JP6932900B2 - Polyurethane (meth) acrylate and its composition, cured product - Google Patents

Description

The present invention relates to a novel polyurethane (meth) acrylate having a polycarbonate skeleton as a repeating unit, a composition thereof, and a cured product. Polyurethane (meth) acrylate is a compound useful as a main component of various coating agents of the type that are cured by active energy rays.

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

(1) 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 is disclosed (for example, a patent). Reference 1).
(2) A polyurethane acrylate obtained by reacting a 2-hydroxyethyl acrylate with a terminal of a polyurethane synthesized from a polycarbonate diol polyol made from 1,6-hexanediol and a hydrogenated xylylene diisocyanate is disclosed. (See, for example, Patent Document 2).
(3) 1,6-Hexanediol A polyurethane acrylate obtained by reacting a 2-hydroxyethyl acrylate with a hexamethylene diisocyanate allophanate adduct of a polycarbonate diol is disclosed (see, for example, Patent Document 3).

(4) Polycarbonate polyol made from 1,4-cyclohexanedimethanol, or a polyurethane terminal synthesized from a polycarbonate polyol made from 1,6-hexanediol and 1,4-cyclohexanedimethanol, and isophorone diisocyanate. Discloses a polyurethane acrylate obtained by reacting 2-hydroxyethyl acrylate (see, for example, Patent Document 4).

(5) Polycarbonate polyols made from 3-methyl-1,5-pentanediol and 1,6-hexanediol, polycarbonate polyols made from 1,5-pentanediol and 1,6-hexanediol, 2-methyl At the end of polyurethane synthesized from polycarbonate polyols made from -1,3-propanediol and 1,4-butanediol, or polycarbonate polyols made from 1,6-hexanediol, and various polyisocyanates, 2 Polyurethane acrylates obtained by reacting -hydroxyethyl acrylate are disclosed (see, for example, Patent Document 5).
(6) Disclosed is a polyurethane acrylate obtained by reacting a 2-hydroxyethyl acrylate with the terminal of a polyurethane synthesized from a polycarbonate polyol made from 1,6-hexanediol and neopentyl glycol as a raw material and isophorone diisocyanate. (See, for example, Patent Document 6).

(7) A polyurethane acrylate obtained by reacting an ethylene glycol monoacrylate with the terminal of a polyurethane synthesized from a polycarbonate polyol made from 1,6-hexanediol and ε-caprolactone and isophorone diisocyanate is disclosed. (See, for example, Patent Document 7).

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

Japanese Unexamined Patent Publication No. 2013-35920 Japanese Patent No. 4598122 Japanese Unexamined Patent Publication No. 2013-184988 JP-A-2009-227915 Japanese Unexamined Patent Publication No. 2012-36290 Japanese Unexamined Patent Publication No. 2010-215585 Japanese Unexamined Patent Publication No. 2012-184385 Japanese Patent No. 5544209

Polycarbonate polyols are superior to polyester polyols and polyether polyols in terms of mechanical properties, hydrolysis resistance, heat resistance, chemical resistance, weather resistance, etc., and therefore polyurethane (meth) obtained from this material. The acrylate and its cured product may have the same effect.

However, the urethane (meth) acrylate specifically shown in Examples in Patent Documents 1 to 8 is a combination of urethane obtained from several types of polycarbonate polyols and a hydroxyl group-containing monofunctional acrylate (2-hydroxyethyl acrylate). Only the synthesis and the function and characteristics of the obtained cured product have been evaluated.
That is, regarding the composition and combination of the repeating unit of the polycarbonate polyol and the terminal group of the polyurethane (meth) acrylate, the effective function is exhibited when the polyurethane (meth) acrylate is used as a cured product. It was not fully evaluated and examined.

Therefore, the raw material is a polycarbonate polyol having a specific repeating unit that satisfies the functions and properties required when the polyurethane (meth) acrylate is made into a cured product, that is, high flexibility and high scratch repair property. , Urethane (meth) acrylate having a specific terminal group has been sought.

An object of the present invention is to solve the above-mentioned problems and to provide a polyurethane (meth) acrylate having high flexibility and high scratch repair property, a composition thereof, and a cured product.

The subject of the present invention is a repeating unit represented by the following formula (1a), a repeating unit represented by the following formula (1b), a repeating unit represented by the following formula (2), and a polyfunctional (meth) acrylic at the end. Polyurethane (meth) acrylate having a group
The repeating unit of the formula (1a) includes the repeating unit represented by the following formulas (A-1) and (A-2).
The repeating unit of the above formula (1b) includes the repeating unit represented by the following formulas (B-1) and (B-2).
The polyfunctional (meth) acrylic group is at least one of the groups represented by the following formulas (a-1) to (b-2).
It is solved by polyurethane (meth) acrylate.

(During the ceremony,
Z ^a represents a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, and n ¹ is the number of repeating units of the formula (1a).
Here, Z ^a1 represents a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, and ^{Z a2} is a ^{divalent linear aliphatic hydrocarbon having 2 to 12 carbon atoms different from Z a1.} Indicates a hydrocarbon group.
Z ^b represents a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms or a divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms, and n ² is the formula (1b). Is the number of repeating units of.
Here, Z ^b1 represents a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, and Z ^b2 represents a divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms.
Further, 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 a divalent group having 6 to 18 carbon atoms. The cyclic aliphatic hydrocarbon group of the above, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms is shown. )

(In the formula, A represents a (meth) acryloyl group. A part of A of a plurality of A may be hydrogen.)

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an excellent polyurethane (meth) acrylate having high flexibility and high scratch repair property, a composition thereof, and a cured product.
Therefore, coating applications (coating materials) such as inks, paints, adhesives and adhesives, various mobile devices that require high appearance and high durability, films, building interior / exterior, automobile interior / exterior, etc. It can be applied to molding applications (molding materials) such as (laminated materials) and cured molded products such as ultraviolet curable lenses.

The present invention
A repeating unit represented by the following formula (1a), a repeating unit represented by the following formula (1b), a repeating unit represented by the following formula (2), and a polyurethane (meth) having a polyfunctional (meth) acrylic group at the end. ) Acryloyl
The repeating unit of the formula (1a) includes the repeating unit represented by the following formulas (A-1) and (A-2).
The repeating unit of the above formula (1b) includes the repeating unit represented by the following formulas (B-1) and (B-2).
The polyfunctional (meth) acrylic group is at least one of the groups represented by the following formulas (a-1) to (b-2).
It is a polyurethane (meth) acrylate.

(During the ceremony,
Z ^a represents a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, and n ¹ is the number of repeating units of the formula (1a).
Here, Z ^a1 represents a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, and ^{Z a2} is a ^{divalent linear aliphatic hydrocarbon having 2 to 12 carbon atoms different from Z a1.} Indicates a hydrocarbon group.
Z ^b represents a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms or a divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms, and n ² is the formula (1b). Is the number of repeating units of.
Here, Z ^b1 represents a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, and Z ^b2 represents a divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms.
Further, 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 a divalent group having 6 to 18 carbon atoms. The cyclic aliphatic hydrocarbon group of the above, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms is shown. )

(In the formula, A represents a (meth) acryloyl group. A part of A of a plurality of A may be hydrogen.)

The "polyurethane (meth) acrylate" is a general term for a polyurethane acrylate having an acrylic group at the end and a polyurethane methacrylate having a methacrylic group at the end.
Further, the "(meth) acryloyl group" is a functional group excluding the hydroxyl group of (meth) acrylic acid, and the "polyfunctional (meth) acrylic group" is an atomic group having a plurality of (meth) acryloyl groups. The "monofunctional (meth) acrylic group" refers to an atomic group having one (meth) acryloyl group. The meaning of "(meta)" is synonymous with that described in "polyurethane (meth) acrylate".

(Repeating unit represented by equation (1a))
The repeating unit represented by the formula (1a) is a component derived from one of the polycarbonate polyols used in synthesizing the polyurethane (meth) acrylate.
Wherein (1a), Z ^a represents a linear divalent 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". Shown, for example, ethylene group, trimethylene group (propylene group), tetramethylene group (butylene group), pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodeca. Examples thereof include a methylene group, but a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable.

Note that n ¹ is the number of repeating units of the formula (1a), which depends on the number average molecular weight of the polycarbonate polyol, but is preferably 1 to 40, more preferably 2 to 30, and even more preferably 3 to 25.

The repeating unit of the formula (1a) includes the repeating unit represented by the formula (A-1) and the formula (A-2). Here, the ratio of (A-1) and (A-2) in the formula (1) is preferably 95 mol% or more, more preferably 98 mol% or more, and more preferably 99% or more.
Within this range, a polyurethane (meth) acrylate having high flexibility and high scratch repair property can be obtained.

In the repeating unit represented by the formula (A-1), ^Za1 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 the same as that represented by the formula (1a).

In the repeating unit represented by the formula (A-2), Z ^a2 represents a "divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms" different from ^{Z a1.}
The "divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms" is the same as that represented by the formula (1a).

The ratio of the formula (A-1) to the formula (A-2) is preferably 10/90 to 90/10, more preferably 15/85 to 85 as the formula (A-1) / formula (A-2). / 15, more preferably 20/80 to 80/20.
Within this range, a polyurethane (meth) acrylate having high flexibility and high scratch repair property can be obtained.

(Repeating unit represented by equation (1b))
The repeating unit represented by the formula (1b) is a component derived from one of the polycarbonate polyols used in synthesizing the polyurethane (meth) acrylate.
In formula (1b), Z ^b represents a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms or a divalent cyclic aliphatic 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". Shown, for example, ethylene group, trimethylene group (propylene group), tetramethylene group (butylene group), pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodeca. Examples thereof include a methylene group, but a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable.

The "divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms" refers to a group obtained by removing two hydrogens from the "cyclic aliphatic hydrocarbon having 6 to 18 carbon atoms", for example, 1 , 3-Cyclohexylene group, 1,4-cyclohexylene group, 1,4-cyclohexanedimethylene group and the like, but 1,4-cyclohexanedimethylene group is preferable.

In addition, n ² is the number of repeating units of the formula (1b) and depends on the number average molecular weight of the polycarbonate polyol, but is preferably 1 to 40, more preferably 2 to 30, and more preferably 3 to 25.

The repeating unit of the formula (1b) includes the repeating unit represented by the formula (B-1) and the formula (B-2). Here, the ratio of (B-1) and (B-2) in the formula (1) is preferably 95 mol% or more, more preferably 98 mol% or more, and more preferably 99% or more.
Within this range, a polyurethane (meth) acrylate having high flexibility and high scratch repair property can be obtained.

In the repeating unit represented by the formula (B-1), Z ^b1 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 the same as that represented by the formula (1b).

In the repeating unit represented by the formula (B-2), Z ^b2 represents "a divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms".
The "divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms" is the same as that represented by the formula (1b).

The ratio of the formula (B-1) to the formula (B-2) is preferably 10/90 to 90/10, more preferably 15/85 to 85 as the formula (B-1) / formula (B-2). / 15, more preferably 20/80 to 80/20.
Within this range, a polyurethane (meth) acrylate having high flexibility and high scratch repair property can be obtained.

(Repeating unit represented by equation (2))
The repeating unit represented by the formula (2) is a component derived from polyisocyanate when synthesizing polyurethane (meth) acrylate.
In 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. It represents 18 divalent cyclic aliphatic hydrocarbon groups or divalent aromatic hydrocarbon groups having 6 to 18 carbon atoms.

The "divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms" includes, for example, an ethylene group, a trimethylene group (propylene group), a tetramethylene group (butylene group), a pentamethylene group, and a hexamethylene group. , Heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group and the like, but tetramethylene group, pentamethylene group and hexamethylene group are preferable.

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". For example, 2- or 3-methyl-1,5-pentyl group, 2,2,4- or 2,4,4-trimethylhexamethylene group and the like can be mentioned.

The "divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms" refers to a group obtained by removing two hydrogens from the "cyclic aliphatic hydrocarbon having 6 to 18 carbon atoms", for example, 1 , 4-cyclohexylene group, methylcyclohexylene group, 1,3-dimethylenecyclohexylene group, 5- (1,3,3,-trimethylcyclohexyl) -1-methylene group (group derived from isophorone diisocyanate), 4, Examples thereof include a 4'-dicyclohexylene methylene group (a group derived from 4,4'-dicyclohexylmethane diisocyanate) and a norbornylene group.

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 group having 6 to 18 carbon atoms", for example, a phenylene group. , Trilen group, xylylene group, tetramethylxylylene group, 4,4'-diphenylene methylene group and the like.

(Multifunctional (meth) acrylic group)
The terminal of the urethane (meth) acrylate of the present invention has at least one polyfunctional (meth) acrylic group among the groups represented by the following formulas (a-1) to (b-2).
The present invention also includes those in which these groups are modified with alkyleneoxy groups such as "ethyleneoxy group" and "propyleneoxy group".

(In the formula, A represents a (meth) acryloyl group. A part of A of a plurality of A may be hydrogen.)

A represents a (meth) acryloyl group (a group obtained by removing a hydroxyl group from (meth) acrylic acid). These A's may be the same or different.
A part of the plurality of A may be hydrolyzed to hydrogen.

Since the polyurethane (meth) acrylate of the present invention has a polycarbonate skeleton, it is excellent in mechanical properties, hydrolysis resistance, heat resistance, chemical resistance, weather resistance, etc., but there are a plurality of types of linear aliphatic compounds in the structure. By having a polycarbonate structure composed of hydrocarbon groups and a polycarbonate structure composed of linear aliphatic hydrocarbon groups and cyclic aliphatic hydrocarbon groups, high flexibility and high scratches are achieved without impairing mechanical properties and the like. Repairability can be expressed.
Further, by having a polyfunctional (meth) acrylic group at the end, a cured product having higher crosslink density, higher hardness and higher elastic modulus can be obtained.

(Manufacturing of polyurethane (meth) acrylate)
The polyurethane (meth) acrylate of the present invention has a "polypolypolyol" (hereinafter, also referred to as a first polycarbonate polyol) having as a repeating unit represented by the formula (1a) and a repeating unit represented by the formula (1b). "Polyolethane polyol" (hereinafter, also referred to as a second polycarbonate polyol), "polyisocyanate" having a repeating unit represented by the formula (2), and formulas (a-1) to (b-2). A "hydroxyl-containing polyfunctional (meth) acrylate compound" (having at least one hydroxyl group reactive with the terminal isocyanate group of polyurethane and a plurality of (meth) acryloyl groups" capable of introducing a polyfunctional (meth) acrylic group represented by). It can be obtained by reacting with (compound) (hereinafter, may be referred to as the reaction of the present invention). The reaction form is not particularly limited, and a known one-shot method or prepolymer method can be appropriately selected.
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 of the same type but having different molecular weights may be used. Further, a plurality of types of polyisocyanates may be used for the same reason.

[Polycarbonate polyol]
The first polycarbonate polyol used in the reaction of the present invention has a skeleton represented by the formula (1a) and contains the formulas (A-1) and (A-2) in the formula (1a). It is a skeleton.
Such a first polycarbonate polyol can be obtained, for example, by reacting a plurality of types of linear aliphatic polyols with a carbonic acid ester in the presence of a catalyst.

The second polycarbonate polyol used in the reaction of the present invention has a skeleton represented by the formula (1b) and contains the formulas (B-1) and (B-2) in the formula (1b). It's a waste.
Such a second polycarbonate polyol can be obtained, for example, by reacting a linear aliphatic polyol, a cyclic aliphatic polyol, and a carbonic acid ester in the presence of a catalyst.

(Linear aliphatic polyol)
The linear aliphatic polyol is the origin of the formulas (A-1), (A-2) and (B-1), and is, for example, ethylene glycol, propanediol, butanediol, and pentane. Examples thereof include diol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol and dodecanediol, but butanediol, pentanediol and hexanediol are preferably used.
These linear aliphatic polyols may be used alone or in combination of two or more. Further, a small amount of ether bond may be contained in the molecule of the polyol so as not to impair the function and characteristics of the target polyurethane (meth) acrylate, and a small amount of branched aliphatic polyol is contained. Is also good.

(Cyclic aliphatic polyol)
The cyclic aliphatic polyol is derived from the formula (B-2), and examples thereof include 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. , Preferably 1,4-cyclohexanedimethanol is used.
These cyclic aliphatic polyols may be used alone or in combination of two or more. Further, a small amount of ether bond may be contained in the molecule of the cyclic aliphatic polyol so as not to impair the function and characteristics of the target polyurethane (meth) acrylate, and a small amount of aromatic polyol is contained. Is also good.

(Carbonate ester)
Examples of the carbonic acid 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, but dimethyl carbonate and diethyl carbonate are preferable. , Ethylene carbonate is used.
In addition, these carbonic acid esters may be used individually or in mixture of 2 or more types.

The amount of the carbonic acid ester used is preferably 0.8 to 2.0 mol, more preferably 0.9 to 1 mol, based on 1 mol of the total polyol (linear aliphatic polyol + cyclic aliphatic polyol). It is 5.5 mol.
Within this range, the desired polycarbonate polyol can be efficiently obtained at a sufficient reaction rate.

(Reaction temperature and reaction pressure)
The reaction temperature at the time of synthesizing the polycarbonate polyol is appropriately adjusted according to the type of the polyol and the carbonic acid ester, but is preferably 120 to 180 ° C, more preferably 130 to 170 ° C.
Further, the reaction pressure in the reaction of the present invention is not particularly limited as long as the pressure is such that the reaction is carried out while removing the low boiling point component, and the reaction is preferably carried out under normal pressure or reduced pressure.
Within this range, the desired polycarbonate polyol can be efficiently obtained without causing sequential reactions or side reactions.

(catalyst)
Known ester exchange catalysts can be used as catalysts in the synthesis of polycarbonate polyols, such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, etc. Examples include metals such as zirconium, cobalt, germanium, tin and cerium, and their hydroxides, alkoxides, carboxylates, carbonates, hydrogen carbonates, sulfates, phosphates, nitrates and organic metals. Preferably, sodium hydride, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, dibutyltin dilaurate, dibutyltin dimethoxyde, dibutyltin oxide are used.
These catalysts may be used alone or in combination of two or more.

The amount of the catalyst used is preferably 0.1 to 100 mmol, more preferably 0.5 to 50 mmol, more preferably 0.5 to 100 mmol, based on the total polyol (linear aliphatic polyol + cyclic aliphatic polyol). It is 1 to 20 mmol.
Within this range, the desired polycarbonate polyol can be efficiently obtained without complicating post-treatment.
The catalyst may be used collectively at the start of the reaction, or may be divided and used (added) at the start of the reaction and after the start of the reaction.

[Polyisocyanate]
The polyisocyanate used in the reaction of the present invention has a skeleton represented by the formula (2), and the polyisocyanate to be used is appropriately selected according to the purpose and application. Aliphatic 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-cyclohexamethylene diisocyanate, methylcyclohexamethylene diisocyanate, 4,4'-methylenebiscyclohexyldiisocyanate, isophorone diisocyanate, cyclohexane-1,3-diylbis (methylene) diisocyanate, norbornyldiisocyanate;
Phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate , Polymethylene polyphenyl isocyanate, tetramethyl xylylene diisocyanate, xylylene diisocyanate (XDI) and other aromatic aliphatic diisocyanates;
Is used.
These polyisocyanates may be used alone or in combination of two or more, and a part or all of the structure may be derivatized such as isocyanurate-forming, carbodiimide-forming, or biuret-forming.

[Hydroxy group-containing polyfunctional (meth) acrylate compound]
The "hydroxyl-containing polyfunctional (meth) acrylate compound" used in the reaction of the present invention has a group represented by the formulas (a-1) to (b-2) (also, these ethyleneoxy-modified products and lactones). (Including modified products) is not particularly limited, and a part of A among the plurality of A may be hydrogen, for example.
Pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropandi (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, ditrimethylol propantri (meth) acrylate, ditrimethylol propandi (meth) acrylate, or these ethyleneoxy-modified products or propyleneoxy-modified products. Examples thereof include products and lactone-modified products, but pentaerythritol tri (meth) acrylate, dipetaerythritol penta (meth) acrylate, and dipentaerythritol tetra (meth) acrylate are preferably used.
These hydroxyl group-containing polyfunctional (meth) acrylate compounds may be used alone or in admixture of a plurality of types, or may contain a saturated polyfunctional (meth) acrylate compound containing no hydroxyl group.

In the reaction of the present invention, the total hydroxyl group amount (OH group) of the hydroxyl group of the polycarbonate polyol and the hydroxyl group of the hydroxyl group-containing acrylate compound and the molar ratio (OH group / NCO group) of the isocyanate group (NCO group) of the polyisocyanate are preferable. It is 0.8 / 1 to 1.4 / 1, more preferably 0.9 / 1 to 1.3 / 1, and more preferably 1/1 to 1.2 / 1.
Within this range, the terminal isocyanate groups of the polyurethane can be substantially converted into terminal groups 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, but it affects the cured product itself or when it is cured. In this case, for example, a monofunctional (meth) acrylic group represented by the following formula (c) can be introduced to impart curing activity to the isocyanate group.

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

Examples of the hydroxyl group-containing monofunctional (meth) acrylate compound having the formula (c) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, and hydroxy. Hexyl (meth) acrylate, hydroxy (heptyl) methacrylate, hydroxyoctyl (meth) acrylate and the like can be mentioned, but hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate are preferably used. NS.
These hydroxyl group-containing monofunctional group (meth) acrylate compounds may be used alone or in admixture of a plurality of types, and include various variants. Further, it may contain a saturated monofunctional (meth) acrylate compound that does not contain a hydroxyl group.

(catalyst)
In the reaction of the present invention, a known polymerization catalyst can be used to improve the reaction rate, for example, an organic tin compound such as dibutyltin diacetate or dibutyltin dilaurate, titanium tetraacetylacetonate, or titanium diisopropoxybis. Organic titanium compounds such as (ethylacetacetate), organic zirconium compounds such as zirconium tetraacetylacetonate and zirconium dibutoxybis (ethylacetacetate), and tertiary amines such as triethylamine are preferably used.
For the catalyst, refer to pages 23 to 32 of "Polyurethane Resin" by Keiji Yoshida (published by Nikkan Kogyo Shimbun, 1969).

The amount of the catalyst used is preferably 0.0005 to 0.1% by mass, more preferably 0.001 to 0.05, based on the total amount of the polycarbonate polyol, the polyisocyanate, and the hydroxyl group-containing (meth) acrylate compound. It is mass%.
Within this range, a sufficient reaction rate can be obtained, and the residual amount of the catalyst is small, so that the post-treatment is not complicated.

(solvent)
In the reaction of the present invention, a solvent that does not react with the isocyanate group can be appropriately used, and for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene. Esters such as glycol 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, Ethers such as dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and tetramethylbenzene; amides such as dimethylformamide, diethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide can be used.
In addition, these solvents may be used individually or in mixture of 2 or more types. Further, by using a solvent, a solvent solution of polyurethane (meth) acrylate can be obtained.

The amount of the solvent used is preferably 5 to 200% by mass, more preferably 10 to 100% by mass, more preferably 10 to 100% by mass, based on the total amount of the polycarbonate polyol, the polyisocyanate, and the hydroxyl group-containing polyfunctional (meth) acrylate compound. It is 20 to 80% by mass.
Within this range, the uniformity and agitation of the reaction solution are improved.

(Polymerization inhibitor)
In the reaction of the present invention, it is desirable to have a polymerization inhibitor or an antioxidant in order to suppress the polymerization and oxidation of the hydroxyl group-containing polyfunctional (meth) acrylate compound as a raw material and the produced polyurethane (meth) acrylate. For example, 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. Will be done.
These polymerization inhibitors and antioxidants may be used alone or in admixture of a plurality of types.

The amount of the polymerization inhibitor or antioxidant added is preferably 0.00005 to 0.01% by mass, more preferably 0.00005 to 0.01% by mass, based on the total amount of the polycarbonate polyol, the polyisocyanate, and the hydroxyl group-containing polyfunctional (meth) acrylate compound. Is 0.0001 to 0.005% by mass, more preferably 0.0003 to 0.003% by mass.
Within this range, polymerization and oxidation can be sufficiently suppressed, and these post-treatments are 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 application, and 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, tricyclodecanedimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl ] Propane, low molecular weight polyols such as bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane;
Polymer polyols such as polyester polyols, polyesteramide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, and polyolefin polyols;
Polyamines such as ethylenediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine are used.
For the chain extender, for example, "Latest Polyurethane Applied Technology" (CMC Co., Ltd., published in 1985) can be referred to, and for the polymer polyol, for example, "Polyurethane form" (polymer). Publications, 1987) can be referred to.

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

Since the obtained polyurethane (meth) acrylate is not always stable to light and oxygen in the atmosphere, it is desirable to use it in a necessary application as a solvent solution of polyurethane (meth) acrylate without particularly isolating and purifying it. ..

[Curable resin composition]
The curable resin composition of the present invention contains the polyurethane (meth) acrylate, a polymerization initiator, and a polymerizable compound, if necessary.

(Polymerization initiator)
Examples of the polymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, benzoin ethyl ether, and benzoin-n-propyl ether. , Benzoine isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl-α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2,4,6, -trimethylbenzophenone , 4-Methylbenzophenone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethanone and the like, but 1-hydroxycyclohexylphenylketone is preferable. , Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide is used.
These polymerization initiators may be used alone or in combination of two or more.

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.
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, and isobutyl (meth) acrylate. Monofunctional (meth) such as (meth) acrylic acid alkyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate compound;
Butanediol di (meth) acrylate, hexanediol 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, Neopentyl glycol di (meth) acrylate ethoxylated, Trimethylol propanetri (meth) acrylate, Trimethylol propantri (meth) acrylate ethoxylated, Propoxy Trimethylol propantri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tri (meth) acrylate such as glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Tri (meth) acrylate, ditrimethylol propanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Polyfunctional (meth) acrylate compounds such as ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylol propanehexa (meth) acrylate, or these or ethyleneoxy-modified products or propyleneoxy thereof. Modified products and lactone-modified products can be used.
In addition, these polymerizable compounds may be used individually or in mixture of 2 or more types.

When the hydroxyl group-containing polyfunctional (meth) acrylate compound is excessively used in the production of polyurethane (meth) acrylate, the remaining hydroxyl group-containing polyfunctional (meth) acrylate compound can be used as a substitute for the polymerizable compound. ..
Further, when a mixture of a hydroxyl group-containing polyfunctional (meth) acrylate compound and a saturated polyfunctional (meth) acrylate compound (acrylate compound containing no hydroxyl group) is used in producing polyurethane (meth) acrylate, it is saturated. Since the polyfunctional (meth) acrylate compound remains without being involved in the production of the polyurethane (meth) acrylate, it can be substituted as the polymerizable compound.

The amount of the polymerizable compound used is preferably not more than this molar amount with respect to urethane (meth) acrylate.

[Cured product]
The curable resin composition of the present invention is adjusted to an appropriate viscosity by adding an organic solvent as necessary, and then applied onto a substrate, for example, ultraviolet light, visible light, laser light, electron beam, X-ray. By irradiating with active energy rays such as γ-rays, plasma, and microwaves, it can be polymerized and cured to obtain a cured product.
It is also possible to produce a cured product by heat without irradiating it with active energy rays.

The organic solvent may be the same as the organic solvent used in producing polyurethane (meth) acrylate, and examples thereof include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate and 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; aromatic hydrocarbons such as benzene, toluene, xylene and tetramethylbenzene; amides such as dimethylformamide, diethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide Can be used.
In addition, these solvents may be used individually or in mixture of 2 or more types.

As the base material, for example, resins such as metal, plastic, inorganic material, wood, ABS resin, polycarbonate resin, polyimide resin, polyamide resin, and polyester resin can be used.

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 method]
(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 polyurethane (meth) acrylate was measured by gel permission chromatography (GPC). The measurement conditions are as follows.
Equipment: HPLC-8220 (manufactured by Tosoh Corporation)
Column configuration: TSKgel SuperHZ3000 + TSKgel SuperH
Z1000 (both manufactured by Tosoh)
Detector: Differential refractive index detector (RI detector)
Eluent: Tetrahydrofuran Eluent flow rate: 0.6 ml / min
Temperature: 40 ° C
Temperature rise rate: Constant temperature without temperature rise Calibration: Polystyrene-equivalent sample concentration: 0.01 g / 5 mL
(Pencil hardness)
The cured product was measured by a method according to JIS K 5600-5-4. A load of 750 g was applied to scratch the pencil to make it the hardest pencil without scratches.
(Elastic modulus)
The elastic modulus of the cured product was measured by a method according to 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.
(Scratch repairability)
The scratch repairability of the cured product is measured from immediately after 500 scratches on the surface of the cured product with a brass brush at a temperature of 23 ° C. and a humidity of 50% until the scratches cannot be visually confirmed. Was judged.
⊚; less than 10 seconds ○; 10 seconds or more and less than 1 minute Δ; 1 minute or more ×; no scratch repairability (breaking point elongation, breaking point stress)
A polyurethane film having a thickness of about 0.05 mm was formed, and this film was cut into strips of 10 mm × 80 mm and cured in a thermostatic chamber at 23 ° C. and 50% RH for one day as an evaluation sample.
The sample was pulled in a thermostatic chamber at 23 ° C. and 50% RH using a Tensilon tensile tester (RTC-1250A, manufactured by ORIENTEC) at a chuck distance of 20 mm and a tensile speed of 100 mm / min. Breaking point stress Stress (MPa) was measured.
(Adhesion)
The adhesion of the cured product was determined according to JIS K 5600-5-6: 1999 "Cross-cut method". After applying polyurethane (meth) acrylate to various resin panels, cuts are made at intervals of 2 mm to form a grid portion of 100 squares, and the adhesive tape is crimped to the grid portion and peeled off by repeating the process 10 times. rice field. The evaluation criteria were also evaluated according to the same standards.
⊚; Mass 100 that did not peel off
◯; Mass 80 or more and 99 or less that did not peel off ×; Mass 79 or less that did not peel off (acid resistance and solvent resistance)
The cured product was immersed in an acid or a solvent for 24 hours, and the swelling rate was measured. The smaller the swelling rate, the better the resistance.
◎; No swelling was observed.
◯; Almost no swelling was observed.
Δ: Swelling was observed.
×; Swelling occurred violently.

Example 1 (Synthesis of Polyurethane Acrylate)
In a container with an internal volume of 1 L equipped with a stirrer, a thermometer and a cooler, 200 g (0.2 mol) of polycarbonate polyol (ETERNACOLL (registered trademark) PH-100 manufactured by Ube Kosan Co., Ltd.) and polycarbonate polyol (Ube Kosan Co., Ltd.) ETERNACOLL (registered trademark) PH-50) 95 g (0.19 mol), Polycarbonate polyol (manufactured by Ube Kosan Co., Ltd., ETERNACOLL (registered trademark) UM-90 (3/1)) 9 g (0.01 mol) and butyl acetate After 483 g was added and the liquid temperature was adjusted to 50 ° C., 0.34 g of dibutyltin (IV) dilaurate and 111 g (0.5 mol) of isophorone diisocyanate were added, and the reaction was carried out at 80 to 83 ° C. for 3 hours with stirring.
Then, 0.24 g of p-methoxyphenol, 0.24 g of 2,6-t-butyl-p-cresol, and a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Toa Synthetic Co., Ltd., Aronix (registered trademark) M306). , Acrylate; 65-70%) 66.2 g (0.186 mol) was added and further reacted at 82-85 ° C. Then, 2 g (0.021 mol) of 2-hydroxyethyl acrylate was added and reacted again at the same temperature. After confirming that the isocyanate group had disappeared, the mixture was cooled to obtain a butyl acetate solution of polyurethane acrylate.
The viscosity of the butyl acetate solution of the obtained polyurethane acrylate was 1700 cP / 25 ° C.

Example 2 (Synthesis of Polyurethane Acrylate)
In a container with an internal volume of 1 L equipped with a stirrer, a thermometer and a cooler, 200 g (0.2 mol) of polycarbonate polyol (ETERNACOLL (registered trademark) PH-100 manufactured by Ube Kosan Co., Ltd.) and polycarbonate polyol (Ube Kosan Co., Ltd.) ETERNACOLL (registered trademark) PH-50) 95 g (0.19 mol), Polycarbonate polyol (manufactured by Ube Kosan Co., Ltd., ETERNACOLL (registered trademark) UM-90 (3/1)) 9 g (0.01 mol) and methyl ethyl ketone 206 g To 50 ° C., 0.39 g of dibutyltin (IV) dilaurate and 111 g (0.5 mol) of isophorone diisocyanate were added, and the reaction was carried out at 76 to 79 ° C. for 3 hours with stirring.
Then, 0.24 g of p-methoxyphenol, 0.24 g of 2,6-t-butyl-p-cresol, and a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Toa Synthetic Co., Ltd., Aronix (registered trademark) M306). , Acrylate; 65-70%) 64 g (0.18 mol) was added and further reacted at the same temperature. Then, 2 g (0.021 mol) of 2-hydroxyethyl acrylate was added and reacted again at the same temperature. After confirming that the isocyanate group had disappeared, the mixture was cooled to obtain a methyl ethyl ketone solution of polyurethane acrylate.
The viscosity of the methyl ethyl ketone solution of the obtained polyurethane acrylate was 31000 cP / 25 ° C.

Example 3 (Synthesis of Polyurethane Acrylate)
In a container with an internal volume of 1 L equipped with a stirrer, thermometer and cooler, 200 g (0.1 mol) of polycarbonate polyol (ETERNACOLL (registered trademark) PH-200 manufactured by Ube Kosan Co., Ltd.) and polycarbonate polyol (Ube Kosan Co., Ltd.) ETERNACOLL (registered trademark) PH-50) 95 g (0.19 mol), Polycarbonate polyol (manufactured by Ube Kosan Co., Ltd., ETERNACOLL (registered trademark) UM-90 (3/1)) 9 g (0.01 mol) and butyl acetate After adding 461 g to bring the liquid temperature to 50 ° C., 0.32 g of dibutyltin (IV) dilaurate and 88.8 g (0.4 mol) of isophorone diisocyanate were added, and the reaction was carried out at 80 to 83 ° C. for 3 hours with stirring.
Then, 0.23 g of p-methoxyphenol, 0.23 g of 2,6-t-butyl-p-cresol, and a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Toagosei Co., Ltd., Aronix (registered trademark) M306). , Acrylate; 65-70%) 66.2 g (0.186 mol) was added and further reacted at the same temperature. Then, 2 g (0.021 mol) of 2-hydroxyethyl acrylate was added and reacted again at the same temperature. After confirming that the isocyanate group had disappeared, the mixture was cooled to obtain a butyl acetate solution of polyurethane acrylate.
The viscosity of the butyl acetate solution of the obtained polyurethane acrylate was 5600 cP / 25 ° C.

Example 4 (Synthesis of Polyurethane Acrylate)
In a container with an internal volume of 1 L equipped with a stirrer, thermometer and cooler, 350 g (0.175 mol) of polycarbonate polyol (ETERNACOLL (registered trademark) PH-200 manufactured by Ube Kosan Co., Ltd.) and polycarbonate polyol (Ube Kosan Co., Ltd.) UM-90 (registered trademark) UM-90 (3/1) 67 g (0.075 mol) and butyl acetate 510 g were added to bring the liquid temperature to 50 ° C., and then dibutyltin (IV) dilaurate 0.46 g and isophorone diisocyanate 66. 6 g (0.3 mol) was added, and the reaction was carried out at 78 to 81 ° C. for 3 hours with stirring.
Then, 0.25 g of p-methoxyphenol, 0.25 g of 2,6-t-butyl-p-cresol, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Toa Synthetic Co., Ltd., Aronix®). ) M403, penta-form; 50-60%) 15.2 g (0.027 mol) was added and further reacted at 81-85 ° C. Then, 11 g (0.076 mol) of 4-hydroxybutyl acrylate was added and reacted again at the same temperature. After confirming that the isocyanate group had disappeared, the mixture was cooled to obtain a butyl acetate solution of polyurethane acrylate.
The viscosity of the butyl acetate solution of the obtained polyurethane acrylate was 12100 cP / 25 ° C.

Comparative Example 1 (Synthesis of Polyurethane Acrylate)
150 g (0.15 mol) of polycarbonate polyol (ETERNACOLL (registered trademark) UH-100, manufactured by Ube Industries, Ltd.) and 390 g of methyl ethyl ketone are added to a container having an internal volume of 1 L equipped with a stirrer, a thermometer and a cooler, and the liquid temperature is changed. To 50 ° C., 0.1 g of dibutyltin (IV) dilaurate and 66.6 g (0.3 mol) of isophorone diisocyanate were added, and the reaction was carried out at 75 to 85 ° C. for 3 hours with stirring.
Then, 0.2 g of p-methoxyphenol, 0.2 g of 2,6-t-butyl-p-cresol, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Toa Synthetic Co., Ltd., Aronix®) ) M403, penta-form; 50-60%) 173 g (0.3 mol) was added, and the mixture was further reacted at the same temperature. After confirming that the isocyanate group had disappeared, the mixture was cooled to obtain a methyl ethyl ketone solution of polyurethane acrylate.
The viscosity of the methyl ethyl ketone solution of the obtained polyurethane acrylate was 80 cP / 25 ° C.

Comparative Example 2 (Synthesis of Polyurethane Acrylate)
180 g (0.2 mol) of polycarbonate polyol (ETERNACOLL (registered trademark) UM-90 (1/3), manufactured by Ube Kosan Co., Ltd.) and 315 g of methyl ethyl ketone in a container having an internal volume of 1 L equipped with a stirrer, a thermometer and a cooler. To 50 ° C., 0.05 g of dibutyltin (IV) dilaurate and 88.8 g (0.4 mol) of isophorone diisocyanate were added, and the reaction was carried out at 75 to 85 ° C. for 3 hours with stirring.
Then, 0.15 g of p-methoxyphenol, 0.15 g of 2,6-t-butyl-p-cresol, and 46.4 g (0.4 mol) of 2-hydroxyethyl acrylate were added and further reacted at the same temperature to carry out isocyanate. After confirming that the groups had disappeared, the mixture was cooled to obtain a methyl ethyl ketone solution of polyurethane acrylate.
The viscosity of the methyl ethyl ketone solution of the obtained polyurethane acrylate was 75 cP / 25 ° C.

(Manufacturing of composition and cured product)
0.5 g of 1-hydroxycyclohexylphenyl ketone (Irgacure (registered trademark) 184, manufactured by BASF) was mixed with 20 g of a methyl ethyl ketone solution of polyurethane acrylate obtained in Examples and Comparative Examples to prepare a curable resin composition. bottom.
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 ultraviolet rays of ^{1000 mJ / cm 2 to produce a cured product.}

The above results are summarized in Table 1.
The abbreviations used in the table are as follows.
PCD PH-50; Polycarbonate polyol obtained from a mixture of 1,5-pentanediol and 1,6-hexanediol as a raw material (ETERNACOLL® PH-50, molecular weight; 500, manufactured by Ube Industries, Ltd.)
PCD PH-100; Polycarbonate polyol obtained from a mixture of 1,5-pentanediol and 1,6-hexanediol as a raw material (ETERNACOLL® PH-100, molecular weight; 1000, manufactured by Ube Industries, Ltd.)
PCD PH-200; Polycarbonate polyol obtained from a mixture of 1,5-pentanediol and 1,6-hexanediol as a raw material (ETERNACOLL® PH-200, molecular weight; 2000, manufactured by Ube Kosan Co., Ltd.)
PCD UM-90 (3/1); Polycarbonate polyol obtained from a mixture (3: 1) of 1,4-cyclohexanedimethanol and 1,6-hexanediol (manufactured by Ube Industries, Ltd., ETERNAL COLL (registered trademark)) ) UM-90 (3/1))
PCD UM-90 (1/1); Polycarbonate polyol obtained from a mixture (1: 1) of 1,4-cyclohexanedimethanol and 1,6-hexanediol (manufactured by Ube Industries, Ltd., ETERNAL COLL (registered trademark)) ) UM-90 (1/1))
IPDI; Isophorone diisocyanate PETA M-306; Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Toagosei Co., Ltd., Aronix® M306, tri-form; 65-70%)
DPHA M-403; Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Toagosei Co., Ltd., Aronix® M403, penta-form; 50-60%)
HEA; 2-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 example was excellent in each function and property of high flexibility and high scratch repair property. It became clear in comparison with the cured product.
Therefore, the polyurethane (meth) acrylate of the present invention and its composition are required to have high appearance and durability, for example, for coating applications (coating materials) such as inks, paints, adhesives and adhesives. It can be suitably used for laminating applications (laminated materials) such as various mobile devices, films, building interiors and exteriors, automobile interiors and exteriors, and molding applications (molding materials) such as cured molded products such as ultraviolet curable lenses.

The present invention relates to a novel polyurethane (meth) acrylate having a polycarbonate skeleton as a repeating unit, a composition thereof, and a cured product. Polyurethane (meth) acrylate is a compound useful as a main component of various coating agents of the type that are cured by active energy rays.

Claims (6)

A repeating unit represented by the following formula (1a), a repeating unit represented by the following formula (1b), a repeating unit represented by the following formula (2), and a polyurethane (meth) having a polyfunctional (meth) acrylic group at the end. ) Acryloyl
A first polycarbonate polyol having a repeating unit represented by the formula (1a), a second polycarbonate polyol having a repeating unit represented by the formula (1b), and a polyisocyanate having a repeating unit represented by the formula (2). , a formula (a-1) ~ (b -2) a hydroxyl group-containing polyfunctional (meth) acrylate compound represented by the polyurethane (meth) acrylates obtained by reacting,
The repeating unit of the formula (1a) includes the repeating unit represented by the following formulas (A-1) and (A-2).
The repeating unit of the above formula (1b) includes the repeating unit represented by the following formulas (B-1) and (B-2).
The polyfunctional (meth) acrylic group is at least one of the groups represented by the following formulas (a-1) to (b-2).
Polyurethane (meth) acrylate.

(During the ceremony,
Z ^a represents a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, and n ¹ is the number of repeating units of the formula (1a).
Here, Z ^a1 represents a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, and ^{Z a2} is a ^{divalent linear aliphatic hydrocarbon having 2 to 12 carbon atoms different from Z a1.} Indicates a hydrocarbon group.
Z ^b represents a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms or a divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms, and n ² is the formula (1b). Is the number of repeating units of.
Here, Z ^b1 represents a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, and Z ^b2 represents a divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms.
In addition, R represents a 5- (1,3,3, -trimethylcyclohexyl) -1-methylene group . )

(In the formula, A represents a (meth) acryloyl group. A part of A of a plurality of A may be hydrogen.) The polyurethane (meth) acrylate according to claim 1, further comprising a monofunctional acrylic group represented by the following formula (c) at the end.

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