JP2022148526A - Active energy ray-curable resin composition and coating agent using the same and sheet - Google Patents

Abstract

To provide an active energy ray-curable resin composition which has excellent adhesiveness to a substrate and spreadability when cured, has no surface tackiness feeling, and has excellent solvent resistance and excellent processability and productivity, and to provide a coating agent using the same and a sheet.SOLUTION: There is provided an active energy ray-curable resin composition which comprises a urethane (meth)acrylate-based compound (A) having a structural unit derived from a polyvalent isocyanate-based compound (a1), a structural unit derived from a polyol compound (a2) and a structural unit derived from a hydroxyl group-containing (meth)acrylate-based compound (a3), wherein the polyol compound (a2) contains a polyether polycarbonate diol (a2-1) represented by the following formula (1). (In formula (1), R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is an integer of 2 to 30 and m is an integer of 1 to 20. In addition, a plurality of R1 may be the same or different.)SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable resin composition. The present invention relates to an excellent active energy ray-curable resin composition, a coating agent using the same, and a sheet.

Plastic substrates such as polycarbonate and polymethyl methacrylate are widely used for home appliances, automotive products, liquid crystal display members, etc., because they are excellent in optical properties such as workability, impact resistance, and transparency.

However, since the surface of these plastic substrates is easily scratched, the surface of the plastic substrate is sometimes coated with a hard coating agent in order to impart scratch resistance. As the hard coating agent, an active energy ray-curable resin composition is often used because of its excellent adhesion to plastic substrates and high curing speed, which contributes to improved productivity.

In addition, the active energy ray-curable resin composition is sometimes used in decorative molding for imparting design properties.
Conventional methods for decorative molding include molding by kneading pigments into thermoplastic resin, spraying paint on the surface of resin products after molding, and using molds to decorate. insert molding, in-mold molding, and TOM molding (three dimen
The application of three-dimensional molding such as the ion overlay method (three-dimensional surface coating method) is also under consideration.

In addition, in the active energy ray-curable resin composition used in the above-described decorative molding, etc., it is particularly important to have workability such that cracks do not occur even when molded into a complicated shape, conformability to molds, and elongation. degree is required.
Moreover, when the active energy ray-curable resin composition is used as the outermost surface material of a molded product, surface hardness and scratch resistance are required. Furthermore, solvent resistance is required because a solvent may be used in combination with other members.

Here, for example, Patent Document 1 below discloses a decorative molded sheet having a skin layer made of a reaction-cured product of a resin composition containing a polycarbonate-based polyurethane and a non-yellowing polyisocyanate. Patent Document 1 discloses that a molded product using the decorative molded sheet forms a complicated surface shape and has excellent scratch resistance.
In addition, for example, in Patent Document 2 below, by using urethane acrylate using polycarbonate polyol and polyether polyol, a cured product having excellent balance of tensile strength and tensile elongation and moderate hardness and flexibility can be obtained. shown to be

JP 2014-128922 A Patent No. 5384963

However, the resin composition disclosed in Patent Document 1 contains polyisocyanate as a heat curing agent, and in order to complete the curing of the coating film, it is necessary to apply heat or provide an aging period. Therefore, it is inferior in productivity.
Moreover, although the composition disclosed in Patent Document 2 is excellent in tensile strength and tensile elongation, it is inferior in wear resistance because stickiness remains on the surface of the coating film.

The present invention has been made in view of such circumstances, and when cured, the adhesion to the substrate,
To provide an active energy ray-curable resin composition having excellent elongation, no surface tackiness, excellent solvent resistance, and excellent workability and productivity, a coating agent using the same, and a sheet.

The inventor of the present invention has made intensive studies to solve the above problems. In the course of the research, the use of a polyvalent isocyanate as the isocyanate used in the urethane (meth)acrylate reaction and the use of a polyether polycarbonate diol as the polyol used in the urethane (meth)acrylate reaction were investigated. As a result, the present inventors have found that it is possible to form a coating film having good elongation properties under high temperature conditions, excellent wear resistance, and further good solvent resistance, and have completed the present invention.

（上記式（１）において、Ｒ１は炭素数２～１０の二価の炭化水素基を表し、ｎは２～３
０の整数であり、ｍは１～２０の整数である。なお、式（１）中、複数のＲ１は同一であ
ってもよく、異なるものであってもよい。）
［２］ 前記ポリオール化合物（ａ２）が、さらに数平均分子量３００以下のポリオール
（ａ２－２）を含むことを特徴とする［１］に記載の活性エネルギー線硬化性組成物。
［３］ 前記ポリエーテルポリカーボネートジオール（ａ２－１）とポリオール（ａ２－
２）との比率（ａ２－１／ａ２－２）が、重量比で９９／１～５０／５０であることを特
徴とする［２］に記載の活性エネルギー線硬化性樹脂組成物。
［４］ 前記ポリエーテルポリカーボネートジオール（ａ２－１）が、数平均分子量５０
０～２０，０００であることを特徴とする［１］～［３］のいずれか一項に記載の活性エ
ネルギー線硬化性樹脂組成物。
［５］ 前記水酸基含有（メタ）アクリレート（ａ３）が、分子中に（メタ）アクリロイ
ル基を１個以上有する（メタ）アクリレートであることを特徴とする［１］～［４］のい
ずれか一項に記載の活性エネルギー線硬化性樹脂組成物。
［６］ ［１］～［５］のいずれか一項に記載の活性エネルギー線硬化性樹脂組成物を含
有することを特徴とするコーティング剤。
［７］ ［１］～［５］のいずれか一項に記載の活性エネルギー線硬化性樹脂組成物の硬
化物を有するシート。 That is, the above problems are solved by the present inventions [1] to [7] below.
[1] A structural unit derived from a polyvalent isocyanate compound (a1), a polyol compound (a
2) and a urethane (meth)acrylate compound (A) having a structural unit derived from a hydroxyl group-containing (meth)acrylate compound (a3), and the polyol compound (a2) is the following An active energy ray-curable composition comprising a polyether polycarbonate diol (a2-1) represented by formula (1).

(In the above formula (1), R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is 2 to 3
is an integer of 0 and m is an integer of 1-20. In formula (1), a plurality of R1 may be the same or different. )
[2] The active energy ray-curable composition according to [1], wherein the polyol compound (a2) further contains a polyol (a2-2) having a number average molecular weight of 300 or less.
[3] The polyether polycarbonate diol (a2-1) and the polyol (a2-
The active energy ray-curable resin composition according to [2], wherein the ratio (a2-1/a2-2) with 2) is 99/1 to 50/50 in weight ratio.
[4] The polyether polycarbonate diol (a2-1) has a number average molecular weight of 50
The active energy ray-curable resin composition according to any one of [1] to [3], which is 0 to 20,000.
[5] Any one of [1] to [4], wherein the hydroxyl group-containing (meth)acrylate (a3) is a (meth)acrylate having one or more (meth)acryloyl groups in the molecule. The active energy ray-curable resin composition according to the item.
[6] A coating agent comprising the active energy ray-curable resin composition according to any one of [1] to [5].
[7] A sheet having a cured product of the active energy ray-curable resin composition according to any one of [1] to [5].

（上記式（１）において、Ｒ１は炭素数２～１０の二価の炭化水素基を表し、ｎは２～３
０の整数であり、ｍは１～２０の整数である。なお、式（１）中、複数のＲ１は同一であ
ってもよく、異なるものであってもよい。）を含み、さらに数平均分子量３００以下のポ
リオール（ａ２－２）を含むことができる。このため、本発明の活性エネルギー線硬化性
樹脂組成物により形成される塗膜、本発明の活性エネルギー線硬化性樹脂組成物を含有し
てなるコーティング剤により形成される塗膜、および本発明の活性エネルギー線硬化性樹
脂組成物の硬化体からなるシートは、高温条件下での良好な伸び特性、耐摩耗性、更には
耐溶剤性に優れるようになる。また、上記活性エネルギー線硬化性樹脂組成物を用いて形
成された塗膜等は、基材に対する追従性に優れ、さらに、伸縮性を有する強靱な基材とし
ても有用であり、これらの特性を生かした各種用途に用いることもできる。 Thus, the active energy ray-curable resin composition of the present invention includes structural units derived from the polyvalent isocyanate compound (a1), structural units derived from the polyol compound (a2), and hydroxyl group-containing (meth)acrylate It is characterized by containing a urethane (meth)acrylate compound (A) having a structural unit derived from the compound (a3), wherein the polyol compound (a2) is represented by the following formula (1) Polyether polycarbonate diol (a2-1)

(In the above formula (1), R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is 2 to 3
is an integer of 0 and m is an integer of 1-20. In formula (1), a plurality of R1 may be the same or different. ), and may further contain a polyol (a2-2) having a number average molecular weight of 300 or less. For this reason, a coating film formed from the active energy ray-curable resin composition of the present invention, a coating film formed from a coating agent containing the active energy ray-curable resin composition of the present invention, and A sheet made of a cured product of an active energy ray-curable resin composition has excellent elongation properties, wear resistance, and solvent resistance under high-temperature conditions. In addition, the coating film or the like formed using the active energy ray-curable resin composition has excellent conformability to a substrate, and is also useful as a stretchable and tough substrate. It can also be used for various uses.

In particular, the polyether polycarbonate diol (a2-1) and polyol (a2-
2) when the ratio (a2-1/a2-2) is 99/1 to 50/50 by weight, it is easy to impart more wear resistance and high elongation, and fine adjustment of physical properties is possible. can.

Then, the polyether polycarbonate diol (a2-1) has a number average molecular weight of 5
When it is from 00 to 20,000, the elongation is more excellent.

Furthermore, when the hydroxyl group-containing (meth)acrylate (a3) is a (meth)acrylate having one or more (meth)acryloyl groups in the molecule, it imparts an appropriate crosslinked structure to the cured coating film, resulting in abrasion resistance. can be given.

Next, an embodiment of the present invention will be described in detail. However, the present invention is not limited to this embodiment.

Active energy ray-curable resin composition of the present invention (hereinafter sometimes abbreviated as "resin composition")
is obtained using urethane (meth)acrylate (A).
First, each component material constituting the active energy ray-curable resin composition will be described.

（上記式（１）において、Ｒ１は炭素数２～１０の二価の炭化水素基を表し、ｎは２～３
０の整数であり、ｍは１～２０の整数である。なお、式（１）中、複数のＲ１は同一であ
ってもよく、異なるものであってもよい。）
すなわち、本発明で用いられるウレタン（メタ）アクリレート（Ａ）は、多価イソシア
ネート（ａ１）由来の構造単位、ポリエーテルポリカーボネートジオール（ａ２－１）由
来の構造単位、水酸基含有（メタ）アクリレート（ａ３）由来の構造単位を備えた化合物
である。さらにウレタン（メタ）アクリレート（Ａ）はポリオール（ａ２）として数平均
分子量３００以下のポリオール（ａ２－２）を含むことができる。なお、本発明の作用効
果の観点から、ポリオール（ａ２）全体の５０重量％以上、特には８０重量％以上がポリ
エーテルポリカーボネートジオール（ａ２－１）およびポリオール（ａ２－２）からなる
ことが好ましく、ポリオール（ａ２）の全てがポリエーテルポリカーボネートジオール（
ａ２－１）およびポリオール（ａ２－２）からなることが、より好ましい。 <<Urethane (meth)acrylate (A)>>
The urethane (meth)acrylate (A) used in the present invention is a polyvalent isocyanate (a
1), a polyol (a2), and a hydroxyl group-containing (meth)acrylate (a3). The polyol (a2) contains a polyether polycarbonate diol (a2-1) represented by the following formula (1).

(In the above formula (1), R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is 2 to 3
is an integer of 0 and m is an integer of 1-20. In formula (1), a plurality of R1 may be the same or different. )
That is, the urethane (meth)acrylate (A) used in the present invention includes a structural unit derived from the polyisocyanate (a1), a structural unit derived from the polyether polycarbonate diol (a2-1), a hydroxyl group-containing (meth)acrylate (a3 ) are compounds with structural units derived from Further, the urethane (meth)acrylate (A) can contain a polyol (a2-2) having a number average molecular weight of 300 or less as the polyol (a2). From the viewpoint of the effects of the present invention, it is preferable that 50% by weight or more, particularly 80% by weight or more of the entire polyol (a2) is composed of the polyether polycarbonate diol (a2-1) and the polyol (a2-2). , all of the polyol (a2) is a polyether polycarbonate diol (
More preferably, it consists of a2-1) and polyol (a2-2).

In the present invention, (meth)acryl means acryl or methacryl, (meth)acryloyl means acryloyl or methacryloyl, and (meth)acrylate means acrylate or methacrylate.

[Polyvalent isocyanate (a1)]
Polyvalent isocyanate (a1) is to be reacted with polyol (a2) and hydroxyl group-containing (meth)acrylate (a3), specifically, for example,
aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate;
Aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate;
Alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane;
Alternatively, trimer compounds or polymer compounds of these polyisocyanates, allophanate-type polyisocyanates, burette-type polyisocyanates, water-dispersed polyisocyanates (e.g., Tosoh Corporation "Aquanate 100", "Aquanate 105", "Aquanate 120", "Aquanate 210", etc.), and the like.
These can be used singly or in combination of two or more.

Among these, alicyclic polyisocyanates and aromatic polyisocyanates are preferred in terms of weather resistance and strength, and isophorone diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, and tolylene diisocyanate are particularly preferred. .

[Polyol (a2)]
As the polyol (a2), as described above, the polyether polycarbonate diol (a2-1) is used, and a polyol (a2-2) having a number average molecular weight of 300 or less can be used in combination.

In particular, polyether polycarbonate diol (a2-1) and polyol (a2-2)
(a2-1/a2-2) is preferably 99/1 to 50/50 in terms of weight ratio because high elongation can be easily imparted and physical properties can be finely adjusted. From the same point of view, the above ratio (weight ratio) is more preferably (a2-1/a2-2) = 98.5/15.5 to
51/49, particularly preferably (a2-1/a2-2)=98/2 to 52/48.

Further, the polyether polycarbonate diol (a2-1) has a number average molecular weight of 500 to
20,000, and the polyol (a2-2) is preferably a polyol having a number average molecular weight of 60 to 300, since high elongation can be easily imparted and physical properties can be finely adjusted. From a similar point of view, the polyether polycarbonate diol (a2-1) has a number average molecular weight of 6
00 to 15,000 polyol, and the polyol (a2-2) has a number average molecular weight of 70 to
250 polyol is more preferred, and particularly preferably the polyether polycarbonate diol (a2-1) has a number average molecular weight of 700 to 10,000, and the polyol (a2-2) has a number average molecular weight of 80 to 200. is the case.

In addition, let number average molecular weight be the number average molecular weight calculated based on the hydroxyl value measured based on JISK1557. Specifically, the hydroxyl value is measured, and by the terminal group quantification method, (
56.1×1000×valence)/hydroxyl value [mgKOH/g]. In the above formula, the valence is the number of hydroxyl groups in one molecule.

（上記式（１）において、Ｒ１は炭素数２～１０の二価の炭化水素基を表し、ｎは２～３
０の整数であり、ｍは１～２０の整数である。なお、式（１）中、複数のＲ１は同一であ
ってもよく、異なるものであってもよい。） <Polyether polycarbonate diol (a2-1)>
Polyether polycarbonate diol (a2-1) is represented by the following formula (1). In the following formula (1), when m = 1, "polyether polycarbonate diol"
However, in the present invention, the polyether carbonate diol represented by formula (1) is also referred to as "polyether polycarbonate diol (1)".

(In the above formula (1), R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is 2 to 3
is an integer of 0 and m is an integer of 1-20. In formula (1), a plurality of R1 may be the same or different. )

In the above formula (1), R1 preferably has 2 to 10 carbon atoms, more preferably 3 to
A linear or branched alkylene group having 6 carbon atoms, particularly preferably a butylene group having 4 carbon atoms or a 2-methylbutylene group having 5 carbon atoms, and particularly preferably an n-butylene group. That is, formula (1)
Among them, R1-O- is preferably derived from polytetramethylene ether glycol from the viewpoint of industrial availability and excellent physical properties of the resulting urethane (meth)acrylate.

In the above formula (1), if n is less than 2, the flexibility of the resulting urethane (meth)acrylate tends to be poor, and if it exceeds 30, the viscosity and crystallinity of the resulting polyether polycarbonate diol are increased, resulting in poor handleability. As the compatibility with other polyols deteriorates, the obtained urethane (meth)acrylate tends to have low transparency. Therefore, n is 2-30, preferably 3-25, more preferably 3-20.

In the above formula (1), if m is less than 1, the durability of the urethane (meth)acrylate tends to be poor, and if it exceeds 20, the viscosity increases and handling may become difficult.
Therefore, m is 1-20, preferably 2-10, more preferably 2-6.

Polyether polycarbonate diol (a2-1) can be produced by polymerizing polyoxyalkylene glycol and a carbonate compound in the presence of a catalyst according to a conventional method.

Polyoxyalkylene glycols used in the production of polyether polycarbonate diol (a2-1) include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, copolymerized polytetramethylene ether glycol of 3-methyltetrahydrofuran and tetrahydrofuran, and neopentyl glycol. and tetrahydrofuran copolymer polyether polyol, ethylene oxide and tetrahydrofuran copolymer polyether polyol, propylene oxide and tetrahydrofuran copolymer polyether glycol, etc. are preferable from the viewpoint of the mechanical strength of the resulting urethane (meth)acrylate. Methylene ether glycol (PTMG) is more preferred.
In addition, said polyoxyalkylene glycol may use only 1 type, and may use 2 or more types together.

The number average molecular weight (Mn) obtained from the hydroxyl value of the polyoxyalkylene glycol used for producing the polyether polycarbonate diol (a2-1) is preferably 150 to 20.
00, more preferably 200-1500, more preferably 250-1200. If the molecular weight is less than 300, the resulting urethane (meth)acrylate tends to have poor flexibility, and if it exceeds 2,000, the resulting polyether polycarbonate diol (a2-1) has high viscosity and crystallinity, resulting in poor handleability. At the same time, the compatibility with other polyols deteriorates, and the obtained urethane (meth)acrylate tends to have low transparency. The number average molecular weight (Mn) determined from the hydroxyl value is specifically measured by the method described in the section of Examples below.

The carbonate compound that can be used for producing the polyether polycarbonate diol (a2-1) is not limited as long as it does not impair the effects of the present invention, and includes dialkyl carbonate, diaryl carbonate and alkylene carbonate. These are 1
It may be a species or a plurality of species. Of these, dialkyl carbonates and alkylene carbonates are preferred from the viewpoint of reactivity.

Specific examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate and the like, with dimethyl carbonate and ethylene carbonate being preferred.

When producing the polyether polycarbonate diol (a2-1), a transesterification catalyst may be used as necessary to promote polymerization.
As the transesterification catalyst, any compound generally considered to have transesterification ability can be used without limitation.

Examples of transesterification catalysts include compounds of long period periodic table (hereinafter simply referred to as "periodic table") Group 1 metals (excluding hydrogen) such as lithium, sodium, potassium, rubidium, and cesium; Compounds of Group 2 metals of the periodic table such as magnesium, calcium, strontium and barium; compounds of Group 4 metals of the periodic table such as titanium and zirconium; compounds of Group 5 metals of the periodic table such as hafnium; Compounds of Group 9 metals; periodic table 1 such as zinc
Group 2 metal compounds; periodic table group 13 metal compounds such as aluminum; periodic table group 14 metal compounds such as germanium, tin and lead; periodic table group 15 metal compounds such as antimony and bismuth; Compounds of lanthanide-based metals such as cerium, europium, ytterbium, and the like are included. Among these, from the viewpoint of increasing the transesterification reaction rate, periodic table group 1 metal compounds (excluding hydrogen), periodic table group 2 metal compounds, periodic table group 4 metal compounds, periodic table 5 Group metal compounds, periodic table group 9 metal compounds, periodic table group 12 metal compounds, periodic table group 13 metal compounds, periodic table group 14 metal compounds are preferred, and periodic table group 1 metals ( excluding hydrogen) and compounds of metals of Group 2 of the periodic table are more preferred, and compounds of metals of Group 2 of the periodic table are even more preferred. Among the compounds of Group 1 metals (excluding hydrogen) of the periodic table, lithium, potassium and sodium compounds are preferred, lithium and sodium compounds are more preferred, and sodium compounds are even more preferred. Among the compounds of Group 2 metals of the periodic table, compounds of magnesium, calcium and barium are preferred, compounds of calcium and magnesium are more preferred, and compounds of magnesium are even more preferred. These metal compounds are mainly used as hydroxides, salts and the like. Examples of salts when used as salts include halide salts such as chlorides, bromides and iodides; carboxylates such as acetates, formates and benzoates; inorganic acid salts such as carbonates and nitrates. sulfonates such as methanesulfonic acid, toluenesulfonic acid and trifluoromethanesulfonic acid; phosphorus-containing salts such as phosphates, hydrogen phosphates and dihydrogen phosphates; acetylacetonate salts; Catalyst metals can also be used as alkoxides such as methoxides and ethoxides.

Among these, preferably, at least one metal selected from group 2 metals of the periodic table, such as acetate, nitrate, sulfate, carbonate, phosphate, hydroxide, halide, acetylacetonate salt, Alkoxides are used, more preferably acetates and carbonates of Group 2 metals of the periodic table,
Hydroxides and acetylacetonate salts are used, more preferably magnesium and calcium acetates, carbonates, hydroxides and acetylacetonate salts are used, particularly preferably magnesium and calcium acetates and acetylacetonate. Salts are used, most preferably magnesium acetylacetonate.

In the production of the polyether polycarbonate diol (a2-1), the amount of the carbonate compound used is not particularly limited. It is 0.50, more preferably 0.60, and the upper limit is preferably 1.00, more preferably 0.98, still more preferably 0.97. If the amount of the carbonate compound used exceeds the above upper limit, the proportion of non-hydroxy terminal groups in the polyether polycarbonate diol (a2-1) obtained may increase, or the molecular weight may not fall within the predetermined range. Polymerization may not proceed up to the molecular weight of

When the transesterification catalyst described above is used in the production of the polyether polycarbonate diol (a2-1), the amount used is the same as that of the resulting polycarbonate diol (a2
-1) It is preferable that the amount is such that even if it remains in the solution, it does not affect the performance.

The upper limit of the amount of the transesterification catalyst used is preferably 500 ppm by weight, more preferably 100 ppm by weight, and more preferably 50 ppm by weight, as the weight ratio of the metal to the weight of the raw material polyoxyalkylene glycol. More preferably, 10 ppm by weight
is particularly preferred. On the other hand, the lower limit is 0.01 as the amount at which sufficient polymerization activity can be obtained.
It is preferably ppm by weight, more preferably 0.1 ppm by weight, even more preferably 1 ppm by weight.

The reaction temperature for the transesterification reaction can be arbitrarily adopted as long as it is a temperature at which a practical reaction rate can be obtained. The lower limit of the normal reaction temperature is preferably 70°C, more preferably 100°C, and even more preferably 130°C. The upper limit of the reaction temperature is generally preferably 250°C, more preferably 230°C, and even more preferably 200°C. By setting the reaction temperature to the above upper limit or lower, it is possible to prevent quality problems such as coloration of the obtained polyether polycarbonate diol (1) and formation of an ether structure.

Furthermore, the reaction temperature is preferably 180° C. or lower, more preferably 170° C. or lower, and 160° C. or lower throughout the entire transesterification process for producing the polyether polycarbonate diol (a2-1). is more preferred. By keeping the reaction temperature at 180° C. or lower throughout the entire process, it is possible to prevent coloration from occurring depending on the conditions.

Although the transesterification reaction can be carried out under normal pressure, the transesterification reaction is an equilibrium reaction, and the reaction can be biased toward the production system by distilling off the low-boiling components to be produced out of the system. Therefore, in the latter half of the reaction, it is usually preferable to adopt reduced pressure conditions and carry out the reaction while distilling off the low-boiling components. Alternatively, it is also possible to carry out the reaction while gradually lowering the pressure from the middle of the reaction to distill off the low-boiling components produced. In particular, if the reaction is carried out with the degree of reduced pressure increased at the end of the reaction,
It is preferable because by-products such as monoalcohols, phenols and cyclic carbonates can be distilled off. In this case, the upper limit of the reaction pressure at the end of the reaction is preferably 10 kPa, more preferably 5 kPa, and even more preferably 1 kPa. In order to effectively distill off the light-boiling components, the reaction can be carried out while passing an inert gas such as nitrogen, argon and helium through the reaction system.

When a low-boiling carbonate compound is used in the transesterification reaction, the initial reaction is carried out near the boiling point of the carbonate compound, and as the reaction progresses, the temperature is gradually raised to allow the reaction to proceed further. methods can also be employed. By doing so, it is possible to prevent the unreacted carbonate compound from being distilled off in the initial stage of the reaction.

Furthermore, in order to prevent these raw materials from being distilled off, it is possible to attach a reflux pipe to the reactor and carry out the reaction while refluxing the carbonate compound. can be adjusted to

The polymerization reaction can be carried out in a batch system or a continuous system, but is preferably carried out in a continuous system from the viewpoint of product stability and the like. The apparatus to be used may be of any type of tank type, tubular type or tower type, and known polymerization tanks equipped with various stirring blades and the like can be used. The atmosphere during heating of the device is not particularly limited, but from the viewpoint of product quality, it is preferable to carry out the heating in an inert gas such as nitrogen gas under normal pressure or reduced pressure.

The polymerization reaction is terminated when the target molecular weight is reached while measuring the molecular weight of the polyether polycarbonate diol (a2-1) produced. The reaction time required for polymerization varies greatly depending on the polyoxyalkylene glycol used, the carbonate compound, and the presence or absence and type of catalyst used. It is more preferably 30 hours or less, and even more preferably 20 hours or less.

When a catalyst is used in the polymerization reaction, the catalyst usually remains in the obtained polyether polycarbonate diol (a2-1), and the remaining catalyst may make it impossible to control the polyurethane formation reaction. In order to suppress the influence of this remaining catalyst, it is preferable to add a catalyst deactivator such as a phosphorus-based compound in a molar amount substantially equal to that of the transesterification catalyst used to deactivate the transesterification catalyst. Furthermore, after adding the catalyst deactivator, heat treatment etc. as described later,
The transesterification catalyst can be efficiently deactivated.

Phosphorus compounds used for inactivating the transesterification catalyst include, for example, inorganic phosphoric acids such as phosphoric acid and phosphorous acid, dibutyl phosphate, tributyl phosphate, trioctyl phosphate,
Examples include organic phosphates such as triphenyl phosphate and triphenyl phosphite.
These may be used individually by 1 type, and may use 2 or more types together.

The amount of the phosphorus-based compound to be used is not particularly limited, but may be approximately equimolar to the transesterification catalyst used. Specifically, the upper limit is preferably 5 mol per 1 mol of the transesterification catalyst used. , more preferably 2 mol, and the lower limit is preferably 0.8 mol
l, more preferably 1.0 mol. When a phosphorus-based compound is used in an amount less than this, the deactivation of the transesterification catalyst in the reaction product is insufficient, and the obtained polyether polycarbonate diol (a2-1) is used for urethane (meth)acrylate production. In some cases, the reactivity of the polyether polycarbonate diol (1) with respect to isocyanate groups cannot be sufficiently reduced when used as a raw material for a polyether polycarbonate diol (1). Also, if a phosphorus-based compound exceeding this range is used, the obtained polyether polycarbonate diol (a2-1) may be colored.

Deactivation of the transesterification catalyst by adding a phosphorus-based compound can be performed at room temperature, but is more efficient with heat treatment. The temperature of this heat treatment is not particularly limited, but the upper limit is preferably 180°C, more preferably 150°C, and still more preferably 120°C.
° C., particularly preferably 100 ° C., the lower limit is preferably 50 ° C., more preferably 60 ° C.
, and more preferably 70°C. If the temperature is lower than this, deactivation of the transesterification catalyst takes a long time and is not efficient, and the degree of deactivation may be insufficient. On the other hand, 1
At temperatures above 80° C., the resulting polyether polycarbonate diol (a2-1)
may be colored. The reaction time with the phosphorus compound is not particularly limited,
It is usually 1 to 5 hours.

The amount of catalyst remaining in the polyether polycarbonate diol (a2-1) is 100 ppm by weight or less, particularly 10 ppm by weight in terms of metal, from the viewpoint of controlling the polyurethane formation reaction.
m or less is preferable. On the other hand, the necessary catalyst amount is 0.01 weight p in terms of metal
pm or more, particularly 0.1 weight ppm or more, and particularly preferably 5 weight ppm or more.

In the polyether polycarbonate diol (a2-1), the carbonate compound used as a raw material during production may remain. The amount of the carbonate compound remaining in the polyether polycarbonate diol (a2-1) is not limited, but is preferably as small as possible. is 3% by weight, more preferably 1% by weight. If the content of the carbonate compound in the polyether polycarbonate diol (a2-1) is too high, the reaction during polyurethane formation may be inhibited. On the other hand, the lower limit is not particularly limited, but is preferably 0.1% by weight, more preferably 0.01% by weight, and still more preferably 0% by weight.

The polyether polycarbonate diol (a2-1) may contain residual polyoxyalkylene glycol used during production. Polyether polycarbonate diol (
The residual amount of polyoxyalkylene glycol in a2-1) is not limited, but is preferably as small as possible. It is 1% by weight or less, more preferably 0.05% by weight or less. If the residual amount of polyoxyalkylene glycol in the polyether polycarbonate diol (a2-1) is large, the molecular length of the soft segment portion when converted to urethane (meth)acrylate is insufficient, and desired physical properties may not be obtained. be.

The lower limit of the hydroxyl value of the polyether polycarbonate diol (a2-1) is usually 22.4
mg-KOH/g, preferably 28.1 mg-KOH/g, more preferably 37.4 mg
-KOH/g, the upper limit is usually 187.0 mg-KOH/g, preferably 140.3 mg-
KOH/g, more preferably 112.2 mg-KOH/g. If the hydroxyl value is less than the above lower limit, the viscosity becomes too high, and handling during polyurethane formation may become difficult. If the above upper limit is exceeded, the resulting urethane (meth)acrylate may lack flexibility.
Specifically, the hydroxyl value of the polyether polycarbonate diol (a2-1) is measured by the method described in the Examples section below.

The lower limit of the number average molecular weight (Mn) obtained from the hydroxyl value of the polyether polycarbonate diol (a2-1) used in the present invention is preferably 600, more preferably 80.
0, more preferably 1000. On the other hand, the upper limit is preferably 5,000, more preferably 4,000, still more preferably 3,000. When the Mn of the polyether polycarbonate diol is less than the above lower limit, there are cases where sufficient flexibility cannot be obtained when it is made into urethane (meth)acrylate. On the other hand, when the above upper limit is exceeded, the viscosity increases, which may impair the handling during polyurethane formation.

<Polyol other than polyether polycarbonate diol (a2-1)>
In the polyurethane-forming reaction for producing the urethane (meth)acrylate compound (A) of the present invention, the polyether polycarbonate diol (a2-1) may be used in combination with other polyols, if necessary. Here, the polyol other than the polyether polycarbonate diol (a2-1) is not particularly limited as long as it is used in ordinary polyurethane production. Polycarbonate polyols may be mentioned. In particular, it is preferable to use a polyol (a2-2) having a number average molecular weight of 300 or less, since the balance between elongation and abrasion resistance can be adjusted.

<Polyol (a2-2)>
Examples of the polyol (a2-2) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2- butyl-2-ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol,
1,5-pentamethylenediol, 1,6-hexamethylenediol, 3-methyl-1,
5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, pentaerythritol diacrylate, 1,9-nonanediol, 2-methyl-1,3-hexanediol, 2-methyl-1,8 - fatty alcohols such as octanediol, 1,
Alicyclic diols such as 4-cyclohexanediol, cyclohexyldimethanol and tricyclodecanedimethanol; bisphenols such as bisphenol A; can be used in combination.
Among these, from the viewpoint of yellowing of the cured coating film, compounds having a structure containing no aromatic ring or unsaturated group are preferred, aliphatic alcohols are particularly preferred, and neopentyl glycol is more preferred.

[Hydroxyl group-containing (meth)acrylate (a3)]
Examples of hydroxyl group-containing (meth)acrylates (a3) include 2-hydroxyethyl (
meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, etc., where the alkyl group has 1 to 16 carbon atoms (preferably 1 to 1
2) Hydroxyalkyl (meth)acrylate; 2-hydroxyethyl acryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth) (Meth)acryloyl such as acrylate, fatty acid-modified glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, etc. a compound having one group; glycerin di(meth)acrylate,
2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)
Acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, succinic acid-modified pentaerythritol Examples thereof include compounds having two or more (meth)acryloyl groups such as tri(meth)acrylate.
These may be used individually by 1 type, and may be used in combination of 2 or more types.

Among these, a hydroxyl group-containing (meth)acrylate having two or more (meth)acryloyl groups in the molecule is preferable because it can impart an appropriate crosslinked structure to the cured coating film and impart abrasion resistance. Glycerin di (
meth)acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate.

[Preparation of urethane (meth)acrylate (A)]
The urethane (meth)acrylate (A) used in the present invention includes, for example, the polyvalent isocyanate (a1), polyether polycarbonate diol (a2-1), polyol (
a2-2), which can be produced by charging a reactor together or separately using a hydroxyl group-containing (meth)acrylate (a3) and reacting the polyether polycarbonate diol (a2-1) and the polyol (a2) -2) and a polyvalent isocyanate (a1)
It is useful from the viewpoint of stability of the reaction, reduction of by-products, and the like, to react the hydroxyl group-containing (meth)acrylate (a3) with the reaction product obtained by reacting in advance.

Then, in order to obtain urethane (meth)acrylate (A) in good yield, polyvalent isocyanate (a1), polyether polycarbonate diol (a2-1), polyol (a2
-2), the molar ratio of the hydroxyl group-containing (meth)acrylate (a3) is preferably as follows.

Alicyclic structure-containing polyvalent isocyanate (a1), polyether polycarbonate diol (
A known reaction means can be used for the reaction of a2-1) and polyol (a2-2). At that time, for example, the isocyanate groups in the polyvalent isocyanate (a1) and the hydroxyl groups in the polyol ((the sum of the hydroxyl groups in the polyether polycarbonate diol (a2-1) and the hydroxyl groups in the polyol (a2-2)) The ratio is usually isocyanate group: hydroxyl group = 2:
By making the ratio about 1 to 15:14, a terminal isocyanate group-containing urethane (meth)acrylate with residual isocyanate groups can be obtained. Then, the terminal isocyanate group can undergo an addition reaction with the hydroxyl group-containing (meth)acrylate (a3).

A reaction product obtained by pre-reacting the alicyclic structure-containing polyvalent isocyanate (a1), the polyether polycarbonate diol (a2-1), and the polyol (a2-2), and a hydroxyl group-containing (meth)acrylate ( Known reaction means can also be used for the addition reaction with a3).

The reaction molar ratio between the reaction product and the hydroxyl group-containing (meth)acrylate (a3) is, for example, two isocyanate groups in the polyvalent isocyanate (a1) and one hydroxyl group in the hydroxyl group-containing (meth)acrylate (a3). , the reaction product: the hydroxyl group-containing (meth)acrylate (a3) is about 1:2, the polyvalent isocyanate (a1) has three isocyanate groups, and the hydroxyl group-containing (meth)acrylate (a3) has one hydroxyl group, the ratio of reaction product to hydroxyl group-containing (meth)acrylate (a3) is about 1:3.

In the addition reaction between this reaction product and the hydroxyl group-containing (meth)acrylate (a3),
Urethane (meth)acrylate (A) is obtained by terminating the reaction when the residual isocyanate group content in the reaction system becomes 0.3% by weight or less.

Regarding the reaction conditions, for example, the reaction temperature is urethane (meth)acrylate (
In order to obtain A) in good yield, it is preferable to set the temperature in the range of about 30 to 80°C, but from the point of view of being able to control the heat of reaction, it is appropriate to carry out the reaction at 60 to 70°C. , usually 2 to
10 hours, preferably 3-8 hours.

The polyvalent isocyanate (a1) and the polyether polycarbonate diol (a2-
1) and the reaction with the polyol (a2-2), and further in the reaction between the reaction product and the hydroxyl group-containing (meth)acrylate (a3), it is also preferable to use a catalyst for the purpose of promoting the reaction. Examples include dibutyltin dilaurate, dibutyltin diacetate,
Organometallic compounds such as trimethyltin hydroxide, tetra-n-butyltin, zinc bisacetylacetonate, zirconium tris(acetylacetonate)ethylacetoacetate, zirconium tetraacetylacetonate, tin octoate, zinc hexanoate, octenoic acid zinc, zinc stearate, zirconium 2-ethylhexanoate, cobalt naphthenate,
Metal salts such as stannous chloride, stannic chloride, potassium acetate, triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1
,8-diazabicyclo[5,4,0]-7-undecene, N,N,N',N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmorpholine and other amine catalysts , bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc., organic bismuth compounds such as dibutyl bismuth dilaurate, dioctyl bismuth dilaurate,
Bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate salts, bismuth-based catalysts such as organic acid bismuth salts such as bismuth salicylate, bismuth disalicylate, and bismuth digallate. ,0]-7-undecene is preferred. These may be used individually by 1 type, and can also be used in combination of 2 or more types.

The blending amount of the above catalyst is usually 0.01 to 1,000 ppm, preferably 0.1 to 500 ppm, particularly preferably 1 to 300 ppm, based on the total sum of the reaction components.

An organic solvent can also be used as necessary in the above reaction. Examples of the organic solvent include ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; cellosolves such as ethyl cellosolve; aromatics such as toluene and xylene; etc. can be given. These organic solvents may be used alone or in combination of two or more.

The number of ethylenically unsaturated groups contained in the urethane (meth)acrylate (A) is
It is preferably 1-10, more preferably 1-6, and particularly preferably 1-4.

The weight average molecular weight of the urethane (meth)acrylate (A) is preferably 1,000
to 50,000, more preferably 3,000 to 45,000, particularly preferably 5,000
000 to 40,000. If the weight-average molecular weight of the urethane (meth)acrylate (1) is too small, the concentration of ethylenically unsaturated groups in the cured coating film will be relatively high, and the cured coating film will not have elongation properties. urethane (meth)acrylate (A)
If the weight average molecular weight of is too large, the viscosity tends to increase and reaction control tends to be difficult, and the concentration of ethylenically unsaturated groups in the cured coating film becomes relatively small, resulting in a low crosslink density. Although the elongation of this type can be obtained, the wear resistance tends to be low.

In addition, the weight average molecular weight is the weight average molecular weight in terms of standard polystyrene molecular weight.
One SKguardcolumn SuperHZ-L, TSKgel SuperHZ
It is measured by using two MMs and one TSKgel SuperHZ2000 in series for a total of four.

<<Photoinitiator (B)>>
The active energy ray-curable resin composition of the present invention preferably further contains a photopolymerization initiator (B) in order to impart curability.

The photopolymerization initiator (B) is not particularly limited as long as it generates radicals by the action of light. Examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)
Phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-
2-methyl-1-propan-1-one, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone , 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)
Acetophenones such as phenyl]propanone oligomers; Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether;
4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2
, 4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-
(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4
-benzoylbenzyl) trimethylammonium chloride and other benzophenones; Thioxanthones such as dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthon-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl )-2,
acylphosphine oxides such as 4,4-trimethyl-pentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide;
etc. In addition, these photoinitiators (B) may be used individually by 1 type, and can also use 2 or more types together.

Also, as auxiliary agents for the photopolymerization initiator (B), triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2, It is also possible to use 4-diisopropylthioxanthone or the like in combination. These auxiliaries may be used singly or in combination of two or more.

Regarding the content of the photopolymerization initiator (B), the specific urethane (meth) acrylate (A
) and the later-described ethylenically unsaturated compound (C) are preferably used in an amount of 0.1 to 20 parts by weight, particularly preferably 0.5 to 10
parts by weight, more preferably 1 to 7.5 parts by weight. If the content is too low, curing will be poor and the coating film will tend to be difficult to form.

<<Ethylenically unsaturated compound (C)>>
If necessary, the active energy ray-curable resin composition contains a photopolymerization initiator (B),
Ethylenically unsaturated compounds (C) other than urethane (meth)acrylate compounds (A), polymers such as acrylic resins, surface conditioners, leveling agents, polymerization inhibitors, etc. can be added, and dyes and pigments can be added. , oils, plasticizers, waxes, desiccants, dispersants, wetting agents, emulsifiers, gelling agents, antioxidants, flame retardants, antistatic agents, electrolyte salts, fillers, stabilizers, reinforcing agents, matting agents , Cross-linking agents, UV absorbers, weathering agents, light stabilizers, thickeners, rust inhibitors, adhesion improvers, film-forming aids, abrasives, organic fine particles, inorganic particles, etc. can be added. . Furthermore, as a cross-linking agent,
Compounds having the action of causing cross-linking by heat, specifically epoxy compounds, azilysine compounds, melamine compounds, isocyanate compounds, chelate compounds and the like can also be used.

As the ethylenically unsaturated compound [except urethane (meth)acrylate compound (A)] (C), for example, urethane (meth)acrylate compound (C1) and/or ethylenically unsaturated monomer (C2) Preferably.

[Urethane (meth)acrylate compound (C1)]
The urethane (meth)acrylate compound (C1) is required to be a urethane (meth)acrylate compound (C1-1) represented by the following general formula (2) even when used for various purposes. It is preferable in that it is easy to impart physical properties to the material.

（上記式（２）中、Ｒ1は多価イソシアネート系化合物のウレタン結合残基、Ｒ2は水酸基
含有（メタ）アクリレート系化合物のウレタン結合残基、ｎは２～１０の整数である。）

(In formula (2) above, R1 is the urethane bond residue of the polyvalent isocyanate compound, R2 is the urethane bond residue of the hydroxyl group-containing (meth)acrylate compound, and n is an integer of 2 to 10.)

The urethane (meth)acrylate (C1-1) represented by the above formula (2) (hereinafter sometimes abbreviated as "urethane (meth)acrylate compound (C1-1)") is a polyvalent isocyanate compound and It is obtained by reacting a hydroxyl group-containing (meth)acrylate compound.

n in the above formula (2) may be an integer of 2 to 10, preferably 2 to 6, particularly preferably 2 to 3.

Examples of such a polyvalent isocyanate compound include those exemplified as the polyvalent isocyanate compound (a1) in the description of the urethane (meth)acrylate (A).

Examples of such a hydroxyl group-containing (meth)acrylate compound include those exemplified as the hydroxyl group-containing (meth)acrylate compound (a3) in the description of the urethane (meth)acrylate (A). be done.

The urethane (meth)acrylate compound (C1-1) may be produced according to a known general method for producing a urethane (meth)acrylate compound.

The number of ethylenically unsaturated groups contained in the urethane (meth)acrylate compound (C1-1) is preferably 2 to 30, particularly preferably 2 to 15, and still more preferably 2 to 6. be.
If the number of ethylenically unsaturated groups is too small, the hardness and scratch resistance of the coating film tend not to be obtained. tend to become

The weight average molecular weight of the urethane (meth)acrylate compound (C1) is 400 to 800
,000, more preferably 800-50,000, especially 1000-10,
000 is preferred. If the weight-average molecular weight is too small, it tends to be difficult to maintain a balance between coating film hardness and shrinkage resistance. tend to become

[Ethylenically unsaturated monomer (C2)]
The ethylenically unsaturated monomer (C2) is an ethylenically unsaturated monomer having one or more ethylenically unsaturated groups in one molecule (excluding urethane (meth)acrylate compounds (C1)). Common examples include monofunctional monomers, bifunctional monomers, and tri- or higher functional monomers.

The monofunctional monomer may be a monomer containing one ethylenically unsaturated group,
For example, styrene, vinyltoluene, chlorostyrene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, acrylonitrile, vinyl acetate, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl ( meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (
meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate,
Octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (meth) ) acrylates, nonylphenol propylene oxide-modified (meth)acrylates, half ester (meth)acrylates of phthalic acid derivatives such as 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, furfuryl (meth)acrylate,
Carbitol (meth)acrylate, benzyl (meth)acrylate, butoxyethyl (
meth)acrylate, allyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide, N-methylol (meth)acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, 2-(meth)acryloyloxyethyl acid phosphate monoester etc.

In addition to the above monofunctional monomers, Michael adducts of acrylic acid, or 2-acryloyloxyethyldicarboxylic acid monoesters may also be mentioned. Michael adducts of acrylic acid include acrylic acid dimer, methacrylic acid dimer, acrylic acid Examples include trimers, methacrylic acid trimers, acrylic acid tetramers, methacrylic acid tetramers, and the like. again,
Examples of 2-acryloyloxyethyldicarboxylic acid monoesters, which are carboxylic acids having specific substituents, include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyloxyethyl phthalic acid. monoester, 2-methacryloyloxyethyl phthalate monoester, 2-acryloyloxyethyl hexahydrophthalate monoester, 2-methacryloyloxyethyl hexahydrophthalate monoester, and the like. Furthermore, oligoester acrylates are also mentioned.

The bifunctional monomer may be any monomer containing two ethylenically unsaturated groups,
For example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)
Acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth) Acrylates, neopentyl glycol di(meth)acrylate, ethylene oxide-modified bisphenol A-type di(meth)acrylate, propylene oxide-modified bisphenol A-type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,6- Hexanediol Ethylene oxide-modified di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid di(meth)acrylate glycidyl ester di(meth)acrylate, hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate, isocyanuric acid ethylene oxide-modified diacrylate, 2-
(Meth) acryloyloxyethyl acid phosphate diester and the like.

The trifunctional or higher monomer may be a monomer containing 3 or more ethylenically unsaturated groups, such as trimethylolpropane tri(meth)acrylate, glycerin triacrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol. tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane,
Glycerin polyglycidyl ether poly(meth)acrylate, isocyanuric acid ethylene oxide-modified triacrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate ) acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol Tetra (
meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, and the like.

These ethylenically unsaturated monomers (C2) may be used alone or in combination of two or more.

In addition, since the ethylenically unsaturated monomer (C2) is easy to adjust the elongation and scratch resistance properties, , pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

As the ethylenically unsaturated compound (C), a urethane (meth)acrylate compound (C1
) and the ethylenically unsaturated monomer (C2), the content ratio (weight ratio) of (C1) and (C2) is (C1):(C2) = 5:95 to 95:5. is preferred, and (C1):(C2)=20:80 to 80:20 is particularly preferred.

The content of the ethylenically unsaturated compound (C) is not particularly limited as long as it does not impair the physical properties.
It is preferably parts by weight, more preferably 0 to 95 parts by weight, particularly preferably 0 to 90 parts by weight.
parts by weight, more preferably 0 to 85 parts by weight.

"Additive"
The surface conditioner is not particularly limited, and examples thereof include cellulose resins and alkyd resins. The cellulose resin has the effect of improving the surface smoothness of the coating film, and the alkyd resin has the effect of imparting film-forming properties during coating.

As the leveling agent, known general leveling agents can be used as long as they have the effect of imparting wettability to the base material of the coating liquid and the effect of lowering the surface tension. Examples include silicone-modified resins, fluorine-modified resins, An alkyl-modified resin or the like can be used.

Examples of polymerization inhibitors include p-benzoquinone, naphthoquinone, tolquinone, 2,5
-diphenyl-p-benzoquinone, hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, pt-butylcatechol and the like.

It is also preferable to use an organic solvent for dilution of the active energy ray-curable resin composition of the present invention, if necessary, in order to obtain an appropriate viscosity at the time of coating. Examples of such organic solvents include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol and isobutanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; and cellosolves such as ethyl cellosolve. aromatics such as toluene and xylene, glycol ethers such as propylene glycol monomethyl ether, acetic esters such as methyl acetate, ethyl acetate, butyl acetate, and 2-methoxy-1-methylethyl acetate, diacetone alcohol, tetrahydrofuran etc. These organic solvents may be used alone or in combination of two or more.

In producing the active energy ray-curable resin composition of the present invention, the method of mixing the urethane (meth)acrylate compound (A) and other components is not particularly limited, and various methods are used for mixing. can do.

The active energy ray-curable resin composition of the present invention is effectively used as a curable resin composition for forming coating films, such as top coating agents and anchor coating agents for various substrates. After coating the resin composition on the substrate (in the case of applying a composition diluted with an organic solvent, after further drying), it is cured by irradiating with active energy rays.

《Coating agents, sheets》
The active energy ray-curable resin composition of the present invention is used, for example, as a coating agent.

Furthermore, using the active energy ray-curable resin composition as a coating agent,
A sheet can be produced by coating a substrate to form a coating film, curing the coating film by irradiation with an active energy ray, and peeling it off.

In the present invention, the term "sheet" conceptually includes sheets and films.

Examples of the method for applying the active energy ray-curable resin composition of the present invention include spraying,
Wet coating methods such as showering, dipping, roll coating, spin coating, screen printing, etc. may be mentioned, and the base material may be coated under normal temperature conditions.

The active energy rays used for curing the active energy ray-curable resin composition coated on the substrate include light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, and electromagnetic waves such as X rays and γ rays. In addition, electron beams, proton beams, neutron beams, etc. can be used, but curing by ultraviolet irradiation is advantageous in terms of curing speed, availability of irradiation equipment, price, and the like. When electron beam irradiation is performed, curing can be performed without using the photopolymerization initiator (B) described above.

Substrates to be coated with the active energy ray-curable resin composition of the present invention include polyolefin resins, polyester resins, polycarbonate resins, acrylic resins, acrylonitrile-butadiene-styrene copolymers (ABS), and polystyrene. resins, cellulose resins, etc., and plastic substrates such as their molded products (films, sheets, cups, etc.),
Metal (
aluminum, copper, iron, SUS, zinc, magnesium, alloys thereof, etc.) and substrates such as glass having a primer layer provided thereon.

In addition, the active energy ray-curable resin composition of the present invention can be used even without a solvent.
Coating is preferred.

As the coating film thickness (film thickness after curing), a photopolymerization initiator (
Considering light transmission so that B) reacts uniformly, the thickness may be 3 to 1,000 μm, preferably 5 to 500 μm, and particularly preferably 10 to 200 μm.

As for the drying conditions when diluting with the above organic solvent, the temperature is usually 40 to 120
° C. (preferably 50 to 100 ° C.), the drying time is usually 1 to 20 minutes (preferably 2 to 10
minutes).

When curing the active energy ray-curable resin composition of the present invention by ultraviolet irradiation, 1
High-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, LEDs that emit light in the wavelength range of 50 to 450 nm
etc., usually 30 to 3000 mJ/cm2 (preferably 100 to 1500 mJ/cm2
) can be irradiated with ultraviolet rays.
After the ultraviolet irradiation, heating may be performed as necessary to ensure complete curing. Examples of the heating conditions at that time include a temperature of 120 to 200°C.

<<Active energy ray-curable resin composition>>
The active energy ray-curable resin composition of the present invention includes the specific urethane (meth)acrylate (A), the photopolymerization initiator (B), the specific ethylenically unsaturated monomer (C), and the above various It can be manufactured by blending and mixing additives in a predetermined compounding amount.

Due to its properties, the active energy ray-curable resin composition of the present invention is used, for example, as a hard coating agent applied to the surface of plastic parts, etc., mobile phones such as smartphones,
It can be used as a material for forming the surface layers of automobile interior and exterior parts, sign poles, hairdressing equipment, amusement equipment, and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In addition, "parts" and "%" in the examples mean weight standards.
The weight average molecular weight, number average molecular weight and viscosity were measured according to the methods described above.

[Synthesis of Polyether Polycarbonate Diol]
A 2 L glass separable flask equipped with a stirrer, a distillate trap, a pressure regulator, a distillation column with 30 mm diameter regular packing, and a fractionator was filled with polytetramethylene ether glycol PTMG#250 (number average molecular weight: 220) manufactured by Mitsubishi Chemical Corporation. : 279 g (1.27 mol), ethylene carbonate (EC): 125 g (1.42 mol), magnesium (II) acetylacetonate: 108 mg (0.49 mmol) were added, and the pressure was lowered to 5 kPa while stirring. Then, the internal temperature was raised to 150° C., and the reaction was carried out while reducing the pressure to 1 kPa over 17.5 hours while removing ethylene glycol and ethylene carbonate out of the system with an azeotropic composition.
33.2 g and 19.4 g of EC were added to the reaction solution at the 7 hour and 14 hour reaction time points. 1H-
It was confirmed by NMR that the number average molecular weight was about 2000, and a polyether polycarbonate diol-containing composition was obtained. Thereafter, 0.45 g of an 8.5% aqueous phosphoric acid solution was added to the polyether polycarbonate diol-containing composition to deactivate the catalyst. Thereafter, the distillation column was removed, and residual monomers were removed at 0.5 kPa and 170° C. to obtain a polyether polycarbonate diol-containing composition.

The obtained polyether polycarbonate diol-containing composition was fed to a thin film distillation apparatus at a flow rate of 100 g/min, and thin film distillation (temperature: 190°C, pressure: 133 Pa) was performed to obtain polyether polycarbonate diol (a2-1). Obtained. As a thin film distillation apparatus, a diameter of 50 m
A molecular distillation apparatus MS-300 special type manufactured by Shibata Kagaku Co., Ltd. with an internal condenser and a jacket having a height of 200 mm and an area of 0.0314 m 2 was used.

[Production Example 1]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet,
300.0 g of ethyl acetate, 249.9 g of hydrogenated xylylene diisocyanate (a1) (1.
29 mol), neopentyl glycol (a2-1) (weight average molecular weight (Mw); 104)
100.5 g (0.96 mol) and 0.04 g of dibutyltin dilaurate as a reaction catalyst were charged and reacted at 70°C. Polyether carbonate diol (a2-1) (hydroxyl value 57.9 mgKOH/g) 311 when the residual isocyanate groups became 4.2% or less
. 7 g (0.16 mol) was added and allowed to react further. 37.9 g (0.33 mol) of 2-hydroxyethyl acrylate and 0.4 g of 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor when the residual isocyanate groups became 1.4% or less was added and reacted at 60° C. When the residual isocyanate groups reached 0.3% or less, the reaction was terminated to obtain a urethane acrylate compound (A-1) (weight average molecular weight: 17568).

[Production Example 2]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet,
300.0 g of ethyl acetate, 202.4 g of hydrogenated xylylene diisocyanate (a1) (1.
04 mol), neopentyl glycol (a2-1) (weight average molecular weight (Mw); 104)
72.3 g (0.69 mol) and 0.04 g of dibutyltin dilaurate as a reaction catalyst were charged and reacted at 70°C. Polyether carbonate diol (a2-1) (hydroxyl value: 57.9 mgKOH/g) at 336.9 mg KOH/g when the residual isocyanate group was 5.1% or less.
6 g (0.17 mol) was added and allowed to react further. When the residual isocyanate groups became 1.6% or less, glycerin diacrylate (hydroxyl value: 223.0 mgKOH/g) was 88.
7 g (0.35 mol) and 0.4 g of 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor were further charged and reacted at 60° C. until residual isocyanate groups became 0.3% or less. The reaction was terminated at the time point, and a urethane acrylate compound (A-2) (weight average molecular weight: 18903) was obtained.

[Comparative Production Example 1]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet,
300.0 g of ethyl acetate, 281.4 g of hydrogenated xylylene diisocyanate (a1) (1.
45 mol), neopentyl glycol (a2-1) (weight average molecular weight (Mw); 104)
100.6 g (0.97 mol) and 0.04 g of dibutyltin dilaurate as a reaction catalyst were charged and reacted at 70°C. When the residual isocyanate groups became 6.0% or less, polycarbonate diol (a2-3) ("Duranol T5650J" manufactured by Asahi Kasei Corp.:
194.7 g (0.24 mol) of hydroxyl value 139.2 mg KOH/g) was added and further reacted. When the residual isocyanate groups became 2.3% or less, 123.3 g (0.49 mol) of glycerin diacrylate (hydroxyl value: 223.0 mgKOH/g), 2,6-di-tert-butyl- 0.4 g of 4-methylphenol was further added and heated to 60°C.
and terminated when the residual isocyanate groups became 0.3% or less to obtain a urethane acrylate compound (A-3) (weight average molecular weight: 11719).

[Comparative Production Example 2]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet,
300.0 g of ethyl acetate, 299.9 g of hydrogenated xylylene diisocyanate (a1) (1.
54 mol), neopentyl glycol (a2-1) (weight average molecular weight (Mw); 104)
107.2 g (1.03 mol) and 0.04 g of dibutyltin dilaurate as a reaction catalyst were charged and reacted at 70°C. When the residual isocyanate groups became 6.1% or less, polyether diol (a2-4) (“PTG-650SN” manufactured by Hodogaya Chemical Co., Ltd.: hydroxyl value 178.9 mg KOH / g) 161.4 g (0 .26 mol) was added and allowed to react further.
When the residual isocyanate groups became 2.5% or less, 131.4 g (0.52 mol) of glycerin diacrylate (hydroxyl value: 223.0 mg KOH/g), 2,6 as a polymerization inhibitor
-Di-tert-butyl-4-methylphenol 0.4 g was further charged and reacted at 60 ° C. When the residual isocyanate group became 0.3% or less, the reaction was terminated, and the urethane acrylate compound (A- 4) (weight average molecular weight: 10464) was obtained.

[Example 1]
For 100 parts of the resin content of the urethane acrylate compound (A-1) prepared in Production Example 1, 1-hydroxycyclohexyl-phenyl-ketone (BASF
A photocurable resin composition was obtained by adding 4 parts of Irgacure 184 (trade name, manufactured by Japan Co., Ltd.) and adding ethyl acetate as a diluting solvent to the above composition so that the solid content was 40%.

[Example 2, Comparative Examples 1 and 2]
Instead of the urethane acrylate compound (A-1) in Example 1, as described in Table 1 below, except that the urethane acrylate compounds produced in Production Example 2 and Comparative Production Examples 1 and 2 were used. , to obtain a photocurable resin composition in the same manner as in Example 1.

Using the active energy ray-curable resin composition thus obtained, a measurement sample was prepared as follows, and the elongation, abrasion resistance, and solvent resistance of the sample were evaluated as follows. did. The results are shown in Table 1 below.

[Preparation of sample for measurement of elongation, abrasion resistance, and solvent resistance]
The photocurable resin compositions blended in Examples and Comparative Examples were applied to an easily moldable polyethylene terephthalate (PET) film (manufactured by Teijin DuPont Films Ltd., easily moldable PET, thickness 100).
μm), and dried at 60° C. for 3 minutes, then irradiated with ultraviolet rays with a high-pressure mercury lamp so that the cumulative light intensity was 800 mJ/cm ) and cured to prepare a coating film sample for evaluation having a film thickness of 10 μm.
Subsequent evaluations were performed using the coating film sample for evaluation obtained above.

<Elongation>
The resulting cured coating film was cut into a size of 40 mm in length and 10 mm in width, and a sample piece was pulled using a tensile tester "Force measurement model MX-500N-FA" (IMA
(manufactured by DA Co., Ltd.), a tensile test was performed in an atmosphere of 180° C. in accordance with JIS K 7127. The base film was pulled at a pulling speed of 40 mm/min, and the elongation at the breaking point of the coating film was measured and evaluated according to the following criteria.
O: Elongation at break of 80% or more.
Δ: Elongation at break of 60% or more and less than 80%.
×: Less than 60% elongation at break.

<Scratch resistance>
The resulting cured coating film was cut into 10 cm squares, and "ROTARY ABRASION TE
STER" (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used to perform an abrasion resistance test in accordance with JIS K5600-5-9. [CS-10] was used as the wear wheel, 500 rotations were performed under a load of 500 g, and the change in haze (ΔH) before and after the test was evaluated according to the following criteria.
〇・・・ΔH is less than 20% ×・・・ΔH is 20% or more

<Chemical resistance>
toluene (Mitsui Bussan Chemicals Co., Ltd., trade name "toluene") on the resulting cured coating film,
and methyl ethyl ketone (manufactured by Idemitsu Kosan Co., Ltd., trade name "MEK") were dropped, and after standing for about 1 hour, the coating film surface was visually observed.
◯: No change in the coating film, or slight traces of the solvent are observed.
Δ: Solvent traces are observed on the coating film.
×: Whitening and swelling are observed in the coating film. The coating dissolves.

<Comprehensive judgment>
Based on each of the above measurement evaluations, a comprehensive judgment evaluation was performed according to the following criteria.
◯: An evaluation of “◯” was obtained in all the evaluations.
×: There was at least one evaluation of “×”.

From the above results, it can be seen that in all the examples, the elongation at 180° C. is good, and the wear resistance and solvent resistance are also excellent.
On the other hand, in Comparative Example 1, a urethane acrylate (A-3) having a polycarbonate skeleton containing a polycarbonate diol was used, and in Comparative Example 2, a urethane acrylate (A-4) having a polyether skeleton containing a polyether polyol was used. All of them resulted in inferior wear resistance and chemical resistance. In Comparative Example 3, the urethane acrylate (A-3) having a polycarbonate skeleton and the urethane acrylate (A-4) having a polyether skeleton containing polyether polyol were used in combination. and solvent resistance.

The present invention provides an active energy ray-curable resin capable of forming a coating film having high transparency, good elongation properties, high abrasion resistance, and excellent chemical resistance when made into a cured coating film. The present invention also provides a coating agent and a sheet using the composition. Therefore, it is very useful, for example, for home electric appliances, automotive products, coating agents for smartphones, coating agents for displays, coating agents for touch panels, and external coating materials for optical fibers and flexible tubular objects. Furthermore, the coating film or the like has high transparency, little deterioration in physical properties at high temperatures, and excellent chemical resistance, so that it can be used in various applications making use of these characteristics.

Claims (7)

Structural unit derived from polyvalent isocyanate compound (a1), polyol compound (a2)
and a urethane (meth)acrylate compound (A) having a structural unit derived from a hydroxyl group-containing (meth)acrylate compound (a3), and the polyol compound (a2) is represented by the following formula ( 1) An active energy ray-curable composition containing a polyether polycarbonate diol (a2-1) represented by the formula.

(In the above formula (1), R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is 2 to 3
is an integer of 0 and m is an integer of 1-20. In formula (1), a plurality of R1 may be the same or different. ) The polyol compound (a2) is further a polyol (a2) having a number average molecular weight of 300 or less
-2), the active energy ray-curable composition according to claim 1. The polyether polycarbonate diol (a2-1) and the polyol (a2-2
) and the ratio (a2-1/a2-2) is 99/1 to 50/50 in weight ratio, claim 2
The active energy ray-curable resin composition according to . The polyether polycarbonate diol (a2-1) has a number average molecular weight of 500 to 2
0,000, the active energy ray-curable resin composition according to any one of claims 1 to 3. The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the hydroxyl group-containing (meth)acrylate (a3) has one or more (meth)acryloyl groups. A coating agent containing the active energy ray-curable resin composition according to any one of claims 1 to 5. A sheet having a cured product of the active energy ray-curable resin composition according to any one of claims 1 to 5.