JP7027730B2 - Varnish composition, offset printing inks and printed matter - Google Patents

Description

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

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

In particular, in active energy ray-curable printing inks, polyfunctional acrylates such as dipentaerythritol hexaacrylate and ditrimethylolpropane tetraacrylate are widely used as reactive diluents because they have excellent curability and film hardness. There is.

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

Japanese Patent No. 5683757

In the conventional styrene acrylic resin and polyester resin, there is a trade-off relationship between ink fluidity and misting resistance, and the current situation is that a resin having both of these performances has not been obtained. On the other hand, the allyl phthalate resin is obtained by polymerizing a diallyl phthalate monomer and does not have a polar functional group such as a hydroxyl group or a carboxyl group, so that the usage mode is limited. Further, since the unreacted diallyl phthalate monomer remaining in the resin is a substance of very high concern with mutagenicity (see paragraph [0009] of Patent Document 1 above), a resin that can replace the diallyl phthalate resin is required. Has been done.

The problem to be solved by the present invention is a varnish composition which has excellent ink fluidity and misting resistance and is a raw material of a printing ink capable of introducing a polar functional group, and excellent ink fluidity and misting resistance. It is an object of the present invention to provide an offset printing ink having the above ink and a printed matter using the above ink.

As a result of diligent studies, the present inventors can solve the above-mentioned problems by using a varnish composition containing a resin produced by using a thiol-based chain transfer agent and a reactive diluent having a plurality of (meth) acryloyl groups. I found.

（式中、Ｒ^１は水素又はメチル基であり、Ｒ^ａは、水素又はアルキル基である）
及び構成単位２

（式中、Ｒ^ｂはアルキレン基である）
を含む、樹脂（１）、並びに
反応性希釈剤（２）を含む、ワニス組成物。
（項目２）
前記樹脂（１）が構成単位３

（式中、Ｒ^１は水素又はメチル基であり、Ｒ^ｃ１～Ｒ^ｃ５はそれぞれ独立に、水素、アルキル基及びアリール基からなる群から選択される基である。）
を含む、上記項目に記載のワニス組成物。
（項目３）
前記樹脂（１）が構成単位４

（式中、Ｒ^１は水素又はメチル基であり、Ｒ^ｄはＣＯＮＲ^ｄ１Ｒ^ｄ２、ＣＯＯ（ＣＨ_２）_２ＮＲ^ｄ１Ｒ^ｄ２及び

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

（式中、Ｒ^ｅ１、Ｒ^ｅ２、及びＲ^ｅ３は、それぞれ独立に、ニトリル基、アルキル基、極性基置換アルキル基、アルケニル基、又は極性基である。）
をポリマー鎖末端に含む、上記項目のいずれか１項に記載のワニス組成物。
（項目５）
前記樹脂（１）が構成単位６

（式中、Ｒ^ｆは、アシル基、アルキル基、又はアリール基である。）
をポリマー鎖末端に含む、上記項目のいずれか１項に記載のワニス組成物。
（項目６）
前記反応性希釈剤（２）が

（式中、ｎは０～２の整数であり、ｍは０～２の整数であり、ｐは０から7の整数であり、Ｒ^ｂ１～Ｒ^ｂ１４は、それぞれ独立に水素原子、

であり、
Ｒ^ｂ１５～Ｒ^ｂ１６は、それぞれ独立に

であり、Ｒ^ｂ１６はそれぞれ独立に、アルキレン基であり、
構造式（Ａ）～（Ｃ）中、Ｒ^ｂ１～Ｒ^ｂ１４から選択される２個以上の基が

であり、
ｑはそれぞれ独立に０～１６の整数であり、Ｒ^１はそれぞれ独立に、水素原子又はアルキル基である。なお、Ｒ^ｂ４、Ｒ^ｂ５、Ｒ^ｂ９、及びＲ^ｂ１３は各構成単位ごとに基が異なっていてもよい。）
である、上記項目のいずれか１項に記載のワニス組成物。
（項目７）
オフセットインキ用に用いられる、上記項目のいずれか１項に記載のワニス組成物。
（項目８）
上記項目のいずれか１項に記載のワニス組成物及び顔料を含む、オフセット印刷インキ。
（項目９）
上記項目に記載のオフセット印刷インキの硬化層を有する、印刷物。 The disclosure provides the following items:
(Item 1)
Configuration unit 1

(In the formula, R ¹ is a hydrogen or methyl group and ^Ra is a hydrogen or alkyl group).
And constituent unit 2

(In the formula, R ^b is an alkylene group)
A varnish composition comprising a resin (1) and a reactive diluent (2).
(Item 2)
The resin (1) is the constituent unit 3

(In the formula, R ¹ is a hydrogen or methyl group, and R ^c1 to R ^c5 are independently selected from the group consisting of hydrogen, an alkyl group and an aryl group.)
The varnish composition according to the above item, which comprises.
(Item 3)
The resin (1) is the constituent unit 4

(In the formula, R ¹ is a hydrogen or methyl group, R ^d is CONR ^d1 R ^d2 , COO (CH ₂ ) ₂ NR ^d1 R ^d2 and

It is a group selected from the group consisting of
In the formula, R ^d1 and R ^d2 are an alkyl group or hydrogen, or R ^d1 and R ^d2 are groups that form a ring structure together, k is an integer of 1 or more, and R ^d3 is. , Hydrogen, methyl group or hydroxyl group, where 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 the hydroxyl group. .. )
The varnish composition according to any one of the above items, which comprises.
(Item 4)
The resin (1) is a constituent unit 5

(In the formula, R ^e1 , R ^e2 , and R ^e3 are independently nitrile groups, alkyl groups, polar group-substituted alkyl groups, alkenyl groups, or polar groups, respectively.)
The varnish composition according to any one of the above items, which comprises at the end of the polymer chain.
(Item 5)
The resin (1) is a constituent unit 6

(In the formula, R ^f is an acyl group, an alkyl group, or an aryl group.)
The varnish composition according to any one of the above items, which comprises at the end of the polymer chain.
(Item 6)
The reactive diluent (2)

(In the equation, n is an integer of 0 to 2, m is an integer of 0 to 2, p is an integer of 0 to 7, and R ^b1 to R ^b14 are independently hydrogen atoms, respectively.

And
R ^b15 to R ^b16 are independent of each other.

R ^b16 is an alkylene group independently of each other.
In the structural formulas (A) to (C), two or more groups selected from R ^b1 to R ^b14 are

And
q is an independently integer from 0 to 16, and R ¹ is independently a hydrogen atom or an alkyl group. The groups of R ^b4 , R ^b5 , R ^b9 , and R ^b13 may be different for each structural unit. )
The varnish composition according to any one of the above items.
(Item 7)
The varnish composition according to any one of the above items, which is used for offset ink.
(Item 8)
An offset printing ink containing the varnish composition and pigment according to any one of the above items.
(Item 9)
A printed matter having a cured layer of the offset printing ink according to the above item.

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

When the varnish composition according to the present invention is used, it is excellent while having various ink performances (adhesion, coating film hardness, emulsifying property, image reproducibility, glossiness, blocking resistance, coating film smoothness, etc.). It is possible to obtain an offset printing ink having ink flowability and misting resistance. By using the above ink, it becomes possible to improve the productivity at the time of offset printing.

（式中、Ｒ^１は水素又はメチル基であり、Ｒ^ａは、水素又はアルキル基である）
及び構成単位２

（式中、Ｒ^ｂはアルキレン基である）
を含む樹脂を提供する。本開示において「樹脂」は、ポリマーと同義の意味を有する。 (1. Resin (1))
The present disclosure is based on structural unit 1.

(In the formula, R ¹ is a hydrogen or methyl group and ^Ra is a hydrogen or alkyl group).
And constituent unit 2

(In the formula, R ^b is an alkylene group)
To provide a resin containing. In the present disclosure, "resin" has the same meaning as a polymer.

(Structure unit 1)
The structural unit 1 is a structural unit contained in the polymer chain when (meth) acrylic acid or (meth) acrylic acid alkyl ester is used as the monomer.

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

Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid linear alkyl ester, (meth) acrylic acid branched alkyl ester and the like. Two or more kinds of (meth) acrylic acid alkyl esters can be used in combination.

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

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

An example of the upper limit of the ratio of the constituent unit 1 to all the constituent units is 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40 with respect to 100 mass% of all the constituent units. , 35, 30, 25, 21, 20, 15, 10% by mass, etc., and examples of the lower limit are 98, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 21, 20, 15, 10, 5 mass% and the like can be mentioned. The range of the ratio of the structural unit 1 to all the structural units can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the structural unit 1 is preferably 5 to 99% by mass with respect to 100% by mass of all the structural units from the viewpoint of monomer solubility and pigment dispersibility.

In the present disclosure, "100% by mass of all constituent units" is synonymous with the mass of the resin.

Examples of the upper limit of the ratio of the constituent unit 1 to all the constituent units are 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40 with respect to 100 mol% of all the constituent units. , 35, 30, 25, 21, 20, 15, 10 mol%, etc., examples of the lower limit are 98, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 21, 20, 15, 10, 5 mol% and the like can be mentioned. The range of the ratio of the structural unit 1 to all the structural units can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the constituent unit 1 is preferably 5 to 99 mol% with respect to 100 mol% of all constituent units from the viewpoint of monomer solubility and pigment dispersibility.

(Structure unit 2)
The structural unit 2 is a structural unit derived from a thiol-based chain transfer agent. Two or more types of thiol chain transfer agents can be used in combination.

（式中、Ｒ^ｂ１～Ｒ^ｂ２は、それぞれ独立にアルキレン基であり、Ｒ^Ｂ１はアルキレン基又は

（式中、ｂは０以上の整数であり、Ｒ^ｂ’はアルキレン基である）
である。）
構成単位２Ｂ

（式中、Ｒ^ｂ３～Ｒ^ｂ５は、それぞれ独立にアルキレン基であり、Ｒ^Ｂ２は３価の炭化水素基又は

（式中、Ｒ^ｂａ～Ｒ^ｂｃは、それぞれ独立にアルキレン基である）
である。）
構成単位２Ｃ

（式中、Ｒ^ｂ６～Ｒ^ｂ９は、それぞれ独立にアルキレン基であり、Ｒ^Ｂ３は４価の炭化水素基である。）
構成単位２Ｄ

（式中、Ｒ^ｂ１０～Ｒ^ｂ１５は、それぞれ独立にアルキレン基であり、Ｒ^Ｂ４は６価の炭化水素基又は

である。）
で示されるもの等が挙げられる。 An example of structural unit 2 is structural unit 2A.

(In the formula, R ^b1 to R ^b2 are independently alkylene groups, and R ^B1 is an alkylene group or

(In the formula, b is an integer of 0 or more, and R ^b'is an alkylene group).
Is. )
Configuration unit 2B

(In the formula, R ^b3 to R ^b5 are independently alkylene groups, and R ^B2 is a trivalent hydrocarbon group or

(In the formula, R ^ba to R ^bc are independently alkylene groups).
Is. )
Configuration unit 2C

(In the formula, R ^b6 to R ^b9 are independently alkylene groups, and R ^B3 is a tetravalent hydrocarbon group.)
Configuration unit 2D

(In the formula, R ^b10 to R ^b15 are independently alkylene groups, and R ^B4 is a hexavalent hydrocarbon group or

Is. )
Examples include those indicated by.

The constituent unit 2A is tetraethylene glycol bis (3-mercaptopropionate), tetrapropylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), and polypropylene glycol bis (3-mercapto). It is a structural unit derived from propionate) and the like.

The structural unit 2B is a structural unit derived from trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) ethyl] -isocyanurate and the like.

The structural unit 2C is a structural unit derived from pentaerythritol tetrakis (3-mercaptopropionate) or the like.

The structural unit 2D is a structural unit derived from dipentaerythritol hexakis (3-mercaptopropionate) or the like.

An example of the upper limit of the ratio of the constituent unit 2 to all the constituent units is 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2 mass%, etc. with respect to 100 mass% of all the constituent units. Examples of the lower limit include 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1% by mass and the like. The range of the ratio of the structural unit 2 to all the structural units can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the structural unit 2 is preferably 1 to 50% by mass with respect to 100% by mass of all the structural units.

An example of the upper limit of the ratio of the constituent unit 2 to all the constituent units is 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2 mol%, etc. with respect to 100 mol% of all the constituent units. Examples of the lower limit are 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1 mol% and the like. The range of the ratio of the structural unit 2 to all the structural units can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the constituent unit 2 is preferably 1 to 50 mol% with respect to 100 mol% of all constituent units.

（式中、Ｒ^１は水素又はメチル基であり、Ｒ^ｃ１～Ｒ^ｃ５はそれぞれ独立に、水素、アルキル基及びアリール基からなる群から選択される基である。）
を含む。 (Structure unit 3)
In one embodiment, the constituent units 3 are added to the constituent unit group.

(In the formula, R ¹ is a hydrogen or methyl group, and R ^c1 to R ^c5 are independently selected from the group consisting of hydrogen, an alkyl group and an aryl group.)
including.

The structural unit 3 is a structural unit contained in the polymer chain when a styrene-based compound is used as the monomer. Examples of the styrene-based compound include styrene, α-methylstyrene, and the like, as well as styrene having at least one alkyl group having 1 to 2 carbon atoms in the aromatic ring. Two or more kinds of styrene compounds can be used in combination.

When the constituent unit 3 is included, an example of the upper limit of the ratio of the constituent unit 3 to all the constituent units is 79, 75, 70, 65, 60, 55, 50, 45, 40, with respect to 100 mass% of all the constituent units. 35, 30, 25, 20, 15, 10, 5, 2 mass% and the like, and examples of the lower limit are 78, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25. , 20, 15, 10, 5, 2, 1% by mass and the like. The range of the ratio of the structural unit 3 to all the structural units can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the structural unit 3 is preferably 1 to 79% by mass with respect to 100% by mass of all the structural units.

When the constituent unit 3 is included, an example of the upper limit of the ratio of the constituent unit 3 to all the constituent units is 79, 75, 70, 65, 60, 55, 50, 45, 40, with respect to 100 mol% of all the constituent units. 35, 30, 25, 20, 15, 10, 5, 2 mol% and the like, and examples of the lower limit are 78, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25. , 20, 15, 10, 5, 2, 1 mol% and the like. The range of the ratio of the structural unit 3 to all the structural units can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the constituent unit 3 is preferably 1 to 79 mol% with respect to 100 mol% of all constituent units.

（式中、Ｒ^１は水素又はメチル基であり、Ｒ^ｄはＣＯＮＲ^ｄ１Ｒ^ｄ２、ＣＯＯ（ＣＨ_２）_２ＮＲ^ｄ１Ｒ^ｄ２及び

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

(In the formula, R ¹ is a hydrogen or methyl group, R ^d is CONR ^d1 R ^d2 , COO (CH ₂ ) ₂ NR ^d1 R ^d2 and

It is a group selected from the group consisting of
In the formula, R ^d1 and R ^d2 are an alkyl group or hydrogen, or R ^d1 and R ^d2 are groups that form a ring structure together, k is an integer of 1 or more, and R ^d3 is. , Hydrogen, methyl group or hydroxyl group, where 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 the hydroxyl group. .. )
including.

The structural unit 4 is contained in the polymer chain when, for example, N, N-dialkyl (meth) acrylamide, N, N-dialkyl (meth) acrylate alkylamine, (meth) acrylate hydroxyalkyl or the like is used as the monomer. It is a structural unit.

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

Examples of N, N-dialkyl (meth) acrylate alkylamines include N, N-dimethylethyl (meth) acrylate, N, N-diethylethyl (meth) acrylate and the like. The number of carbon atoms of the alkyl group on nitrogen (that is, the number of carbon atoms of each of R ^b1 and R ^b2 in the constituent unit 4) is preferably 1 to 2.

等が挙げられる。 As an example of hydroxyalkyl (meth) acrylate

And so on.

When the constituent unit 4 is included, an example of the upper limit of the ratio of the constituent unit 4 to all the constituent units is 50, 45, 40, 35, 30, 25, 20, 15, 10, with respect to 100 mass% of all the constituent units. 5, 2% by mass and the like, and examples of the lower limit include 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1% by mass and the like. The range of the ratio of the structural unit 4 to all the structural units can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the structural unit 4 is preferably 1 to 50% by mass with respect to 100% by mass of all the structural units.

When the constituent unit 4 is included, an example of the upper limit of the ratio of the constituent unit 4 to all the constituent units is 50, 45, 40, 35, 30, 25, 20, 15, 10, with respect to 100 mol% of all the constituent units. 5, 2 mol% and the like, and examples of the lower limit include 49, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1 mol% and the like. The range of the ratio of the structural unit 4 to all the structural units can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the constituent unit 4 is preferably 1 to 50 mol% with respect to 100 mol% of all constituent units.

（式中、Ｒ^ｅ１、Ｒ^ｅ２、及びＲ^ｅ３は、それぞれ独立に、ニトリル基、アルキル基、極性基置換アルキル基、極性基である。）
をポリマー鎖に含む。 (Structure unit 5)
In one embodiment, the resin is a constituent unit 5

(In the formula, R ^e1 , R ^e2 , and R ^e3 are independently a nitrile group, an alkyl group, a polar group-substituted alkyl group, and a polar group, respectively.)
Is included in the polymer chain.

（式中、Ｒ^ｅ１、Ｒ^ｅ２、及びＲ^ｅ３は、それぞれ独立に、ニトリル基、アルキル基、極性基置換アルキル基、アルケニル基、又は極性基である。）アゾ開始剤に由来する構成単位である。アゾ開始剤は２種以上を併用できる。 The 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, a polar group-substituted alkyl group, an alkenyl group, or a polar group.) A structural unit derived from an azo initiator. be. Two or more azo initiators can be used in combination.

Examples of the "polar group" include a hydroxyl group, a carboxyl group, an amino group, a sulfonyl group, a phosphoric acid group, a nitro group, an amide group and the like.

Examples of the azo initiator include an azonitrile-based initiator, an azoamidin-based initiator, and an azoamide-based initiator.

Examples of azonitrile-based initiators are 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis. (Isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) and the like can be mentioned.

Examples of azoamidin-based initiators are 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl)). Propane] disulfate dihydrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2, Examples thereof include 2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n hydrate and the like.

Examples of azoamide-based initiators are 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] and 2,2'-azobis [N- (2-propenyl) -2-methylpropion. Amide], 2,2'-azobis (N-butyl-2-methylpropionamide) and the like.

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

When the constituent unit 5 is included, an example of the upper limit of the ratio of the constituent unit 5 to all the constituent units is 20, 15, 10, 5, 4, 3, 2, 1 mass%, etc. with respect to 100 mass% of all the constituent units. Examples of the lower limit include 19, 15, 10, 5, 4, 3, 2, 1, 0.5% by mass and the like. The range of the ratio of the structural unit 5 to all the structural units can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the structural unit 5 is preferably 0.5 to 20% by mass with respect to 100% by mass of all the structural units.

When the constituent unit 5 is included, an example of the upper limit of the ratio of the constituent unit 5 to all the constituent units is 20, 15, 10, 5, 4, 3, 2, 1 mol%, etc. with respect to 100 mol% of all the constituent units. Examples of the lower limit include 19, 15, 10, 5, 4, 3, 2, 1, 0.5 mol% and the like. The range of the ratio of the structural unit 5 to all the structural units can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the constituent unit 5 is preferably 0.5 to 20 mol% with respect to 100 mol% of all the constituent units.

（式中、Ｒ^ｆは、アシル基、アルキル基、又はアリール基である。）
をポリマー鎖末端に含む。 (Structure unit 6)
In one embodiment, the resin is a constituent unit 6

(In the formula, R ^f is an acyl group, an alkyl group, or an aryl group.)
Is included at the end of the polymer chain.

The structural unit 6 is, for example, R ^{f-O-O-R f having} the following structure.
(In the formula, R ^f is an acyl group, an alkyl group, or an aryl group.) A structural unit derived from a peroxide-based initiator. Two or more types of peroxide-based initiators can be used in combination.

Examples of peroxide-based initiators are (2-ethylhexanoyl) (tert-butyl) peroxide, benzoyl peroxide, di-tert-butyl peroxide, dimethyldioxylane, acetone peroxide, methylethylketone peroxide, hexamethylenetripeloxide. Examples thereof include diamine, cumenehydroperoxide, tert-hexylperoxy-2-ethylhexanoate and the like.

When the constituent unit 6 is included, an example of the upper limit of the ratio of the constituent unit 6 to all the constituent units is 20, 15, 10, 5, 4, 3, 2, 1 mass%, etc. with respect to 100 mass% of all the constituent units. Examples of the lower limit include 19, 15, 10, 5, 4, 3, 2, 1, 0.5% by mass and the like. The range of the ratio of the structural unit 6 to all the structural units can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the structural unit 6 is preferably 0.5 to 20% by mass with respect to 100% by mass of all the structural units.

When the constituent unit 6 is included, an example of the upper limit of the ratio of the constituent unit 6 to all the constituent units is 20, 15, 10, 5, 4, 2, 1 mol%, etc. with respect to 100 mol% of all the constituent units. Examples of the lower limit include 19, 15, 10, 5, 4, 3, 2, 1, 0.5 mol% and the like. The range of the ratio of the structural unit 6 to all the structural units can be appropriately set (for example, by selecting from the above upper and lower limit values). In one embodiment, the constituent unit 6 is preferably 0.5 to 20 mol% with respect to 100 mol% of all the constituent units.

(Other building blocks)
In one embodiment, the resin may also contain structural units other than the structural units 1 to 6 (hereinafter, also referred to as other structural units). Examples of other structural units include structural units derived from (meth) acrylic acid derivatives that are neither structural units 1 nor 4. Examples of structural units derived from (meth) acrylic acid derivatives that are neither structural units 1 nor 4 include (poly) pentaerythritol poly (alkylene oxide-modified or epoxy-modified) (meth) acrylates and (poly) trimethylolpropane poly, which will be described later. Constituent units derived from (alkylene oxide-modified or epoxy-modified) (meth) acrylate, (poly) glycerin poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate, alkylene di (alkylene oxide-modified or epoxy-modified) (meth) acrylate. And so on. In one embodiment, the resin is a crosslinkable group (ethylenically unsaturated bond group, amino group (eg, primary amino group (-NH ₂ )), epoxy group, thiol group (-SH), halogen group). It is a resin that does not have.

When including other structural units, an example of the upper limit of the ratio of other structural units to all structural units is 30, 25, 20, 15, 10, 5, 2 mass%, etc. with respect to 100 mass% of all structural units. Examples of the lower limit include 29, 25, 20, 15, 10, 5, 2, 1% by mass and the like. The range of the ratio of other constituent units to all the constituent units can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the other structural units are preferably 1 to 30% by mass based on 100% by mass of all the structural units, but less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, and 0. It may be less than 001% by mass and less than 0.0001% by mass.

When including other constituent units, an example of the upper limit of the ratio of other constituent units to all constituent units is 30, 25, 20, 15, 10, 5, 2 mol%, etc. with respect to 100 mol% of all constituent units. Examples of the lower limit include 29, 25, 20, 15, 10, 5, 2, 1 mol% and the like. The range of the ratio of other constituent units to all the constituent units can be set as appropriate (for example, by selecting from the above upper and lower limit values). In one embodiment, the other constituent units are preferably 1 to 30 mol% relative to 100 mol% of all constituent units, but less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, 0. It may be less than 001 mol% and less than 0.0001 mol%.

(Relative ratio between constituent units)
Examples of the upper limit of the mass ratio between the constituent unit 1 and the constituent unit 2 (mass of the constituent unit 1 / mass of the constituent unit 2) are 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, 0.3, 0.2, etc. are mentioned, and examples of the lower limit 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, 0.3, 0.2, 0.1 and the like. The range of the mass ratio between the constituent unit 1 and the constituent unit 2 (mass of the constituent unit 1 / mass of the constituent unit 2) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the mass ratio of the structural unit 1 to the structural unit 2 is preferably 0.1 to 99.0 from the viewpoint of suppressing gelation.

Examples of the upper limit of the molar ratio between the constituent unit 1 and the constituent unit 2 (the amount of the substance of the constituent unit 1 / the amount of the substance of the constituent unit 2) are 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, 0.3, 0.2, etc. are mentioned, and examples of the lower limit 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, 0.3, 0.2, 0.1 and the like. The range of the molar ratio of the constituent unit 1 to the constituent unit 2 (the amount of substance of the constituent unit 1 / the amount of substance of the constituent unit 2) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the molar ratio of the constituent unit 1 to the constituent unit 2 is preferably 0.1 to 99.0 from the viewpoint of suppressing gelation.

Examples of the upper limit of the mass ratio between the constituent unit 1 and the constituent unit 3 (mass of the constituent unit 1 / mass of the constituent unit 3) are 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, 0.25, 0.10, 0.08, 0.07, etc. are mentioned, and examples of the lower limit 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, 0.25, 0.10, 0.08, 0.07, 0.06 And so on. The range of the mass ratio between the constituent unit 1 and the constituent unit 3 (mass of the constituent unit 1 / mass of the constituent unit 3) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the mass ratio between the structural unit 1 and the structural unit 3 is preferably 0.06 to 99.0 from the viewpoint of polarity adjustment.

Examples of the upper limit of the molar ratio between the constituent unit 1 and the constituent unit 3 (the amount of the substance of the constituent unit 1 / the amount of the substance of the constituent unit 3) are 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, 0.25, 0.10, 0.08, 0.07, etc. are mentioned, and examples of the lower limit 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, 0.25, 0.10, 0.08, 0.07, 0 .06 and the like can be mentioned. The range of the molar ratio of the constituent unit 1 to the constituent unit 3 (the amount of substance of the constituent unit 1 / the amount of substance of the constituent unit 3) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the molar ratio of the structural unit 1 to the structural unit 3 is preferably 0.06 to 99.0 from the viewpoint of polarity adjustment.

Examples of the upper limit of the mass ratio between the constituent unit 1 and the constituent unit 4 (mass of the constituent unit 1 / mass of the constituent unit 4) are 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, 0.4, 0.3, 0.2, etc. are mentioned, and examples of the lower limit 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, 0.3, 0.2, 0.1 and the like. The range of the mass ratio between the constituent unit 1 and the constituent unit 4 (mass of the constituent unit 1 / mass of the constituent unit 4) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the mass ratio of the structural unit 1 to the structural unit 4 is preferably 0.1 to 99.0 from the viewpoint of polarity adjustment.

Examples of the upper limit of the molar ratio between the constituent unit 1 and the constituent unit 4 (the amount of the substance of the constituent unit 1 / the amount of the substance of the constituent unit 4) are 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, 0.4, 0.3, 0.2, etc. are mentioned, and examples of the lower limit 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, 0.3, 0.2, 0.1 and the like. The range of the molar ratio of the constituent unit 1 to the constituent unit 4 (the amount of substance of the constituent unit 1 / the amount of substance of the constituent unit 4) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the molar ratio of the structural unit 1 to the structural unit 4 is preferably 0.1 to 99.0 from the viewpoint of polarity adjustment.

Examples of the upper limit of the mass ratio between the constituent unit 1 and the constituent unit 5 (mass of the constituent unit 1 / mass of the constituent unit 5) are 198.0, 190.0, 180.0, 170.0, 160.0, 150.0, 140.0, 130.0, 120.0, 110.0, 100.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30. 0, 25.0, 20.0, 15.0, 10.0, 5.0, 1.0, 0.50, 0.40, 0.35, 0.30, 0.26 and the like. Examples of the lower limit are 197.0, 190.0, 180.0, 170.0, 160.0, 150.0, 140.0, 130.0, 120.0, 110.0, 100.0, 90. 0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5.0, 1.0, Examples thereof include 0.50, 0.40, 0.35, 0.30, 0.25 and the like. The range of the mass ratio between the constituent unit 1 and the constituent unit 5 (mass of the constituent unit 1 / mass of the constituent unit 5) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the mass ratio of the structural unit 1 to the structural unit 5 is preferably 0.25 to 198.0 from the viewpoint of suppressing gelation.

Examples of the upper limit of the molar ratio between the constituent unit 1 and the constituent unit 5 (the amount of the substance of the constituent unit 1 / the amount of the substance of the constituent unit 5) are 198.0, 190.0, 180.0, 170.0, 160. 0, 150.0, 140.0, 130.0, 120.0, 110.0, 100.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5.0, 1.0, 0.50, 0.40, 0.35, 0.30, 0.26 and the like. Examples of the lower limit are 197.0, 190.0, 180.0, 170.0, 160.0, 150.0, 140.0, 130.0, 120.0, 110.0, 100.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5.0, 1. Examples thereof include 0, 0.50, 0.40, 0.35, 0.30, 0.25 and the like. The range of the molar ratio of the constituent unit 1 to the constituent unit 5 (the amount of substance of the constituent unit 1 / the amount of substance of the constituent unit 5) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the molar ratio of the constituent unit 1 to the constituent unit 5 is preferably 0.25 to 198.0 from the viewpoint of suppressing gelation.

Examples of the upper limit of the mass ratio between the constituent unit 1 and the constituent unit 6 (mass of the constituent unit 1 / mass of the constituent unit 6) are 198.0, 190.0, 180.0, 170.0, 160.0, 150.0, 140.0, 130.0, 120.0, 110.0, 100.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30. 0, 25.0, 20.0, 15.0, 10.0, 5.0, 1.0, 0.50, 0.40, 0.35, 0.30, 0.26 and the like. Examples of the lower limit are 197.0, 190.0, 180.0, 170.0, 160.0, 150.0, 140.0, 130.0, 120.0, 110.0, 100.0, 90. 0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5.0, 1.0, Examples thereof include 0.50, 0.40, 0.35, 0.30, 0.25 and the like. The range of the mass ratio between the constituent unit 1 and the constituent unit 6 (mass of the constituent unit 1 / mass of the constituent unit 6) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the mass ratio of the constituent unit 1 to the constituent unit 6 is preferably 0.25 to 198.0 from the viewpoint of suppressing gelation.

Examples of the upper limit of the molar ratio between the constituent unit 1 and the constituent unit 6 (the amount of the substance of the constituent unit 1 / the amount of the substance of the constituent unit 6) are 198.0, 190.0, 180.0, 170.0, 160. 0, 150.0, 140.0, 130.0, 120.0, 110.0, 100.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5.0, 1.0, 0.50, 0.40, 0.35, 0.30, 0.26 and the like. Examples of the lower limit are 197.0, 190.0, 180.0, 170.0, 160.0, 150.0, 140.0, 130.0, 120.0, 110.0, 100.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 25.0, 20.0, 15.0, 10.0, 5.0, 1. Examples thereof include 0, 0.50, 0.40, 0.35, 0.30, 0.25 and the like. The range of the molar ratio of the constituent unit 1 to the constituent unit 6 (the amount of substance of the constituent unit 1 / the amount of substance of the constituent unit 6) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the molar ratio of the constituent unit 1 to the constituent unit 6 is preferably 0.25 to 198.0 from the viewpoint of suppressing gelation.

Examples of the upper limit of the mass ratio between the constituent unit 2 and the constituent unit 3 (mass of the constituent unit 2 / mass of the constituent unit 3) are 79.0, 70.0, 60.0, 50.0, 40.0, Examples include 30.0, 40.0, 30.0, 20.0, 10.0, 5.0, 1.0, 0.08, 0.06, 0.04, 0.03, and the lower limit. 78.0, 70.0, 60.0, 50.0, 40.0, 30.0, 40.0, 30.0, 20.0, 10.0, 5.0, 1.0, Examples thereof include 0.08, 0.06, 0.04 and 0.02. The range of the mass ratio between the constituent unit 2 and the constituent unit 3 (mass of the constituent unit 2 / mass of the constituent unit 3) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the mass ratio of the constituent unit 2 to the constituent unit 3 is preferably 0.02 to 79.0 from the viewpoint of suppressing gelation.

Examples of the upper limit of the molar ratio between the constituent unit 2 and the constituent unit 3 (the amount of the substance of the constituent unit 2 / the amount of the substance of the constituent unit 3) are 79.0, 70.0, 60.0, 50.0, 40. 0, 30.0, 40.0, 30.0, 20.0, 10.0, 5.0, 1.0, 0.08, 0.06, 0.04, 0.03, and the lower limit Examples are 78.0, 70.0, 60.0, 50.0, 40.0, 30.0, 40.0, 30.0, 20.0, 10.0, 5.0, 1.0. , 0.08, 0.06, 0.04, 0.02. The range of the molar ratio of the constituent unit 2 to the constituent unit 3 (the amount of substance of the constituent unit 2 / the amount of substance of the constituent unit 3) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the molar ratio of the constituent unit 2 to the constituent unit 3 is preferably 0.02 to 79.0 from the viewpoint of suppressing gelation.

An example of the upper limit of the mass ratio between the constituent unit 2 and the constituent unit 4 (mass of the constituent unit 2 / mass of the constituent unit 4) is 50.0, 40.0, 30.0, 40.0, 30.0, 20.0, 10.0, 5.0, 1.0, 0.08, 0.06, 0.04, 0.03 are given, and examples of the lower limit are 49.0, 40.0, 30. 0, 40.0, 30.0, 20.0, 10.0, 5.0, 1.0, 0.08, 0.06, 0.04, 0.02. The range of the mass ratio between the constituent unit 2 and the constituent unit 4 (mass of the constituent unit 2 / mass of the constituent unit 4) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the mass ratio of the structural unit 2 to the structural unit 4 is preferably 0.02 to 50.0 from the viewpoint of suppressing gelation.

Examples of the upper limit of the molar ratio between the constituent unit 2 and the constituent unit 4 (the amount of the substance of the constituent unit 2 / the amount of the substance of the constituent unit 4) are 50.0, 40.0, 30.0, 40.0, 30. 0, 20.0, 10.0, 5.0, 1.0, 0.08, 0.06, 0.04, 0.03, and examples of the lower limit are 49.0, 40.0, Examples thereof include 30.0, 40.0, 30.0, 20.0, 10.0, 5.0, 1.0, 0.08, 0.06, 0.04 and 0.02. The range of the molar ratio of the constituent unit 2 to the constituent unit 4 (the amount of substance of the constituent unit 2 / the amount of substance of the constituent unit 4) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the molar ratio of the constituent unit 2 to the constituent unit 4 is preferably 0.02 to 50.0 from the viewpoint of suppressing gelation.

Examples of the upper limit of the mass ratio between the constituent unit 2 and the constituent unit 5 (mass of the constituent unit 2 / mass of the constituent unit 5) are 100.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 20.0, 10.0, 5.0, 3.0, 1.0, 0.5, 0.4, 0.3, 0.2, 0. 1, 0.06 are mentioned, and examples of the lower limit are 99.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 20.0, Examples thereof include 10.0, 5.0, 3.0, 1.0, 0.5, 0.4, 0.3, 0.2, 0.1 and 0.05. The range of the mass ratio between the constituent unit 2 and the constituent unit 5 (mass of the constituent unit 2 / mass of the constituent unit 5) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the mass ratio of the constituent unit 2 to the constituent unit 5 is preferably 0.05 to 100.0 from the viewpoint of suppressing gelation.

Examples of the upper limit of the molar ratio between the constituent unit 2 and the constituent unit 5 (the amount of the substance of the constituent unit 2 / the amount of the substance of the constituent unit 5) are 100.0, 90.0, 80.0, 70.0, 60. 0, 50.0, 40.0, 30.0, 20.0, 10.0, 5.0, 3.0, 1.0, 0.5, 0.4, 0.3, 0.2, Examples of the lower limit are 99.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 20. Examples thereof include 0, 10.0, 5.0, 3.0, 1.0, 0.5, 0.4, 0.3, 0.2, 0.1 and 0.05. The range of the molar ratio of the constituent unit 2 to the constituent unit 5 (the amount of substance of the constituent unit 2 / the amount of substance of the constituent unit 5) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the molar ratio of the constituent unit 2 to the constituent unit 5 is preferably 0.05 to 100.0 from the viewpoint of suppressing gelation.

Examples of the upper limit of the mass ratio between the constituent unit 2 and the constituent unit 6 (mass of the constituent unit 2 / mass of the constituent unit 6) are 100.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 20.0, 10.0, 5.0, 3.0, 1.0, 0.5, 0.4, 0.3, 0.2, 0. 1, 0.06 are mentioned, and examples of the lower limit are 99.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 20.0, Examples thereof include 10.0, 5.0, 3.0, 1.0, 0.5, 0.4, 0.3, 0.2, 0.1 and 0.05. The range of the mass ratio between the constituent unit 2 and the constituent unit 6 (mass of the constituent unit 2 / mass of the constituent unit 6) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the mass ratio of the constituent unit 2 to the constituent unit 6 is preferably 0.05 to 100.0 from the viewpoint of suppressing gelation.

Examples of the upper limit of the molar ratio between the constituent unit 2 and the constituent unit 6 (the amount of the substance of the constituent unit 2 / the amount of the substance of the constituent unit 6) are 100.0, 90.0, 80.0, 70.0, 60. 0, 50.0, 40.0, 30.0, 20.0, 10.0, 5.0, 3.0, 1.0, 0.5, 0.4, 0.3, 0.2, Examples of the lower limit are 99.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 20. Examples thereof include 0, 10.0, 5.0, 3.0, 1.0, 0.5, 0.4, 0.3, 0.2, 0.1 and 0.05. The range of the molar ratio of the constituent unit 2 to the constituent unit 6 (the amount of substance of the constituent unit 2 / the amount of substance of the constituent unit 6) can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the molar ratio of the constituent unit 2 to the constituent unit 6 is preferably 0.05 to 100.0 from the viewpoint of suppressing gelation.

(Physical characteristics of resin, etc.)
The weight average molecular weight (Mw) of the resin according to the present invention is not particularly limited, but examples of the upper limit thereof are 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, and so on. 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, 000, 15,000, 13,000, 11,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,500, 5,000, 4,500 and the like can be mentioned. Examples of the lower limit 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. The range of the weight average molecular weight of the resin according to the present invention can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the weight average molecular weight (Mw) of the resin is preferably 4,000 to 500,000.

Examples of the upper limit of the number average molecular weight (Mn) of the resin according to the present invention are 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, Examples include 20,000, 15,000, 10,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, and examples of the lower limit are 95,000, 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 can be mentioned. The range of the number average molecular weight (Mn) of the resin according to the present invention can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the number average molecular weight (Mn) of the resin is preferably 800 to 100,000.

The weight average molecular weight and the number average molecular weight are determined as polystyrene-equivalent values measured under an appropriate solvent by, for example, gel permeation chromatography (GPC).

Examples of the upper limit of the molecular weight distribution (Mw / Mn) are 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, 1.5, etc., and examples of the lower limit 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, 1.0 and the like can be mentioned. The range of the molecular weight distribution (Mw / Mn) of the resin according to the present invention can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the molecular weight distribution (Mw / Mn) is preferably 1.0 to 55.

Examples of the upper limit of the hydroxyl value of the resin according to the present invention include 483, 480, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 5, 1, etc., and examples of the lower limit are 480, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 5, 1, 0 and the like can be mentioned. The range of the hydroxyl value of the resin according to the present invention can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the hydroxyl value of the resin is preferably 0 to 483.

Examples of the upper limit of the acid value of the resin according to the present invention are 799, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 1, etc. Examples of the lower limit include 790, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 1, 0 and the like. The range of the acid value of the resin according to the present invention can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the acid value of the resin is preferably 0 to 799.

Examples of the upper limit of the softening point of the resin according to the present invention include 150, 140, 130, 120, 110, 100, 90, 80 ° C., and examples of the lower limit are 140, 130, 120, 110, 100, 90. , 80, 75 ° C. and the like. The range of the softening point of the resin according to the present invention can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the softening point of the resin is preferably 75 to 150 ° C.

Examples of the upper limit of the intrinsic viscosity (η) with respect to the absolute molecular weight (M) of 50,000 according to the present invention are 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. are mentioned, and examples of the lower limit are 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.12, 0.11, 0.10, Examples thereof include 0.09, 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) with respect to the absolute molecular weight (M) 50,000 of the resin according to the present invention can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the intrinsic viscosity (η) is preferably 0.01 to 0.20.

Examples of the upper limit of the glass transition temperature (Tg) of the resin according to the present invention include 230, 200, 150, 100, 50, 0, −50, −70 ° C., and examples of the lower limit are 225, 200, 150. , 100, 50, 0, -50, -80 ° C and the like. The range of the glass transition temperature (Tg) of the resin according to the present invention can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the glass transition temperature (Tg) is preferably −80 to 230 ° C.

(Resin manufacturing method)
The method for producing a resin according to the present invention comprises a step of polymerizing a (meth) acrylic acid ester and, if necessary, a monomer containing styrene or the like at an appropriate reaction temperature in the presence of a thiol-based chain transfer agent and a polymerization initiator. include.

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

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

In the above production method, additives other than the monomer, the polymerization initiator, and the solvent can be used to the extent that the effects of the present invention are not impaired. Examples of additives other than monomers and polymerization initiators include emulsifiers, ATRP polymerization reagents and the like. When an additive is used, it is usually 1 to 5 parts by mass with respect to 100 parts by mass of the monomer, but less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0.001 parts by mass. It may be less than, less than 0.0001 parts by mass. Further, the resin described in the present disclosure can be produced without using an additive.

（式中、ｎは０～２の整数であり、ｍは０～２の整数であり、ｐは０から7の整数であり、Ｒ^ｂ１～Ｒ^ｂ１４は、それぞれ独立に水素原子、

であり、
Ｒ^ｂ１５～Ｒ^ｂ１６は、それぞれ独立に

であり、Ｒ ^ｂ１７ はそれぞれ独立に、アルキレン基であり、
構造式（Ａ）～（Ｃ）中、Ｒ^ｂ１～Ｒ^ｂ１４から選択される２個以上の基が

であり、
ｑはそれぞれ独立に０～１６の整数であり、Ｒ^１はそれぞれ独立に、水素原子又はアルキル基である。なお、Ｒ^ｂ４、Ｒ^ｂ５、Ｒ^ｂ９、及びＲ^ｂ１３は各構成単位ごとに基が異なっていてもよい。）
である。 (2. Reactive diluent (2))
The above reactive diluent

(In the equation, n is an integer of 0 to 2, m is an integer of 0 to 2, p is an integer of 0 to 7, and R ^b1 to R ^b14 are independently hydrogen atoms, respectively.

And
R ^b15 to R ^b16 are independent of each other.

R ^b17 is an alkylene group independently of each other.
In the structural formulas (A) to (C), two or more groups selected from R ^b1 to R ^b14 are

And
q is an independently integer from 0 to 16, and R ¹ is independently a hydrogen atom or an alkyl group. The groups of R ^b4 , R ^b5 , R ^b9 , and R ^b13 may be different for each structural unit. )
Is.

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

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

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

Examples of pentaerythritol poly (meth) acrylates are pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, and pentaerythritol hexa (meth) acrylate. And so on.

Examples of pentaerythritol polyalkylene oxide-modified 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.

Examples of pentaerythritol polyepoxy-modified acrylates are pentaerythritol diepoxy (meth) acrylate, pentaerythritol triepoxy (meth) acrylate, pentaerythritol tetraepoxy (meth) acrylate, pentaerythritol pentaepoxy (meth) acrylate, and pentaerythritol hexaepoxy. Examples thereof include (meth) acrylate.

Examples of polypentaerythritol poly (meth) acrylates are dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta. Elythritol 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 Examples include deca (meth) acrylate.

Examples of polypentaerythritol polyalkylene oxide-modified (meth) acrylates are dipentaerythritol di (ethylene oxide-modified (meth) acrylate), dipentaerythritol tri (ethylene oxide-modified (meth) acrylate), and 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), di Pentaerythritol 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 (propylene oxide-modified)) Meta) 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) , Pentaerythritol tri (propylene oxide modified (meth) acrylate), tripentae Lithritol tetra (propylene oxide-modified (meth) acrylate), tripentaerythritol penta (propylene oxide-modified (meth) acrylate), tripentaerythritol hexa (propylene oxide-modified (meth) acrylate), tripentaerythritol hepta (propylene oxide-modified (propylene oxide-modified)) Meta) acrylate), tripentaerythritol octa (propylene oxide-modified (meth) acrylate), tripentaerythritol nona (propylene oxide-modified (meth) acrylate), tripentaerythritol deca (propylene oxide-modified (meth) acrylate) and the like. ..

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

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

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

Examples of trimethylolpropane polyalkylene oxide-modified (meth) acrylates include trimethylolpropane di (ethylene oxide-modified (meth) acrylate), trimethylolpropane tri (ethyleneoxide-modified (meth) acrylate), and trimethylolpropane di (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.

Examples of polytrimethylolpropane polyalkylene oxide-modified (meth) acrylates are ditrimethylolpropane di (ethylene oxide-modified (meth) acrylate), ditrimethylolpropane tri (ethylene oxide-modified (meth) acrylate), and ditrimethylolpropane di (propylene). Oxide-modified (meth) acrylate), ditrimethylolpropane tri (propylene oxide-modified (meth) acrylate) and the like can be mentioned.

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

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

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

Examples of polyglycerin poly (meth) acrylates are diglycerin di (meth) acrylate, diglycerin tri (meth) acrylate, diglycerin tetra (meth) acrylate, triglycerin di (meth) acrylate, triglycerin tri (meth) acrylate, and tri. Examples thereof include glycerin tetra (meth) acrylate and triglycerin penta (meth) acrylate.

Examples of glycerin polyalkylene oxide-modified (meth) acrylates are glycerindi (ethylene oxide-modified (meth) acrylate), glycerintri (ethylene oxide-modified (meth) acrylate), glycerinjiri (propylene oxide-modified (meth) acrylate), and glycerin. Examples thereof include tri (propylene oxide-modified (meth) acrylate).

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

Examples of polyglycerin polyalkylene oxide-modified (meth) acrylates are diglycerin di (ethylene oxide-modified (meth) acrylate), diglycerin tri (ethylene oxide-modified (meth) acrylate), and diglycerin tetra (ethylene oxide-modified (meth) acrylate). , Triglycerin 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)) Acrylic) Diglycerin di (propylene oxide-modified (meth) acrylate), diglycerintri (propylene oxide-modified (meth) acrylate), diglycerin tetra (propylene oxide-modified (meth) acrylate), triglycerindi (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.

Examples of polyglycerin polyepoxy-modified (meth) acrylates are diglycerin diepoxy (meth) acrylate, diglycerin triepoxy (meth) acrylate, diglycerin tetraepoxy (meth) acrylate, triglycerin diepoxy (meth) acrylate, and tri. Examples thereof include glycerin triepoxy (meth) acrylate, triglycerin tetraepoxy (meth) acrylate, and triglycerin pentaepoxy (meth) acrylate.

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

Examples of alkylene di (meth) acrylates are 1,2-ethylenediol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-. Pentandiol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol Examples thereof include di (meth) acrylate and 1,10-decanediol di (meth) acrylate.

Examples of alkylenedialkylene oxide-modified (meth) acrylates are 1,2-ethylenedioldi (ethyleneoxide-modified (meth) acrylate), 1,3-propanedioldi (ethyleneoxide-modified (meth) acrylate), 1,4. -Butandioldi (ethyleneoxide-modified (meth) acrylate), 1,5-pentanedioldi (ethyleneoxide-modified (meth) acrylate), 1,6-hexanedioldi (ethyleneoxide-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-propanedioldi (propylene oxide-modified (meth) acrylate), 1,4-Butanediol di (propylene oxide-modified (meth) acrylate), 1,5-pentanediol di (propylene oxide-modified (meth) acrylate), 1,6-hexanediol di (propylene oxide-modified (meth) acrylate) , 1,7-Heptanediol di (propylene oxide-modified (meth) acrylate), 1,8-octanediol di (propylene oxide-modified (meth) acrylate), 1,9-nonanediol di (propylene oxide-modified (meth) acrylate) ), 1,10-decanediol di (propylene oxide-modified (meth) acrylate) and the like.

Examples of alkylene diepoxy-modified (meth) acrylates are 1,2-ethylenediol diepoxy (meth) acrylates, 1,3-propanediol diepoxy (meth) acrylates, and 1,4-butanediol diepoxy (meth) acrylates. , 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.

(3. Varnish composition)
The present disclosure provides a varnish composition containing the above resin and the above reactive diluent.

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

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

Examples of the upper limit of the mass ratio (mass of resin / mass of reactive diluent) between the resin and the reactive diluent in the varnish composition are 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 examples of the lower limit Is 1.49, 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 and the like can be mentioned. The range of the mass ratio (mass of resin / mass of reactive diluent) between the resin and the reactive diluent in the varnish composition can be appropriately set (for example, selected from the above upper and lower limit values). In one embodiment, the mass ratio of the resin to the reactive diluent in the varnish composition is preferably 0.11 to 1.50 from the viewpoint of film strength and curability.

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

The varnish composition may contain components other than the resin and the reactive diluent (hereinafter, also referred to as “other components”). Examples of the upper limit of the content of other components with respect to the total mass of the resin and the reactive diluent include 20, 15, 10, 5, 1, 0.5, 0.1, 0.01 mass% and the like, and the lower limit. Examples of the above include 15, 10, 5, 1, 0.5, 0.1, 0.01, 0% by mass and the like. The range of the content of other components with respect to the total mass of the resin and the reactive diluent can be set as appropriate (eg, selected from the above upper and lower limit values). In one embodiment, the other components are preferably 0 to 20% by weight based on the total weight of the resin and the reactive diluent.

Examples of the upper limit of the content of other components with respect to the total mass of the varnish composition include 17, 15, 10, 5, 1, 0.5, 0.1, 0.01 mass% and the like, and the lower limit. Examples of the above include 15, 10, 5, 1, 0.5, 0.1, 0.01, 0% by mass and the like. The range of content of other components can be set as appropriate (eg, selected from the above upper and lower limit values). In one embodiment, the content of the other components is preferably 0 to 17% by mass with respect to the total mass of the entire varnish composition.

In one embodiment, the varnish composition according to the present invention is an active energy ray curable type and is used, for example, for inks, preferably offset inks. Since offset printing is used while transferring ink from roller to roller, it is necessary to use high-viscosity ink. Since the viscosity of the ink produced by using the varnish composition according to the present invention is high, it is suitable for offset ink. Since ink jet printing is a printing method in which ink is sucked from a tank and ejected from a fine nozzle, it is known that it is necessary to use low-viscosity ink.

In one embodiment, the varnish composition according to the present invention is a varnish composition for a non-hydrophilic substrate, which is preferably used for those whose substrate (support) is not hydrophilic.

(4. Offset printing ink)
The present disclosure provides an offset printing ink containing the above varnish composition, optionally a photopolymerization initiator, and a pigment.

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

The pigment used in the offset printing ink according to the present invention is not particularly limited, and an inorganic or organic pigment usually used can be blended. Specific examples include white pigments such as titanium oxide, zinc flower, lead white, lithobon, and antimony oxide, black pigments such as aniline black, iron black, and carbon black, yellow lead, yellow iron oxide, titanium yellow, and Hansa yellow (10G,). 5G, 3G, etc.), yellow pigments such as disazo yellow, benzine yellow, permanent yellow, orange pigments such as chrome vermillion, permanent orange, vulcan first orange, indance lembrilliant orange, iron oxide, permanent brown, para brown, etc. of brown pigment, red iron oxide, cadmium red, antimony vermilion, permanent red, rhodamine lake, alizarin lake, thioindigo red, PV Carmine, mono light fast red, red pigments such as quinacridone red pigment, cobalt violet, manganese violet, fast violet , Methyl Violet Lake, Indance Rem Brilliant Violet, Dioxazine Violet, etc. , Blue pigments such as indigo, chrome green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malakite green lake, phthalocyanine green, polychlorobrom copper phthalocyanine and other green pigments, as well as various fluorescent pigments, Examples include metal powder pigments. These pigments are preferably blended in the range of about 1 to 50 parts by mass with respect to 100 parts by mass of the offset printing ink, and more preferably 5 to 30 parts by mass.

The offset printing ink according to the present invention is an active energy ray-curable type and contains a resin for printing ink, a polymerizable monomer and a pigment according to the present invention, but further includes a surface conditioner, a defoaming agent, and light. A sensitizer, an antioxidant, a light stabilizer, and a leveling agent can also be used. These optional components are in an amount 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 (specifically, 95, 90, 80, 50, 40, 30, 20, 10, 5, 2.1, 0.1 part by mass or less) is preferable. Further, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine and N-nitrosophenylhydroxylamine aluminum salt can be blended. When a polymerization inhibitor is blended, it is preferably used in the range of about 0.01 to 2 parts by mass with respect to the offset printing ink.

(5. Printed matter)
The present disclosure provides a printed matter having a cured layer of the offset printing ink.

As the base material, various known materials can be used without particular limitation. Examples of base materials include paper (art paper, cast coated paper, foam paper, PPC paper, high quality coated paper, kraft paper, polyethylene laminated paper, glassin paper, etc.), plastic base materials (polyolefin, polycarbonate, polymethacrylate, polyester, etc.). (Epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin, etc.) and the like can be mentioned.

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

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

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to the embodiments and examples specifically described in the present disclosure, and is limited only by the scope of claims. In the following, "parts" and "%" mean parts by mass and% by mass, respectively, unless otherwise specified.

The weight average molecular weight and the number average molecular weight were determined as polystyrene-equivalent values measured under a THF solvent by gel permeation chromatography (GPC). An HLC-8020 (manufactured by Tosoh Corporation) was used as the GPC apparatus, and a TSKgel superHZM (manufactured by Tosoh Corporation) was used as the column. The molecular weight distribution (Mw / Mn) was calculated from the obtained number average molecular weight and weight average molecular weight.

Production Example 1
400 g of xylene was charged in a reaction vessel equipped with a stirrer, a reflux condenser with a water divider, a thermometer and a dropping funnel. Add 390 g of methyl methacrylate, 90 g of acrylic acid, 60 g of 2-ethylhexyl acrylate and 60 g of pentaerythritol tetrakis (3-mescaptopropionate) to the dropping funnel, and add 6 g of azobisisobutyronitrile as an initiator. A dropping polymerization reaction was carried out under stirring at 90 ° C. for 2 hours, and the temperature was kept warm for 6 hours. Then, the temperature was raised to 170 ° C., the solvent was distilled off while continuing stirring at normal pressure, the pressure was further reduced to 50 mHg or less at the same temperature, and the solvent was completely distilled off to obtain 600 g of the resin 1. The weight average molecular weight (Mw) was 10,000, the number average molecular weight (Mn) was 3,570, and Mw / Mn was 2.8. The results are shown in Table 1.

Production Examples 2 to 5 and Comparative Production Examples 1 and 2.
Resins 2 to 5 and comparative resins 1 and 2 were manufactured by the same procedure as in Production Example 1 except that the resin composition was changed to that shown in Table 1.

The abbreviations in Table 1 are as follows.
A-1: Methyl Methacrylate A-2: Acrylic Acid A-3: Butyl methacrylate A-4: 2-Ethylhexyl acrylate B-1: Styrene C-1: Acryloylmorpholin C-2: N, N-Dimethylacrylamide C- 3: N, N-dimethylaminoethyl methacrylate D-1: 2-hydroxyethyl methacrylate D-2: 2-hydroxypropyl acrylate D-3: 2-hydroxy-3-phenoxypropyl acrylate E-1: trimethyl propanthris ( 3-Mercaptopropionate)
E-2: Tris-[(3-mercaptopropionyloxy) ethyl] -isocyanurate E-3: pentaerythritol tetrakis (3-mercaptopropionate)
E-4: Dipentaerythritol hexakis (3-mercaptopropionate)
F-1: 2,2'-azobis (2-methylbutyronitrile)
F-2: t-butyl peroxy-2-ethylhexanoate

Example 1
The obtained resin 1 (14.5 g) was used as a reactive diluent to contain dipentaerythritol (29.5 g), trimethylolpropane tetraacrylate (26.0 g), and trimethylolpropane triacrylate (10.0 g), respectively. In addition, 0.1 g of methquinone, which is a polymerization inhibitor, was added and dissolved by stirring at 120 ° C. for 1 hour under air bubbling to obtain 65.6 g of an offset printing varnish. To 65.6 g of the obtained varnish, 15 g of MA100, which is a black pigment, and 5 g of Irgacure 907, which is a photopolymerization initiator, are charged, and after smelting with three rollers, a tack at 40 ° C. and 400 rpm is used. The offset printing ink shown in Example 1 of Table 2 was obtained by appropriately adjusting the value to 9 ± 0.5.

Examples 2 to 5, Comparative Examples 1 to 2
It was prepared in the same manner as in Example 1 except that the ratio of the resin and the reactive diluent was changed.

The abbreviations in Table 2 are as follows.
G-1: Dipentaerythritol Tetraacrylate G-2: Ditrimethylolpropane Tetraacrylate G-3: Trimethylolpropane Triacrylate

(Measurement of liquidity)
1.30 ml of ink was placed on a glass plate tilted at 60 °, and the distance through which the ink flowed after being left for 30 minutes was measured. The evaluation criteria are shown below.
◯: 201 mm or more Δ: 200 to 101 mm
×: 100 mm or less

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

Claims (8)

Configuration unit 1

(In the formula, R ¹ is a hydrogen or methyl group and ^Ra is a hydrogen or alkyl group).
And constituent unit 2

(In the formula, R ^b is an alkylene group)
Including
The structural unit 2 is one or more selected from the group consisting of the structural unit 2B, the structural unit 2C, and the structural unit 2D, and the structural unit 1 and the structural unit 2 are bonded by a covalent bond. A varnish composition for offset inks comprising the resin (1) and the reactive diluent (2).
Configuration unit 2B

(In the formula, R ^b3 to R ^b5 are independently alkylene groups, and R ^B2 is a trivalent hydrocarbon group or

(In the formula, R ^ba to R ^bc are independently alkylene groups).
Is. )
Configuration unit 2C

(In the formula, R ^b6 to R ^b9 are independently alkylene groups, and R ^B3 is a tetravalent hydrocarbon group.)
Configuration unit 2D

(In the formula, R ^b10 to R ^b15 are independently alkylene groups, and R ^B4 is a hexavalent hydrocarbon group or

Is. ) The resin (1) is the constituent unit 3

(In the formula, R ¹ is a hydrogen or methyl group, and R ^c1 to R ^c5 are independently selected from the group consisting of hydrogen, an alkyl group and an aryl group.)
The varnish composition for offset ink according to claim 1. The resin (1) is the constituent unit 4

(In the formula, R ¹ is a hydrogen or methyl group, R ^d is CONR ^d1 R ^d2 , COO (CH ₂ ) ₂ NR ^d1 R ^d2 and

It is a group selected from the group consisting of
In the formula, R ^d1 and R ^d2 are an alkyl group or hydrogen, or R ^d1 and R ^d2 are groups that form a ring structure together, k is an integer of 1 or more, and R ^d3 is. , Hydrogen, methyl group or hydroxyl group, where 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 the hydroxyl group. .. )
The varnish composition for offset ink according to claim 1 or 2. The resin (1) is a constituent unit 5

(In the formula, R ^e1 , R ^e2 , and R ^e3 are independently nitrile groups, alkyl groups, polar group-substituted alkyl groups, alkenyl groups, or polar groups, respectively.)
The varnish composition for offset ink according to any one of claims 1 to 3, wherein the varnish composition for offset ink is contained at the end of the polymer chain. The resin (1) is a constituent unit 6

(In the formula, R ^f is an acyl group, an alkyl group, or an aryl group.)
The varnish composition for offset ink according to any one of claims 1 to 4, wherein the varnish composition for offset ink is contained at the end of the polymer chain. The reactive diluent (2)

(In the equation, n is an integer of 0 to 2, m is an integer of 0 to 2, p is an integer of 0 to 7, and R ^b1 to R ^b14 are independently hydrogen atoms, respectively.

And
R ^b15 to R ^b16 are independent of each other.

R ^b17 is an alkylene group independently of each other.
In the structural formulas (A) to (C), two or more groups selected from R ^b1 to R ^b14 are

And
q is an independently integer from 0 to 16, and R ¹ is independently a hydrogen atom or an alkyl group. The groups of R ^b4 , R ^b5 , R ^b9 , and R ^b13 may be different for each structural unit. )
The varnish composition for offset ink according to any one of claims 1 to 5. An offset printing ink comprising the varnish composition for offset ink and the pigment according to any one of claims 1 to 6. A printed matter having a cured layer of the offset printing ink according to claim 7.