and the composition of the distillate was adjusted to be the azeotropic composition of methanol and dimethyl carbonate or in the vicinity thereof.

Thereafter, the pressure was gradually reduced to 100 mmHg, and the ester exchange reaction was further carried out at 195 ° C. for 4 hours while distilling off the mixture of methanol and dimethyl carbonate with stirring. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction solution was cooled to room temperature to obtain 280 g of a polycarbonate diol copolymer. The transesterification reaction was performed in a nitrogen stream. The obtained polycarbonate diol copolymer had a number average molecular weight of 996, APHA of 60, hydroxyl value of 112.6 mgKOH / g, acid value of 0.01 mgKOH / g, and water content of 120 ppm.

(2) Synthesis of polyurethane compound In a 1000 ml glass separable flask equipped with a stirrer, thermometer, and cooling tube, 199.2 g (0.20 mol) of the polycarbonate diol copolymer obtained in (1) above, butyl acetate After charging 224.1 g and setting the reaction temperature to 70 ° C., 0.10 g of zirconium tetraacetylacetonate and 89.3 g (0.40 mol) of isophorone diisocyanate were added, and the isocyanato group was converted at a reaction temperature of 80 ° C. to 90 ° C. The reaction was carried out until the rate reached 50%. Thereafter, 0.34 g of p-methoxyphenol, 0.13 g of zirconium tetraacetylacetonate and 48.9 g (0.42 mol) of ethylene glycol monoacrylate were added, and the conversion of the isocyanato group was 99 at a reaction temperature of 80 ° C. to 90 ° C. The reaction was carried out until the ratio reached at least%. The solid content of the butyl acetate solution of the obtained polyurethane compound was 61%, and the viscosity was 211 cp / 40 ° C.

(3) Production of polyurethane composition and cured product A well-mixed mixture of 1 part by weight of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 19 parts by weight of ethyl acetate, and the polyurethane obtained in (2) above A polyurethane composition (curable resin composition) was prepared by thoroughly mixing 80 parts by weight of a butyl acetate solution of the compound. This cured resin composition was applied to a glass plate using a 50 μm applicator, dried at 80 ° C. for 30 minutes, and then irradiated with 1000 mJ / cm ² of ultraviolet rays with an ultraviolet curing device to obtain a cured product. The hardness of the obtained cured product was 111 seconds in terms of amplitude decay time.

(4) Synthesis of aqueous polyurethane dispersion In a reactor equipped with a stirrer and a heater, 27.9 g (0.028 mol) of the polycarbonate diol copolymer obtained in (1) above and 2,2-dimethylolpropion were obtained. Acid (DMPA, 11.1 grams) and isophorone diisocyanate (IPDI, 57.5 grams) in N-ethylpyrrolidone (43.9 grams) in the presence of 0.13 g of zirconium tetraacetylacetonate under a nitrogen atmosphere. And heated at 80-90 ° C. for 2.5 hours. 2,6-Di-tert-butyl-4-methylphenol (0.2 gram) and 4-methoxyphenol (0.2 gram) were added and the atmosphere was air. Furthermore, 48.9 g (0.42 mol) of ethylene glycol monoacrylate, dipentaerythritol hexaacrylate (DPHA, 79.9 grams) and triethylamine (8.9 grams) were added and mixed. The reaction mixture (226 grams) was added into water (386 grams) under vigorous stirring to obtain an aqueous polyurethane resin dispersion.

[Example 2]
A mixture of 1 part by weight of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 19 parts by weight of 2-hydroxyethyl methacrylate, and a butyl acetate solution 80 of the polyurethane compound obtained in Example 1 (2) Part by weight was mixed well to prepare a polyurethane composition (cured resin composition). The polyurethane composition was applied to a glass plate using a 50 μm applicator, dried at 80 ° C. for 30 minutes, and then irradiated with 1000 mJ / cm ² of ultraviolet rays using an ultraviolet curing device to obtain a cured product. The hardness of the obtained cured product was 162 seconds in terms of amplitude decay time, the elastic modulus was 210 MPa, the tensile strength was 27 MPa, the elongation at break was 89%, and the wear resistance was a weight loss of 32.9 mg at 400 revolutions. .

[Comparative Example 1]
(1) Synthesis of polyurethane compound To a 1000 ml glass separable flask equipped with a stirrer, a thermometer, and a condenser, polycarbonate diol (manufactured by Ube Industries, trade name: ETERRNACOLL UH-100, 1,6-hexanediol and Polycarbonate diol obtained by reacting with dimethyl carbonate, number average molecular weight 1004, APHA 10, hydroxyl value 111.7 mgKOH / g, acid value 0.02 mgKOH / g, moisture 400 ppm) 200.8 g (0.20 mol), butyl acetate 224 0.1 g was added and the reaction temperature was raised to 70 ° C., then 0.10 g of zirconium tetraacetylacetonate and 90.0 g (0.40 mol) of isophorone diisocyanate were added, and the conversion rate of the isocyanate group at a reaction temperature of 80 ° C. to 90 ° C. Reaction until 50% Carried out it was. Thereafter, 0.34 g of p-methoxyphenol, 0.10 g of zirconium tetraacetylacetonate and 50.0 g (0.43 mol) of ethylene glycol monoacrylate were added, and the conversion of the isocyanato group was 99 at a reaction temperature of 80 ° C. to 90 ° C. The reaction was carried out until the ratio reached at least%. The solid content of the butyl acetate solution of the obtained polyurethane compound was 62%, and the viscosity was 192 cp / 40 ° C.

(2) Production of polyurethane composition and cured product A well-mixed mixture of 1 part by weight of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 19 parts by weight of ethyl acetate, and the polyurethane obtained in (1) above A polyurethane composition (curable resin composition) was prepared by thoroughly mixing 80 parts by weight of a butyl acetate solution of the compound. The polyurethane composition was applied to a glass plate using a 50 μm applicator, dried at 80 ° C. for 30 minutes, and then irradiated with 1000 mJ / cm ² of ultraviolet rays using an ultraviolet curing device to obtain a cured product. The hardness of the obtained cured product was 52 seconds in terms of amplitude decay time.

[Comparative Example 2]
A mixture of 1 part by weight of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 19 parts by weight of 2-hydroxyethyl methacrylate and a butyl acetate solution of the polyurethane compound obtained in Comparative Example 1 (1) A polyurethane composition (curable resin composition) was prepared by thoroughly mixing 80 parts by weight. Each of the polyurethane compositions was applied to a glass plate using a 50 μm applicator, dried at 80 ° C. for 30 minutes, and then irradiated with 1000 mJ / cm ² of ultraviolet rays using an ultraviolet curing device to obtain a cured product. The hardness of the obtained cured product was 55 seconds in terms of amplitude decay time, elastic modulus was 46 MPa, tensile strength was 27 MPa, elongation at break was 113%, and abrasion was a weight loss of 55.8 mg at 400 revolutions. .

The polyurethane compound, aqueous polyurethane dispersion, and polyurethane solution of the present invention can be used as materials such as energy ray curable paints and energy ray curable coating agents. The polyurethane composition of the present invention can also be used as a raw material for the energy ray-curable coating material and the energy ray-curable coating agent or as such. The cured product of the present invention can be used as a film in various fields such as a decorative film and a cutting film.

Claims (15)

Polycarbonate diol (A) having at least a repeating unit represented by the following formula (1) and having one hydroxyl group at each end of the molecular end chain, a polyisocyanate compound (B), and one or more in the molecule A polyurethane compound obtained by reacting a (meth) acrylate compound (C) having a hydroxyl group.

(In the formula, Z ¹ and Z ² each independently represent a linear or branched alkanediyl group having 1 to 10 carbon atoms.) The polycarbonate diol (A) has a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2) and has one hydroxyl group at both ends of the molecular chain. Item 4. The polyurethane compound according to Item 1.

(In the formula, Z ³ represents an optionally substituted linear or branched alkanediyl group having 2 to 10 carbon atoms, or an optionally substituted cycloalkanediyl group having 3 to 10 carbon atoms. Or an alkanediyl group having 5 to 10 carbon atoms having an alicyclic structure in the main chain which may have a substituent. Furthermore, the polyurethane compound of Claim 1 or 2 obtained by making an acidic group containing polyol (D) react. The polyurethane compound according to any one of claims 1 to 3, which is obtained by further reacting with a chain extender (E). An aqueous polyurethane dispersion in which at least the polyurethane compound according to any one of claims 1 to 4 is dispersed in an aqueous medium. A polyurethane solution in which at least the polyurethane compound according to any one of claims 1 to 4 is dispersed or dissolved in an organic solvent. A polyurethane composition comprising the polyurethane compound according to any one of claims 1 to 4, a polymerization initiator (G), and, if necessary, a compound (F) having a polymerizable unsaturated bond. A cured product obtained by curing the polyurethane composition according to claim 7. At least the polyurethane compound according to any one of claims 1 to 4, a polymerization initiator (G), and, if necessary, a compound (F) having a polymerizable unsaturated bond are dispersed in an aqueous medium. An aqueous polyurethane dispersion composition. A cured product obtained by applying the aqueous polyurethane dispersion composition according to claim 9, drying and curing the composition. After reacting the polycarbonate diol (A) with the polyisocyanate compound (B) to obtain a polyurethane prepolymer having an isocyanato group at the terminal, the polyurethane prepolymer and the molecule have one or more hydroxyl groups (meth) The manufacturing method of the polyurethane compound of Claim 1 or 2 with which an acrylate compound (C) is made to react. After reacting the polycarbonate diol (A), the polyisocyanate compound (B), and the acidic group-containing polyol (D) to obtain a polyurethane prepolymer having an isocyanato group at the terminal, the polyurethane prepolymer and one in the molecule The method for producing a polyurethane compound according to claim 3, wherein the (meth) acrylate compound (C) having the above hydroxyl group is reacted. After reacting the polycarbonate diol (A), the polyisocyanate compound (B) and, if necessary, the acidic group-containing polyol (D) to obtain a polyurethane prepolymer having an isocyanato group at the terminal, a chain extender (E) And then reacting with a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule. After reacting the polycarbonate diol (A), the polyisocyanate compound (B) and the acidic group-containing polyol (D) to obtain a polyurethane prepolymer having an isocyanato group at the terminal, the acidic group derived from the acidic group-containing polyol Is neutralized and dispersed in an aqueous medium, then reacted with a chain extender (E) as necessary, and then reacted with a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule. The method for producing an aqueous polyurethane dispersion according to claim 5. Necessary after reacting the polycarbonate diol (A), the polyisocyanate compound (B) and, if necessary, the acidic group-containing polyol (D) in an organic solvent to obtain a polyurethane prepolymer having an isocyanate group at the terminal. The method for producing a polyurethane solution according to claim 6, wherein the polyurethane solution is reacted with the chain extender (E) and reacted with the (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule.