JP7338226B2 - Resins, varnish compositions, printing inks and printed matter - Google Patents

Description

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

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

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

Japanese Patent No. 5683757

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

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

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

The following items are provided by this disclosure.
(Item 1)
structural unit 1,
[In the formula, R ^a1 is a hydrogen atom or an alkyl group, and R ^a2 is
<wherein R ^aa is an alkylene group or a single bond, R ^ab to R ^ac are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group,
^Rad is
(In the formula,
represents a single or double bond)
or a substituted or unsubstituted aryl group. ＞
including resin.
(Item 2)
Building block 2:
[Wherein, n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, R ^b1 to R ^b17 are each independently a hydrogen atom,
<wherein q and r are each independently an integer of 0 to 16, s and t are each independently an integer of 1 or more, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group, R ¹ and R ⁴ may have different groups for each unit, and R ^A to R ^B are each independently a structural unit containing the structural unit 1. ＞
and
R ^b18 to R ^b19 are each independently
<wherein q and r are each independently an integer of 0 to 16, s and t are each independently an integer of 1 or more, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group, R ¹ and R ⁴ may have different groups for each unit, and R ^A to R ^B are each independently a structural unit containing the structural unit 1. ＞
and
R ^b20 is an alkylene group,
R ^b4 , R ^b5 , R ^b9 and R ^b13 may have different groups for each structural unit,
In the general formulas (A) to (D)
<wherein q and r are each independently an integer of 0 to 16, s and t are each independently an integer of 1 or more, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group, R ¹ and R ⁴ may have different groups for each unit, and R ^A to R ^B are each independently a structural unit containing the structural unit 1. ＞
contains two or more. ]
The resin according to the above items, comprising
(Item 3)
A varnish composition comprising the resin according to any one of the above items.
(Item 4)
A printing ink comprising a varnish composition and a pigment as described above.
(Item 5)
A printed material having a cured layer of the printing ink as described above.

In the present disclosure, one or more of the features described above may be provided in further combinations in addition to the explicit combinations.

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

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

[resin]
The present disclosure provides structural units 1,
[In the formula, R ^a1 is a hydrogen atom or an alkyl group, and R ^a2 is
<In the formula, R ^aa is an alkylene group or a single bond, R ^ab to R ^ac are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group,
^Rad is
(In the formula,
represents a single or double bond)
or a substituted or unsubstituted aryl group. ＞
A resin is provided comprising:

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

In one embodiment, the resin comprises structural unit 2:
[Wherein, n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, R ^b1 to R ^b17 are each independently a hydrogen atom,
<wherein q and r are each independently an integer of 0 to 16, s and t are each independently an integer of 1 or more, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group, R ¹ and R ⁴ may have different groups for each unit, and R ^A to R ^B are each independently a structural unit containing the structural unit 1. ＞
and
R ^b18 to R ^b19 are each independently
<wherein q and r are each independently an integer of 0 to 16, s and t are each independently an integer of 1 or more, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group, R ¹ and R ⁴ may have different groups for each unit, and R ^A to R ^B are each independently a structural unit containing the structural unit 1. ＞
and
R ^b20 is an alkylene group,
R ^b4 , R ^b5 , R ^b9 and R ^b13 may have different groups for each structural unit,
In the general formulas (A) to (D)
<wherein q and r are each independently an integer of 0 to 16, s and t are each independently an integer of 1 or more, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group, R ¹ and R ⁴ may have different groups for each unit, and R ^A to R ^B are each independently a structural unit containing the structural unit 1. ＞
contains two or more. ]
including.

In one embodiment, the resin comprises structural unit 3
(In the formula, R ^c1 is a hydrogen atom or an alkyl group, and R ^c2 to R ^c6 are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group.)
including.

In one embodiment, the resin comprises structural unit 4
(wherein R ^D is a hydrogen atom or an alkyl group, R ^d is CONR ^d1 R ^d2 , COO(CH ₂ ) ₂ NR ^d1 R ^d2 and
A group selected from the group consisting of
In the formula, R ^d1 and R ^d2 are alkyl groups or hydrogen atoms, or R ^d1 and R ^d2 together form a ring structure group, k is an integer of 1 or more, and R ^d3 is a hydrogen atom, a methyl group or a hydroxyl group, and R ^d4 is OH, CH ₂ OH, CH ₂ CH ₂ OH, CH ₂ OCH ₃ or CH ₂ OPh, where either R ^d3 or R ^d4 is a hydroxyl group is. )
including.

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

In one embodiment, the resin comprises structural unit 6
(In the formula, R ^f1 is a hydrogen atom or an alkyl group, and R ^f2 is a hydrogen atom or an alkyl group.)
including.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The monocyclic cycloalkenylene group is exemplified by a cyclopentenylene group, a cyclohexenylene group, a cycloheptenylene group, a cyclodecenylene group, a 3,5,5-trimethylcyclohexenylene group and the like.

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

Examples of the above monovalent substituents include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, hydroxyl groups, groups combining these groups and, if necessary, ether bonds, ester bonds and the like. Examples of groups obtained by combining these groups include alkylalkoxy groups, alkylaryl groups (benzyl group, etc.), alkyloxyaryl groups, alkyloxyarylaryl groups, alkyloxyalkylaryl groups, and the like. More specifically,
(In the formula, v represents an integer of 1 or more.)
etc. are exemplified.

<Constituent unit 1>
Structural unit 1, when a resin containing an epoxy group-containing (meth)acrylic acid ester as a monomer is reacted with a carboxylic acid containing rosins, epoxy-modified rosins such as glycidyl-modified rosins and (meth)acrylic It is a structural unit contained in a polymer chain when a reaction product with an acid is polymerized. Structural unit 1 may be contained 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".

Epoxy group-containing (meth)acrylic acid esters may be used alone or in combination of two or more. Epoxy group-containing (meth)acrylic acid esters include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, (meth)acrylate- Examples include 5,6-epoxyhexyl and 6,7-epoxyheptyl (meth)acrylate.

Carboxylic acids may be used alone or in combination of two or more. Carboxylic acids are exemplified by aliphatic carboxylic acids, aromatic carboxylic acids, rosins and the like.

Aliphatic carboxylic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, Examples include icosanoic acid and the like.

Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, cinnamic acid, trimellitic acid, and trimellitic anhydride.

Rosins include raw rosins such as gum rosin, tall oil rosin and wood rosin, purified products of the above raw rosins (refined rosins); is exemplified. The species of pine used as the raw material rosin is not particularly limited, and examples thereof include merukushi pine, slash pine (wetland pine), and Umao pine. In addition, the production area of the raw material rosin is not particularly limited, and examples thereof include China, Vietnam, Indonesia, and Brazil.

Resin acids contained in the above rosins include abietic acid, dihydroabietic acid, dehydroabietic acid, tetrahydroabietic acid, parastric acid, levopimaric acid, neoabietic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, comic acid and dihydro Agatic acid and the like are exemplified.

In one embodiment, the ^Rad from rosins is
etc. are exemplified.

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

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

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

When obtaining a resin containing structural unit 1, the reaction conditions are not particularly limited. The reaction conditions are, for example, a temperature of about 100 to 210° C. and a reaction time of about 30 minutes to 8 hours. In addition, during or after the reaction of each component, the pressure in the reaction system may be reduced to remove residual monomers.

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

<Constituent unit 2>
Structural unit 2 is a structural unit derived from a polyfunctional monomer described below. In addition, the polyfunctional monomer may be used alone or in combination of two or more.

(Constituent unit 2A)
Structural unit 2A has the general formula A' as a monomer
[wherein n is an integer of 0 to 2, R ^b1′ to R ^b6′ are each independently a hydrogen atom,
{Wherein, q is each independently an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have different groups for each unit. good. }
and
R ^b4′ and R ^b5′ may have different groups for each structural unit,
In the general formula (A ^' )
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
contains two or more. ]
It is a structural unit contained in the polymer chain when using (poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate represented by.

In the present disclosure, "each structural unit may have a different group" means, for example, in general formula (A), when n is 2,
It means that R ^b4A and R ^b4B may be different groups, and R ^b5A and R ^b5B may be different groups.

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

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

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

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

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

Polypentaerythritol polyalkylene oxide-modified (meth)acrylates include dipentaerythritol di (ethylene oxide-modified (meth)acrylate), dipentaerythritol tri (ethylene oxide-modified (meth)acrylate), dipentaerythritol tetra (ethylene oxide-modified ( meth) acrylate), dipentaerythritol penta (ethylene oxide-modified (meth) acrylate), dipentaerythritol hexa (ethylene oxide-modified (meth) acrylate), dipentaerythritol hepta (ethylene oxide-modified (meth) acrylate), dipentaerythritol Octa (ethylene oxide-modified (meth)acrylate), dipentaerythritol di (propylene oxide-modified (meth)acrylate), dipentaerythritol tri (propylene oxide-modified (meth)acrylate), dipentaerythritol tetra (propylene oxide-modified (meth)acrylate) acrylate), dipentaerythritol penta (propylene oxide-modified (meth)acrylate), dipentaerythritol hexa (propylene oxide-modified (meth)acrylate), dipentaerythritol hepta (propylene oxide-modified (meth)acrylate), dipentaerythritol octa ( Propylene oxide-modified (meth)acrylate), tripentaerythritol di (ethylene oxide-modified (meth)acrylate), tripentaerythritol tri (ethylene oxide-modified (meth)acrylate), tripentaerythritol tetra (ethylene oxide-modified (meth)acrylate) , tripentaerythritol penta (ethylene oxide-modified (meth)acrylate), tripentaerythritol hexa (ethylene oxide-modified (meth)acrylate), tripentaerythritol hepta (ethylene oxide-modified (meth)acrylate), tripentaerythritol octa (ethylene oxide) modified (meth)acrylate), tripentaerythritol nona (ethylene oxide-modified (meth)acrylate), tripentaerythritol deca (ethylene oxide-modified (meth)acrylate), tripentaerythritol di (propylene oxide-modified (meth)acrylate), tri Pentaerythritol tri (propylene oxide-modified (meth)acrylate), tripentaerythritol 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) and the like are exemplified.

Polypentaerythritol polyepoxy-modified (meth)acrylates are dipentaerythritol diepoxy (meth)acrylate, dipentaerythritol triepoxy (meth)acrylate, dipentaerythritol tetraepoxy (meth)acrylate, dipentaerythritol pentaepoxy (meth)acrylate Acrylate, dipentaerythritol hexaepoxy (meth)acrylate, dipentaerythritol heptaepoxy (meth)acrylate, dipentaerythritol octaepoxy (meth)acrylate, tripentaerythritol diepoxy (meth)acrylate, tripentaerythritol triepoxy (meth)acrylate Acrylates, Tripentaerythritol Tetraepoxy (meth)acrylate, Tripentaerythritol Pentaepoxy (meth)acrylate, Tripentaerythritol Hexepoxy (meth)acrylate, Tripentaerythritol Heptaepoxy (meth)acrylate, Tripentaerythritol Octaepoxy (meth)acrylate Examples include acrylates, tripentaerythritol nonaepoxy (meth)acrylate, and tripentaerythritol decaepoxy (meth)acrylate.

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

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

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

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

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

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

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

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

<Constituent unit 2C>
Structural unit 2C is a monomer of general formula C'
[wherein p is an integer of 0 to 7, R ^b11′ to R ^b14′ are each independently a hydrogen atom,
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
and
R ^b13′ may have different groups for each structural unit,
In the general formula (C ^' )
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
contains two or more. ]
It is a structural unit contained in the polymer chain when using (poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate as shown in.

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

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

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

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

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

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

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

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

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

<Constituent unit 2E>
Structural unit 2E has the general formula E' as a monomer
[Wherein, R ^b18′ to R ^b19′ are each independently
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
and
R ^b20' is an alkylene group. ]
It is a structural unit contained in the polymer chain when using alkylene di (alkylene oxide-modified or epoxy-modified) (meth) acrylate as represented by.

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

Alkylene di(meth)acrylates include 1,2-ethylenediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol Di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate Examples include meth)acrylate, 1,10-decanediol di(meth)acrylate, and the like.

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

Alkylene diepoxy-modified (meth)acrylates include 1,2-ethylenediol diepoxy (meth) acrylate, 1,3-propanediol diepoxy (meth) acrylate, 1,4-butanediol diepoxy (meth) acrylate, 1 ,5-pentanediol diepoxy (meth)acrylate, 1,6-hexanediol diepoxy (meth)acrylate, 1,7-heptanediol diepoxy (meth)acrylate, 1,8-octanediol diepoxy (meth)acrylate , 1,9-nonanediol diepoxy(meth)acrylate, 1,10-decanediol diepoxy(meth)acrylate, and the like.

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

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

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

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

The upper limit of the ratio of structural unit 3 to all structural units is 79, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 relative to 100 mol% of all structural units. , 10, 5, 2 mol%, etc., and the lower limits are 78, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2 Examples include 1 and 0 mol %. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). When the structural unit 3 is included, in one embodiment, the ratio of the structural unit 3 to the total structural units is preferably 1 to 79 mol%.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Constituent unit 6)
Structural unit 6 is a structural unit contained in the polymer chain when (meth)acrylic acid or (meth)acrylic acid ester is used as the monomer. (Meth)acrylic acid or (meth)acrylic acid ester can be used alone or in combination of two or more.

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

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

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

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

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

The upper limit of the ratio of the structural unit 6 to all structural units is exemplified by 80, 70, 60, 50, 40, 30, 20, 10, 5% by mass, etc., and the lower limit is 70. , 60, 50, 40, 30, 20, 10, 5, 0% by mass, and the like. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, the ratio of structural unit 6 to all structural units is preferably 0 to 80% by mass with respect to the mass of all structural units.

The upper limit of the ratio of the structural unit 6 to all structural units is exemplified by 80, 70, 60, 50, 40, 30, 20, 10, 5 mol% with respect to 100 mol% of all structural units, and the lower limit is Examples include 70, 60, 50, 40, 30, 20, 10, 5, 0 mol%. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, the ratio of structural unit 6 to 100 mol % of all structural units is preferably 0 to 80 mol %.

(Other structural units)
The resin of the present disclosure may also contain structural units other than structural units 1-6. Examples of other structural units include structural units derived from (meth)acrylic acid derivatives other than structural units 1 to 4 and 6, structural units derived from chain transfer agents, and the like.

When other structural units are included, the upper limit of the ratio of other structural units to all structural units is exemplified by 30, 25, 20, 15, 10, 5, 2% by mass, etc., and the lower limit is 29, 25, 20, 15, 10, 5, 2, 1 mass % and the like are exemplified. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, the proportion of other structural units in all structural units is 1 to 30% by mass, less than 30% by mass, less than 20% by mass, less than 10% by mass, less than 9% by mass, less than 5% by mass, Less than 4% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, less than 0.001% by mass, less than 0.0001% by mass, 0% by mass, and the like are exemplified.

The upper limit of the ratio of other structural units to 100 mol% of all structural units is exemplified by 30, 25, 20, 15, 10, 5, 2 mol%, and the lower limit is 29, 25, 20, 15, 10. , 5, 2, 1, 0 mol %, and the like. The range of the ratio can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, the ratio of other structural units to 100 mol% of all structural units is 1 to 30 mol%, less than 30 mol%, less than 20 mol%, less than 10 mol%, less than 9 mol%, 5 mol %, less than 4 mol%, less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, less than 0.001 mol%, less than 0.0001 mol%, and 0 mol%. When other structural units are included, in one embodiment, the ratio of other structural units to 100 mol % of all structural units is preferably 1 to 30 mol %.

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

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

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

When the structural unit 3 is included, the upper limit of the molar ratio of the structural unit 1 and the structural unit 3 (substance amount of the structural unit 1 /substance amount of the structural unit 3) is 99.0, 95.0, 90.0, 85 .0, 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0 , 20.0, 15.0, 10.0, 5.0, 1.0, 0.5, etc., and the lower limits are 98.0, 95.0, 90.0, 85.0, 80.0. 0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5.0, 1.0, 0.5, 0.25 and the like are exemplified. The range of the above molar ratio can be set appropriately (for example, by selecting from the above upper limit and lower limit values). In one embodiment, when the structural unit 3 is included, the molar ratio of the structural unit 1 to the structural unit 3 (the amount of substance of the structural unit 1/the amount of substance of the structural unit 3) is 0.00 from the viewpoint of suppressing gelation. 25 to 99.0 are preferred.

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

When the structural unit 4 is included, the upper limit of the molar ratio between the structural unit 1 and the structural unit 4 (substance amount of the structural unit 1/substance amount of the structural unit 4) is 99.0, 95.0, 90.0, 85 .0, 80.0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0 , 20.0, 15.0, 10.0, 5.0, 1.0, 0.5, etc., and the lower limits are 98.0, 95.0, 90.0, 85.0, 80.0. 0, 75.0, 70.0, 65.0, 60.0, 55.0, 50.0, 45.0, 40.0, 35.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5.0, 1.0, 0.5, 0.4 and the like are exemplified. The range of the molar ratio can be appropriately set (for example, selected from the above upper and lower limits). In one embodiment, when the structural unit 4 is included, the molar ratio between the structural unit 1 and the structural unit 4 (the amount of substance of the structural unit 1/the amount of substance of the structural unit 4) is 0.00 from the viewpoint of suppressing gelation. 4 to 99.0 are preferred.

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

When the structural unit 5 is included, the upper limit of the molar ratio of the structural unit 1 and the structural unit 5 (substance amount of the structural unit 1 /substance amount of the structural unit 5) is 33.0, 30.0, 25.0, 20 0, 15.0, 10.0, 5.0, 1.0, 0.5, etc., and the lower limits are 32.0, 30.0, 25.0, 20.0, 15.0, 10 .0, 5.0, 1.0, 0.4 and the like are exemplified. The range of the above molar ratio can be set appropriately (for example, by selecting from the above upper limit and lower limit values). In one embodiment, when the structural unit 5 is included, the molar ratio between the structural unit 1 and the structural unit 5 (the amount of substance of the structural unit 1/the amount of substance of the structural unit 5) is 0.00 from the viewpoint of suppressing gelation. 4 to 33.0 are preferred.

When the structural unit 6 is included, the upper limit of the mass ratio between the structural unit 6 and the structural unit 1 (the mass of the structural unit 6/the mass of the structural unit 1) is 4, 3, 2, 1, 0.5, and the like. , the lower limit is exemplified by 3, 2, 1, 0.5, 0, and the like. The mass ratio range can be set as appropriate (for example, by selecting from the upper and lower limits). In one embodiment, when the structural unit 6 is included, the mass ratio of the structural unit 6 to the structural unit 1 (mass of the structural unit 6/mass of the structural unit 1) is preferably 0-4.

When the structural unit 6 is included, the upper limit of the molar ratio between the structural unit 6 and the structural unit 1 (substance amount of the structural unit 6/substance amount of the structural unit 1) is 4, 3, 2, 1, 0.5, etc. 3, 2, 1, 0.5, 0, etc. are exemplified as lower limits. The range of the above molar ratio can be set appropriately (for example, by selecting from the above upper limit and lower limit values). In one embodiment, when the structural unit 6 is included, the molar ratio of the structural unit 6 to the structural unit 1 (substance amount of the structural unit 6/substance amount of the structural unit 1) is preferably 0 to 4.

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

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

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

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

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

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

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

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

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

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

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

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

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

[Reactive diluent]
Various known reactive diluents can be used, and one or more of them can be used in combination. Reactive diluents are
[Wherein, n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, R ^b1′ to R ^b17′ are each independently a hydrogen atom,
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
and
R ^b18′ to R ^b19′ are each independently
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
and
R ^b20′ is an alkylene group,
R ^b4′ , R ^b5′ , R ^b9′ and R ^b13′ may have different groups for each structural unit,
In the general formulas (A ^' ) to (D ^' )
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit. }
contains two or more. ]
etc. are exemplified.

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

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

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

The upper limit of the ratio of resin to reactive diluent (mass of resin/mass of reactive diluent) is 1.50, 1.40, 1.30, 1.20, 1.10, 1.00, 0 .90, 0.80, 0.70, 0.6, 0.5, 0.4, 0.3, 0.2, 0.15, etc., and the lower limits are 1.40, 1.30, 1 .20, 1.10, 1.00, 0.90, 0.80, 0.70, 0.6, 0.5, 0.4, 0.3, 0.2, 0.15, 0.11 etc. are exemplified. The range of the above ratio can be set as appropriate (for example, by selecting from the above upper limit and lower limit values). In one embodiment, the ratio of the resin to the reactive diluent (mass of resin/mass of reactive diluent) is preferably 0.11 to 1.50 from the viewpoint of film strength and curability.

The varnish composition may contain components other than the resin and reactive diluent (hereinafter also referred to as other components). The upper limit of the content of other components is exemplified by 20, 15, 10, 5, 1% by mass, etc., and the lower limit is 15, 10, 5, 1, 0, based on the total mass of the resin and reactive diluent. % by mass and the like are exemplified. The range of the content can be appropriately set (for example, selected from the above upper limit and lower limit values). In one embodiment, the content of other components is preferably 0 to 20% by mass with respect to the total mass of the resin and reactive diluent.

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

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

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

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

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

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

The above printing ink contains the above resin, polymerizable monomer and pigment, and may further contain surface conditioners, antifoaming agents, photosensitizers, antioxidants, light stabilizers and leveling agents. can. The amount of these optional components is such that the total amount thereof is in the range of about 100 parts by mass or less (specifically, 95, 90, 80, 50, 40, 30, 20 , 10, 5, 1 part by mass or less). Furthermore, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, phenothiazine and N-nitrosophenylhydroxylamine aluminum salt can be blended. When a polymerization inhibitor is blended, it is preferably used in an amount of about 0.01 to 2 parts by mass with respect to 100 parts by mass of the offset printing ink.

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

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

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

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

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

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

Example 1-1
A reaction vessel equipped with a stirrer, a reflux condenser with a water divider, a thermometer and a dropping funnel was charged with 290 g of butyl acetate. A dropping funnel was charged with 290 g of glycidyl methacrylate, and 40 g of 2,2′-azobisisobutyronitrile was added. Under a nitrogen atmosphere, a dropping polymerization reaction was carried out with stirring at 121° C. for 3.0 hours, and the temperature was maintained for 1 hour. Then, after adding 710 g of hydrogenated rosin (manufactured by Arakawa Chemical, trade name Hyperel CH) and 4.0 g of triphenylphosphine, the mixture was stirred at 120° C. for 12 hours. Thereafter, the solvent was distilled off while the temperature was raised to 190° C. under normal pressure, and the solvent was completely distilled off under reduced pressure of 50 mmHg or less to obtain a resin.

Example 1 other than Example 1-1 and Comparative Examples were produced in the same manner as in Example 1 except for the changes shown in the table below.

Example 2-1
60.1 parts by mass of the reactive diluent ditrimethylolpropane tetraacrylate was added to 19.9 parts by mass of the resin 1 obtained in Example 1-1, and dissolved under stirring at 130 ° C. for 1 hour under air bubbling to obtain a varnish. A composition was obtained. 5 parts by mass of Irgacure 907 (manufactured by BASF) and 15 parts by mass of MA100 (manufactured by Mitsubishi Chemical Corporation) were added to the obtained varnish composition, and the mixture was mixed with three rollers to prepare an ink. Based on the above formulation, the printing ink was obtained by appropriately adjusting the tack value at 40° C. and 400 rpm to 9±0.5.

Examples 2 and Comparative Examples other than Example 2-1 were prepared in the same manner as Example 2-1, except that the types and usage ratios of the resin and reactive diluent were changed as shown in the table below. .

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

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

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

Claims (3)

A varnish composition comprising a resin,
The resin contains more than 30 mol% of structural unit 1,
A varnish composition further comprising structural units 2 derived from monomers represented by the following general formulas (A) to (E) .
[In the formula, R ^a1 is a hydrogen atom or an alkyl group, and R ^a2 is
<wherein R ^aa is an alkylene group or a single bond, R ^ab to R ^ac are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group,
^Rad is
(In the formula,
represents a single or double bond)
is. ＞
[Wherein, n and m are each independently an integer of 0 to 2, p is an integer of 0 to 7, R b1 ^to R ^b17 are each independently a hydrogen atom,
<In the formula, q is each independently an integer of 0 to 16, R ¹ to R ³ are each independently a hydrogen atom or an alkyl group, and R ¹ and R ³ may have different groups for each unit. good. ＞
and
R ^b18 to R ^b19 are each independently
<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 and R ³ may have different groups for each unit. good. ＞
and
R ^b20 is an alkylene group,
R ^b4 , R ^b5 , R ^b9 and R ^b13 may have different groups for each structural unit,
In the general formulas (A) to (D)
<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 and R ³ may have different groups for each unit. good. ＞
contains two or more. ] A printing ink comprising the varnish composition of claim 1 and a pigment. A printed matter comprising a cured layer of the printing ink according to claim 2 .