JP7073834B2 - Resins, varnish compositions, offset printing inks and printed matter - Google Patents

Description

The present disclosure relates to resins, varnish compositions, offset printing inks and printed matter.

The active energy ray-curable printing ink, which is cured by active energy rays such as ultraviolet rays and electron beams, may contain a reactive diluent, a resin, a photopolymerization initiator and an additive. As the reactive diluent, polyfunctional acrylates such as dipentaerythritol hexaacrylate and ditrimethylolpropane tetraacrylate are widely used because they are excellent in curability and film hardness.

On the other hand, diallyl phthalate resin, styrene acrylic resin, polyester resin and the like are widely used for the purpose of improving printability.

Japanese Patent No. 5683757

In the conventional styrene acrylic resin and polyester resin, there is a trade-off relationship between ink fluidity and misting resistance, and the current situation is that a resin having both of these performances has not been obtained. On the other hand, the diallyl phthalate resin is obtained by polymerizing a diallyl phthalate monomer and does not have a hydroxyl group, a carboxyl group, or the like, 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.

An object to be solved by the present invention is to provide a resin which is a raw material of a printing ink having excellent ink fluidity and misting resistance.

As a result of diligent studies, the present inventors have found that the above-mentioned problems can be solved by a predetermined resin.

［式中、Ｒ^ａ１は水素原子又はアルキル基であり、Ｒ^ａ２は、水素原子、置換若しくは非置換のアルキル基又は

｛式中、ａは１以上の整数であり、ｂ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。｝
である。］
であり、
前記構成単位２は一般式

［式中、ｎ及びｍはそれぞれ独立に０～２の整数であり、ｐは０～７の整数であり、Ｒ^ｂ１～Ｒ^ｂ１７は、それぞれ独立に水素原子、

｛式中、ｑ及びｒはそれぞれ独立に０～１６の整数であり、ｓ及びｔはそれぞれ独立に１以上の整数であり、Ｒ^１～Ｒ^６はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１及びＲ^３は各単位ごとに基が異なっていてもよく、Ｒ^Ａ～Ｒ^Ｂはそれぞれ独立に前記構成単位１を含む構成単位群から選択される構成単位である。｝
であり、
Ｒ^ｂ１８～Ｒ^ｂ１９は、それぞれ独立に

｛式中、ｑ及びｒはそれぞれ独立に０～１６の整数であり、ｓ及びｔはそれぞれ独立に１以上の整数であり、Ｒ^１～Ｒ^６はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１及びＲ^３は各単位ごとに基が異なっていてもよく、Ｒ^Ａ～Ｒ^Ｂはそれぞれ独立に該構成単位１を含む構成単位である。｝
であり、
Ｒ^ｂ２０はアルキレン基であり、
Ｒ^ｂ４、Ｒ^ｂ５、Ｒ^ｂ９、及びＲ^ｂ１３は各構成単位ごとに基が異なっていてもよく、
一般式（Ａ）～（Ｄ）中において

｛式中、ｑ及びｒはそれぞれ独立に０～１６の整数であり、ｓ及びｔはそれぞれ独立に１以上の整数であり、Ｒ^１～Ｒ^６はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１及びＲ^３は各単位ごとに基が異なっていてもよく、Ｒ^Ａ～Ｒ^Ｂはそれぞれ独立に該構成単位１を含む構成単位である。｝
が２個以上含まれる。］
である、樹脂。
（項目２）
前記構成単位群に構成単位３

（式中、Ｒ^ｃ１は水素原子又はアルキル基であり、Ｒ^ｃ２～Ｒ^ｃ６はそれぞれ独立に、水素原子、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。）
が含まれる、上記項目に記載の樹脂。
（項目３）
前記構成単位群に構成単位４

（式中、Ｒ^Ｄは水素原子又はアルキル基であり、Ｒ^ｄはＣＯＮＲ^ｄ１Ｒ^ｄ２、ＣＯＯ（ＣＨ_２）_２ＮＲ^ｄ１Ｒ^ｄ２及び

からなる群から選択される基であり、
式中、Ｒ^ｄ１及びＲ^ｄ２は、アルキル基若しくは水素原子であるか、又はＲ^ｄ１及びＲ^ｄ２が一緒になって環構造を形成する基であり、ｋは１以上の整数であり、Ｒ^ｄ３は、水素原子、メチル基又は水酸基であり、Ｒ^ｄ４は、ＯＨ、ＣＨ_２ＯＨ、ＣＨ_２ＣＨ_２ＯＨ、ＣＨ_２ＯＣＨ_３又はＣＨ_２ＯＰｈであるが、Ｒ^ｄ３又はＲ^ｄ４のどちらかが水酸基である。）
が含まれる、上記項目のいずれか１項に記載の樹脂。
（項目４）
構成単位５

（式中、Ｒ^ｅ１～Ｒ^ｅ３は、それぞれ独立に、ニトリル基、アルキル基、又はアルケニル基である。）
を含む、上記項目のいずれか１項に記載の樹脂。
（項目５）
（メタ）アクリル酸エステル、並びに（ポリ）ペンタエリスリトールポリ（アルキレンオキサイド変性又はエポキシ変性）（メタ）アクリレート、（ポリ）トリメチロープロパンルポリ（アルキレンオキサイド変性又はエポキシ変性）（メタ）アクリレート、（ポリ）グリセリンポリ（アルキレンオキサイド変性又はエポキシ変性）（メタ）アクリレート、及びアルキレンジ（アルキレンオキサイド変性又はエポキシ変性）（メタ）アクリレートからなる群から選択される１種以上を含むモノマーを、モノマー濃度１０～７０質量％で、該モノマー１００質量部に対して３～５０質量部の重合開始剤存在下、７０～２００℃で重合させる工程を含む、上記項目のいずれか１項に記載の樹脂の製造方法。
（項目６）
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、ワニス組成物。
（項目７）
前記反応性希釈剤が

［式中、ｎ及びｍはそれぞれ独立に０～２の整数であり、ｐは０～７の整数であり、Ｒ^ｂ１’～Ｒ^{ｂ１７ ’}は、それぞれ独立に水素原子、

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^３’はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、
Ｒ^ｂ１８’～Ｒ^{ｂ１９ ’}は、それぞれ独立に

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、
Ｒ^ｂ２０’はアルキレン基であり、
Ｒ^ｂ４’、Ｒ^ｂ５’、Ｒ^ｂ９’、及びＲ^ｂ１３’は各構成単位ごとに基が異なっていてもよく、
一般式（Ａ^’）～（Ｄ^’）中において

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
が２個以上含まれる。］
である、上記項目に記載のワニス組成物。
（項目８）
オフセット印刷インキに用いられる、上記項目のいずれか１項に記載のワニス組成物。
（項目９）
上記項目のいずれか１項に記載のワニス組成物及び顔料を含む、オフセット印刷インキ。
（項目１０）
上記項目に記載のオフセット印刷インキの硬化層を有する、印刷物。
The disclosure provides the following items:
(Item 1)
A resin having a molecular weight distribution (Mw / Mn) of 1.5 to 55, which comprises the following structural units 1 and 2, wherein the structural unit 1 is

[In the formula, R ^a1 is a hydrogen atom or an alkyl group, and R ^a2 is a hydrogen atom, a substituted or unsubstituted alkyl group or

{In the formula, a is an integer of 1 or more, b is an integer of 0 or more, and R ^aa is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted. It is an aryloxy group, and R ^ab is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
Is. ]
And
The structural unit 2 is a general formula.

[In the equation, n and m are independently integers of 0 to 2, p is an integer of 0 to 7, and R ^b1 to R ^b17 are independently hydrogen atoms.

{In the equation, q and r are independently integers of 0 to 16, s and t are independently integers of 1 or more, and R ¹ to R ⁶ are independently hydrogen atoms or alkyl groups, respectively. The groups of R ¹ and ^{R 3} may be different for each unit, and ^RA to RB are constituent units independently selected from the constituent unit group including the constituent unit 1. }
And
R b18 to R ^b19 are independent of each ^other .

{In the equation, q and r are independently integers of 0 to 16, s and t are independently integers of 1 or more, and R ¹ to R ⁶ are independently hydrogen atoms or alkyl groups, respectively. The groups of R ¹ and ^{R 3} may be different for each unit, and ^RA to RB are structural units including the structural unit 1 independently. }
And
R ^b20 is an alkylene group and is an alkylene group.
R ^b4 , R ^b5 , R ^b9 , and R ^b13 may have different groups for each structural unit.
In the general formulas (A) to (D)

{In the equation, q and r are independently integers of 0 to 16, s and t are independently integers of 1 or more, and R ¹ to R ⁶ are independently hydrogen atoms or alkyl groups, respectively. The groups of R ¹ and ^{R 3} may be different for each unit, and ^RA to RB are structural units including the structural unit 1 independently. }
Is included in two or more. ]
Is a resin.
(Item 2)
Constituent unit 3 in the constituent unit group

(In the formula, R ^c1 is a hydrogen atom or an alkyl group, and R ^c2 to R ^c6 are independently selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group.)
The resin according to the above item, which comprises.
(Item 3)
Constituent unit 4 in the constituent unit group

(In the formula, ^RD is a hydrogen atom or an alkyl group, and R ^d is CONR ^d1 R ^d2 , COO (CH ₂ ) ₂ NR ^d1 R ^d2 and

It is a group selected from the group consisting of
In the formula, R ^d1 and R ^d2 are an alkyl group or a hydrogen atom, or R ^d1 and R ^d2 are a group forming a ring structure together, k is an integer of 1 or more, and R ^d3 . Is a hydrogen atom, a methyl group or a hydroxyl group, and R ^d4 is OH, CH ₂ OH, CH ₂ CH ₂ OH, CH ₂ OCH ₃ or CH ₂ OPh, but either R ^d3 or R ^d4 is a hydroxyl group. Is. )
The resin according to any one of the above items, which comprises.
(Item 4)
Configuration unit 5

(In the formula, R ^e1 to R ^e3 are independently nitrile groups, alkyl groups, or alkenyl groups.)
The resin according to any one of the above items, which comprises.
(Item 5)
(Meta) Acrylic Acid Ester, and (Poly) Pentaerythritol Poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, (Poly) Trimethylopropanulpoly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, (poly) ) A monomer containing one or more selected from the group consisting of glycerin poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate and alkylene di (alkylene oxide-modified or epoxy-modified) (meth) acrylate, having a monomer concentration of 10 to 10 to The method for producing a resin according to any one of the above items, which comprises a step of polymerizing at 70 to 200 ° C. in the presence of 3 to 50 parts by mass of a polymerization initiator with respect to 100 parts by mass of the monomer at 70% by mass. ..
(Item 6)
A varnish composition containing the resin according to any one of the above items and a reactive diluent.
(Item 7)
The reactive diluent

[In the equation, n and m are independently integers of 0 to 2, p is an integer of 0 to 7, and R ^b1'to R ^b17'are independent hydrogen atoms.

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
And
R ^b18'to R ^b19'are independent of each other

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
And
R ^b20'is an alkylene group and is
R ^b4' , R ^b5' , R ^b9' , and R ^b13'may have different groups for each structural unit.
In the general formulas (A ^' ) to (D ^' )

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
Is included in two or more. ]
The varnish composition according to the above item.
(Item 8)
The varnish composition according to any one of the above items, which is used for offset printing ink.
(Item 9)
An offset printing ink containing the varnish composition and pigment according to any one of the above items.
(Item 10)
A printed matter having a cured layer of the offset printing ink according to the above item.

In the present disclosure, the above-mentioned features may be provided in combination in addition to the specified combinations. One of ordinary skill in the art can recognize further embodiments and advantages other than the above by reading and understanding the following detailed description as necessary.

When the resin of the present invention is used, it has excellent ink fluidity while having various ink performances (adhesion, coating hardness, emulsifying property, image reproducibility, glossiness, blocking resistance, coating film smoothness, etc.). It is possible to obtain an offset printing ink having a misting resistance.

［式中、Ｒ^ａ１は水素原子又はアルキル基であり、Ｒ^ａ２は、水素原子、置換若しくは非置換のアルキル基又は

｛式中、ａは１以上の整数であり、ｂ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。｝
である。］
であり、
前記構成単位２は一般式

［式中、ｎ及びｍはそれぞれ独立に０～２の整数であり、ｐは０～７の整数であり、Ｒ^ｂ１～Ｒ^ｂ１７は、それぞれ独立に水素原子、

｛式中、ｑ及びｒはそれぞれ独立に０～１６の整数であり、ｓ及びｔはそれぞれ独立に１以上の整数であり、Ｒ^１～Ｒ^６はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１及びＲ^３は各単位ごとに基が異なっていてもよく、Ｒ^Ａ～Ｒ^Ｂはそれぞれ独立に前記構成単位１を含む構成単位群から選択される構成単位である。｝
であり、
Ｒ^ｂ１８～Ｒ^ｂ１９は、それぞれ独立に

｛式中、ｑ及びｒはそれぞれ独立に０～１６の整数であり、ｓ及びｔはそれぞれ独立に１以上の整数であり、Ｒ^１～Ｒ^６はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１及びＲ^３は各単位ごとに基が異なっていてもよく、Ｒ^Ａ～Ｒ^Ｂはそれぞれ独立に該構成単位１を含む構成単位である。｝
であり、
Ｒ^ｂ２０はアルキレン基であり、
Ｒ^ｂ４、Ｒ^ｂ５、Ｒ^ｂ９、及びＲ^ｂ１３は各構成単位ごとに基が異なっていてもよく、
一般式（Ａ）～（Ｄ）中において

｛式中、ｑ及びｒはそれぞれ独立に０～１６の整数であり、ｓ及びｔはそれぞれ独立に１以上の整数であり、Ｒ^１～Ｒ^６はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１及びＲ^３は各単位ごとに基が異なっていてもよく、Ｒ^Ａ～Ｒ^Ｂはそれぞれ独立に該構成単位１を含む構成単位である。｝
が２個以上含まれる。］
である、樹脂を提供する。
[1. resin]
The present disclosure is a resin having a molecular weight distribution (Mw / Mn) of 1.5 to 55, which comprises the following structural units 1 and 2, wherein the structural unit 1 is a resin.

[In the formula, R ^a1 is a hydrogen atom or an alkyl group, and R ^a2 is a hydrogen atom, a substituted or unsubstituted alkyl group or

{In the formula, a is an integer of 1 or more, b is an integer of 0 or more, and R ^aa is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted. It is an aryloxy group, and R ^ab is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
Is. ]
And
The structural unit 2 is a general formula.

[In the equation, n and m are independently integers of 0 to 2, p is an integer of 0 to 7, and R ^b1 to R ^b17 are independently hydrogen atoms.

{In the equation, q and r are independently integers of 0 to 16, s and t are independently integers of 1 or more, and R ¹ to R ⁶ are independently hydrogen atoms or alkyl groups, respectively. The groups of R ¹ and ^{R 3} may be different for each unit, and ^RA to RB are constituent units independently selected from the constituent unit group including the constituent unit 1. }
And
R b18 to R ^b19 are independent of each ^other .

{In the equation, q and r are independently integers of 0 to 16, s and t are independently integers of 1 or more, and R ¹ to R ⁶ are independently hydrogen atoms or alkyl groups, respectively. The groups of R ¹ and ^{R 3} may be different for each unit, and ^RA to RB are structural units including the structural unit 1 independently. }
And
R ^b20 is an alkylene group and is an alkylene group.
R ^b4 , R ^b5 , R ^b9 , and R ^b13 may have different groups for each structural unit.
In the general formulas (A) to (D)

{In the equation, q and r are independently integers of 0 to 16, s and t are independently integers of 1 or more, and R ¹ to R ⁶ are independently hydrogen atoms or alkyl groups, respectively. The groups of R ¹ and ^{R 3} may be different for each unit, and ^RA to RB are structural units including the structural unit 1 independently. }
Is included in two or more. ]
The resin is provided.

In the present disclosure, "resin" is synonymous with polymer.

（式中、Ｒ^ｃ１は水素原子又はアルキル基であり、Ｒ^ｃ２～Ｒ^ｃ６はそれぞれ独立に、水素原子、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。）
が含まれる。 In one embodiment, the constituent units 3 are added to the constituent unit group.

(In the formula, R ^c1 is a hydrogen atom or an alkyl group, and R ^c2 to R ^c6 are independently selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group.)
Is included.

（式中、Ｒ^Ｄは水素原子又はアルキル基であり、Ｒ^ｄはＣＯＮＲ^ｄ１Ｒ^ｄ２、ＣＯＯ（ＣＨ_２）_２ＮＲ^ｄ１Ｒ^ｄ２及び

からなる群から選択される基であり、
式中、Ｒ^ｄ１及びＲ^ｄ２は、アルキル基若しくは水素原子であるか、又はＲ^ｄ１及びＲ^ｄ２が一緒になって環構造を形成する基であり、ｋは１以上の整数であり、Ｒ^ｄ３は、水素原子、メチル基又は水酸基であり、Ｒ^ｄ４は、ＯＨ、ＣＨ_２ＯＨ、ＣＨ_２ＣＨ_２ＯＨ、ＣＨ_２ＯＣＨ_３又はＣＨ_２ＯＰｈであるが、Ｒ^ｄ３又はＲ^ｄ４のどちらかが水酸基である。）
が含まれる。 In one embodiment, the constituent units 4 are added to the constituent unit group.

(In the formula, ^RD is a hydrogen atom or an alkyl group, and R ^d is CONR ^d1 R ^d2 , COO (CH ₂ ) ₂ NR ^d1 R ^d2 and

It is a group selected from the group consisting of
In the formula, R ^d1 and R ^d2 are an alkyl group or a hydrogen atom, or R ^d1 and R ^d2 are a group forming a ring structure together, k is an integer of 1 or more, and R ^d3 . Is a hydrogen atom, a methyl group or a hydroxyl group, and R ^d4 is OH, CH ₂ OH, CH ₂ CH ₂ OH, CH ₂ OCH ₃ or CH ₂ OPh, but either R ^d3 or R ^d4 is a hydroxyl group. Is. )
Is included.

（式中、Ｒ^ｅ１～Ｒ^ｅ３は、それぞれ独立に、ニトリル基、アルキル基、又はアルケニル基である。）
を含む。 In one embodiment, the resin is a constituent unit 5

(In the formula, R ^e1 to R ^e3 are independently nitrile groups, alkyl groups, or alkenyl groups.)
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.

Examples of the alkenyl group include a linear alkenyl group, a branched alkenyl group, a cycloalkenyl group and the like.

Examples of the linear alkenyl group include a vinyl group, a propenyl group, an n-butenyl group and the like.

The branched alkenyl group is a group in which at least one hydrogen of the linear alkenyl group is substituted with an alkyl group, and examples thereof include 1-methylvinyl group, 1-methylpropenyl group, 1-methylbutenyl group and the like.

Examples of the cycloalkenyl group include a monocyclic cycloalkenyl group.

Examples of the monocyclic cycloalkenyl group include a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclodecenyl group, a 3,5,5-trimethylcyclohexenyl group and the like.

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 condensed 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.

In the present disclosure, the "substituent A group" means a group in which one or more hydrogen atoms contained in the A group are substituted with a group other than a hydrogen atom (such as a monovalent substituent). For example, a substituted alkyl group means a group in which one or more hydrogen atoms contained in an alkyl group are substituted with a group other than a hydrogen atom. Further, the substituted A group also includes a group in which a plurality of substituents are combined to form a ring structure.

（式中、ｖは１以上の整数を表す。）
等が例示される。
なお、構成単位１のＲ^ａ２に該当する部分の置換基は、

が好ましいものとして例示される。また、構成単位１中のＲ^ａａ及びＲ^ａｂの置換基は、

が好ましいものとして例示される。 Examples of the monovalent substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, a hydroxyl group, and a group in which these groups and, if necessary, an ether bond, an ester bond and the like are combined. Examples of the group combining these groups include an alkylalkoxy group, an alkylaryl group (benzyl group and the like), an alkyloxyaryl group, an alkyloxyarylaryl group, an alkyloxyalkylaryl group and the like, and more specifically,

(In the formula, v represents an integer of 1 or more.)
Etc. are exemplified.
The substituent of the portion corresponding to Ra ² of the structural unit 1 is

Is exemplified as preferable. Further, the substituents of R ^aa and R ^ab in the constituent unit 1 are

Is exemplified as preferable.

<Structure unit 1>
The structural unit 1 is a structural unit contained in the polymer chain when (meth) acrylic acid or (meth) acrylic acid ester is used as the monomer. The (meth) acrylic acid and the (meth) acrylic acid ester may be used alone or in combination of two or more.

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".

Examples of the (meth) acrylic acid ester include (meth) acrylic acid linear alkyl ester, (meth) acrylic acid branched alkyl ester, (meth) acrylic acid cycloalkyl ester, and (meth) acrylic acid substituted alkyl ester.

The (meth) acrylic acid linear alkyl ester is methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, n-butyl (meth) acrylic acid, n-butyl (meth) acrylic acid. Examples thereof include pentyl, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, stearyl (meth) acrylate, and lauryl (meth) acrylate.

The (meth) acrylic acid branched alkyl ester is (meth) acrylic acid iso-propyl, (meth) acrylic acid iso-butyl, (meth) acrylic acid sec-butyl, (meth) acrylic acid tert-butyl, (meth) acrylic. Examples thereof include iso-octyl acid, 2-ethylhexyl (meth) acrylate, and the like.

Examples of the (meth) acrylic acid cycloalkyl ester include (meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl and the like.

Examples of the (meth) acrylic acid substituted alkyl ester include glycidyl (meth) acrylic acid.

The upper limit of the ratio of the constituent unit 1 to all the constituent units is 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, with respect to the mass of all the constituent units (100% by mass of all the constituent units). 50, 45, 40, 35, 30, 25, 21% by mass and the like are exemplified, and the lower limit is 98, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35. , 30, 25, 21, 20% by mass and the like are exemplified. The range of the above proportions can be set as appropriate (eg, selected from the above upper and lower limit values). In one embodiment, from the viewpoint of suppressing gelation, the ratio of the constituent unit 1 to 100% by mass of all the constituent units is preferably 20 to 99% by mass.

In the present disclosure, "mass of all constituent units" is synonymous with the mass of resin.

The upper limit of the ratio of the constituent unit 1 to all the constituent units is 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35 with respect to 100 mol% of all the constituent units. , 30, 25, 21 mol%, etc., and the lower limit is 98, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 21, 20 mol% and the like are exemplified. The range of the above proportions can be set as appropriate (eg, selected from the above upper and lower limit values). In one embodiment, from the viewpoint of suppressing gelation, the ratio of the constituent unit 1 to 100 mol% of all the constituent units is preferably 20 to 99 mol%.

<Structure unit 2>
The structural unit 2 is a structural unit derived from the polyfunctional monomer described below. The polyfunctional monomer may be used alone or in combination of two or more.

［式中、ｎは０～２の整数であり、Ｒ^ｂ１’～Ｒ^{ｂ６ ’}は、それぞれ独立に水素原子、

｛式中、ｑはそれぞれ独立に０～１６の整数であり、Ｒ^１’～Ｒ^３’はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、
Ｒ^ｂ４’、及びＲ^ｂ５’は各構成単位ごとに基が異なっていてもよく、
一般式（Ａ^’）中において

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
が２個以上含まれる。］
で示される（ポリ）ペンタエリスリトールポリ（アルキレンオキサイド変性又はエポキシ変性）（メタ）アクリレートを用いた場合にポリマー鎖に含まれる構成単位である。 (Constituent unit 2A)
The structural unit 2A is a monomer of the general formula A'.

[In the equation, n is an integer of 0 to 2, and R ^b1'to R ^b6'are independent hydrogen atoms.

{In the equation, q is an independently integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'is a different group for each unit. good. }
And
R ^b4'and R ^b5' may have different groups for each structural unit.
In the general formula (A ^' )

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
Is included in two or more. ]
It is a structural unit contained in a polymer chain when (poly) pentaerythritol poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate represented by is used.

Ｒ^ｂ４ＡとＲ^ｂ４Ｂとは異なる基であってよく、Ｒ^ｂ５ＡとＲ^ｂ５Ｂとは異なる基であってよいことを意味する。 In the present disclosure, "the group may be different for each structural unit" means, for example, when n is 2 in the general formula (A).

It means that R ^b4A and R ^b4B may be different groups, and R ^b5A and R ^b5B may be different groups.

In the present disclosure, "(poly) pentaerythritol poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate" refers to "pentaerythritol poly (meth) acrylate, pentaerythritol polyalkylene oxide-modified (meth) acrylate, pentaerythritol polyepoxy-modified". Means at least one selected from the group consisting of (meth) acrylate, polypentaerythritol poly (meth) acrylate, polypentaerythritol polyalkylene oxide-modified (meth) acrylate, and polypentaerythritol polyepoxy-modified (meth) acrylate. do.

Pentaerythritol poly (meth) acrylates include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, and pentaerythritol hexa (meth) acrylate. Illustrated.

Pentaerythritol polyalkylene oxide-modified (meth) acrylates include pentaerythritol di (ethylene oxide-modified (meth) acrylate), pentaerythritol tri (ethylene oxide-modified (meth) acrylate), and pentaerythritol tetra (ethylene oxide-modified (meth) acrylate). , Pentaerythritol penta (ethylene oxide-modified (meth) acrylate), pentaerythritol hexa (ethylene oxide-modified (meth) acrylate), pentaerythritol di (propylene oxide-modified (meth) acrylate), pentaerythritol tri (propylene oxide-modified (meth) acrylate) Examples thereof include pentaerythritol tetra (propylene oxide-modified (meth) acrylate), pentaerythritol penta (propylene oxide-modified (meth) acrylate), and pentaerythritol hexa (propylene oxide-modified (meth) acrylate).

Pentaerythritol polyepoxy-modified (meth) acrylates are pentaerythritol diepoxy (meth) acrylate, pentaerythritol triepoxy (meth) acrylate, pentaerythritol tetraepoxy (meth) acrylate, pentaerythritol pentaepoxy (meth) acrylate, and pentaerythritol hexa. Epoxy (meth) acrylate and the like are exemplified.

Polypentaerythritol poly (meth) acrylate includes dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa. (Meta) acrylate, dipentaerythritol hepta (meth) acrylate, dipentaerythritol octa (meth) acrylate, tripentaerythritol di (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol tetra (meth) acrylate, Tripentaerythritol Penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol nona (meth) acrylate, tripentaerythritol deca ( Meta) acrylate and the like are exemplified.

Polypentaerythritol polyalkylene oxide-modified (meth) acrylate includes dipentaerythritol di (ethylene oxide-modified (meth) acrylate), dipenta-erythritol tri (ethylene oxide-modified (meth) acrylate), and dipenta-erythritol tetra (ethylene oxide-modified (ethylene oxide-modified)). Meta) acrylate), dipentaerythritol penta (ethylene oxide-modified (meth) acrylate), dipentaerythritol hexa (ethylene oxide-modified (meth) acrylate), dipentaerythritol hepta (ethylene oxide-modified (meth) acrylate), dipentaerythritol Octa (ethylene oxide-modified (meth) acrylate), dipenta-erythritol di (propylene oxide-modified (meth) acrylate), dipenta-erythritol tri (propylene oxide-modified (meth) acrylate), dipenta-erythritol tetra (propylene oxide-modified (meth)) Pentaerythritol Penta (propylene oxide-modified (meth) acrylate), dipentaerythritol hexa (propylene oxide-modified (meth) acrylate), dipentaerythritol hepta (propylene oxide-modified (meth) acrylate), dipentaerythritol octa Pentaerythritol modified (meth) acrylate), tripentaerythritol di (ethylene oxide modified (meth) acrylate), tripentaerythritol tri (ethylene oxide modified (meth) acrylate), tripentaerythritol tetra (ethylene oxide modified (meth) acrylate) , Tripentaerythritol Penta (ethylene oxide-modified (meth) acrylate), tripentaerythritol hexa (ethylene oxide-modified (meth) acrylate), tripentaerythritol hepta (ethylene oxide-modified (meth) acrylate), tripentaerythritol octa (ethylene oxide) Modified (meth) acrylate), tripentaerythritol nona (ethylene oxide modified (meth) acrylate), tripentaerythritol deca (ethylene oxide modified (meth) acrylate), tripentaerythritol di (propylene oxide modified (meth) acrylate), tri Pentaerythritol tri (propylene oxide-modified (meth) acrylate), tripentae Lithritol tetra (propylene oxide-modified (meth) acrylate), tripentaerythritol penta (propylene oxide-modified (meth) acrylate), tripentaerythritol hexa (propylene oxide-modified (meth) acrylate), tripentaerythritol hepta (propylene oxide-modified (propylene oxide-modified)) Meta) acrylate), tripentaerythritol octa (propylene oxide-modified (meth) acrylate), tripentaerythritol nona (propylene oxide-modified (meth) acrylate), tripentaerythritol deca (propylene oxide-modified (meth) acrylate) and the like are exemplified. To.

Polypentaerythritol polyepoxy-modified (meth) acrylates are dipentaerythritol diepoxy (meth) acrylate, dipentaerythritol triepoxy (meth) acrylate, dipentaerythritol tetraepoxy (meth) acrylate, and dipentaerythritol pentaepoxy (meth) acrylate. Acrylate, dipentaerythritol hexaepoxy (meth) acrylate, dipentaerythritol heptaepoxy (meth) acrylate, dipentaerythritol octaepoxy (meth) acrylate, tripentaerythritol diepoxy (meth) acrylate, tripentaerythritol triepoxy (meth) Acrylate, tripentaerythritol tetraepoxy (meth) acrylate, tripentaerythritol pentaepoxy (meth) acrylate, tripentaerythritol hexaepoxy (meth) acrylate, tripentaerythritol heptaepoxy (meth) acrylate, tripentaerythritol octaepoxy (meth) Examples thereof include acrylate, tripentaerythritol nonaepoxy (meth) acrylate, and tripentaerythritol decaepoxy (meth) acrylate.

［式中、ｍは０～２の整数であり、Ｒ^ｂ７’～Ｒ^{ｂ１０ ’}は、それぞれ独立に水素原子、

｛式中、ｑはそれぞれ独立に０～１６の整数であり、Ｒ^１’～Ｒ^３’はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、
Ｒ^ｂ９’は各構成単位ごとに基が異なっていてもよく、
一般式（Ｂ^’）中において

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
が２個以上含まれる。］
で示される（ポリ）トリメチロールプロパンポリ（アルキレンオキサイド変性又はエポキシ変性）（メタ）アクリレートを用いた場合にポリマー鎖に含まれる構成単位である。 <Structure unit 2B>
The structural unit 2B is a monomer of the general formula B'.

[In the equation, m is an integer of 0 to 2, and R ^b7'to R ^b10'are independent hydrogen atoms.

{In the equation, q is an independently integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'is a different group for each unit. good. }
And
R ^b9'may have a different group for each structural unit.
In the general formula (B ^' )

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
Is included in two or more. ]
It is a structural unit contained in a polymer chain when (poly) trimethylolpropane poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate represented by is used.

In the present disclosure, "(poly) trimethylolpropane poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate" means "trimethylolpropane poly (meth) acrylate, trimethylolpropane polyalkylene oxide-modified (meth) acrylate, tri. Select from the group consisting of methylolpropane polyepoxy-modified (meth) acrylates, polytrimethylolpropane poly (meth) acrylates, polytrimethylolpropane polyalkylene oxide-modified (meth) acrylates, and polytrimethylolpropane polyepoxy-modified (meth) acrylates. It means "at least one that is done".

Examples of the trimethylolpropane poly (meth) acrylate include trimethylolpropane di (meth) acrylate and trimethylolpropane tri (meth) acrylate.

The trimethylolpropane polyalkylene oxide-modified (meth) acrylate includes trimethylolpropane di (ethylene oxide-modified (meth) acrylate), trimethylolpropane tri (ethylene oxide-modified (meth) acrylate), and trimethylolpropane di (propylene oxide-modified (propylene oxide-modified)). Meta) acrylate), trimethylolpropane tri (propylene oxide-modified (meth) acrylate) and the like are exemplified.

Examples of the trimethylolpropane polyepoxy-modified (meth) acrylate include trimethylolpropane diepoxy (meth) acrylate and trimethylolpropane triepoxy (meth) acrylate.

Examples of the polytrimethylolpropane poly (meth) acrylate include ditrimethylolpropane di (meth) acrylate and ditrimethylolpropane di (meth) acrylate.

Polytrimethylolpropane Polyalkylene oxide-modified (meth) acrylates include ditrimethylolpropane di (ethylene oxide-modified (meth) acrylate), ditrimethylolpropane tri (ethylene oxide-modified (meth) acrylate), and ditrimethylolpropane di (propylene oxide-modified). (Meta) acrylate), ditrimethylolpropane tri (propylene oxide-modified (meth) acrylate) and the like are exemplified.

Examples of the polytrimethylolpropane polyepoxy-modified (meth) acrylate include ditrimethylolpropane diepoxy (meth) acrylate and ditrimethylolpropane diepoxy (meth) acrylate.

［式中、ｐは０～７の整数であり、Ｒ^ｂ１１’～Ｒ^{ｂ１４ ’}は、それぞれ独立に水素原子、

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^３’はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、
Ｒ^ｂ１３’は各構成単位ごとに基が異なっていてもよく、
一般式（Ｃ^’）中において

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
が２個以上含まれる。］
で示されるような（ポリ）グリセリンポリ（アルキレンオキサイド変性又はエポキシ変性）（メタ）アクリレートを用いた場合にポリマー鎖に含まれる構成単位である。 <Structure unit 2C>
The structural unit 2C has the general formula C'as a monomer.

[In the equation, p is an integer from 0 to 7, and R ^b11'to R ^b14'are independent hydrogen atoms.

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
And
R ^b13'may have a different group for each structural unit.
In the general formula (C ^' )

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
Is included in two or more. ]
It is a structural unit contained in a polymer chain when (poly) glycerin poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate as shown by is used.

In the present disclosure, "(poly) glycerin poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate" refers to "glycerin poly (meth) acrylate, glycerin polyalkylene oxide-modified (meth) acrylate, glycerin polyepoxy-modified (meth) acrylate". , At least one selected from the group consisting of polyglycerin poly (meth) acrylates, polyglycerin polyalkylene oxide-modified (meth) acrylates, and polyglycerin polyepoxy-modified (meth) acrylates. "

Examples of the glycerin poly (meth) acrylate include glycerin di (meth) acrylate and glycerin tri (meth) acrylate.

Glycerin polyalkylene oxide-modified (meth) acrylate includes glycerindi (ethylene oxide-modified (meth) acrylate), glycerintri (ethylene oxide-modified (meth) acrylate), glycerindi (propylene oxide-modified (meth) acrylate), and glycerintri (glycerintri (methane) acrylate). (Propylene oxide-modified (meth) acrylate) and the like are exemplified.

Examples of the glycerin polyepoxy-modified (meth) acrylate include glycerin diepoxy (meth) acrylate and glycerin triepoxy (meth) acrylate.

Polyglycerin poly (meth) acrylates include diglycerin di (meth) acrylate, diglycerin tri (meth) acrylate, diglycerin tetra (meth) acrylate, triglycerin di (meth) acrylate, triglycerin tri (meth) acrylate, and triglycerin tetra. Examples thereof include (meth) acrylate and triglycerin penta (meth) acrylate.

Polyglycerin polyalkylene oxide-modified (meth) acrylate includes diglycerin di (ethylene oxide-modified (meth) acrylate), diglycerin tri (ethylene oxide-modified (meth) acrylate), diglycerin tetra (ethylene oxide-modified (meth) acrylate), and tri. Glycerin di (ethylene oxide-modified (meth) acrylate), triglycerin tri (ethylene oxide-modified (meth) acrylate), triglycerin tetra (ethylene oxide-modified (meth) acrylate), triglycerin penta (ethylene oxide-modified (meth) acrylate) Diglycerin di (propylene oxide modified (meth) acrylate), diglycerin tri (propylene oxide modified (meth) acrylate), diglycerin tetra (propylene oxide modified (meth) acrylate), triglycerin di (propylene oxide modified (meth) acrylate), Examples thereof include triglycerintri (propylene oxide-modified (meth) acrylate), triglycerin tetra (propylene oxide-modified (meth) acrylate), and triglycerin penta (propylene oxide-modified (meth) acrylate).

Polyglycerin polyepoxy-modified (meth) acrylates include diglycerin diepoxy (meth) acrylate, diglycerin triepoxy (meth) acrylate, diglycerin tetraepoxy (meth) acrylate, triglycerin diepoxy (meth) acrylate, and triglycerintri. Examples thereof include epoxy (meth) acrylate, triglycerin tetraepoxy (meth) acrylate, and triglycerin pentaepoxy (meth) acrylate.

［式中、Ｒ^ｂ１５’～Ｒ^{ｂ１７ ’}は、それぞれ独立に水素原子、

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^３’はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、一般式（Ｄ^’）中において

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
が２個以上含まれる。］
で示されるようなイソシアヌレート構造含有モノマーを用いた場合にポリマー鎖に含まれる構成単位である。 <Structural unit 2D>
The structural unit 2D is a monomer of the general formula D'.

[In the formula, R b15'to R ^{b17' are} independent hydrogen atoms, respectively.

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
And in the general formula (D ^' )

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
Is included in two or more. ]
It is a structural unit contained in a polymer chain when an isocyanurate structure-containing monomer as shown by is used.

Examples of the isocyanurate structure-containing monomer include isocyanuric acid ethylene oxide-modified di (meth) acrylate and isocyanuric acid ethylene oxide-modified tri (meth) acrylate.

［式中、Ｒ^ｂ１８’～Ｒ^{ｂ１９ ’}は、それぞれ独立に

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、
Ｒ^ｂ２０’は、アルキレン基である。］
で示されるようなアルキレンジ（アルキレンオキサイド変性又はエポキシ変性）（メタ）アクリレートを用いた場合にポリマー鎖に含まれる構成単位である。 <Structure unit 2E>
The structural unit 2E is a monomer of the general formula E'.

[In the formula, R ^b18'to R ^b19' are independent of each other.

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
And
R ^b20'is an alkylene group. ]
It is a structural unit contained in a polymer chain when an alkylene di (alkylene oxide-modified or epoxy-modified) (meth) acrylate as shown by is used.

In the present disclosure, the "alkylene di (alkylene oxide-modified or epoxy-modified) (meth) acrylate" comprises "alkylene di (meth) acrylate, alkylene dialkylene oxide-modified (meth) acrylate, and alkylene diepoxy-modified (meth) acrylate. It means "at least one selected from the group".

The alkylene di (meth) acrylate includes 1,2-ethylenediol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,5-pentanediol. Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di ( Examples thereof include meta) acrylate and 1,10-decanediol di (meth) acrylate.

The alkylenedialkylene oxide-modified (meth) acrylate includes 1,2-ethylenediol di (ethylene oxide-modified (meth) acrylate), 1,3-propanedioldi (ethylene oxide-modified (meth) acrylate), and 1,4-butane. Glycoldi (ethylene oxide-modified (meth) acrylate), 1,5-pentanedioldi (ethyleneoxide-modified (meth) acrylate), 1,6-hexanedioldi (ethyleneoxide-modified (meth) acrylate), 1,7- Heptanedioldi (ethyleneoxide-modified (meth) acrylate), 1,8-octanedioldi (ethyleneoxide-modified (meth) acrylate), 1,9-nonanedioldi (ethyleneoxide-modified (meth) acrylate), 1,10 -Decandioldi (ethylene oxide-modified (meth) acrylate), 1,2-ethylenedioldi (propylene oxide-modified (meth) acrylate), 1,3-propanedioldi (propylene oxide-modified (meth) acrylate), 1, 4-butanediol di (propylene oxide-modified (meth) acrylate), 1,5-pentanediol di (propylene oxide-modified (meth) acrylate), 1,6-hexanediol di (propylene oxide-modified (meth) acrylate), 1 , 7-Heptanediol di (propylene oxide-modified (meth) acrylate), 1,8-octanediol di (propylene oxide-modified (meth) acrylate), 1,9-nonanediol di (propylene oxide-modified (meth) acrylate), Examples thereof include 1,10-decanediol di (propylene oxide-modified (meth) acrylate).

The alkylene diepoxy-modified (meth) acrylates are 1,2-ethylenediol diepoxy (meth) acrylate, 1,3-propanediol diepoxy (meth) acrylate, and 1,4-butanediol diepoxy (meth) acrylate, 1. , 5-Pentanediol diepoxy (meth) acrylate, 1,6-hexanediol diepoxy (meth) acrylate, 1,7-heptanediol diepoxy (meth) acrylate, 1,8-octanediol diepoxy (meth) acrylate , 1,9-Nonandiol diepoxy (meth) acrylate, 1,10-decanediol diepoxy (meth) acrylate and the like are exemplified.

The upper limit of the ratio of the constituent unit 2 (one or more of the group consisting of the constituent units 2A, 2B, 2C, 2D and 2E) to the total constituent units is 50, 45, 40, 35 with respect to the mass of all the constituent units. 30, 25, 20, 15, 10, 5, 2 mass% and the like are exemplified, and the lower limit is 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1 mass% and the like. Illustrated. The range of the above proportions can be set as appropriate (eg, selected from the above upper and lower limit values). In one embodiment, the ratio of the structural unit 2 (one or more of the group consisting of the structural units 2A, 2B, 2C, 2D and 2E) to the total structural units is preferably 1 to 50% by mass.

The upper limit of the ratio of the constituent unit 2 (one or more of the group consisting of the constituent units 2A, 2B, 2C, 2D and 2E) to the total constituent units is 50, 45, 40, 35 with respect to 100 mol% of all the constituent units. , 30, 25, 20, 15, 10, 5, 2 mol%, etc., and the lower limit is 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1 mol%, etc. Is exemplified. The range of the above proportions can be set as appropriate (eg, selected from the above upper and lower limit values). In one embodiment, the ratio of the constituent unit 2 (one or more of the group consisting of the constituent units 2A, 2B, 2C, 2D and 2E) to the total constituent units is preferably 1 to 50 mol%.

(Structure unit 3)
The structural unit 3 is a structural unit contained in the polymer chain when alkenylaryl is used as the monomer. One type or two or more types of alkenylaryl can be used. Examples of the alkenylaryl include styrene, α-methylstyrene and the like, as well as styrene having at least one alkyl group having 1 to 2 carbon atoms in the aromatic ring.

The upper limit of the ratio of the constituent unit 3 to all the constituent units is 79, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, with respect to the mass of all the constituent units. 10, 5, 2% by mass and the like are exemplified, and the lower limit is 78, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1 , 0% by mass, etc. are exemplified. The range of the above proportions can be set as appropriate (eg, selected from the above upper and lower limit values). When the constituent unit 3 is included, the ratio of the constituent unit 3 to the total constituent units is preferably 1 to 79% by mass in one embodiment.

The upper limit of the ratio of the constituent unit 3 to all the constituent units is 79, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 with respect to 100 mol% of all the constituent units. 10, 5, 2 mol%, etc. are exemplified, and the lower limit is 78, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, ,. 1,0 mol% and the like are exemplified. The range of the above proportions can be set as appropriate (eg, selected from the above upper and lower limit values). When the constituent unit 3 is included, the ratio of the constituent unit 3 to the total constituent units is preferably 1 to 79 mol% in one embodiment.

(Structure unit 4)
The structural unit 4 is a polymer chain when (meth) acrylic acid, N, N-dialkyl (meth) acrylamide, N, N-dialkylaminealkyl (meth) acrylate, and (meth) hydroxyalkyl acrylate are used as the monomers. It is a structural unit included in.

Examples of N, N-dialkyl (meth) acrylamide include dimethylacrylamide, diethylacrylamide, acryloylmorpholine and the like.

Examples of the N, N-dialkylamine alkyl (meth) acrylate include N, N-dimethylamine ethyl (meth) acrylate and N, N-diethylamine ethyl (meth) acrylate. The number of carbon atoms of the alkyl group on nitrogen (that is, the number of carbon atoms of R ^d1 and R ^d2 in the constituent unit 4) is preferably 1 to 2.

Hydroxyalkyl (meth) acrylates are hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, (meth). Examples thereof include acrylic 2-hydroxypropyl and 3-hydroxypropyl (meth) acrylic acid.

The upper limit of the ratio of the constituent unit 4 to all the constituent units is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2 mass%, etc. with respect to the mass of all the constituent units. The lower limit is exemplified by 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0% by mass and the like. The range of the above proportions can be set as appropriate (eg, selected from the above upper and lower limit values). When the constituent unit 4 is included, the ratio of the constituent unit 4 to the total constituent units is preferably 1 to 50% by mass in one embodiment.

The upper limit of the ratio of the constituent unit 4 to all the constituent units is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2 mol%, etc. with respect to 100 mol% of all the constituent units. As the lower limit, 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0 mol% and the like are exemplified. The range of the above proportions can be set as appropriate (eg, selected from the above upper and lower limit values). When the constituent unit 4 is included, the ratio of the constituent unit 4 to the total constituent units is preferably 1 to 50 mol% in one embodiment.

（式中、Ｒ^ｅ１、Ｒ^ｅ２、及びＲ^ｅ３は、それぞれ独立に、ニトリル基、アルキル基、又はアルケニル基である。）アゾ開始剤に由来する構成単位である。 (Structure unit 5)
The structural unit 5 has, for example, the following structure.

(In the formula, R ^e1 , R ^e2 , and R ^e3 are independently nitrile groups, alkyl groups, or alkenyl groups, respectively.) A structural unit derived from an azo initiator.

Examples of the azo initiator include an azonitrile initiator, an azoamidine initiator, and an azoamide initiator.

The azonitrile initiators are 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (isobuty). Lonitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) and the like are exemplified.

The azoamidine initiators are 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] di. Sulfate dihydrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'- Examples thereof include azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n-hydrate.

The azoamide initiator is 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], Examples thereof include 2,2'-azobis (N-butyl-2-methylpropionamide).

Examples of other azo initiators include dimethyl 2,2'-azobis (isobutyrate), 4,4'-azobis (4-cyanovaleric acid) and the like.

The upper limit of the ratio of the constituent unit 5 to all the constituent units is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4 mass%, etc. with respect to the mass of all the constituent units. The lower limit is exemplified by 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 0% by mass and the like. The range of the above proportions can be set as appropriate (eg, selected from the above upper and lower limit values). When the constituent unit 5 is included, in one embodiment, the ratio of the constituent unit 5 to the total constituent units is preferably 3 to 50% by mass with respect to the mass of all the constituent units.

The upper limit of the ratio of the constituent unit 5 to all the constituent units is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4 mol%, etc. with respect to 100 mol% of all the constituent units. As the lower limit, 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 0 mol% and the like are exemplified. The range of the above proportions can be set as appropriate (eg, selected from the above upper and lower limit values). When the constituent unit 5 is included, the ratio of the constituent unit 5 to 100 mol% of all the constituent units is preferably 3 to 50 mol% in one embodiment.

(Other building blocks)
The resin of the present disclosure may also contain other structural units other than the structural units 1 to 5. Examples of other structural units include structural units derived from (meth) acrylic acid derivatives other than structural units 1 to 4, structural units derived from chain transfer agents, and the like.

When other constituent units are included, the upper limit of the ratio of the other constituent units to all the constituent units is exemplified by 30, 25, 20, 15, 10, 5, 2 mass% and the like, and the lower limit is 29, 25, 20, 15, 10, 5, 2, 1% by mass and the like are exemplified. The range of the above proportions can be set as appropriate (eg, selected from the above upper and lower limit values). In one embodiment, the proportion of other building blocks in the total building blocks is 1-30% by weight, less than 30% by weight, less than 20% by weight, less than 10% by weight, less than 9% by weight, less than 5% by weight, Examples include less than 4% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, less than 0.001% by mass, less than 0.0001% by mass, 0% by mass and the like.

The upper limit of the ratio of other constituent units to 100 mol% of all constituent units is exemplified by 30, 25, 20, 15, 10, 5, 2 mol%, etc., and the lower limit is 29, 25, 20, 15, 10 5, 2, 1, 0 mol% and the like are exemplified. The range of the above proportions can be set as appropriate (eg, selected from the above upper and lower limit values). In one embodiment, the proportion of other constituent units in 100 mol% of all constituent units is 1-30 mol%, less than 30 mol%, less than 20 mol%, less than 10 mol%, less than 9 mol%, 5 mol. % Less than 4 mol%, less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, less than 0.001 mol%, less than 0.0001 mol%, 0 mol% and the like. When other constituent units are included, in one embodiment, the ratio of the other constituent units to 100 mol% of all the constituent units is preferably 1 to 30 mol%.

The upper limit of the mass ratio between the constituent unit 1 and the constituent unit 2 (mass of the constituent unit 1 / mass of the constituent unit 2) is 99.0, 95.0, 90.0, 85.0, 80.0, 75. 0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5.0, 1.0, 0.5, etc. are exemplified, and the lower limit is 98.0, 95.0, 90.0, 85.0, 80.0, 75.0, 70.0. , 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5 .0, 1.0, 0.5, 0.4 and the like are exemplified. The range of the mass ratio can be set as appropriate (for example, by selecting from the upper and lower limit values). In one embodiment, the mass ratio of the constituent unit 1 to the constituent unit 2 (mass of the constituent unit 1 / mass of the constituent unit 2) is preferably 0.4 to 99.0 from the viewpoint of suppressing gelation.

The upper limit of the molar ratio between the constituent unit 1 and the constituent unit 2 (the amount of the substance of the constituent unit 1 / the amount of the substance of the constituent unit 2) is 99.0, 95.0, 90.0, 85.0, 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15. 0, 10.0, 5.0, 1.0, 0.5, etc. are exemplified, and the lower limit is 98.0, 95.0, 90.0, 85.0, 80.0, 75.0, 70. .0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15.0, 10.0 , 5.0, 1.0, 0.5, 0.4 and the like. The range of the molar ratio can be set as appropriate (for example, by selecting from the 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) is preferably 0.4 to 99.0 from the viewpoint of suppressing gelation. ..

When the constituent unit 3 is included, the upper limit of the mass ratio between the constituent unit 1 and the constituent unit 3 (mass of the constituent unit 1 / mass of the constituent unit 3) is 99.0, 95.0, 90.0, 85.0. , 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20 .0, 15.0, 10.0, 5.0, 1.0, 0.5, etc. are exemplified, and the lower limit is 98.0, 95.0, 90.0, 85.0, 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15. 0, 10.0, 5.0, 1.0, 0.5, 0.25 and the like are exemplified. The range of the mass ratio can be set as appropriate (for example, by selecting from the upper and lower limit values). In one embodiment, when the constituent unit 3 is included, the mass ratio between the constituent unit 1 and the constituent unit 3 (mass of the constituent unit 1 / mass of the constituent unit 3) is 0.25 to 99 from the viewpoint of polarity adjustment. .0 is preferable.

When the constituent unit 3 is included, the upper limit of the molar ratio between the constituent unit 1 and the constituent unit 3 (the amount of the substance of the constituent unit 1 / the amount of the substance of the constituent unit 3) is 99.0, 95.0, 90.0, 85. .0, 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0 , 20.0, 15.0, 10.0, 5.0, 1.0, 0.5, etc., and the lower limit is 98.0, 95.0, 90.0, 85.0, 80. 0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5.0, 1.0, 0.5, 0.25 and the like are exemplified. The range of the molar ratio can be set as appropriate (for example, by selecting from the upper and lower limit values). In one embodiment, when the constituent unit 3 is included, the molar ratio of the constituent unit 1 to the constituent unit 3 (the amount of substance of the constituent unit 1 / the amount of substance of the constituent unit 3) is 0. 25-99.0 is preferable.

When the constituent unit 4 is included, the upper limit of the mass ratio between the constituent unit 1 and the constituent unit 4 (mass of the constituent unit 1 / mass of the constituent unit 4) is 99.0, 95.0, 90.0, 85.0. , 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20 .0, 15.0, 10.0, 5.0, 1.0, 0.5, etc. are exemplified, and the lower limit is 98.0, 95.0, 90.0, 85.0, 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15. 0, 10.0, 5.0, 1.0, 0.5, 0.4 and the like are exemplified. The range of the mass ratio can be set as appropriate (for example, by selecting from the upper and lower limit values). In one embodiment, when the constituent unit 4 is included, the mass ratio between the constituent unit 1 and the constituent unit 4 (mass of the constituent unit 1 / mass of the constituent unit 4) is 0.4 to 99 from the viewpoint of polarity adjustment. .0 is preferable.

When the constituent unit 4 is included, the upper limit of the molar ratio between the constituent unit 1 and the constituent unit 4 (the amount of the substance of the constituent unit 1 / the amount of the substance of the constituent unit 4) is 99.0, 95.0, 90.0, 85. .0, 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0 , 20.0, 15.0, 10.0, 5.0, 1.0, 0.5, etc., and the lower limit is 98.0, 95.0, 90.0, 85.0, 80. 0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5.0, 1.0, 0.5, 0.4 and the like are exemplified. The range of the molar ratio can be set as appropriate (for example, by selecting from the upper and lower limit values). In one embodiment, when the constituent unit 4 is included, the molar ratio of the constituent unit 1 to the constituent unit 4 (the amount of substance of the constituent unit 1 / the amount of substance of the constituent unit 4) is 0. 4 to 99.0 is preferable.

When the constituent unit 5 is included, the upper limit of the mass ratio between the constituent unit 1 and the constituent unit 5 (mass of the constituent unit 1 / mass of the constituent unit 5) is 33.0, 30.0, 25.0, 20.0. , 15.0, 10.0, 5.0, 1.0, 0.5, etc. are exemplified, and the lower limit is 32.0, 30.0, 25.0, 20.0, 15.0, 10.0. , 5.0, 1.0, 0.4 and the like are exemplified. The range of the mass ratio can be set as appropriate (for example, by selecting from the upper and lower limit values). In one embodiment, when the constituent unit 5 is included, the mass ratio between the constituent unit 1 and the constituent unit 5 (mass of the constituent unit 1 / mass of the constituent unit 5) is 0.4 to 0 from the viewpoint of suppressing gelation. 33.0 is preferable.

When the constituent unit 5 is included, the upper limit of the molar ratio between the constituent unit 1 and the constituent unit 5 (the amount of the substance of the constituent unit 1 / the amount of the substance of the constituent unit 5) is 33.0, 30.0, 25.0, 20. .0, 15.0, 10.0, 5.0, 1.0, 0.5, etc. are exemplified, and the lower limit is 32.0, 30.0, 25.0, 20.0, 15.0, 10 .0, 5.0, 1.0, 0.4 and the like are exemplified. The range of the molar ratio can be set as appropriate (for example, by selecting from the upper and lower limit values). In one embodiment, when the constituent unit 5 is included, the molar ratio of the constituent unit 1 to the constituent unit 5 (the amount of substance of the constituent unit 1 / the amount of substance of the constituent unit 5) is 0. 4 to 33.0 is preferable.

When the constituent unit 5 is included, the upper limit of the mass ratio between the constituent unit 2 and the constituent unit 5 (mass of the constituent unit 2 / mass of the constituent unit 5) is 16.7, 16, 15, 10, 5, 1, 0. .5, 0.1, 0.05 are exemplified, and the lower limit is 16, 15, 10, 5, 1, 0.5, 0.1, 0.05, 0.02. 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, when the constituent unit 5 is included, the mass ratio between the constituent unit 2 and the constituent unit 5 (mass of the constituent unit 2 / mass of the constituent unit 5) is 0.02 or more from the viewpoint of suppressing gelation. 16.7 is preferable.

When the constituent unit 5 is included, the upper limit of the molar ratio between the constituent unit 2 and the constituent unit 5 (the amount of substance of the constituent unit 2 / the amount of substance of the constituent unit 5) is 16.7, 16, 15, 10, 5, 1 , 0.5, 0.1, 0.05, and the lower limit is 16, 15, 10, 5, 1, 0.5, 0.1, 0.05, 0.02. The range of the molar ratio can be set as appropriate (for example, by selecting from the upper and lower limit values). In one embodiment, when the constituent unit 5 is included, the molar ratio of the constituent unit 2 to the constituent unit 5 (the amount of substance of the constituent unit 2 / the amount of substance of the constituent unit 5) is 0. 02 to 16.7 is preferable.

The upper limit of the mass ratio (mass of the structural unit 2 / mass of the structural unit derived from the monofunctional monomer) between the structural unit 2 and the structural unit derived from the monofunctional monomer (constituent units 1, 3, 4, etc.) is 1.00, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, etc. are exemplified, and the lower limit is , 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, 0.01 and the like. The range of the mass ratio can be set as appropriate (for example, by selecting from the upper and lower limit values). In one embodiment, the mass ratio of the structural unit 2 to the structural unit (constituent unit 1, 3, 4, etc.) derived from the monofunctional monomer (mass of the structural unit 2 / the structural unit derived from the monofunctional monomer). The mass) is preferably 0.01 to 1.00 from the viewpoint of suppressing gelation.

Upper limit of the molar ratio (material amount of structural unit 2 / substance amount of structural unit derived from monofunctional monomer) between structural unit 2 and structural unit derived from monofunctional monomer (constituent units 1, 3, 4, etc.) Is exemplified by 1.00, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05 and the like. The lower limit is exemplified by 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, 0.01 and the like. To. The range of the molar ratio can be set as appropriate (for example, by selecting from the upper and lower limit values). In one embodiment, the molar ratio of the constituent unit 2 to the constituent unit derived from the monofunctional monomer (the amount of substance of the constituent unit 1 / the amount of substance of the constituent unit derived from the monofunctional monomer) is the suppression of gelation. From the viewpoint, 0.01 to 1.00 is preferable.

(Denaturation of resin)
The resin can be modified. Examples of the modification include modification in which only the epoxide is reacted with the carboxyl group or the hydroxyl group contained in the resin, or the epoxide is reacted with the anhydrous carboxylic acid.

［式中、Ｒ^ａ１－１は水素原子又はアルキル基であり、Ｒ^ａ１－２は、

｛式中、ａ１は１以上の整数であり、ｂ１は０以上の整数であり、Ｒ^ａ１－ａ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^ａ１－ｂ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。］
等が例示される。
The structural unit generated by the modification of the carboxyl group contained in the above resin with the epoxide alone or with the epoxide and the carboxylic acid anhydride is

[In the formula, R ^a1-1 is a hydrogen atom or an alkyl group, and R ^a1-2 is

{In the formula, a1 is an integer of 1 or more, b1 is an integer of 0 or more, and ^Ra1-a is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or non-substituted It is a substituted aryloxy group, and ^Ra1-b is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
Is. ]
Etc. are exemplified.

［式中、Ｒ^{ａ２－１’}は水素原子又はアルキル基であり、Ｒ^{ａ２－２’}は、アルキレン基である］
に対し、エポキシドのみ、又はエポキシドと無水カルボン酸とを反応させることにより生じる、

［式中、Ｒ^ａ２－１は水素原子又はアルキル基であり、Ｒ^ａ２－２は、アルキレン基であり、Ｒ^ａ２－３は、

｛式中、ａ２は１以上の整数であり、ｂ２は０以上の整数であり、Ｒ^ａ２－ａ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^ａ２－ｂ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。］
等が例示される。 The structural unit generated by the modification of the hydroxyl group contained in the above resin with the epoxide alone or the epoxide and the carboxylic acid anhydride is the structural unit contained in the resin before the modification.

[In the formula, R ^a2-1'is a hydrogen atom or an alkyl group, and R ^a2-2'is an alkylene group]
On the other hand, it is produced by reacting only the epoxide or the epoxide with the carboxylic acid anhydride.

[In the formula, R ^a2-1 is a hydrogen atom or an alkyl group, R ^a2-2 is an alkylene group, and R ^a2-3 is.

{In the formula, a2 is an integer of 1 or more, b2 is an integer of 0 or more, and ^Ra2-a is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or non-substituted alkoxy group. It is a substituted aryloxy group, and ^Ra2-b is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
Is. ]
Etc. are exemplified.

(Epoxide)
Two or more types of epoxides can be used together. Examples of the epoxide include a polymerizable double bond-free aromatic epoxide, a polymerizable double bond-containing aromatic epoxide, and the like.

(Polymerizable double bond-free aromatic epoxide)
Examples of the polymerizable double bond-free aromatic epoxide include an aromatic ring-containing monoglycidyl ether, an aromatic-containing diglycidyl ether, and a 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, an aromatic ring-containing monoglycidyl ether is preferable, and a phenylglycidyl ether is particularly preferable, from the viewpoints of compatibility between the obtained resin and the reactive diluent described later, curability of the ink of the present invention, gloss and the like.

(Epoxide containing polymerizable double bond)
Examples of the polymerizable double bond-containing epoxide include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and rosing lysidyl ester.

(Epoxides that are neither polymerizable double bond-free aromatic epoxides nor polymerizable double bond-containing epoxides)
At the time of modification, an epoxide other than the above-mentioned polymerizable double bond-free aromatic epoxide and the polymerizable double bond-containing epoxide may be used. Neither polymerizable double bond-free aromatic epoxides nor polymerizable double bond-containing epoxides are aliphatic epoxides such as glycidyl triethyl ether, butylene oxide, cyclohexene oxide, and neodecanoic acid glycidyl ester;
Diepoxides such as 1,6-hexanediol diglycidyl ether and butanediol diglycidyl ether;
Examples thereof include polyepoxides such as sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol triglycidyl ether, trimethylolpropane polyglycidyl ether, and 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 a polymerizable double-bond-free aromatic epoxide and an epoxide containing a polymerizable double-bond and / or a non-polymerizable double-bond-containing aromatic epoxide and / or a polymerizable double-bond-containing epoxide are used in combination, they are used in combination. The usage ratio of the above is not particularly limited, but the molar ratio [polymerizable double bond-free aromatic epoxide / {polymerizable double bond-containing epoxide and / or polymerizable double bond-free aromatic epoxide is also polymerizable double bond. Epoxides that are not contained in epoxides}] are preferably about 1/9 to 9/1.

The amount of epoxide used is not particularly limited, but from the viewpoint of compatibility with the reactive diluent and the curability of the ink, the amount of epoxide used is preferably about 10 to 200 parts by mass with respect to 100 parts by mass of the resin. About 10 to 150 parts by mass is more preferable.

(Carboxylic acid anhydride)
Two or more kinds of carboxylic acid anhydrides can be used in combination. Carboxylic acid anhydrides include aromatic carboxylic acid anhydrides 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;
Alibocarboxylic acid anhydrides such as glutaric anhydride, pyromellitic anhydride, adipic acid anhydride, succinic acid anhydride, itaconic acid 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 carboxylic acid anhydride is used, the amount of the carboxylic acid anhydride used is not particularly limited, but the carboxylic acid anhydride is obtained with respect to 100 parts by mass of the resin from the viewpoint of compatibility with the reactive diluent and the curability of the ink. The amount of the substance used is preferably about 10 to 200 parts by mass, more preferably about 10 to 150 parts by mass.

At the time of modification, the order and reaction conditions for reacting the resin, epoxide and carboxylic acid anhydride are not particularly limited. Specifically, [1] a method of reacting all the components in one pot, and [2] a method of reacting a carboxylic acid anhydride in the presence of a resin and then further reacting an epoxide and a carboxylic acid anhydride are 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.

Further, the modification can be performed 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).

<Physical characteristics of the resin of the present invention>
The molecular weight distribution (Mw / Mn) is calculated from, for example, the weight average molecular weight and the number average molecular weight obtained as polystyrene-equivalent values measured under an appropriate solvent by gel permeation chromatography (GPC). Derived by the procedure.

The upper limit of the molecular weight distribution (Mw / Mn) of the resin in the present disclosure is 55, 50, 45, 40, 35, 32, 30, 25, 20, 19, 18.3, 15, 14.3, 10, 5, ,. Examples are 4.5, 4.2, 4.1, 3.8, 3.3, 3.2, 2, etc., and the lower limit is 54, 50, 45, 40, 35, 32, 30, 25, 20. , 19, 18.3, 15, 14.3, 10, 5, 4.5, 4.2, 4.1, 3.8, 3.3, 3.2, 3, 2, 1.5, etc. Illustrated. The range of the molecular weight distribution (Mw / Mn) can be appropriately set (for example, selected from the upper and lower limit values). In one embodiment, 1.5-55 is preferred.

The upper limit of the weight average molecular weight (Mw) of the resin in the present disclosure is 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 150,000, 100,000. , 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 32,000, 30,000, 27,000, 20,000, 15,000, 13,000, 11 , 000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,500, etc. are exemplified, and the lower limit is 490,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 150,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 32,000, 30,000, 000, 27,000, 20,000, 15,000, 13,000, 11,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,500, 5,000, 4,500, 4,000 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 4,000 to 500,000.

The upper limit of the number average molecular weight (Mn) of the resin in the present disclosure is 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000. , 15,000, 10,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900 and the like, and the lower limit is 100,000, 90,000, 80,000, 70. 000, 60,000, 50,000, 40,000, 30,000, 20,000, 19,000, 15,000, 10,000, 5,000, 4,000, 3,000, 2,000 , 1,000, 900, 800 and the like are exemplified. The range of the number average molecular weight (Mn) can be appropriately set (for example, selected from the upper and lower limit values). In one embodiment, the number average molecular weight of the resin is preferably 800 to 100,000.

The upper limit of the hydroxyl value of the resin in the present disclosure is exemplified by 483, 480, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 5, 1 mgKOH / g and the like, and the lower limit is 480. Examples thereof include 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 5, 1, 0 mgKOH / g. The range of the hydroxyl value can be appropriately set (for example, selected from the upper and lower limit values). In one embodiment, the hydroxyl value of the resin is preferably 0 to 483 mgKOH / g. The hydroxyl value of the resin can be measured by adding an acetylation reagent to the sample, heating the sample, allowing it to cool, adding a phenolphthalein solution as an indicator, and titrating with a potassium hydroxide ethanol solution.

The upper limit of the acid value of the resin in the present disclosure is 799, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 1 mgKOH / g and the like. Illustrated, the lower limit is 790, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 1, 0 mgKOH / g and the like. 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 0 to 799 mgKOH / g. For the acid value of the resin, dissolve the sample in water or acetone or a mixed solution of toluene / ethanol = 20/80 (volume ratio), add a phenolphthaline indicator as an indicator, and titrate with water or ethanol solution of potassium hydroxide. Can be measured.

The upper limit of the softening point of the resin in the present disclosure is exemplified by 150, 140, 130, 120, 110, 100, 90, 80 ° C. and the like, and the lower limit is 140, 130, 120, 110, 100, 90, 80, 75 ° C. Etc. are exemplified. 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 75 to 150 ° C. The softening point of the resin can be measured by an automatic softening point measuring device (EX-719PD, manufactured by SIENTIFIC).

The upper limit of the intrinsic viscosity (η) for the absolute molecular weight (M) 50,000 of the resin in the present disclosure is 0.20, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14. , 0.13, 0.12, 0.11, 0.10, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, etc. Illustrated, the lower limit is 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.12, 0.11, 0.10, 0.09, 0 .08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, 0.01 and the like are exemplified. The range of the intrinsic viscosity (η) can be appropriately set (for example, selected from the upper and lower limit values). In one embodiment, the intrinsic viscosity (η) of the resin with respect to the absolute molecular weight (M) of 50,000 is preferably 0.01 to 0.20. The intrinsic viscosity (η) of the resin with respect to the absolute molecular weight (M) 50,000 can be measured by triple detection GPC (ViscoteK TDA305, Malvern).

The upper limit of the glass transition temperature (Tg) of the resin in the present disclosure is exemplified by 230, 200, 150, 100, 50, 0, -50, -70 ° C., and the lower limit is 225, 200, 150, 100, 50, 0, -50, -80 ° C and the like are exemplified. The range of the glass transition temperature (Tg) can be appropriately set (for example, selected from the upper and lower limit values). In one embodiment, the glass transition temperature of the resin is preferably −80 to 230 ° C. The glass transition temperature of the resin can be measured by differential scanning calorimetry.

In one embodiment, the resin of the present invention is preferably used as a resin for ink, more preferably a resin for offset printing ink. Offset printing is used while transferring ink from roller to roller. Ink jet printing is a printing method in which ink is sucked from a tank and sprayed from a thin nozzle. Therefore, it is a well-known fact that the required physical properties (viscosity, etc.) differ between the resin used for offset printing and the resin used for ink jet printing.

[2. Resin manufacturing method]
Monofunctional monomers such as (meth) acrylic acid ester, (poly) pentaerythritol poly (alkylene oxide modified) (meth) acrylate, (poly) trimethylpropanpoly (alkylene oxide modified) (meth) acrylate, (poly) glycerin A monomer containing a polyfunctional monomer such as poly (alkylene oxide-modified) (meth) acrylate or alkylene di (alkylene oxide-modified) (meth) acrylate is suitable at an appropriate monomer concentration in the presence of an appropriate amount of a polymerization initiator. A production method including a step of polymerizing at a reaction temperature produces a resin that does not gel, that is, has a narrow molecular weight distribution (Mw / Mn).

In one embodiment, the polymerization initiator is a radical polymerization initiator. Examples of the radical polymerization initiator include an azo initiator, a peroxide initiator and the like.

In the present disclosure, the "peroxide initiator" is an organic peroxide, that is, a compound having a peroxy group (-O-O-) in the molecule. Peroxide initiators are (2-ethylhexanoyl) (tert-butyl) peroxide, benzoyl peroxide, di-tert-butyl peroxide, dimethyldioxylan, acetone peroxide, methylethylketone peroxide, hexamethylenetripeloxidediamine, cumene. Examples thereof include hydroperoxide, tert-hexylperoxy-2-ethylhexanoate and the like.

In one embodiment, alkenylaryl is used as the monomer.

In one embodiment, a polar group-containing monofunctional monomer such as N, N-dialkyl (meth) acrylamide, N, N-dialkylamine alkyl (meth) acrylic acid, or (meth) hydroxyalkyl acrylate is used as the monomer.

Specific examples of the monomer, polymerization initiator, etc. used in the above production method, the range of the molecular weight distribution (Mw / Mn) of the produced resin, and the like are the same as those described in the item (1. Resin).

The upper limit of the monomer concentration in the above production method is exemplified by 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 11% by mass and the like, and the lower limit is 69, 65, 60. , 55, 50, 45, 40, 35, 30, 25, 20, 15, 11, 10% by mass and the like. The range of the monomer concentration in the above-mentioned production method can be appropriately set (for example, selected from the above-mentioned upper limit and lower limit values). In one embodiment, the monomer concentration is preferably 10 to 70% by mass. In the present disclosure, the "monomer concentration" is a concentration calculated by the mass of the monomer / (mass of the solvent + mass of the monomer).

The upper limit of the amount of the polymerization initiator in the above production method is 50, 45, 40, 35, 30, 25, 20, 15, 10, 6, 5.1, 5, 4 mass with respect to the total amount of the monomer (100% by mass). % Etc. are exemplified, and the lower limit is 50, 45, 40, 35, 30, 25, 20, 15, 10, 6, 5.1, 5, 4, 3 mass% and the like with respect to 100% by mass of the monomer. To. The range of the amount of the polymerization initiator in the above production method can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the amount of the polymerization initiator is preferably 3 to 50% by mass with respect to 100% by mass of the monomer.

Examples of the upper limit of the reaction temperature in the above production method are 200, 190, 180, 170, 160, 150, 140, 130, 121, 120, 110, 100, 90, 85 ° C., and the lower limit is 195, 190. 180, 170, 160, 150, 140, 130, 121, 120, 110, 100, 90, 85, 80, 70 ° C. are exemplified. The reaction temperature range in the above production method can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the reaction temperature is preferably 70-200 ° C.

In the above production method, the upper limit of the amount of (meth) acrylic acid ester and (meth) acrylic acid used is 99, 95, 90, 85, 80, 75, 70, 65 with respect to the total amount of monomers (100% by mass). 60, 55, 50, 45, 40, 35, 30, 25, 21 mass% and the like are exemplified, and the lower limit is 98, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, Examples include 40, 35, 30, 25, 20% by mass and the like. The range of usage may be set as appropriate (eg, selected from the upper and lower limits). In one embodiment, the amount of the (meth) acrylic acid ester and the (meth) acrylic acid used is preferably 20 to 99% by mass with respect to the total amount of the monomers (100% by mass) from the viewpoint of adjusting the polarity.

In the above production method, the upper limit of the amount of (meth) acrylic acid ester and (meth) acrylic acid used is 99, 95, 90, 85, 80, 75, 70, 65, based on the total amount of monomers (100 mol%). 60, 55, 50, 45, 40, 35, 30, 25, 21 mol% and the like are exemplified, and the lower limit is 98, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, Examples include 40, 35, 30, 25, 20 mol% and the like. The range of usage may be set as appropriate (eg, selected from the upper and lower limits). In one embodiment, the amount of the (meth) acrylic acid ester and the (meth) acrylic acid used is preferably 20 to 99 mol% with respect to the total amount of the monomers (100 mol%) from the viewpoint of adjusting the polarity.

In the above production method, the upper limit of the amount of the polyfunctional monomer used is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc. with respect to the total amount of the monomers (100% by mass). As the lower limit, 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass and the like are exemplified. In the above production method, the range of the amount of the polyfunctional monomer used can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, from the viewpoint of suppressing gelation, the amount of the polyfunctional monomer used is exemplified by 1 to 50% by mass with respect to the total amount of the monomers (100% by mass).

In the above production method, the upper limit of the amount of the polyfunctional monomer used is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 5 mol%, etc. with respect to the total amount of the monomers (100 mol%). The lower limit is exemplified by 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1 mol% and the like. In the above production method, the range of the amount of the polyfunctional monomer used can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, from the viewpoint of suppressing gelation, the amount of the polyfunctional monomer used is exemplified by 1 to 50 mol% with respect to the total amount of the monomers (100 mol%).

In the above production method, the upper limit of the amount of alkenylaryl used is 79,75,70,65,60,55,50,45,40,35,30,25,20, relative to the total amount of monomers (100% by mass). 15, 10, 5% by mass, etc. are exemplified, and the lower limit is 78, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1% by mass. Etc. are exemplified. In the above production method, the range of the amount of alkenylaryl used can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, from the viewpoint of polarity adjustment, the amount of alkenylaryl used is preferably 1 to 79% by mass with respect to the total amount of monomers (100% by mass).

In the above production method, the upper limit of the amount of alkenylaryl used is 79,75,70,65,60,55,50,45,40,35,30,25,20, relative to the total amount of monomers (100 mol%). 15, 10, 5 mol%, etc. are exemplified, and the lower limit is 78, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1 mol%. Etc. are exemplified. In the above production method, the range of the amount of alkenylaryl used can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, from the viewpoint of polarity adjustment, the amount of alkenylaryl used is preferably 1 to 79 mol% with respect to the total amount of monomers (100 mol%).

In the above production method, the upper limit of the amount of the polar group-containing monofunctional monomer used is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2% by mass and the like, and the lower limit is 49. , 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1% by mass and the like are exemplified. In the above production method, the range of the amount of the polar group-containing monofunctional monomer used can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, from the viewpoint of polarity adjustment, the amount of the polar group-containing monofunctional monomer used is preferably 1 to 50% by mass with respect to the total amount of the monomers.

In the above production method, the mass ratio of the amount of (meth) acrylic acid ester and (meth) acrylic acid used to the amount of polyfunctional monomer used (mass of (meth) acrylic acid ester and (meth) acrylic acid used for polymerization). / The upper limit of the mass of the polyfunctional monomer used for polymerization) is 99.0, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1, 0.5, etc., and the lower limit. Is 95, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1, 0.5, 0.4 and the like. In the above manufacturing method, the range of the mass ratio can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, from the viewpoint of suppressing gelation, the mass ratio of the amount of (meth) acrylic acid ester and (meth) acrylic acid used to the amount of polyfunctional monomer used ((meth) acrylic acid ester used for polymerization). And the mass of (meth) acrylic acid / the mass of the polyfunctional monomer used for the polymerization) is preferably 0.4 to 99.0.

In the above production method, the upper limit of the ratio of the amount of acrylic acid ester used to the amount of alkenylaryl used (mass of acrylic acid ester used for polymerization / mass of alkenylaryl used for polymerization) is 9.90, 9. 8, 7, 6, 5, 4, 3, 2, 1, 0.5, etc. are exemplified, and the lower limit is 9.50, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0. .5, 0.33 and the like are exemplified. In the above manufacturing method, the range of the mass ratio can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, from the viewpoint of polarity adjustment, the ratio of the amount of acrylic acid ester used to the amount of alkenylaryl used (mass of acrylic acid ester used for polymerization / mass of alkenylaryl used for polymerization) is 0. It is preferably .33 to 9.90.

In the above production method, the upper limit of the ratio of the amount of acrylic acid ester used to the amount of polar group-containing monofunctional monomer used (mass of acrylic acid ester used for polymerization / mass of polar group-containing monofunctional monomer used for polymerization). Is 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, etc., and the lower limit is 0.9, 0.8, 0.7, 0.6, 0. 5, 0.4 and the like are exemplified. In the above manufacturing method, the range of the mass ratio can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, from the viewpoint of polarity adjustment, the ratio of the amount of the acrylic acid ester used to the amount of the polar group-containing monofunctional monomer used (mass of the acrylic acid ester used for polymerization / polar group-containing single used for polymerization). The mass of the functional monomer) is preferably 0.4 to 1.0.

In the above production method, the upper limit of the ratio of the amount of the polyfunctional monomer used to the amount of the initiator used (mass of the polyfunctional monomer used for polymerization / mass of the initiator used for polymerization) is 16.67, 16. Examples include 15, 13, 10, 5, 1, 0.5, 0.1, 0.05, and the lower limit is 16, 15, 13, 10, 5, 1, 0.5, 0.1, 0. 0.05, 0.02, etc. are exemplified. In the above manufacturing method, the range of the mass ratio can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the ratio of the amount of the polyfunctional monomer used to the amount of the initiator used (mass of the polyfunctional monomer used for polymerization / mass of initiator used for polymerization) is determined from the viewpoint of suppressing gelation. It is preferably 0.02 to 16.67.

In the above production method, the upper limit of the ratio (mass of polyfunctional monomer / mass of monofunctional monomer) between the amount of polyfunctional monomer used and the amount of monofunctional monomer used is 1.00, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, etc. are exemplified, and the lower limit is 0.95, 0.9, 0.8. , 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, 0.01 and the like. In the above manufacturing method, the range of the mass ratio can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the ratio of the amount of the polyfunctional monomer used to the amount of the monofunctional monomer used (mass of the polyfunctional monomer / mass of the monofunctional monomer) is 0.01 to 1. from the viewpoint of suppressing gelation. 00 is preferable.

The solvent used in the above production method is not particularly limited, and examples thereof include water and organic solvents. The organic solvent is a ketone solvent such as cyclohexanone, methylcyclohexanone, methylisobutylketone, methylethylketone, methyl-n-butylketone, diacetone alcohol, diacetone alcohol, isobutyl alcohol, isopropyl alcohol, cyclohexanol, isopentyl alcohol, 1-butanol, 2 -Alcohol solvents such as butanol, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ether solvents such as ethylene glycol mono-n-butyl ether, aromatic solvents such as xylene and toluene, isobutyl acetate, isopropyl acetate, isopentyl acetate, etc. Examples thereof include acetate solvents such as acetate-n-butyl, acetate-n-propyl and acetate-n-pentyl, and amide solvents such as N, N-dimethylformamide.

In the above production method, additives other than the monomer, the polymerization initiator, and the solvent can be used to the extent that the effects of the present invention are not impaired. Examples of additives other than the monomer, the polymerization initiator, and the solvent include emulsifiers, chain transfer agents, RAFT reagents, ATRP polymerization reagents, and the like. The amount of the additive used is 1 to 5 parts by mass, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, less than 0.001 part by mass, 0.0001 with respect to 100 parts by mass of the monomer. Examples include less than parts by mass, parts by mass 0, and the like. The resin described in the present disclosure can be produced without using an additive.

In addition, [1. Items described in [Resin] and [2. The matters described in [Resin manufacturing method] can be referred to each other.

［式中、ｎ及びｍはそれぞれ独立に０～２の整数であり、ｐは０～７の整数であり、Ｒ^ｂ１’～Ｒ^{ｂ１７ ’}は、それぞれ独立に水素原子、

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^３’はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、
Ｒ^ｂ１８’～Ｒ^{ｂ１９ ’}は、それぞれ独立に

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
であり、
Ｒ^ｂ２０’はアルキレン基であり、
Ｒ^ｂ４’、Ｒ^ｂ５’、Ｒ^ｂ９’、及びＲ^ｂ１３’は各構成単位ごとに基が異なっていてもよく、
一般式（Ａ^’）～（Ｄ^’）中において

｛式中、ｑは０～１６の整数であり、Ｒ^１’～Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。｝
が２個以上含まれる。］
等が例示される。 [3. Reactive diluent]
As the reactive diluent, various known ones can be used, and one kind or two or more kinds can be used in combination. Reactive diluent is

[In the equation, n and m are independently integers of 0 to 2, p is an integer of 0 to 7, and R ^b1'to R ^b17'are independent hydrogen atoms.

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
And
R ^b18'to R ^b19'are independent of each other

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
And
R ^b20'is an alkylene group and is
R ^b4' , R ^b5' , R ^b9' , and R ^b13'may have different groups for each structural unit.
In the general formulas (A ^' ) to (D ^' )

{In the formula, q is an integer of 0 to 16, R ^1'to R ^3'is an independent hydrogen atom or an alkyl group, and R ^1'may have a different group for each unit. }
Is included in two or more. ]
Etc. are exemplified.

The reactive diluent represented by the above general formulas (A ^' ) to (E ^' ) is [1. It is the same as the polyfunctional monomer represented by the general formulas (A ^' ) to (E ^' ) described in the item of <Constituent unit 2> of [Resin].

[4. Varnish composition]
The upper limit of the resin content in the varnish composition is 60, 59, 55, 50, 45, 40, 35, 30, 25, 20, 15, 11% by mass, etc. with respect to the total mass of the varnish composition. Illustrated, the lower limit is 59, 55, 50, 45, 40, 35, 30, 25, 20, 15, 11, 10% by mass and the like. The range of the resin content in the varnish composition can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the content of the resin in the varnish composition is preferably 10 to 60% by mass with respect to the total mass of the varnish composition from the viewpoint of film strength and curability.

The upper limit of the content of the reactive diluent in the varnish composition is 90, 89, 85, 80, 75, 70, 65, 60, 55, 50, 45, 41 with respect to the total mass in the varnish composition. Mass% and the like are exemplified, and the lower limit is 89, 85, 80, 75, 70, 65, 60, 55, 50, 45, 41, 40 mass% and the like. The range of the content of the reactive diluent in the varnish composition can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the content of the reactive diluent in the varnish composition is preferably 40 to 90% by mass with respect to the total mass in the varnish composition from the viewpoint of film strength and curability.

The upper limit of the ratio of the resin to the reactive diluent (mass of resin / mass of reactive diluent) is 1.50, 1.40, 1.30, 1.20, 1.10, 1.00, 0. .90, 0.80, 0.70, 0.6, 0.5, 0.4, 0.3, 0.2, 0.15, etc. are exemplified, and the lower limit is 1.40, 1.30, 1 .20, 1.10, 1.00, 0.90, 0.80, 0.70, 0.6, 0.5, 0.4, 0.3, 0.2, 0.15, 0.11 Etc. 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 resin to the reactive diluent (mass of the resin / mass of the reactive diluent) is preferably 0.11 to 1.50 from the viewpoint of film strength and curability.

The varnish composition may contain components other than the resin and the reactive diluent (hereinafter, also referred to as other components). The upper limit of the content of other components is exemplified by 20, 15, 10, 5, 1% by mass, etc. with respect to the total mass of the resin and the reactive diluent, and the lower limit is 15, 10, 5, 1, 0. 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, the content of the other components is preferably 0 to 20% by mass with respect to the total mass of the resin and the reactive diluent.

Further, the upper limit of the content of other components with respect to the total mass of the entire varnish composition is exemplified by 17, 15, 10, 5, 1% by mass and the like, and the lower limit is 15, 10, 5, 1, 0% by mass. Etc. are exemplified. The content range may be set as appropriate (eg, selected from the upper and lower limit values). In one embodiment, the content of the other components is preferably 0 to 17% by mass with respect to the total mass of the entire varnish composition.

The upper limit of the viscosity of the varnish composition is 800, 750, 700, 600, 500, 400, 300, 200, 100, 50, 10 Pa · s / 25 ° C., and the lower limit is 750, 700, 600, 500, 400. , 300, 200, 100, 50, 10, 5 Pa · s / 25 ° C. The range of viscosity of the varnish composition can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the viscosity of the varnish composition is preferably 5 to 800 Pa · s / 25 ° C., more preferably 10 to 200 Pa · s / 25 ° C. from the viewpoint of transferability to a roller and workability.

In one embodiment, the varnish composition of the present invention is active energy ray curable and is preferably used for inks, more preferably offset printing inks.

[5. Offset printing ink]
The present disclosure provides an offset printing ink containing the above varnish composition, optionally a photopolymerization initiator, and a pigment.

The photopolymerization initiator is not particularly limited, and various known ones can be used. Specific examples thereof include benzophenone, o-benzoylbenzoic acid methyl ester, p-dimethylaminobenzoic acid ester, p-dimethylacetophenone, thioxanthone, alkylthioxanthone, amines and the like. In addition, Irgacure 1173, Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 2959, Irgacure 127, Irgacure 369, Irgacure 369E, Irgacure 379, Irgacure 379EG, Irgacure TPO, Irgacure 819, etc. May be used as it is. The amount of the photopolymerization initiator used is preferably about 1 to 15% from the viewpoint of dryness.

The pigment used in the offset printing ink of the present invention is not particularly limited, and an inorganic or organic pigment usually used can be blended. Specific examples include white pigments such as titanium oxide, zinc flower, lead white, lithobon, and antimony oxide, black pigments such as aniline black, iron black, and carbon black, yellow lead, yellow iron oxide, titanium yellow, and Hansa yellow (10G). , 5G, 3G, etc.), yellow pigments such as disazo yellow, benzidine yellow, permanent yellow, orange pigments such as chrome vermillion, permanent orange, vulcan first orange, indance lembrilliant orange, iron oxide, permanent brown, para brown等の褐色顔料、ベンガラ、カドミウムレッド、アンチモン朱、パーマネントレッド、ローダミンレーキ、アリザリンレーキ、チオインジゴレッド、ＰＶカーミン、モノライトファーストレッド、キナクドリン系赤色顔料等の赤色顔料、コバルト紫、マンガン紫、ファーストViolet, Methyl Violet Lake, Indance Len Brilliant Violet, Dioxazine Violet and other purple pigments, ultramarine, dark blue, cobalt blue, alkaline blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, copper phthalocyanine blue, induslen Blue pigments such as blue and indigo, chrome green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malakite green lake, phthalocyanine green, polychlorobrom copper phthalocyanine and other green pigments, as well as various fluorescent pigments. , Metal powder pigments and the like are exemplified. These pigments are preferably about 1 to 50 parts by mass, more preferably about 5 to 30 parts by mass with respect to 100 parts by mass of the offset printing ink.

The active energy ray-curable offset printing ink of the present invention contains the resin for printing ink, the polymerizable monomer and the pigment of the present invention, but further includes a surface conditioner, a defoaming agent, a photosensitizer and an oxidation. Preventive agents, light stabilizers, and leveling agents can also be used. These optional components are in an amount (specifically, 95, 90, 80, 50, 40, 30, 20) in which the total amount thereof is in the range of about 100 parts by mass or less with respect to 100 parts by mass of the offset printing ink. , 10, 5, 1 part by mass or less) is preferable. Further, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine and N-nitrosophenylhydroxylamine aluminum salt can be blended. When a polymerization inhibitor is blended, it is preferably used in the range of about 0.01 to 2 parts by mass with respect to 100 parts by mass of the offset printing ink.

[6. Printed matter]
The present disclosure provides a printed matter having a cured layer of the active energy ray-curable printing ink.

As the base material, various known materials can be used without particular limitation. 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, norbornene-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 amount of coating is not particularly limited, but the mass after drying is preferably about 0.1 to 30 g / m ² , and more preferably about 1 to 20 g / m ² .

The curing means is exemplified by an electron beam or 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 specifically described 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. Therefore, the scope of the present invention is not limited to the embodiments and examples specifically described in the present disclosure, and is limited only by the scope of claims.

The weight average molecular weight and the number average molecular weight were determined as polystyrene-equivalent values measured under a THF solvent by gel permeation chromatography (GPC). Measurement was performed using HLC-8020 (manufactured by Tosoh Corporation) as the GPC device and TSKgel superHZM (manufactured by Tosoh Corporation) as the column under the conditions of flow velocity: 1.00 mL / min and sample concentration: 0.5%. did. The molecular weight distribution (Mw / Mn) was calculated from the obtained number average molecular weight and weight average molecular weight.

Example 1-1
680 g of anon (cyclohexanone) was charged in a reaction vessel equipped with a stirrer, a reflux condenser with a water divider, a thermometer and a dropping funnel. 217.6 g of methyl methacrylate, 32 g of acrylic acid, 60.8 g of 2-ethylhexyl acrylate, 9.6 g of pentaerythritol tetraacrylate were added to the dropping funnel, and 25.6 g of 2,2'-azobisisobutyronitrile was added. .. A dropping polymerization reaction was carried out under a nitrogen atmosphere at 121 ° C. for 3.0 hours with stirring, and the mixture was kept warm for 1 hour. Then, the temperature was raised to 190 ° C., the solvent was distilled off while continuing stirring at normal pressure, the pressure was further reduced to 50 mHg or less at the same temperature, and the solvent was completely distilled off to obtain 320 g of the resin 1. The weight average molecular weight (Mw) was 11,000, the number average molecular weight Mn was 2,900, and the molecular weight distribution (Mw / Mn) was 3.8. The results are shown in Table 1.

Examples 1-2 to 1-27 and Comparative Examples 1-1 to 1-5
The resin was produced by the same procedure as in Example 1 except that the composition was changed to that shown in the table below.

The abbreviations of the raw materials in the above table are as follows.
A-1 Methyl methacrylate A-2 Acrylate A-3 Butyl methacrylate A-4 2-Ethylhexyl acrylate A-5 Phenoxyethyl methacrylate A-6 benzyl methacrylate A-7 Tetrahydrofurryl methacrylate A-8 Isobornyl methacrylate B- 1 Pentaerythritol Tetraacrylate B-2 Dipentaerythritol (Tri / Tetra) Acrylate B-3 Tripentaerythritol Octaacrylate B-4 Trimethylol Propaneethylene Oxide Modified Triacrylate B-5 Ditrimethylol Propanetetraacrylate B-6 Glycerin Propylene Oxide Modified Triacrylate B-7 Diglycerin Ethylene Oxide Modified Acrylate B-8 Glycerin Triepoxy Acrylate B-9 1,6-Hexanediol Diacrylate B-10 Isocyanuric Acid Modified Di and Triacrylate C-1 Stylide D-1 Acryloylmorpholin D -2 N, N-dimethylacrylamide D-3 N, N-dimethylaminoethyl methacrylate E-1 2-hydroxyethyl methacrylate E-2 hydroxypropyl acrylate E-3 2-hydroxy-3-phenoxypropyl acrylate E-4 4- Hydroxybutyl Acrylate F-1 2,2'-azobis (2-methylbutyronitrile)
F-2 t-butyl peroxy-2-ethylhexanoate F-3 4,4'-azobiz (4-cyanovaleric acid)
F-4 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamide]

Example 1-28
Under a nitrogen atmosphere in a reaction vessel equipped with a stirrer, a reflux condenser with a water divider, a thermometer and a dropping funnel, 100 g of the resin obtained in Example 1-21, 86 g of phthalic anhydride, 114 g of phenylglycidyl ether, and 300 g of butyl acetate. Was charged and the temperature was raised to 120 ° C. Then, after adding 0.3 part of triphenylphosphine, the mixture was stirred for 8 hours. Then, the solvent was distilled off while raising the temperature to 160 ° C. at normal pressure, and the solvent was completely distilled off while reducing the pressure at 160 mmHg or less to obtain a resin.

Examples 1-29 to 1-31
The resin was produced by the same procedure as in Example 1-28, except that the composition was changed to that shown in the table below.

Example 2-1
Reactive diluent with respect to the resin (25.8 g) obtained in Example 1-1 Dipentaerythritol (penta / hexa) acrylate (134.2 g), 4-methoxyphenol (0.2 g), N-nitroso -N-Phenylhydroxylamine ammonium (0.1 g) was added, and the mixture was stirred and dissolved at 130 ° C. for 1 hour under air bubbling to obtain a varnish composition. To the obtained varnish composition, 10 g of Irgacure 907 (manufactured by BASF) and 30 g of MA100 (manufactured by Mitsubishi Chemical Corporation) were charged, and the ink was prepared by smelting with three rollers. Based on the above formulation, the ink was appropriately adjusted so that the tack value at 40 ° C. and 400 rpm was 9 ± 0.5 to obtain an ink. This ink contains 12.9 parts by mass of a resin, 67.1 parts by mass of a reactive diluent, 5 parts by mass of an initiator, and 15 parts by mass of a pigment with respect to 100 parts by mass of the ink.

Examples 2-2 to 2-13, Comparative Examples 2-1 to 2-3
It was prepared in the same manner as in Example 2-1 except that the types and ratios of the resin and the reactive diluent were changed as shown in the table below. Resins 1 to 10 are the resins of Examples 1-1 to 1-10, and resins 11 to 13 are the resins of Comparative Examples 1-1 to 1-3.

The abbreviations for the diluted monomers in the above table are as follows.
R-1 Pentaerythritol Tetraacrylate R-2 Dipentaerythritol (Penta / Hexa) Acrylate R-3 Tripentaerythritol Octaacrylate R-4 Trimethylolpropane Ethyleneoxide Modified Triacrylate R-5 Ditrimethylolpropane Tetraacrylate R-6 Glycerin Propylene Oxide Modified Triacrylate R-7 Diglycerin Ethylene Oxide Modified Acrylate R-8 Glycerin Triepoxy Acrylate Irgacure 907 2-Methyl-1- (4-Methylthiophenyl) -2-morpholinopropane-1-one (manufactured by BASF)
MA100 Carbon Black (manufactured by Mitsubishi Chemical Corporation)

(Measurement of liquidity)
1.30 ml of ink was placed on a glass plate tilted at 60 °, and the flow of ink after being left for 30 minutes was measured. The evaluation criteria are as follows.
□ ◎: 301 mm or more ○: 300-201 mm
Δ: 200 to 101 mm
×: 100 mm or less

(Misching resistance)
An OHP film cut into a 13 cm × 21 cm square was attached to the wall surface behind the roller of the incometer, the roller temperature was adjusted to 40 ° C., and 2.6 ml of ink was placed on the roller. The roller was rotated at 1200 rpm × 2 minutes and the mass of the ink adhering to the film was weighed. The evaluation criteria are as follows.
□ ◎: 19 mg or less ○: 20-59 mg
Δ: 60 to 99 mg
×: 100 mg or more

Claims (4)

A resin solution for offset printing ink containing a resin for offset printing ink having a molecular weight distribution (Mw / Mn) of 1.5 to 55 and a weight average molecular weight of 10,000 to 40,000 , which comprises the following structural units 1 and 2. Therefore, the structural unit 1 is

[In the formula, R ^a1 is a hydrogen atom or an alkyl group, and R ^a2 is

{In the formula, a is an integer of 1 or more, b is an integer of 0 or more, and R ^aa is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted. It is an aryloxy group, and R ^ab is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
Is. ]
And
The structural unit 2 is a general formula.

[In the equation, n and m are independently integers of 0 to 2, p is an integer of 0 to 7, and R ^b1 to R ^b17 are independently hydrogen atoms.

{In the equation, q is an independently integer of 0 to 16, R ¹ to R ³ are independent hydrogen atoms or alkyl groups, and R ¹ and R ³ have different groups for each unit. good. }
And
R b18 to R ^b19 are independent of each ^other .

{In the equation, q is an independently integer of 0 to 16, R ¹ to R ³ are independent hydrogen atoms or alkyl groups, and R ¹ and R ³ have different groups for each unit. good. }
And
R ^b20 is an alkylene group and is an alkylene group.
R ^b4 , R ^b5 , R ^b9 , and R ^b13 may have different groups for each structural unit.
In the general formulas (A) to (D)

{In the equation, q is an independently integer of 0 to 16, R ¹ to R ³ are independent hydrogen atoms or alkyl groups, and R ¹ and R ³ have different groups for each unit. good. }
Is included in two or more. ]
A resin solution for offset printing ink derived from the monomer represented by. Configuration unit 3

(In the formula, R ^c1 is a hydrogen atom or an alkyl group, and R ^c2 to R ^c6 are independently selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group.)
The resin solution for offset printing ink according to claim 1. Configuration unit 4

(In the formula, ^RD is a hydrogen atom or an alkyl group, and R ^d is CONR ^d1 R ^d2 , COO (CH ₂ ) ₂ NR ^d1 R ^d2 and

It is a group selected from the group consisting of
In the formula, R ^d1 and R ^d2 are an alkyl group or a hydrogen atom, or R ^d1 and R ^d2 are a group forming a ring structure together, k is an integer of 1 or more, and R ^d3 . Is a hydrogen atom, a methyl group or a hydroxyl group, and R ^d4 is OH, CH ₂ OH, CH ₂ CH ₂ OH, CH ₂ OCH ₃ or CH ₂ OPh, but either R ^d3 or R ^d4 is a hydroxyl group. Is. )
The resin solution for offset printing ink according to claim 1 or 2. (Meta) Acrylic Acid Ester, and (Poly) Pentaerythritol Poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, (Poly) Trimethylol Propane Poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, (poly) Monomers containing one or more selected from the group consisting of glycerin poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate and alkylene di (alkylene oxide-modified or epoxy-modified) (meth) acrylate, with a monomer concentration of 10 to 70. The resin solution for offset printing ink according to claim 1 or 2 , which comprises a step of polymerizing at 70 to 200 ° C. in the presence of 3 to 50 parts by mass of a polymerization initiator with respect to 100 parts by mass of the monomer. Production method.