JP2017165948A - Polyurethane (meth) acrylate, composition, cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane (meth) acrylate having excellent compatibility and excellent stain resistance; a coating agent, a laminate material or a molding material comprising the polyurethane (meth) acrylate; a composition comprising the polyurethane (meth) acrylate; a cured product thereof.SOLUTION: A polyurethane (meth) acrylate comprises a polycarbonate polyol-derived structure and a polyisocyanate-derived structure, and comprises a hydroxy group-containing (meth) acrylate-derived structure at a terminal.SELECTED DRAWING: None

Description

  The present invention relates to polyurethane (meth) acrylate, a coating agent containing the same, a laminate material or a molding material, a composition containing polyurethane (meth) acrylate, and a cured product thereof. Polyurethane (meth) acrylate is a useful compound as a main component of various types of coating agents that are cured with active energy rays.

  Conventionally, as a polyurethane (meth) acrylate having a polycarbonate skeleton as a repeating unit, as described below, at the end of a polyurethane synthesized from one or more linear, branched or cyclic polycarbonate polyols and polyisocyanates. Various polyurethane (meth) acrylates obtained by reacting monohydroxyalkyl (meth) acrylate are disclosed.

  (1) For example, Patent Document 1 discloses a polyurethane acrylate obtained by reacting 2-hydroxyethyl acrylate with a terminal of a polyurethane synthesized from a polycarbonate polyol made from 1,6-hexanediol and isophorone diisocyanate. It is disclosed.

  (2) For example, in Patent Document 2, it is obtained by reacting 2-hydroxyethyl acrylate with the end of a polyurethane synthesized from polycarbonate diol polyol using 1,6-hexanediol as a raw material and hydrogenated xylylene diisocyanate. Polyurethane acrylates are disclosed.

  (3) For example, Patent Document 3 discloses a polyurethane acrylate obtained by reacting the end of a hexamethylene diisocyanate allophanate adduct of 1,6-hexanediol polycarbonate diol with 2-hydroxyethyl acrylate.

  (4) For example, Patent Document 4 discloses a polycarbonate polyol made from 1,4-cyclohexanedimethanol, or a polycarbonate polyol made from 1,6-hexanediol and 1,4-cyclohexanedimethanol, and isophorone diisocyanate. Polyurethane acrylate obtained by reacting 2-hydroxyethyl acrylate with the terminal of the polyurethane synthesized from the above is disclosed.

  (5) For example, Patent Document 5 discloses a polycarbonate polyol, 1,5-pentanediol and 1,6-hexanediol starting from 3-methyl-1,5-pentanediol and 1,6-hexanediol. Synthesis from polycarbonate polyols, polycarbonate polyols using 2-methyl-1,3-propanediol and 1,4-butanediol as raw materials, or polycarbonate polyols using 1,6-hexanediol as raw materials, and various polyisocyanates Polyurethane acrylate obtained by reacting 2-hydroxyethyl acrylate with the terminal of the obtained polyurethane is disclosed.

  (6) For example, in Patent Document 6, 2-hydroxyethyl acrylate is reacted with the end of a polyurethane synthesized from a polycarbonate polyol made from 1,6-hexanediol and neopentyl glycol and isophorone diisocyanate. The resulting polyurethane acrylate is disclosed.

  (7) For example, Patent Document 7 is obtained by reacting ethylene glycol monoacrylate with the end of a polyurethane synthesized from a polycarbonate polyol using 1,6-hexanediol and ε-caprolactone as raw materials and isophorone diisocyanate. Polyurethane acrylates are disclosed.

  (8) For example, Patent Document 8 discloses a polycarbonate polyol prepared from 1,4-cyclohexanedimethanol as a raw material to a polyurethane synthesized from polycarbonate polyol using 1,6-hexanediol as a raw material and isophorone diisocyanate ( Polyurethane methacrylate having a ratio of 3/4 of polycarbonate polyol and polyisocyanate obtained by reacting 2-hydroxyethyl methacrylate with the end of polyurethane obtained by reacting with a lower molecular weight than the previous polycarbonate polyol is disclosed. Has been.

JP 2013-35920 A Japanese Patent No. 4598122 JP 2013-184988 A JP 2009-227915 A JP 2012-36290 A JP 2010-215585 A JP 2012-184385 A Japanese Patent No. 542029

  Polycarbonate polyol is superior in mechanical properties, hydrolysis resistance, heat resistance, chemical resistance, weather resistance, etc. compared to polyester polyol and polyether polyol. Polyurethane (meta) obtained from this as a raw material Similar effects are expected for acrylates and their cured products.

  However, the urethane (meth) acrylate specifically shown in Examples of Patent Documents 1 to 8 is a combination of urethane obtained from several kinds of polycarbonate polyols and a hydroxyl group-containing monofunctional acrylate (2-hydroxyethyl acrylate). Only the synthesis and the evaluation of the function and properties of the cured product obtained have been made.

  That is, when the polycarbonate polyol repeating unit or the end group of the polyurethane (meth) acrylate is in any configuration or combination, when the polyurethane (meth) acrylate is used as a cured product, an effective function is expressed. There was not enough evaluation or examination.

  Therefore, a polycarbonate polyol having a specific repeating unit that satisfies the functions and characteristics required when polyurethane (meth) acrylate is used as a cured product, that is, good compatibility and good stain resistance is used as a raw material. And urethane (meth) acrylates having specific end groups have been demanded.

  The object of the present invention is to solve the above-mentioned problems, ie, a polyurethane (meth) acrylate having good compatibility and good stain resistance, a coating agent comprising the same, a laminate material or a molding material, polyurethane (meth) acrylate It is providing the composition containing these and those hardened | cured material.

The subject of the present invention is
A polyurethane (meth) acrylate having a structure derived from a polycarbonate polyol and a structure derived from a polyisocyanate, and having a structure derived from a hydroxyl group-containing (meth) acrylate at the end,
The polycarbonate polyol has a structure derived from a polyol represented by the following formula (1A) and a structure derived from a lactone represented by the following formula (1B).
The polyisocyanate is represented by the following formula (2),
The hydroxyl group-containing polyfunctional (meth) acrylate is represented by the following formulas (a-1) to (b-2).
Solved by polyurethane (meth) acrylate.

（式（１Ａ）中、Ｚ^１は炭素原子数２〜１２の二価の直鎖状脂肪族炭化水素基を示す。
式（１Ｂ）中、Ｚ^２は炭素原子数１〜８の二価の直鎖状脂肪族炭化水素基を示す。
式（２）中、Ｒは炭素原子数２〜１２の二価の直鎖状脂肪族炭化水素基、炭素原子数３〜１２の二価の分岐状脂肪族炭化水素基、炭素原子数６〜１８の二価の環状脂肪族炭化水素基、又は炭素原子数６〜１８の二価の芳香族炭化水素基を示す。）
式（ａ−１）〜（ｂ−２）中、Ａは（メタ）アクリロイル基を示す。なお、複数のＡの一部のＡが水素となっていても良い。）

(In the formula (1A), Z ¹ represents a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms.
In the formula (1B), Z ² represents a divalent linear aliphatic hydrocarbon group having 1 to 8 carbon atoms.
In the formula (2), R is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and 6 to 6 carbon atoms. 18 is a divalent cyclic aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. )
In formulas (a-1) to (b-2), A represents a (meth) acryloyl group. A part of the plurality of A may be hydrogen. )

  The first cured product according to the present invention is a cured product obtained by curing the polyurethane (meth) acrylate according to the present invention.

  The composition according to the present invention comprises the polyurethane (meth) acrylate according to the present invention.

  The second cured product according to the present invention is a cured product obtained by curing the composition according to the present invention.

  The first coating material, laminated material, or molding material according to the present invention includes the polyurethane (meth) acrylate according to the present invention.

  The second coating material, laminate material, or molding material according to the present invention includes a composition containing the polyurethane (meth) acrylate according to the present invention.

  According to the present invention, a polyurethane (meth) acrylate having good compatibility and good stain resistance, a coating agent containing the same, a laminate material or a molding material, a composition containing polyurethane (meth) acrylate, and a cured product thereof are provided. can do.

  Therefore, the polyurethane (meth) acrylate according to the present invention is a coating application (coating material) such as an ink, a paint, an adhesive, and a pressure sensitive adhesive, various mobile devices and films that require high appearance and high durability, It can be applied to laminate applications (laminate materials) such as architectural interiors and exteriors and automobile interiors and exteriors, and molding applications (molding materials) such as cured molded products such as ultraviolet curable lenses.

The polyurethane (meth) acrylate of the present invention is
A polyurethane (meth) acrylate having a structure derived from a polycarbonate polyol and a structure derived from a polyisocyanate, and having a structure derived from a hydroxyl group-containing (meth) acrylate at the end,
The polycarbonate polyol has a structure derived from a polyol represented by the following formula (1A) and a structure derived from a lactone represented by the following formula (1B).
The polyisocyanate is represented by the following formula (2),
The hydroxyl group-containing polyfunctional (meth) acrylate is represented by the following formulas (a-1) to (b-2).
Polyurethane (meth) acrylate.

（式（１Ａ）中、Ｚ^１は炭素原子数２〜１２の二価の直鎖状脂肪族炭化水素基を示す。
式（１Ｂ）中、Ｚ^２は炭素原子数１〜８の二価の直鎖状脂肪族炭化水素基を示す。
式（２）中、Ｒは炭素原子数２〜１２の二価の直鎖状脂肪族炭化水素基、炭素原子数３〜１２の二価の分岐状脂肪族炭化水素基、炭素原子数６〜１８の二価の環状脂肪族炭化水素基、又は炭素原子数６〜１８の二価の芳香族炭化水素基を示す。
式（ａ−１）〜（ｂ−２）中、Ａは（メタ）アクリロイル基を示す。なお、複数のＡの一部のＡが水素となっていても良い。）

(In the formula (1A), Z ¹ represents a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms.
In the formula (1B), Z ² represents a divalent linear aliphatic hydrocarbon group having 1 to 8 carbon atoms.
In the formula (2), R is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and 6 to 6 carbon atoms. 18 is a divalent cyclic aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
In formulas (a-1) to (b-2), A represents a (meth) acryloyl group. A part of the plurality of A may be hydrogen. )

  “Polyurethane (meth) acrylate” is a general term for polyurethane acrylate having an acrylic group at the terminal and polyurethane methacrylate having a methacrylic group at the terminal.

  The “(meth) acryloyl group” means a functional group excluding the hydroxyl group of (meth) acrylic acid, and the “polyfunctional (meth) acryl group” means an atomic group having a plurality of (meth) acryloyl groups. The “monofunctional (meth) acryl group” refers to an atomic group having one (meth) acryloyl group. The meaning of “(meth)” is the same as that described for “polyurethane (meth) acrylate”.

[Structure derived from polycarbonate polyol]
The structure derived from a polycarbonate polyol refers to a group derived from a polycarbonate polyol other than the bonding group in the polyurethane (meth) acrylate. The “polycarbonate polyol” in the polycarbonate polyol-derived structure is specifically a polycarbonate polyol having a polyol-derived structure represented by the following formula (1A) and a lactone-derived structure represented by the following formula (1B). is there. That is, in the present invention, “a structure derived from a polycarbonate polyol” means a structure derived from a polycarbonate polyol having a structure derived from a polyol represented by the following formula (1A) and a structure derived from a lactone represented by the following formula (1B). That is.

（式（１Ａ）中、Ｚ^１は炭素原子数２〜１２の二価の直鎖状脂肪族炭化水素基を示す。
式（１Ｂ）中、Ｚ^２は炭素原子数１〜８の二価の直鎖状脂肪族炭化水素基を示す。）

(In the formula (1A), Z ¹ represents a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms.
In the formula (1B), Z ² represents a divalent linear aliphatic hydrocarbon group having 1 to 8 carbon atoms. )

In the formula (1A), Z ¹ represents a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms.
The “divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms” is a group obtained by removing two hydrogens from the “linear aliphatic hydrocarbon group having 2 to 12 carbon atoms”. Show. Examples of the divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms include ethylene group, trimethylene group (propylene group), tetramethylene group (butylene group), pentamethylene group, hexamethylene group, hepta. A methylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group and the like can be mentioned, and a tetramethylene group, a pentamethylene group and a hexamethylene group are preferred.

In the formula (1B), Z ² represents a divalent linear aliphatic hydrocarbon group having 1 to 8 carbon atoms.
The “divalent linear aliphatic hydrocarbon group having 1 to 8 carbon atoms” refers to a group obtained by removing two hydrogens from the “linear aliphatic hydrocarbon group having 1 to 8 carbon atoms”. . Examples of the divalent linear aliphatic hydrocarbon group having 1 to 8 carbon atoms include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group and the like. Among them, a tetramethylene group and a pentamethylene group are preferable.

(Polyol represented by formula (1A))
Examples of the polyol represented by the formula (1A) (hereinafter sometimes referred to as polyol (1A)) include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and nonane. Examples include diol, decane diol, undecane diol, and dodecane diol. Preferably, butane diol, pentane diol, and hexane diol are used.
In addition, you may use multiple types of polyol (1A) together. In addition, a polyol containing a small amount of an ether bond in the molecule of the polyol (1A) may be used in combination so as not to impair the function and characteristics of the target polyurethane (meth) acrylate. A polyol containing a small amount of a group polyol may be used in combination.

(Lactone represented by the formula (1B))
Examples of the lactone represented by the formula (1B) (hereinafter also referred to as lactone (1B)) include propiolactone, butyrolactone, valerolactone, caprolactone, laurolactone, and the like, but preferably caprolactone Is used.
In addition, only 1 type may be used for lactone (1B), multiple types may be used together, and the hydroxycarboxylic acid which is a hydrolyzate of lactone can also be used. The lactone (1B) may contain a small amount of a branched structure, a cyclic structure and an unsaturated bond to such an extent that the functions and properties of the target polyurethane (meth) acrylate are not impaired.

(Polycarbonate polyol)
More specifically, the polycarbonate polyol is a polyol represented by the formula (1A) and a lactone-derived structure represented by the formula (1B) and a polycarbonate polyol having a carbonate bond. For example, the polyol (1A), It can be obtained by reacting lactone (1B) with a carbonate ester in the presence of a catalyst.
It can also be obtained by further reacting a lactone with a polycarbonate polyol obtained by reacting the polyol (1A) with a carbonate ester in the presence of a catalyst.
A plurality of types of polycarbonate polyols having the same or different molecular weights may be used in combination so as not to impair the functions and properties of the target polyurethane (meth) acrylate.

(Carbonate ester)
Examples of the carbonate ester include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate; diaryl carbonates such as diphenyl carbonate; and cyclic carbonates such as ethylene carbonate and propylene carbonate. Carbonate and ethylene carbonate are used.
A plurality of these carbonate esters may be used in combination.

The amount of the carbonate ester to be used is preferably 0.8 to 2.0 mol, more preferably 0.9 to 1. mol per mol of the total polyol (total amount of polyol (1A) and lactone (1B)). 5 moles.
By setting the amount of carbonate used within this range, the desired polycarbonate polyol can be efficiently obtained at a sufficiently high reaction rate.

(Reaction temperature and reaction pressure)
The reaction temperature at the time of synthesizing the polycarbonate polyol can be appropriately adjusted according to the kind of the polyol (1A), lactone (1B) or carbonate, but is preferably 120 to 180 ° C, more preferably 130 to 170 ° C. It is.

The reaction pressure when synthesizing the polycarbonate polyol is not particularly limited as long as it is a pressure that allows the reaction while removing the low-boiling components, and the polycarbonate polyol is preferably synthesized under normal pressure or reduced pressure. Is called.
By setting the reaction pressure when synthesizing the polycarbonate polyol within this range, it is possible to suppress the occurrence of sequential reactions and side reactions, and to efficiently obtain the target polycarbonate polyol.

(Catalyst used when synthesizing polycarbonate polyol)
As a catalyst used when synthesizing a polycarbonate polyol, a known transesterification catalyst can be used. For example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium And metals such as zirconium, cobalt, germanium, tin and cerium, and their hydroxides, alkoxides, carboxylates, carbonates, bicarbonates, sulfates, phosphates, nitrates, and organic metals. , Preferably sodium hydride, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, dibutyltin dilaurate, dibutyltin dimethoxide, dibutyl Dibutyltin oxide is used.
A plurality of these catalysts may be used in combination.

The amount of the catalyst used is preferably 0.1 to 100 mmol, more preferably 0.5 to 50 mmol, more preferably 1 to 20 mmol with respect to the total amount of polyol (1A) and lactone (1B). is there.
By making the usage-amount of a catalyst into this range, it can suppress that the post-process after the reaction which synthesize | combines a polycarbonate polyol becomes complicated, and can obtain the target polycarbonate polyol efficiently.
The catalyst may be used (added) in a lump at the start of the reaction, or may be used (added) separately at the start of the reaction and after the start of the reaction.

In the polycarbonate polyol, the molar ratio of the structure derived from the polyol represented by the formula (1A) and the structure derived from the lactone represented by the formula (1B) (formula (1A) / formula (1B)) is preferably 10 / 90 to 90/10, more preferably 15/85 to 85/15, and more preferably 20/80 to 80/20.
By setting the formula (1A) / formula (1B) within this range, a polyurethane (meth) acrylate having a high hardness can be obtained.

The total amount of the structure derived from the polyol represented by the formula (1A) and the structure derived from the lactone represented by the formula (1B) is preferably 95 mol% or more, more preferably 98 mol based on the polycarbonate polyol. It is at least mol%, more preferably at least 99%.
By making the total amount of the structure derived from the polyol represented by the formula (1A) and the structure derived from the lactone represented by the formula (1B) with respect to the polycarbonate polyol within this range, good compatibility and good contamination resistance A polyurethane (meth) acrylate having properties can be obtained.

  As such a polycarbonate polyol, for example, a polycarbonate polyol obtained by using 1,6-hexanediol and caprolactone as raw materials (ETERNACOLL (registered trademark) UHC, manufactured by Ube Industries, Ltd.) can be preferably used.

[Structure derived from polyisocyanate]
The structure derived from polyisocyanate refers to a group derived from polyisocyanate other than a bonding group in polyurethane (meth) acrylate. The “polyisocyanate” in the structure derived from the polyisocyanate is specifically a polyisocyanate represented by the following formula (2).

  (In the formula (2), R is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and 6 carbon atoms. Represents a divalent cycloaliphatic hydrocarbon group having 18 to 18 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.)

  The “divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms” is a group obtained by removing two hydrogens from the “linear aliphatic hydrocarbon group having 2 to 12 carbon atoms”. Show. Examples of the divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms include ethylene group, trimethylene group (propylene group), tetramethylene group (butylene group), pentamethylene group, hexamethylene group, hepta. A methylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group and the like can be mentioned, and a tetramethylene group, a pentamethylene group and a hexamethylene group are preferred.

  The “divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms” refers to a group obtained by removing two hydrogen atoms from the “branched aliphatic hydrocarbon group having 3 to 12 carbon atoms”. Examples of the divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms include 2- or 3-methyl-1,5-pentyl group, 2,2,4- or 2,4,4-trimethyl. Examples include a hexamethylene group.

  The “divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms” refers to a group obtained by removing two hydrogens from the “cycloaliphatic hydrocarbon having 6 to 18 carbon atoms”. Examples of the divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms include 1,4-cyclohexylene group, methylcyclohexylene group, 1,3-dimethylenecyclohexylene group, 5- (1,3 , 3, -trimethylcyclohexyl) -1-methylene group (group derived from isophorone diisocyanate), 4,4'-dicyclohexylenemethylene group (group derived from 4,4'-dicyclohexylmethane diisocyanate), norbornylene group and the like. .

  The “divalent aromatic hydrocarbon group having 6 to 18 carbon atoms” refers to a group obtained by removing two hydrogen atoms from the “aromatic hydrocarbon having 6 to 18 carbon atoms”. Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms include phenylene group, tolylene group, xylylene group, tetramethylxylylene group, 4,4'-diphenylenemethylene group and the like.

(Polyisocyanate)
The polyisocyanate can be appropriately selected according to the purpose and application.
Linear aliphatic diisocyanates such as hexamethylene diisocyanate;
Branched aliphatic diisocyanates such as 2- or 3-methyl-1,5-pentyl diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate;
Cyclic aliphatic diisocyanates such as 1,4-cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, 4,4′-methylenebiscyclohexyl diisocyanate, isophorone diisocyanate, cyclohexane-1,3-diylbis (methylene) diisocyanate, norbornyl diisocyanate;
Phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate Araliphatic diisocyanates such as polymethylene polyphenyl isocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate (XDI);
Etc. are used.
A plurality of these polyisocyanates may be used in combination, and part or all of the structure thereof may be derivatized such as isocyanurate, carbodiimidization, or biuretization.

[Structure derived from hydroxyl-containing polyfunctional (meth) acrylate]
The structure derived from a hydroxyl group-containing polyfunctional (meth) acrylate refers to a structure derived from a hydroxyl group-containing polyfunctional (meth) acrylate other than the bonding group in the polyurethane (meth) acrylate. The “hydroxyl group-containing polyfunctional (meth) acrylate” in the structure derived from the hydroxyl group-containing polyfunctional (meth) acrylate specifically includes the following formulas (a-1), (a-2), and (b-1). , (B-2) is a hydroxyl group-containing polyfunctional (meth) acrylate.
In addition, in this invention, what modified | denatured hydroxyl group containing polyfunctional (meth) acrylate with alkyleneoxy groups, such as "ethyleneoxy group" and "propyleneoxy group", is included.

（式（ａ−１）、（ａ−２）、（ｂ−１）、（ｂ−２）において、Ａは（メタ）アクリロイル基を示す。なお、複数のＡの一部のＡが水素となっていても良い。）

(In the formulas (a-1), (a-2), (b-1), and (b-2), A represents a (meth) acryloyl group. It may be.)

(Hydroxyl-containing polyfunctional (meth) acrylate)
Examples of the hydroxyl group-containing polyfunctional (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol. Tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane di (meth) acrylate Or these ethyleneoxy modified products, propyleneoxy modified products, lactone modified products,
Preferably, pentaerythritol tri (meth) acrylate, dipetaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate are mentioned,
More preferably, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Toa Gosei Co., Ltd., Aronix (registered trademark) M306, tri-isomer; 65 to 70%), dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, (Toa Gosei Co., Ltd., Aronix (registered trademark) M403, pentamer; 50 to 60%) is used.
A plurality of these hydroxyl group-containing polyfunctional (meth) acrylates may be used in combination, or a saturated polyfunctional (meth) acrylate containing no hydroxyl group may be used in combination.

  The polyurethane (meth) acrylate of the present invention may further include a structure derived from a hydroxyl group-containing monofunctional (meth) acrylate represented by the following formula (c) at the terminal.

（式中、Ａは（メタ）アクリロイル基を示し、ｍは２〜８の整数を示す。）

(In the formula, A represents a (meth) acryloyl group, and m represents an integer of 2 to 8.)

  In the polyurethane (meth) acrylate of the present invention, the proportion of the structure derived from the hydroxyl group-containing monofunctional (meth) acrylate represented by the formula (c) is 10% by mass or less with respect to the total amount of the terminal (meth) acrylic group. It is preferable. By making the ratio of the structure derived from a hydroxyl group-containing monofunctional (meth) acrylate within this range, the effect of developing the structure derived from a hydroxyl group-containing polyfunctional acrylic group is not impaired.

(Manufacture of polyurethane (meth) acrylate)
The polyurethane (meth) acrylate of the present invention can be obtained by reacting a polycarbonate polyol, polyisocyanate, and a hydroxyl group-containing polyfunctional (meth) acrylate (hereinafter also referred to as “reaction of the present invention”). is there).

  The reaction form of the reaction of the present invention is not particularly limited. As the reaction method of the present invention, a known one-shot method or prepolymer method can be appropriately selected. After producing a polyurethane by reacting a polycarbonate polyol and a polyisocyanate, a hydroxyl group-containing polyfunctional (meth) acrylate is reacted. The method is preferably employed.

  In addition, in order to improve the function and characteristics of the target polyurethane (meth) acrylate, a plurality of types of polycarbonate polyols or polycarbonate polyols having the same molecular weight but different molecular weights may be used in combination. Further, for the same reason, plural kinds of polyisocyanates may be used in combination, or plural kinds of hydroxyl group-containing polyfunctional (meth) acrylates may be used in combination.

In the reaction of the present invention, the total hydroxyl amount (OH group) of the hydroxyl group of the polycarbonate polyol and the hydroxyl group of the hydroxyl group-containing (meth) acrylate and the molar ratio of the isocyanate group (NCO group) of the polyisocyanate (OH group / NCO group) is: Preferably it is 0.8 / 1-1.4 / 1, More preferably, it is 0.9 / 1-1.3 / 1, More preferably, it is 1/1-1.2 / 1.
By setting the OH group / NCO group within this range, the terminal isocyanate group of the polyurethane is substantially converted into a terminal group having a plurality of (meth) acryloyl groups, and the remaining unreacted isocyanate groups can be reduced. .

  Even if an isocyanate group remains at the end of the polyurethane (meth) acrylate, it may be left as it is as long as it does not inhibit the subsequent conversion to a cured product. However, when cured, the cured product itself is affected. In such a case, for example, a hydroxyl group-containing monofunctional (meth) acrylate represented by the following formula (c) is reacted to form a hydroxyl group-containing monofunctional (meth) acrylate-derived structure at the end, thereby increasing the curing activity. It can also be granted.

（式（ｃ）中、Ａは（メタ）アクリロイル基を示し、ｍは２〜８の整数を示す。）

(In the formula (c), A represents a (meth) acryloyl group, and m represents an integer of 2 to 8.)

(Hydroxyl-containing monofunctional (meth) acrylate)
Examples of the hydroxyl group-containing monofunctional (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxy ( Although heptyl) methacrylate, hydroxyoctyl (meth) acrylate, and the like can be mentioned, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate are preferably used.
A plurality of these hydroxyl group-containing monofunctional (meth) acrylates may be used in combination, or a plurality of hydroxyl group-containing monofunctional (meth) acrylates may be used in combination. Moreover, you may use together the saturated monofunctional (meth) acrylate which does not contain a hydroxyl group.

(Catalyst that can be used in the reaction of the present invention)
In the reaction of the present invention, a known polymerization catalyst can be used to improve the reaction rate. For example, organic tin compounds such as dibutyltin diacetate and dibutyltin dilaurate, titanium tetraacetylacetonate, titanium diisopropoxybis Organic titanium compounds such as (ethyl acetoacetate), organic zirconium compounds such as zirconium tetraacetylacetonate and zirconium dibutoxybis (ethylacetoacetate), bismuth 2-ethylhexanoate, bismuth neodecanoate, bismuth naphthenate, dibutyl phosphate Bismuth and tertiary amines such as triethylamine are preferably used.
As for the catalyst, pages 23 to 32 of Keiji Yoshida “Polyurethane resin” (published by Nihon Kogyo Shimbun, 1969) may be used, and a plurality of types of catalysts may be used in combination.

The amount of the catalyst used is preferably 0.0005 to 0.1% by mass, more preferably 0.001 based on the total amount of the polycarbonate polyol, polyisocyanate, and hydroxyl group-containing polyfunctional / monofunctional (meth) acrylate. It is -0.05 mass%.
By setting the amount of the catalyst used within this range, a sufficient reaction rate can be obtained, and the post-treatment is not complicated because the remaining amount of the catalyst is small.

(solvent)
In the reaction of the present invention, a solvent that does not participate in the reaction can be appropriately used. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Esters such as monoethyl ether acetate and dipropylene glycol monomethyl ether acetate; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofuran, dioxane Ethers such as benzene, toluene, xylene, Aromatic hydrocarbons such as tetramethyl benzene; dimethylformamide, diethylformamide, amides such as dimethylacetamide; sulfoxides such as dimethyl sulfoxide can be used.
A plurality of these solvents may be used in combination. Moreover, the solution of a polyurethane (meth) acrylate can be obtained by using a solvent.

The amount of the solvent used is preferably 5 to 200% by mass, more preferably 10 to 100% by mass, based on the total amount of the polycarbonate polyol, polyisocyanate, and hydroxyl group-containing polyfunctional / monofunctional (meth) acrylate. Preferably it is 20-80 mass%.
By making the usage-amount of a solvent into this range, the uniformity and stirring property of a reaction liquid improve.

(Polymerization inhibitor)
In the reaction of the present invention, in order to suppress polymerization and oxidation of the raw material hydroxyl group-containing polyfunctional / monofunctional (meth) acrylate and the generated polyurethane (meth) acrylate, a polymerization inhibitor and an antioxidant should be present. Is desirable. Examples of the polymerization inhibitor and the antioxidant include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-t-butyl-p-cresol, p-benzoquinone, 2,5 -Dihydroxy-p-benzoquinone and the like are used.
A plurality of these polymerization inhibitors and antioxidants may be used in combination.

The addition amount of the polymerization inhibitor and the antioxidant is preferably 0.00005 to 0.01% by mass with respect to the total amount of the polycarbonate polyol, polyisocyanate, and hydroxyl group-containing polyfunctional / monofunctional (meth) acrylate. More preferably, it is 0.0001-0.005 mass%, More preferably, it is 0.0003-0.003 mass%.
By setting the addition amount of the polymerization inhibitor and the antioxidant within this range, the polymerization and oxidation can be sufficiently suppressed, and the post-treatment of the reaction of the present invention is not complicated.

(Chain extender)
In the reaction of the present invention, a chain extender can be used for the purpose of increasing the molecular weight. The chain extender to be used can be appropriately selected according to the purpose and use, for example,
water;
Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl Low molecular polyols such as propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane;
Polymer polyols such as polyester polyols, polyester amide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols;
Polyamines such as ethylenediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine are used.
As for the chain extender, for example, “Latest Polyurethane Application Technology” (CMC Co., Ltd., issued in 1985) can be referred to. For the polymer polyol, for example, “Polyurethane Form” (polymer) Publication Society, 1987), and a plurality of chain extenders may be used in combination.

  In the reaction of the present invention, polycarbonate polyol, polyisocyanate, catalyst, and solvent are mixed, and preferably reacted at 0 to 150 ° C., more preferably at 20 to 100 ° C., and then polymerization is prohibited in the obtained reaction solution. An agent, an antioxidant, and a hydroxyl group-containing (meth) acrylate are added, and the reaction is preferably performed at the same temperature.

  Since the obtained polyurethane (meth) acrylate is not necessarily stable to light and atmospheric oxygen, it is desirable to use it as a solvent solution for polyurethane (meth) acrylate without requiring isolation or purification. .

  Since the polyurethane (meth) acrylate of the present invention has a polycarbonate skeleton, it has excellent mechanical properties, hydrolysis resistance, heat resistance, chemical resistance, weather resistance, etc., but a linear aliphatic hydrocarbon group in the structure. Since it has a (polyol (1A) -derived group), a linear aliphatic hydrocarbon group, and an ester group (group derived from a lactone (1B)), the cured product of the polyurethane (meth) acrylate of the present invention has a good phase. It has solubility and good stain resistance.

  Moreover, when the polyurethane (meth) acrylate of the present invention has a (meth) acrylic group (a hydroxyl group-containing polyfunctional / monofunctional (meth) acrylate-derived group) at the terminal, the crosslinking density is further improved upon curing and higher. A cured product having a hardness and a higher elastic modulus can be obtained.

  In the polyurethane (meth) acrylate of the present invention, the proportion of the aliphatic ring derived from the polycarbonate polyol or polyisocyanate is preferably 10 to 34% by mass, more preferably 11 to 30% by mass, more preferably 12 to 25% by mass. It is. By setting it as this range, it has further better compatibility and good stain resistance.

(Other polyols)
The polyurethane (meth) acrylate of the present invention can also be produced in the presence of other polyols as appropriate in order to further improve the function. In other words, the polyurethane (meth) acrylate of the present invention may further contain a structure derived from other polyols.
Examples of other polyols include linear polyols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, and dodecanediol;
Branched polyols such as 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,5-hexanediol;
Cyclic polyols such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol;
Polycarbonate polyols obtained using the above polyol as a raw material (however, excluding the polycarbonate polyol having a structure derived from the polyol represented by the formula (1A) and a structure derived from the lactone represented by the formula (1B)) are preferable, Is a polyol (lactone of formula (1A) or formula (1B)) used as a raw material when producing a polycarbonate polyol constituting polyurethane (meth) acrylate.
A plurality of these other polyols may be used in combination.

  Moreover, these low molecular polyols may have an acidic group such as a carboxyl group, a thiocarboxyl group, a sulfone group, and a phenolic hydroxyl group as long as the functions and characteristics of the polyurethane (meth) acrylate are not impaired. Examples of the acidic group include 2,2-dimethylolpropionic acid that is generally used when an aqueous polyurethane resin dispersion is produced.

(Acid group-containing compound)
The polyurethane (meth) acrylate of the present invention may further contain an acidic group-containing compound as appropriate in order to further improve its function.

  Examples of the acidic group of the acidic group-containing compound include a carboxyl group, a thiocarboxyl group, a sulfone group, and a phenolic hydroxyl group.

Examples of the acidic group-containing compound include organic carboxylic acids such as propionic acid, butanoic acid, pentanoic acid, hexanoic acid, oxalic acid, succinic acid, adipic acid, benzoic acid, phthalic acid, and terephthalic acid; Thiocarboxylic acids in which part or all of the carbon is replaced with sulfur; sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; phenols such as phenol, cresol, catechol, and hydroquinone It is done.
A plurality of these acidic group-containing compounds may be used in combination.

[Composition]
The composition of this invention may contain the said polyurethane (meth) acrylate, the polymerization initiator, and the polymeric compound as needed.

(Polymerization initiator)
Examples of the polymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, 4,4′-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-hydroxycyclohexyl phenyl ketone 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpro -1-one, 2,4,6, -trimethylbenzophenone, 4-methylbenzophenone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethane Examples thereof include 1-hydroxycyclohexyl phenyl ketone and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
A plurality of these polymerization initiators may be used in combination.

The amount of the polymerization initiator used is preferably 0.3 to 10% by mass, more preferably 0.5 to 5% by mass, based on the polyurethane (meth) acrylate.
By setting the amount of the polymerization initiator used within this range, a sufficient reaction rate can be obtained, and the residual amount of the polymerization initiator is small, so that the post-treatment is not complicated.

(Polymerizable compound)
Examples of the polymerizable compound include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, and lauryl. Alkyl (meth) acrylates such as (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, phenoxymethyl (meth) acrylate, and phenoxyethyl (meth) acrylate (Meth) acrylic acid aralkyl esters such as esters, benzyl (meth) acrylate, and phenethyl (meth) acrylate And Le, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, monofunctional (meth) acrylates such as 4-hydroxybutyl (meth) acrylate;
Butanediol di (meth) acrylate, hexanediol di (meth) acrylate, octanediol di (meth) acrylate, nonanediol di (meth) acrylate, dodecanediol di (meth) acrylate, ethoxylated 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) acrylate, ethoxylated neopentyl glycol di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylo Tri (meth) acrylates such as lepropane tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) Acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acryl Polyfunctional (meth) acrylates such as over bets or or thereof, these ethyleneoxy-modified products and propyleneoxy modified products, lactone-modified products can be used.
A plurality of these polymerizable compounds may be used in combination.

  When producing a polyurethane (meth) acrylate, if an excessive amount of hydroxyl group-containing polyfunctional / monofunctional (meth) acrylate is used, the remaining hydroxyl group-containing polyfunctional / monofunctional (meth) acrylate is substituted for the polymerizable compound. You can also

  Moreover, when manufacturing a polyurethane (meth) acrylate, when other acrylic compounds are contained in the hydroxyl group-containing polyfunctional / monofunctional (meth) acrylate, it may be substituted as a polymerizable compound. it can.

  The amount of the polymerizable compound used is preferably equal to or less than that of urethane (meth) acrylate.

[Hardened product]
The composition of the present invention is adjusted to an appropriate viscosity by adding an organic solvent to the polyurethane (meth) acrylate or the polyurethane (meth) acrylate composition as necessary, and then applied onto a substrate, for example, By irradiating active energy rays such as ultraviolet rays, visible light, laser light, electron beams, X-rays, γ rays, plasma, and microwaves, they can be polymerized and cured to be cured.
In addition, a hardened | cured material can also be manufactured with a heat | fever, without irradiating an active energy ray, and you may use a heat | fever and an active energy ray together.

The organic solvent may be the same as the organic solvent used in the production of polyurethane (meth) acrylate, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate , Esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, Ethers such as triethylene glycol diethyl ether, tetrahydrofuran and dioxane ; Benzene, toluene, xylene, aromatic hydrocarbons such as tetramethyl benzene; dimethylformamide, diethylformamide, amides such as dimethylacetamide; sulfoxides such as dimethyl sulfoxide can be used.
A plurality of these solvents may be used in combination.

Examples of the base material that can be used include metals, plastics, inorganic materials, wood, ABS resin, polycarbonate resin, polyimide resin, polyamide resin, and polyester resin.
A plurality of these substrates may be used in combination.

  Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.

[Measurement and evaluation methods]
(viscosity)
The viscosity of the polyurethane (meth) acrylate was measured at 25 ° C. using an E-type viscometer (“BROOLFIELD viscometer LV DV-II + Pro” manufactured by BROOKFIELD).

(Average molecular weight)
The average molecular weight of the polyurethane (meth) acrylate was measured using gel permeation chromatography (GPC). The measurement conditions are as follows.
Apparatus: HPLC-8220 (manufactured by Tosoh Corporation)
Column configuration: TSKgel SuperHZ3000 + TSKgel SuperH
Z1000 (both manufactured by Tosoh Corporation)
Detector: Differential refractive index detector (RI detector)
Eluent: Tetrahydrofuran Eluent flow rate: 0.6 ml / min
Temperature: 40 ° C
Temperature increase rate: Constant temperature without temperature increase Calibration: Polystyrene conversion Sample concentration: 0.01 g / 5 mL

(Pencil hardness)
The cured product was measured by a method according to JIS K 5600-5-4. It was scratched with a load of 750 g and the hardness of the hardest pencil without any scratches.

(Elastic modulus)
The elastic modulus of the cured product was measured by a method based on JIS K 7311. The measurement conditions are a measurement temperature of 23 ° C., a humidity of 50%, and a tensile speed of 100 mm / min.

(Adhesion)
The adhesiveness of the cured product was determined in accordance with JIS K 5600-5-6: 1999 “Cross Cut Method”. After applying polyurethane (meth) acrylate to various resin panels (propylene carbonate (PC) panel or acrylonitrile, butadiene, styrene copolymer synthetic resin (ABS) panel), cuts are made at intervals of 2 mm to form 100 square grids. Then, the process of pressure-bonding the adhesive tape to the grid area and peeling it off was repeated 10 times. Evaluation criteria were also evaluated according to the same standard.
◎: When the mass that did not peel is 100 squares ○: When the mass that did not peel is 80 or more and 99 or less ×;

(Compatibility)
Compatibility is 1% by weight of UV absorber (TINUBIN (registered trademark) 479, manufactured by BASF Corp.) with respect to the organic solvent solution of polyurethane acrylate, and after sufficiently stirring, the state of the solution is visually confirmed. And evaluated according to the following criteria.
A: The solution is not turbid and the UV absorber is completely dissolved.
○: There is almost no turbidity in the solution.
Δ: The solution is slightly turbid.
X: The solution is turbid and the UV absorber is not dissolved.
That is, in the present invention, “compatible” means compatible with an ultraviolet absorber.

(Contamination resistance)
Contamination resistance was obtained by applying polyurethane (meth) acrylate to a polycarbonate substrate and then painting the coated film with a bold type oil marker (magic ink) so that the area becomes 1 cm ² or more. After standing for 1 minute, the ink was lifted with isopropyl alcohol, gently wiped with paper, and the color change before and after the test was visually evaluated according to the following criteria.
A: There is no ink residue and the coating film is transparent.
○: Little ink remains and the coating film becomes slightly black. Δ: A little ink remains and the coating film becomes slightly black.
X: Ink remains and the coating film becomes black.

Example 1 (Synthesis of polyurethane acrylate)
In a container having a volume of 1 L equipped with a stirrer, a thermometer and a cooler, 70 g (0.14 mol) of polycarbonate polyol (UTE Kosan Co., Ltd., ETERNCOLL (registered trademark) UHC50-50), polycarbonate polyol (Ube Industries, Ltd.) ETERNACOLL (registered trademark) UHC50-100) (140 g, 0.14 mol) and butyl acetate (400 g) were added, and the liquid temperature was adjusted to 50 ° C., followed by dibutyltin (IV) dilaurate (0.36 g) and isophorone diisocyanate (93 g (0.42 mol)). And the reaction was conducted at 80 to 83 ° C. for 3 hours with stirring.
Subsequently, 0.20 g of p-methoxyphenol, 0.20 g of 2,6-t-butyl-p-cresol, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Toa Gosei Co., Ltd., Aronix (registered trademark) M306, Tri-isomer: 65-70%) 92.7 g (0.26 mol) and 4-hydroxyethyl acrylate 3.41 g (0.03 mol) were added and further reacted at the same temperature, after confirming the disappearance of the isocyanate group Upon cooling, a butyl acetate solution of polyurethane acrylate was obtained.
The viscosity of the resulting butyl acetate solution of polyurethane acrylate was 230 cP / 25 ° C.

Example 2 (Synthesis of polyurethane acrylate)
To a container having an internal volume of 1 L equipped with a stirrer, a thermometer and a cooler, 300 g (0.15 mol) of polycarbonate polyol (manufactured by Ube Industries, ETERNACOLL (registered trademark) UHC50-200) and 381 g of butyl acetate are added, After the liquid temperature was adjusted to 50 ° C., 0.26 g of dibutyltin (IV) dilaurate and 44 g (0.20 mol) of isophorone diisocyanate were added, and the reaction was performed at 78 to 81 ° C. for 3 hours with stirring.
Subsequently, 0.19 g of p-methoxyphenol, 0.19 g of 2,6-t-butyl-p-cresol, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Toa Gosei Co., Ltd., Aronix®) M403, pentamer; 50-60%) 29.5 g (0.05 mol) and 4-hydroxybutyl acrylate 7.4 g (0.05 mol) were added, and further reacted at the same temperature, and the isocyanate group disappeared. It cooled after confirmation and the butyl acetate solution of the polyurethane acrylate was obtained.
The viscosity of the resulting butyl acetate solution of polyurethane acrylate was 6900 cP / 25 ° C.

Example 3 (Synthesis of polyurethane acrylate)
In a container having a volume of 1 L equipped with a stirrer, a thermometer and a cooler, 70 g (0.14 mol) of polycarbonate polyol (UTE Kosan Co., Ltd., ETERNCOLL (registered trademark) UHC50-50), polycarbonate polyol (Ube Industries, Ltd.) Manufactured by ETERNACOLL (registered trademark) UHC50-100) (140 g, 0.14 mol) and butyl acetate (336 g) were added, and the liquid temperature was adjusted to 50 ° C., followed by dibutyltin (IV) dilaurate 0.17 g and isophorone diisocyanate 78 g (0.35 mol). The reaction was carried out at 80 to 83 ° C. for 3 hours with stirring.
Subsequently, 0.17 g of p-methoxyphenol, 0.17 g of 2,6-t-butyl-p-cresol, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Toa Gosei Co., Ltd., Aronix (registered trademark) M306, Tri-isomer: 65-70%) 46.4 g (0.13 mol) and 4-hydroxyethyl acrylate 1.7 g (0.01 mol) were added, and further reacted at the same temperature, after confirming the disappearance of the isocyanate group Upon cooling, a butyl acetate solution of polyurethane acrylate was obtained.
The viscosity of the resulting butyl acetate solution of polyurethane acrylate was 1300 cP / 25 ° C.

Example 4 (Synthesis of polyurethane acrylate)
150 g (0.15 mol) of polycarbonate polyol (ETERNACOLL (registered trademark) UHC50-100, manufactured by Ube Industries, Ltd.) and 391 g of butyl acetate are added to a 1 L internal volume container equipped with a stirrer, a thermometer and a condenser. After the liquid temperature was adjusted to 50 ° C., 0.23 g of dibutyltin (IV) dilaurate and 67 g (0.30 mol) of isophorone diisocyanate were added, and the reaction was performed at 78 to 81 ° C. for 3 hours with stirring.
Next, 0.20 g of p-methoxyphenol, 0.20 g of 2,6-t-butyl-p-cresol, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Toa Gosei Co., Ltd., Aronix®) M403, pentamer; 50 to 60%) 172 g (0.30 mol) and 4-hydroxybutyl acrylate 1.3 g (0.01 mol) were added and further reacted at the same temperature, after confirming the disappearance of the isocyanate group Upon cooling, a butyl acetate solution of polyurethane acrylate was obtained.
The viscosity of the resulting butyl acetate solution of polyurethane acrylate was 80 cP / 25 ° C.

Example 5 (Synthesis of polyurethane acrylate)
To a 1 L internal vessel equipped with a stirrer, a thermometer and a cooler, 200 g (0.20 mol) of polycarbonate polyol (ETERNACOLL (registered trademark) UHC50-100, manufactured by Ube Industries, Ltd.) and 384 g of methyl ethyl ketone were added. After the temperature was raised to 50 ° C., 0.23 g of dibutyltin (IV) dilaurate and 58 g (0.30 mol) of cyclohexane-1,3-diylbis (methylene) diisocyanate were added, and the reaction was carried out at 78 to 81 ° C. for 3 hours with stirring. It was.
Subsequently, 0.19 g of p-methoxyphenol, 0.19 g of 2,6-t-butyl-p-cresol, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Toa Gosei Co., Ltd., Aronix®) M403, pentamer; 50-60%) 115 g (0.20 mol) and 4-hydroxyethyl acrylate 0.7 g (0.01 mol) were added, and further reacted at the same temperature, after confirming the disappearance of the isocyanate group It cooled and the methyl ethyl ketone solution of the polyurethane acrylate was obtained.
The viscosity of the resulting methyl acrylate solution of polyurethane acrylate was 150 cP / 25 ° C.

Comparative Example 1 (Synthesis of polyurethane acrylate)
To a container having a volume of 1 L equipped with a stirrer, a thermometer, and a cooler, 150 g (0.15 mol) of polycarbonate polyol (manufactured by Ube Industries, ETERNACOLL (registered trademark) UH-100) and 390 g of methyl ethyl ketone were added, and the liquid temperature Was adjusted to 50 ° C., 0.1 g of dibutyltin (IV) dilaurate and 67 g (0.30 mol) of isophorone diisocyanate were added, and the reaction was performed at 75 to 85 ° C. for 3 hours with stirring.
Subsequently, 0.20 g of p-methoxyphenol, 0.20 g of 2,6-t-butyl-p-cresol, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Toa Gosei Co., Ltd., Aronix (registered trademark)) ) M403, pentamer; 50-60%) 173 g (0.30 mol) was added and further reacted at the same temperature. After confirming the disappearance of the isocyanate group, the mixture was cooled to obtain a methyl ethyl ketone solution of polyurethane acrylate.
The viscosity of the resulting methyl acrylate solution of polyurethane acrylate was 220 cP / 25 ° C.

(Production of composition and cured product)
0.5 g of 1-hydroxycyclohexyl phenyl ketone (Irgacure (registered trademark) 184, manufactured by BASF) is mixed with 20 g of a methyl ethyl ketone solution of polyurethane acrylate obtained in each Example and Comparative Example, and a curable resin composition is prepared. Manufactured.

The curable resin composition was applied to a polycarbonate resin base material or an ABS resin base material, dried at 80 ° C. for 30 minutes, and then irradiated with 1000 mJ / cm ² of ultraviolet rays to produce a cured product.

The above results are summarized in Table 1.
Abbreviations used in the table are as follows.
PCD UHC50-50; polycarbonate polyol obtained by using a mixture of 1,6-hexanediol and caprolactone as a raw material (Ube Industries, Ltd., ETERNACOLL (registered trademark) UHC50-50, molecular weight: 500)
PCD UHC50-100; polycarbonate polyol obtained by using a mixture of 1,6-hexanediol and caprolactone as a raw material (Ube Industries, Ltd., ETERNACOLL (registered trademark) UHC50-100, molecular weight: 1000)
PCD UHC50-200; polycarbonate polyol obtained by using a mixture of 1,6-hexanediol and caprolactone as a raw material (Ube Industries, Ltd., ETERNACOLL (registered trademark) UHC50-200, molecular weight: 2000)
PCD UH-100: Polycarbonate polyol obtained using 1,6-hexanediol as a raw material (Ube Industries, Ltd., ETERRNACOLL (registered trademark) UH-100, molecular weight: 1000)
IPDI; isophorone diisocyanate H6XDI; cyclohexane-1,3-diylbis (methylene) diisocyanate PETA M-306; a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Toa Gosei Co., Ltd., Aronix (registered trademark) M306, tribody; 65-70%)
DPHA M-403; a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Toa Gosei Co., Ltd., Aronix (registered trademark) M403, pentamer; 50-60%)
HEA; 4-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.)
HBA; 4-hydroxybutyl acrylate (manufactured by Nippon Shokubai Co., Ltd.)

From the above results, it was produced from the polyurethane acrylate obtained in the comparative example that the cured product produced from the polyurethane acrylate obtained in the examples was excellent in each of the properties of good compatibility and good stain resistance. It became clear in comparison with the cured product.
Therefore, the polyurethane (meth) acrylate of the present invention and the composition thereof are required to have, for example, coating applications (coating materials) such as inks, paints, adhesives, and adhesives, and high appearance and durability. It can be suitably used for various mobile devices, films, architectural interiors and exteriors, automotive interiors and exteriors (lamination materials), and molding applications such as UV-cured lenses (molding materials).

  The present invention relates to a novel polyurethane (meth) acrylate having a structure derived from a polycarbonate polyol, a composition thereof, and a cured product. Polyurethane (meth) acrylate is a useful compound as a main component of various types of coating agents that are cured with active energy rays.

Claims (10)

A polyurethane (meth) acrylate having a structure derived from a polycarbonate polyol and a structure derived from a polyisocyanate, and having a structure derived from a hydroxyl group-containing (meth) acrylate at the end,
The polycarbonate polyol has a structure derived from a polyol represented by the following formula (1A) and a structure derived from a lactone represented by the following formula (1B).
The polyisocyanate is represented by the following formula (2),
The hydroxyl group-containing polyfunctional (meth) acrylate is represented by the following formulas (a-1) to (b-2).
Polyurethane (meth) acrylate.

(In the formula (1A), Z ¹ represents a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms.
In the formula (1B), Z ² represents a divalent linear aliphatic hydrocarbon group having 1 to 8 carbon atoms.
In the formula (2), R is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and 6 to 6 carbon atoms. 18 is a divalent cyclic aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
In formulas (a-1) to (b-2), A represents a (meth) acryloyl group. A part of the plurality of A may be hydrogen. ) The polyurethane (meth) acrylate according to claim 1, further comprising a structure derived from a hydroxyl group-containing monofunctional (meth) acrylate represented by the following formula (c) at the end.

(In the formula (c), A represents a (meth) acryloyl group, and m represents an integer of 2 to 8.)   The polyurethane (meth) acrylate according to claim 1 or 2, wherein the proportion of the structure derived from the hydroxyl group-containing monofunctional (meth) acrylate represented by the formula (c) is 10% by mass or less with respect to the total amount of terminal acrylic groups. .   Hardened | cured material obtained by hardening | curing the polyurethane (meth) acrylate of Claims 1-3.   The composition containing the polyurethane (meth) acrylate of any one of Claims 1-3.   A cured product obtained by curing the composition according to claim 5.   The composition of claim 6 further comprising a polymerizable compound.   A cured product obtained by curing the composition according to claim 7.   The coating material, laminated material, or molding material containing the polyurethane (meth) acrylate of any one of Claims 1-3.   The coating material, laminated material, or molding material containing the composition containing the polyurethane (meth) acrylate of any one of Claims 1-3.