WO2011093166A1

WO2011093166A1 - Method for producing relief printing plate

Info

Publication number: WO2011093166A1
Application number: PCT/JP2011/050710
Authority: WO
Inventors: 圭一足立
Original assignee: 富士フイルム株式会社
Priority date: 2010-01-27
Filing date: 2011-01-18
Publication date: 2011-08-04
Also published as: JP2011152719A

Abstract

Disclosed is a method for producing a relief printing plate, wherein a rinsing liquid for the production of a relief printing plate, which is capable of easily removing dust produced on the printing plate during the engraving and has a small effect on the relief printing plate, is used. Specifically disclosed is a method for producing a relief printing plate, which is characterized by comprising, in the following order: a step of preparing a relief printing original plate that has, on a supporting body, a relief-forming layer containing a non-elastomer binder polymer, a plasticizer and a photothermal converter; a step of engraving the relief printing original plate by exposure to light using a laser; and a step of removing engraving dust with a rinsing liquid for the production of a relief printing plate, said dust being produced by the engraving. The method for producing a relief printing plate is also characterized in that the rinsing liquid for the production of a relief printing plate contains a nonionic surfactant.

Description

Making a relief printing plate

The present invention relates to a method for making a relief printing plate.

As a plate making method of a relief printing plate, many so-called “direct engraving CTP methods” have been proposed in which a relief forming layer of a relief printing plate precursor is directly engraved with a laser to make a plate (see Patent Document 1, etc.). In such a plate making method, engraving debris generated during engraving is removed with a cleaning solution after engraving with a laser (see, for example, Patent Document 2).
As a technique for improving the rinsing property of debris after engraving, a technique has been proposed in which porous inorganic fine particles are contained in a relief forming layer, and liquid debris is adsorbed on the particles to improve removability (for example, patents). Reference 3).
Moreover, in the Example described in Patent Document 4, an aspect in which engraving residue is cleaned with an alkaline cleaning solution is also disclosed.

US Pat. No. 5,798,202 US Patent Application Publication No. 2008/0061036 JP 2004-174758 A International Publication No. 2009/084682 Pamphlet

However, with the rinsing liquid used in the conventional method for making a relief printing plate, it has been difficult to sufficiently remove the residue on the plate generated during engraving. Furthermore, the relief printing plate may be greatly affected by the rinsing liquid because the relief layer of the relief printing plate absorbs the rinsing liquid and swells.

An object of the present invention is to provide a plate making method of a relief printing plate using a rinsing liquid for relief printing plate making, which can easily remove the residue on the plate generated during engraving and has a small influence on the relief printing plate. It is.

The above-described problems of the present invention have been solved by the means described in <1> or <5> below. It is described below together with <2> to <4> and <6> to <11>, which are preferred embodiments.
<1> A step of preparing a relief printing plate precursor having a relief-forming layer containing a non-elastomer binder polymer, a plasticizer, and a photothermal conversion agent on a support, and the relief printing plate precursor is exposed by laser exposure. A step of engraving and a step of removing engraving residue generated by engraving with a rinsing liquid for relief printing plate making in this order, and the rinsing liquid for relief printing plate making contains a nonionic surfactant A method for making a relief printing plate characterized by
<2> The above-mentioned rinsing liquid for making a relief printing plate contains at least one nonionic surfactant selected from the group consisting of compounds represented by the following formulas (1-1) to (1-6): The plate making method of the relief printing plate as described in <1>,

(In the formula (1-1) and the formulas (1-3) to (1-5), R represents an alkyl group having 6 to 23 carbon atoms, and in the formula (1-1), n is 3 to 100. In formula (1-2), n represents an integer of 3 to 30, and in formulas (1-3) and (1-4), m and n each satisfy 3 ≦ m + n ≦ 50. And in formulas (1-5) and (1-6), X represents a hydrogen atom or a methyl group, and in formula (1-5), n is an integer of 3 to 50 In formula (1-6), l, m and n each independently represents an integer of 2 to 30.)

<3> The method for making a relief printing plate according to <1> or <2> above, wherein the content of the nonionic surfactant in the rinsing liquid for relief printing plate making is 0.1 to 20% by weight,
<4> The above-mentioned <1> to <1>, wherein the rinsing liquid for relief printing plate making contains at least one solvent selected from the group consisting of alcohol solvents, ether solvents, glycol solvents, and glycol ether solvents. <3> A method for making a relief printing plate according to any one of the above,
<5> A step of preparing a relief printing plate precursor having a relief-forming layer containing a non-elastomer binder polymer, a plasticizer, and a photothermal conversion agent on a support, and the relief printing plate precursor is exposed by laser exposure. A step of engraving, and a step of removing engraving residue generated by engraving with a rinsing liquid for relief printing plate making in this order, wherein the rinsing liquid for relief printing plate making comprises an alcohol solvent, an ether solvent, A process for making a relief printing plate comprising a glycol solvent and at least one solvent selected from the group consisting of glycol ether solvents,
<6> The method for making a relief printing plate according to the above <4> or <5>, wherein the content of the solvent in the rinsing liquid for making a relief printing plate is 1 to 40% by weight,
<7> The method for making a relief printing plate according to any one of the above <1> to <6>, wherein the pH of the rinsing liquid for relief printing plate making is 9 or more,
<8> The method for making a relief printing plate according to any one of the above <1> to <7>, wherein the binder polymer is polyvinyl butyral and / or a derivative thereof,
<9> The method for making a relief printing plate according to any one of the above <1> to <8>, wherein the relief forming layer contains a compound containing a group represented by the following formula (I):
* -M (R ¹ ) (R ² ) _n (I)
(In the formula (I), R ¹ represents OR ³ or a halogen atom, M represents Si, Ti, or Al. When M is Si, n is 2, and when M is Ti, n is 2. And when M is Al, n is 1, each R ² independently represents a hydrocarbon group, OR ³ or a halogen atom, R ³ represents a hydrogen atom or a hydrocarbon group, and * (Represents the bonding position with other structures)
<10> The plate making method of a relief printing plate according to <9>, wherein the relief forming layer contains a compound containing a group represented by the following formula (i):
* -Si (OR ³ ) (R ² ) ₂ (i)
(In formula (i), two R ^{2 s} each independently represent a hydrocarbon group, OR ³ or a halogen atom, R ³ represents a hydrogen atom or a hydrocarbon group, and * represents a bonding position with another structure. Represents.)
<11> The above-mentioned <1> to <10, wherein the engraving step is a step of engraving an exposed area by scanning exposure of the relief printing plate precursor using a fiber-coupled semiconductor laser having a maximum wavelength of 700 to 1,300 nm. The plate making method of the relief printing plate as described in any one of>.

According to the present invention, there is provided a plate making method of a relief printing plate using a rinsing liquid for making a relief printing plate, which can easily remove the residue on the plate generated during engraving and has little influence on the relief printing plate. I was able to.

The method for making a relief printing plate of the present invention comprises a step of preparing a relief printing plate precursor for laser engraving having a relief forming layer containing a non-elastomeric binder polymer, a plasticizer, and a photothermal conversion agent on a support, the laser The relief printing plate making includes the steps of engraving the relief printing plate precursor for engraving by exposure using a laser, and removing the engraving residue generated by engraving with a rinse solution for relief printing plate making in this order. The rinsing liquid for use is a nonionic surfactant and / or at least one solvent selected from the group consisting of alcohol solvents, ether solvents, glycol solvents, and glycol ether solvents (hereinafter also referred to as specific solvents). .).
Hereinafter, the rinsing liquid for relief printing plate making used in the method for making a relief printing plate of the present invention will be described first.
In the present invention, the description of “lower limit to upper limit” representing a numerical range represents “lower limit or higher and lower limit or lower”, and the description of “upper limit to lower limit” represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit.

(Rinse for relief printing plate making)
The rinsing liquid for relief printing plate making used in the present invention (hereinafter also referred to as “the rinsing liquid for relief printing plate making of the present invention”, “the rinsing liquid of the present invention”, or simply “the rinsing liquid”), It contains a nonionic surfactant and / or a specific solvent.
The rinsing liquid for relief printing plate making preferably contains at least one nonionic surfactant selected from the group consisting of compounds represented by the following formulas (1-1) to (1-6).

<Compounds Represented by Formula (1-1) to Formula (1-6)>
The rinsing liquid for relief printing plate making of the present invention is selected from the group consisting of compounds represented by the above formulas (1-1) to (1-6) as a nonionic surfactant (nonionic surfactant). It is preferable to contain at least one selected from the above.
In addition, the rinsing liquid for relief printing plate making of the present invention may be used alone or in combination of any one of the compounds represented by the formulas (1-1) to (1-6). May be used in combination.

In the formula (1-1) and the formulas (1-3) to (1-5), R represents an alkyl group having 6 to 23 carbon atoms, and the carbon number in R is 6 to 20 Preferably, it is 8-18. The alkyl group represented by R may be linear or branched.

In the formula (1-5) and formula (1-6), X represents a hydrogen atom or a methyl group. In the formula (1-6) in which a plurality of X are present in the molecule, the plurality of X may be the same or different from each other.

In the above formulas (1-1) to (1-6), l, m, or n represents the number of repeating ethylene oxide (EO) units.
In the formula (1-1), n represents an integer of 3 to 100, preferably an integer of 4 to 30, and more preferably an integer of 4 to 18.
In the formula (1-2), n represents an integer of 3 to 30, preferably an integer of 5 to 23, and more preferably an integer of 7 to 18.
M and n in the formula (1-3) and the formula (1-4) satisfy 3 ≦ m + n ≦ 50 and represent an integer of 0 or more, preferably 4 ≦ m + n ≦ 30, and 8 ≦ It is more preferable to satisfy m + n ≦ 20.
In the formula (1-5), n represents an integer of 3 to 50, preferably an integer of 5 to 50, and more preferably an integer of 10 to 50.
In the formula (1-6), l, m, and n each independently represents an integer of 2 to 30, preferably satisfying 10 ≦ l + m + n ≦ 45, and more preferably satisfying 10 ≦ l + m + n ≦ 40.

Specific examples of the compound represented by the formula (1-1) include compounds in which R is C ₈ H ₁₇ and n is 4, 7, or 12, R is C ₁₂ H ₂₅ and n is And a compound in which R is C ₂₀ H ₄₁ and n is 15.
Specific examples of the compound represented by the formula (1-2) include compounds in which n is 10, 13, or 18.
Specific examples of the compound represented by the formula (1-3) include compounds in which R is C ₁₂ H ₂₅ and m + n is 10 or 20.
Specific examples of the compound represented by the formula (1-4) include compounds in which R is C ₁₂ H ₂₅ and m + n is 10 or 20.
Specific examples of the compound represented by the formula (1-5) include a compound in which R is C ₁₂ H ₂₅ and n is 10, and a compound in which R is C ₂₀ H ₄₁ and n is 15. Can be mentioned.
Specific examples of the compound represented by the formula (1-6) include compounds in which l + m + n is 30 or 40.

<Other nonionic surfactants>
The rinsing liquid for relief printing plate making of the present invention may be used in place of or together with the nonionic surfactant selected from the group consisting of the compounds represented by formulas (1-1) to (1-6): It is also preferable to contain a nonionic surfactant selected from the group consisting of compounds represented by formulas (1-7) to (1-17).

(In Formula (1-7), m represents an integer of 1 to 50, n represents an integer of 0 to 50, and in Formula (1-8), R represents an alkyl group having 1 to 23 carbon atoms; n represents an integer of 1 to 30, and in formula (1-9), R represents an alkyl group having 5 to 50 carbon atoms, n represents an integer of 1 to 30, and R in formula (1-10) Represents an alkyl group having 1 to 12 carbon atoms, and in formula (1-11), A represents a hydrogen atom or —COR, R represents an alkyl group having 1 to 23 carbon atoms, and n represents an integer of 1 to 30 In formula (1-12), R represents an alkyl group having 1 to 12 carbon atoms.)

(In the formulas (1-13) and (1-14), R represents an alkyl group having 1 to 20 carbon atoms. In the formula (1-15), X represents a hydrogen atom or —COR, and R represents carbon. Represents an alkyl group of several 10 to 50, n represents an integer of 3 to 30, and in formula (1-16), R represents an alkyl group of 3 to 50 carbon atoms, and each of l, m, and n represents (20 ≦ l + m + n ≦ 80 is satisfied and represents an integer of 0 or more, and in formula (1-17), R represents an alkyl group having 1 to 20 carbon atoms.)

The rinsing liquid for relief printing plate making of the present invention is represented by the compounds represented by the formulas (1-1) to (1-6) and the formulas (1-7) to (1-17). Any one of these compounds may be used alone, or two or more may be used in combination.

In the formula (1-8), R represents an alkyl group having 1 to 23 carbon atoms, and the carbon number in R is preferably 4 to 16, and more preferably 8 to 12.
In the formula (1-9), R represents an alkyl group having 5 to 50 carbon atoms, and the carbon number in R is preferably 5 to 40, and more preferably 5 to 30.
In the formula (1-10), R represents an alkyl group having 1 to 12 carbon atoms, and the number of carbon atoms in R is preferably 1 to 8, and more preferably 1 to 6.
In the formula (1-11), R represents an alkyl group having 1 to 23 carbon atoms, and the number of carbon atoms in R is preferably 4 to 16, and more preferably 8 to 12.
In the formula (1-12), R represents an alkyl group having 1 to 12 carbon atoms, and the number of carbon atoms in R is preferably 1 to 8, and more preferably 1 to 6.
In the formulas (1-13) and (1-14), R represents an alkyl group having 1 to 20 carbon atoms, and the carbon number in R is preferably 2 to 12, and preferably 8 to 12. Is more preferable.
In the formula (1-15), R represents an alkyl group having 10 to 50 carbon atoms, and the carbon number in R is preferably 12 to 40, and more preferably 12 to 20.
In the formula (1-16), R represents an alkyl group having 3 to 50 carbon atoms, and the carbon number in R is preferably 15 to 50, and more preferably 20 to 40.
In the formula (1-17), R represents an alkyl group having 1 to 20 carbon atoms, and the number of carbon atoms in R is preferably 3 to 15, and more preferably 3 to 8.
In addition, the alkyl group represented by R in the above formulas may be linear or branched.

In the formula (1-11), A represents a hydrogen atom or —COR. In the formula (1-15), X represents a hydrogen atom or —COR. In the formula (1-11) in which a plurality of R are present in the molecule, when A represents —COR, and in the formula (1-15), X represents —COR, the plurality of R may be the same as each other. May be different.

In the formula (1-7), m represents the number of repeating propylene oxide group (PO group) units, and n represents the number of repeating EO group units.
In the formula (1-7), m represents an integer of 1 to 50, n represents an integer of 0 to 50, and m is preferably an integer of 3 to 30, more preferably an integer of 5 to 20. Preferably, n is an integer of 0 to 50, more preferably an integer of 5 to 20.
In the formula (1-8), formula (1-9), formula (1-11), formula (1-15), and formula (1-16), l, m, or n represents the number of repeating EO group units. Represents.
N in the formula (1-8) represents an integer of 1 to 30, preferably an integer of 3 to 20, and more preferably an integer of 5 to 15.
N in the formula (1-9) represents an integer of 1 to 30, preferably an integer of 3 to 20, and more preferably an integer of 5 to 15.
N in the formula (1-11) represents an integer of 1 to 30, preferably an integer of 3 to 25, and more preferably an integer of 5 to 20.
N in the formula (1-15) represents an integer of 3 to 30, preferably an integer of 6 to 20, and more preferably an integer of 8 to 16.
In the formula (1-16), l, m, and n each satisfy 20 ≦ l + m + n ≦ 80 and represent an integer of 0 or more, preferably 30 ≦ l + m + n ≦ 60, and satisfy 40 ≦ l + m + n ≦ 50. It is more preferable.

Specific examples of the compound represented by the formula (1-7) include compounds in which m is 7 and n is 5.
Specific examples of the compound represented by the formula (1-8) include compounds in which R is C ₈ H ₁₇ and n is 10.
Specific examples of the compound represented by the formula (1-9) include compounds in which R is C ₈ H ₁₇ and n is 15.
Specific examples of the compound represented by the formula (1-10) include compounds in which R is C ₆ H ₁₃ .
Specific examples of the compound represented by the formula (1-11) include compounds in which R is C ₁₂ H ₂₅ , A is a hydrogen atom, and n is 12.
Specific examples of the compound represented by the formula (1-12) include compounds in which R is C ₄ H ₉ .
Specific examples of the compound represented by the formula (1-13) include compounds in which R is C ₁₂ H ₂₅ .
Specific examples of the compound represented by the formula (1-14) include compounds wherein R is C ₁₀ H ₂₁ .
Specific examples of the compound represented by the formula (1-15) include a compound in which R is C ₁₂ H ₂₅ and n is 12, and a compound in which R is C ₁₆ H ₃₃ and n is 10. Can be mentioned.
Specific examples of the compound represented by the formula (1-16) include compounds in which R is C ₂₀ H ₄₁ and l, m, and n are each 15.
Specific examples of the compound represented by the formula (1-17) include compounds in which R is C ₈ H ₁₇ .

The total content of the nonionic surfactant containing the compounds represented by the formulas (1-1) to (1-17) in the rinsing liquid for relief printing plate making of the present invention is 0.1 to 20% by weight. It is preferably 1 to 15% by weight, more preferably 3 to 12% by weight. When the addition amount is within the above range, good rinsing properties can be obtained.

The HLB (Hydrophile-Lipophile Balance) value of the nonionic surfactant contained in the rinsing solution for relief printing plate making of the present invention is preferably 8 to 20, and more preferably 10 to 17. The HLB value is calculated according to the Griffin equation. When the HLB value is within the above range, the surfactant itself has water solubility, and the affinity of the engraving residue with the hydrophobic substance is improved. When the HLB value is 8 or more, the surfactant has sufficient water solubility and is excellent in solubility in water. On the other hand, when the HLB value is 20 or less, the dispersibility of the hydrophobic material of engraving residue is excellent.

<Anionic surfactant>
In the rinsing liquid for relief printing plate making of the present invention, an anionic surfactant can be used in combination with the nonionic surfactant, or an anionic surfactant can be used alone. The anionic surfactant preferably contains a compound selected from the group consisting of compounds represented by the following formulas (2-1) to (2-10).

(In the formulas (2-1) to (2-10), M represents an alkali metal or an alkaline earth metal, and the formulas (2-1) to (2-5) and (2-7) to In (2-10), R represents an alkyl group having 6 to 20 carbon atoms, and in formula (2-6), R ¹ to R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Wherein at least one of R ¹ to R ³ represents an alkyl group having 1 to 8 carbon atoms, and in formula (2-4), m and n each independently represents an integer of 1 to 10, In (2-5), n represents an integer of 1 to 10.)

In the formulas (2-1) to (2-5) and formulas (2-7) to (2-10), R represents an alkyl group having 6 to 20 carbon atoms, and the carbon number in R is 8 Is preferably 18 and more preferably 8-16. The alkyl group represented by R may be linear or branched.
In the formula (2-6), R ¹ to R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and at least one of R ¹ to R ³ has 1 to 8 carbon atoms. Represents an alkyl group. If R ¹ ~ R ³ in the formula (2-6) represents an alkyl group having 1 to 8 carbon atoms, the number of carbon atoms in R ¹ ~ R ³ is preferably 2-5, is 3-4 It is more preferable. The alkyl group represented by R ¹ to R ³ may be linear or branched.

In the above formulas (2-1) to (2-10), M represents an alkali metal or an alkaline earth metal. Examples of the alkali metal include Li, Na, and K. Examples of the alkaline earth metal include Mg and Ca. When M is an alkaline earth metal, the compounds represented by formulas (2-1) to (2-10) exist as dimers.

M and n in the formula (2-4) represent the number of repeating methylene group units, and n in the formula (2-5) represents the number of repeating EO group units.
M and n in the formula (2-4) each independently represent an integer of 1 to 10, preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.
N in the formula (2-5) represents an integer of 1 to 10, preferably an integer of 1 to 6, and more preferably an integer of 2 to 4.

Specific examples of the compound represented by the formula (2-1) include compounds in which R is C ₁₂ H ₂₅ and M is Na.
Specific examples of the compound represented by the formula (2-2) include compounds in which R is C ₁₂ H ₂₅ and M is Na.
Specific examples of the compound represented by the formula (2-3) include compounds in which R is C ₈ H ₁₇ and M is Na.
Specific examples of the compound represented by the formula (2-4) include compounds in which R is C ₁₁ H ₂₃ , M is Na, and m and n are both 2.
Specific examples of the compound represented by the formula (2-5) include compounds in which R is C ₈ H ₁₇ , M is Na, and n is 2.
Specific examples of the compound represented by the formula (2-6) include compounds in which R ¹ is C ₄ H ₉ , R ² and R ³ are both hydrogen atoms, M is Na, and R ¹ to R ³ are any And C ₃ H ₇ , a compound in which M is Na, a compound in which R ¹ and R ² are both C ₄ H ₉ , R ³ is a hydrogen atom, and M is Na.
Specific examples of the compound represented by the formula (2-7) include compounds in which R is C ₁₁ H ₂₃ and M is Na.
Specific examples of the compound represented by the formula (2-8) include compounds wherein R is C ₁₂ H ₂₅ .
Specific examples of the compound represented by the formula (2-9) include compounds in which R is C ₁₂ H ₂₅ and M is Na.
Specific examples of the compound represented by the formula (2-10) include compounds in which R is C ₁₂ H ₂₅ and M is Na.

The rinsing liquid for relief printing plate making of the present invention may be any one of the anionic surfactants represented by the above formulas (2-1) to (2-10). More than one species may be used in combination.
The total content of the anionic surfactant containing the compounds represented by the formulas (2-1) to (2-10) in the rinsing liquid for relief printing plate making of the present invention is 0.1 to 20 wt. %, Preferably 1 to 15% by weight, more preferably 3 to 12% by weight.

<Cationic surfactant>
In the rinsing liquid for relief printing plate making of the present invention, a cationic surfactant can be used in combination with the nonionic surfactant, or a cationic surfactant can be used alone. The anionic surfactant preferably contains a compound selected from the group consisting of compounds represented by the following formulas (3-1) to (3-3).

(In the formulas (3-1) to (3-3), R represents an alkyl group having 6 to 20 carbon atoms, and A ⁻ represents a counter anion.)

In the formulas (3-1) to (3-3), R represents an alkyl group having 6 to 20 carbon atoms, and the carbon number in R is preferably 8 to 16, and preferably 12 to 16. Is more preferable. In the formulas (3-2) and (3-3) in which a plurality of R are present in the molecule, the plurality of Rs may be the same or different from each other. The alkyl group represented by R may be linear or branched.
A ⁻ in the formulas (3-1) to (3-3) represents a counter anion, for example, a halogen ion. Examples of the halogen ion include Cl ⁻ , Br ⁻ , and I ⁻ .

Specific examples of the compound represented by the formula (3-1) include compounds in which R is C ₁₂ H ₂₅ and A ⁻ is Cl ⁻ .
Specific examples of the compound represented by the formula (3-2) include compounds in which R is C ₁₂ H ₂₅ and A ⁻ is Cl ⁻ .
Specific examples of the compound represented by the formula (3-3) include compounds in which R is C ₈ H ₁₇ and A ⁻ is Cl ⁻ .

The rinsing liquid for relief printing plate making of the present invention may be any one of the cationic surfactants represented by the above formulas (3-1) to (3-3). More than one species may be used in combination.
The total content of the cationic surfactant containing the compounds represented by formulas (3-1) to (3-3) in the rinsing liquid for relief printing plate making of the present invention is 0.1 to 20% by weight. Preferably, it is 1 to 15% by weight, more preferably 3 to 12% by weight.

The relief printing plate rinsing liquid of the present invention preferably contains water as a main component.

The rinsing liquid for relief printing plate making of the present invention preferably contains at least one solvent selected from the group consisting of alcohol solvents, ether solvents, glycol solvents, and glycol ether solvents. Rinsability can be further improved by using such a solvent in combination with the nonionic surfactant. Moreover, you may use a solvent together with the said anionic surfactant or a cationic surfactant.
The rinsing liquid for relief printing plate making of the present invention contains not only the solvent and the nonionic surfactant, the anionic surfactant or the cationic surfactant, but also these surfactants. It may contain the said solvent, without doing. Even when the surfactant is not contained, the rinsing property can be improved by the solvent.
Moreover, the said solvent may be used individually by 1 type, or may use 2 or more types together.

Preferred examples of the solvent contained in the rinsing liquid for relief printing plate making of the present invention include solvents S-1 to S-45 represented by R1-R2 shown in Table 1 below. Among them, the solvents S-1, S-3, S-9, S-10, S-12, S-17, S-22, S-28, S-29, S-34, S-39, S -41 and S-44 are more preferable. In addition, the solvent shown in following Table 1 can be obtained as a commercial item.

The content of the solvent in the rinsing solution for relief printing plate making of the present invention is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, and preferably 10 to 25% by weight. Further preferred.
When the solvent and the surfactant are used in combination, the content in the rinsing liquid for relief printing plate making of the present invention is preferably 1 to 40% by weight, and preferably 3 to 30% by weight. More preferred is 5 to 25% by weight.

The pH of the rinsing liquid for relief printing plate making of the present invention is preferably 9 or more, more preferably 9 to 14, still more preferably 9.5 to 13.5, and 10.0 to 13.3 is particularly preferable, and 10.0 to 12.5 is most preferable.
The rinsing liquid for relief printing plate making of the present invention preferably contains a basic compound in order to achieve the above pH, and more preferably contains a water-soluble basic compound.
There is no restriction | limiting in particular as a basic compound, Although a well-known basic compound can be used, It is preferable that it is an inorganic basic compound, and it is an alkali metal salt compound and an alkaline-earth metal salt compound Is more preferable, and an alkali metal hydroxide is more preferable.
Examples of the basic compound include sodium hydroxide, ammonium, potassium, lithium, sodium silicate, potassium, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, Examples thereof include inorganic alkali salts such as ammonium, sodium carbonate, potassium, ammonium, sodium hydrogen carbonate, potassium, ammonium, sodium borate, potassium and ammonium.

The rinsing liquid for relief printing plate making of the present invention preferably contains an antifoaming agent.
As the antifoaming agent, a general silicon-based self-emulsifying type, emulsifying type, surfactant nonionic HLB (Hydrophile-Lipophile Balance) value of 5 or less can be used. Silicon antifoaming agents are preferred. Among them, an emulsified dispersion type and a solubilized type can be used.
Specific examples of antifoaming agents include TSA731 and TSA739 (above, manufactured by Toray Dow Corning Co., Ltd.).
The content of the antifoaming agent is preferably 0.001 to 1.0% by weight in the rinsing liquid for relief printing plate making.

The rinsing liquid for relief printing plate making of the present invention may contain a preservative, an inorganic acid, and / or a chelating agent, if necessary.
As the preservative, the inorganic acid, and the chelating agent, known ones can be used.

(Relief printing plate making method)
The plate making method of the relief printing plate of the present invention comprises a step of preparing a relief printing plate precursor having a relief forming layer containing a non-elastomeric binder polymer, a plasticizer, and a photothermal conversion agent on a support (hereinafter referred to as “preparation step”). ), A step of engraving the relief printing plate precursor by exposure using a laser (hereinafter also referred to as “engraving step”), and a step of removing engraving residue generated by engraving with a rinse liquid (hereinafter referred to as “engraving step”). (Also referred to as “rinsing process”) in this order.

<Preparation process>
The plate making method of the relief printing plate of the present invention includes a step of preparing a relief printing plate precursor having a relief forming layer (preparation step).
Although there is no restriction | limiting in particular as a relief printing plate precursor which has a relief forming layer which can be used for the platemaking method of the relief printing plate of this invention, It is preferable that it is a relief printing plate precursor for laser engraving.
In the present invention, the “relief-forming layer” refers to a layer that can be engraved. For example, when a crosslinking agent is used, it refers to a layer that is crosslinked by light or heat. When a crosslinking agent is used, the layer before being crosslinked by light or heat is referred to as an “uncrosslinked relief forming layer”.
In the present invention, the “relief printing plate precursor for laser engraving” refers to a relief printing plate precursor that can be engraved. For example, when a cross-linking agent is used, the relief-forming layer having a crosslinkability made of a resin composition is an optical Or the state hardened | cured with the heat. A “relief printing plate” is produced by laser engraving the printing plate precursor.

The preparation step includes (A) a layer formation step of coating the resin composition on a support to form an uncrosslinked relief forming layer, and the uncrosslinked relief forming layer by at least one of light and heat. A cross-linking step of obtaining a relief printing plate precursor having a relief forming layer by crosslinking, or (B) a step of forming a non-cross-linked relief forming layer by coating the resin composition into a film, the uncross-linked relief forming layer A layer forming step of obtaining a relief printing plate precursor having a relief forming layer by crosslinking with at least one of irradiation with actinic light and heating, and curing one surface of the uncrosslinked relief forming layer or the crosslinked relief forming layer Preferably, it is a crosslinking step, (A) a layer forming step of coating the resin composition on a support to form an uncrosslinked relief forming layer, and the uncrosslinked relief forming layer is subjected to light and heat. And more preferably not even a crosslinking step of obtaining a crosslinked relief printing plate precursor having a relief forming layer by one.
Moreover, it is preferable to dry the coated uncrosslinked relief forming layer as needed. In the present invention, the term “coating” includes not only coating and providing, but also means providing by casting.

As described above, the relief printing plate precursor that can be used in the present invention preferably has a relief forming layer cured by crosslinking. In order to obtain such a relief forming layer, it is preferable that the preparation step includes a step of crosslinking an uncrosslinked relief forming layer in the relief printing plate precursor by light and / or heat.

The light is generally applied to the entire relief forming layer. Examples of light (also referred to as “active light”) include visible light, ultraviolet light, and electron beam, and ultraviolet light is the most common. If the support side of the relief forming layer is the back side, the surface may only be irradiated with light. However, if the support is a transparent film that transmits actinic rays, it is preferable that the back side is further irradiated with light. When the protective film exists, the irradiation from the surface may be performed while the protective film is provided, or may be performed after the protective film is peeled off. Since polymerization inhibition may occur in the presence of oxygen, actinic rays may be irradiated after the relief forming layer is covered with a vinyl chloride sheet and evacuated.

When the relief forming layer contains a thermal polymerization initiator (the photopolymerization initiator can also be a thermal polymerization initiator), the relief forming layer is crosslinked by heating the relief printing plate precursor for laser engraving. (Step of crosslinking by heat). Examples of the heating means include a method of heating the printing plate precursor in a hot air oven or a far infrared oven for a predetermined time, and a method of contacting the heated roll for a predetermined time.

As a method for crosslinking the relief forming layer, thermal crosslinking is preferred from the viewpoint that the relief forming layer can be uniformly cured (crosslinked) from the surface to the inside.
By crosslinking the relief forming layer, there is an advantage that the relief formed first after laser engraving becomes sharp, and second, the adhesiveness of engraving residue generated during laser engraving is suppressed.

Further, the plate making method of the relief printing plate of the present invention comprises a resin composition comprising at least a polymer having a hydroxyl group (—OH) and a compound having a group represented by the formula (I) described later in the preparation step. A step of forming an uncrosslinked relief forming layer by coating on the surface, and a step of obtaining a relief printing plate precursor having a relief forming layer by crosslinking the uncrosslinked relief forming layer with light and / or heat. Is particularly preferred.
By the above process, a relief printing plate precursor having a relief forming layer containing a binder having a group represented by the formula (I) such as an alkoxysilyl group can be easily obtained.
Moreover, when the said non-crosslinked relief forming layer is bridge | crosslinked with light, it is preferable that the photothermal conversion agent mentioned later is contained in the said resin composition.
The resin composition preferably contains a polymerizable compound described later from the viewpoint of improving printing durability.

When the relief forming layer contains a photopolymerization initiator, the relief forming layer can be crosslinked by irradiating the relief forming layer with an actinic ray that triggers the photopolymerization initiator.
The irradiation with actinic rays is generally performed on the entire surface of the relief forming layer. Visible light, ultraviolet light, or an electron beam is mentioned as actinic light, but ultraviolet light is the most common. If the substrate side for immobilizing the relief forming layer, such as a support for the relief forming layer, is the back side, the surface may only be irradiated with actinic rays, but the support used is transparent to transmit actinic rays. In the case of a film, it is also preferable to irradiate actinic rays from the back side. When the protective film exists, the irradiation from the surface may be performed while the protective film is provided, or may be performed after the protective film is peeled off. Since polymerization inhibition may occur in the presence of oxygen, actinic rays may be irradiated after the crosslinkable relief forming layer is covered with a vinyl chloride sheet and evacuated.

When the crosslinking step is a step of crosslinking by light, an apparatus for irradiating actinic rays is relatively expensive, but the printing plate precursor does not become high temperature, so there are almost no restrictions on the raw materials of the printing plate precursor. Absent.
When the crosslinking step is a step of crosslinking by heat, there is an advantage that an extra expensive apparatus is not required, but since the printing plate precursor becomes high temperature, the thermoplastic polymer that becomes flexible at high temperature is not heated. The raw materials to be used must be carefully selected because they may be deformed.
A thermal polymerization initiator may be added during the thermal crosslinking. As the thermal polymerization initiator, it can be used as a commercial thermal polymerization initiator for free radical polymerization. Examples of such a thermal polymerization initiator include compounds containing a suitable peroxide, hydroperoxide, or azo group. Representative vulcanizing agents can also be used for crosslinking. Thermal crosslinking can also be performed by adding a heat-curable resin, such as an epoxy resin, as a crosslinking component to the layer.

As a crosslinking method of the relief forming layer in the crosslinking step, crosslinking by heat is preferable from the viewpoint that the relief forming layer can be uniformly cured (crosslinked) from the surface to the inside.
By crosslinking the relief forming layer, there is an advantage that the relief formed first after laser engraving becomes sharp, and second, the adhesiveness of engraving residue generated during laser engraving is suppressed. When an uncrosslinked relief-forming layer is laser engraved, unintended portions are likely to melt and deform due to residual heat that has propagated around the laser-irradiated portion, and a sharp relief layer may not be obtained. In addition, as a general property of a material, a material having a low molecular weight tends to be liquid rather than solid, that is, the adhesiveness tends to be strong. The engraving residue generated when engraving the relief forming layer tends to become more tacky as more low-molecular materials are used. Since the polymerizable compound which is a low molecule becomes a polymer by crosslinking, the generated engraving residue tends to be less tacky.

<Engraving process>
The plate making method of the relief printing plate of the present invention includes a step of engraving the relief printing plate precursor by exposure (engraving step).
In the engraving step, it is preferable that a relief is formed by irradiating a laser beam corresponding to an image to be formed with a specific laser to be described later to form a relief.
Specifically, the relief layer is formed by engraving the crosslinked relief forming layer by irradiating a laser beam corresponding to the image to be formed. Preferably, a step of controlling the laser head with a computer based on digital data of an image to be formed and performing scanning irradiation on the relief forming layer can be mentioned. When the infrared laser is irradiated, the molecules in the relief forming layer undergo molecular vibration and heat is generated. When a high-power laser such as a carbon dioxide laser or a YAG laser is used as an infrared laser, a large amount of heat is generated in the laser irradiation portion, and molecules in the photosensitive layer are selectively cut by molecular cutting or ionization, that is, Sculpture is made. At this time, since the exposed region also generates heat due to the photothermal conversion agent in the relief forming layer, the heat generated by the photothermal conversion agent also promotes this removability.
The advantage of laser engraving is that the engraving depth can be set arbitrarily, so that the structure can be controlled three-dimensionally. For example, by engraving with a shallow or shoulder on the part where fine halftone dots are printed, it is possible to prevent the relief from falling down due to printing pressure, and deeply engrave the part of the groove where fine cut characters are printed. Thus, it becomes difficult for the groove to be filled with ink, and it is possible to suppress the crushing of the extracted characters.
In particular, when engraving with an infrared laser corresponding to the maximum absorption wavelength of the photothermal conversion agent, heat generation from the above-described photothermal conversion agent is efficiently performed, so that a more sensitive and sharp relief layer can be obtained.
As an infrared laser used for engraving, a carbon dioxide laser or a semiconductor laser is preferably used from the viewpoint of productivity, cost, etc. Among them, a semiconductor infrared laser with a fiber described in detail below is particularly preferably used.

In general, a semiconductor laser can be downsized with high efficiency and low cost in laser oscillation compared to a CO ₂ laser. Moreover, since it is small, it is easy to form an array. The control of the beam diameter is performed using an imaging lens and a specific optical fiber. The semiconductor laser with fiber is effective for image formation in the present invention because it can efficiently output laser light by attaching an optical fiber. Furthermore, the beam shape can be controlled by processing the fiber. For example, the beam profile can have a top hat shape, and energy can be stably given to the plate surface. Details of semiconductor lasers are described in “Laser Handbook 2nd Edition” edited by Laser Society, Practical Laser Technology, Electronic Communication Society, etc.
Further, a plate making apparatus equipped with a fiber-coupled semiconductor laser that can be suitably used in a method for producing a relief printing plate using a relief printing plate precursor is disclosed in Japanese Patent Application Nos. 2008-15460 and 2008 filed by the present applicant. -58160, which can be used to make relief printing plates.

The semiconductor laser used for laser engraving preferably has a wavelength of 700 nm to 1,300 nm, more preferably 800 nm to 1,200 nm, still more preferably 860 nm to 1,200 nm, and 900 nm to 1,100 nm. Those are particularly preferred.
Since the band gap of GaAs is 860 nm at room temperature, an AlGaAs-based active layer is generally preferably used in a region less than 860 nm. On the other hand, a semiconductor active layer material of InGaAs type is used at 860 nm or more. In general, since Al is easily oxidized, a semiconductor laser having an InGaAs-based material in its active layer is more reliable than an AlGaAs-based material, and therefore, 860 nm to 1,200 nm is preferable.
Furthermore, as a practical semiconductor laser, considering not only the active layer material but also the composition of the clad material, a semiconductor laser having an InGaAs-based material in the active layer has a more preferable wavelength of 900 nm to 1,100 nm. It is easy to obtain a higher output and higher reliability in the range. Therefore, it is easy to achieve low cost and high productivity by using a fiber-coupled semiconductor laser having an active layer of an InGaAs material with a wavelength of 900 nm to 1,100 nm.
In order to realize a laser engraving relief printing system that is inexpensive and highly productive and has good image quality, a relief printing plate precursor having a relief forming layer using a resin composition for laser engraving as described later is used. In addition, it is preferable to use a semiconductor laser with a specific wavelength as described above and a fiber-attached semiconductor laser.

By using a semiconductor laser with a fiber, in the control of the shape to be engraved, the engraving area can be changed by changing the beam shape of the semiconductor laser with fiber or changing the amount of energy supplied to the laser without changing the beam shape. This also has the advantage that the shape of the can be changed.

In the method for making a relief printing plate of the present invention, the engraving residue preferably contains a polymer (compound) having a group represented by the following formula (I). That is, it is preferable that the resin composition for laser engraving forming the relief forming layer and the relief forming layer formed thereby contain a compound having a group represented by the following formula (I).
* -M (R ¹ ) (R ² ) _n (I)
(In the formula (I), R ¹ represents OR ³ or a halogen atom, M represents Si, Ti, or Al. When M is Si, n is 2, and when M is Ti, n is 2. And when M is Al, n is 1, each R ² independently represents a hydrocarbon group, OR ³ or a halogen atom, R ³ represents a hydrogen atom or a hydrocarbon group, and * (Represents the bonding position with other structures)
In the group represented by the formula (I), M is preferably Si, and is preferably a group represented by the following formula (i).
* -Si (OR ³ ) (R ² ) ₂ (i)
(In formula (i), two R ^{2 s} each independently represent a hydrocarbon group, OR ³ or a halogen atom, R ³ represents a hydrogen atom or a hydrocarbon group, and * represents a bonding position with another structure. Represents.)
R ¹ ~ R ^3, n and M in the polymer having a group represented by the formula (I), R ¹ ~ R ³ in the compound having a group represented by the formula (I) described below, n and the M It is synonymous and the preferable range is also the same.

<Rinsing process>
The plate making method of the relief printing plate of the present invention includes a step of removing engraving residue generated by engraving with a rinsing liquid (rinsing treatment step).
As the rinsing liquid in the rinsing process, the rinsing liquid for relief printing plate making of the present invention is used.
The relief printing plate immediately after engraving has engraving residue on the surface. In the rinsing process, the engraving residue is removed with the relief printing plate rinsing liquid of the present invention.
The amount of the rinsing liquid used is required to cover at least the entire plate with the liquid. The amount used varies depending on the plate, but is preferably 10 mL / m ² or more, more preferably 50 mL / m ² or more, and further preferably 70 mL / m ² or more. The amount of the rinse solution used is particularly preferably 70 to 500 mL / m ² from the viewpoint of the cost of the treatment solution.
The means for rinsing in the rinsing process is not particularly limited, but a method of simply washing with a rinsing liquid, a method of spraying a high-pressure rinsing liquid, a batch type or a conveying type known as a photosensitive resin letterpress developing machine. And a method of brushing the engraved surface mainly in the presence of a rinsing liquid.
Further, the rinsing operation may be performed manually, or a plate making apparatus such as a commercially available cleaning apparatus may be used. In the case of processing with a cleaning device, a rinsing liquid can be charged into the tank in the cleaning device for processing. In this case, the liquid is charged in accordance with the tank capacity and processing is performed. As the cleaning device, JOW-1824-WF manufactured by JEOL Seiki Co., Ltd. can be used.

Moreover, in the plate-making method of the relief printing plate of this invention, the following drying process and / or a post-crosslinking process may be included as needed.
Drying step: a step of drying the engraved relief layer.
Post-crosslinking step: a step of imparting energy to the relief layer after engraving and further crosslinking the relief layer.
The plate making method of the relief printing plate of the present invention preferably includes a step of drying the engraved relief forming layer to volatilize the rinse liquid.
The plate making method of the relief printing plate of the present invention may further include a step of further crosslinking the relief forming layer, if necessary. By performing the post-crosslinking step, the relief formed by engraving can be further strengthened.
Moreover, when a post-crosslinking process is included, it is preferable that the used relief printing plate precursor has a relief forming layer cured by crosslinking.

<Relief printing plate precursor>
The relief printing plate precursor that can be used in the present invention is not particularly limited as long as it has a relief-forming layer containing a non-elastomeric binder polymer, a plasticizer, and a photothermal conversion agent on a support, and is a known relief. Although a printing plate precursor can be used, it is preferably a relief printing plate precursor for laser engraving, more preferably a relief forming layer made of a resin composition for laser engraving. The relief forming layer preferably has a crosslinked structure, and is preferably a layer crosslinked by heat and / or light.
The relief forming layer is not particularly limited and a known layer can be used, and it is a layer made of a resin composition for laser engraving described later, or a layer obtained by curing a resin composition for laser engraving described later. Is preferred. The relief forming layer is preferably provided on the support.

If necessary, the relief printing plate precursor for laser engraving may further have an adhesive layer between the support and the relief forming layer, and a slip coat layer and a protective film on the relief forming layer.
The relief forming layer can be formed, for example, by using a coating liquid composition and molding it into a sheet or sleeve. As a coating liquid composition, the resin composition for laser engraving mentioned later can be illustrated preferably.

<Support>
The relief printing plate precursor that can be used in the present invention may have a support.
The material used for the support in the relief printing plate precursor is not particularly limited, but materials having high dimensional stability are preferably used. For example, metals such as steel, stainless steel, and aluminum, polyester resins (for example, PET, PBT, PAN) ) And plastic resins such as polyvinyl chloride, synthetic rubbers such as styrene-butadiene rubber, and plastic resins reinforced with glass fibers (such as epoxy resins and phenol resins). As the support, a PET (polyethylene terephthalate) film or a steel substrate is preferably used. The form of the support is determined depending on whether the relief forming layer is a sheet or a sleeve.
Also, a laser engraving produced by applying a crosslinkable resin composition for laser engraving and curing it from the back surface (opposite to the surface on which laser engraving is performed, including cylindrical ones) with light or heat. In the relief printing plate precursor for use, since the back side of the cured resin composition for laser engraving functions as a support, the support is not always essential.

<Adhesive layer>
An adhesive layer may be provided between the relief forming layer and the support for the purpose of enhancing the adhesive force between the two layers. Examples of materials (adhesives) that can be used for the adhesive layer include I.I. Those described in the edition of Skeist, “Handbook of Adhesives”, the second edition (1977) can be used.

<Protective film, slip coat layer>
For the purpose of preventing scratches and dents on the surface of the relief forming layer, a protective film may be provided on the surface of the relief forming layer. The thickness of the protective film is preferably 25 to 500 μm, more preferably 50 to 200 μm. As the protective film, for example, a polyester film such as PET (polyethylene terephthalate) or a polyolefin film such as PE (polyethylene) or PP (polypropylene) can be used. The surface of the film may be matted. When providing a protective film on a relief forming layer, the protective film must be peelable.

When the protective film is not peelable or, on the contrary, difficult to adhere to the relief forming layer, a slip coat layer may be provided between both layers. The material used for the slip coat layer is a resin that can be dissolved or dispersed in water, such as polyvinyl alcohol, polyvinyl acetate, partially saponified polyvinyl alcohol, hydroxyalkyl cellulose, alkyl cellulose, polyamide resin, etc. It is preferable that

-Relief printing plate precursor preparation method-
Next, a method for producing a relief printing plate precursor will be described.
The formation of the relief forming layer in the relief printing plate precursor is not particularly limited. For example, a relief forming layer coating solution composition (containing a resin composition for laser engraving) is prepared, and this relief forming layer is used. The method of melt-extruding on a support after removing a solvent from a coating liquid composition is mentioned. Or the method of casting the coating liquid composition for relief forming layers on a support body, drying this in oven, and removing a solvent from a coating liquid composition may be sufficient.
Thereafter, a protective film may be laminated on the relief forming layer as necessary. Lamination can be performed by pressure-bonding the protective film and the relief forming layer with a heated calendar roll or the like, or by bringing the protective film into close contact with the relief forming layer impregnated with a small amount of solvent on the surface.
When a protective film is used, a method of first laminating a relief forming layer on the protective film and then laminating the support may be employed.
When providing an adhesive layer, it can respond by using the support body which apply | coated the adhesive layer. When providing a slip coat layer, it can respond by using the protective film which apply | coated the slip coat layer.

The coating composition for the relief forming layer can be produced, for example, by dissolving a binder polymer, a photothermal conversion agent and a plasticizer in an appropriate solvent, and then dissolving a polymerizable compound and a polymerization initiator. Since most of the solvent components need to be removed at the stage of producing the relief printing plate precursor, the solvent is a low-molecular alcohol that easily volatilizes (for example, methanol, ethanol, n-propanol, isopropanol, propylene glycol monomethyl ether). ) And the like, and adjusting the temperature, it is preferable to keep the total amount of the solvent added as small as possible.

Here, in the present invention, in the case of a relief printing plate precursor for laser engraving, as described above, it refers to a state where the relief forming layer is crosslinked. In the method of crosslinking the relief forming layer, it is preferable to perform a step of crosslinking the relief forming layer by irradiation with active light and / or heating.
The term “crosslinking” as used herein is a concept including a crosslinking reaction for linking polymers, and a relief caused by a polymerization reaction between polymerizable compounds having an ethylenically unsaturated bond or a reaction between a polymer and a polymerizable compound. It is a concept that includes the curing reaction of the formation layer.

The thickness of the relief forming layer in the relief printing plate precursor is preferably from 0.05 mm to 10 mm, more preferably from 0.05 mm to 7 mm, particularly preferably from 0.05 mm to 3 mm.

The Shore A hardness of the relief layer of the relief printing plate is preferably 50 ° or more and 90 ° or less.
When the Shore A hardness of the relief forming layer is 50 ° or more, even if the fine halftone dots formed by engraving are subjected to the strong printing pressure of the relief printing press, they do not collapse and can be printed normally. In addition, when the Shore A hardness of the relief layer is 90 ° or less, it is possible to prevent faint printing in a solid portion even in flexographic printing with a printing pressure of kiss touch.
In addition, the Shore A hardness in this specification is measured by measuring the amount of deformation (indentation depth) by pressing and deforming an indenter (called a push needle or indenter) on the surface of the object to be measured at 25 ° C. and 50% RH. The value measured with a durometer (spring type rubber hardness meter) for digitization.

The relief printing plate produced by the method for making a relief printing plate of the present invention can be printed with oil-based ink or UV ink by a relief printing press, and can also be printed with UV ink by a flexographic printing press. is there.

<Resin engraving resin composition>
The resin composition for laser engraving (hereinafter also simply referred to as “resin composition”) that can be used in the present invention contains at least a non-elastomeric binder polymer, a plasticizer, and a photothermal conversion agent.

As an application mode of the resin composition, specifically, an image forming layer of an image forming material that forms an image by laser engraving, a relief forming layer of a printing plate precursor that forms a convex relief by laser engraving, an intaglio, and a stencil , Stamps and the like, but are not limited thereto.
Hereinafter, the components of the resin composition for laser engraving will be described.

[Binder polymer]
The resin composition for laser engraving preferably contains a binder polymer (hereinafter also referred to as “binder”).
The rinsing liquid for making a relief printing plate of the present invention is suitable for removing engraving residue generated when a relief forming layer containing a non-elastomeric binder is laser engraved, and is contained in a resin composition for laser engraving. The binder is preferably a non-elastomer. Below, after explaining the binder in general which can apply this invention, the binder preferably used in this invention is demonstrated.
The binder is a polymer component contained in the resin composition for laser engraving, and a general polymer compound can be appropriately selected and used alone or in combination of two or more. In particular, when a resin composition for laser engraving is used for a printing plate precursor, it is necessary to select it in consideration of various performances such as laser engraving property, ink acceptability, and engraving residue dispersibility.
The binder includes polystyrene resin, polyester resin, polyamide resin, polyurea resin, polyamideimide resin, polyurethane resin, polysulfone resin, polyethersulfone resin, polyimide resin, polycarbonate resin, hydrophilic polymer containing hydroxyethylene units, acrylic resin, acetal. A resin, an epoxy resin, a polycarbonate resin, rubber, a thermoplastic elastomer, or the like can be selected and used.

For example, from the viewpoint of laser engraving sensitivity, a polymer containing a partial structure that is thermally decomposed by exposure or heating is preferable. Preferred examples of such a polymer include those described in paragraph 0038 of JP2008-163081A. For example, when the purpose is to form a soft and flexible film, a soft resin or a thermoplastic elastomer is selected. This is described in detail in paragraphs 0039 to 0040 of JP-A-2008-163081. Furthermore, if the resin composition for laser engraving is applied to the relief forming layer in the relief printing plate precursor for laser engraving, the ease of preparation of the composition for relief forming layer and the oil-based ink in the obtained relief printing plate It is preferable to use a hydrophilic or alcoholic polymer from the viewpoint of improving the resistance to water. As the hydrophilic polymer, those described in detail in paragraph 0041 of JP-A-2008-163081 can be used.

In addition, when used for the purpose of curing by heating or exposure and improving the strength, a polymer having a carbon-carbon unsaturated bond in the molecule is preferably used.
As such a binder, examples of the polymer containing a carbon-carbon unsaturated bond in the main chain include SB (polystyrene-polybutadiene), SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), SEBS. (Polystyrene-polyethylene / polybutylene-polystyrene) and the like.
As a polymer having a carbon-carbon unsaturated bond in the side chain, a carbon-carbon unsaturated bond such as an allyl group, an acryloyl group, a methacryloyl group, a styryl group, or a vinyl ether group is introduced into the side chain of the polymer. Can be obtained. The method for introducing a carbon-carbon unsaturated bond into a polymer side chain is as follows. (1) A structural unit having a polymerizable group precursor formed by bonding a protective group to a polymerizable group is copolymerized with the polymer to remove the protective group. (2) preparing a polymer compound having a plurality of reactive groups such as hydroxyl group, amino group, epoxy group and carboxyl group, and reacting with these reactive groups and carbon- A known method such as a method of introducing a compound having a carbon unsaturated bond by polymer reaction can be employed. According to these methods, the amount of unsaturated bonds and polymerizable groups introduced into the polymer compound can be controlled.

As the binder, it is particularly preferable to use a polymer having a hydroxyl group (—OH) (hereinafter also referred to as “specific polymer”). The skeleton of the specific polymer is not particularly limited, but an acrylic resin, an epoxy resin, a hydrophilic polymer containing a hydroxyethylene unit, a polyvinyl acetal resin, a polyester resin, and a polyurethane resin are preferable.
As the acrylic monomer used for the synthesis of the acrylic resin having a hydroxyl group, for example, (meth) acrylic acid esters and crotonic acid esters (meth) acrylamides having a hydroxyl group in the molecule are preferable. Specific examples of such a monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. A copolymer obtained by polymerizing these and a known (meth) acrylic monomer or vinyl monomer can be preferably used.
It is also possible to use an epoxy resin having a hydroxy group in the side chain as the specific polymer. As a preferable specific example, an epoxy resin obtained by polymerizing an adduct of bisphenol A and epichlorohydrin as a raw material monomer is preferable.
As the polyester resin, a polyester resin composed of hydroxyl carboxylic acid units such as polylactic acid can be preferably used. Specific examples of the polyester resin include polyhydroxyalkanoate (PHA), lactic acid-based polymer, polyglycolic acid (PGA), polycaprolactone (PCL), poly (butylene succinic acid), and derivatives or mixtures thereof. Those selected from the group consisting of are preferred.

The specific polymer is preferably a polymer having an atom and / or group capable of reacting with the compound (I), and is a polymer having an atom and / or group capable of reacting with the compound (I) and is insoluble in water. More preferably, the binder polymer is soluble in an alcohol having 1 to 4 carbon atoms.
Although it does not specifically limit as an atom and / or group which can react with the said compound (I), An ethylenically unsaturated bond, an epoxy group, an amino group, a (meth) acryloyl group, a mercapto group, a hydroxy group is illustrated, These Of these, hydroxy groups are preferred.

As a specific polymer in the present invention, polyvinyl butyral (PVB), an acrylic resin having a hydroxyl group in a side chain, and a film having good engraving sensitivity and good film property while achieving both water-based ink suitability and UV ink suitability Preferred examples include an epoxy resin having a hydroxyl group in the side chain.

The specific polymer that can be used in the present invention is a photothermal conversion capable of absorbing light having a wavelength of 700 to 1,300 nm, which will be described later, which is a preferred combined component of the resin composition for laser engraving constituting the relief forming layer in the present invention. When combined with an agent, a glass transition temperature (Tg) of 20 ° C. or higher is particularly preferable because engraving sensitivity is improved. Hereinafter, a polymer having such a glass transition temperature is referred to as a non-elastomer. That is, an elastomer is generally defined academically as a polymer having a glass transition temperature of room temperature or lower (see Science Dictionary, Second Edition, Editor, International Science Promotion Foundation, published by Maruzen Co., Ltd., P154). . Therefore, a non-elastomer refers to a polymer having a glass transition temperature exceeding normal temperature. Although there is no restriction | limiting in the upper limit of the glass transition temperature of a specific polymer, it is preferable from a viewpoint of handleability that it is 200 degrees C or less, and it is more preferable that it is 25 degreeC or more and 120 degrees C or less.

When a polymer having a glass transition temperature of room temperature (20 ° C.) or higher is used, the specific polymer takes a glass state at room temperature. Therefore, compared to a rubber state, the thermal molecular motion is considerably suppressed. It is in. In laser engraving, in addition to the heat imparted by the infrared laser during laser irradiation, the heat generated by the function of the photothermal conversion agent used in combination with the desired heat is transferred to a specific polymer around it, which decomposes and dissipates. As a result, the recess is formed by engraving.
When a specific polymer is used, if a photothermal conversion agent is present in a state where thermal molecular motion of the specific polymer is suppressed, heat transfer to the specific polymer and thermal decomposition are considered to occur effectively. It is presumed that the engraving sensitivity is further increased due to various effects.

Specific examples of polymers that are non-elastomers preferably used in the present invention are illustrated below.

(1) Polyvinyl acetal and derivatives thereof Polyvinyl acetal is a compound obtained by cyclic acetalization of polyvinyl alcohol (obtained by saponifying polyvinyl acetate). Further, the polyvinyl acetal derivative is obtained by modifying the polyvinyl acetal or adding another copolymer component.
The acetal content in the polyvinyl acetal (mole% of vinyl alcohol units to be acetalized with the total number of moles of vinyl acetate monomer as the raw material being 100%) is preferably 30 to 90%, more preferably 50 to 85%, 55 ˜78% is particularly preferred.
The vinyl alcohol unit in the polyvinyl acetal is preferably 10 to 70 mol%, more preferably 15 to 50 mol%, particularly preferably 22 to 45 mol%, based on the total number of moles of the vinyl acetate monomer as a raw material.
Further, the polyvinyl acetal may have vinyl acetate units as other components, and the content thereof is preferably 0.01 to 20 mol%, more preferably 0.1 to 10 mol%. The polyvinyl acetal derivative may further have other copolymer units.
Examples of the polyvinyl acetal include polyvinyl butyral, polyvinyl propylal, polyvinyl ethylal, and polyvinyl methylal. Among these, polyvinyl butyral (PVB) is preferable.
Polyvinyl butyral is usually a polymer obtained by converting polyvinyl alcohol into butyral. A polyvinyl butyral derivative may also be used.
Examples of polyvinyl butyral derivatives include acid-modified PVB in which at least part of the hydroxyl group is modified to an acid group such as a carboxyl group, modified PVB in which part of the hydroxyl group is modified to a (meth) acryloyl group, and at least part of the hydroxyl group is an amino group Modified PVB, modified PVB in which ethylene glycol, propylene glycol, or a multimer thereof is introduced into at least a part of the hydroxyl group.
The molecular weight of polyvinyl acetal is preferably 5,000 to 800,000, and more preferably 8,000 to 500,000 as a weight average molecular weight from the viewpoint of maintaining a balance between engraving sensitivity and film property. Further, from the viewpoint of improving the rinsing property of engraving residue, it is particularly preferably 50,000 to 300,000.

Hereinafter, although polyvinyl butyral (PVB) and its derivative (s) are mentioned and demonstrated as a particularly preferable example of polyvinyl acetal, it is not limited to this.
As PVB, it can also be obtained as a commercial product, and preferred specific examples thereof include “ESREC B” series and “ESREC K” manufactured by Sekisui Chemical Co., Ltd. from the viewpoint of alcohol solubility (particularly ethanol solubility). (KS) "series," Denkabutyral "manufactured by Denki Kagaku Kogyo Co., Ltd. are preferred. More preferably, from the viewpoint of alcohol solubility (especially ethanol), “S Lec B” series manufactured by Sekisui Chemical Co., Ltd. and “Denka Butyral” manufactured by Denki Kagaku Kogyo Co., Ltd. are particularly preferable. In the “ESREC B” series manufactured by the same company, “BL-1”, “BL-1H”, “BL-2”, “BL-5”, “BL-S”, “BX-L”, “BM-” "# 3000-1", "# 3000-2", "# 3000-4", "# 4000-2", "S", "BH-S", and "Denkabutyral" manufactured by Denki Kagaku Kogyo Co., Ltd. “# 6000-C”, “# 6000-EP”, “# 6000-CS”, “# 6000-AS”.
When forming a relief forming layer using PVB as a specific polymer, a method of casting and drying a solution dissolved in a solvent is preferable from the viewpoint of the smoothness of the surface of the membrane.

In addition to the polyvinyl acetal and its derivatives, as the specific polymer, an acrylic resin obtained by using a known acrylic monomer having a hydroxyl group in the molecule can be used. In addition, a novolak resin that is a resin obtained by condensing phenols and aldehydes under acidic conditions can also be used as the specific polymer. Moreover, it is also possible to use the epoxy resin which has a hydroxyl group in a side chain as a specific polymer.

Among the specific polymers, polyvinyl butyral and its derivatives are particularly preferable from the viewpoint of rinsing properties and printing durability when used as a relief forming layer.
The hydroxyl group content in the specific polymer in the present invention is preferably 0.1 to 15 mmol / g, more preferably 0.5 to 7 mmol / g in any of the above-described polymers. .
Only 1 type of specific binder polymers may be used for a resin composition, and 2 or more types may be used together.
The weight average molecular weight (in terms of polystyrene by GPC measurement) of the binder that can be used in the present invention is preferably 5,000 to 1,000,000, more preferably 8,000 to 750,000. Most preferably, it is from 1,000,000 to 500,000.
The preferred content of the specific polymer in the resin composition that can be used in the present invention is 2 to 95% by weight in the total solid content from the viewpoint of satisfying a good balance of form retention, water resistance and engraving sensitivity of the coating film. It is preferably 5 to 80% by weight, particularly preferably 10 to 60% by weight.

[Combination polymer]
In the resin composition for laser engraving, in addition to the specific polymer, a known polymer that is not included in the specific polymer, such as a polymer having no hydroxyl group, can be used in combination. Hereinafter, such a polymer is also referred to as a combined polymer.
The combined polymer constitutes the main component contained in the resin composition for laser engraving together with the specific polymer, and a general polymer compound not included in the specific polymer is appropriately selected, and one or two or more types are used. Can be used in combination. In particular, when a relief forming plate precursor is used as a printing plate precursor, it is necessary to select it in consideration of various performances such as laser engraving property, ink acceptability, and engraving residue dispersibility.
As the combined polymer, for example, among the polymers described above as the binder, a polymer that does not have a hydroxyl group and is not included in the specific polymer can be used.

The weight average molecular weight (in terms of polystyrene by GPC measurement) of the combined polymer in the present invention is preferably from 50,000 to 500,000. If the weight average molecular weight is 50,000 or more, the form retainability as a single resin is excellent, and if it is 500,000 or less, it is easy to dissolve in a solvent such as water, which is convenient for preparing a relief forming layer. The weight average molecular weight of the combined polymer is more preferably 10,000 to 400,000, particularly preferably 15,000 to 300,000.

The total content of the polymer (binder polymer) (the total content of the specific polymer and the combined polymer) is preferably 5 to 95% by weight, preferably 15 to 80% by weight, based on the total solid content of the resin composition for laser engraving. Is more preferable, and 20 to 65% by weight is still more preferable.
For example, when the resin composition for laser engraving is applied to the relief forming layer of a relief printing plate precursor, the resulting relief printing plate can be used as a printing plate by setting the binder polymer content to 5% by weight or more. Insufficient printing durability is obtained, and by making it 95% by weight or less, other components are not deficient, and flexibility sufficient to be used as a printing plate even when a relief printing plate is used as a flexographic printing plate. Obtainable.

[Plasticizer]
The resin composition for laser engraving contains a plasticizer.
The plasticizer has a function of softening a film formed of the resin composition for laser engraving and needs to be compatible with the polymer.
As the plasticizer, for example, dioctyl phthalate, didodecyl phthalate, tributyl citrate and the like, polyethylene glycols, polypropylene glycol (monool type and diol type), polypropylene glycol (monool type and diol type) and the like are preferably used. .

[Photothermal conversion agent]
The relief forming layer contains a photothermal conversion agent.
The resin composition for laser engraving preferably contains a photothermal conversion agent.
It is considered that the photothermal conversion agent promotes thermal decomposition of the cured product of the resin composition for laser engraving by absorbing laser light and generating heat. Therefore, it is preferable to select a photothermal conversion agent that absorbs light having a laser wavelength used for engraving.

When a laser (YAG laser, semiconductor laser, fiber laser, surface emitting laser, etc.) emitting an infrared ray having a wavelength of 700 nm to 1,300 nm is used as a light source for laser engraving, the relief forming layer in the present invention has a relief layer of 700 nm to 1,300 nm. It is preferable to contain the photothermal conversion agent which can absorb the light of this wavelength.
Various dyes and / or pigments are used as the photothermal conversion agent in the present invention.
More preferably, the photothermal conversion agent is at least one photothermal conversion agent selected from pigments and dyes having absorption at 800 nm to 1,200 nm.
The photothermal conversion agent is preferably a pigment.

Among the photothermal conversion agents, as the dye, commercially available dyes and known ones described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include those having a maximum absorption wavelength in the range of 700 nm to 1,300 nm. Azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, diimmonium compounds, quinone imine dyes , Methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes. In particular, cyanine dyes such as heptamethine cyanine dye, oxonol dyes such as pentamethine oxonol dye, and phthalocyanine dyes are preferably used. Examples thereof include the dyes described in paragraphs 0124 to 0137 of JP-A-2008-63554.

Among the photothermal conversion agents used in the present invention, commercially available pigments and color index (CI) manuals, “latest pigment manuals” (edited by the Japan Pigment Technical Association, published in 1977), “latest pigment application” The pigments described in “Technology” (CMC Publishing, 1986) and “Printing Ink Technology” CMC Publishing, 1984) can be used.

Examples of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

As long as the dispersibility in the composition is stable, carbon black can be used regardless of the classification according to ASTM or the use (for example, for color, for rubber, for dry battery, etc.). Carbon black includes, for example, furnace black, thermal black, channel black, lamp black, acetylene black and the like. In addition, black colorants such as carbon black can be used as color chips or color pastes previously dispersed in nitrocellulose or the like by using a dispersant as necessary in order to facilitate dispersion. Chips and pastes are easily available as commercial products.

In the present invention, it is also possible to use carbon black having a relatively low specific surface area and relatively low DBP absorption and even finer carbon black having a large specific surface area. Examples of suitable carbon blacks include Printex® U, Printex® A, or Specialschwarz® 4 (from Degussa).

The carbon black that can be used in the present invention preferably has a dibutyl phthalate (DBP) oil absorption of less than 150 ml / 100 g.
In addition, as the carbon black, conductive carbon black having a specific surface area of at least 150 m ² / g is preferable from the viewpoint of improving engraving sensitivity by efficiently transferring heat generated by photothermal conversion to surrounding polymers and the like. .

The content of the photothermal conversion agent in the laser forming layer or the resin composition for laser engraving varies greatly depending on the molecular extinction coefficient inherent to the molecule, but is 0% of the total solid weight of the resin composition. The range of 0.01 to 20% by weight is preferable, the range of 0.05 to 10% by weight is more preferable, and the range of 0.1 to 5% by weight is particularly preferable.

[Crosslinking agent]
The resin composition for laser engraving preferably contains a crosslinking agent.
In the present invention, from the viewpoint of forming a crosslinked structure in the relief forming layer, the resin composition for the relief forming layer preferably contains a crosslinking agent in order to form the crosslinked structure.
The crosslinking agent that can be used in the present invention is not particularly limited as long as it can be polymerized by a chemical reaction caused by light or heat to cure the relief forming layer. In particular, a polymerizable compound having an ethylenically unsaturated group (hereinafter also referred to as “polymerizable compound”), a reactive silane compound having a reactive silyl group such as an alkoxysilyl group or a halogenated silyl group, and a reactive titanium compound. A reactive aluminum compound is preferably used, and a reactive silane compound is more preferably used. These compounds may form a crosslinked structure in the relief forming layer by reacting with the binder, or may form a crosslinked structure by reacting with each other, and both of these reactions. A cross-linked structure may be formed.
The polymerizable compound that can be used here can be arbitrarily selected from compounds having at least one ethylenically unsaturated group, preferably two or more, and more preferably 2 to 6.

The resin composition for laser engraving preferably contains a compound having a group represented by the following formula (I) (hereinafter also referred to as “compound (I)”).
* -M (R ¹ ) (R ² ) _n (I)
(In the formula (I), R ¹ represents OR ³ or a halogen atom, M represents Si, Ti, or Al. When M is Si, n is 2, and when M is Ti, n is 2. And when M is Al, n is 1, each R ² independently represents a hydrocarbon group, OR ³ or a halogen atom, R ³ represents a hydrogen atom or a hydrocarbon group, and * (Represents the bonding position with other structures)

In formula (I), M represents Si, Ti, or Al. Among these, M is preferably Si or Ti, and more preferably Si.
In the formula (I), R ¹ represents OR ³ or a halogen atom, R ³ represents a hydrogen atom or a hydrocarbon group, and the hydrocarbon group includes an alkyl group having 1 to 30 carbon atoms and a carbon number of 6 to 30 Aryl groups having 2 to 30 carbon atoms, aralkyl having 7 to 37 carbon atoms, and the like. Among these, R ³ is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 6 to 6 carbon atoms. 10 aryl groups are more preferable, and a methyl group or ethyl group is particularly preferable. That is, R ¹ is particularly preferably a methoxy group or an ethoxy group.
R ¹ is -M (R ²⁾ _n O when treated with an alkaline rinse solution ^- is preferably one that ionized.

In the formula (I), R ² represents a hydrocarbon group, OR ³ or a halogen atom. R ³ is as described above, and the preferred range is also the same.
R ² is preferably OR ³ or a halogen atom, and more preferably OR ³ .

N is 2 when M is Si. When M is Si, a plurality of R ² may be the same or different, and is not particularly limited.
N is 2 when M is Ti. When M is Ti, a plurality of R ² may be the same or different and are not particularly limited.
When M is Al, n represents 1.

In addition, the compound (I) may be one in which a group represented by the above formula (I) is introduced into the polymer by reaction with a polymer, and has a group represented by the above formula (I) before the reaction, A group represented by the above formula (I) may be introduced into the polymer.

As the compound (I), an embodiment in which M is Si is particularly preferable.
When M is Si, it is also possible to use a silane coupling agent as the compound having the group represented by the formula (I) (compound (I)). The silane coupling agent is a compound having a group capable of reacting with an inorganic component such as an alkoxysilyl group and a group capable of reacting with an organic component such as a methacryloyl group, and capable of binding the inorganic component and the organic component. is there. The same applies to titanium coupling agents and aluminate coupling agents.
Compound (I) has a reactive group such as a vinyl group, an epoxy group, a methacryloyloxy group, an acryloyloxy group, a mercapto group, and an amino group, and reacts with the polymer with the reactive group, whereby the polymer has the formula (I It is also preferred that a group represented by

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- Methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimeth Sisilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercapto Examples thereof include propyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and γ-ureidopropyltriethoxysilane.
As the compound (I), a compound having a plurality of groups represented by the formula (I) is also preferably used. In such a case, the group represented by the formula (I) can be introduced into the polymer by reacting a part of the group represented by the formula (I) with the polymer. For example, the R ¹ group and optionally the R ² group of compound (I) reacts with an atom and / or group (eg, hydroxyl group (—OH)) capable of reacting with the compound in the polymer (eg, alcohol exchange). react. In addition, when a plurality of groups represented by the formula (I) are bonded to the polymer, the compound (I) also functions as a crosslinking agent and can form a crosslinked structure.
Such a compound (I) is preferably a compound having a plurality of groups represented by the formula (I), preferably a compound having 2 to 6 groups represented by the formula (I). More preferred is a compound having 2 to 3 groups represented by the formula (I).
Although the compounds shown below are preferred, the present invention is not limited to these compounds.

In the above formulas, R represents a partial structure selected from the following structures. When a plurality of R and R ¹ are present in the molecule, these may be the same or different from each other, and are preferably the same in terms of synthesis suitability.

In the above formulas, R represents a partial structure shown below. R ¹ has the same meaning as described above. When a plurality of R and R ¹ are present in the molecule, these may be the same or different from each other, and are preferably the same in terms of synthesis suitability.

In the present invention, silica particles, titanium oxide particles, aluminum oxide particles and the like can also be used as the compound (I). These particles can react with a polymer described later to introduce a group represented by the above formula (I) into the polymer. For example, —SiOH is introduced by a reaction between silica particles and a polymer described later.
Other examples of titanium coupling agents include Ajinomoto Fine Techno Co., Ltd. Preneact, Matsumoto Fine Chemical Co., Ltd. Titanium Tetraisopropoxide, Nippon Soda Co., Ltd. Titanium-i-propoxybis (acetylacetonato) titanium. As the aluminate coupling agent, acetoalkoxyaluminum diisopropylate is exemplified.

In this invention, said compound (I) may be used individually by 1 type, and may use 2 or more types together.
In the present invention, the content of the compound (I) contained in the resin composition for a relief forming layer is preferably 0.1 to 80% by weight, more preferably 1 to 40% by weight in terms of solid content. Preferably, it is 5 to 30% by weight.

In the present invention, from the viewpoint of forming a crosslinked structure in the relief forming layer, the relief forming layer coating liquid preferably contains a polymerizable compound in order to form the crosslinked structure.
The polymerizable compound that can be used here can be arbitrarily selected from compounds having at least one ethylenically unsaturated group, preferably two or more, and more preferably 2-6.
In addition, in the present invention, in addition to the purpose of forming a crosslinked structure, a compound having only one ethylenically unsaturated group (monofunctional polymerizable compound, monofunctional monomer) from the viewpoint of film properties such as flexibility and brittleness ) May be used.

[Polymerizable compound]
Hereinafter, a compound (monofunctional monomer) having one ethylenically unsaturated group in the molecule and a compound (polyfunctional monomer) having two or more ethylenically unsaturated groups in the molecule used as a polymerizable compound explain.
Since the relief forming layer is required to have a crosslinked structure in the film, a polyfunctional monomer is preferably used. The molecular weight of these polyfunctional monomers is preferably 200 to 2,000.
Examples of monofunctional monomers and polyfunctional monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters of polyhydric alcohol compounds, unsaturated carboxylic acids, Examples include amides with polyvalent amine compounds.

In the present invention, from the viewpoint of improving engraving sensitivity, a compound having a sulfur atom in the molecule is preferably used as the polymerizable compound.
Thus, as a polymeric compound which has a sulfur atom in a molecule | numerator, from a viewpoint of engraving sensitivity improvement, it has two or more ethylenically unsaturated bonds especially, and connects between two ethylenically unsaturated bonds among them. It is preferable to use a polymerizable compound having a carbon-sulfur bond at the site (hereinafter also referred to as “sulfur-containing polyfunctional monomer” as appropriate).

Examples of the functional group containing a carbon-sulfur bond in the sulfur-containing polyfunctional monomer in the present invention include sulfide, disulfide, sulfoxide, sulfonyl, sulfonamide, thiocarbonyl, thiocarboxylic acid, dithiocarboxylic acid, sulfamic acid, thioamide, and thiocarbamate. , Functional groups containing dithiocarbamate, or thiourea.
In addition, examples of the linking group containing a carbon-sulfur bond that connects two ethylenically unsaturated bonds in the sulfur-containing polyfunctional monomer include —C—S—, —C—S—S—, —NH (C = It is preferably at least one unit selected from the group consisting of S) O—, —NH (C═O) S—, —NH (C═S) S—, and —C—SO ₂ —.

Further, the number of sulfur atoms contained in the molecule of the sulfur-containing polyfunctional monomer is not particularly limited as long as it is 1 or more, and can be appropriately selected according to the purpose. However, engraving sensitivity and solubility in a coating solvent are not limited. From the viewpoint of the balance, 1 to 10 is preferable, 1 to 5 is more preferable, and 1 to 2 is still more preferable.
On the other hand, the number of ethylenically unsaturated groups contained in the molecule is not particularly limited as long as it is 2 or more, and can be appropriately selected according to the purpose. -10 are preferable, 2-6 are more preferable, and 2-4 are more preferable.

The molecular weight of the sulfur-containing polyfunctional monomer in the present invention is preferably 120 to 3,000, more preferably 120 to 1,500, from the viewpoint of the flexibility of the formed film.
Moreover, although the sulfur-containing polyfunctional monomer in this invention may be used independently, you may use it as a mixture with the polyfunctional polymerizable compound and monofunctional polymerizable compound which do not have a sulfur atom in a molecule | numerator.
From the viewpoint of engraving sensitivity, it is preferable to use the sulfur-containing polyfunctional monomer alone or as a mixture of the sulfur-containing polyfunctional monomer and the monofunctional monomer, and use it as a mixture of the sulfur-containing polyfunctional monomer and the monofunctional monomer. An embodiment is more preferred.

In the relief forming layer, film properties such as brittleness and flexibility can be adjusted by using a polymerizable compound such as a sulfur-containing polyfunctional monomer.
Further, the total content of the polymerizable compound including the sulfur-containing polyfunctional monomer in the relief forming layer is preferably 10 to 60% by weight with respect to the nonvolatile component from the viewpoint of flexibility and brittleness of the crosslinked film. A range of 15 to 45% by weight is more preferable.
In addition, when using together a sulfur-containing polyfunctional monomer and another polymeric compound, 5 weight% or more is preferable and, as for the quantity of the sulfur-containing polyfunctional monomer in all the polymeric compounds, 10 weight% or more is more preferable.

〔solvent〕
In the present invention, the solvent used for preparing the resin composition is preferably mainly an aprotic organic solvent from the viewpoint of promptly proceeding the reaction between the compound (I) and the specific polymer. More specifically, it is preferable to use aprotic organic solvent / protic organic solvent = 100/0 to 50/50 (weight ratio). More preferably, it is 100/0 to 70/30, and particularly preferably 100/0 to 90/10.
Preferred specific examples of the aprotic organic solvent include acetonitrile, tetrahydrofuran, dioxane, toluene, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl lactate, N, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
Preferred specific examples of the protic organic solvent are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, ethylene glycol, diethylene glycol, and 1,3-propanediol.

[Alcohol exchange reaction catalyst]
When compound (I) is used in the resin composition, it is preferable to contain an alcohol exchange reaction catalyst in order to promote the reaction between compound (I) and the specific binder polymer.
The alcohol exchange reaction catalyst can be applied without limitation as long as it is a commonly used reaction catalyst.
Hereinafter, an acid or basic catalyst, which is a typical alcohol exchange reaction catalyst, and a metal complex catalyst will be sequentially described.

-Acid or basic catalyst-
As the catalyst, an acid or a basic compound is used as it is, or a catalyst dissolved in a solvent such as water or an organic solvent (hereinafter referred to as an acidic catalyst and a basic catalyst, respectively). The concentration at the time of dissolving in the solvent is not particularly limited, and may be appropriately selected according to the characteristics of the acid or basic compound used, the desired content of the catalyst, and the like.
The type of acidic catalyst or basic catalyst is not particularly limited. Specifically, examples of the acidic catalyst include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, Examples of the basic catalyst include carboxylic acids such as formic acid and acetic acid, substituted carboxylic acids obtained by substituting R in the structural formula represented by RCOOH with other elements or substituents, sulfonic acids such as benzenesulfonic acid, and phosphoric acid. Include ammoniacal bases such as aqueous ammonia and amines such as ethylamine and aniline. From the viewpoint of promptly promoting the alcohol exchange reaction in the layer, methanesulfonic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, phosphoric acid, phosphonic acid, and acetic acid are preferable, and methanesulfonic acid, p-toluenesulfonic acid Phosphoric acid is particularly preferred.

-Metal complex catalyst-
The metal complex catalyst used as the alcohol exchange reaction catalyst in the present invention is preferably a metal element selected from the group consisting of Groups 2, 4, 5 and 13 of the periodic table and β-diketone (acetylacetone is preferred), It is composed of an oxo or hydroxy oxygen compound selected from the group consisting of ketoesters, hydroxycarboxylic acids or esters thereof, amino alcohols, and enolic active hydrogen compounds.
Furthermore, among the constituent metal elements, group 2 elements such as Mg, Ca, St, and Ba, group 4 elements such as Ti and Zr, group 5 elements such as V, Nb, and Ta, and 13 such as Al and Ga. Group elements are preferred and each form a complex with an excellent catalytic effect. Among them, complexes obtained from Zr, Al, or Ti are excellent, and ethyl orthotitanate is particularly preferable.
These are excellent in stability in aqueous coating solutions and in gelation promoting effect in sol-gel reaction during heating and drying. Among them, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), di ( Particularly preferred are acetylacetonato) titanium complex and zirconium tris (ethylacetoacetate).

In the resin composition, only one alcohol exchange reaction catalyst may be used, or two or more kinds may be used in combination. The content of the alcohol exchange reaction catalyst in the resin composition is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the polymer having a hydroxyl group.

(Polymerization initiator)
The resin composition for laser engraving preferably contains a polymerization initiator, and more preferably uses a compound having an ethylenically unsaturated group and a polymerization initiator in combination.
A well-known thing can be used for a polymerization initiator without a restriction | limiting. Hereinafter, although the radical polymerization initiator which is a preferable polymerization initiator is explained in full detail, this invention is not restrict | limited by these description.

In the present invention, preferred radical polymerization initiators include (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (F) ketoxime ester compound, (g) borate compound, (h) azinium compound, (i) metallocene compound, (j) active ester compound, (k) compound having carbon halogen bond, (l) azo compound, etc. Is mentioned. Specific examples of the above (a) to (l) are given below, but the present invention is not limited to these.

In the present invention, from the viewpoint of engraving sensitivity and a good relief edge shape when applied to a relief forming layer of a relief printing plate precursor, (c) an organic peroxide and (l) an azo compound are more Preferably, (c) an organic peroxide is particularly preferable.

(A) aromatic ketones, (b) onium salt compounds, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) ketoxime ester compounds, (g) borate compounds, (h) azinium compounds As compounds (i) metallocene compounds, (j) active ester compounds, and (k) compounds having a carbon halogen bond, the compounds listed in paragraphs 0074 to 0118 of JP-A-2008-63554 are preferably used. it can.

Also, the polymerization initiator can be roughly classified into a photopolymerization initiator and a thermal polymerization initiator. In the present invention, a thermal polymerization initiator is preferably used from the viewpoint of improving the degree of crosslinking. As the thermal polymerization initiator, (c) an organic peroxide and (l) an azo compound are preferably used. In particular, the following compounds are preferred.

(C) Organic peroxide As a radical polymerization initiator that can be used in the present invention, preferred (c) organic peroxide is 3,3′4,4′-tetra (t-butylperoxycarbonyl) benzophenone. 3,3′4,4′-tetra (t-amylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′4,4′- Tetra (t-octylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra (cumylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, Peroxide esters such as di-t-butyldiperoxyisophthalate are preferred.

(L) Azo-based compound As a radical polymerization initiator that can be used in the present invention, preferred (l) azo-based compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobispropio Nitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2, 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2- Methylpropionamidooxime), 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl)] - -Hydroxyethyl] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2 , 2′-azobis (N-cyclohexyl-2-methylpropionamide), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (2,4,4) 4-trimethylpentane) and the like.

The polymerization initiator in the present invention may be used alone or in combination of two or more.
The polymerization initiator can be added in a proportion of preferably 0.01 to 10% by weight, more preferably 0.1 to 3% by weight, based on the total solid content of the resin composition for laser engraving.

<Other additives>
The resin composition for laser engraving and the relief layer of the relief printing plate precursor may contain known additives in addition to those described above.
The resin composition for laser engraving is more preferably added with nitrocellulose or a highly thermally conductive substance as an additive for improving engraving sensitivity. Since nitrocellulose is a self-reactive compound, it generates heat during laser engraving and assists in the thermal decomposition of coexisting polymers such as hydrophilic polymers. As a result, it is estimated that the engraving sensitivity is improved. The high thermal conductive material is added for the purpose of assisting heat transfer, and examples of the thermal conductive material include inorganic compounds such as metal particles and organic compounds such as conductive polymers. As the metal particles, gold fine particles, silver fine particles, and copper fine particles having a particle size of micrometer order to several nanometers order are preferable. As the conductive polymer, a conjugated polymer is particularly preferable, and specific examples include polyaniline and polythiophene.
Moreover, the sensitivity at the time of photocuring the resin composition for laser engraving can be further improved by using a co-sensitizer.
Furthermore, it is preferable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition.
A colorant such as a dye or pigment may be added for the purpose of coloring the resin composition for laser engraving. Thereby, properties such as the visibility of the image portion and the suitability of the image density measuring device can be improved.
Furthermore, in order to improve the physical properties of the cured film of the resin composition for laser engraving, a known additive such as a filler may be added.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(Examples 1-1 to 1-25 and Comparative Examples 1-1 to 1-5, and Examples 2-1 to 2-27 and Comparative Example 2-1: Preparation of Rinse Solution for Relief Printing Plate Making)
According to the following Formulation Examples 1 to 3, Examples 1-1 to 1-25 and Comparative Examples were carried out with the types of surfactants (W agents) and / or solvents listed in Tables 2 to 5, and the addition concentrations and pH. The rinsing liquids for relief printing plate making of 1-1 to 1-5 and Examples 2-1 to 2-27 and Comparative Example 2-1 were prepared.
If necessary, the pH of the rinse solution was adjusted to the alkaline side by adding sodium hydroxide.
In addition, the addition of the antifoaming agent in the formulation examples 1 and 2 mainly suppresses foaming during the preparation of the rinsing liquid such as stirring and filling into the bottle, and brushing during the rinsing process This is to suppress foaming at the time.

<Prescription Example 1>
・ Water (main component, the remainder of the ingredients listed below)
・ Sodium hydroxide (solid)
・ Surfactants and / or solvents listed in Tables 2 to 5 (contents listed in Tables 2 to 5)
・ TSA731 (0.07% by weight, antifoaming agent, silicone antifoaming agent manufactured by Toray Dow Corning Co., Ltd.)

<Prescription Example 2>
・ Water (main component, the remainder of the ingredients listed below)
・ Potassium hydroxide (solid)
・ Surfactants and / or solvents listed in Tables 2 to 5 (contents listed in Tables 2 to 5)
・ TSA739 (0.15% by weight, antifoaming agent, silicone antifoaming agent manufactured by Toray Dow Corning Co., Ltd.)

<Prescription Example 3>
・ Water (main component, the remainder of the ingredients listed below)
・ Sodium hydroxide (solid)
・ Surfactants and / or solvents listed in Tables 2 to 5 (contents listed in Tables 2 to 5)

<Preparation of relief printing plate precursor 1>
1. Preparation of resin composition for laser engraving In a three-necked flask equipped with a stirring blade and a cooling tube, 50 parts by weight of GOHSENAL T-215 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., water-soluble PVA) as a specific polymer, as a solvent 47 parts by weight of propylene glycol monomethyl ether acetate was added and heated at 70 ° C. for 120 minutes with stirring to dissolve the polymer. Thereafter, the solution was brought to 40 ° C., 15 parts by weight of tributyl citrate as a plasticizer, 8 parts by weight of Bremer LMA (manufactured by NOF Corporation) as a polymerizable compound (monofunctional), and perbutyl Z ( 1.6 parts by weight of NOF Co., Ltd.) and 1 part by weight of carbon black (Show Black N110, Cabot Japan Co., Ltd., DBP oil absorption 115 ml / 100 g) as a photothermal conversion agent were added for 30 minutes. Stir. Thereafter, (A) Compound (I) (SC-1) [The structure is shown below. 15 parts by weight of a trade name, KBE-846 available from Shin-Etsu Chemical Co., Ltd.) and 0.4 parts by weight of phosphoric acid as a catalyst were added and stirred at 40 ° C. for 10 minutes. By this operation, a fluid coating solution for a relief forming layer (laser engraving resin composition) was obtained.

Et represents an ethyl group.

2. Preparation of relief printing plate precursor for laser engraving Place a spacer (frame) of a predetermined thickness on a PET substrate, and gently cast the relief-forming layer coating solution obtained above from the spacer (frame). Then, it was dried in an oven at 90 ° C. for 3 hours to provide a relief forming layer having a thickness of about 1 mm to prepare a relief printing plate precursor 1 for laser engraving.

<Preparation of relief printing plate precursor 2>
A relief forming layer was prepared in the same manner as in the production of the relief printing plate precursor 1 except that GOHSENAL T-215 was replaced with DENKA Butyral # 3000-2 (manufactured by Denki Kagaku Kogyo Co., Ltd., polyvinyl butyral, Mw = 90,000). A relief coating plate precursor 2 for laser engraving was prepared.

<Preparation of relief printing plate precursor 3>
Except that SC-1 and phosphoric acid were not used, a relief forming layer coating solution was prepared in the same manner as the preparation of the relief printing plate precursor 2 to prepare a relief printing plate precursor 3 for laser engraving.

<Preparation of relief printing plate precursor 4>
In a three-necked flask equipped with a stirring blade and a condenser tube, 50 parts by weight of ELASTOSIL (registered trademark: type R300 / 30S, Wacker silicone rubber) and 47 parts by weight of tetrahydrofuran as a solvent are stirred and stirred to dissolve the polymer. I let you. Thereafter, 0.8 parts by weight of carbon black (Show Black N110, manufactured by Cabot Japan Co., Ltd., DBP oil absorption 115 ml / 100 g) was added as a photothermal conversion agent and stirred for 30 minutes. By this operation, a fluid coating solution for a relief forming layer (laser engraving resin composition) was obtained.
A relief forming layer coating solution was prepared by the same method as the preparation of the relief printing plate precursor 1 except that the relief forming layer coating solution was used, and a relief printing plate precursor 4 for laser engraving was prepared.

<Preparation of relief printing plate>
The relief forming layer of the obtained relief printing plate precursor for laser engraving was heated at 80 ° C. for 3 hours and further at 100 ° C. for 3 hours to thermally crosslink the relief forming layer.
The relief forming layer after crosslinking was engraved with a carbon dioxide laser (CO ₂ laser) or a semiconductor laser with a fiber to obtain a relief printing plate. In addition, the thickness of the relief layer which the obtained relief printing plate has was about 1 mm.
<Carbon dioxide laser engraving>
As a carbon dioxide laser engraving machine, engraving by laser irradiation was performed using a high-quality CO ₂ laser marker ML-9100 series (manufactured by Keyence Corporation). After peeling off the protective film from the printing plate precursor 1 for laser engraving, a carbon dioxide laser engraving machine is used to raster engrave a 1 cm square solid part under the conditions of output: 12 W, head speed: 200 mm / sec, pitch setting: 2,400 DPI did.
<Semiconductor laser engraving with fiber>
A laser recording apparatus equipped with a fiber-coupled semiconductor laser (FC-LD) SDL-6390 (manufactured by JDSU, wavelength 915 nm) was used as a fiber-coupled semiconductor laser engraving machine. A 1 cm square solid part was raster engraved with a semiconductor laser engraving machine under conditions of laser output: 7.5 W, head speed: 409 mm / second, pitch setting: 2,400 DPI.

(Evaluation)
Examples 1-1 to 1-25 and Comparative Examples 1-1 to 1- 1 were prepared by using the relief printing plate precursors listed in Tables 2 to 5 engraved with the carbon dioxide laser or the semiconductor laser with fiber. 5 and the rinsing solutions for relief printing plate making of Examples 2-1 to 2-27 and Comparative Example 2-1 were evaluated as follows.

<Rinse evaluation>
The rinsing liquid was applied to the engraved relief printing plate at about 200 mL / m ^2, and the engraved portion was rubbed 15 times in the vertical and horizontal directions with a toothbrush (manufactured by Lion Corporation, Clinica Habrush Flat). Then, when observed with an optical microscope, the relief layer with no debris was 6, 6 with little remaining, 3 with a little remaining (allowable level), 1 with no debris removed, An intermediate evaluation between 5 and 3 was 4, and an intermediate evaluation between 4, 3 and 1 was 2.

<Evaluation of impact on relief printing plate (sensitive material)>
The relief printing plate which was not engraved was immersed in the rinse liquid, and the weight change was measured.
The weight change was very small, 3; the weight change was small and practically acceptable; 2; the weight change was large and practically unacceptable.

In Tables 2 to 5, the nonionic surfactant, the anionic surfactant, and the nonionic surfactant used as the surfactant contained in the rinse liquid are as follows.
The nonionic surfactant has a predetermined alkyl group R and EO chain length (n, m + n, or l + m + n) among the nonionic surfactants represented by the formulas (1-1) to (1-6). Is. The alkyl groups R in these nonionic surfactants are all linear.
The anionic surfactant is an anionic surfactant represented by the following formula (2-6-1) and formula (2-11). In the anionic surfactant represented by the formula (2-6-1), the alkyl group C ₄ H ₉ is an isobutyl group, and in the anionic surfactant represented by the formula (2-11), C ₈ H ₁₇ is linear. belongs to.
The cationic surfactant is a cationic surfactant represented by the following formula (3-4). The alkyl group C ₁₂ H ₂₅ in this cationic surfactant is linear.

In Tables 4 and 5, the solvent used in the rinse liquid is any one of the solvents S-1 to S-45.

In addition to the above, the abbreviations in Tables 2 to 5, the binders used in Tables 2 to 5, and the compound (I) are as shown below.
PVA: GOHSENAL T-215 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., water-soluble PVA)
PVB: polyvinyl butyral (Mw = 90,000, Denka Butyral # 3000-2 manufactured by Denki Kagaku Kogyo Co., Ltd.)
Rubber: ELASTOSIL (registered trademark: type R300 / 30S, manufactured by Wacker, silicone rubber)
Compound (I): SC-1 below

Et represents an ethyl group.

Claims

Preparing a relief printing plate precursor having a relief-forming layer containing a non-elastomer binder polymer, a plasticizer, and a photothermal conversion agent on a support;
Engraving the relief printing plate precursor by exposure using a laser; and
A step of removing engraving residue generated by engraving with a rinsing liquid for relief printing plate making in this order,
The method for making a relief printing plate, wherein the rinsing liquid for making a relief printing plate contains a nonionic surfactant.
The rinsing liquid for relief printing plate making contains at least one nonionic surfactant selected from the group consisting of compounds represented by the following formulas (1-1) to (1-6): A method for making a relief printing plate as described.

(In the formula (1-1) and the formulas (1-3) to (1-5), R represents an alkyl group having 6 to 23 carbon atoms, and in the formula (1-1), n is 3 to 100. In formula (1-2), n represents an integer of 3 to 30, and in formulas (1-3) and (1-4), m and n each satisfy 3 ≦ m + n ≦ 50. And in formulas (1-5) and (1-6), X represents a hydrogen atom or a methyl group, and in formula (1-5), n is an integer of 3 to 50 In formula (1-6), l, m and n each independently represents an integer of 2 to 30.)
3. The method for making a relief printing plate according to claim 1, wherein the content of the nonionic surfactant in the rinsing liquid for relief printing plate making is 0.1 to 20% by weight.
4. The relief printing plate making rinse solution contains at least one solvent selected from the group consisting of alcohol solvents, ether solvents, glycol solvents, and glycol ether solvents. 2. A method for making a relief printing plate according to item 1.
Preparing a relief printing plate precursor having a relief-forming layer containing a non-elastomer binder polymer, a plasticizer, and a photothermal conversion agent on a support;
Engraving the relief printing plate precursor by exposure using a laser; and
A step of removing engraving residue generated by engraving with a rinsing liquid for relief printing plate making in this order,
The relief printing plate rinsing solution contains at least one solvent selected from the group consisting of alcohol solvents, ether solvents, glycol solvents, and glycol ether solvents. Plate making method.
The method for making a relief printing plate according to claim 4 or 5, wherein the content of the solvent in the rinsing liquid for relief printing plate making is 1 to 40% by weight.
The relief printing plate making method according to any one of claims 1 to 6, wherein the pH of the rinsing solution for relief printing plate making is 9 or more.
The method for making a relief printing plate according to any one of claims 1 to 7, wherein the binder polymer is polyvinyl butyral and / or a derivative thereof.
The plate making method of a relief printing plate according to any one of claims 1 to 8, wherein the relief forming layer contains a compound containing a group represented by the following formula (I).
* -M (R 1 ) (R 2 ) n (I)
(In the formula (I), R 1 represents OR 3 or a halogen atom, M represents Si, Ti, or Al. When M is Si, n is 2, and when M is Ti, n is 2. And when M is Al, n is 1, each R 2 independently represents a hydrocarbon group, OR 3 or a halogen atom, R 3 represents a hydrogen atom or a hydrocarbon group, and * (Represents the bonding position with other structures)
The plate-making method of the relief printing plate of Claim 9 in which the said relief forming layer contains the compound containing group represented by following formula (i).
* -Si (OR 3 ) (R 2 ) 2 (i)
(In formula (i), two R 2 s each independently represent a hydrocarbon group, OR 3 or a halogen atom, R 3 represents a hydrogen atom or a hydrocarbon group, and * represents a bonding position with another structure. Represents.)
11. The engraving step is a step of engraving an exposure area by scanning exposure of the relief printing plate precursor using a fiber-coupled semiconductor laser having a maximum wavelength of 700 to 1,300 nm. A process for making a relief printing plate as described in 1.