JP7226071B2 - Resins, varnish compositions, printing inks and printed matter - Google Patents

Description

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

Active energy ray-curable printing inks that are cured by active energy rays such as ultraviolet rays and electron beams may contain reactive diluents, resins, photopolymerization initiators, and additives. Polyfunctional acrylates such as dipentaerythritol hexaacrylate and ditrimethylolpropane tetraacrylate are widely used as reactive diluents because of their excellent curability and film hardness.

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

Japanese Patent No. 5683757

In conventional styrene-acrylic resins and polyester resins, there is a trade-off relationship between ink fluidity and anti-misting properties, and the current situation is that no resin has been obtained that satisfies both of these properties. On the other hand, the diallyl phthalate resin is obtained by polymerizing a diallyl phthalate monomer, and since it does not have a hydroxyl group, a carboxyl group, or the like, its usage is limited. In addition, since the unreacted diallyl phthalate monomer remaining in the resin is a mutagenic substance of high concern (see paragraph [0009] of Patent Document 1 above), a resin that can be substituted for the diallyl phthalate resin is desired. It is

The problem to be solved by the present invention is to provide a resin which is a raw material for printing ink and has excellent ink fluidity, misting resistance and curability.

As a result of intensive studies, the inventors of the present invention have found that the above-described problems can be solved by using 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、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^４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^４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^４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を含む構成単位である。｝
が２個以上含まれる。］
であり、
前記末端構成単位Ａは、

［式中、Ｒ^Ａ１は、アルキレン基であり、Ｒ^Ａ２～Ｒ^Ａ４はそれぞれ独立に、水素原子、アリール基又はアルキル基である］
である、樹脂。
（項目２）
上記項目に記載の樹脂を含む、ワニス組成物。
（項目３）
上記項目に記載のワニス組成物及び顔料を含む、印刷インキ。
（項目４）
上記項目に記載のインキの硬化層を有する、印刷物。 The following items are provided by this disclosure.
(Item 1)
A resin containing the following structural units 1 and 2 and a terminal structural unit A, 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

{Wherein, R ^aa is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, R ^ab is a substituted or unsubstituted arylene group, a substituted Alternatively, it is an unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
is. ]
and
The structural unit 2 has the general formula

[Wherein, n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, R ^b1 to R ^b17 are each independently a hydrogen atom,

{wherein q and r are each independently an integer of 0 to 16, s and t are each independently an integer of 1 or more, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group, R ¹ and R ⁴ may have different groups for each unit, and R ^A to R ^B are each independently a structural unit containing the structural unit 1. }
and
R ^b18 to R ^b19 are each independently

{wherein q and r are each independently an integer of 0 to 16, s and t are each independently an integer of 1 or more, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group, R ¹ and R ⁴ may have different groups for each unit, and R ^A to R ^B are each independently a structural unit containing the structural unit 1. }
and
R ^b20 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)

{wherein q and r are each independently an integer of 0 to 16, s and t are each independently an integer of 1 or more, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group, R ¹ and R ⁴ may have different groups for each unit, and R ^A to R ^B are each independently a structural unit containing the structural unit 1. }
contains two or more. ]
and
The terminal structural unit A is

[Wherein, R ^A1 is an alkylene group, and R ^A2 to R ^A4 are each independently a hydrogen atom, an aryl group, or an alkyl group]
is a resin.
(Item 2)
A varnish composition comprising the resin as described above.
(Item 3)
A printing ink comprising a varnish composition and a pigment as described above.
(Item 4)
A printed material having a cured layer of the ink according to any one of the above items.

In the present disclosure, one or more of the features described above may be provided in further combinations in addition to the explicit combinations. Those of ordinary skill in the art will recognize further embodiments and advantages beyond those described above upon reading and understanding the following detailed description, as appropriate.

By using the resin of the present invention, a printing ink having excellent ink fluidity, misting resistance and curability can be obtained.

［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、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^４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^４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^４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を含む構成単位である。｝
が２個以上含まれる。］
であり、
前記末端構成単位Ａは、

［式中、Ｒ^Ａ１は、アルキレン基であり、Ｒ^Ａ２～Ｒ^Ａ４はそれぞれ独立に、水素原子又はアルキル基である］
である、樹脂を提供する。 [1. resin]
The present disclosure provides a resin comprising the following structural units 1 and 2 and a terminal structural unit A, 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

{Wherein, R ^aa is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, R ^ab is a substituted or unsubstituted arylene group, a substituted Alternatively, it is an unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
is. ]
and
The structural unit 2 has the general formula

[Wherein, n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, R ^b1 to R ^b17 are each independently a hydrogen atom,

{wherein q and r are each independently an integer of 0 to 16, s and t are each independently an integer of 1 or more, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group, R ¹ and R ⁴ may have different groups for each unit, and R ^A to R ^B are each independently a structural unit containing the structural unit 1. }
and
R ^b18 to R ^b19 are each independently

{wherein q and r are each independently an integer of 0 to 16, s and t are each independently an integer of 1 or more, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group, R ¹ and R ⁴ may have different groups for each unit, and R ^A to R ^B are each independently a structural unit containing the structural unit 1. }
and
R ^b20 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)

{wherein q and r are each independently an integer of 0 to 16, s and t are each independently an integer of 1 or more, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group, R ¹ and R ⁴ may have different groups for each unit, and R ^A to R ^B are each independently a structural unit containing the structural unit 1. }
contains two or more. ]
and
The terminal structural unit A is

[Wherein, R ^A1 is an alkylene group, and R ^A2 to R ^A4 are each independently a hydrogen atom or an alkyl group]
provides a resin.

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 resin comprises structural unit 3

(In the formula, R ^c1 is a hydrogen atom or an alkyl group, and R ^c2 to R ^c6 are each independently a group 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 resin comprises structural unit 4

(wherein R ^D is a hydrogen atom or an alkyl group, R ^d is CONR ^d1 R ^d2 , COO(CH ₂ ) ₂ NR ^d1 R ^d2 and

A group selected from the group consisting of
In the formula, R ^d1 and R ^d2 are alkyl groups or hydrogen atoms, or R ^d1 and R ^d2 together form a ring structure group, 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, where 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 comprises structural unit 5

(In the formula, R ^e1 to R ^e3 are each independently a nitrile group, an alkyl group, or an alkenyl group.)
including.

Alkyl groups are exemplified by linear alkyl groups, branched alkyl groups, cycloalkyl groups and the like.

A straight-chain alkyl group can be represented by a general formula of -C _n H _2n+1 (n is an integer of 1 or more). Linear alkyl groups include methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decamethyl group, etc. are exemplified.

A branched alkyl group is a group in which at least one hydrogen of a straight-chain alkyl group has been replaced by an alkyl group. Branched alkyl groups are exemplified by diethylpentyl group, trimethylbutyl group, trimethylpentyl group, trimethylhexyl group (trimethylhexamethyl group) and the like.

The cycloalkyl group is exemplified by a monocyclic cycloalkyl group, a bridged ring cycloalkyl group, a condensed ring cycloalkyl group and the like.

In the present disclosure, monocyclic means a cyclic structure with no internal bridging structure formed by covalent carbon bonds. Fused rings also refer to cyclic structures in which two or more single rings share two atoms (ie, each ring shares (condenses) only one edge with each other). Bridged ring means a cyclic structure in which two or more single rings share three or more atoms.

Monocyclic cycloalkyl groups are exemplified by cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl and 3,5,5-trimethylcyclohexyl groups.

The bridging ring cycloalkyl group is exemplified by a tricyclodecyl group, an adamantyl group, a norbornyl group and the like.

The condensed ring cycloalkyl group is exemplified by a bicyclodecyl group and the like.

Alkenyl groups are exemplified by linear alkenyl groups, branched alkenyl groups, cycloalkenyl groups and the like.

Linear alkenyl groups are exemplified by vinyl groups, propenyl groups, n-butenyl groups and the like.

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

Cycloalkenyl groups are exemplified by monocyclic cycloalkenyl groups and the like.

Monocyclic cycloalkenyl groups are exemplified by cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclodecenyl and 3,5,5-trimethylcyclohexenyl groups.

An alkoxy group can be represented by a general formula of —OR ^Al (R ^Al is an alkyl group). Examples of the alkyl group in the above general formula include those mentioned above.

The aryl group is exemplified by a monocyclic aryl group, a condensed ring aryl group, and the like. A monocyclic aryl group is exemplified by a phenyl group, and a condensed ring aryl group is exemplified by a naphthyl group and the like. Substituted aryl groups are exemplified by tolyl groups, xylyl groups and the like.

An aryloxy group can be represented by the general formula -OR ^Ar (R ^Ar is an aryl group). The aryl group in the above general formula is exemplified by those mentioned above.

The arylene group is exemplified by a monocyclic arylene group, condensed ring arylene group and the like. The monocyclic arylene group is exemplified by a phenylene group, and the condensed ring arylene group is exemplified by a naphthylene group and the like. The substituted arylene group is exemplified by a tolylene group, a xylylene group and the like.

The alkylene group is exemplified by a linear alkylene group, a branched alkylene group, a cycloalkylene group and the like.

A straight-chain alkylene group can be represented by the general formula —(CH ₂ ) _n — (n is an integer of 1 or more). Straight-chain alkylene group includes methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decamethylene group, etc. are exemplified.

A branched alkylene group is a group in which at least one hydrogen of a linear alkylene group has been replaced by an alkyl group. The branched alkylene group is exemplified by a diethylpentylene group, trimethylbutylene group, trimethylpentylene group, trimethylhexylene group (trimethylhexamethylene group) and the like.

The cycloalkylene group is exemplified by a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, a condensed ring cycloalkylene group and the like.

The monocyclic cycloalkylene group is exemplified by a cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclodecylene group, 3,5,5-trimethylcyclohexylene group and the like.

The bridging ring cycloalkylene group is exemplified by a tricyclodecylene group, an adamantylene group, a norbornylene group and the like.

The condensed ring cycloalkylene group is exemplified by a bicyclodecylene group and the like.

Alkenylene groups are exemplified by linear alkenylene groups, branched alkenylene groups, cycloalkenylene groups and the like.

The linear alkenylene group is exemplified by vinylene group, propenylene group, n-butenylene group and the like.

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

A monocyclic cycloalkenylene group etc. are illustrated as a cycloalkenylene group.

The monocyclic cycloalkenylene group is exemplified by 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 “substituted A group” means a group in which one or more hydrogen atoms of the A group have been 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 the alkyl group are substituted with groups other than hydrogen atoms. The substituted A group also includes a group in which a plurality of substituents together 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 above monovalent substituents include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, hydroxyl groups, groups combining these groups and, if necessary, ether bonds, ester bonds and the like. Examples of groups obtained by combining these groups include alkylalkoxy groups, alkylaryl groups (benzyl group, etc.), alkyloxyaryl groups, alkyloxyarylaryl groups, alkyloxyalkylaryl groups, and the like. More specifically,

(In the formula, v represents an integer of 1 or more.)
etc. are exemplified.
The substituent of the portion corresponding to R ^a2 of structural unit 1 is

is exemplified as being preferred. Further, the substituents of R ^aa and R ^ab in structural unit 1 are

is exemplified as being preferred.

<Constituent unit 1>
Structural unit 1 is a structural unit contained in a polymer chain when (meth)acrylic acid or (meth)acrylic acid ester is used as a monomer. (Meth)acrylic acid and (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 acrylate and methacrylate". Similarly, "(meth)acryl" means "at least one selected from the group consisting of acryl and methacryl".

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

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

(Meth)acrylic acid branched alkyl esters include iso-propyl (meth)acrylate, iso-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acryl Examples include iso-octyl acid and 2-ethylhexyl (meth)acrylate.

Examples of (meth)acrylic acid cycloalkyl esters include cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate.

Examples of (meth)acrylic acid-substituted alkyl esters include glycidyl (meth)acrylate and the like.

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

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

The upper limit of the ratio of structural unit 1 to all structural units is 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, relative to 100 mol% of all structural units. , 30, 25, 21 mol%, etc., and the lower limits are 20 mol % and the like are exemplified. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, from the viewpoint of suppressing gelation, the ratio of structural unit 1 to 100 mol % of all structural units is preferably 20 to 99 mol %.

<Constituent unit 2>
Structural unit 2 is a structural unit derived from a polyfunctional monomer described below. In addition, 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)
Structural unit 2A has the general formula A' as a monomer

[wherein n is an integer of 0 to 2, R ^b1′ to R ^b6′ are each independently a hydrogen atom,

{Wherein, q is each independently an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have different groups 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′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
contains two or more. ]
It is a structural unit contained in the polymer chain when using (poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate represented by.

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, "each structural unit may have a different group" means, for example, in general formula (A), when n is 2,

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" means "pentaerythritol poly(meth)acrylate, pentaerythritol polyalkylene oxide-modified (meth)acrylate, pentaerythritol polyepoxy-modified At least one selected from the group consisting of (meth)acrylates, polypentaerythritol poly(meth)acrylates, polypentaerythritol polyalkylene oxide-modified (meth)acrylates, and polypentaerythritol polyepoxy-modified (meth)acrylates. do.

Pentaerythritol poly(meth)acrylate includes pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol penta(meth)acrylate, pentaerythritol hexa(meth)acrylate, etc. exemplified.

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), pentaerythritol tetra (propylene oxide-modified (meth)acrylate), pentaerythritol penta (propylene oxide-modified (meth)acrylate), pentaerythritol hexa (propylene oxide-modified (meth)acrylate), and the like.

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

Polypentaerythritol poly(meth)acrylate is dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa (meth) 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 ( meth)acrylate and the like are exemplified.

Polypentaerythritol polyalkylene oxide-modified (meth)acrylates include dipentaerythritol di (ethylene oxide-modified (meth)acrylate), dipentaerythritol tri (ethylene oxide-modified (meth)acrylate), dipentaerythritol tetra (ethylene oxide-modified ( meth) 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), dipentaerythritol di (propylene oxide-modified (meth)acrylate), dipentaerythritol tri (propylene oxide-modified (meth)acrylate), dipentaerythritol tetra (propylene oxide-modified (meth)acrylate) acrylate), dipentaerythritol penta (propylene oxide-modified (meth)acrylate), dipentaerythritol hexa (propylene oxide-modified (meth)acrylate), dipentaerythritol hepta (propylene oxide-modified (meth)acrylate), dipentaerythritol octa ( Propylene oxide-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 Rithritol 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 (meth)acrylate) meth) 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. be.

Polypentaerythritol polyepoxy-modified (meth)acrylates are dipentaerythritol diepoxy (meth)acrylate, dipentaerythritol triepoxy (meth)acrylate, dipentaerythritol tetraepoxy (meth)acrylate, 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 Acrylates, Tripentaerythritol Tetraepoxy (meth)acrylate, Tripentaerythritol Pentaepoxy (meth)acrylate, Tripentaerythritol Hexepoxy (meth)acrylate, Tripentaerythritol Heptaepoxy (meth)acrylate, Tripentaerythritol Octaepoxy (meth)acrylate Examples include acrylates, 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。 <Constituent unit 2B>
Structural unit 2B is represented by general formula B' as a monomer.

[Wherein, m is an integer of 0 to 2, R ^b7′ to R ^b10′ are each independently a hydrogen atom,

{Wherein, q is each independently an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have different groups for each unit. good. }
and
R ^b9′ may have different groups 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′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
contains two or more. ]
is a structural unit contained in the 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 Selected from the group consisting of methylolpropane polyepoxy-modified (meth)acrylate, polytrimethylolpropane poly(meth)acrylate, polytrimethylolpropane polyalkylene oxide-modified (meth)acrylate, and polytrimethylolpropane polyepoxy-modified (meth)acrylate means "at least one

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

Trimethylolpropane polyalkylene oxide-modified (meth)acrylates include trimethylolpropane di (ethylene oxide-modified (meth)acrylate), trimethylolpropane tri (ethylene oxide-modified (meth)acrylate), trimethylolpropane di (propylene oxide-modified ( meth)acrylate), trimethylolpropane tri(propylene oxide-modified (meth)acrylate), and the like.

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

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

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

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

［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。 <Constituent unit 2C>
Structural unit 2C is a monomer of general formula C'

[wherein p is an integer of 0 to 7, R ^b11′ to R ^b14′ are each independently a hydrogen atom,

{In the formula, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
and
R ^b13′ may have different groups 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′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
contains two or more. ]
It is a structural unit contained in the polymer chain when using (poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate as shown in.

In the present disclosure, "(poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "glycerin poly(meth)acrylate, glycerin polyalkylene oxide-modified (meth)acrylate, glycerin polyepoxy-modified (meth)acrylate , polyglycerin poly(meth)acrylate, polyglycerin polyalkylene oxide-modified (meth)acrylate, and polyglycerin polyepoxy-modified (meth)acrylate”.

Glycerin poly(meth)acrylate is exemplified by glycerin di(meth)acrylate, glycerin tri(meth)acrylate and the like.

Glycerin polyalkylene oxide-modified (meth)acrylates include glycerin di (ethylene oxide-modified (meth)acrylate), glycerin tri (ethylene oxide-modified (meth)acrylate), glycerin di (propylene oxide-modified (meth)acrylate), glycerin tri ( Propylene oxide-modified (meth)acrylate) and the like are exemplified.

Glycerin polyepoxy-modified (meth)acrylates are exemplified by glycerin diepoxy(meth)acrylate, glycerin triepoxy(meth)acrylate, and the like.

Polyglycerin poly(meth)acrylate is diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, triglycerin di(meth)acrylate, triglycerin tri(meth)acrylate, triglycerin tetra (Meth)acrylate, triglycerin penta(meth)acrylate and the like are exemplified.

Polyglycerin polyalkylene oxide-modified (meth)acrylates include diglycerin di (ethylene oxide-modified (meth)acrylate), diglycerin tri (ethylene oxide-modified (meth)acrylate), diglycerin tetra (ethylene oxide-modified (meth)acrylate), 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), Triglycerin tri(propylene oxide-modified (meth)acrylate), triglycerin tetra(propylene oxide-modified (meth)acrylate), triglycerin penta(propylene oxide-modified (meth)acrylate) and the like are exemplified.

Polyglycerin polyepoxy-modified (meth)acrylates include diglycerin diepoxy (meth)acrylate, diglycerin triepoxy (meth)acrylate, diglycerin tetraepoxy (meth)acrylate, triglycerin diepoxy (meth)acrylate, triglycerin tri Examples 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。 <Constituent unit 2D>
Structural unit 2D has the general formula D' as a monomer

[Wherein, R ^b15′ to R ^b17′ are each independently a hydrogen atom,

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

Examples of the isocyanurate structure-containing monomer include ethylene oxide isocyanurate-modified di(meth)acrylate and ethylene oxide isocyanurate-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。 <Constituent unit 2E>
Structural unit 2E has the general formula E' as a monomer

[Wherein, R ^b18′ to R ^b19′ are each independently

{In the formula, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a 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 the polymer chain when using alkylene di (alkylene oxide-modified or epoxy-modified) (meth) acrylate as represented by.

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

Alkylene di(meth)acrylates include 1,2-ethylenediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 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(meth)acrylate Examples include meth)acrylate, 1,10-decanediol di(meth)acrylate, and the like.

Alkylenedialkylene oxide-modified (meth)acrylates include 1,2-ethylenediol di(ethylene oxide-modified (meth)acrylate), 1,3-propanediol di(ethylene oxide-modified (meth)acrylate), 1,4-butane Diol di(ethylene oxide-modified (meth)acrylate), 1,5-pentanediol di(ethylene oxide-modified (meth)acrylate), 1,6-hexanediol di(ethylene oxide-modified (meth)acrylate), 1,7- Heptanediol di(ethylene oxide-modified (meth)acrylate), 1,8-octanediol di(ethylene oxide-modified (meth)acrylate), 1,9-nonanediol di(ethylene oxide-modified (meth)acrylate), 1,10 -decanediol di(ethylene oxide-modified (meth)acrylate), 1,2-ethylenediol di(propylene oxide-modified (meth)acrylate), 1,3-propanediol di(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).

Alkylene diepoxy-modified (meth)acrylates include 1,2-ethylenediol diepoxy (meth) acrylate, 1,3-propanediol diepoxy (meth) acrylate, 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-nonanediol diepoxy(meth)acrylate, 1,10-decanediol diepoxy(meth)acrylate, and the like.

The upper limit of the proportion of structural unit 2 (one or more of the group consisting of structural units 2A, 2B, 2C, 2D and 2E) in all structural units is 50, 45, 40, 35, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2% by mass, etc. are exemplified, and the lower limit is 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1% by mass, etc. exemplified. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, the ratio of structural unit 2 (one or more of the group consisting of structural units 2A, 2B, 2C, 2D and 2E) to all structural units is preferably 1 to 50% by mass.

The upper limit of the proportion of structural unit 2 (one or more of the group consisting of structural units 2A, 2B, 2C, 2D and 2E) in all structural units is 50, 45, 40, 35 with respect to 100 mol% of all structural units. , 30, 25, 20, 15, 10, 5, 2 mol%, etc., and the lower limits are 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1 mol%, etc. are exemplified. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, the ratio of structural unit 2 (one or more of the group consisting of structural units 2A, 2B, 2C, 2D and 2E) to all structural units is preferably 1 to 50 mol%.

［式中、Ｒ^Ａ１’は、アルキレン基であり、Ｒ^Ａ２’～Ｒ^Ａ４’、Ｒ^’～Ｒ^’’’はそれぞれ独立に、水素原子、アリール基又はアルキル基である］
を用いた場合にポリマー鎖に含まれる構成単位である。 <Terminal structural unit A>
Terminal structural unit A, as a monomer, the formula (1)

[Wherein, R ^A1′ is an alkylene group, and R ^A2′ to R ^A4′ and R ^′ to R ^′″ are each independently a hydrogen atom, an aryl group, or an alkyl group]
is a structural unit contained in the polymer chain when is used.

Examples of the compound represented by the above formula (1) include α-alkylalkenylaryl dimers. Examples of α-alkylalkenylaryl dimers include α-methylstyrene dimers.

The upper limit of the ratio of the terminal structural unit A to all structural units is exemplified by 20, 19, 15, 14, 10, 9, 7, 5, 4, 1, 0.9, 0.7% by mass, and the lower limit is exemplified by 19, 15, 14, 10, 9, 7, 5, 4, 1, 0.9, 0.7, 0.5% by mass. In one embodiment, the ratio of terminal structural units A to all structural units is preferably 0.5 to 20% by mass.

The upper limit of the ratio of the terminal structural unit A to all structural units is exemplified by 20, 19, 15, 14, 10, 9, 7, 5, 4, 1, 0.9, 0.7 mol%, and the lower limit is exemplified by 19, 15, 14, 10, 9, 7, 5, 4, 1, 0.9, 0.7, 0.5 mol %. In one embodiment, the ratio of terminal structural units A to all structural units is preferably 0.5 to 20 mol %.

The upper limit of the mass ratio between the structural unit 1 and the terminal structural unit A (mass of the structural unit 1/mass of the terminal structural unit A) is 198, 195, 190, 175, 150, 125, 100, 75, 50, 25, 10, 9, 5, 4, 1, 0.9, 0.5, etc. are exemplified, and the lower limits are 195, 190, 175, 150, 125, 100, 75, 50, 25, 10, 9, 5, 4 , 1, 0.9, 0.5, 0.25, and the like. In one embodiment, the mass ratio between the structural unit 1 and the terminal structural unit A (mass of the structural unit 1/mass of the terminal structural unit A) is preferably 0.25 to 198.0 from the viewpoint of suppressing gelation. .

The upper limit of the molar ratio between the structural unit 1 and the terminal structural unit A (substance amount of the structural unit 1/substance amount of the terminal structural unit A) is 198, 195, 190, 175, 150, 125, 100, 75, 50, 25, 10, 9, 5, 4, 1, 0.9, 0.5, etc. are exemplified, and the lower limits are 195, 190, 175, 150, 125, 100, 75, 50, 25, 10, 9, 5 , 4, 1, 0.9, 0.5, 0.25, and the like. In one embodiment, the molar ratio between the structural unit 1 and the terminal structural unit A (substance amount of the structural unit 1/substance amount of the terminal structural unit A) is 0.25 to 198.0 from the viewpoint of suppressing gelation. is preferred.

The upper limit of the mass ratio between the structural unit 2 and the terminal structural unit A (mass of the structural unit 2/mass of the terminal structural unit A) is 100, 90, 75, 50, 25, 10, 9, 5, 1, 0. 9, 0.5, 0.1, 0.09, etc. are exemplified, and the lower limits are 90, 75, 50, 25, 10, 9, 5, 1, 0.9, 0.5, 0.1, 0 0.09, 0.05, etc. are exemplified. In one embodiment, the mass ratio between the structural unit 2 and the terminal structural unit A (mass of the structural unit 2/mass of the terminal structural unit A) is preferably 0.05 to 100 from the viewpoint of suppressing gelation.

The upper limit of the molar ratio between the structural unit 2 and the terminal structural unit A (substance amount of the structural unit 2 /substance amount of the terminal structural unit A) is 100, 90, 75, 50, 25, 10, 9, 5, 1, Examples include 0.9, 0.5, 0.1, 0.09, etc., and the lower limits are 90, 75, 50, 25, 10, 9, 5, 1, 0.9, 0.5, 0.1. , 0.09, 0.05, and the like. In one embodiment, the molar ratio between the structural unit 2 and the terminal structural unit A (substance amount of the structural unit 2/substance amount of the terminal structural unit A) is preferably 0.05 to 100 from the viewpoint of suppressing gelation. .

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

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

The upper limit of the ratio of structural unit 3 to all structural units is 79, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 relative to 100 mol% of all structural units. , 10, 5, 2 mol%, etc., and the lower limits are Examples include 1 and 0 mol %. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). When the structural unit 3 is included, in one embodiment, the ratio of the structural unit 3 to the total structural units is preferably 1 to 79 mol%.

(Constituent unit 4)
Structural unit 4 is a polymer chain when (meth)acrylic acid, N,N-dialkyl(meth)acrylamide, N,N-dialkylamine alkyl(meth)acrylate, or hydroxyalkyl(meth)acrylate is used as a monomer. It is a structural unit contained in

N,N-dialkyl(meth)acrylamides are exemplified by dimethylacrylamide, diethylacrylamide, acryloylmorpholine and the like.

Examples of N,N-dialkylamine alkyl (meth)acrylates include N,N-dimethylamineethyl (meth)acrylate and N,N-diethylamineethyl (meth)acrylate. The number of carbon atoms in the alkyl group on nitrogen (that is, the number of carbon atoms in R ^d1 and R ^d2 in structural unit 4) is preferably 1-2.

Hydroxyalkyl (meth)acrylate includes hydroxymethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, (meth)acrylate, Examples include 2-hydroxypropyl acryl and 3-hydroxypropyl (meth)acrylate.

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

The upper limit of the ratio of the structural unit 4 to all structural units is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2 mol% with respect to 100 mol% of all structural units. , the lower limit is 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0 mol%, and the like. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). When the structural unit 4 is included, in one embodiment, the ratio of the structural unit 4 to all structural units is preferably 1 to 50 mol %.

（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。 (Constituent unit 5)
Structural unit 5 has, for example, the following structure

(In the formula, R ^e1 , R ^e2 , and R ^e3 are each independently a nitrile group, an alkyl group, or an alkenyl group.) It is a structural unit derived from an azo initiator.

Azo initiators are exemplified by azonitrile initiators, azoamidine initiators and azoamide initiators.

Azonitrile initiators include 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(isobutyl ronitrile), 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1-carbonitrile) and the like.

Azoamidine initiators include 2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 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′- Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n-hydrate and the like are exemplified.

Azoamide initiators include 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2′-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide) and the like are exemplified.

Other azo initiators are exemplified by dimethyl 2,2'-azobis(isobutyrate), 4,4'-azobis(4-cyanovaleric acid) and the like.

The upper limit of the ratio of the structural unit 5 to all structural units is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4% by mass, etc. with respect to the mass of all structural units, The lower limit is exemplified by 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 0% by mass. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). When the structural unit 5 is included, in one embodiment, the ratio of the structural unit 5 to all structural units is preferably 3 to 50% by mass with respect to the mass of all structural units.

The upper limit of the proportion of structural unit 5 in all structural units is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4 mol%, etc. relative to 100 mol% of all structural units. , the lower limit is 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 0 mol%, and the like. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). When the structural unit 5 is included, in one embodiment, the ratio of the structural unit 5 to 100 mol% of all structural units is preferably 3 to 50 mol%.

(Other structural units)
The resin of the present disclosure may also contain structural units other than structural units 1-5. 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 structural units are included, the upper limit of the ratio of other structural units to all structural units is exemplified by 30, 25, 20, 15, 10, 5, 2% by mass, etc., and the lower limit is 29, 25, 20, 15, 10, 5, 2, 1 mass % and the like are exemplified. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, the proportion of other structural units in all structural units is 1 to 30% by mass, less than 30% by mass, less than 20% by mass, less than 10% by mass, less than 9% by mass, less than 5% by mass, 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 are exemplified.

The upper limit of the ratio of other structural units to 100 mol% of all structural units is exemplified by 30, 25, 20, 15, 10, 5, 2 mol%, and the lower limit is 29, 25, 20, 15, 10. , 5, 2, 1, 0 mol %, and the like. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, the ratio of other structural units to 100 mol% of all structural units is 1 to 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%, and 0 mol%. When other structural units are included, in one embodiment, the ratio of other structural units to 100 mol % of all structural units is preferably 1 to 30 mol %.

The upper limit of the mass ratio of structural unit 1 to structural unit 2 (mass of structural unit 1/mass of structural unit 2) is 99.0, 95.0, 90.0, 85.0, 80.0, 75.0. 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 limits are 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 mass ratio range can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, the mass ratio of structural unit 1 to structural unit 2 (mass of structural unit 1/mass of structural unit 2) is preferably 0.4 to 99.0 from the viewpoint of suppressing gelation.

The upper limit of the molar ratio between structural unit 1 and structural unit 2 (substance amount of structural unit 1/substance amount of structural 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 limits are 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 above molar ratio can be set appropriately (for example, by selecting from the above upper limit and lower limit values). In one embodiment, the molar ratio between structural unit 1 and structural unit 2 (substance amount of structural unit 1/substance amount of structural unit 2) is preferably 0.4 to 99.0 from the viewpoint of suppressing gelation. .

When structural unit 3 is included, the upper limit of the mass ratio between structural unit 1 and structural unit 3 (mass of structural unit 1/mass of structural 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 limits are 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. Examples include 0, 10.0, 5.0, 1.0, 0.5, 0.25 and the like. The mass ratio range can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, when structural unit 3 is included, the mass ratio of structural unit 1 to structural unit 3 (mass of structural unit 1/mass of structural unit 3) is 0.25 to 99 from the viewpoint of polarity adjustment. .0 is preferred.

When the structural unit 3 is included, the upper limit of the molar ratio of the structural unit 1 and the structural unit 3 (substance amount of the structural unit 1 /substance amount of the structural 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 limits are 98.0, 95.0, 90.0, 85.0, 80.0. 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 above molar ratio can be set appropriately (for example, by selecting from the above upper limit and lower limit values). In one embodiment, when the structural unit 3 is included, the molar ratio of the structural unit 1 to the structural unit 3 (the amount of substance of the structural unit 1/the amount of substance of the structural unit 3) is 0.00 from the viewpoint of suppressing gelation. 25 to 99.0 are preferred.

When the structural unit 4 is included, the upper limit of the mass ratio between the structural unit 1 and the structural unit 4 (mass of the structural unit 1/mass of the structural 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 limits are 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. Examples include 0, 10.0, 5.0, 1.0, 0.5, 0.4 and the like. The mass ratio range can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, when the structural unit 4 is included, the mass ratio between the structural unit 1 and the structural unit 4 (mass of the structural unit 1/mass of the structural unit 4) is 0.4 to 99 from the viewpoint of polarity adjustment. .0 is preferred.

When the structural unit 4 is included, the upper limit of the molar ratio between the structural unit 1 and the structural unit 4 (substance amount of the structural unit 1/substance amount of the structural 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 limits are 98.0, 95.0, 90.0, 85.0, 80.0. 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 above molar ratio can be set appropriately (for example, by selecting from the above upper limit and lower limit values). In one embodiment, when the structural unit 4 is included, the molar ratio between the structural unit 1 and the structural unit 4 (the amount of substance of the structural unit 1/the amount of substance of the structural unit 4) is 0.5 from the viewpoint of suppressing gelation. 4 to 99.0 are preferred.

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

When the structural unit 5 is included, the upper limit of the molar ratio of the structural unit 1 and the structural unit 5 (substance amount of the structural unit 1/substance amount of the structural unit 5) is 33.0, 30.0, 25.0, 20 0, 15.0, 10.0, 5.0, 1.0, 0.5, etc., and the lower limits are 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 above molar ratio can be set appropriately (for example, by selecting from the above upper limit and lower limit values). In one embodiment, when the structural unit 5 is included, the molar ratio between the structural unit 1 and the structural unit 5 (the amount of substance of the structural unit 1/the amount of substance of the structural unit 5) is 0.00 from the viewpoint of suppressing gelation. 4 to 33.0 are preferred.

When the structural unit 5 is included, the upper limit of the mass ratio between the structural unit 2 and the structural unit 5 (mass of the structural unit 2/mass of the structural unit 5) is 16.7, 16, 15, 10, 5, 1, 0. .5, 0.1 and 0.05 are exemplified, and the lower limits are exemplified by 16, 15, 10, 5, 1, 0.5, 0.1, 0.05 and 0.02. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper limit and lower limit values). In one embodiment, when the structural unit 5 is included, the mass ratio of the structural unit 2 to the structural unit 5 (mass of the structural unit 2/mass of the structural unit 5) is 0.02 to 0.02 from the viewpoint of suppressing gelation. 16.7 is preferred.

When the structural unit 5 is included, the upper limit of the molar ratio of the structural unit 2 and the structural unit 5 (substance amount of the structural unit 2 /substance amount of the structural unit 5) is 16.7, 16, 15, 10, 5, 1 , 0.5, 0.1 and 0.05, and the lower limits are exemplified as 16, 15, 10, 5, 1, 0.5, 0.1, 0.05 and 0.02. The range of the above molar ratio can be set appropriately (for example, by selecting from the above upper limit and lower limit values). In one embodiment, when the structural unit 5 is included, the molar ratio of the structural unit 2 to the structural unit 5 (the amount of substance of the structural unit 2/the amount of substance of the structural unit 5) is 0.00 from the viewpoint of suppressing gelation. 02 to 16.7 are preferred.

The upper limit of the mass ratio (mass of structural unit 2 / mass of structural unit derived from monofunctional monomer) between structural unit 2 and structural units derived from monofunctional monomers (structural 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., 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 mass ratio range can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, the mass ratio of structural unit 2 and structural units derived from monofunctional monomers (structural units 1, 3, 4, etc.) (mass of structural unit 2 / structural unit derived from monofunctional monomer mass) is preferably 0.01 to 1.00 from the viewpoint of suppressing gelation.

The upper limit of the molar ratio between the structural unit 2 and the structural units derived from the monofunctional monomer (structural units 1, 3, 4, etc.) (substance amount of the structural unit 2/substance amount of the structural unit derived from the monofunctional monomer) 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, etc. 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, etc. be. The range of the above molar ratio can be set appropriately (for example, by selecting from the above upper limit and lower limit values). In one embodiment, the molar ratio of the structural unit 2 and the structural unit derived from the monofunctional monomer (substance amount of the structural unit 1 /substance amount of the structural unit derived from the monofunctional monomer) is the amount of gelation suppression. From the point of view, 0.01 to 1.00 is preferable.

(Modification of resin)
The above resins can be modified. Modification is exemplified by modifying the carboxyl group or hydroxyl group contained in the resin by reacting the epoxide alone, or the epoxide and the carboxylic anhydride.

［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 modifying the carboxyl group contained in the resin by reacting only the epoxide or the epoxide and carboxylic anhydride,

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

{Wherein, a1 is an integer of 1 or more, b1 is an integer of 0 or more, R ^a1-a is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted It is a substituted aryloxy group, and R ^a1-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 modifying the hydroxyl group contained in the resin by reacting only the epoxide or the epoxide with carboxylic anhydride is the structural unit contained in the resin before modification.

[Wherein, R ^a2-1′ is a hydrogen atom or an alkyl group, and R ^a2-2′ is an alkylene group]
generated by reacting the epoxide alone or the epoxide with a 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

{Wherein, a2 is an integer of 1 or more, b2 is an integer of 0 or more, R ^a2-a is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted It is a substituted aryloxy group, and R ^a2-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 epoxides can be used in combination. Examples of epoxides include polymerizable double bond-free aromatic epoxides and polymerizable double bond-containing aromatic epoxides.

(Polymerizable double bond-free aromatic epoxide)
Examples of the polymerizable double bond-free aromatic epoxide include aromatic ring-containing monoglycidyl ethers, aromatic-containing diglycidyl ethers, bisphenol type epoxy resins, and the like.
The aromatic ring-containing monoglycidyl ethers are exemplified by phenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, styrene oxide and the like.
The aromatic-containing diglycidyl ether is exemplified by resorcinol diglycidyl ether, hydroquinone diglycidyl ether and the like.
The bisphenol type epoxy resin is exemplified by bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and the like. Among these, aromatic ring-containing monoglycidyl ethers are preferred, and phenylglycidyl ethers are particularly preferred, from the viewpoints of compatibility between the obtained resin and a reactive diluent described later, curability of the ink of the present invention, and gloss.

(Polymerizable double bond-containing epoxide)
Polymerizable double bond-containing epoxides are exemplified by allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, rosin glycidyl ester and the like.

(Epoxides that are neither polymerizable double bond-free aromatic epoxides nor polymerizable double bond-containing epoxides)
In the modification, epoxides other than the polymerizable double bond-free aromatic epoxide and the polymerizable double bond-containing epoxide may be used. Epoxides that are neither polymerizable double bond-free aromatic epoxides nor polymerizable double bond-containing epoxides include aliphatic epoxides such as glycidyl triethyl ether, butylene oxide, cyclohexene oxide, neodecanoic acid glycidyl ester;
Diepoxides such as 1,6-hexanediol diglycidyl ether and butanediol diglycidyl ether;
Examples 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 preferred from the viewpoint of compatibility between the obtained resin and a reactive diluent described below, curability of the ink of the present invention, gloss, and the like.

When a polymerizable double bond-free aromatic epoxide is used in combination with a polymerizable double bond-containing epoxide and/or an epoxide that is neither a polymerizable double bond-containing aromatic epoxide nor a polymerizable double bond-containing epoxide, 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 Epoxide which is not contained epoxide}] is preferably about 1/9 to 9/1.

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

(Carboxylic anhydride)
Two or more carboxylic anhydrides can be used in combination. Carboxylic anhydrides include aromatic carboxylic anhydrides such as phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride and benzophenonetetracarboxylic dianhydride. thing;
Alicyclic carboxylic anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic anhydride;
Aliphatic carboxylic anhydrides such as glutaric anhydride, pyromellitic anhydride, adipic anhydride, succinic anhydride, itaconic anhydride and butane-1,2,3,4-tetracarboxylic dianhydride;
Polymers starting from the above acid anhydrides (maleic anhydride homopolymer, maleic anhydride-vinyl acetate polymer, maleic anhydride-styrene polymer, maleic anhydride-acrylonitrile polymer, etc.) are exemplified.
Among these, the above aromatic carboxylic acid anhydrides, particularly phthalic anhydride, are preferred from the viewpoint of compatibility between the obtained resin and the reactive diluent described below, curability, and the like.

When a carboxylic anhydride is used, the amount of the carboxylic anhydride used is not particularly limited. The amount used is preferably about 10 to 200 parts by mass, more preferably about 10 to 150 parts by mass.

During 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 components in one pot, and [2] a method of reacting a carboxylic anhydride in the presence of a resin and then further reacting an epoxide and a carboxylic 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. In addition, during or after the reaction of each component, the pressure in the reaction system may be reduced to remove residual monomers.

Further, the modification can be carried out under various known catalysts. Two or more catalysts can be used in combination. Catalysts include triphenylphosphine, 2-methylimidazole, 1-methylimidazole, triethylamine, diphenylamine, diazabicycloundecene, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate. , zinc oxide and zinc octylate. The amount of the catalyst used is not particularly limited, but it is preferably about 0.01 to 5 parts by mass, more preferably about 0.10 to 2 parts by mass, per 100 parts by mass of component (A).

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

The upper limit of the molecular weight distribution (Mw/Mn) of the resin in the present disclosure is 4.5, 4.2, 4.1, 3.8, 3.3, 3.2, 2, etc. are exemplified, and the lower limits are 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. exemplified. The range of the molecular weight distribution (Mw/Mn) can be appropriately set (for example, selected from the upper and lower limits described above). In one embodiment, 1.5-55 is preferred.

The upper limits for the weight average molecular weight (Mw) of the resin in the present disclosure are , 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., and the lower limits are 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, 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 weight-average molecular weight range can be appropriately set (for example, selected from the upper and lower limits). In one embodiment, the resin preferably has a weight average molecular weight of 4,000 to 500,000.

The upper limits for the number average molecular weight (Mn) of the resins in this disclosure are , 15,000, 10,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, etc., and the lower limits are 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 limits above). In one embodiment, the resin preferably has a number average molecular weight of 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, etc., and the lower limit is 480, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 5, 1, 0 mgKOH/g and the like are exemplified. The range of the hydroxyl value can be appropriately set (for example, selected from the above upper and lower limits). In one embodiment, the hydroxyl value of the resin is preferably 0-483 mgKOH/g. The hydroxyl value of a resin can be measured by adding an acetylation reagent to a sample, heating it, allowing it to cool, adding a phenolphthalein solution as an indicator, and titrating with an ethanol solution of potassium hydroxide.

The upper limit of the acid value of the resin in the present disclosure 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 are exemplified as lower limits. The above acid value range can be set as appropriate (for example, by selecting from the above upper and lower limits). In one embodiment, the acid value of the resin is preferably 0-799 mgKOH/g. The acid value of the resin is determined by dissolving the sample in water or acetone or toluene/ethanol = 20/80 (volume ratio) mixed solution, adding phenolphthalein indicator as an indicator, and titrating 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 lower limit is 140, 130, 120, 110, 100, 90, 80, 75 ° C. etc. are exemplified. The softening point range can be appropriately set (for example, selected from the upper and lower limits). In one embodiment, the softening point of the resin is preferably 75-150°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 resin absolute molecular weight (M) of 50,000 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. The lower limits are 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.12, 0.11, 0.10, 0.09, 0. 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, 0.01 and the like. The range of the intrinsic viscosity (η) can be appropriately set (for example, selected from the upper and lower limits). In one embodiment, the intrinsic viscosity (η) for a resin with an absolute molecular weight (M) of 50,000 is preferably 0.01 to 0.20. The intrinsic viscosity (η) for an absolute molecular weight (M) of 50,000 for the resin 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 above upper and lower limits). In one embodiment, the glass transition temperature of the resin is preferably -80 to 230°C. The glass transition temperature of a resin can be measured by differential scanning calorimetry.

In one embodiment, the resins of the present invention are preferably used as ink resins, more preferably as offset printing ink resins. Offset printing involves transferring ink from roller to roller. Inkjet printing is a printing method that sucks ink from a tank and jets it from a narrow nozzle. Therefore, it is a well-known fact that a resin used for offset printing and a resin used for ink jet printing are required to have different physical properties (viscosity, etc.).

In one embodiment, the resin is produced by a production method including a step of polymerizing at an appropriate monomer concentration in the presence of an appropriate amount of polymerization initiator at an appropriate reaction temperature.

In one embodiment, the polymerization initiator is a radical polymerization initiator. Radical polymerization initiators are exemplified by azo initiators, peroxide initiators and the like.

In the present disclosure, a "peroxide initiator" is an organic peroxide, ie, a compound having a peroxy group (--O--O--) in its molecule. Peroxide initiators include (2-ethylhexanoyl)(tert-butyl) peroxide, benzoyl peroxide, di-tert-butyl peroxide, dimethyldioxirane, acetone peroxide, methyl ethyl ketone peroxide, hexamethylene triperoxide diamine, cumene Examples include hydroperoxide, tert-hexylperoxy-2-ethylhexanoate and the like.

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, etc., 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 production method can be appropriately set (for example, selected from the above upper and lower limits). In one embodiment, the monomer concentration is preferably 10-70% by weight. In the present disclosure, "monomer concentration" is a concentration calculated by mass of monomer/(mass of solvent+mass of monomer).

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

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

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

［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。 [Reactive diluent]
Various known reactive diluents can be used, and one or more of them can be used in combination. Reactive diluents are

[Wherein, n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, R ^b1′ to R ^b17′ are each independently a hydrogen atom,

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

{In the formula, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
and
R ^b20′ 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 formula, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
contains two or more. ]
etc. are exemplified.

The reactive diluents represented by the general formulas (A ^' ) to (E ^' ) are the following [1. Resin], the same polyfunctional monomers represented by general formulas (A ¹ ) to (E ¹ ) described in the item <Constituent Unit 2>.

[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., relative to the total mass of the varnish composition. The lower limit is exemplified by 59, 55, 50, 45, 40, 35, 30, 25, 20, 15, 11, 10% by mass. The range of the content of the resin in the varnish composition can be appropriately set (for example, selected from the above upper and lower limits). In one embodiment, the content of the resin in the varnish composition is preferably 10 to 60% by mass based on the total mass of the varnish composition from the viewpoint of film strength and curability.

The upper limit of the content of reactive diluents in the varnish composition is 90, 89, 85, 80, 75, 70, 65, 60, 55, 50, 45, 41, relative to the total weight in the varnish composition. % by mass, etc., and the lower limit is exemplified by 89, 85, 80, 75, 70, 65, 60, 55, 50, 45, 41, 40% by mass. 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 limits). In one embodiment, from the viewpoint of film strength and curability, the content of the reactive diluent in the varnish composition is preferably 40 to 90% by mass based on the total mass of the varnish composition.

The upper limit of the ratio of resin to 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., and the lower limits are 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 limit and lower limit values). In one embodiment, the ratio of the resin to the reactive diluent (mass of resin/mass of 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 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., and the lower limit is 15, 10, 5, 1, 0, based on the total mass of the resin and reactive diluent. % by mass and the like are exemplified. The range of the content can be appropriately set (for example, selected from the above upper limit and lower limit values). In one embodiment, the content of other components is preferably 0 to 20% by mass with respect to the total mass of the resin and reactive diluent.

Further, the upper limit of the content of other components is exemplified by 17, 15, 10, 5, 1% by mass, etc., and the lower limit is 15, 10, 5, 1, 0% by mass with respect to the total mass of the entire varnish composition. etc. are exemplified. The range of the content can be appropriately set (for example, selected from the above upper limit and lower limit values). In one embodiment, the content of 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 viscosity range of the varnish composition can be appropriately set (for example, selected from the above upper and lower limits). 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 for offset printing inks.

[Printing ink]
The present disclosure provides a printing ink comprising the varnish composition described above, optionally a photoinitiator, and a pigment.

The photopolymerization initiator is not particularly limited, and various known ones can be used. Specific examples include benzophenone, o-benzoylbenzoic acid methyl ester, p-dimethylaminobenzoic acid ester, p-dimethylacetophenone, thioxanthone, alkylthioxanthone, and amines. Irgacure 1173, Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 2959, Irgacure 127, Irgacure 369, Irgacure 369E, Irgacure 379, Irgacure 379EG, Irgacure TPO, Irgacure 819 (all manufactured by BASF Japan), etc. are commercially available. can be used as is. The amount of the photopolymerization initiator to be used is preferably about 1 to 15% from the viewpoint of drying property.

Pigments used in the printing ink are not particularly limited, and commonly used inorganic or organic pigments can be blended. Specific examples include white pigments such as titanium oxide, zinc white, lead white, litobone, and antimony oxide; black pigments such as aniline black, iron black, and carbon black; yellow lead; yellow iron oxide; titanium yellow; , 5G, 3G, etc.), yellow pigments such as disazo yellow, benzidine yellow, permanent yellow, orange pigments such as chrome vermillion, permanent orange, vulcan first orange, indanthrene brilliant orange, iron oxide, permanent brown, para brown red pigments such as brown pigments such as red iron oxide, cadmium red, antimony vermillion, permanent red, rhodamine lake, alizarin lake, thioindigo red, PV carmine, monolite fast red, quinacdrine red pigments, cobalt purple, manganese purple, fast Violet, methyl violet lake, indanthrene brilliant violet, dioxazine violet and other purple pigments, ultramarine blue, Prussian blue, cobalt blue, alkali blue lake, peacock blue lake, victoria blue lake, metal-free phthalocyanine blue, copper phthalocyanine blue, indanthrene In addition to blue pigments such as blue and indigo, green pigments such as chrome green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malachite green lake, phthalocyanine green, and polychlorobrom copper phthalocyanine, various fluorescent pigments , metal powder pigments, and the like. These pigments are preferably about 1 to 50 parts by mass, more preferably about 5 to 30 parts by mass, per 100 parts by mass of the offset printing ink.

The above printing ink contains the above resin, polymerizable monomer and pigment, and may further contain surface conditioners, antifoaming agents, photosensitizers, antioxidants, light stabilizers and leveling agents. can. The amount of these optional components is such that the total amount thereof is in the range of about 100 parts by mass or less (specifically, 95, 90, 80, 50, 40, 30, 20 , 10, 5, 1 part by mass or less). Furthermore, polymerization inhibitors 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 an amount of about 0.01 to 2 parts by mass with respect to 100 parts by mass of the offset printing ink.

[Print]
The present disclosure provides a printed material having a cured layer of the above printing ink.

Various known substrates can be used without particular limitation. In addition to paper (art paper, cast coated paper, foam paper, PPC paper, fine coated paper, kraft paper, polyethylene laminated paper, glassine paper, etc.), plastic substrates (polyolefin, polycarbonate, polymethacrylate, polyester, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin, etc.) and the like.

Examples of the printing method (coating method) include offset printing, flexographic printing, screen printing, bar coater coating, Meyer bar coating, air knife coating, gravure coating and the like. The coating amount is not particularly limited, but the weight after drying is preferably about 0.1 to 30 g/m ² , more preferably about 1 to 20 g/m ² .

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

Hereinafter, the present invention will be described in detail through examples and comparative examples. However, the above description of preferred embodiments and the following examples are provided for illustrative purposes only and not for the purpose of limiting the invention. Accordingly, the scope of the present invention is not limited to the embodiments or examples specifically described herein, but only by the claims. Further, in each example and comparative example, numerical values such as parts and % are based on mass unless otherwise specified.

The weight-average molecular weight and number-average molecular weight were obtained as polystyrene-equivalent values measured in THF solvent by gel permeation chromatography (GPC). HLC-8020 (manufactured by Tosoh Corporation) was used as the GPC device, and TSKgel superHZM (manufactured by Tosoh Corporation) was used as the column, flow rate: 1.00 mL/min, sample concentration: 0.5%. bottom. A molecular weight distribution (Mw/Mn) was calculated from the determined number average molecular weight and weight average molecular weight.

Example 1-1
A reaction vessel equipped with a stirrer, a reflux condenser with a water separator, a thermometer and a dropping funnel was charged with butyl acetate as a solvent, and 7.5 parts of acrylic acid, 69.5 parts of styrene and butyl methacrylate were added to the dropping funnel. 15 parts were charged, and 1.5 parts of ABN-E (2,2′-azobis(2-methylbutyronitrile)) and 10 parts of α-methylstyrene dimer were added. Under a nitrogen atmosphere, a dropping polymerization reaction was carried out at 121° C. for 3.0 hours with stirring at a polymerization concentration of 50, and the temperature was maintained for 1 hour. Then, the temperature is raised to 190° C. and the solvent is distilled off while stirring at normal pressure. distribution (Mw/Mn) of 11.2, softening point of 131°C).

In Examples other than Example 1-1, resins were produced in the same procedure as in Example 1-1, except that the compositions were changed to those shown in the table below.

The abbreviations of the raw materials in the above table are as follows.
A-1 methyl methacrylate A-2 acrylic acid A-3 butyl methacrylate A-4 2-ethylhexyl acrylate A-5 phenoxyethyl methacrylate A-6 benzyl methacrylate A-7 tetrahydrofuryl methacrylate A-8 isobornyl methacrylate B- 1 pentaerythritol tetraacrylate B-2 dipentaerythritol (tri/tetra) acrylate B-3 tripentaerythritol octaacrylate B-4 trimethylolpropane ethylene oxide-modified triacrylate B-5 ditrimethylolpropane tetraacrylate B-6 glycerin propylene oxide Modified triacrylate B-7 Diglycerin ethylene oxide-modified acrylate B-8 Glycerin triepoxyacrylate B-9 1,6-hexanediol diacrylate B-10 Isocyanuric acid-modified di- and triacrylate C-1 Styrene D-1 Acryloylmorpholine 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]

Examples 1-35, 1-36
100 parts of the resin obtained in Example 1-1, 86 parts of phthalic anhydride, 114 parts of phenylglycidyl ether were placed in a reaction vessel equipped with a stirrer, a reflux condenser with a water separator, a thermometer and a dropping funnel under a nitrogen atmosphere. 300 parts of butyl acetate was charged, and the temperature was raised to 120°C. After adding 0.3 parts of triphenylphosphine, the mixture was stirred for 8 hours. Thereafter, the solvent is distilled off while the temperature is raised to 160° C. at normal pressure, and the solvent is completely distilled off while reducing the pressure at 160 mmHg or less to obtain a resin (weight average molecular weight 76000, molecular weight distribution (Mw / Mn) 18.5. , softening point 106° C.).

For Comparative Examples, resins were produced in the same procedure as in Example 1-1, except that the compositions were changed to those shown in the table below.

Example 2-1
58.8 parts of reactive diluent ditrimethylolpropane tetraacrylate, 0.1 part of 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine ammonium for 21.2 parts of the resin obtained in Example 1-1 0.01 part was added, and under air bubbling, the mixture was stirred and dissolved at 130°C for 1 hour to obtain a varnish composition. Five parts of Irgacure 907 (manufactured by BASF) and 15 parts of MA100 (manufactured by Mitsubishi Chemical Corporation) were added to the obtained varnish composition, and the mixture was kneaded with three rollers to prepare an ink.

Examples and comparative examples other than Example 2-1 were prepared in the same manner as in Example 2-1, except that the type of resin was changed as shown in the table below.

Abbreviations in the above table are as follows.
Irgacure 907 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (manufactured by BASF)
MA100 carbon black (manufactured by Mitsubishi Chemical Corporation)

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

(Misting resistance)
An OHP film cut into a square of 13 cm×21 cm was attached to the wall surface behind the roller of the incomometer, and after adjusting the roller temperature to 40° C., 2.6 ml of ink was put on the roller. The roller was rotated at 1200 rpm for 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 to 59 mg
△: 60 to 99 mg
×: 100 mg or more

(Curability)
Passing the coated ink through a UV irradiator at a light intensity of 72 mJ/cm ² was defined as one pass, and the passes were repeated until the ink was cured. The evaluation criteria are as follows.
◎: Cured in 1 pass ○: Cured in 2 to 4 passes △: Cured in 5 to 7 passes ×: Cured in 8 passes or more

Claims (4)

A resin solution for offset printing ink,
The resin solution for offset printing ink contains a resin,
The resin contains the following structural units 1 and 2 and a terminal structural unit A,
The structural unit 1 is represented by the following general formula,

[In the formula, R ^a1 is a hydrogen atom or an alkyl group, and R ^a2 is a hydrogen atom or a substituted or unsubstituted alkyl group . ]
The structural unit 2 is derived from monomers represented by the following general formulas (A) to (E),

[Wherein, n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, R ^b1 to R ^b17 are each independently a hydrogen atom,

{wherein q is each independently an integer of 0 to 16 , R ¹ to R ³ are each independently a hydrogen atom or an alkyl group, and R ¹ and R ³ may have different groups Good. }
and
R ^b18 to R ^b19 are each independently

{wherein q is each independently an integer of 0 to 16 , R ¹ to R ³ are each independently a hydrogen atom or an alkyl group, and R ¹ and R ³ may have different groups Good. }
and
R ^b20 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)

{wherein q is each independently an integer of 0 to 16 , R ¹ to R ³ are each independently a hydrogen atom or an alkyl group, and R ¹ and R ³ may have different groups good. }
contains two or more. ]
A resin solution for offset printing ink, wherein the terminal structural unit A is represented by the following general formula .

[Wherein, R ^A1 is an alkylene group, and R ^A2 to R ^A4 are each independently a hydrogen atom, an aryl group, or an alkyl group] A varnish composition for offset printing ink, comprising the resin solution for offset printing ink according to claim 1 . An offset printing ink comprising the varnish composition for offset printing inks according to claim 2 and a pigment. A printed product comprising a cured layer of the offset printing ink according to claim 3.