JP6996284B2 - Resin and its manufacturing method, active energy ray-curable resin composition, cured product, active energy ray-curable printing ink, and printed matter. - Google Patents

Description

The present disclosure relates to a resin and a method for producing the same, an active energy ray-curable resin composition, a cured product, an active energy ray-curable printing ink, and a printed matter.

A resin composition that is cured by an active energy ray such as an ultraviolet ray or an electron beam (hereinafter referred to as an active energy ray-curable resin composition) contains a reactive diluent, a resin, a photopolymerization initiator and an additive, and is an energy-saving type. As an industrial material, it is used in various fields such as coating agents, paints, and printing inks.

In particular, active energy ray-curable printing inks are excellent in curability and film hardness, and therefore polyfunctional acrylates such as dipentaerythritol hexaacrylate and ditrimethylolpropane tetraacrylate are widely used as reactive diluents. A diallyl phthalate resin is widely used as a binder resin because of its excellent compatibility with polyfunctional acrylates and curability (see paragraph [0009] of Patent Document 1).

Japanese Patent No. 5683757

However, the diallyl phthalate resin is obtained by polymerizing a diallyl phthalate monomer and has a polymerizable double bond, but does not have a polar functional group such as a hydroxyl group or a carboxyl group, so that the usage mode is limited. Further, since the unreacted diallyl phthalate monomer remaining in the resin is a substance of very high concern with mutagenicity (see paragraph [0009] of Patent Document 1 above), a resin that can replace the diallyl phthalate resin is required. Has been done.

The problem to be solved by the present invention is that, when used as a binder for an active energy ray-curable ink, the ink has good curability and solvent resistance, and as a result, a novel resin that can be replaced with a diallyl phthalate resin can be obtained. Will be provided.

In the present invention, the predetermined resin has a carboxyl group and a hydroxyl group, is well compatible with the reactive diluent like the diallyl phthalate resin, and has curability and solvent resistance of the printing ink containing the above-mentioned predetermined resin. It was found that the performance such as gloss is equal to or higher than the performance of the printing ink containing diallyl phthalate resin.

（Ｒ^１ａは水素又はアルキル基であり、Ｒ^１ｂ～Ｒ^１ｆはそれぞれ独立に、水素、アルキル基及びアリール基からなる群から選択される基である。）
及び、構成単位２

［Ｒ^２ａは水素又はアルキル基であり、Ｒ^２ｂは、下記構成単位２ａ

｛ａ１は１以上の整数であり、ａ２は０以上の整数であり、Ｒ^ａａは水素原子、置換若しくは非置換のアルキル基、置換若しくは非置換のアリール基、置換若しくは非置換のアルコキシ基、又は置換若しくは非置換のアリールオキシ基であり、Ｒ^ａｂは置換若しくは非置換のアリーレン基、置換若しくは非置換のアルキレン基、又は置換若しくは非置換のアルケニレン基である。｝
を含む樹脂鎖である。］
を含む、樹脂。
（項目２）
前記樹脂鎖が、構成単位２ｂ

［Ｒ^ｂ１ａ～Ｒ^ｂ１ｃはそれぞれ独立に、置換若しくは非置換のアリーレン基、置換若しくは非置換のアルキレン基、又は置換若しくは非置換のアルケニレン基であり、
Ｒ^ｂ２ａ～Ｒ^ｂ２ｃはそれぞれ独立に、

であって、Ｒ^ｂ２ａ～Ｒ^ｂ２ｃの少なくとも１つが

であり、
｛Ｂは１以上の整数であり、
Ｒ^Ｂは

（ｂ１は１以上の整数であり、ｂ２は０以上の整数であり、Ｒ^ｂａは水素原子、置換若しくは非置換のアルキル基、置換若しくは非置換のアリール基、置換若しくは非置換のアルコキシ基、又は置換若しくは非置換のアリールオキシ基であり、Ｒ^ｂｂは置換若しくは非置換のアリーレン基、置換若しくは非置換のアルキレン基、又は置換若しくは非置換のアルケニレン基である。）
である。｝
Ｒ^ｂ３ａ～Ｒ^ｂ３ｃはそれぞれ独立に、置換若しくは非置換のアリール基、置換又は非置換のアルキル基、又は置換若しくは非置換のアルケニル基である］
を含む、上記項目に記載の樹脂。
（項目３）
酸価が０．１～１５０ｍｇＫＯＨ／ｇである、上記項目のいずれか１項に記載の樹脂。
（項目４）
重量平均分子量が１，０００～２００,０００である、上記項目のいずれか１項に記載の樹脂。
（項目５）
軟化点が４０～１５０℃である、上記項目のいずれか１項に記載の樹脂。
（項目６）
カルボキシル基及びアリール基を有する重合体（Ａ）と
エポキシド（Ｂ）又はエポキシド（Ｂ）及びカルボン酸無水物（Ｃ）とを反応させる工程を含む、上記項目のいずれか１項に記載の樹脂の製造方法。
（項目７）
上記項目のいずれか１項に記載の樹脂及び反応性希釈剤を含む、活性エネルギー線硬化型樹脂組成物。
（項目８）
上記項目に記載の活性エネルギー線硬化型樹脂組成物の硬化物。
（項目９）
上記項目に記載の活性エネルギー線硬化型樹脂組成物及び顔料を含む、活性エネルギー線硬化型印刷インキ。
（項目１０）
上記項目に記載の活性エネルギー線硬化型印刷インキの硬化層を含む、印刷物。 (Item 1)
Configuration unit 1

(R ^1a is a hydrogen or an alkyl group, and R ^1b to R ^1f are independently selected from the group consisting of a hydrogen, an alkyl group and an aryl group.)
And the structural unit 2

[R ^2a is a hydrogen or an alkyl group, and R ^2b is the following structural unit 2a.

{A1 is an integer of 1 or more, a2 is an integer of 0 or more, R ^aa is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or It is a substituted or unsubstituted aryloxy group, and ^Rab is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
It is a resin chain containing. ]
Including resin.
(Item 2)
The resin chain is the structural unit 2b.

[R ^b1a to R ^b1c are independently substituted or unsubstituted arylene groups, substituted or unsubstituted alkylene groups, or substituted or unsubstituted alkenylene groups, respectively.
R ^b2a to R ^b2c are independent of each other.

And at least one of R ^b2a to R ^b2c

And
{B is an integer greater than or equal to 1 and
^RB is

(B1 is an integer of 1 or more, b2 is an integer of 0 or more, R ^ba is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or It is a substituted or unsubstituted aryloxy group, and ^Rbb is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group).
Is. }
R ^b3a to R ^b3c are independently substituted or unsubstituted aryl groups, substituted or unsubstituted alkyl groups, or substituted or unsubstituted alkenyl groups.]
The resin according to the above item, including.
(Item 3)
The resin according to any one of the above items, which has an acid value of 0.1 to 150 mgKOH / g.
(Item 4)
The resin according to any one of the above items, which has a weight average molecular weight of 1,000 to 200,000.
(Item 5)
The resin according to any one of the above items, which has a softening point of 40 to 150 ° C.
(Item 6)
The resin according to any one of the above items, which comprises a step of reacting a polymer (A) having a carboxyl group and an aryl group with an epoxide (B) or an epoxide (B) and a carboxylic acid anhydride (C). Production method.
(Item 7)
An active energy ray-curable resin composition containing the resin according to any one of the above items and a reactive diluent.
(Item 8)
A cured product of the active energy ray-curable resin composition according to the above item.
(Item 9)
An active energy ray-curable printing ink containing the active energy ray-curable resin composition and pigment according to the above items.
(Item 10)
A printed matter containing a cured layer of the active energy ray-curable printing ink according to the above item.

Since the resin of the present invention has a carboxyl group, a hydroxyl group, and optionally a polymerizable carbon-carbon double bond, it can be subjected to various modifications. Examples of the modification include an esterification reaction with a compound containing a carboxylic acid or a hydroxyl group, an addition reaction with an epoxide, and the like.

Further, the resin has good compatibility with various reactive diluents, particularly polyfunctional acrylates such as dipentaerythritol hexaacrylate, like the diallyl phthalate resin. Further, the resin improves the solvent resistance of the printing ink using the resin as a binder resin.

The active energy ray-curable printing ink containing the resin of the present invention is excellent in curability and gloss like the ink containing a diallyl phthalate resin. Further, the solvent resistance of the resin of the present invention is superior to the solvent resistance of the diallyl phthalate resin. Therefore, it is particularly suitable as an active energy ray-curable offset printing ink.

（Ｒ^１ａは水素又はアルキル基であり、Ｒ^１ｂ～Ｒ^１ｆはそれぞれ独立に、水素、アルキル基及びアリール基からなる群から選択される基である。）
及び、構成単位２

［Ｒ^２ａは水素又はアルキル基であり、Ｒ^２ｂは、下記構成単位２ａ

｛ａ１は１以上の整数であり、ａ２は０以上の整数であり、Ｒ^ａａは水素原子、置換若しくは非置換のアルキル基、置換若しくは非置換のアリール基、置換若しくは非置換のアルコキシ基、又は置換若しくは非置換のアリールオキシ基であり、Ｒ^ａｂは置換若しくは非置換のアリーレン基、置換若しくは非置換のアルキレン基、又は置換若しくは非置換のアルケニレン基である。｝
を含む樹脂鎖である。］
を含む、樹脂を提供する。 (1. Resin)
The present disclosure is based on structural unit 1.

(R ^1a is a hydrogen or an alkyl group, and R ^1b to R ^1f are independently selected from the group consisting of a hydrogen, an alkyl group and an aryl group.)
And the structural unit 2

[R ^2a is a hydrogen or an alkyl group, and R ^2b is the following structural unit 2a.

{A1 is an integer of 1 or more, a2 is an integer of 0 or more, R ^aa is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or It is a substituted or unsubstituted aryloxy group, and ^Rab is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
It is a resin chain containing. ]
To provide a resin, including.

Examples of the alkyl group include a linear alkyl group, a branched alkyl group, a cycloalkyl group and the like.

The linear alkyl group can be expressed by the general formula of −C _n H _{2n + 1} (n is an integer of 1 or more). The linear alkyl group includes a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decamethyl group and the like. Is exemplified.

A branched alkyl group is a group in which at least one hydrogen of a linear alkyl group is substituted with an alkyl group. Examples of the branched alkyl group include a diethylpentyl group, a trimethylbutyl group, a trimethylpentyl group, a trimethylhexyl group (trimethylhexamethyl group) and the like.

Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a crosslinked ring cycloalkyl group, and a condensed ring cycloalkyl group.

In the present disclosure, a single ring means a cyclic structure having no bridging structure inside formed by a covalent bond of carbon. Further, a fused ring means a cyclic structure in which two or more monocycles share two atoms (that is, only one side of each ring is shared (condensed) with each other). A crosslinked ring means a cyclic structure in which two or more monocycles share three or more atoms.

Examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, a 3,5,5-trimethylcyclohexyl group and the like.

Examples of the crosslinked ring cycloalkyl group include a tricyclodecyl group, an adamantyl group, a norbornyl group and the like.

Examples of the fused ring cycloalkyl group include a bicyclodecyl group.

The alkoxy group can be expressed by the general formula of -OR ^Al ( ^RA is an alkyl group). Examples of the alkyl group in the above general formula include those described above.

Examples of the aryl group include a monocyclic aryl group and a condensed ring aryl group. The monocyclic aryl group is exemplified by a phenyl group, and the condensed ring aryl group is exemplified by a naphthyl group or the like. Examples of the substituted aryl group include a tolyl group and a xylyl group.

The aryloxy group can be expressed by the general formula of -OR ^Ar (R ^Ar is an aryl group). Examples of the aryl group in the above general formula include those described above.

Examples of the arylene group include a monocyclic arylene group and a condensed ring arylene group. The monocyclic arylene group is exemplified by a phenylene group, and the fused ring arylene group is exemplified by a naphthylene group or the like. Examples of the substituted arylene group include a trilene group and a xylylene group.

Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

The linear alkylene group can be expressed by the general formula of-(CH ₂ ) _n- (n is an integer of 1 or more). The linear alkylene group includes a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decamethylene group and the like. Is exemplified.

A branched alkylene group is a group in which at least one hydrogen of a linear alkylene group is substituted with an alkyl group. Examples of the branched alkylene group include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, a trimethylhexylene group (trimethylhexamethylene group) and the like.

Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a crosslinked ring cycloalkylene group, and a fused ring cycloalkylene group.

Examples of the monocyclic cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, a 3,5,5-trimethylcyclohexylene group and the like.

Examples of the crosslinked ring cycloalkylene group include a tricyclodecylene group, an adamantylene group, a norbornene group and the like.

Examples of the fused ring cycloalkylene group include a bicyclodecylene group.

Examples of the alkenylene group include a linear alkenylene group, a branched alkenylene group, a cycloalkenylene group and the like.

Examples of the linear alkenylene group include a vinylene group, a propenylene group, an n-butenylene group and the like.

The branched alkenylene group is a group in which at least one hydrogen of the linear alkenylene group is substituted with an alkyl group, and examples thereof include a 1-methylbinylene group, a 1-methylpropenylene group and a 1-methylbutenylene group.

Examples of the cycloalkenylene group include a monocyclic cycloalkenylene group.

Examples of the monocyclic cycloalkenylene group include a cyclopentenylene group, a cyclohexenylene group, a cycloheptenylene group, a cyclodecenylene group, a 3,5,5-trimethylcyclohexenylene group and the like.

（Ｒ^１ａ’は水素又はアルキル基であり、Ｒ^１ｂ’～Ｒ^{１ｆ ’}はそれぞれ独立に、水素、アルキル基及びアリール基からなる群から選択される基である。）
で表わされる化合物をモノマーとして用いた場合に樹脂に含まれる構成単位である。 (Structure unit 1)
The structural unit 1 is the general formula 1.

(R ^1a'is a hydrogen or an alkyl group, and R ^1b'to R ^1f' are independently selected from the group consisting of hydrogen, an alkyl group and an aryl group.)
It is a structural unit contained in the resin when the compound represented by is used as a monomer.

Examples of the compound represented by the general formula 1 include styrene, dimethylstyrene, t-butylstyrene, α-methylstyrene and the like.

The upper limit of the ratio of the constituent unit 1 in the resin is exemplified by 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15% by mass and the like, and the lower limit is 69, 65, 60. , 55, 50, 45, 40, 35, 30, 25, 20, 15, 10% by mass and the like are exemplified. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the ratio of the constituent unit 1 in the resin is preferably 10 to 70% by mass from the viewpoint of compatibility with the reactive diluent and the like.

The upper limit of the ratio of the constituent unit 1 in the resin is exemplified by 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 mol% and the like, and the lower limit is 69, 65, 60. , 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 mol% and the like are exemplified. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the ratio of the constituent unit 1 in the resin is preferably 10 to 70 mol% from the viewpoint of compatibility with the reactive diluent and the like.

（Ｒ^２ａ’は水素又はアルキル基である。）
に対し、エポキシド（Ｂ）と反応させるか、又はエポキシド（Ｂ）及びカルボン酸無水物（Ｃ）とを反応（重合）させることにより生じる構成単位である。ここで、上記構成単位１及び構成単位２’を含む樹脂は、後述する（Ａ）カルボキシル基とアリール基を有する重合体の１例である。なお、（Ａ）カルボキシル基とアリール基を有する重合体、エポキシド（Ｂ）、カルボン酸無水物（Ｃ）は、それぞれ独立に２種以上を併用してもよい。 (Structure unit 2)
The structural unit 2 is a structural unit 2'generated after synthesizing a resin using an unsaturated carboxylic acid as a monomer.

(R ^2a'is a hydrogen or alkyl group.)
On the other hand, it is a structural unit generated by reacting with epoxide (B) or reacting (polymerizing) with epoxide (B) and carboxylic acid anhydride (C). Here, the resin containing the structural unit 1 and the structural unit 2'is an example of (A) a polymer having a carboxyl group and an aryl group, which will be described later. In addition, (A) a polymer having a carboxyl group and an aryl group, an epoxide (B), and a carboxylic acid anhydride (C) may be used in combination of two or more independently.

The upper limit of the ratio of the constituent unit 2 in the resin is exemplified by 85, 80, 70, 60, 50, 40, 30, 25% by mass and the like, and the lower limit is 80, 70, 60, 50, 40, 30, 25. , 20% by mass is exemplified. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the ratio of the constituent unit 2 in the resin is preferably 20 to 85% by mass from the viewpoint of compatibility with the reactive diluent and the like.

The upper limit of the ratio of the constituent unit 2 in the resin is exemplified by 85, 80, 70, 60, 50, 40, 30, 25 mol% and the like, and the lower limit is 80, 70, 60, 50, 40, 30, 25. , 20 mol% is exemplified. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the ratio of the constituent unit 2 in the resin is preferably 20 to 85 mol% from the viewpoint of compatibility with the reactive diluent and the like.

｛ａ１は１以上の整数であり、ａ２は０以上の整数であり、Ｒ^ａａは水素原子、置換若しくは非置換のアルキル基、置換若しくは非置換のアリール基、置換若しくは非置換のアルコキシ基、又は置換若しくは非置換のアリールオキシ基であり、Ｒ^ａｂは置換若しくは非置換のアリーレン基、置換若しくは非置換のアルキレン基、又は置換若しくは非置換のアルケニレン基である。｝
で表わされる基である。 (Structure unit 2a)
The structural unit 2a is a general formula 2a.

{A1 is an integer of 1 or more, a2 is an integer of 0 or more, R ^aa is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or It is a substituted or unsubstituted aryloxy group, and ^Rab is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
It is a group represented by.

で表わされ、ａ２が０であるとき、一般式２ａ－２

で表わされる。一般式２ａ－１及び一般式２ａ－２中のａ１等の記号は、一般式２ａ中のものと同じ意味を有する。 The structural unit 2a has the general formula 2a-1 when a2 is 1 or more.

When a2 is 0, it is represented by the general formula 2a-2.

It is represented by. Symbols such as a1 in the general formula 2a-1 and the general formula 2a-2 have the same meanings as those in the general formula 2a.

The upper limit of the ratio of the constituent unit 2a in the denatured site (R ^2b of the constituent unit 2) is exemplified by 100, 99, 98, 95, 90, 85, 80, 75, 70, 65% by mass, etc., and the lower limit is 99, 98, 95, 90, 85, 80, 75, 70, 65, 60% by mass and the like are exemplified. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the ratio of the constituent unit 2a in the modified portion (R ^2b of the constituent unit 2) is 60 to 100% by mass from the viewpoint of compatibility with the reactive diluent and curability when made into an ink. Is preferable.

The upper limit of the ratio of the constituent unit 2a in the denatured site (R ^2b of the constituent unit 2) is exemplified by 100, 99, 98, 97, 96, 95, 94, 93, 92, 91 mol% and the like, and the lower limit is 99, 98, 95, 94, 93, 92, 91, 90 mol% and the like are exemplified. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the ratio of the constituent unit ^2a in the modified portion (R2b of the constituent unit 2) is 90 to 100 mol from the viewpoint of compatibility with the reactive diluent and curability when made into an ink. % Is preferable.

［Ｒ^ｂ１ａ～Ｒ^ｂ１ｃはそれぞれ独立に、置換若しくは非置換のアリーレン基、置換若しくは非置換のアルキレン基、又は置換若しくは非置換のアルケニレン基であり、
Ｒ^ｂ２ａ～Ｒ^ｂ２ｃはそれぞれ独立に、

であって、Ｒ^ｂ２ａ～Ｒ^ｂ２ｃの少なくとも１つが

であり、
｛Ｂは１以上の整数であり、
Ｒ^Ｂは

（ｂ１は１以上の整数であり、ｂ２は０以上の整数であり、Ｒ^ｂａは水素原子、置換若しくは非置換のアルキル基、置換若しくは非置換のアリール基、置換若しくは非置換のアルコキシ基、又は置換若しくは非置換のアリールオキシ基であり、Ｒ^ｂｂは置換若しくは非置換のアリーレン基、置換若しくは非置換のアルキレン基、又は置換若しくは非置換のアルケニレン基である。）
である。｝
Ｒ^ｂ３ａ～Ｒ^ｂ３ｃはそれぞれ独立に、置換若しくは非置換のアリール基、置換又は非置換のアルキル基、又は置換若しくは非置換のアルケニル基である］
も含む樹脂鎖である。 (Structure unit 2b)
In one embodiment, R ^2b in the constituent unit 2 is the constituent unit 2b in addition to the constituent unit 2a.

[R ^b1a to R ^b1c are independently substituted or unsubstituted arylene groups, substituted or unsubstituted alkylene groups, or substituted or unsubstituted alkenylene groups, respectively.
R ^b2a to R ^b2c are independent of each other.

And at least one of R ^b2a to R ^b2c

And
{B is an integer greater than or equal to 1 and
^RB is

(B1 is an integer of 1 or more, b2 is an integer of 0 or more, R ^ba is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or It is a substituted or unsubstituted aryloxy group, and ^Rbb is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group).
Is. }
R ^b3a to R ^b3c are independently substituted or unsubstituted aryl groups, substituted or unsubstituted alkyl groups, or substituted or unsubstituted alkenyl groups.]
It is a resin chain that also contains.

［Ｒ^ｂ１ａ’～Ｒ^{ｂ１ｃ ’}はそれぞれ独立に、置換若しくは非置換のアリーレン基、置換若しくは非置換のアルキレン基、又は置換若しくは非置換のアルケニレン基であり、
Ｒ^ｂ２ａ’～Ｒ^{ｂ２ｃ ’}は

であり、
Ｒ^ｂ３ａ’～Ｒ^{ｂ３ｃ ’}はそれぞれ独立に、置換若しくは非置換のアリール基、置換又は非置換のアルキル基、又は置換若しくは非置換のアルケニル基である］
化合物を反応（重合）させることにより生じる構成単位である。 The structural unit 2b is based on the above structural unit 2'.

[R ^b1a'to R ^b1c' are independently substituted or unsubstituted arylene groups, substituted or unsubstituted alkylene groups, or substituted or unsubstituted alkenylene groups, respectively.
R ^b2a'to R ^b2c'

And
R ^b3a'to R ^b3c' are independently substituted or unsubstituted aryl groups, substituted or unsubstituted alkyl groups, or substituted or unsubstituted alkenyl groups.]
It is a structural unit generated by reacting (polymerizing) a compound.

Two or more kinds of monomers expressed by the above structural formula and incorporated as the structural unit 2b in the resin chain may be used in combination. Examples of the monomer incorporated as the structural unit 2b include epoxidized soybean oil and the like.

Examples of the substituent of the substituted aryl group, the substituted aryloxy group, the substituted arylene group, and the substituted alkenylene group in the constituent units 2 and 2b include an alkyl group and the like.

The upper limit of the ratio of the constituent unit 2b in the denatured site (R ^2b of the constituent unit 2) is 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2, 1, 0.5, 0. .1 mass% and the like are exemplified, and the lower limit is 39, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2, 1, 0.5, 0.1, 0 mass% and the like. Will be done. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the ratio of the constituent unit 2b in the modified portion (R ^2b of the constituent unit 2) is 0 to 40% by mass from the viewpoint of compatibility with the reactive diluent and curability when made into an ink. Is preferable.

The upper limit of the ratio of the constituent unit 2b in the denatured site (R ^2b of the constituent unit 2) is 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1 mol%. Etc. are exemplified, and the lower limit is exemplified by 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0 mol% and the like. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the ratio of the constituent unit 2b in the modified site (R ^2b of the constituent unit 2) is 0 to 10 mol from the viewpoint of compatibility with the reactive diluent and curability when made into an ink. % Is preferable.

(Structural unit that is neither 1 nor 2 (also referred to as "other structural unit"))
Examples of the constituent units that are neither the constituent units 1 nor 2 include structural units derived from acrylic acid, methacrylic acid, maleic acid, fumaric acid, and half esters thereof.

The upper limit of the ratio of the structural units that are neither 1 nor 2 in the resin is 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass, etc. Is exemplified, and the lower limit is 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0% by mass and the like. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, from the viewpoint of compatibility with the reactive diluent and the like, the ratio of the structural units in the resin that are neither 1 nor 2 is preferably 0 to 70% by mass.

The upper limit of the ratio of the constituent units that are neither 1 nor 2 in the resin is 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1 mol%, etc. Is exemplified, and the lower limit is 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0 mol% and the like. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, from the viewpoint of compatibility with the reactive diluent and the like, the ratio of the structural units in the resin that are neither 1 nor 2 is preferably 0 to 70 mol%.

(Relative ratio between each structural unit)
The upper limit of the mass ratio between the constituent unit 1 and the constituent unit 2 in the resin (mass of the constituent unit 1 / mass of the constituent unit 2) is 3.5, 3, 2.5, 2, 1.5, 1, 0. .5, 0.2 and the like are exemplified, and the lower limit is 3, 2.5, 2, 1.5, 1, 0.5, 0.2, 0.1 and the like. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the mass ratio of the structural unit 1 to the structural unit 2 (mass of the structural unit 1 / mass of the structural unit 2) in the resin is preferably 0.1 to 3.5.

The upper limit of the molar ratio of the constituent unit 1 and the constituent unit 2 in the resin (the amount of substance of the constituent unit 1 / the amount of substance of the constituent unit 2) is 3.5, 3, 2.5, 2, 1.5, 1 , 0.5, 0.2 and the like, and the lower limit is 3, 2.5, 2, 1.5, 1, 0.5, 0.2, 0.1 and the like. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the molar ratio of the constituent unit 1 to the constituent unit 2 (the amount of substance of the constituent unit 1 / the amount of substance of the constituent unit 2) in the resin is preferably 0.1 to 3.5.

The upper limit of the mass ratio between the other structural units and the structural unit 1 in the resin (mass of the other structural units / mass of the structural unit 1) is 7, 6, 5, 4, 3, 2, 1, 0.5. , 0.1 and the like, and the lower limit is 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0 and the like. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the mass ratio of the other structural units to the structural unit 1 in the resin (mass of the other structural units / mass of the structural unit 1) is preferably 0 to 7.

The upper limit of the molar ratio of the other constituent units to the constituent unit 1 in the resin (the amount of substance of the other constituent units / the amount of substance of the constituent unit 1) is 7, 6, 5, 4, 3, 2, 1, 0. .5, 0.1 and the like are exemplified, and the lower limit is 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0 and the like. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the molar ratio of the other structural unit to the structural unit 1 in the resin (the amount of substance of the other structural unit / the amount of substance of the structural unit 1) is preferably 0 to 7.

The upper limit of the mass ratio between the other structural units and the structural unit 2 in the resin (mass of the other structural units / mass of the structural unit 2) is 3.5, 3, 2.5, 2, 1.5, 1 , 0.5, 0.1 and the like, and the lower limit is 3, 2.5, 2, 1.5, 1, 0.5, 0.1, 0 and the like. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the mass ratio of the other structural units to the structural unit 2 in the resin (mass of the other structural units / mass of the structural unit 2) is preferably 0 to 3.5.

The upper limit of the molar ratio between the other constituent units and the constituent unit 2 in the resin (the amount of substance of the other constituent units / the amount of substance of the constituent unit 2) is 3.5, 3, 2.5, 2, 1.5. 1, 0.5, 0.1 and the like are exemplified, and the lower limit is 3, 2.5, 2, 1.5, 1, 0.5, 0.1, 0 and the like. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the molar ratio of the other structural unit to the structural unit 2 in the resin (the amount of substance of the other structural unit / the amount of substance of the structural unit 2) is preferably 0 to 3.5.

The upper limit of the mass ratio between the structural unit 2b and the structural unit 2a in the resin (mass of the structural unit 2b / mass of the structural unit 2a) is 0.7, 0.6, 0.5, 0.4, 0.3. , 0.2, 0.1 and the like, and the lower limit is 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0 and the like. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the mass ratio of the structural unit 2b and the structural unit 2a (mass of the structural unit 2b / mass of the structural unit 2a) in the resin is preferably 0 to 0.7.

The upper limit of the molar ratio of the constituent unit 2b and the constituent unit 2a in the resin (the amount of substance of the constituent unit 2b / the amount of substance of the constituent unit 2a) is 0.2, 0.15, 0.1, 0.05, 0. 0.01 and the like are exemplified, and the lower limit is 0.15, 0.1, 0.05, 0.01, 0 and the like. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the molar ratio of the structural unit 2b to the structural unit 2a (the amount of substance of the structural unit 2b / the amount of substance of the structural unit 2a) in the resin is preferably 0 to 0.2.

(Physical characteristics of resin)
The upper limit of the acid value of the above resin is 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15.1, 10, 6, 10, 9.6. , 8.2, 7.9, 5, 4.5, 1 mgKOH / g, etc., and the lower limit is 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20. , 15.1, 10, 6, 10, 9.6, 8.2, 7.9, 5, 4.5, 1, 0.1 mgKOH / g and the like are exemplified. The acid value range may be set as appropriate (eg, selected from the upper and lower limits). In one embodiment, the acid value of the resin is preferably about 0.1 to 150 mgKOH / g from the viewpoint of compatibility with the reactive diluent and curability when the active energy ray-curable resin composition is obtained.

The upper limit of the weight average molecular weight of the resin is 200,000, 190,000, 180,000, 170,000, 160,000, 150,000, 140,000, 130,000, 120,000, 111,000, 110,000, 104,000, 100,000, 90,000, 80,000, 70,000, 69,000, 60,000, 50,000, 42,000, 40,000, 30,000, 20, 000, 19,000, 15,000, 10,000, 5,000, etc. are exemplified, and the lower limit is 190,000, 180,000, 170,000, 160,000, 150,000, 140,000, 130. 000, 120,000, 111,000, 110,000, 104,000, 100,000, 90,000, 80,000, 70,000, 69,000, 60,000, 50,000, 42,000 40,000, 30,000, 20,000, 19,000, 15,000, 10,000, 5,000, 1,000 and the like are exemplified. The range of the weight average molecular weight can be appropriately set (for example, selected from the upper and lower limit values). In one embodiment, the weight average molecular weight of the resin is preferably about 1,000 to 200,000 from the viewpoint of compatibility with the reactive diluent and curability when the active energy ray-curable resin composition is obtained. ..

The upper limit of the number average molecular weight of the resin is 150,000, 140,000, 130,000, 120,000, 110,000, 100,000, 90,000, 80,000, 70,000, 60,000, Examples include 50,000, 40,000, 30,000, 20,000, 15,000, 10,000, 5,000, 2,500, 1,000, 750, etc., and the lower limit is 140,000, 130. 000, 120,000, 110,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 15,000 Examples thereof include 10,000, 5,000, 2,500, 1,000, 750, and 500. The range of the number average molecular weight can be set as appropriate (for example, by selecting from the upper and lower limit values). In one embodiment, the number average molecular weight of the resin is preferably about 500 to 150,000.

The weight average molecular weight and the number average molecular weight can be measured as polystyrene-equivalent values measured in a suitable solvent, for example, by gel permeation chromatography (GPC).

The upper limit of the softening point of the resin is 150, 140, 130, 120, 114.0, 110, 109.5, 106.5, 105.0, 104.5, 102.5, 100, 90, 80, 70. , 60, 50 ° C., etc., and the lower limit is 140, 130, 120, 114.0, 110, 109.5, 106.5, 105.0, 104.5, 102.5, 100, 90, 80, Examples include 70, 60, 50, 40 ° C. and the like. The range of the softening points can be set as appropriate (for example, by selecting from the upper and lower limit values). In one embodiment, the softening point of the resin is preferably about 40 to 150 ° C. from the viewpoint of compatibility with the reactive diluent and curability when it is included in the active energy ray-curable resin composition. The softening point can be measured, for example, by a method according to JIS K5601.

The resin can be used for conventional applications for diallyl phthalate resins, for example, active energy ray-curable inks (particularly offset printing inks), binder resins for paints, and the like. That is, the resin can be a resin for active energy ray-curable ink, a resin for offset printing ink, and a binder resin for active energy ray-curable paint.

[2. Resin manufacturing method]
The present disclosure provides a method for producing a resin, which comprises a step of reacting a polymer (A) having a carboxyl group and an aryl group with an epoxide (B) or an epoxide (B) and a carboxylic acid anhydride (C).

(A) Polymer having a carboxyl group and an aryl group (component (A))
As the component (A), two or more kinds can be used in combination. The component (A) is a compound having one or more radically polymerizable carbon-carbon double bonds and one or more carboxyl groups (a1) (also referred to as a component (a1)) and one or more radically polymerizable carbon-carbon double bonds. Examples of the compound having a bond and one or more aryl groups (also referred to as a component (a2)) are radical polymers and the like.

Examples of the component (a1) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and half esters thereof.

Examples of the component (a2) include styrene, dimethylstyrene, t-butylstyrene, α-methylstyrene and the like.

Further, the constituent component of the component (A) is a compound (component (a3)) having at least one radically polymerizable carbon-carbon double bond, which is neither the component (a1) nor the component (a2). It may be a thing. The component (a3) is to methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclo (meth) acrylate. (Meta) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms such as xyl and isobornyl acrylate; vinyl monomer having an amide group such as acrylamide, 2-hydroxyethylacrylamide, N, N-dimethylacrylamide and acryloylmorpholin. Etc. are exemplified.

Commercial products of the component (A) are Alastair 700, Alastair 700S (above, manufactured by Arakawa Chemical Industry Co., Ltd.), John Krill 67, John Krill 68, John Krill J680, John Krill J682 (above, manufactured by BASF Japan Ltd.). ) Etc. are exemplified.

(A) The upper limit of the weight average molecular weight of the component is 50,000, 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 15,000, 10,000, 6, 000, 5,000, 2,000, etc. are exemplified, and the lower limit is 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 15,000, 10,000, 6, 000, 5,000, 2,000, 1,000 and the like are exemplified. The range of the weight average molecular weight can be appropriately set (for example, selected from the upper and lower limit values). In one embodiment, the weight average molecular weight of the component (A) is preferably about 1,000 to 50,000 from the viewpoint of compatibility between the resin and the reactive diluent.

Further, the upper limit of the acid value of the component (A) is exemplified by 300, 250, 200, 150, 100, 50, 20 mgKOH / g and the like, and the lower limit is 250, 200, 150, 100, 50, 20, 10 mgKOH / g and the like. Is exemplified. The acid value range may be set as appropriate (eg, selected from the upper and lower limits). In one embodiment, the acid value of the component (A) is preferably about 10 to 300 mgKOH / g from the viewpoint of reactivity.

(B) Epoxide (component (B))
(B) Two or more kinds of components can be used in combination. Examples of the component (B) include a polymerizable double bond-free aromatic epoxide (b1) and a polymerizable double bond-containing aromatic epoxide (b2).

(Polymerizable double bond-free aromatic epoxide (b1))
Examples of the component (b1) include aromatic ring-containing monoglycidyl ether, aromatic-containing diglycidyl ether, and bisphenol type epoxy resin.
Examples of the aromatic ring-containing monoglycidyl ether include phenylglycidyl ether, p-sec-butylphenylglycidyl ether, p-tert-butylphenylglycidyl ether, and styrene oxide.
Examples of the aromatic-containing diglycidyl ether include resorcinol diglycidyl ether and hydroquinone diglycidyl ether.
Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Among these, aromatic ring-containing monoglycidyl ether is preferable, and phenylglycidyl ether is particularly preferable, from the viewpoint of compatibility between the obtained resin and the reactive diluent described later, curability of the ink of the present invention, gloss and the like.

(Polymerizable double bond-containing epoxide (b2))
Examples of the component (b2) include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, rosing lysidyl ester and the like.

(Epoxide (b3) that is neither a component (b1) nor a component (b2))
The component (B) may include an epoxide (hereinafter, component (b3)) that is neither a component (b1) nor a component (b2), if necessary. The component (b3) is an aliphatic epoxide such as glycidyl triethyl ether, butylene oxide, cyclohexene oxide, neodecanoic acid glycidyl ester;
Diepoxides such as 1,6-hexanediol diglycidyl ether and butanediol diglycidyl ether;
Examples thereof include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol triglycidyl ether, trimethylolpropane polyglycidyl ether, and polyepoxides such as epoxidized soybean oil. Among these, epoxidized soybean oil is particularly preferable from the viewpoint of compatibility between the obtained resin and the reactive diluent described later, curability of the ink of the present invention, gloss and the like.

When the component (b1) is used in combination with the component (b2) and / or the component (b3), the ratio of their use is not particularly limited, but the molar ratio [(b1) component / {(b2) component and / or ( b3) Component}] is preferably about 1/9 to 9/1.

The amount of the component (B) used is not particularly limited, but from the viewpoint of compatibility with the reactive diluent and the curability of the ink, the amount of the component (B) used is 100 parts by mass of the component (A). About 10 to 200 parts by mass is preferable, and about 10 to 150 parts by mass is more preferable.

(C) Carboxylic acid anhydride (component (C))
Two or more kinds of the component (C) can be used together. The component (C) is aromatic carboxylic acid anhydride such as phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride and benzophenone tetracarboxylic acid dianhydride. object;
Alicyclic carboxylic acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic anhydride;
An aliphatic carboxylic acid anhydrides such as glutaric anhydride, pyromellitic anhydride, adipic acid anhydride, succinic anhydride, itaconic anhydride and butane-1,2,3,4-tetracarboxylic acid dianhydride;
Polymers using the above acid anhydride as a raw material (maleic anhydride homopolymer, maleic anhydride-vinyl acetate polymer, maleic anhydride-styrene polymer, maleic anhydride-acrylonitrile polymer, etc.) and the like are exemplified.
Among these, the aromatic carboxylic acid anhydride is particularly preferable from the viewpoint of compatibility and curability of the obtained resin and the reactive diluent described later.

When the component (C) is used, the amount of the component (C) used is not particularly limited, but from the viewpoint of compatibility with the reactive diluent and the curability of the ink, the amount of the component (A) is 100 parts by mass. The amount of the component (C) used is preferably about 10 to 200 parts by mass, more preferably about 10 to 150 parts by mass.

The order and reaction conditions for reacting the component (A), the component (B) and the component (C) are not particularly limited. Specifically, [1] a method of reacting all the components in one pot, [2] in the presence of the component (A), the component (C) is reacted, and then the components (B) and (C) are further reacted. The method is exemplified. The reaction conditions are, for example, a temperature of about 100 to 210 ° C. and a reaction time of about 30 minutes to 8 hours. Further, the reaction system may be depressurized during the reaction of each component or after the reaction is completed to remove the residual monomer.

In addition, the reaction can be carried out under various known catalysts. Two or more types of catalysts can be used in combination. The catalysts are triphenylphosphine, 2-methylimidazole, 1-methylimidazole, triethylamine, diphenylamine, diazabicycloundecene, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate. , Zinc oxide, zinc octylate and the like are exemplified. The amount of the catalyst used is not particularly limited, but is preferably about 0.01 to 5 parts by mass, more preferably about 0.10 to 2 parts by mass with respect to 100 parts by mass of the component (A).

[3. Active energy ray-curable resin composition]
The present disclosure provides an active energy ray-curable resin composition containing the above resin and a reactive diluent.

The active energy ray curable resin composition may contain a plurality of resins of the present invention. In one embodiment, the active energy ray-curable resin composition contains two types of a resin containing the constituent unit 2b in the resin and a resin containing no constituent unit 2b in the resin.

Examples of the reactive diluent include mono (meth) acrylate and poly (meth) acrylate. Two or more kinds of reactive diluents can be used in combination.

In the present disclosure, "(meth) acrylate" means "at least one selected from the group consisting of acrylates and methacrylates". Similarly, "(meth) acrylic" means "at least one selected from the group consisting of acrylic and methacrylic".

(Mono (meth) acrylate)
Examples of the mono (meth) acrylate include a linear alkyl mono (meth) acrylate, a branched alkyl mono (meth) acrylate, a cycloalkyl mono (meth) acrylate, and a substituted alkyl mono (meth) acrylate.

Examples of the branched alkyl mono (meth) acrylate include 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and isooctyl (meth) acrylate.

Examples of the cycloalkyl mono (meth) acrylate include cyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate.

Examples of the substituted alkyl mono (meth) acrylate include benzyl (meth) acrylate.

(Poly (meth) acrylate)
Poly (meth) acrylates include alkylene poly (meth) acrylate, trimethylolpropane poly (meth) acrylate, dimethylolpropane poly (meth) acrylate, pentaerythritol poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, and glycerol. Examples thereof include poly (meth) acrylate.

The alkylene poly (meth) acrylate includes 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. ) Acrylate and the like are exemplified.

Examples of the trimethylolpropane poly (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and propylene oxide-modified trimethylolpropane tri (meth) acrylate.

Examples of the ditrimethylolpropane poly (meth) acrylate include ditrimethylolpropane tetra (meth) acrylate and ethylene oxide-modified ditrimethylolpropane tetra (meth) acrylate.

Examples of the pentaerythritol poly (meth) acrylate include pentaerythritol tetra (meth) acrylate and ethylene oxide-modified pentaerythritol tetra (meth) acrylate.

Examples of the dipentaerythritol poly (meth) acrylate include dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

Examples of the glycerol poly (meth) acrylate include a glycerol tri (meth) acrylate.

Examples of the poly (meth) acrylate other than the above include diethylene glycol di (meth) acrylate, ethylene oxide-modified di (meth) acrylate of bisphenol A, polyurethane poly (meth) acrylate, and polymer (meth) acrylate.

The mass ratio of the resin of the present invention to the reactive diluent is not particularly limited, but considering the balance of compatibility, curability, etc., the mass ratio of the resin of the present invention to the reactive diluent ((resin of the present invention) / The upper limit of (reactive diluent)) is exemplified by 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, etc., and the lower limit is 70/30, 60/40, 50 /. Examples thereof include 50, 40/60, 30/70, 20/80 and the like. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the mass ratio of the resin of the present invention to the reactive diluent ((resin of the present invention) / (reactive diluent)) is preferably about 20/80 to 80/20, and is preferably about 20/80 to 80/20. 60/40 is more preferable.

(Photopolymerization initiator)
Further, the active energy ray-curable resin composition of the present invention may further contain a photopolymerization initiator. Two or more kinds of photopolymerization initiators can be used in combination. Photopolymerization initiators are 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethane. -1-one, 1-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- Examples thereof include 2-methyl-1-propane-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide, 4-methylbenzophenone and the like.

The content of the photopolymerization initiator in the active energy ray-curable resin composition is not particularly limited, but the upper limit of the content of the photopolymerization initiator with respect to a total of 100 parts by mass of the resin and the reactive diluent of the present invention is 10. 9, 8, 7, 6, 5, 4, 3, 2 parts by mass and the like are exemplified, and the lower limit is 9, 8, 7, 6, 5, 4, 3, 2, 1 part by mass and the like. The content range may be set as appropriate (eg, selected from the upper and lower limit values). In one embodiment, the content of the photopolymerization initiator in the active energy ray-curable resin composition is preferably about 1 to 10 parts by mass with respect to 100 parts by mass in total of the resin and the reactive diluent of the present invention. ..

(Radical polymerization inhibitor)
Further, the active energy ray-curable resin composition of the present invention may further contain a radical polymerization inhibitor. Two or more radical polymerization inhibitors can be used in combination. Radical polymerization inhibitors include quinone-based polymerization inhibitors such as methquinone, hydroquinone, methoxyhydroquinone, and benzoquinone, 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2-t-butyl-4, Alkylphenol polymerization inhibitors such as 6-dimethylphenol, 2,4,6-tri-t-butylphenol, amine-based polymerization such as alkylated diphenylamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine Examples thereof include prohibited agents, nitrosoamine-based polymerization inhibitors such as N-nitrosophenyl hydroxylamine ammonium salt, 2,4-dinitrophenol, and 2-methyl-N-nitrosoaniline.

The content of the radical polymerization inhibitor in the active energy ray-curable resin composition is not particularly limited, but the upper limit is 10, 9, 8, 7, with respect to a total of 100 parts by mass of the resin and the reactive diluent of the present invention. 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05 parts by mass, etc. are exemplified, and the lower limit is 9, 8, 7, 6, 5, 4, 3, 2, 1, Examples thereof include 0.5, 0.1, 0.05, and 0.01 parts by mass. The content range may be set as appropriate (eg, selected from the upper and lower limit values). In one embodiment, the content of the radical polymerization inhibitor is preferably about 0.01 to 10 parts by mass with respect to 100 parts by mass of the total of the resin and the reactive diluent of the present invention.

(Additive)
The active energy ray-curable resin composition of the present invention may contain components other than the resin, the reactive diluent, the photopolymerization initiator, and the radical polymerization inhibitor as additives. Examples of the additive include a colorant, a photosensitizer, an antioxidant, a light stabilizer, a leveling agent and the like.

The upper limit of the content of the above additive in the active energy ray-curable resin composition is 1, 0.09, 0.08, 0.07, with respect to 100 parts by mass of the total of the resin and the reactive diluent of the present invention. 0.06, 0.05, 0.04, 0.03, 0.02, 0.01 parts by mass, etc. are exemplified, and the lower limit is 0.09, 0.08, 0.07, 0.06, 0. 05, 0 parts by mass and the like are exemplified. The content range may be set as appropriate (eg, selected from the upper and lower limit values). In one embodiment, about 0 to 1 part by mass is preferable with respect to 100 parts by mass in total of the resin and the reactive diluent of the present invention.

The upper limit of the content of the additive with respect to 100 parts by mass of the resin of the present invention is 1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0. 02, 0.01 parts by mass and the like are exemplified, and the lower limit is 0.09, 0.08, 0.07, 0.06, 0.05, 0 parts by mass and the like. The content range may be set as appropriate (eg, selected from the upper and lower limit values). In one embodiment, about 0 to 1 part by mass is preferable with respect to a total of 100 parts by mass of the resin of the present invention.

The method for preparing the active energy ray-curable resin composition is not particularly limited. The above preparation method is a method in which the resin and the reactive diluent of the present invention, and if necessary, a photopolymerization initiator, a radical polymerization inhibitor and an additive are mixed at an appropriate temperature and stirred until a homogeneous solution is obtained. Etc. are exemplified.

The active energy ray-curable resin composition should be adjusted to a viscosity (100 to 600 Pa · s / 25 ° C.) at which ink can be easily prepared. Examples of the viscosity adjusting method include a method of appropriately changing the ratio of the resin and the reactive diluent of the present invention.

Since the active energy ray-curable resin composition has excellent compatibility and curability, it is used for active energy ray-curable inks (particularly offset printing inks), binder resin compositions for active energy ray-curable paints, and the like. obtain. That is, the active energy ray-curable resin composition can be a resin composition for active energy ray-curable ink, a resin composition for offset printing ink, and a binder resin composition for active energy ray-curable paint.

[4. Hardened product]
The present disclosure provides a cured product of the above active energy ray-curable resin composition. The cured product is obtained by applying the active energy ray-curable resin composition to a base material and curing it with active energy rays. Examples of the base material, coating means, coating amount, and curing means are the same as those described in the item of “printed matter” described later.

[5. Active energy ray-curable printing ink]
The present disclosure provides an active energy ray-curable printing ink containing the above-mentioned active energy ray-curable resin composition and pigment. Examples of the pigment include inorganic pigments such as zinc oxide, calcium carbonate, titanium dioxide, cadmium red and carbon black, and organic pigments such as isoindolinone-based, quinacridone-based, phthalocyanine-based and perylene-based pigments. The ink preparing means is not particularly limited, and examples thereof include a three-roll mill and the like.

The composition of the ink of the present invention is not particularly limited, but an example is as follows.
Resin of the present invention About 10 to 30% by mass Reactive diluent About 40 to 79.9% by mass Pigment About 10 to 30% by mass (components that can be added as appropriate)
Radical polymerization inhibitor About 0.01 to 1% by mass Photopolymerization initiator About 0 to 15% by mass Additive About 0 to 10% by mass

[6. Printed matter]
The printed matter of the present invention is obtained by printing an active energy ray-curable offset printing ink on a substrate and curing it.

The base material is paper (art paper, cast coated paper, foam paper, PPC paper, high quality coated paper, kraft paper, polyethylene laminated paper, glassin paper, etc.), as well as plastic base materials (polyolefin, polycarbonate, polymethacrylate, polyester, etc.). Epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornen-based resin, etc.) are exemplified.

Examples of the printing method (coating method) include offset printing, flexographic printing, screen printing, bar coater coating, Mayer bar coating, air knife coating, and gravure coating.

The printing amount (coating amount) is not particularly limited, but the mass after curing is preferably about 0.1 to 30 g / m ² , and more preferably about 1 to 20 g / m ² .

Examples of the curing means include electron beams and ultraviolet rays. Examples of the ultraviolet light source include a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, and a UV-LED. The amount of light, the arrangement of the light source, and the transport speed are not particularly limited, but when a high-pressure mercury lamp is used, the transport speed is preferably about 5 to 50 m / min for one lamp having a light amount of about 80 to 160 W / cm. ..

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the description in the above preferred embodiment and the following examples are provided only for the purpose of illustration, and are not provided for the purpose of limiting the present invention. Accordingly, the scope of the invention is not limited to the embodiments or examples specifically described herein, but only by the claims. Further, unless otherwise specified, parts or% are based on mass in each Example and Comparative Example.

<Example of resin synthesis>
Production Example 1
100 parts of butyl acetate was added to a container equipped with a stirrer, a cooling tube, and a nitrogen introduction tube, and 60 parts of styrene, 15 parts of 98% acrylic acid, and 25 parts of butyl methacrylate were charged in a dropping funnel. 10 parts of 2,2-azobis (2-methylbutyronitrile) (ABN-E) was added as a polymerization initiator, and the polymerization was carried out under reflux and stirring at 140 ° C. for 1.5 hours and kept warm for 1 hour. Then, the temperature was set to 160 ° C., and the solvent was distilled off to obtain a styrene-acrylic resin (A-1) having an acid value of 100 mgKOH / g and a weight average molecular weight of 6,000 (hereinafter referred to as (A-1)). Subsequently, 100 parts of (A-1), 100 parts of phthalic anhydride, and 100 parts of phenylglycidyl ether were charged in a container equipped with a stirrer, a cooling pipe, and a nitrogen introduction pipe, and the temperature was raised to 140 ° C. Then, after adding 0.3 part of triphenylphosphine, the mixture was stirred at 160 ° C. for 4 hours. Then, the pressure was reduced to −0.08 MPa to obtain a resin.

Manufacturing example 2
Add 100 parts of butyl acetate to a container equipped with a stirrer, a condenser, and a nitrogen introduction tube, and add 55 parts of styrene, 10 parts of 98% acrylic acid, 20 parts of 2-ethylhexyl acrylate, and 15 parts of acryloylmorpholine to the dropping funnel. Preparation. 10 parts of 2,2-azobis (2-methylbutyronitrile) (ABN-E) was added as a polymerization initiator, and the polymerization was carried out under reflux and stirring at 140 ° C. for 1.5 hours and kept warm for 1 hour. Then, the temperature was set to 160 ° C., and the solvent was distilled off to obtain a styrene-acrylic resin (A-2) having an acid value of 75 mgKOH / g and a weight average molecular weight of 5,000 (hereinafter referred to as (A-2)). Subsequently, 50 parts of (A-2), 50 parts of (A-1) obtained in Production Example 1, 80 parts of phthalic anhydride, and 80 parts of phenylglycidyl ether were placed in a container equipped with a stirrer, a cooling pipe, and a nitrogen introduction pipe. Was charged and the temperature was raised to 140 ° C. Then, after adding 0.3 part of triphenylphosphine, the mixture was stirred at 160 ° C. for 4 hours. Then, the pressure was reduced to −0.08 MPa to obtain a resin.

Production example 3
100 parts of (A-1) obtained in Production Example 1, 100 parts of phthalic anhydride, 100 parts of phenylglycidyl ether, epoxidized soybean oil (New Japan Rika Co., Ltd.) in a container equipped with a stirrer, a cooling pipe, and a nitrogen introduction pipe. )) 5 parts were charged and the temperature was raised to 140 ° C. Then, after adding 0.3 part of triphenylphosphine, the mixture was stirred at 160 ° C. for 4 hours. Then, the pressure was reduced to −0.08 MPa to obtain a resin.

Production example 4
100 parts of (A-2) obtained in Production Example 2, 50 parts of phthalic anhydride, 50 parts of phenylglycidyl ether, epoxidized soybean oil (New Japan Rika Co., Ltd.) in a container equipped with a stirrer, a cooling pipe, and a nitrogen introduction pipe. )) 5 parts were charged and the temperature was raised to 140 ° C. Then, after adding 0.3 part of triphenylphosphine, the mixture was stirred at 160 ° C. for 4 hours. Then, the pressure was reduced to −0.08 MPa to obtain a resin.

Production Example 5
100 parts of (A-1) obtained in Production Example 1 and 25 parts of phenylglycidyl ether were charged in a container equipped with a stirrer, a cooling pipe and a nitrogen introduction pipe, and the temperature was raised to 140 ° C. Then, after adding 0.3 part of triphenylphosphine, the mixture was stirred at 160 ° C. for 4 hours. Then, the pressure was reduced to −0.08 MPa to obtain a resin.

The following physical properties were measured for the resins obtained in Production Examples 1 to 5.

<Acid value>
It was measured by a method according to JIS K5601. The results are shown in Table 1.

<Weight average molecular weight>
It was measured by a polystyrene calibration curve using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8320). The results are shown in Table 1.

<Softening point>
It was measured by a method according to JIS K5601. The results are shown in Table 1.

<Preparation of active energy ray-curable resin composition>
Example 1
In a reaction vessel equipped with a stirrer and a cooling tube, 40.0 parts of the resin obtained in Production Example 1, 60.0 parts of ditrimethylolpropanetetraacrylate (Beamset 730 manufactured by Arakawa Chemical Industries, Ltd.), and methquinone as a polymerization inhibitor. Add 0.1 part (manufactured by Seiko Kagaku Co., Ltd., the same applies hereinafter) and 0.05 part of Q-1301 (manufactured by Wako Pure Chemical Industries, Ltd., the same applies hereinafter), stir at 120 ° C. for 1 hour, and activate energy beam. A curable resin composition was obtained.

Examples 2 to 5 and Comparative Example 1
An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that the type of resin and the amounts of resin and ditrimethylolpropane tetraacrylate used were changed to Table 2.

The following physical characteristics of the active energy ray-curable resin compositions obtained in Examples 1 to 5 and Comparative Example 1 were measured.

<E-type viscosity>
It was measured by a method according to JIS Z8803. The results are shown in Table 2.

ジアリルフタレート樹脂：ダイソーダップＡ（大阪ソーダ製）

Dialyl phthalate resin: Daiso Dap A (manufactured by Osaka Soda)

<Preparation of active energy ray-curable ink>
As a black pigment, 15.0 parts of carbon black, 50.0 parts of the active energy ray-curable resin composition prepared in Example 1, 30 parts of beam set 730, 0.1 parts of methquinone, and a photopolymerization initiator. As a result, 5.0 parts of Irgacure 907 (manufactured by BASF) was charged, and an active energy ray-curable ink was prepared by a conventional method using a three-roll mill. The active energy ray-curable ink was prepared in the same manner for Examples 2 to 5 and Comparative Example 1.

The active energy ray-curable ink prepared as described above is applied to coated paper using an RI tester (manufactured by Ming Seisakusho Co., Ltd.), and an ultraviolet irradiator (80 W / cm, irradiation distance 25 cm, conveyor speed 8.0 m). The printed matter was obtained by irradiating with ultraviolet rays at (/ min).

<Ink performance evaluation>
The following tests were performed on the inks of Examples and Comparative Examples.

<Ink curing speed>
Table 3 shows the irradiation amount required for producing the printed matter. Even if the irradiation amount is small, the one that is cured has good curability.

<Ink gloss>
The gloss value of the cured film obtained by producing the printed matter was measured with an integrated gloss meter HVG-2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.). The results are shown in Table 3. The higher the gloss value, the better the gloss.

<Solvent resistance of ink>
The state of the coating film surface after rubbing the cured film obtained by producing the printed matter 40 times with a cotton swab impregnated with ethyl acetate was visually confirmed, and the solvent resistance was evaluated according to the following criteria. The results are shown in Table 3.
◯: Almost no change △: Rubbing marks remain ×: Ink disappears and the base material can be confirmed

Claims (8)

Configuration unit 1

(R ^1a is a hydrogen or an alkyl group, and R ^1b to R ^1f are independently selected from the group consisting of a hydrogen, an alkyl group and an aryl group.)
And the structural unit 2

[R ^2a is a hydrogen or an alkyl group, and R ^2b is the following structural unit 2a.

{A1 is an integer of 1 or more, a2 is an integer of 0 or more, R ^aa is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or It is a substituted or unsubstituted aryloxy group, ^Rab is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group, and the substituent is an alkyl group or an aryloxy group. It is a group . }
It is a resin chain containing. ]
Including resin
An active energy ray-curable resin composition comprising a reactive diluent . The resin chain is the structural unit 2b.

[R ^b1a to R ^b1c are independently substituted or unsubstituted arylene groups, substituted or unsubstituted alkylene groups, or substituted or unsubstituted alkenylene groups, respectively.
R ^b2a to R ^b2c are independent of each other.

And at least one of R ^b2a to R ^b2c

And
{B is an integer greater than or equal to 1 and
^RB is

(B1 is an integer of 1 or more, b2 is an integer of 0 or more, R ^ba is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or It is a substituted or unsubstituted aryloxy group, and ^Rbb is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group).
Is. }
R ^b3a to R ^b3c are independently substituted or unsubstituted aryl groups, substituted or unsubstituted alkyl groups, or substituted or unsubstituted alkenyl groups.]
The active energy ray-curable resin composition according to claim 1. The active energy ray-curable resin composition according to claim 1 or 2, wherein the acid value of the resin is 0.1 to 150 mgKOH / g. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the resin has a weight average molecular weight of 1,000 to 200,000. The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the softening point of the resin is 40 to 150 ° C. A cured product of the active energy ray-curable resin composition according to any one of claims 1 to 5 . An active energy ray-curable printing ink containing the active energy ray-curable resin composition and pigment according to any one of claims 1 to 5 . A printed matter comprising a cured layer of the active energy ray-curable printing ink according to claim 7 .