JP2018123320A - Resin, varnish composition, offset-printing ink, and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin, a varnish composition, an offset-printing ink, and printed matter.SOLUTION: This disclosure provides a resin with a molecular-weight distribution (Mw/Mn) of 1.5-55 produced from monomers including (poly)pentaerythritol poly(alkylene oxide modified or epoxy modified) (meth)acrylate, (poly)trimethylolpropane poly(alkylene oxide modified or epoxy modified) (meth)acrylate, (poly)glycerine poly(alkylene oxide modified or epoxy modified) (meth)acrylate, or alkylene di(alkylene oxide modified or epoxy modified) (meth)acrylate. Also provided are a varnish composition, an offset-printing ink and printed matter that comprise the resin.SELECTED DRAWING: None

Description

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

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

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

Japanese Patent No. 5683757

  Conventional styrene acrylic resins and polyester resins have a trade-off relationship between ink fluidity and misting resistance, and the present situation is that no resin having both of these performances has been obtained. On the other hand, the diallyl phthalate resin is obtained by polymerizing a diallyl phthalate monomer and does not have a hydroxyl group, a carboxyl group, or the like, so that the usage mode is limited. In addition, since unreacted diallyl phthalate monomer remaining in the resin is a highly mutagenic substance (see paragraph [0009] of Patent Document 1 above), a resin that can replace diallyl phthalate resin is desired. It has been.

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

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

The present disclosure provides the following items.
(Item 1)
A resin having a molecular weight distribution (Mw / Mn) of 1.5 to 55 including the following structural units 1 and 2, wherein the structural unit 1 is:
[Wherein, R ^a1 represents a hydrogen atom or an alkyl group, and R ^a2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or
{Wherein, a is an integer of 1 or more, b is an integer of 0 or more, and ^Raa is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted group R ^ab is an aryloxy group, R ^ab is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
It is. ]
And
The structural unit 2 is a general formula
[ ^Wherein , n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, and R ^{b1 to} R ^b17 are each independently a hydrogen atom,
{In the formula, 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 ³ may have different groups for each unit, and R ^{A to} R ^B are structural units independently selected from the structural unit group including the structural unit 1. }
And
R ^{b18 to} R ^b19 are each independently
{In the formula, 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 ³ may have different groups for each unit, and R ^{A to} R ^B are each a structural unit including the structural unit 1 independently. }
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 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 ³ may have different groups for each unit, and R ^{A to} R ^B are each a structural unit including the structural unit 1 independently. }
2 or more are included. ]
Is resin.
(Item 2)
Structural unit 3 in the structural unit group
(Wherein 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.)
The resin according to the above item, comprising:
(Item 3)
Structural unit 4 in the structural unit group
(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 an alkyl group or a hydrogen atom, or R ^d1 and R ^d2 together form a ring structure, k is an integer of 1 or more, and R ^d3 Is a hydrogen atom, a methyl group or a hydroxyl group, and R ^d4 is OH, CH ₂ OH, CH ₂ CH ₂ OH, CH ₂ OCH ₃ or CH ₂ OPh, but either R ^d3 or R ^d4 is a hydroxyl group It is. )
The resin according to any one of the above items, wherein
(Item 4)
Structural unit 5
(In formula, R ^<e1> -R ^<e3> is a nitrile group, an alkyl group, or an alkenyl group each independently.)
The resin according to any one of the above items, comprising:
(Item 5)
(Meth) acrylic acid ester, (poly) pentaerythritol poly (alkylene oxide modified or epoxy modified) (meth) acrylate, (poly) trimethylopropanel poly (alkylene oxide modified or epoxy modified) (meth) acrylate, (poly ) A monomer containing at least one monomer selected from the group consisting of glycerin poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate and alkylenedi (alkylene oxide-modified or epoxy-modified) (meth) acrylate. The method for producing a resin according to any one of the above items, comprising a step of polymerizing at 70 to 200 ° C. in the presence of 3 to 50 parts by mass of a polymerization initiator at 100% by mass with respect to 100 parts by mass of the monomer. .
(Item 6)
A varnish composition comprising the resin according to any one of the above items and a reactive diluent.
(Item 7)
The reactive diluent is
[ ^Wherein , n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, and 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 ′} each independently represent a hydrogen atom or an alkyl group, and R ^{1 ′} may have a group different 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 ′} each independently represent 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 ′} each independently represent a hydrogen atom or an alkyl group, and R ^{1 ′} may have a different group for each unit. }
2 or more are included. ]
The varnish composition as described in the above item.
(Item 8)
The varnish composition according to any one of the above items, which is used in an offset printing ink.
(Item 9)
An offset printing ink comprising the varnish composition according to any one of the above items and a pigment.
(Item 10)
A printed matter having a cured layer of the offset printing ink described in the above item.

  In the present disclosure, one or more of the features described above may be provided in further combinations in addition to the express combinations. Those skilled in the art will recognize additional embodiments and advantages other than those described above upon reading and understanding the following detailed description as necessary.

  By using the resin of the present invention, it has excellent ink fluidity while having various ink performances (adhesion, coating film hardness, emulsifying property, image reproducibility, glossiness, blocking resistance, coating film smoothness, etc.). An offset printing ink having misting resistance can be obtained.

[1. resin]
The present disclosure is a resin having a molecular weight distribution (Mw / Mn) of 1.5 to 55 including the following structural units 1 and 2, wherein the structural unit 1 includes:
[Wherein, R ^a1 represents a hydrogen atom or an alkyl group, and R ^a2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or
{Wherein, a is an integer of 1 or more, b is an integer of 0 or more, and ^Raa is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted group R ^ab is an aryloxy group, R ^ab is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
It is. ]
And
The structural unit 2 is a general formula
[ ^Wherein , n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, and R ^{b1 to} R ^b17 are each independently a hydrogen atom,
{In the formula, 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 ³ may have different groups for each unit, and R ^{A to} R ^B are structural units independently selected from the structural unit group including the structural unit 1. }
And
R ^{b18 to} R ^b19 are each independently
{In the formula, 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 ³ may have different groups for each unit, and R ^{A to} R ^B are each a structural unit including the structural unit 1 independently. }
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 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 ³ may have different groups for each unit, and R ^{A to} R ^B are each a structural unit including the structural unit 1 independently. }
2 or more are included. ]
A resin is provided.

  In the present disclosure, “resin” is synonymous with polymer.

In one embodiment, the structural unit group includes structural units 3
(Wherein 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.

In one embodiment, the structural unit group includes 4 structural units.
(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 an alkyl group or a hydrogen atom, or R ^d1 and R ^d2 together form a ring structure, k is an integer of 1 or more, and R ^d3 Is a hydrogen atom, a methyl group or a hydroxyl group, and R ^d4 is OH, CH ₂ OH, CH ₂ CH ₂ OH, CH ₂ OCH ₃ or CH ₂ OPh, but either R ^d3 or R ^d4 is a hydroxyl group It is. )
Is included.

In one embodiment, the resin comprises structural unit 5
(In formula, R ^<e1> -R ^<e3> is a nitrile group, an alkyl group, or an alkenyl group each independently.)
including.

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

The linear alkyl group can be represented by a general formula of —C _n H _{2n + 1} (n is an integer of 1 or more). Straight chain alkyl groups include methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decamethyl, etc. Is exemplified.

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

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

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

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

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

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

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

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

  The 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 a 1-methylvinyl group, a 1-methylpropenyl group, and a 1-methylbutenyl group.

  Examples of the cycloalkenyl group include a monocyclic cycloalkenyl group.

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

The 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 described above.

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

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

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

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

The linear alkylene group can be represented by a general formula of — (CH ₂ ) _n — (n is an integer of 1 or more). Straight chain alkylene groups include methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decamethylene, etc. Is exemplified.

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

  Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, and a condensed ring cycloalkylene group.

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

  Examples of the bridged cycloalkylene group include a tricyclodecylene group, an adamantylene group, and a norbornylene group.

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

  The alkenylene group is exemplified by a linear alkenylene group, a branched alkenylene group, a cycloalkenylene group, and the like.

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

  The 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 a 1-methylvinylene group, a 1-methylpropenylene group, and a 1-methylbutenylene group.

  Examples of the cycloalkenylene group include a monocyclic cycloalkenylene group.

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

  In the present disclosure, the “substituted A group” means a group in which one or more hydrogen atoms of the A group are substituted with groups other than hydrogen atoms (monovalent substituents and the like). For example, a substituted alkyl group means a group in which one or more hydrogen atoms contained in the alkyl group are substituted with a group other than a hydrogen atom. The substituted A group also includes a group in which a plurality of substituents are combined to form a ring structure.

Examples of the monovalent substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, a hydroxyl group, and a group obtained by combining these groups and, if necessary, an ether bond and an ester bond. Examples of the group obtained by combining these groups include an alkylalkoxy group, an alkylaryl group (such as a benzyl group), an alkyloxyaryl group, an alkyloxyarylaryl group, and an alkyloxyalkylaryl group. More specifically,
(In the formula, v represents an integer of 1 or more.)
Etc. are exemplified.
Note that the substituent of the portion corresponding to R ^a2 of the structural unit 1 is
Is illustrated as preferred. In addition, the substituents of R ^aa and R ^{ab in} the structural unit 1 are
Is illustrated as preferred.

<Structural unit 1>
The 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”.

  (Meth) acrylic acid ester is exemplified by (meth) acrylic acid linear alkyl ester, (meth) acrylic acid branched alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid substituted alkyl ester, and the like.

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

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

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

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

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

<Structural unit 2>
The structural unit 2 is a structural unit derived from a polyfunctional monomer described below. In addition, a polyfunctional monomer may be used individually or in mixture of 2 or more types.

(Structural unit 2A)
The structural unit 2A has a general formula A ′ as a monomer.
[Wherein, n is an integer of 0 to 2, and R ^{b1 ′ to} R ^{b6 ′} each independently represent a hydrogen atom,
{In the formula, 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 be different 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 ′} each independently represent a hydrogen atom or an alkyl group, and R ^{1 ′} may have a different group for each unit. }
2 or more are included. ]
When the (poly) pentaerythritol poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate represented by the formula (1) is used, it is a structural unit contained in the polymer chain.

In the present disclosure, “the group may be different for each structural unit” means, for example, in the general formula (A), when n is 2,
This ^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”. Means "at least one selected from the group consisting of (meth) acrylate, polypentaerythritol poly (meth) acrylate, polypentaerythritol polyalkylene oxide-modified (meth) acrylate, and polypentaerythritol polyepoxy-modified (meth) acrylate" To 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. Illustrated.

  Pentaerythritol polyalkylene oxide modified (meth) acrylate is pentaerythritol di (ethylene oxide modified (meth) acrylate), pentaerythritol tri (ethylene oxide modified (meth) acrylate), 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), pentae Sri penta (propylene oxide-modified (meth) acrylate), pentaerythritol hexa (propylene oxide-modified (meth) acrylate) and the like.

  Pentaerythritol polyepoxy modified (meth) acrylate is pentaerythritol diepoxy (meth) acrylate, pentaerythritol triepoxy (meth) acrylate, pentaerythritol tetraepoxy (meth) acrylate, pentaerythritol pentaepoxy (meth) acrylate, pentaerythritol hexa An epoxy (meth) acrylate etc. are illustrated.

  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, tripentaeryth Toruheputa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol nona (meth) acrylate, tripentaerythritol deca (meth) acrylate and the like.

  Polypentaerythritol polyalkylene oxide modified (meth) acrylate is dipentaerythritol di (ethylene oxide modified (meth) acrylate), dipentaerythritol tri (ethylene oxide modified (meth) acrylate), dipentaerythritol tetra (ethylene oxide modified (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) acrylic) Dipentaerythritol tri (propylene oxide modified (meth) acrylate), dipentaerythritol tetra (propylene oxide modified (meth) 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), tripentaerythritol 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), tripentaerythritol octa (propylene oxide modified (meth) acrylate), tripentaerythritol nona (propylene oxide modified (meth) acrylate), tripentaerythritol deca (propylene oxide modified (meth) acrylate), etc. The

  Polypentaerythritol polyepoxy modified (meth) acrylate is dipentaerythritol diepoxy (meth) acrylate, dipentaerythritol triepoxy (meth) acrylate, dipentaerythritol tetraepoxy (meth) acrylate, dipentaerythritol pentaepoxy (meth) Acrylate, dipentaerythritol hexaepoxy (meth) acrylate, dipentaerythritol heptaepoxy (meth) acrylate, dipentaerythritol octaepoxy (meth) acrylate, tripentaerythritol diepoxy (meth) acrylate, tripentaerythritol triepoxy (meth) Acrylate, tripentaerythritol tetraepoxy (meth) acrylate, tripentaerythritol pen Epoxy (meth) acrylate, tripentaerythritol hexaepoxy (meth) acrylate, tripentaerythritol heptaepoxy (meth) acrylate, tripentaerythritol octaepoxy (meth) acrylate, tripentaerythritol nonaepoxy (meth) acrylate, tripentaerythritol deca An epoxy (meth) acrylate etc. are illustrated.

<Structural unit 2B>
The structural unit 2B is represented by the general formula B ′ as a monomer.
[Wherein, m is an integer of 0 to 2, and R ^{b7 ′ to} R ^{b10 ′} each independently represent a hydrogen atom,
{In the formula, 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 be different for each unit. Good. }
And
R ^{b9 ′} may have a different group for each structural unit;
In the general formula (B ^′ )
{In the formula, q is an integer of 0 to 16, R ^{1 ′ to} R ^{3 ′} each independently represent a hydrogen atom or an alkyl group, and R ^{1 ′} may have a different group for each unit. }
2 or more are included. ]
When (poly) trimethylolpropane poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate represented by the formula (1) is used, it is a structural unit contained in the polymer chain.

  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, 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 of

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

  Trimethylolpropane polyalkylene oxide modified (meth) acrylate is trimethylolpropane di (ethylene oxide modified (meth) acrylate), trimethylolpropane tri (ethylene oxide modified (meth) acrylate), trimethylolpropane di (propylene oxide modified (propylene oxide modified ( (Meth) acrylate), trimethylolpropane tri (propylene oxide modified (meth) acrylate) and the like.

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

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

  Polytrimethylolpropane polyalkylene oxide modified (meth) acrylate is 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 the polytrimethylolpropane polyepoxy-modified (meth) acrylate include ditrimethylolpropane diepoxy (meth) acrylate and ditrimethylolpropane triepoxy (meth) acrylate.

<Structural unit 2C>
The structural unit 2C is represented by the general formula C ′ as a monomer.
[Wherein, p is an integer of 0 to 7, and R ^{b11 ′ to} R ^{b14 ′} each independently represent a hydrogen atom,
{In the formula, q is an integer of 0 to 16, R ^{1 ′ to} R ^{3 ′} each independently represent a hydrogen atom or an alkyl group, and R ^{1 ′} may have a group different for each unit. }
And
R ^{b13 ′} may have a different group for each structural unit;
In the general formula (C ^′ )
{In the formula, q is an integer of 0 to 16, R ^{1 ′ to} R ^{3 ′} each independently represent a hydrogen atom or an alkyl group, and R ^{1 ′} may have a different group for each unit. }
2 or more are included. ]
When a (poly) glycerin poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate as shown in (2) is used, it is a structural unit contained in the polymer chain.

  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”. , At least one selected from the group consisting of polyglycerin poly (meth) acrylate, polyglycerin polyalkylene oxide modified (meth) acrylate, and polyglycerin polyepoxy modified (meth) acrylate.

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

  Glycerin polyalkylene oxide-modified (meth) acrylate is glycerin di (ethylene oxide-modified (meth) acrylate), glycerin tri (ethylene oxide-modified (meth) acrylate), glycerin di (propylene oxide-modified (meth) acrylate), glycerin tri ( And propylene oxide-modified (meth) acrylate).

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

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 Examples include (meth) acrylate and triglycerin penta (meth) acrylate.

  Polyglycerin polyalkylene oxide modified (meth) acrylate is 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 La (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) acrylate is 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.

<Structural unit 2D>
The structural unit 2D has a general formula D ′ as a monomer.
[ ^Wherein , R ^{b15 ′ to} R ^{b17 ′} each independently represent a hydrogen atom,
{In the formula, q is an integer of 0 to 16, R ^{1 ′ to} R ^{3 ′} each independently represent a hydrogen atom or an alkyl group, and R ^{1 ′} may have a group different 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 ′} each independently represent a hydrogen atom or an alkyl group, and R ^{1 ′} may have a different group for each unit. }
2 or more are included. ]
Is a structural unit contained in the polymer chain when an isocyanurate structure-containing monomer as shown in FIG.

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

<Structural unit 2E>
The structural unit 2E is represented by 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 ′} each independently represent 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. ]
When the alkylene di (alkylene oxide modified or epoxy modified) (meth) acrylate is used, it is a structural unit contained in the polymer chain.

  In the present disclosure, “alkylene di (alkylene oxide modified or epoxy modified) (meth) acrylate” is composed of “alkylene di (meth) acrylate, alkylene dialkylene oxide modified (meth) acrylate, and alkylene diepoxy modified (meth) acrylate”. Means at least one selected from the group ".

  Alkylene di (meth) acrylate is 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 ( Examples include (meth) acrylate and 1,10-decanediol di (meth) acrylate.

  Alkylene dialkylene oxide modified (meth) acrylate is 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 -Decandi 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-butane Diol 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), 1,1 - such decanediol di (propylene oxide-modified (meth) acrylate) is exemplified.

  The alkylene diepoxy-modified (meth) acrylates are 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 ratio of the structural unit 2 (one or more members of the group consisting of the structural units 2A, 2B, 2C, 2D, and 2E) to the total structural units is 50, 45, 40, 35, based on the mass of all the structural units. 30, 25, 20, 15, 10, 5, 2% by mass and the like are exemplified, and the lower limit is 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1% by mass, etc. Illustrated. The range of the ratio can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, the proportion of the structural unit 2 (one or more members of the group consisting of the structural units 2A, 2B, 2C, 2D, and 2E) in all the structural units is preferably 1 to 50% by mass.

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

(Structural unit 3)
The structural unit 3 is a structural unit contained in the polymer chain when alkenylaryl is used as the monomer. 1 type (s) or 2 or more types can be used for alkenyl aryl. Examples of the alkenyl aryl include styrene and 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, with respect to the mass of all structural units. 10, 5, 2% by mass, etc. are exemplified, and the lower limit is 78, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, , 0% by mass and the like. The range of the ratio can be set as appropriate (for example, selected from the above upper limit and lower limit values). When the structural unit 3 is included, in one embodiment, the proportion of the structural unit 3 in all the 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 with respect to 100 mol% of all structural units. 10, 5, 2 mol% and the like are exemplified, and the lower limit is 78, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, Examples thereof include 1 and 0 mol%. The range of the ratio can be set as appropriate (for example, selected from the above upper limit and lower limit values). When the structural unit 3 is included, in one embodiment, the proportion of the structural unit 3 in all the structural units is preferably 1 to 79 mol%.

(Structural unit 4)
The 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. Is a structural unit included in.

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

Examples of the N, N-dialkylamine alkyl (meth) acrylate include N, N-dimethylamine ethyl (meth) acrylate and N, N-diethylamine ethyl (meth) acrylate. As for carbon number (namely, carbon number of ^Rd1 and ^{Rd2 in} the structural unit 4) of the alkyl group on nitrogen, 1-2 are preferable.

  Hydroxyalkyl (meth) acrylate is hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, (meth) Examples include acrylic 2-hydroxypropyl, 3-hydroxypropyl (meth) acrylate, and the like.

  The upper limit of the ratio of the structural unit 4 to the total 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, Examples of the lower limit include 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0% by mass and the like. The range of the ratio can be set as appropriate (for example, selected from the above upper limit and lower limit values). In the case where the structural unit 4 is included, in one embodiment, the proportion of the structural unit 4 in all the structural units is preferably 1 to 50% by mass.

  The upper limit of the ratio of the structural unit 4 to the total structural units is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2 mole%, etc. with respect to 100 mole% of all structural units. The lower limit is exemplified by 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, selected from the above upper limit and lower limit values). In the case where the structural unit 4 is included, in one embodiment, the proportion of the structural unit 4 in all the structural units is preferably 1 to 50 mol%.

(Structural unit 5)
The structural unit 5 has the following structure, for example.
(Wherein R ^e1 , R ^e2 , and R ^e3 are each independently a nitrile group, an alkyl group, or an alkenyl group.) A structural unit derived from an azo initiator.

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

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

  Azoamidine initiators are 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] 2 Sulfate dihydrate, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′- Examples thereof include azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n hydrate.

  Azoamide initiators include 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], Examples include 2,2′-azobis (N-butyl-2-methylpropionamide).

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

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

  The upper limit of the ratio of the structural unit 5 to all the structural units is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4 mole%, etc. with respect to 100 mole% of all structural units. The lower limit is exemplified by 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, selected from the above upper limit and lower limit values). In the case where the structural unit 5 is included, in one embodiment, the proportion of the structural unit 5 in 100% by mole of all the structural units is preferably 3 to 50% by mole.

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

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

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

  The upper limit of the mass ratio between the structural unit 1 and the structural unit 2 (mass of the structural unit 1 / mass of the 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 limit is 98.0, 95.0, 90.0, 85.0, 80.0, 75.0, 70.0. 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5 0.0, 1.0, 0.5, 0.4 and the like. The range of the mass ratio can be set as appropriate (for example, selected from the upper and lower limit values). In one embodiment, the mass ratio between the structural unit 1 and the structural unit 2 (mass of the structural unit 1 / mass of the structural unit 2) is preferably 0.4 to 99.0 from the viewpoint of gelation suppression.

  The upper limit of the molar ratio between the structural unit 1 and the structural unit 2 (amount of substance of the structural unit 1 / amount of substance of the 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 limit is 98.0, 95.0, 90.0, 85.0, 80.0, 75.0, 70. 0.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15.0, 10.0 , 5.0, 1.0, 0.5, 0.4 and the like. The range of the molar ratio can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, the molar ratio between the structural unit 1 and the structural unit 2 (amount of substance of the structural unit 1 / amount of substance of the structural unit 2) is preferably 0.4 to 99.0 from the viewpoint of suppressing gelation. .

  When the structural unit 3 is included, the upper limit of the mass ratio between the structural unit 1 and the structural unit 3 (mass of the structural unit 1 / mass 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 0.0, 15.0, 10.0, 5.0, 1.0, 0.5, etc. are exemplified, and the lower limit is 98.0, 95.0, 90.0, 85.0, 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15. Examples are 0, 10.0, 5.0, 1.0, 0.5, 0.25 and the like. The range of the mass ratio can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, when the structural unit 3 is included, the mass ratio between the structural unit 1 and the structural unit 3 (mass of the structural unit 1 / mass of the structural unit 3) is 0.25 to 99 from the viewpoint of polarity adjustment. 0.0 is preferred.

  When the structural unit 3 is included, the upper limit of 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 99.0, 95.0, 90.0, 85 0.0, 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0 20.0, 15.0, 10.0, 5.0, 1.0, 0.5, etc. are exemplified, and the lower limit is 98.0, 95.0, 90.0, 85.0, 80. 0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, Examples are 15.0, 10.0, 5.0, 1.0, 0.5, 0.25 and the like. The range of the molar ratio can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, when the constitutional unit 3 is included, the molar ratio between the constitutional unit 1 and the constitutional unit 3 (the amount of the substance of the constitutional unit 1 / the amount of the substance of the constitutional unit 3) is 0. 25-99.0 is 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 0.0, 15.0, 10.0, 5.0, 1.0, 0.5, etc. are exemplified, and the lower limit is 98.0, 95.0, 90.0, 85.0, 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15. Examples are 0, 10.0, 5.0, 1.0, 0.5, 0.4 and the like. The range of the mass ratio can be set as appropriate (for example, selected from the above upper limit and lower limit values). 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. 0.0 is preferred.

  When the constitutional unit 4 is included, the upper limit of the molar ratio of the constitutional unit 1 to the constitutional unit 4 (substance amount of constitutional unit 1 / substance amount of constitutional unit 4) is 99.0, 95.0, 90.0, 85 0.0, 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0 20.0, 15.0, 10.0, 5.0, 1.0, 0.5, etc. are exemplified, and the lower limit is 98.0, 95.0, 90.0, 85.0, 80. 0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, Examples are 15.0, 10.0, 5.0, 1.0, 0.5, 0.4 and the like. The range of the molar ratio can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, when the constitutional unit 4 is included, the molar ratio between the constitutional unit 1 and the constitutional unit 4 (amount of substance of the constitutional unit 1 / amount of substance of the constitutional unit 4) is 0. 4-99.0 is 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 limit is 32.0, 30.0, 25.0, 20.0, 15.0, 10.0. , 5.0, 1.0, 0.4 and the like. The range of the mass ratio can be set as appropriate (for example, selected 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 1 to the structural unit 5 (mass of the structural unit 1 / mass of the structural unit 5) is 0.4 to 33.0 is preferred.

  When the structural unit 5 is included, the upper limit of 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 33.0, 30.0, 25.0, 20 0.0, 15.0, 10.0, 5.0, 1.0, 0.5, etc. are exemplified, and the lower limit is 32.0, 30.0, 25.0, 20.0, 15.0, 10 0.0, 5.0, 1.0, 0.4 and the like. The range of the molar ratio can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, when the constitutional unit 5 is included, the molar ratio of the constitutional unit 1 to the constitutional unit 5 (the amount of substance of the constitutional unit 1 / the amount of substance of the constitutional unit 5) is 0. 4-33.0 is 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, 0.05 are exemplified, and the lower limit is exemplified by 16, 15, 10, 5, 1, 0.5, 0.1, 0.05, 0.02. The range of the ratio can be set as appropriate (for example, selected from the upper and lower limit values). In one embodiment, when the structural unit 5 is included, 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 0.02 to 0.02 from the viewpoint of gelation suppression. 16.7 is preferred.

  When the structural unit 5 is included, the upper limit of the molar ratio between 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, 0.05 are exemplified, and the lower limit is exemplified by 16, 15, 10, 5, 1, 0.5, 0.1, 0.05, 0.02. The range of the molar ratio can be set as appropriate (for example, selected 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 (amount of substance of the structural unit 2 / amount of substance of the structural unit 5) is 0. 02 to 16.7 are preferable.

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

  Upper limit of molar ratio of constituent unit 2 and constituent unit derived from monofunctional monomer (constituent units 1, 3, 4, etc.) (substance amount of constituent unit 2 / substance amount of constituent unit derived from 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. The The range of the molar ratio can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, the molar ratio between the structural unit 2 and the structural unit derived from the monofunctional monomer (the amount of the structural unit 1 / the amount of the structural unit derived from the monofunctional monomer) From the viewpoint, 0.01 to 1.00 is preferable.

(Modification of resin)
The resin can be modified. Examples of the modification include a modification in which only an epoxide or an epoxide and a carboxylic anhydride are reacted with a carboxyl group or a hydroxyl group contained in the resin.

For the carboxyl group contained in the resin, the structural unit produced by modification of reacting epoxide alone or epoxide with carboxylic anhydride,
[Wherein, R ^a1-1 represents a hydrogen atom or an alkyl group, and R ^a1-2 represents
{Wherein, a1 is an integer of 1 or more, b1 is an integer of 0 or more, and R ^a1-a is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or non-substituted group. R ^a1-b is a substituted aryloxy group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
It is. ]
Etc. are exemplified.

The structural unit produced by modification of reacting epoxide alone or epoxide and carboxylic anhydride with respect to the hydroxyl group contained in the resin is a 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]
On the other hand, it is produced by reacting epoxide alone or epoxide with carboxylic anhydride,
[Wherein, 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, and R ^a2-a is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or non-substituted group. 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. }
It is. ]
Etc. are exemplified.

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

(Polymerizable double bond-free aromatic epoxide)
Examples of the polymerizable double bond-free aromatic epoxide include aromatic ring-containing monoglycidyl ether, aromatic-containing diglycidyl ether, and bisphenol type epoxy resin.
Examples of aromatic ring-containing monoglycidyl ethers include phenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, and styrene oxide.
Examples of the aromatic-containing diglycidyl ether include resorcinol diglycidyl ether and hydroquinone diglycidyl ether.
Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Among these, an aromatic ring-containing monoglycidyl ether is preferable, and phenyl glycidyl ether is particularly preferable 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)
Examples of the polymerizable double bond-containing epoxide include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and rosin glycidyl ester.

(Epoxides that are neither a polymerizable double bond-containing aromatic epoxide nor a polymerizable double bond-containing epoxide)
In the modification, an epoxide other than the polymerizable double bond-containing aromatic epoxide and the polymerizable double bond-containing epoxide may be used. Epoxides that are neither a polymerizable double bond-containing aromatic epoxide nor a polymerizable double bond-containing epoxide are 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 sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol triglycidyl ether, trimethylolpropane polyglycidyl ether, and polyepoxides such as epoxidized soybean oil. Among these, epoxidized soybean oil is particularly preferable from the viewpoints of compatibility between the obtained resin and a reactive diluent described later, 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-free 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 polymerizable double bond The epoxide which is not a contained epoxide}] is preferably about 1/9 to 9/1.

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

(Carboxylic anhydride)
Two or more carboxylic acid anhydrides can be used in combination. Carboxylic anhydrides are aromatic carboxylic anhydrides such as phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride. object;
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;
Examples include polymers made from the above acid anhydrides (maleic anhydride homopolymer, maleic anhydride-vinyl acetate polymer, maleic anhydride-styrene polymer, maleic anhydride-acrylonitrile polymer, etc.) and the like.
Among these, the aromatic carboxylic acid anhydride is preferable, and phthalic anhydride is particularly preferable from the viewpoint of compatibility between the obtained resin and a reactive diluent described later, curability, and the like.

  When the carboxylic acid anhydride is used, the amount of the carboxylic acid anhydride is not particularly limited, but the carboxylic acid anhydride is used with respect to 100 parts by mass of the resin from the viewpoints of compatibility with the reactive diluent and ink curability. The amount of the product used is preferably about 10 to 200 parts by weight, more preferably about 10 to 150 parts by weight.

  At the time of modification, the order of reacting the resin, epoxide and carboxylic anhydride and the reaction conditions are not particularly limited. Specifically, [1] a method of reacting all components in one pot, and [2] a method of reacting a carboxylic acid anhydride in the presence of a resin and further reacting an epoxide and a carboxylic acid anhydride are exemplified. The reaction conditions are, for example, a temperature of about 100 to 210 ° C. and a reaction time of about 30 minutes to 8 hours. In addition, the reaction system may be decompressed during or after the reaction of each component to remove residual monomers.

  The modification can be performed under various known catalysts. Two or more catalysts can be used in combination. Catalysts are triphenylphosphine, 2-methylimidazole, 1-methylimidazole, triethylamine, diphenylamine, diazabicycloundecene, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium bicarbonate, potassium bicarbonate Zinc oxide and zinc octylate are exemplified. Although the usage-amount of a catalyst is not specifically limited, About 0.01-5 mass parts is preferable with respect to 100 mass parts of (A) component, and about 0.10-2 mass parts is more preferable.

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

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

  The upper limit of the weight average molecular weight (Mw) of the resin in the present disclosure is 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 150,000, 100,000. 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 32,000, 30,000, 27,000, 20,000, 15,000, 13,000, 11 , 10,000, 9,000, 8,000, 7,000, 6,000, 5,500, etc., and the lower limit is 490,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 150,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 32,000, 30,000 000 27,000, 20,000, 15,000, 13,000, 11,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,500, 5,000, 4, 500, 4,000, etc. are exemplified. The range of the weight average molecular weight can be appropriately set (for example, selected from the above upper limit and lower limit values). In one embodiment, the weight average molecular weight of the resin is preferably 4,000 to 500,000.

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

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

  The upper limit of the acid value of the resin in the present disclosure is 799, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 1 mgKOH / g, etc. The lower limit is exemplified by 790, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 1, 0 mg KOH / g, and the like. The range of the acid value can be appropriately set (for example, selected from the above upper limit and lower limit values). In one embodiment, the acid value of the resin is preferably 0 to 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 range of the softening point can be set as appropriate (for example, selected from the upper and lower limit values). In one embodiment, the softening point of the resin is preferably 75 to 150 ° C. The softening point of the resin can be measured by an automatic softening point measuring device (EX-719PD, manufactured by SIENTIFIC).

  In the present disclosure, the upper limit of the intrinsic viscosity (η) with respect to the absolute molecular weight (M) of 50,000 of the resin 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 limit is 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.12, 0.11, 0.10, 0.09, 0 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, 0.01, etc. are exemplified. The range of the intrinsic viscosity (η) can be appropriately set (for example, selected from the upper and lower limit values). In one embodiment, the intrinsic viscosity (η) with respect to the absolute molecular weight (M) of 50,000 of the resin is preferably 0.01 to 0.20. The intrinsic viscosity (η) for an absolute molecular weight (M) of 50,000 of the resin can be measured by triple detection GPC (Viscote K TDA305, produced by 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, Examples are 0, −50, −80 ° C. and the like. The range of the glass transition temperature (Tg) can be set as appropriate (for example, selected from the upper and lower limit values). In one embodiment, the glass transition temperature of the resin is preferably -80 to 230 ° C. The glass transition temperature of the resin can be measured by differential scanning calorimetry.

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

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

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

  In the present disclosure, the “peroxide initiator” is an organic peroxide, that is, a compound having a peroxy group (—O—O—) in the molecule. Peroxide initiators 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.

  In one embodiment, alkenyl aryl is used as the monomer.

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

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

  The upper limit of the monomer concentration in the above production method is exemplified by 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 11% by mass, and the lower limit is 69, 65, 60. 55, 50, 45, 40, 35, 30, 25, 20, 15, 11, 10% by mass, and the like. The range of the monomer concentration in the above production method can be appropriately set (for example, selected from the above upper limit and lower limit values). In one embodiment, the monomer concentration is preferably 10 to 70% by mass. In the present disclosure, “monomer concentration” is a concentration calculated by the 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%). The lower limit is exemplified by 50, 45, 40, 35, 30, 25, 20, 15, 10, 6, 5.1, 5, 4, 3 mass%, etc. with respect to 100 mass% of the monomer. The The range of the polymerization initiator amount in the production method can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, 3-50 mass% is preferable with respect to 100 mass% of monomers for the amount of polymerization initiators.

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

  In the said manufacturing method, the upper limit of the usage-amount of (meth) acrylic acid ester and (meth) acrylic acid is 99, 95, 90, 85, 80, 75, 70, 65 with respect to monomer whole quantity (100 mass%). 60, 55, 50, 45, 40, 35, 30, 25, 21% by mass, etc. are exemplified, and the lower limit is 98, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20% by mass and the like are exemplified. The range of the amount used can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, from the viewpoint of polarity adjustment, the use amount of (meth) acrylic acid ester and (meth) acrylic acid is preferably 20 to 99% by mass with respect to the total amount of monomer (100% by mass).

  In the said manufacturing method, the upper limit of the usage-amount of (meth) acrylic acid ester and (meth) acrylic acid is 99, 95, 90, 85, 80, 75, 70, 65 with respect to monomer whole quantity (100 mol%). 60, 55, 50, 45, 40, 35, 30, 25, 21 mol% and the like are exemplified, and the lower limit is 98, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 mol% and the like are exemplified. The range of the amount used can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, from the viewpoint of polarity adjustment, the use amount of (meth) acrylic acid ester and (meth) acrylic acid is preferably 20 to 99 mol% with respect to the total amount of monomers (100 mol%).

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

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

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

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

  In the said manufacturing method, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2 mass% etc. are illustrated for the upper limit of the usage-amount of a polar group containing monofunctional monomer, and a minimum is 49 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1% by mass, and the like. In the said manufacturing method, the range of the usage-amount of a polar group containing monofunctional monomer can be set suitably (for example, selecting from the value of the said upper limit and minimum). In one embodiment, from the viewpoint of polarity adjustment, the usage amount of the polar group-containing monofunctional monomer is preferably 1 to 50% by mass with respect to the total amount of monomers.

  In the above production method, the mass ratio of the amount of (meth) acrylic acid ester and (meth) acrylic acid used to the amount of polyfunctional monomer (the mass of (meth) acrylic acid ester and (meth) acrylic acid used for polymerization) / 9, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1, 0.5, etc. are exemplified as the upper limit of / mass of the polyfunctional monomer used for polymerization) 95, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1, 0.5, 0.4, and the like. In the manufacturing method, the range of the mass ratio can be set as appropriate (for example, selected from the upper and lower limit values). In one embodiment, from the viewpoint of gelation suppression, the mass ratio of the amount of (meth) acrylic acid ester and (meth) acrylic acid to the amount of polyfunctional monomer used ((meth) acrylic acid ester used for polymerization) Further, the mass of (meth) acrylic acid / mass of polyfunctional monomer used for polymerization is preferably 0.4 to 99.0.

  In the above production method, the upper limit of the ratio of the amount of acrylate ester used to the amount of alkenyl aryl (mass of acrylate ester used for polymerization / mass of alkenyl aryl used for polymerization) is 9.90, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, etc. are exemplified, and the lower limit is 9.50, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0 .5, 0.33, etc. In the manufacturing method, the range of the mass ratio can be set as appropriate (for example, selected from the upper and lower limit values). In one embodiment, from the viewpoint of polarity adjustment, the ratio of the amount of acrylate ester used to the amount of alkenyl aryl used (mass of acrylate ester used for polymerization / mass of alkenyl aryl used for polymerization) is 0. .33 to 9.90 are preferred.

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

  In the above production method, the upper limit of the ratio between the amount of the polyfunctional monomer used and the amount of the initiator used (the mass of the polyfunctional monomer used for the polymerization / the mass of the initiator used for the polymerization) is 16.67, 16, 15, 13, 10, 5, 1, 0.5, 0.1, 0.05, etc. are exemplified, and the lower limit is 16, 15, 13, 10, 5, 1, 0.5, 0.1, 0 .05, 0.02, etc. In the manufacturing method, the range of the mass ratio can be set as appropriate (for example, selected from the upper and lower limit values). In one embodiment, from the viewpoint of suppressing gelation, the ratio of the amount of polyfunctional monomer used and the amount of initiator used (mass of polyfunctional monomer used for polymerization / mass of initiator used for polymerization) is: 0.02 to 16.67 is preferable.

  In the above production method, the upper limit of the ratio of the amount of the polyfunctional monomer to the amount of the monofunctional monomer (the mass of the polyfunctional monomer / the mass of the monofunctional monomer) is 1.00, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, etc. are exemplified, and the lower limit is 0.95, 0.9, 0.8 , 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, 0.01 and the like. In the manufacturing method, the range of the mass ratio can be set as appropriate (for example, selected from the upper and lower limit values). In one embodiment, the ratio of the usage amount of the polyfunctional monomer and the usage amount of the monofunctional monomer (the mass of the polyfunctional monomer / the mass of the monofunctional monomer) is 0.01 to 1. 00 is preferred.

  Although the solvent used in the said manufacturing method is not restrict | limited in particular, Water, an organic solvent, etc. are illustrated. The organic solvent is cyclohexanone, methylcyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, methyl-n-butyl ketone, ketone solvent such as 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, Acetic acid ester solvents such as acetic acid-n-butyl, acetic acid-n-propyl, acetic acid-n-pentyl, and solvents such as N, N-dimethylformamide De solvents and the like.

  In the said manufacturing method, additives other than a monomer, a polymerization initiator, and a solvent can be used to such an extent that the effect of this invention is not impaired. Examples of additives other than monomers, polymerization initiators and solvents include emulsifiers, chain transfer agents, RAFT reagents, ATRP polymerization reagents, and the like. The additive is used in an amount of 1 to 5 parts by weight, less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, less than 0.001 part by weight, and 0.0001 to 100 parts by weight of the monomer. Examples are less than part by mass, 0 part by mass, and the like. Note that the resin described in the present disclosure can be manufactured without using an additive.

  In addition, [1. Resin] and [2. The items described in [Production method of resin] can be referred to each other.

[3. Reactive diluent]
As the reactive diluent, various known ones can be used, and one kind or two or more kinds can be used in combination. Reactive diluent is
[ ^Wherein , n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, and 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 ′} each independently represent a hydrogen atom or an alkyl group, and R ^{1 ′} may have a group different 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 ′} each independently represent 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 ′} each independently represent a hydrogen atom or an alkyl group, and R ^{1 ′} may have a different group for each unit. }
2 or more are included. ]
Etc. are exemplified.

The reactive diluents represented by the above general formulas (A ^′ ) to (E ^′ ) are [1. Resin] is the same as the polyfunctional monomer represented by the general formulas (A ^′ ) to (E ^′ ) described in <Constitutional unit 2>.

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

  The upper limit of the content of the reactive diluent in the varnish composition is 90, 89, 85, 80, 75, 70, 65, 60, 55, 50, 45, 41 with respect to the total mass in the varnish composition. Examples of the lower limit include 89, 85, 80, 75, 70, 65, 60, 55, 50, 45, 41, and 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 limit and lower limit values). 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 with respect to the total mass in the varnish composition.

  The upper limit of the ratio of resin to reactive diluent (resin mass / reactive diluent mass) 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 limit is 1.40, 1.30, 1 .20, 1.10, 1.00, 0.90, 0.80, 0.70, 0.6, 0.5, 0.4, 0.3, 0.2, 0.15, 0.11 Etc. are exemplified. The range of the ratio can be set as appropriate (for example, selected from the upper and lower limit values). In one embodiment, from the viewpoint of film strength and curability, the ratio of resin to reactive diluent (resin mass / reactive diluent mass) is preferably 0.11 to 1.50.

  The varnish composition may contain components other than the resin and the reactive diluent (hereinafter also referred to as other components). The upper limit of the content of other components is exemplified by 20, 15, 10, 5, 1% by mass, etc. with respect to the total mass of the resin and the reactive diluent, and the lower limit is 15, 10, 5, 1, 0. Examples include mass%. The range of the content can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, as for content of another component, 0-20 mass% is preferable with respect to the total mass of resin and a reactive diluent.

  Further, the upper limit of the content of other components with respect to the total mass of the varnish composition is exemplified by 17, 15, 10, 5, 1% by mass, and the lower limit is 15, 10, 5, 1, 0% by mass. Etc. are exemplified. The range of the content can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, as for content of another component, 0-17 mass% is preferable with respect to the total mass of the whole varnish composition.

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

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

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

  It does not specifically limit as a photoinitiator, Various well-known things can be used. Specific examples thereof include benzophenone, o-benzoylbenzoic acid methyl ester, p-dimethylaminobenzoic acid ester, p-dimethylacetophenone, thioxanthone, alkylthioxanthone, amines and the like. Also, Irgacure 1173, Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 2959, Irgacure 127, Irgacure 369, Irgacure 369E, Irgacure 379, Irgacure 379EG, Irgacure TPO, Irgacure 819 manufactured by BASF Japan May be used as they are. As a usage-amount of a photoinitiator, it is preferable to use about 1 to 15% from a dry viewpoint.

  The pigment used in the offset printing ink of the present invention is not particularly limited, and a commonly used inorganic or organic pigment can be blended. Specific examples include white pigments such as titanium oxide, zinc white, lead white, lithobon, and antimony oxide, black pigments such as aniline black, iron black, and carbon black, yellow lead, yellow iron oxide, titanium yellow, and Hansa Yellow (10G 5G, 3G, etc.), yellow pigments such as disazo yellow, benzidine yellow and permanent yellow, orange pigments such as chrome vermilion, permanent orange, balkan first orange, indanthrene brilliant orange, iron oxide, permanent brown, para brown Brown pigments such as Bengala, Cadmium Red, Antimony Zhu, Permanent Red, Rhodamine Lake, Alizarin Lake, Thioindigo Red, PV Carmine, Monolite First Red, Quinacdrine Red Pigment, etc.Cobalt , Manganese Purple, First Violet, Methyl Violet Lake, Indanthrene Brilliant Violet, Dioxazine Violet and other purple pigments, ultramarine, bitumen, cobalt blue, alkali blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, copper Blue pigments such as phthalocyanine blue, indanthrene blue, indigo, and other green pigments such as chromium green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malachite green lake, phthalocyanine green, polychlorobrom copper phthalocyanine Examples include various fluorescent pigments and metal powder pigments. These pigments are preferably about 1 to 50 parts by weight, more preferably about 5 to 30 parts by weight with respect to 100 parts by weight of the offset printing ink.

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

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

  Various known materials can be used as the substrate without particular limitation. In addition to paper (art paper, cast coated paper, foam paper, PPC paper, high-quality coated paper, craft paper, polyethylene laminated paper, glassine paper, etc.), the plastic substrate (polyolefin, polycarbonate, polymethacrylate, polyester, Epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.).

Examples of the printing method (coating method) include offset printing, flexographic printing, screen printing, bar coater coating, Mayer bar coating, air knife coating, and gravure coating. Although not coated amount particularly limited, the mass after drying is preferably about 0.1 to 30 g / ^{m 2,} about from 1 to 20 g / ^{m 2} is more preferable.

  The curing means is exemplified by an electron beam or ultraviolet rays. Examples of the ultraviolet light source include a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, and a UV-LED. The amount of light, light source arrangement, and conveyance speed are not particularly limited, but when a high-pressure mercury lamp is used, the conveyance 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 description in the above preferred embodiment and the following examples are provided for illustrative purposes only and are not intended to limit the present invention. Accordingly, the scope of the present invention is not limited to the embodiments or examples specifically described in the present disclosure, but is limited only by the claims.

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

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

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

Abbreviations of 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 Tetrahydrofurryl 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 Glycerol propylene oxide Modified Triacrylate B-7 Diglycerol Ethylene Oxide Modified Acrylate B-8 Glycerin Triepoxy Acrylate B-9 , 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]

Example 1-28
100 g of the resin obtained in Example 1-21, 86 g of phthalic anhydride, 114 g of phenylglycidyl ether, 300 g of butyl acetate 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. Was heated up to 120 ° C. Subsequently, after adding 0.3 part of triphenylphosphine, it stirred for 8 hours. Thereafter, the solvent was distilled off while raising the temperature to 160 ° C. at normal pressure, and the solvent was completely distilled off under reduced pressure at 160 mmHg or less to obtain a resin.

Examples 1-29 to 1-31
A resin was produced by the same procedure as in Example 1-28, except that the composition was changed to the one described in the following table.

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

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

Abbreviations for the dilution monomers in the above table are as follows.
R-1 pentaerythritol tetraacrylate R-2 dipentaerythritol (penta / hexa) acrylate R-3 tripentaerythritol octaacrylate R-4 trimethylolpropane ethylene oxide modified triacrylate R-5 ditrimethylolpropane tetraacrylate R-6 glycerin Propylene oxide modified triacrylate R-7 Diglycerin ethylene oxide modified acrylate R-8 Glycerin triepoxyacrylate Irgacure 907 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by BASF)
MA100 carbon black (manufactured by Mitsubishi Chemical Corporation)

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

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

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

Claims (10)

A resin having a molecular weight distribution (Mw / Mn) of 1.5 to 55 including the following structural units 1 and 2, wherein the structural unit 1 is:
[Wherein, R ^a1 represents a hydrogen atom or an alkyl group, and R ^a2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or
{Wherein, a is an integer of 1 or more, b is an integer of 0 or more, and ^Raa is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted group R ^ab is an aryloxy group, R ^ab is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenylene group. }
It is. ]
And
The structural unit 2 is a general formula
[ ^Wherein , n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, and R ^{b1 to} R ^b17 are each independently a hydrogen atom,
{In the formula, 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 ³ may have different groups for each unit, and R ^{A to} R ^B are structural units independently selected from the structural unit group including the structural unit 1. }
And
R ^{b18 to} R ^b19 are each independently
{In the formula, 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 ³ may have different groups for each unit, and R ^{A to} R ^B are each a structural unit including the structural unit 1 independently. }
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 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 ³ may have different groups for each unit, and R ^{A to} R ^B are each a structural unit including the structural unit 1 independently. }
2 or more are included. ]
Is resin. Structural unit 3 in the structural unit group
(Wherein 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.)
The resin according to claim 1, wherein Structural unit 4 in the structural unit group
(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 an alkyl group or a hydrogen atom, or R ^d1 and R ^d2 together form a ring structure, k is an integer of 1 or more, and R ^d3 Is a hydrogen atom, a methyl group or a hydroxyl group, and R ^d4 is OH, CH ₂ OH, CH ₂ CH ₂ OH, CH ₂ OCH ₃ or CH ₂ OPh, but either R ^d3 or R ^d4 is a hydroxyl group It is. )
The resin according to claim 1 or 2, wherein Structural unit 5
(In formula, R ^<e1> -R ^<e3> is a nitrile group, an alkyl group, or an alkenyl group each independently.)
The resin according to any one of claims 1 to 3, comprising: (Meth) acrylic acid ester, and (poly) pentaerythritol poly (alkylene oxide modified or epoxy modified) (meth) acrylate, (poly) trimethylolpropane poly (alkylene oxide modified or epoxy modified) (meth) acrylate, (poly) Monomers having a monomer concentration of 10 to 70 are monomers containing at least one selected from the group consisting of glycerin poly (alkylene oxide modified or epoxy modified) (meth) acrylate and alkylene di (alkylene oxide modified or epoxy modified) (meth) acrylate. The resin according to any one of claims 1 to 4, comprising a step of polymerizing at 70 to 200 ° C in the presence of 3 to 50 parts by mass of a polymerization initiator with respect to 100 parts by mass of the monomer. Production method. A varnish composition comprising the resin according to any one of claims 1 to 4 and a reactive diluent. The reactive diluent is
[ ^Wherein , n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, and R ^{b1 ′ to} R ^{b17 ′} are each independently a hydrogen atom,
{In the formula, 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 be different for each unit. Good. }
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 ′} each independently represent 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 ′} each independently represent a hydrogen atom or an alkyl group, and R ^{1 ′} may have a different group for each unit. }
2 or more are included. ]
The varnish composition according to claim 6, wherein The varnish composition of Claim 6 or 7 used for offset printing ink. Offset printing ink containing the varnish composition and pigment of any one of Claims 6-8. A printed matter comprising a cured layer of the offset printing ink according to claim 9.