JP2007021794A - Lithographic printing plate material, and methods for making lithographic printing plates of positive type, processless positive type, negative type and processless negative type - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel lithographic printing plate material which is a single-layer phase change type sensitive material forming an image part with exposure, of which the polarity is inverted by that a thermally responsive polarity change material contained in a capsule is made uniformly compatible with a resin layer by heating with the exposure, while the polarity thereof is inverted, and the temperature turns back subsequently to a normal, and which can thereby produce an essentially high strength and high polarity difference. <P>SOLUTION: The lithographic printing plate material comprises an image forming layer containing the microcapsule and a hydrophilic substrate, wherein the microcapsule contains a compound which reversibly causes a change in the polarity according to the temperature. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a lithographic printing plate material, a method for producing a positive lithographic printing plate using the same, a method for producing a processless positive lithographic printing plate, a method for producing a negative lithographic printing plate, and a processless negative lithographic plate The present invention relates to a method for producing a printing plate.

  In recent years, digitization technology that electronically processes, stores, and outputs image information using a computer has become widespread, and in printing plate preparation technology for offset printing, directivity is determined according to digitized image information. A so-called CTP system that scans a high laser beam and directly records it on a photosensitive lithographic printing plate has been developed, and its practical application is progressing.

  Such typographic printing plate materials for CTP include high-sensitivity photopolymer type, silver salt DTR type, electrophotographic type, etc., but in recent years, demand from printing users has been increased from the viewpoint of handling in a bright room, etc. The thermal type is attracting attention.

  On the other hand, there is a need for a printing plate material that does not require development processing using a processing solution containing a special agent (for example, alkali, acid, solvent, etc.) and can be applied to a conventional printing machine. There are known printing plate materials for the dry CTP system, such as phase change type printing plate materials that are not required and printing plate materials that are developed at the initial stage of printing on a printing machine and that do not require a development process. These methods are very preferable methods.

  For example, JP-A-8-507727, JP-A-6-186750, JP-A-6-199064, JP-A-7-314934, JP-A-10-58636, and JP-A-10-244773 are used for the CTP system as described above. Ablation type methods described in the above, and a method in which a heat-sensitive image forming layer is provided on a substrate and an image portion is formed on a hydrophilic layer by image-like heat generation by laser exposure (for example, Patent Document 1, (See Patent Document 2 and Patent Document 3.) Generally, image formation by ablation has problems such as contamination of the head / device due to ablation residue, removal of ablation residue is insufficient, and initial reproducibility becomes unstable. .

  On the other hand, a method of generating heat like an image and changing the characteristics of the exposed portion is a preferable method. As such a method, a hot-melt type material that converts laser light into heat and forms an image portion on a hydrophilic layer has been actively developed. This light-sensitive material has a heat-sensitive image forming layer and a hydrophilic layer, and a method of forming an image part by melting the image forming layer by exposure to form an image part on the hydrophilic layer is generally used.

  Such a method is preferable because it does not cause ablation residue and can increase the difference in polarity between the image area and the non-image area. However, a low polarity image is formed on the high polarity hydrophilic layer. Therefore, there is a problem that the adhesiveness of the image portion is essentially low and the printing durability is not sufficient.

  Another method that does not generate ablation residue is a phase change type. This method is a single-layer material that undergoes a phase change by light, and a sufficient performance material that can replace a printing plate has not yet been completed. However, since this method forms an image by modifying only a single-layer exposed portion, high printing durability can be expected in essence. At present, there is a problem that the difference in characteristics between the image area and the non-image area due to exposure is small, and a product that can be satisfactorily printed has not been obtained, and the present invention has such a single-layer phase change type photosensitive material. It provides a new approach.

The present invention has been made in view of the above. That is, it is a single-layer phase-change type photosensitive material that forms an image portion by exposure, and the resin layer is uniformly formed while reversing the polarity of the heat-responsive polarity change material contained in the capsule by heating by exposure. An object of the present invention is to provide a new lithographic printing plate material in which the polarity is reversed by recombination and then returning to room temperature, and an essentially high strength and high polarity difference can be produced.
JP 2001-96710 A Japanese Patent Laid-Open No. 2001-138852 JP 2001-113848 A

  The present invention has been made in view of the above, and an object of the present invention is a single-layer phase change type light-sensitive material that forms an image portion by exposure, and is a thermally responsive polarity change material encapsulated in a capsule. New lithographic printing that can be mixed with the resin layer uniformly while reversing the polarity by heating by exposure and then reversing the polarity by returning to room temperature, resulting in essentially high strength and high polarity difference It is to provide plate material.

  Another object of the present invention is to provide a lithographic printing plate material having a novel photosensitive mechanism and excellent in sensitivity and the number of printing wastes, and to produce essentially high printing durability using the lithographic printing plate material. An object of the present invention is to provide a method for producing a positive lithographic printing plate, a method for producing a processless positive lithographic printing plate, a method for producing a negative lithographic printing plate, and a method for producing a processless negative lithographic printing plate.

  In particular, it is possible to provide a lithographic printing plate material that can be developed on a single-layer printing machine, thereby providing a high printing durability processless thermal CTP system.

  The above object of the present invention can be achieved by the following constitution.

(Claim 1)
In a lithographic printing plate material comprising an image forming layer containing a microcapsule and a hydrophilic support, the microcapsule contains a compound that reversibly changes its polarity with temperature. A planographic printing plate material.

(Claim 2)
2. The lithographic printing plate material according to claim 1, wherein the compound that reversibly changes its polarity with temperature is water-soluble at room temperature.

(Claim 3)
The lithographic printing plate material according to claim 1 or 2, wherein the microcapsule comprises a shell having a thermoplastic resin as a main component and a core containing a compound that reversibly changes its polarity depending on temperature.

(Claim 4)
The lithographic printing plate material according to any one of claims 1 to 3, wherein the image forming layer contains at least a photothermal conversion agent, a water-insoluble resin, and the microcapsules.

(Claim 5)
2. The lithographic printing plate material according to claim 1, wherein the compound that reversibly changes polarity with temperature is insoluble in water at room temperature.

(Claim 6)
6. The lithographic printing plate material according to claim 5, wherein the microcapsule comprises a shell having a thermoplastic resin as a main component and a core containing a compound that reversibly changes its polarity depending on temperature.

(Claim 7)
The lithographic printing plate material according to claim 5 or 6, wherein the image forming layer contains at least a photothermal conversion agent, a water-soluble resin, and microcapsules.

(Claim 8)
A method for producing a positive lithographic printing plate, comprising: exposing the lithographic printing plate material according to any one of claims 2 to 4 to a lithographic printing plate by removing an exposed portion after image exposure with a high-power laser; .

(Claim 9)
The lithographic printing plate material according to any one of claims 2 to 4, wherein after image exposure with a high-power laser, the image portion (exposed portion) is removed processlessly on a printing machine to form a lithographic printing plate. A processless positive type lithographic printing plate production method.

(Claim 10)
A lithographic printing plate material according to any one of claims 5 to 7, wherein the lithographic printing plate is formed by removing an unexposed portion after image exposure with a high-power laser and forming a lithographic printing plate. Method.

(Claim 11)
A lithographic printing plate material according to any one of claims 5 to 7 is formed by removing a non-image area (unexposed area) processlessly on a printing machine after image exposure with a high-power laser. A processless negative lithographic printing plate production method characterized by the above.

  According to the present invention, it is a single-layer phase change type light-sensitive material that forms an image portion by exposure, and the heat-responsive polarity-change material encapsulated in the capsule is uniformly heated while reversing the polarity by heating. It is an object of the present invention to provide a new lithographic printing plate material which is compatible with a resin layer and then reverses its polarity by returning to room temperature, and can essentially produce high strength and high polarity difference.

  Also, a lithographic printing plate material having a novel photosensitive mechanism and excellent in sensitivity and the number of printing waste papers, and a method for producing a positive lithographic printing plate having high printing durability using the lithographic printing plate material A processless positive lithographic printing plate production method, a negative lithographic printing plate production method, and a processless negative lithographic printing plate production method can be provided.

  In particular, it is possible to provide a lithographic printing plate material that can be developed on a single layer / printing machine, thereby providing a high printing durability processless thermal CTP system.

  Hereinafter, although the best mode for carrying out the present invention will be described, the present invention is not limited to these.

  The lithographic printing plate material of the present invention is a lithographic printing plate material comprising an image forming layer containing microcapsules and a hydrophilic support, wherein the microcapsules reversibly change in polarity with temperature. It is characterized by containing the resulting compound (reversible thermoresponsive polarity-changing substance).

(Compound that reversibly changes polarity with temperature)
As a compound that reversibly changes its polarity depending on the temperature according to the present invention (hereinafter also referred to as a reversible thermoresponsive polarity-changing substance),
1). A compound that reversibly changes its polarity with temperature, dissolves in water on a lower temperature side than a specific temperature, and becomes insoluble in water on a higher temperature side, and 2). And a compound that reversibly changes its polarity depending on the temperature, is insoluble in water at a lower temperature than a specific temperature, and is soluble in water at a higher temperature.

1). A compound that causes a reversible change in polarity depending on the temperature, dissolves in water on a lower temperature side than a specific temperature, and becomes insoluble in water on a higher temperature side (high temperature responsiveness having a lower critical solution temperature (LCST)) Molecular compound)
1-1).
It is well known to change its structure depending on the temperature in an aqueous solution. It dissolves in water on the low temperature side below a specific temperature (for example, 32 ° C.) and turns into water on the high temperature side above the specific temperature (for example, 32 ° C.). Temperature-responsive polymer compound having a lower critical eutectic temperature (LCST) that becomes insoluble (on the low temperature side, the polymer compound is hydrophilic and swelled and dissolved in water; It is considered that the polymer compound is hydrophobic and aggregates in a contracted state.)
1-1-1.).
Described in JP-A-2004-263063,
(1-1-1-1) Poly (N-isopropylacrylamide)
(1-1-1-2) Polyether (1-1-1-1) Polyvinyl ether and the like can be mentioned, among others,
1-1-2).
Examples include polyurethane copolymers described in JP-A No. 2004-263063. Among them, a polyurethane copolymer represented by the following general formula (PU) is preferable.

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent, and R ¹ and R ² Represents a hydrocarbon chain or a hydrocarbon group which may be bonded to each other through a different atom or may have a substituent, and m and n represent a unit structure ratio.
The polyurethane copolymer represented by the general formula (PU) is aziridines represented by the following general formula (A):

(R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent, and R ¹ and R ² are And represents a hydrocarbon chain or a hydrocarbon group which may have a substituent through a hetero atom.)
Can be obtained by heating in subcritical or supercritical carbon dioxide. For example, the polyurethane copolymer etc. which are obtained by making the pressure of a carbon dioxide into the range of 3.0-30 MPa and making heating temperature into the range of 50-200 degreeC are mentioned.

In the general formula (A), the hydrocarbon group represented by R ¹ , R ² , R ³ , R ⁴ is a chain or cyclic, saturated or unsaturated, aliphatic, alicyclic, or Various kinds of aromatic and heterocyclic rings may be used. For example, this hydrocarbon group is chain-like and saturated, and examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group. R ¹ and R ² may be bonded to each other to form a carbocycle.

  Specific examples of such aziridines (three-membered ring imines) include, for example, aziridine, 2-methylaziridine, 2-ethylaziridine, 2,2-dimethylaziridine, 2,3-dimethylaziridine, 2-phenylaziridine, A cyclohexene imine etc. can be illustrated.

  Examples of the polyurethane copolymer represented by the general formula (PU) include 2-methylaziridine, 2-ethylaziridine, 2,2-dimethylaziridine, cyclohexenimine, etc., carbon dioxide (pressure 10 MPa, And a polyurethane copolymer obtained by reacting at a heating temperature of 100 to 140 ° C. for 24 hours.

  Further, for example, the following polyurethane obtained by reacting 2-methylaziridine (8.8 mol) with carbon dioxide (pressure is 10 MPa, in supercritical carbon dioxide) at a heating temperature of 100 to 140 ° C. for 24 hours. A copolymer etc. are mentioned.

  Specific examples of the temperature-sensitive material of the present invention (temperature-responsive polymer compound having a lower critical solution temperature (LCST)) include the following.

  Each of the polyurethane copolymers represented by the general formula (PU) has a certain lower critical solution temperature, becomes slightly water-soluble (hydrophobized) above the lower critical solution temperature, and is acceptable below the lower critical solution temperature. It has the property of making it water-soluble (hydrophilic). This change is reversible.

1-2).
Moreover, as a reversible thermal response polarity changing substance having a lower critical solution temperature (LCST) used in the present invention, a polymer exhibiting temperature responsiveness having a lower critical solution temperature described in JP-A-7-33224 A temperature sensitive material having
1-2-1.).
The monomer constituting the polymer is composed of at least one of N-substituted (meth) acrylamide derivatives and vinyl methyl ether, and a polymer exhibiting temperature responsiveness having a lower critical solution temperature. Temperature sensitive material.
Etc.

  The lower critical solution temperature is a critical temperature at which the polymer transitions from a hydrated state to a dehydrated state. Below the critical temperature, the polymer is hydrophilic and dissolves in water. Along with this, the molecular chain of the polymer expands and the volume of the entire polymer increases. However, at a temperature higher than the above critical temperature, it is hydrophobic and insoluble in water. As a result, the molecular chain of the polymer shrinks, and the volume of the entire polymer decreases. This change is reversible.

  The polymer exhibiting temperature responsiveness having the lower critical eutectic temperature is a homopolymer of monomers exhibiting the above temperature responsiveness, a copolymer of the monomers, or reacting with the monomer to form a copolymer. And a copolymer with another monomer (auxiliary monomer) that does not exhibit the above-described temperature responsiveness.

  As the monomer exhibiting temperature responsiveness, it is preferable to use at least one of N-substituted (meth) acrylamide derivatives and vinyl methyl ether. The polymer composed of the above monomer is more excellent in temperature responsiveness.

  The N-substituted (meth) acrylamide derivatives are N-substituted acrylamide derivatives and N-substituted methacrylamide derivatives. Examples of the N-substituted acrylamide derivative and N-substituted methacrylamide derivative include N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-ethylacrylamide, and N-ethylmethacrylamide. N-cyclopropylmethacrylamide, N-cyclopropylacrylamide, N, N-diethylacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-isopropylacrylamide, N-methyl-Nn-propylacrylamide, One or more selected from a group such as N-acryloylpiperidine is preferred. The polymer composed of the above monomer is more excellent in temperature responsiveness.

  Examples of the auxiliary monomer include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, styrene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl. One or more selected from groups such as acrylate, methacrylic acid, acrylic acid, itaconic acid, acrylamide, methacrylamide, and the like are preferred.

  By setting it as a copolymer with the said auxiliary monomer, the advantage that a lower critical solution temperature can be changed is acquired. That is, the lower critical solution temperature can be shifted to a low temperature side by copolymerization with a hydrophobic monomer, and can be moved to a high temperature side by copolymerization with a hydrophilic monomer.

  Specific examples of the temperature-sensitive material of the present invention (temperature-responsive polymer compound having a lower critical solution temperature (LCST)) include the following.

About a temperature-sensitive polymer using 480 parts of an aqueous monomer solution composed of 24 parts of N-isopropylacrylamide as a monomer and 456 parts of deionized water and 60 parts of a 0.2% aqueous ammonium persulfate solution,
When 240 parts of an aqueous monomer solution consisting of 12 parts of N-isopropylacrylamide and 228 parts of deionized water is used (1-2-1).

  When 240 parts of an aqueous monomer solution consisting of 14.5 parts of N-isopropylacrylamide, 1.5 parts of 2-hydroxyethyl acrylate, and 224 parts of deionized water is used (1-2-2).

When 330 parts of an aqueous monomer solution consisting of 16.5 parts of N-isopropylacrylamide, 0.5 parts of methyl methacrylate and 313 parts of deionized water is used (1-2-3).
And other temperature-sensitive polymers.

1-3).
Examples of the temperature-responsive polymer compound having a lower critical solution temperature (LCST) include the following compounds described in JP-A No. 2002-256075.

1-3-1.).
A temperature-responsive material in which a skeleton of a non-animal polysaccharide and a segment having cohesiveness are bonded by heating.

1-3-2).
The temperature-responsive material according to 1-3-1), wherein a side chain having cohesive properties is bonded to the skeleton of the non-animal polysaccharide at a temperature of 30 ° C. or higher.

1-3-3).
The temperature-responsive material according to 1-3-1, wherein the non-animal polysaccharide is at least one selected from starch, cellulose, pectin, alginic acid, carrageenan, dextran, pullulan, and chitosan.

1-3-4).
The temperature-responsive material according to the paragraph 1-3-1), wherein the non-animal polysaccharide is a plant polysaccharide.

1-3-5).
The segment having an aggregating property is at least one selected from (1) polyacrylamide derivative, (2) poly-N-vinylacylamide, (3) Val, Leu, Ile, Nle, Pro, His, Phe, Trp The temperature-responsive material according to any one of 1-3-1) to 1-3-4), which is composed of at least one unit selected from peptide units having amino acid residues.

1-3-6).
The segment having a cohesiveness is represented by the following formula (I)
-(Val-Pro-Gly-X-Gly) n- (I)
(Wherein X represents an amino acid residue selected from Val, Pro, Leu, Ile, and Nle, and n represents an integer of 1 or more), and the following formula (II)
—CO—R ₁ —CO—Y—NH—R ₂ —NH— (II)
[Wherein, R ₁ and R ₂ are the same or different and each represents an alkylene group, a cycloalkylene group, or an arylene group, and Y represents-(Val-Pro-Gly-X-Gly) n- (X, n represents The same as the above), which represents an amino acid residue selected from Sar, Val, Pro, Leu, Ile, and Nle], and is composed of at least one unit selected from peptide copolymer units represented by 2-2 The temperature-responsive material according to any one of -1) to 2-2-5).

1-3-7).
The temperature-responsive material according to 1-3-6), wherein in formula (II), R ₁ and R ₂ are C2-6 alkylene groups.

1-3-8).
(1) Polymer of monomer composed of at least N-isopropylacrylamide; (2) Polymer of monomer composed of at least N-vinylisobutyramide; (3) H - in (Val-Pro-Gly-X -Gly) n-NH 2 ( wherein, X represents Val, Pro, Leu, Ile, an amino acid residue selected from Nle, n represents an integer of 2 or more. ); (4) (N′α, N′ε, N ″ α, N ″ ε-tetra (H- (Val-Pro-Gly-X-Gly) n) -Nα, Nε-dilysyl) lysyl-β- Alanine (wherein X and n are the same as above); (5) (N′α, N′ε, N ″ α, N ″ ε-tetra (H-His-Val-Gln-Val-His- (Val -Pro-Gly-X-Gly) n) -Nα, Nε-dilysyl) lysyl-β Alanine (wherein the same X and n); (6) -CO- R 1 -CO- (Val-Pro-Gly-X-Gly) in n-NH-R ₂ -NH- (wherein X , N, R ₁ and R ₂ are as defined above); (7) —CO—R ₁ —CO—Sar—NH—R ₂ —NH— (wherein R ₁ and R ₂ are as defined above); 8) 1-3-1 which is at least one unit selected from —CO—R ₁ —CO—X—NH—R ₂ —NH— (wherein X, R ₁ and R ₂ are the same as above) The temperature-responsive material according to any one of 1) to 1-3-7).

1-3-9).
The temperature-responsive material according to any one of 1-3-1) to 1-3-8), wherein the proportion of the segments having cohesiveness is 3 to 90% by mass of the whole.

1-3-10).
The segment having aggregation properties includes a pH-responsive segment containing 1 to 5 His residues, and exhibits hydrolysis promoting activity in the vicinity of neutrality 1-3-1) to 1-3-9) The temperature-responsive material according to any one of the above.
Etc.

  In the present specification, various amino acid residues are described by the following abbreviations.

  Ala: L-alanine residue Arg: L-arginine residue Asn: L-asparagine residue Asp: L-aspartic acid residue Cys: L-cysteine residue Gln: L-glutamine residue Glu: L-glutamic acid residue Gly: glycine residue His: L-histidine residue Ile: L-isoleucine residue Leu: L-leucine residue Lys: L-lysine residue Met: L-methionine residue Nle: L-norleucine residue Phe: L -Phenylalanine residue Pro: L-proline residue Sar: Sarcosine residue Ser: L-serine residue Thr: L-threonine residue Trp: L-tryptophan residue Tyr: L-tyrosine residue Val: L-valine residue In the present specification, the amino acid sequence of a peptide is represented according to a conventional method, wherein the N-terminal amino acid residue is located on the left side, and C Describe the amino acid residues of the end located on the right side.

  Specific examples of the temperature-sensitive material of the present invention (temperature-responsive polymer compound having a lower critical eutectic temperature (LCST)) include, for example, the following (1-3-1) to (1-3-4): Etc.

Polymer (1-3-1) in which a side chain of poly-N-isopropylacrylamide (PNIPAM) is bonded to the skeleton of potato starch:
5% by weight solution dissolved in 10 mM phosphate buffer (containing 0.15 M NaC1, pH 7.4): a clear liquid at room temperature (about 25 ° C.), a white gel when heated to 37 ° C. When this gelled material was cooled to room temperature, it became a transparent liquid.

Dextran- (N-isopropylacrylamide) copolymer (1-3-2):
A transparent gel was obtained at 37 ° C. All of these polymer solutions became transparent again upon cooling to room temperature.

Starch-peptide (Formula 1) polymer (1-3-3):
A white gel was obtained at 37 ° C. and became a clear liquid again upon cooling to room temperature, and the solution-gel behavior was reversible at 37 ° C.

Alginic acid-peptide (formula 2) polymer (1-3-4):
All gave a white gel at 37 ° C. In addition, the alginic acid-peptide (2) polymer became a transparent liquid again upon cooling to room temperature, and the solution-gel behavior was reversible at 37 ° C.
Etc.

  The temperature-responsive material of the present invention is composed of a non-animal polysaccharide skeleton and an aggregating segment bonded to the polysaccharide. The aggregating segment has a property of aggregating or precipitating by heating or heating. Have.

  Non-animal polysaccharides are polysaccharides derived from non-animals such as plants, algae, and fungi, and may be derivatives from polysaccharides or chemically synthesized polysaccharides. In addition to known pathogens such as viruses, bacteria, and prions, animal-derived polysaccharides are concerned about infection beyond species due to unknown pathogens. It has also been pointed out that the closer the distance between species, the greater the risk of infection across species. That is, the polysaccharide in the present invention is non-animal, and is a polysaccharide derived from a plant (including seaweed), a polysaccharide derived from a microorganism, or an animal polysaccharide derived from a non-mammal (particularly a polysaccharide derived from a plant). Is preferred.

  Polysaccharides include homoglycans (polysaccharides with monosaccharides such as glucose, fructose, mannose, galactose, galacturonic acid, glucosamine) and heteroglycans (glucose, fructose, mannose, galactose, arabinose, xylose, glucuronic acid, etc.) Any polysaccharide).

  Examples of polysaccharides include plant-derived polysaccharides (cellulose, hemicellulose, dextran, inulin, levan, xylan, mannan, galactan, pectin, starch, galactomannan (or guar gum), glucomannan (or konjac mannan), locust bean gum, Tamarind gum, gum arabic, gellan gum, gum tragacanth, caraya gum, arabinogalactan, agar, carrageenan (or carrageenan), alginic acid, etc. Polysaccharides derived from mammals (such as chitin) and their derivatives (dextrin, cyclodextrin, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropyl) Pills cellulose, hydroxypropyl methylcellulose, hydroxypropyl methylcellulose phthalate, cellulose ethers such as carboxymethyl cellulose, cellulose esters such as cellulose acetate phthalate, cellulose ether esters, methoxylated pectin, carboxymethyl starch, chitosan, etc.), and others. These polysaccharides can be used alone or in combination of two or more.

  Among plant-derived polysaccharides or derivatives thereof, starch, cellulose, pectin, alginic acid, carrageenan, dextran, etc. are frequently used, among microorganism-derived polysaccharides or derivatives thereof, pullulan, etc. are frequently used, and derived from non-mammalian animals Chitosan and the like are frequently used as polysaccharides. In particular, plant-derived plant polysaccharides (starch, cellulose, alginic acid, etc.) are preferable.

The molecular weight of the polysaccharide is not particularly limited, and can be appropriately selected from a range of, for example, a number average molecular weight of 500 to 100 × 10 ⁴ , preferably 1000 to 70 × 10 ⁴ (particularly 1 × 10 ⁴ to 50 × 10 ⁴ ). .

  The type of the segment (or fragment, side chain) having a cohesive property is not particularly limited as long as it has a cohesive property by heating in the form of an aqueous solution. For example, the temperature is 30 ° C. or higher (preferably 30 to 50 ° C., more preferably Examples thereof include a segment having a cohesiveness or a precipitation property at 33 to 45 ° C., particularly about 35 to 44 ° C. In such segments, functional groups that normally participate in hydrogen bonding and form stable bonds at low temperatures and functional groups that participate in hydrophobic bonds and form stable bonds on the high temperature side are arranged in a balanced manner. The aggregation temperature can be controlled by the ratio of the functional group (Prog. Biophys. Molec. Biol., Vol. 57, pp. 23-57 (1992)). That is, the aggregation temperature increases as the number of functional groups involved in hydrogen bonding increases, and the aggregation temperature decreases as the number of functional groups involved in hydrophobic bonding increases. The ratio between the number of hydrogen bonds and the number of carbon atoms contained in the hydrophobic group (hereinafter sometimes simply referred to as the ratio of hydrogen bonds / carbon atoms) can be appropriately selected depending on the desired aggregation temperature. The former / the latter = 2/8 to 5/5, preferably about 2.5 / 7.5 to 4.5 / 5.5.

  Examples of the group that forms a hydrogen bond include a hydroxyl group, a carboxyl group, an amino group, an amide group, and a mercapto group, and examples of the hydrophobic group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- Alkyl groups such as butyl, isopentyl and neopentyl groups (such as C1-6 alkyl groups), cycloalkyl groups such as cyclohexyl groups (such as C4-8 cycloalkyl groups), and aryl groups such as phenyl groups (such as C6-12 aryl groups) , An aralkyl group such as benzyl group (phenyl-C1-4 alkyl group etc.), a 5- or 6-membered heterocyclic group containing at least one heteroatom selected from nitrogen, oxygen and sulfur atoms (pyrrolidinyl group, imidazolyl group etc.) And condensed heterocyclic groups (such as indolyl group).

  Examples of the segment (or side chain) having an aggregating property include (a) a polymer segment having a hydrophobic group and a hydrogen bonding group (hereinafter simply referred to as an aggregating polymer), and (b) a hydrophobic group. A peptide segment having a hydrogen bonding group can be exemplified, and this aggregating peptide segment (b) includes (b1) a peptide segment having a hydrophobic amino acid residue and a hydrogen bonding amino acid residue (hereinafter simply referred to as aggregation property). Peptide), (b2) a peptide copolymer segment having an amino acid or a peptide residue (hereinafter simply referred to as an aggregating peptide copolymer), and the like. Furthermore, (a) the aggregating polymer, (b1) the aggregating peptide, and (b2) the aggregating peptide copolymer may be linear, and the chain is branched and extended from an active point such as an amino group. It may be branched. These aggregating segments can be introduced into the polysaccharide skeleton alone or in combination of two or more.

  (A) Examples of the aggregating polymer include acrylamide or derivatives thereof [acrylamide, N-C1-6 alkylacrylamide (N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N- Butyl acrylamide, N-isobutyl acrylamide, Nt-butyl acrylamide, N-hexyl acrylamide etc.)], N-vinyl acylamide (N-vinylformylamide, N-vinylacetamide, N-vinylisobutyric acid amide, N-vinylvaleryl) Examples thereof include polymers of monomers selected from acid amides and N-vinyl C1-10 acylamides such as N-vinylisovaleric acid amide). These monomers can be used alone or in combination, and the polymer may be a homopolymer or a copolymer. Preferred monomers usually have a branched C3-5 alkyl group such as an isopropyl group. Furthermore, if necessary, with other monomers (aromatic vinyl monomers such as styrene, (meth) acrylic monomers, vinyl ester monomers, vinyl alkyl ether monomers, etc.) A copolymer may also be used.

  More specifically, the cohesive polymer (a) is, for example, (a1) a homopolymer or copolymer having at least N-C1-6 alkylacrylamide as a monomer component, particularly at least N-isopropylacrylamide. Constituted monomer polymer (N-isopropylacrylamide polymer), for example, poly-N-isopropylacrylamide (hydrogen bond / carbon atom ratio = 2.9 / 7.1), N-isopropylacrylamide- Acrylamide copolymer, etc .; (a2) a homopolymer or copolymer comprising at least N-vinyl C1-10 acylamide as a monomer component, particularly a monomer polymer composed of at least N-vinylisobutyric acid amide (N- Vinyl isobutyric acid amide polymer), for example, poly-N-vinylacetamide and poly-N-vinylisobutyric acid (Hydrogen bonds / number of ratio = 2.9 / 7.1 carbon atoms), such as N- vinylacetamide -N- Biniruiso acid amide copolymer can be exemplified.

  (B) The aggregating peptide segment has, as amino acid residues, an alkyl group (eg, a C1-6 alkyl group such as methyl, isopropyl, isobutyl, s-butyl, n-butyl group, isopentyl group, neopentyl group), allotrope Or a heterocyclic group (for example, one or more heteroatoms such as C4-8 cycloalkyl group such as cyclohexyl group, aryl group such as phenyl group, phenyl-C1-4 alkyl group such as benzyl group, pyrrolidinyl group, imidazolyl group, etc. (Condensed heterocyclic groups such as 5- or 6-membered heterocyclic groups and indolyl groups) containing (nitrogen, oxygen and sulfur atoms). In particular, the aggregating peptide segment is usually a bulky or bulky group, for example a linear or branched C3-5 alkyl group such as isopropyl, isobutyl, s-butyl, n-butyl group (especially branched C3- 4 alkyl group), phenyl group, benzyl group, 5- or 6-membered heterocyclic group, and condensed heterocyclic group.

  That is, preferred aggregating peptide segments have amino acid residues such as Val, Leu, Ile, Nle, Pro, His, Phe, Trp (particularly, Val, Leu, Ile, Nle, Pro, His). A peptide segment may contain a single amino acid residue of these amino acid residues, but usually a plurality of amino acid residues (eg, from Val, Leu, Ile, Nle, Pro, His, Phe, Trp). The combination of a plurality of amino acid residues includes, for example, a combination of Val and Pro, Val and / or Pro and at least one selected from Leu, Ile, and Nle. And a combination of Val and His, a combination of Pro and His, a combination of His and Leu, Ile, and Nle.

  The peptide constituting the aggregating segment may be a racemate, and may have an optical activity by forming an R-form or an S-form by steric arrangement of amino acid residues.

(B1) The aggregating peptide is usually represented by the following formula (I):
-(Val-Pro-Gly-X-Gly) n- (I)
(Wherein X represents an amino acid residue selected from Val, Pro, Leu, Ile, and Nle, and n represents an integer of 1 or more). The coefficient n is, for example, 1 to 100 (for example, 2 to 100), preferably 1 to 50 (for example, 2 to 50), more preferably about 2 to 30, and usually 2 to 25 (for example, It may be about 2 to 10).

  As an aggregating peptide having such a peptide unit, for example, a peptide represented by the following formula can be exemplified.

(1) H- (Val-Pro -Gly-X-Gly) n-NH 2 ( percentage of X and n have the same meanings as defined above. Hydrogen bonds / carbon atoms = 3.8 / 6.2)
(2) (N′α, N′ε, N ″ α, N ″ ε-tetra (H- (Val-Pro-Gly-X-Gly) n) -Nα, Nε-dilysyl) lysyl-β-alanine ( Wherein X and n are the same as above)
(3) (N′α, N′ε, N ″ α, N ″ ε-tetra (H-His-Val-Gln-Val-His- (Val-Pro-Gly-X-Gly) n) -Nα, Nε-dilysyl) lysyl-β-alanine (wherein X and n are the same as above) (X and n are the same as above, hydrogen bond / carbon atom ratio = 3.8 / 6.2 to 4.3 / 5.7)
(B2) The aggregating peptide copolymer may have the same alkyl group as that of the aggregating peptide segment, an allotrope or a heterocyclic group, and an N-alkylamino group (N-C1-4 alkylamino). Group) and the like.

The peptide copolymer is usually represented by the following formula (II)
—CO—R ₁ —CO—Y—NH—R ₂ —NH— (II)
[Wherein, R ₁ and R ₂ are the same or different and each represents an alkylene group, a cycloalkylene group, or an arylene group, and Y represents-(Val-Pro-Gly-X-Gly) n- (X, n The amino acid residue selected from Sar, Val, Pro, Leu, Ile, and Nle].

Examples of the alkylene group include linear or branched C1-8 alkylene groups such as methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, 3,3-dimethyltrimethylene, and hexamethylene groups. Examples of the cycloalkylene group include C4-8 cycloalkylene groups such as a cyclohexylene group, and examples of the arylene group include a phenylene group and a naphthylene group. Preferred groups R ₁ and R ₂ are alkylene groups forming a copolymer decomposable in vivo, for example, C 2-6 alkylene groups, especially C _2-4 alkylene groups.

  Such a peptide copolymer has, for example, a copolymer unit represented by the following formula.

_{(1) -CO-R 1 -CO-} (Val-Pro-Gly-X-Gly) n-NH-R 2 -NH-
(2) —CO—R ₁ —CO—Sar—NH—R ₂ —NH—
(3) —CO—R ₁ —CO—X—NH—R ₂ —NH—
(Wherein X, n, R ₁ and R ₂ are the same as above)
These coherent peptide copolymers can be used alone or in combination of two or more. When the aggregating peptide copolymer is composed of a plurality of copolymer units (for example, the copolymer units (1) to (3)), the components corresponding to the copolymer units are each 5 to 90 mol%. The total amount may be 100 mol% selected from the range of preferably 10 to 80 mol%, more preferably about 25 to 75 mol%, and may be prepared by copolymerization. In such copolymerization, the ratio of the copolymer unit (1) and / or (3) is usually 5 to 100 mol%, preferably 10 to 100 mol%, more preferably, of the whole aggregated peptide copolymer. Is preferably adjusted to about 25 to 100 mol% (for example, 30 to 95 mol%).

  If necessary, other segments (for example, non-aggregating segments such as non-aggregating polymers, non-aggregating peptides, and non-aggregating peptide copolymers) may be bonded to the polysaccharide. The cohesive segment can be selected from a range of about 10 to 100 mol%, preferably 20 to 100 mol%, more preferably about 30 to 100 mol% of the entire segment bonded to the polysaccharide.

The molecular weight of the cohesive segment is about 3000 to 20 × 10 ^{4 in} terms of pullulan, and is usually 5000 to 10 × 10 ⁴ , preferably 1 × 10 ⁴ to 8 × 10 ⁴ , more preferably 2 ×. It is about 10 ^{4 to} 6 × 10 ⁴ (for example, 2 × 10 ⁴ to 4 × 10 ⁴ ).

  The proportion of the cohesive segment is not particularly limited as long as the cohesiveness is manifested by heating in the form of an aqueous solution, and is, for example, 3 to 90% by mass, preferably 5 to 90% by mass, and more preferably based on the whole polymer. It is about 10-85 mass%, and about 15-80 mass% (for example, 20-80 mass%) may be sufficient.

  The cohesive polymer (poly-N-isopropylacrylamide, poly-N-vinylisobutyric acid amide, etc.) can be prepared by a conventional polymerization method, for example, a corresponding monomer (N-isopropylacrylamide, N-vinylisobutyric acid amide, etc.). , By polymerization using a radical polymerization initiator (an azo compound such as azobisisobutyronitrile or a peroxide such as benzoyl peroxide). Furthermore, the cohesive polymer can be introduced into the polysaccharide by a conventional method. For example, in the polymerization, by reacting in the presence of a chain transfer agent having a reactive group (a chain transfer agent having an amino group or a carboxyl group such as mercaptoethylamine or 3-mercaptopropionic acid), the reactive group is changed. It can introduce | transduce into the cohesive polymer terminal and can couple | bond with the skeleton of a polysaccharide by amide formation reaction etc. through these reactive groups. The molecular weight or length of the cohesive polymer can be controlled by the molar ratio of the monomer, the polymerization initiator, the chain transfer agent, and the like.

  In a preferred method, the synthesis of the polymer and the binding to the backbone of the polysaccharide can be performed simultaneously. For example, Ce ions can act on the skeleton of the polysaccharide to generate a carbon radical, and the monomer can be polymerized using a radical mechanism. Specifically, by mixing the monomer and the polysaccharide in which the radical is generated, a polymer chain grows from the radical site of the polysaccharide, and the side chain of the cohesive polymer and the polysaccharide are bonded. Can be performed simultaneously.

  Examples of other methods include a method of introducing a cohesive polymer chain into a polysaccharide by introducing a polymerizable group into the polysaccharide and polymerizing with the monomer. For example, a polysaccharide is reacted with an acid anhydride having a polymerizable group such as a vinyl group or a (meth) acryloyl group (anhydrous (meth) acrylic acid, maleic anhydride, etc.) to form a polymerizable group by an ester bond. By introducing and subjecting to polymerization with the monomer, a side chain of a cohesive polymer can be introduced into the polysaccharide. Also in this method, the length of the cohesive polymer chain can be controlled by the molar ratio between the polymerizable group introduced into the polysaccharide and the monomer.

  The molecular weight or length of the introduced polymer side chain is determined by hydrolyzing the skeleton of the polysaccharide with an acid (for example, 1M sulfuric acid) and measuring the molecular weight of the remaining side chain by gel permeation chromatography or the like. It can ask for.

  The aggregating peptide can be prepared by an ordinary peptide synthesis method, for example, any of a solid phase synthesis method and a liquid phase synthesis method. A preferred method is a solid-phase synthesis method that is easy to operate [for example, the edition of Nihon Seikagaku, "Second Life Chemistry Experiment Course 2 Protein Chemistry (below)", May 20, 1987, published by Tokyo Chemical Doujin, See pages 641 to 694].

  In the solid-phase synthesis method, a polymer or carrier insoluble in the reaction solvent (styrene-divinylbenzene copolymer modified by chloromethylation, oxymethylation, etc. (chloromethylated resin, hydroxymethylphenylacetamidomethyl-resin, etc.) Benzhydrylamine resins (such as 4-methylbenzhydrylamine-resin) and multi-detachable resins) are used. The peptide synthesis method using these polymers or carriers is a conventional method, for example, by binding an α-carboxyl group of amino acids corresponding to the C-terminus of the target peptide to the polymer or carrier, and then the target peptide. The amino acid or peptide fragment (amino acid or peptide fragment having a free carboxyl group and an amino group protected) is sequentially condensed toward the N-terminal of the amino acid, and the amino group protecting group is removed. By repeating the operation to elongate the peptide chain to form a predetermined peptide chain, desorb the peptide chain from the polymer, remove the protecting group, and generate and purify the target peptide, Peptides can be synthesized.

  In addition, conventional methods can be used for the type of the protecting group, the condensation reaction, and the elimination of the protecting group. For example, as a protecting group for amino group, substituted benzyloxycarbonyl group such as benzyloxycarbonyl group (Z), p-nitrobenzyloxycarbonyl group, p-methoxybenzyloxycarbonyl group, t-butoxycarbonyl group (Boc), Examples include fluorenylmethyloxycarbonyl group (Fmoc), isobornyloxycarbonyl group (Iboc), and the like. As the protective group for carboxyl group, benzyl ester (OBzl), substituted benzyl ester, methyl ester (OMe), ethyl Examples include ester (OEt), t-butyl ester (OBut), phenacyl ester (OPac), cyclohexyl ester (OcHex), and the like. In addition, the side chain of the amino acid can be protected with a conventional protecting group.

  For the condensation reaction, various coupling methods, for example, C-terminal activation method (active esterification method using p-nitrophenyl ester (ONp), N-hydroxysuccinimide ester (ONSu), mixed acid anhydride, Azide method using diphenylphosphoryl azide (DPPA) or the like, dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide (DIPC), N-ethyl-N′-3-dimethylaminopropylcarbodiimide (WSCI) or its hydrochloride, benzotriazole-1- And a coupling reagent method using a condensing agent such as yl-tris- (dimethylamino) phosphonium hexafluorophosphide salt (BOP). In the coupling method, the condensing agent may be used alone or in combination with other components. For example, DCC (or WSCI), N-hydroxysuccinimide (HONSu), hydroxybenzotriazole (HOBt), 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine (HOObt), etc. You may use in combination with the component selected from. Note that these reagents may be water-insoluble, and may be water-soluble, such as WSCI or its hydrochloride.

  For removing the protecting group, a conventional method such as catalytic reduction, acid (sulfonic acids such as trifluoromethanesulfonic acid, trifluoroacetic acid, hydrogen fluoride, etc.) or alkali can be used. The elimination of the peptide chain from the polymer and the removal of the protecting group are preferably performed simultaneously using trifluoroacetic acid from the viewpoint of controlling side reactions. The peptide can be purified using a conventional method, for example, ion exchange resin, various chromatographies, etc., and it is effective to use reverse phase liquid chromatography or gel permeation chromatography.

Furthermore, the cohesive peptide copolymer can be prepared by various methods. For example, a peptide or amino acid represented by the formula H—Y—OH (Y is the same as above) and a dicarboxylic acid corresponding to the group R ₁ or an acid anhydride thereof are reacted to produce HO—CO—R ₁ —CO. -Y-OH (Y is as defined above) to generate, the copolymer is obtained by reacting a diamine corresponding to the group R _2.

Examples of the dicarboxylic acid corresponding to R ₁ include C2-10 aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Examples thereof include acid anhydrides (such as succinic anhydride), C4-8 cycloalkane-dicarboxylic acids such as cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid, and acid anhydrides thereof.

Examples of the diamine corresponding to R ₂ include C 2-6 alkylene diamines such as ethylene diamine, propylene diamine, tetramethylene diamine and hexamethylene diamine, polyalkylene polyamines such as diethylene triamine, C 4-8 alicyclic rings such as cyclohexane diamine and isophorone diamine. Examples thereof include aromatic diamines such as aromatic diamines, phenylene diamines, and xylylene diamines.

In addition, various coupling reactions, such as the said active ester method, can be utilized for reaction with a peptide or an amino acid, dicarboxylic acid or its acid anhydride (succinic anhydride or succinic acid etc.), and diamine (ethylenediamine etc.). For example, peptide copolymer (1): —CO— (CH ₂ ) ₂ —CO— (Val-Pro-Gly-X-Gly) n—NH— (CH ₂ ) ₂ —NH— (wherein X and n are (2): —CO— (CH ₂ ) ₂ —CO—Sar—NH— (CH ₂ ) ₂ —NH—, (3): —CO— (CH ₂ ) ₂ —CO—X—NH _{- (CH 2) 2 -NH- (} X is the same) is, (1a) H- (Val- Pro-Gly-X-Gly) n-OH (X and n have the same meanings as defined above), (2a) H-Sar-OH, (3a) H-Val-OH, H-Leu-OH, H-Ile-OH, and H-Nle-OH were each reacted with succinic anhydride to give (1b) HO-CO- (CH2) 2-CO- (Val-Pro-Gly-X-Gly) n) -OH (X and n are as defined above), (2b) HO _{CO- (CH 2) 2 -CO-} Sar-OH, (3b) HO-CO- (CH 2) 2 -CO-Val-OH, HO-CO- (CH 2) 2 -CO-Leu-OH, HO _{-CO- (CH 2) 2 -CO-} Ile-OH, HO-CO- (CH 2) to produce ₂ -CO-Nle-OH. Next, a coupling agent (water-soluble carbodiimide, 1-hydroxybenzotriazole) is added to an aqueous solution obtained by mixing the components (1b) to (3b) and ethylenediamine in an appropriate range, for example, in the range of 5 to 90 mol%. Etc.) is added and depolycondensed.

  The method of combining the non-animal polysaccharide backbone and the cohesive segment (fragment or side chain) is a combination of the type of functional group contained in the polysaccharide backbone and the type of functional group contained in the cohesive segment. Is appropriately selected. For example, when the non-animal polysaccharide has a carboxyl group and the aggregating segment has an amino group, the polysaccharide and the aggregating segment can be bound by a normal amide group formation reaction. Specifically, a coupling reagent (carbodiimide (DCC, DIPC, WSCI or a hydrochloride thereof or the like), a condensing agent such as BOP alone, DCC (or WSCI) -HONSu, DCC (or WSCI) -HOBt, DCC (or WSCI) And dehydration condensation reaction such as a combination of a coupling reagent such as -HOObt), a method of performing an amide bond formation reaction with an amino group after converting a carboxyl group into an active ester by an active esterification method, and the like.

  In addition, when the functional group of the polysaccharide is a hydroxyl group, the carboxyl group is introduced by reacting the polysaccharide with a halocarboxylic acid (such as chloroacetic acid) in the presence of an alkali, and agglomeration is performed by a normal amide group formation reaction. Joins with segments can be made. Furthermore, the hydroxyl group contained in the polysaccharide can be oxidized to form an aldehyde group, which can be combined with the aggregating segment by undergoing a Schiff base formation reaction with the amino group of the aggregating segment.

  The temperature-responsive material (temperature-responsive polymer) of the present invention has a temperature-responsive property that changes from a solution state to a gel state in response to temperature, and usually changes from a solution to a gel by heating. Preferred temperature-responsive polymers change reversibly or irreversibly between solution form and gel form in response to temperature. The gel is usually cloudy or transparent. Although the said response temperature can be selected suitably, it is 30 degreeC or more normally (preferably 30-50 degreeC, More preferably, it is 33-45 degreeC, Especially about 35-44 degreeC).

1-4).
Examples of the temperature-responsive polymer compound having a lower critical solution temperature (LCST) include the following compounds described in JP-A No. 2004-35791.

1-4-1.).
Temperature responsiveness characterized by comprising a random copolymer comprising as a constituent component a repeating unit (A) represented by the following general formula (1) and a repeating unit (B) represented by the following general formula (2) polymer.

(In the formula, R ¹ represents a hydroxyalkyl group, and R ² represents a hydroxyalkyl group, an alkyl group, or an aryl group different from R ^1. )
1-4-2).
R ¹ is ^{one selected} from 4-hydroxybutyl group, 5-hydroxypentyl group and 6-hydroxyhexyl group, R ² is 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6 -The temperature-responsive polymer according to 1-4-1), which is one selected from a hydroxyhexyl group, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.

1-4-3).
The temperature-responsive polymer according to 1-4-1) or 1-4-2), wherein the molar composition ratio of the repeating units (A) and (B) is 95: 5 to 5:95.

1-4-4).
The temperature-responsive polymer according to any one of 1-4-1) to 1-4-3) having a number average molecular weight in the range of 1,000 to 1,000,000.

1-4-5).
A random copolymer having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B) represented by the following general formula (2) as a constituent component is crosslinked with a polyfunctional compound. Characteristic temperature-responsive gel.

(In the formula, R ¹ represents a hydroxyalkyl group, and R ² represents a hydroxyalkyl group, an alkyl group, or an aryl group different from R ^1. )
1-4-6).
The temperature-responsive gel according to 1-4-5), wherein the polyfunctional compound is a diisocyanate.

1-4-7).
The temperature-responsive gel according to 1-4-5), wherein the polyfunctional compound is α, ω-alkylene diisocyanate.

  The temperature-responsive polymer of the present invention is an α / β-asparagine derivative unit in which both the repeating units (A) and (B) have a substituent on nitrogen. From its chemical structure, it is clear that it is excellent in biocompatibility and biodegradability like conventional polyamino acids already widely used as biomedical materials. In detail, poly (α / β-sodium aspartate), which is well known as a biodegradable polymer aimed at substituting polyacrylic acid, is obtained by thermally polymerizing aspartic acid, and then obtaining the resulting polysuccinimide. Obtained by alkaline hydrolysis. This is because the temperature-responsive polymer of the present invention is obtained by reacting an amine instead of its alkali.

Another important point here is that R ² is different from R ¹ . That is, R ¹ is a hydroxyalkyl group, and R ² is an alkyl group, an aryl group, or a hydroxyalkyl group different from R ¹ . This is because temperature responsiveness is exhibited. Incidentally, a polymer in which R ² is the same as R ¹ has already been synthesized (for example, G. Caldwell et al., J. Appl. Polym. Sci., 66, 911 (1997)). Not shown.

Yet another important point is that at least R ¹ is a hydroxyalkyl group. This is because various functional groups and functional groups can be introduced into each repeating unit (A) to functionalize the polymer.

The combination of R ¹ and R ² is preferably ^{one in} which R ¹ is selected from 4-hydroxybutyl group, 5-hydroxypentyl group and 6-hydroxyhexyl group, R2 is 3-hydroxypropyl group, 4- It is one selected from a hydroxybutyl group, a 5-hydroxypentyl group, a 6-hydroxyhexyl group, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. This is because this combination exhibits particularly sensitive temperature response.

  Moreover, the preferable molar composition ratio of the said repeating unit (A) and (B) is 95: 5-5: 95. When both R1 and R2 are hydroxyalkyl groups, the phase transition temperature increases as the proportion of repeating units having a hydroxyalkyl group having a small number of carbon atoms increases. In particular, when R1 is a 5-hydroxypentyl group and R2 is a 6-hydroxyhexyl group and the molar composition ratio of the repeating units (A) and (B) is in the range of 50:50 to 30:70, Temperature responsiveness is exhibited at 40 ° C.

  The preferred number average molecular weight of the temperature-responsive polymer of the present invention is in the range of 1,000 to 1,000,000. If it is less than 1,000, the material strength is insufficient, and if it exceeds 1,000,000, it takes a very long time to completely biodegrade.

Next, a suitable method for producing the temperature-responsive polymer of the present invention is that when R ¹ represents a hydroxyalkyl group and R ² represents a hydroxyalkyl group, an alkyl group or an aryl group different from R ¹ , a polysuccinimide, R ¹ NH ² and R ² NH ² are mixed in an organic solvent. The polysuccinimide used as a raw material is obtained by thermal polymerization of aspartic acid, but may be used as long as it is commercially available. According to this method, the ratio of the repeating units (A) and (B) in the obtained temperature-responsive polymer can be controlled by the mixing ratio of R ¹ NH ² and R ² NH ² .

  When the above random copolymer is crosslinked with a polyfunctional compound, it gels and becomes a temperature-responsive gel. And when this polyfunctional compound is diisocyanates, such as (alpha), (omega) -alkylene diisocyanate, it will become the temperature-responsive gel which maintained the biodegradability which has a bridge | crosslinking structural unit shown by the following general formula.

(In the formula, X and Z are residues obtained by removing a hydroxyl group from R ¹ or R ² , and Y represents an alkylene group.)
As described above, the temperature-responsive gel of the present invention exhibits an appropriate and sensitive temperature response to the human body by the combination of R ¹ and R ² and the ratio of the repeating units (A) and (B). This can be used as a drug sustained-release material.

The repeating units (A) and (B) of the present invention can be arbitrarily combined as long as they exhibit temperature responsiveness. In the repeating unit (A), specific examples of R ¹ include 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxybutyl group, 2- (hydroxymethyl) propyl. Group, 2-hydroxypentyl group, 3-hydroxy-2,2-dimethylpropyl group, 3-hydroxypentyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, 2-hydroxyhexyl group, 7-hydroxyheptyl group, Examples include hydroxyalkyl groups such as 8-hydroxyoctyl group. In order to develop sensitive temperature responsiveness, a 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group or the like having moderate hydrophilicity is desirable as described above.

R ² in the repeating unit (B) has a structure different from R ^{1 in the} repeating unit (A). Specific examples of R ² include 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxybutyl group, 2- (hydroxymethyl) propyl group, 2-hydroxypentyl. Group, 3-hydroxy-2,2-dimethylpropyl group, 3-hydroxypentyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, 2-hydroxyhexyl group, 7-hydroxyheptyl group, 8-hydroxyoctyl group, etc. Hydroxyalkyl group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, iso-butyl group, 2-butyl group, t-butyl group, n-pentyl group, n-hexyl group , N-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-octadecyl group and the like Group, a phenyl group, a 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, a 1-naphthyl group, and an aryl group such as a 2-naphthyl group. In order to express sensitive temperature responsiveness, as described above, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, methyl group, ethyl group having appropriate hydrophilicity N-propyl group, i-propyl group and the like are desirable.

  When the above temperature-responsive polymer is synthesized by reacting polysuccinimide and two kinds of amines in an organic solvent, the amount of amine is not particularly limited as long as it is greater than polysuccinimide in molar equivalents. 1 to 10 times is preferable. The organic solvent to be used is not particularly limited as long as it dissolves both substrates, and examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide. The reaction temperature and reaction time vary depending on the amine species used, but are in the range of 0 to 150 ° C., 1 minute to 120 hours, preferably 30 to 80 ° C. and 30 minutes to 48 hours.

  There are various methods for producing a temperature-responsive gel from a random copolymer having repeating units (A) and (B) as constituent components. Generally, as described above, the side-chain alcohol of the random copolymer and It can be achieved by reaction with a crosslinking agent. The crosslinking agent is not particularly limited as long as it is a polyfunctional compound that reacts with alcohol. In general, diisocyanates are used in the preparation of biodegradable temperature-responsive gels. Specific examples thereof include 1,2-ethane diisocyanate, 1,3-propane diisocyanate, 1,4-butane diisocyanate, and 1,5-pentane diisocyanate. 1,6-hexane diisocyanate, 1,8-octane diisocyanate, 1,10-decane diisocyanate, 1,12-dodecane diisocyanate, 1,3-toluidine diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, Examples include 1,4-phenylene diisocyanate, succinic acid chloride, glutaric acid chloride, adipic acid chloride, sebacic acid chloride, phthalic acid chloride, and terephthalic acid chloride. A diisocyanate is preferable as a crosslinking agent that expresses a sensitive temperature responsiveness to the gel. Particularly, 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate having an appropriate hydrophilicity, 1,8 -Octane diisocyanate is desirable.

  The usage-amount of a crosslinking agent is 0.1-50 mol% with respect to the total amount of a repeating unit (A) and (B), Preferably it is 2-30 mol%. The organic solvent to be used is not particularly limited as long as the random copolymer is dissolved and does not react with the isocyanate group, but N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, etc. Is mentioned. The reaction temperature and reaction time vary depending on the type of diisocyanate used, but are in the range of 0 to 150 ° C., 1 hour to 120 hours, preferably 30 to 80 ° C., and 3 hours to 48 hours.

  Specific examples of the temperature-sensitive material of the present invention (temperature-responsive polymer compound having a lower critical solution temperature (LCST)) include the following.

Polysuccinimide (0.49 grams, 5.0 mmol monomer unit), 5-aminopentanol (0.52 grams, 5.0 mmol (50 mol% charged molar ratio)), 6-aminohexanol (0.59 grams, Polymer (1-4-1) prepared from 5.0 mmol):
Number average molecular weight 22000, molecular weight distribution 3.1
23 ° C (1% strength by weight solution)
Polymer (1-4-2) in which the charged molar ratio of 5-aminopentanol was changed to 60 mol% for the above:
Number average molecular weight is 17000, molecular weight distribution is 2.9
Phase transition temperature: 29 ° C. (1% strength by weight solution)
About the above polymer (1-4-3) in which the charged molar ratio of 5-aminopentanol was changed to 70 mol%:
Number average molecular weight 15000, molecular weight distribution 2.7
Phase transition temperature: 39 ° C. (1% strength by weight solution)
Polymer (1-4-4) in which the charged molar ratio of 5-aminopentanol was changed to 80 mol% for the above:
Number average molecular weight 18000, molecular weight distribution 2.9
Phase transition temperature: 44 ° C. (1% strength by weight solution)
Etc.

2). A temperature response that has a reversible polarity change with temperature, is insoluble in water on a lower temperature side than a specific temperature, and becomes soluble in water on a higher temperature side (upper critical solution temperature (UCST)) Polymer)
2-1).
Examples of the temperature-responsive polymer compound having an upper critical solution temperature (UCST) that is insoluble in water on the low temperature side and dissolved in water on the high temperature side according to the present invention include the following compounds described in JP-A No. 2000-319335. It is done.

2-1-1).
A polymer compound selected from the group consisting of a polymer containing a repeating unit represented by the following general formula (B-1) and a crosslinked product containing the polymer.

(Wherein n represents 0.005 ≦ n ≦ 0.995 and j represents 0 ≦ j ≦ 0.5. R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom. Or X ¹ , X ² , X ³ and X ⁴ are the same or different and each represents a secondary or tertiary amide group, ester group or ether group, and Y ¹ has 1 to 8 carbon atoms. straight or branched divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms having 3 to 8 carbon atoms .Y ² Is a carbon having a linear or branched divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, or one or more ether groups. A linear or branched divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a linear or branched group having 1 to 8 carbon atoms having one or more hydroxyl groups Represents a divalent aliphatic hydrocarbon group ^{.Z 1, Z 2, Z 3} , Z 5 and Z ⁶ are the same or different, a hydrogen atom, an aliphatic linear or branched C1-8 hydrocarbon A hydrogen group, a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms having 1 or 2 hydroxyl groups, or a straight chain having 1 to 8 carbon atoms having 1 or 2 hydroxyl groups, or A branched alicyclic hydrocarbon group, a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms having one or two or more ether groups, one or two or more ether groups Carbon number having a linear or branched alicyclic hydrocarbon group having 1 to 8 carbon atoms, a glycoside having 3 to 12 carbon atoms, or a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms .Z ¹ showing 3-12 of glycosides, Z ^3, Z ⁵ or Z ^6, when X ^1, X ^2, X ³ or X ⁴ is a tertiary amide A multiplexer for functional group, Z ⁵ and Z ⁶ may also be coupled .Z ⁴ is a hydrogen atom, a hydroxyl group, an amide group, a nitrile group, a straight-chain or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms A linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms having 1 or 2 or more amide groups, or a linear chain having 1 to 8 carbon atoms having 1 or 2 or more carbonyl groups, or 1 to 8 carbon straight chain or branched aliphatic hydrocarbon group having a branched aliphatic hydrocarbon group, 1 or 2 or more nitrile groups, 1 or 2 or more carbon atoms having a hydroxyl group 1 to 8 linear or branched aliphatic hydrocarbon groups.)
2-1-2).
The polymer compound according to 2-1-1), which contains an aromatic hydrocarbon group.

2-1-3).
The high molecular compound which consists of a polymer represented by the following general formula (B-2).

(In the formula, R ⁵ represents a hydrogen atom or a methyl group. X ⁵ represents a secondary or tertiary amide group, ester group or ether group. Y ³ represents a linear or branched group having 1 to 8 carbon atoms. A divalent aliphatic hydrocarbon group or a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, wherein Y ⁴ is a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms or one; Or a C1-C8 linear or branched aliphatic hydrocarbon group having 2 or more hydroxyl groups is shown.)
2-1-4).
The polymer compound according to 2-1-1) or 2-1-3), wherein two or more amide groups or ester groups are the same or different in the repeating unit of the polymer.

  In the present invention, the straight chain or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms is a straight chain or branched alkyl group having 1 to 8 carbon atoms, or a straight chain or branched chain having 2 to 8 carbon atoms. Or a straight chain or branched alkynyl group having 2 to 8 carbon atoms, wherein the number of double bonds of the alkenyl group and the number of triple bonds of the alkynyl group are each 1 or 2 or more . Preferred alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, and n-hexyl. Group, n-heptyl group, n-octyl group and the like, and examples of preferable alkenyl group include vinyl group, propenyl group (1-propenyl group), allyl group, butenyl group (where the position of double bond is ), A pentenyl group (the position of the double bond may be any), a hexenyl group (the position of the double bond may be any), and a heptenyl group (the position of the double bond is any). And octenyl group (position of the double bond may be any), and preferable alkynyl groups include ethynyl group, propargyl group, butynyl group (no position of triple bond) ), A pentynyl group (the position of the triple bond may be any), a hexynyl group (the position of the triple bond may be any), and a heptynyl group (the position of the triple bond is any). And an octynyl group (the position of the triple bond may be any).

  In the present invention, the linear or branched divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms is a linear or branched alkylene group having 1 to 8 carbon atoms or a linear chain having 2 to 8 carbon atoms. Or a branched alkenylene group or a linear or branched alkynylene group having 2 to 8 carbon atoms, wherein the number of double bonds of the alkenylene group and the number of triple bonds of the alkynylene group are 1 or 2, respectively. That's it. Preferred alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and the like. Examples of preferred alkenylene groups include a vinylene group, a propenylene group (double bond Any position), butenylene group (double bond position can be any), pentenylene group (double bond position can be any), hexenylene group (double bond) Can be in any position), heptenylene group (double bond position can be in any position), octenylene group (double bond position can be in any position), and the like, preferred alkynylene groups Examples of ethynylene group, propynylene group (the position of the triple bond may be any), butynylene group (position of the triple bond) Can be any), a pentynylene group (the position of the triple bond can be any), a hexynylene group (the position of the triple bond can be any), or a heptynylene group (the position of the triple bond is any). And an octynylene group (the position of the triple bond may be any).

  In this invention, a C3-C8 bivalent alicyclic hydrocarbon group means either a C3-C8 cycloalkylene group or a C3-C8 cycloalkenylene group. The number of double bonds of the cycloalkenylene group is 1 or 2 or more. Preferred examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group. Examples of the preferred cycloalkenylene group include a cyclopropenylene group ( The position of the double bond may be any), the cyclobutenylene group (the position of the double bond may be any), the cyclopentenylene group (the position of the double bond may be any) , Cyclohexenylene group (the position of the double bond may be any), cycloheptenylene group (the position of the double bond may be any) and cyclooctenylene group (position of the double bond) May be in any case.

  In this invention, a C6-C14 bivalent aromatic hydrocarbon group means a C6-C14 arylene group or an aralkylene group. Examples of preferred aromatic hydrocarbon groups include phenylene group, benzylene group, phenethylene group, naphthylene group, anthrylene group, phenanthrylene group and the like.

  In the present invention, the straight-chain or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms and having 1 or 2 hydroxyl groups means the straight-chain or branched aliphatic carbon group having 1 to 8 carbon atoms. It means an aliphatic hydrocarbon group in which one or more carbon atoms have a hydroxyl group at an arbitrary position in the hydrogen group. In the case of having two hydroxyl groups, two hydroxyl groups may be substituted on one carbon atom.

  In the present invention, the linear or branched divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms and having 1 or 2 hydroxyl groups is the above linear or branched hydrocarbon group having 1 to 8 carbon atoms. It means a divalent aliphatic hydrocarbon group in which one or two or more carbon atoms have a hydroxyl group at an arbitrary position in the divalent aliphatic hydrocarbon group. In the case of having two hydroxyl groups, two hydroxyl groups may be substituted on one carbon atom.

  In the present invention, the linear or branched alicyclic hydrocarbon group having 1 or 2 or more hydroxyl groups and having 1 to 8 carbon atoms refers to the linear or branched alicyclic group having 1 to 8 carbon atoms. It means an aliphatic hydrocarbon group in which one or more carbon atoms have a hydroxyl group at an arbitrary position in the formula hydrocarbon group. In the case of having two or more hydroxyl groups, two hydroxyl groups may be substituted on one carbon atom.

  In the present invention, the linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms and having one or more ether groups is the above linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms. It means an aliphatic hydrocarbon group in which one or more ether groups are incorporated at an arbitrary position in the hydrocarbon group.

  In the present invention, the linear or branched divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms and having one or more ether groups is the above linear or branched chain having 1 to 8 carbon atoms. Means a divalent aliphatic hydrocarbon group in which one or two or more ether groups are incorporated at any position in the aliphatic hydrocarbon group.

  In the present invention, the linear or branched alicyclic hydrocarbon group having 1 to 8 carbon atoms and having 1 or 2 or more ether groups is the above linear or branched fatty acid having 1 to 8 carbon atoms. An alicyclic hydrocarbon group in which one or two or more ether groups are incorporated at an arbitrary position in an aromatic hydrocarbon group.

  In the present invention, the glycoside having 3 to 12 carbon atoms means either aldose or ketose having 3 to 12 carbon atoms bonded to a glycoside. Preferred aldoses or ketoses include arabinose, lyxose, ribose, xylose, glucose, galactose, mannose, fructose and the like.

  In the present invention, the linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms having a glycoside having 3 to 12 carbon atoms is the above linear or branched aliphatic carbon group having 1 to 8 carbon atoms. It means an aliphatic hydrocarbon group in which the glycoside having 3 to 12 carbon atoms is glycosidically bonded at an arbitrary position of the hydrogen group.

  In the present invention, the straight-chain or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms and having one or more amide groups means the straight-chain or branched aliphatic hydrocarbon having 1 to 8 carbon atoms. It means an aliphatic hydrocarbon group in which one or more amide groups are incorporated at any position in the hydrocarbon group.

  In the present invention, the linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms having one or two or more carbonyl groups means the above linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms. It means an aliphatic hydrocarbon group in which one or two or more carbonyl groups are incorporated at any position in the hydrocarbon group.

  In the present invention, the linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms having one or two or more nitrile groups refers to the above linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms. An aliphatic hydrocarbon group having one or two or more carbon atoms having a nitrile group at any position in the hydrogen group. In the case of having two nitrile groups, two nitrile groups may be substituted on one carbon atom.

  The polymer compound of the present invention is produced as follows. One or two or more types of monomers and a polymerization initiator, which are raw materials for the polymer compound, are dissolved in a polymerization solvent, and the polymerization reaction is started by heating or the like. At this time, in order to obtain a crosslinked product containing such a polymer compound, a bifunctional monomer (crosslinking agent) may be dissolved. Further, at this time, a chain transfer agent may be dissolved in a polymerization solvent in order to adjust the molecular weight of the polymer compound or to introduce a reactive functional group at the terminal of the polymer compound. After the polymerization reaction, the target temperature-responsive polymer compound can be obtained by reprecipitation in a solvent that does not dissolve the polymer compound.

  Specific examples of the temperature-sensitive material of the present invention (temperature-responsive polymer compound having an upper critical eutectic temperature (UCST)) include the following.

Poly (acrylamide-co-3-acrylamidoacetanilide)
Acrylamide / 3-acrylamidoacetanilide The preparation ratio is 90:10 (mol / mol) (2-1-1): UCST: 9 ° C.
Charge ratio is 85:15 (mol / mol) (2-1-2): UCST: 69 ° C.
It was found that the temperature responsive temperature can be changed by changing the charging ratio.

A preparation ratio of 85:15 (mol / mol):
Concentration is 0.1 (mass% aqueous solution): UCST: 32 ° C
Concentration: 0.5 (mass% aqueous solution): UCST: 66 ° C.
Concentration is 1.0 (mass% aqueous solution): UCST: 69 ° C
Concentration is 3.0 (mass% aqueous solution): UCST: 72 ° C
It was found that the concentration of the polymer compound can also change UCST.

A preparation ratio of 85:15 (mol / mol):
Number average molecular weight 6500: (mass% aqueous solution) (2-1-3): UCST: 26 ° C.
Number average molecular weight 9300: (mass% aqueous solution) (2-1-4): UCST: 38 ° C
Number average molecular weight: 14200: (mass% aqueous solution) (2-1-5): UCST: 72 ° C.
The molecular weight of the polymer compound can also control UCST.

Cross-linked product containing poly (acrylamide-co-3-acrylamidoacetanilide) Acrylamide (0.85 mmol), 3-acrylamidoacetanilide (0.15 mmol), N, N′-methylenebisacrylamide (0.01 mmol) were radically polymerized. Things (2-1-6): UCST: 90 ° C
Poly (acrylamide-co-4-acrylamidoacetanilide)
Acrylamide (0.8 mmol), 4-acrylamidoacetanilide (0.2 mmol) radical polymerized (2-1-7): UCST: 90 ° C.
Poly (N, N-dimethylacrylamide-co-3-acrylamidoacetanilide)
N, N-dimethylacrylamide (0.9 mmol), 3-acrylamidoacetanilide (0.1 mmol) radical-polymerized (2-1-8): UCST: 90 ° C.
Poly (hydroxymethylacrylamide-co-3-acrylamidoacetanilide)
Hydroxymethylacrylamide (0.87 mmol), 3-acrylamidoacetanilide (0.13 mmol) radical polymerized (2-1-9): UCST: 90 ° C.
Poly (acrylamide-co-4-acrylamidebenzamide)
Acrylamide (0.85 mmol), 4-acrylamide benzamide (0.15 mmol) radically polymerized (2-1-10): UCST: 46 ° C. (3.0 mass% aqueous solution)
Poly (glycerol monomethacrylate-co-4-acrylamidebenzamide)
Glycerol monomethacrylate (0.7 mmol) and 4-acrylamidobenzamide (0.3 mmol) radically polymerized (2-1-11): UCST: 90 ° C.
Poly (glycosyloxyethyl methacrylate-co-4-acrylamidebenzamide)
Glycosyloxyethyl methacrylate (7.7 mmol) and 4-acrylamidobenzamide (5.1 mmol) radical polymerized (2-1-12): UCST: 35 ° C.
Etc.

(Microencapsulation)
In the present invention, it is preferable to form a microcapsule having the above-described thermoresponsive material as a core material and a thermoplastic resin as a shell.

  As a method for microencapsulation, a known method can be applied. For example, as a method for producing microcapsules, a method using coacervation as shown in U.S. Pat. Nos. 2,800,547 and 2,800,498, British Patent No. 990443, U.S. Pat. No. 3,287,154, Japanese Patent Publication No. 38-19574, No. 42-446. No. 42-711, interfacial polymerization method, US Pat. No. 3,418,250, US Pat. No. 3,660,304, method of polymer precipitation, US Pat. No. 3,796,669, method using isocyanate polyol wall material, US Pat. US Pat. No. 3,914,511 shows a method using an isocyanate wall material, US Pat. Nos. 4001140, 4087376, and 4089802 use a urea-formaldehyde-based or urea-formaldehyde-resorcinol-based wall-forming material, A method using a wall material such as melamine-formaldehyde resin and hydroxycellulose, as shown in U.S. Pat. No. 4,025,445, an in situ method by monomer polymerization as shown in JP-B-36-9163 and 51-9079, British Patent 930422, US Pat. And the like, but are not limited thereto, such as the spray drying method found in British Patent Nos. 952807 and 967074.

  A preferable microcapsule wall used in the present invention preferably has thermoplasticity. From this viewpoint, specific examples of the polymer include homopolymers of monomers such as ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, or the like. Mention may be made of copolymers or mixtures thereof, polyureas, polyurethanes, polyesters, polycarbonates, polyamides and the like. Among them, more preferred are polystyrene and polymethyl methacrylate. The average particle size of the microcapsules is preferably 0.01 to 3.0 μm, more preferably 0.05 to 2.0 μm, and particularly preferably 0.10 to 1.0 μm. Within this range, good resolution and stability over time can be obtained.

(Water-soluble resin)
In carrying out the present invention, any hydrophilic resin such as a conventionally known hydrophilic resin can be used without particular limitation. Examples of hydrophilic resins that can be used in the present invention include hydroxyl groups, carboxyl groups, (secondary or tertiary) amine-containing groups, amino groups, amide groups, carbamoyl groups, sulfonic acid groups, sulfonamidic acid groups, and phosphonic acids. And a compound having a hydrophilic group such as a group, a mercapto group, and an alkyl ether group.

  For example, as a hydrophilic resin, polyvinyl alcohol, polysaccharide, polyvinyl pyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, sucrose octaacetate, ammonium alginate, sodium alginate, polyvinylamine, Examples include polyallylamine, polystyrene sulfonic acid, polyacrylic acid, polyamide, maleic anhydride copolymer, polyurethane, and polyester. These compounds can be used alone or in combination of two or more.

  Among these, particularly preferable compounds include gelatin, polyvinyl alcohol, carboxymethyl cellulose, polyamide, polyurethane, and polyester. Of these, gelatin, polyvinyl alcohol, polyurethane and polyester are most preferred. These preferred compounds are described below.

As polyvinyl alcohol, in addition to polyvinyl alcohol having various polymerization degrees, copolymerized polyvinyl alcohol, an anion-modified polyvinyl alcohol modified with anions such as a carboxyl group and a sulfo group containing 50 mol% or more of a polyvinyl alcohol skeleton, an amino group , Random copolymers such as cation-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, alkoxyl-modified polyvinyl alcohol, epoxy-modified polyvinyl alcohol, and thiol-modified polyvinyl alcohol modified with a cation such as an ammonium group; anion-modified, cation-modified, thiol-modified, Water-soluble monomers such as polyvinyl alcohol, acrylamide, and acrylic acid that are modified only on the terminal groups, such as silanol modification, alkoxyl modification, and epoxy modification It introduced a block copolymer of polyvinyl alcohol, graft copolymer of polyvinyl alcohol and silanol group obtained by grafting, further, - copolymerized polyvinyl alcohol where the reactive group is introduced such as (COCH ₂ COCH ₃₎ is used.

  The polyvinyl alcohol preferably has a saponification degree of 70 mol% or more, more preferably 85 mol% or more, and particularly preferably 90% or more. Polyvinyl alcohol having a high saponification degree is preferable because the crystallinity is changed by heat treatment and water resistance can be imparted.

In the copolymerized polyvinyl alcohol, the following monomers can be used as the copolymerization monomer.
(1) Monomers having an aromatic hydroxyl group: for example, o-hydroxystyrene, p-hydroxystyrene, m-hydroxystyrene, o-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate and the like.
(2) Monomers having an aliphatic hydroxyl group: For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxy Pentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.
(3) Monomer having an aminosulfonyl group: for example, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl acrylate, p-aminophenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide N- (p-aminosulfonylphenyl) acrylamide and the like.
(4) Monomers having a sulfonamide group: for example, N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.
(5) α, β-unsaturated carboxylic acids: for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like.
(6) Substituted or unsubstituted alkyl acrylate: for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic Acid decyl, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate and the like.
(7) Substituted or unsubstituted alkyl methacrylate: for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, methacryl Acid decyl, undecyl methacrylate, undecyl methacrylate, dodecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like.
(8) Acrylamide or methacrylamide: For example, acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.
(9) Monomer containing a fluorinated alkyl group: for example, trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N-butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.
(10) Vinyl ethers: For example, ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ethers.
(11) Vinyl esters: For example, vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.
(12) Styrenes: For example, styrene, methyl styrene, chloromethyl styrene and the like.
(13) Vinyl ketones: For example, methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone and the like.
(14) Olefin: For example, ethylene, propylene, isobutylene, butadiene, isoprene and the like.
(15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.
(16) Monomer having a cyano group: for example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o-cyanostyrene, m-cyanostyrene, p-cyanostyrene etc.
(17) Monomer having an amino group: for example, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-isopropylacrylamide, N, N-diethylacrylamide and the like.

  The polyvinyl alcohol used in the present invention is preferably a polyvinyl alcohol having a reactive group introduced therein or a polyvinyl alcohol having an anionic group introduced therein. Among them, polyvinyl alcohol having a reactive group introduced is preferred. Examples of the reactive group include a silanol group, an acetoacetyl group, a thiol group, and an epoxy group. Among these, particularly preferred reactive groups are a silanol group, an acetoacetyl group, and a thiol group.

  The above polyvinyl alcohols may be used alone or in combination of two or more.

  Moreover, when using polyvinyl alcohol, you may use 1 type or 2 or more types of other polymers or mold release agents by mixing said polyvinyl alcohol as a main component, and also 2 types of polymers and mold release agents. You may mix and use the above. Specific polymers include, for example, natural polymers such as starch, modified starch, casein, glue, gelatin, gum arabic, sodium alginate and pectin; semisynthetic polymers such as carboxymethylcellulose, methylcellulose and viscose; polyacrylamide, Synthetic polymers such as polyethyleneimine, sodium polyacrylate, polyethylene oxide, and polyvinylpyrrolidone, and compounds described in JP-A-4-176688 are exemplified. Specific examples of the mold release agent include, for example, JP-A-4 The chemical base described in Japanese Patent No. -186354 can be used in a timely manner.

  Furthermore, compounds such as antistatic agents and surfactants may be mixed for improving the physical properties of polyvinyl alcohol. As specific compounds, for example, the compounds described in JP-A-4-184442 are used as appropriate. These may be used alone or in combination of two or more.

  In the implementation in each aspect of the present invention, the thickness of the heat-sensitive layer is preferably 30 μm or less, more preferably 0.01 to 3 μm.

  Examples of gelatin include alkaline gelatin, acidic gelatin, and modified gelatin (for example, modified gelatin described in JP-B-38-4854, JP-A-40-12237, British Patent 2,525,753, etc.) Etc. can be used alone or in combination of two or more. For example, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate, Bull. Soc. Sci. Photo. Japan. No. 16. Enzyme-treated gelatin as described in P30 (1966) can also be used.

  Examples of the carboxymethyl cellulose include carboxymethyl cellulose and salts thereof, such as sodium salt, calcium salt, potassium salt, aluminum salt, magnesium salt, ammonium salt, etc. Among them, carboxymethyl cellulose, carboxymethyl cellulose sodium salt, carboxymethyl cellulose Ammonium salts are preferred. Among them, carboxymethylcellulose ammonium salt is particularly preferable, and when these are used, they are water-soluble, but are preferable because they have a feature that the solubility in water is lowered by coating and drying on a support.

  Next, polyurethane, polyester, and polyamide as preferable compounds will be described. In the present invention, a polyurethane resin having a hydrophilic group, a polyester resin having a hydrophilic group, and a polyamide resin having a hydrophilic group can be preferably used. In the practice of the present invention, those having a carboxyl group, a hydroxyl group, a sulfonium group, an amino group and a sulfonamide group in the side chain are preferred as the hydrophilic group.

  The preferred polyurethane resin having a hydrophilic group that can be used in the present invention has at least one kind of the above-mentioned hydrophilic group, and at least one kind selected from a urethane bond, a urea bond, a burette bond, and an allophanate bond in the main chain. It is a polymer containing the above repeating units, and such a bond is formed mainly by selecting a reactive group that undergoes an addition reaction with isocyanate.

  Examples of the diisocyanate compound suitably used in this reaction include conventionally known 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane. Aromatic diisocyanate compounds such as diisocyanate, 1,5-naphthalene diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate; trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, Aliphatic diisocyanate compounds such as dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) And alicyclic diisocyanate compounds such as methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, and 3 molecules of these diisocyanate compounds. Trifunctional or higher functional isocyanate compounds produced by the above reaction products, reaction products of these diisocyanate compounds and trihydric or higher polyhydric alcohols can also be suitably used.

  Examples of the polyfunctional alcohol that forms a urethane bond by addition reaction with an isocyanate compound include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, octanediol, diethylene glycol, and triethylene glycol; glycerin and trimethylol Aliphatic polyfunctional alcohols such as ethane, trimethylolpropane, pentaerythritol, diglycerin, 1,2,6-hexanetriol, sorbitol, mannitol, and glucose; a hydroxyl group is formed at the terminal by condensation of dicarboxylic acid and polyhydric alcohol Polyester polyols prepared by ring-opening polymerization of alkylene oxide or polyether polyol added to alkylene oxide and polyhydric alcohol.

  Depending on the alcohol valence of these compounds, the desired reaction product can be obtained by adding and reacting at a ratio of 2 moles of isocyanate to 1 mole of hydroxyl groups.

  In order to impart a hydrophilic group to a polyurethane resin, a method of polymerizing a urethane prepolymer having an isocyanate group remaining at the terminal with a diol having a tertiary amino group and quaternizing the tertiary amino group; an isocyanate group at the terminal A method of polymerizing a urethane prepolymer having a residual amino group with a diol having a tertiary amino group, neutralizing the tertiary amino group with an acid and subjecting to an amine chloride; a urethane prepolymer having an isocyanate group remaining at the terminal has a quaternary salt Method of polymerizing with diols; Method of polymerizing a urethane prepolymer having an isocyanate group remaining at the terminal with a diaminophenylcarboxylate and removing the solvent; Termination of the urethane prepolymer having an isocyanate group remaining at the terminal with sodium bisulfite To block with a compound such as A method of polymerizing a urethane prepolymer that has left an isocyanate group with diaminoalkanesulfonate; A method of polymerizing a urethane prepolymer that has left an isocyanate group with bis (2-cyanoethylamino) ethane; Examples include a method of polymerizing a polymer with an alkylene oxide of a long chain alcohol, and other methods such as those described in Keiji Iwata “Polyurethane Resin Handbook”, Nikkan Kogyo Shimbun, pages 496 to 502 can be arbitrarily employed. .

  In addition, as commercially available polyurethane resins that can be employed in the present invention, Takeda Pharmaceutical Co., Ltd. Takerak W series (W-621, W-6015, W-7004, W-511, W-635, XW-76-P15, XW-74-P6012C, ACW-31H, ACW-54HD, XW-904-X05, XW-97-W4 to polyester urethane self-emulsifying type), the same (W-310, W-512 to polyester urethane forced emulsifying type), Series containing alkoxysilyl groups (XW-77-X25, XW-75-X09, XW-74-X13, XS-72-V01, XS-72-V02, XS-72-V03, XS, manufactured by Takeda Pharmaceutical Co., Ltd. -72-V04, XS-72-V05-polyester urethane self-emulsifying type), manufactured by Toho Chemical Industry Co., Ltd. (S-8531, S-8532, S-8533, S-8530, S-8529, S-8528, S-6254, S-6262, B-1306), NeoRez series (R-) manufactured by Enomoto Kasei Co., Ltd. 960, R-962, R-972, R-974, R-9314, R-9320, R-9617, XR-9621, XR-9624, R-9637, XR-9679, XR-9699, XR-9770 to Aliphatic polyester urethane), NeoRez series manufactured by Enomoto Kasei Co., Ltd. (R-966, R-967, XR-9000, AX-311, AX-7113 to aliphatic polyether urethane), NeoRez series manufactured by Enomoto Kasei Co., Ltd. (R-940, R-9030, XR-9409, R-9920, XR-7061-aromatic polyether urethane), cocoon NeoRez series made by Kasei Co., Ltd. (XU-7015, R-9603, special urethane, aliphatic polycarbonate urethane), Yodozol series made by Kaneboue NSC Co., Ltd. (9D102, 9D250Z, 9D232Z), Toa Gosei Chemical Co., Ltd. Neotan series made by UE1101, UE-1200, UE-1300, UE-1402, UE-2103, UE-2200, UE-2600, UE-2900-polyester urethane, Neotan series made by Toa Gosei Chemical Co., Ltd. (UE-5404, UE-5600 to polyether urethane), N-resin series (R-1489, R-1780) manufactured by Takamatsu Yushi Co., Ltd., Crown bond series (UA-28, UA-41) manufactured by Takamatsu Yushi Co., Ltd. U-176R, RI-793, RI-623, U-113), Dispacol series (U-42, U-53, KA8481, KA8584) manufactured by Sumitomo Bayer Urethane Co., Ltd., and the like.

  A polyester resin having a preferred hydrophilic group that can be used in the present invention is a polymer having at least one hydrophilic group described above and containing a repeating unit of an ester bond in the main chain. As a method for synthesizing a resin having a bond, for example, a hydrophilic group may be introduced into a prepolymer of a polyester resin formed by the method described in “Polyester Resin Handbook”, pages 21 to 28, and polymerized. Examples of commercially available polyester resins that can be used in the present invention include pesresin A series (110, 120, 121, 193, 510, 610, and 810--hydrophilic group is -SO3R) manufactured by Takamatsu Oil Co., Ltd., manufactured by Takamatsu Oil Co., Ltd. Pesresin A series (210, 620, 820-hydrophilic group is -COOR), Pesresin A series (115G, 124G, 124GH, 193G, 215G, 515G, 615G, 813GL to hydrophilic group-SO3R And glycidyl), pesresin A series (124S, 115S-hydrophilic groups are -SO3R and Si (OR) 3) manufactured by Takamatsu Yushi Co., Ltd., plus coat series (Z-3402, Z-4121 manufactured by Kyoyo Chemical Industry Co., Ltd.) , Z-446, Z-461, Z-448, Z-441, Z-450, Z-710, Z-711, Z 770, Z-766 to water soluble), plus coat series (Z-802, Z-3109, Z-3308, Z-857, Z-850, Z-802, Z-856, Z) manufactured by Kyoyo Chemical Industry Co., Ltd. -4201, RZ-27, RZ-50, RZ-56, RZ-105), Toyobo Co., Ltd. Bironal series (MD-1200, MD-1220, MD-1250, MD-1100, MD-1330, MD-1930).

  A preferred polyamide resin having a hydrophilic group that can be used in the present invention is a polymer having at least one hydrophilic group as described above and having a repeating unit of an amide bond in the main chain. A method for synthesizing a resin having a hydrophilic group can be obtained by, for example, adding a hydrophilic group to a prepolymer of a polyamide resin formed by the method described in Tadahiro Miwa, “Chemistry of Basic Synthetic Resin <Parent>”, pages 305 to 306. It may be introduced and polymerized. Alternatively, a polyamide resin having a hydrophilic group can be obtained by referring to the method described in “Polymer synthesis and reaction (2)” edited by Polymer Society of Japan, pages 208 to 209. Examples of commercially available polyamide resins that can be used in the present invention include KW-539 manufactured by Kyoyo Chemical Industry Co., Ltd., KP-2002 and KP-2007 manufactured by Matsumoto Yushi Seiyaku Co., Ltd.

  In the present invention, the hydrophilic resin as described above is preferably used in the range of 10 to 100% by mass, more preferably in the range of 20 to 95% by mass, and still more preferably 30 to 90% by mass. % Range.

  As a preferred embodiment of the present invention, there can be mentioned a constitution comprising at least one selected from gelatin, polyvinyl alcohol, carboxymethyl cellulose, polyamide, polyurethane and polyester as a main component. In addition, a main component means here containing 50% or more of solid content mass addition% of a hydrophilic resin component, More preferably, it is using 70% or more.

  These may be used alone or in combination of two or more, or two or more of the same may be used in combination.

(Water-insoluble resin)
Specific examples of polymers preferable as the water-insoluble resin according to the present invention include monomers such as ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, and vinylcarbazole. Mention may be made of homopolymers or copolymers or mixtures thereof. Among them, more preferred are polystyrene and polymethyl methacrylate.

  An alkali-soluble polymer compound can also be used as the water-insoluble resin according to the present invention.

  The alkali-soluble polymer compound referred to in the present invention is a polymer compound having an acid value, and specifically, copolymers having various structures as described below can be preferably used.

  As the copolymer, acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, other natural resins, etc. are used. I can do it. Two or more of these may be used in combination.

  Among these, a polymer having a carboxyl group and a hydroxyl group is preferably used, and a polymer having a carboxy group is particularly preferably used.

  Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferably used. Furthermore, the copolymer composition is preferably a copolymer of (a) a carboxyl group-containing monomer and (b) (meth) acrylic acid alkyl ester.

  Specific examples of the carboxyl group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. In addition, carboxylic acids such as phthalic acid and 2-hydroxymethacrylate half ester are also preferable.

  Specific examples of alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, (meth ) Unsubstituted such as hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate In addition to alkyl esters, cyclic alkyl esters such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-chloroethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meta And substituted alkyl esters such as acrylates.

  Furthermore, what used the monomer as described in following (1)-(14) as another copolymerization monomer can also be used.

  1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate and the like.

  2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate , 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

  3) A monomer having an aminosulfonyl group, such as m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p -Aminosulfonylphenyl) acrylamide and the like.

  4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

  5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N- Phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.

  6) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N- Butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.

  7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.

  8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.

  9) Styrenes such as styrene, methyl styrene, chloromethyl styrene and the like.

  10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

  11) Olefins such as ethylene, propylene, i-butylene, butadiene, isoprene and the like.

  12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.

  13) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene.

  14) Monomers having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl (meth) acrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropylacrylamide, N, N-dimethylacrylamide, acryloyl Morpholine, Ni-propyl acrylamide, N, N-diethylacrylamide and the like.

  Furthermore, other monomers that can be copolymerized with these monomers may be copolymerized.

  Also, an unsaturated bond-containing vinyl copolymer obtained by addition reaction of a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Are also preferably used.

  Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A No. 11-271969.

  Among these alkali-soluble polymer compounds, compounds having an acid value of 30 to 200 are preferable, and those having a weight average molecular weight of 15,000 to 500,000 are more preferable.

  Among these, those having a polymerizable unsaturated group are preferred, and those having a polymerizable unsaturated group-containing unit of 5 to 50% with respect to the repeating units of the whole polymer compound are particularly preferred.

  In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography (GPC).

  In the present invention, the acid value is the number of mg of potassium hydroxide required to neutralize 1 g of the compound. The acid value can be measured as follows. The sample is diluted 50 times with methyl cellosolve and titrated with 0.1 mol / L potassium hydroxide. The inflection point of the pH curve obtained using a pH meter is taken as the neutralization point. The acid value is calculated from the amount of potassium hydroxide required to reach this neutralization point.

  As the alkali-soluble polymer compound having a polymerizable unsaturated group, a known method can be used without limitation.

  For example, the method of making a glycidyl group react with the below-mentioned carboxyl group, the method of making an isocyanate group react with a hydroxyl group, etc. can be mentioned.

  Specifically, for example, allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl are used as the copolymer having a monomer unit having a carboxyl group. Aliphatic epoxy group-containing unsaturated compounds such as glycidyl ether, monoalkyl monoglycidyl itaconate, monoalkyl monoglycidyl fumarate, monoalkyl monoglycidyl maleate, or 3,4-epoxycyclohexylmethyl (meth) acrylate It is a reaction product obtained by reacting an alicyclic epoxy group or unsaturated group-containing compound such as the above with the carboxyl group. In the present invention, it is preferable that the mole percentage in which the carboxyl group, the epoxy group, and the unsaturated group-containing compound are reacted as a unit ratio, and the unit reacted in terms of sensitivity and printing durability is 5 to 50 mole%. Especially preferably, it is 10-30 mol%.

  The reaction of the copolymer having a monomer unit having a carboxyl group with the epoxy group and unsaturated group-containing compound can be carried out, for example, at a temperature of about 80 to 120 ° C. for about 1 to 50 hours. As a synthesis method of the reaction product, it can be synthesized by a generally known polymerization method. R. Sorenson, T.W. W. It can be synthesized according to the literature described in Campbell, the methods described in JP-A Nos. 10-315598 and 11-271963, and the like.

  The amount of the alkali-soluble polymer compound added is preferably 10 to 90% by mass and more preferably 15 to 70% by mass with respect to the photosensitive layer. Most preferably, it is 20-50 mass%.

Moreover, the copolymer which has at least 1 sort (s) of the monomer of the following (1)-(17) as a copolymer as a copolymer which has a monomer unit which has the said carboxyl group is mentioned.
(1) a monomer having an aromatic hydroxyl group,
(2) a monomer having an aliphatic hydroxyl group,
(3) a monomer having an aminosulfonyl group,
(4) a monomer having a sulfonamide group,
(5) α, β-unsaturated carboxylic acids,
(6) substituted or unsubstituted alkyl acrylate,
(7) substituted or unsubstituted alkyl methacrylate,
(8) Acrylamide or methacrylamides,
(9) a monomer containing an alkyl fluoride group,
(10) vinyl ethers,
(11) vinyl esters,
(12) Styrenes,
(13) vinyl ketones,
(14) olefins,
(15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc.
(16) a monomer having a cyano group,
(17) A monomer having an amino group.

  Specific examples of the compound include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide. Acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic ester such as 1,3-dioxolane acrylate, or methacrylic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, Itaconic acid, crotonic acid, maleic acid ester; for example, ethylene glycol diacrylate, triethylene glycol Coal diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate, neopentyl glycol diacrylate, neopentyl glycol adipate di Acrylate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, Tricyclodecane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, 1,6-hexanediol Difunctional acrylates such as diacrylate of diglycidyl ether, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate; Acrylates, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε- of dipentaerythritol hexaacrylate Caprolactone adduct, pyrogallol triacrylate, propionic acid Polyfunctional acrylic acid ester acid such as pentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, and their EO-modified products, or these acrylates as methacrylate, itaconate, crotonate And methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, etc., instead of maleate.

(Photothermal conversion agent)
When using a photothermal conversion agent, depending on the light source, a substance that absorbs light and efficiently converts it into heat is good.For example, when a semiconductor laser is used as a light source, a substance having an absorption band in the near infrared is preferable. Near-infrared light absorbers include, for example, carbon black, cyanine-based, polymethine-based, azulenium-based, squalium-based, thiopyrylium-based, naphthoquinone-based, anthraquinone-based organic compounds such as phthalocyanine-based, azo-based, and thioamide-based organic metals. Complexes and the like are preferably used, and specifically, JP-A-63-139191, JP-A-64-33547, JP-A-1-160683, JP-A-1-280750, JP-A-1-293342, and JP-A-2-2074. 3-26593, 3-30991, 3-34891, 3-36093, 3-360 No. 4, the same 3-36095 JP, same 3-42281 JP, same 3-97589 Patent, compounds described in the 3-103476 Patent and the like. These can be used alone or in combination of two or more. The film thickness of the photothermal conversion layer is preferably from 0.1 to 3 μm, more preferably from 0.2 to 1.0 μm. The content of the photothermal conversion agent in the photothermal conversion layer is usually determined so that the absorbance at the wavelength of the light source used for image recording is 0.3 to 3.0, more preferably 0.7 to 2.5. it can. When carbon black is used as the light-to-heat conversion layer, if the film thickness of the light-to-heat conversion layer exceeds 1 μm, the sensitivity tends to decrease instead of causing the ink layer to be overheated. Since it changes depending on the absorbance of the photothermal conversion layer, it may be selected as appropriate.

  In addition to this, a vapor deposition layer can also be used as the photothermal conversion layer. Carbon black, gold, silver, aluminum, chromium, nickel, antimony, tellurium, bismuth described in JP-A-52-20842, In addition to the vapor deposition layer of metal black such as selenium, Ib, IIb, IIIa, IVb, Va, Vb, VIa, VIb, VIIb and Group VIII metal elements of the periodic table, and alloys thereof, or these elements and Ia , IIa and IIIb alloys with elements, or mixtures thereof, particularly desirable metals include Al, Bi, Sn, In or Zn and their alloys, or their metals and the periodic table Alloys with Group Ia, IIa and IIIb elements, or mixtures thereof are included. Suitable metal oxides or sulfides include Al, Bi, Sn, In, Zn, Ti, Cr, Mo, W, Co, Ir, Ni, Pb, Pt, Cu, Ag, Au, Zr or Te compounds. Or a mixture thereof. Furthermore, metal phthalocyanines, metal dithiolenes, and anthraquinones are also included.

  Moreover, well-known additives, such as antioxidant, UV absorber, antiseptic | preservative, activator, and antistatic agent, can be used as needed.

(Image exposure)
As the light source for recording an image on the planographic printing plate material of the present invention, various light sources can be used in accordance with the photosensitive wavelength region of the material, but the use of a laser light source is preferred.

  The printing plate is obtained by irradiating a lithographic printing plate material with a laser beam according to image data from the surface having the photosensitive layer to form an image.

  Laser exposure is suitable for direct writing without using a mask material because light exposure can be performed in the form of a beam according to image data. When a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.

  As a laser light source for exposing the lithographic printing plate material of the present invention, a laser light source having an emission wavelength in the infrared and / or near infrared region, that is, a wavelength range of 700 to 1500 nm can be used. Specifically, a YAG laser, a semiconductor laser, or the like can be suitably used. However, the use of a laser capable of continuous oscillation in the 700 to 1200 nm region has the effect of the processless lithographic printing plate material according to the present invention. It is particularly preferable when it is exhibited.

  For example, in the printing method using the processless lithographic printing plate material according to the present invention, one or a plurality of laser beams are applied to the lithographic printing plate material held on the surface of the cylindrical drum on the printing apparatus from the outside of the cylinder. The entire surface of the lithographic printing plate material is exposed to form an image while scanning in the circumferential direction (main scanning direction) by rotation of the drum and moving in the direction perpendicular to the circumferential direction (sub-scanning direction).

  As the light source, a laser light source having an emission wavelength in the ultraviolet and visible short wavelength region can also be used. Specifically, for example, a He—Cd laser (441 nm), a combination of Cr: LiSAF and SHG crystal (430 nm) as a solid laser, KNbO 3, a ring resonator (430 nm), and AlGaInN (350 nm to 450 nm) as a semiconductor laser system. ), AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm), and the like.

  General laser scanning methods that can be used in the present invention include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is the main scanning and the movement of the laser light is the sub scanning.

  In cylindrical inner surface scanning, a recording material is fixed to the inner surface of the drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis.

  In plane scanning, a laser beam main scan is performed by combining a polygon mirror, a galvanometer mirror, and an fθ lens, and a sub-scan is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording. In order to effectively use the energy of the laser beam, the cylindrical outer surface scanning that can simply design the optical system and can shorten the distance between the light source and the recording material is particularly preferable.

In the present invention, image exposure is preferably performed with a plate surface energy (energy on the plate material) of 10 mJ / cm ² or more, and the upper limit is 500 mJ / cm ² . More preferably, it is 10-300 mJ / cm < ² >. For this energy measurement, for example, a laser power meter PDGDO-3W manufactured by Ophir Optronics can be used (processless planographic printing plate material).
The lithographic printing plate material of the present invention can be used as a printing plate material for carrying out a normal development process, but can be preferably used as a so-called processless lithographic printing plate material. Hereinafter, a printing method using the printing plate material as a processless planographic printing plate material will be described.

(Image formation)
One of the processless lithographic printing plate materials according to the present invention has a structure having a photosensitive layer on a support having a hydrophilic surface, and after the image is formed by the above image exposure, printing is performed without performing a development process. It has the feature that can be performed. That is, the printing plate material after image formation is directly attached to the plate cylinder of the printing machine, or image formation is performed after the printing plate material is attached to the plate cylinder of the printing machine, and the water supply roller and By bringing the ink supply roller into contact with the printing plate material, it is possible to supply dampening water and / or ink and remove the non-image area of the image forming layer, thereby obtaining a printing plate. The removal of the non-image portion of these photosensitive layers can be performed by a normal printing sequence using a PS plate, and is performed by so-called on-press development processing.

(Dampening water)
In the printing method using the processless lithographic printing plate material according to the present invention, water containing various preparations can be used as the dampening water supplied from the water supply roller. The fountain solution according to the invention is preferably a fountain solution having a phosphate compound content of 0.005 mol or more and less than 0.04 mol per liter of dampening water.

  In the printing method using the processless lithographic printing plate material according to the present invention, by setting the content of the phosphoric acid compound within the above-mentioned range, the printing plate material machine using the aluminum support in particular is used. In the upper development process, the initial ink inking property and the print image quality can be improved.

  Examples of the phosphoric acid compound used in the fountain solution according to the present invention include phosphates, organic phosphate compounds, phosphites, hypophosphites, condensed phosphates, phytic acid compounds, and phosphonic acid compounds. It is done.

  The phosphate is not particularly limited as long as it is a compound that releases phosphate ions in an aqueous solution. For example, phosphoric acid, ammonium salts of phosphoric acid (3 ammonium phosphate, 2 ammonium phosphate, 2 ammonium phosphate) Etc.), alkali metal salts of phosphoric acid (trisodium phosphate, disodium phosphate hydrogen, sodium dihydrogen phosphate, tripotassium phosphate, etc.), alkaline earth metal salts of phosphoric acid (zinc phosphate, potassium phosphate, Magnesium phosphate, etc.), iron phosphate, manganese phosphate, phosphomolybdic acid and the like.

  Examples of the organic phosphoric acid compounds include phenylphosphonic acid, phenylphosphonic acid, naphthylphosphonic acid, naphthylphosphoric acid, glycerophosphonic acid, glycerophosphoric acid, phenylphosphinic acid, naphthylphosphinic acid, diphenylphosphinic acid, dimethylphosphinic acid, p- Examples thereof include nitrophenylphosphinic acid and p-methoxyphenylphosphinic acid.

  The phosphite is not particularly limited as long as it is a compound that releases phosphite ions in an aqueous solution, and examples thereof include phosphorous acid, ammonium phosphite, sodium phosphite, and potassium phosphite.

  The hypophosphite is not particularly limited as long as it is a compound that releases hypophosphite ions in an aqueous solution. For example, hypophosphite, ammonium hypophosphite, sodium hypophosphite, hypophosphite Potassium etc. are mentioned.

  The condensed phosphate is not particularly limited as long as it is a compound that releases condensed phosphate ions in an aqueous solution. For example, condensed phosphates such as polyphosphoric acid, piceric acid, metaphosphoric acid, and ultraphosphoric acid, or ammonium salts thereof, Examples include alkali metal salts and alkaline earth metal salts.

  The phytic acid compound is not particularly limited as long as it is a compound capable of releasing phytic acid ions in an aqueous solution, and examples thereof include phytic acid, ammonium salts of phytic acid, and alkali metal salts.

  The phosphonic acid compound is not particularly limited as long as it is a compound capable of releasing phosphonic acid ions in an aqueous solution. For example, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra ( Phosphonic acids such as methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid) or ammonium salts thereof, alkali metal salts and the like.

  In this invention, it is the characteristics that content of a phosphoric acid compound is 0.005 mol or more and less than 0.04 mol per liter of dampening water. More preferably, the content of the phosphoric acid compound is 0.01 mol or more and less than 0.04 mol per liter of dampening water.

  For example, when a printing plate material having an aluminum support is subjected to on-press development, if the phosphoric acid compound in the dampening water is less than 0.005 mol, it is generated in the on-press development process in a hydrophilic portion that is a non-image area. The oil-sensitive component that adheres causes a problem in the initial ink setting. That is, the non-image area is not soiled, and the on-machine development becomes insufficient, resulting in an increase in the number of damaged paper at the time of printing. This is probably because an anodized film is usually formed on the aluminum support as a hydrophilization treatment, and the oil-sensitive component that has entered here remains without being removed. However, when the phosphate is in the range of 0.005 mol or more and less than 0.04 mol, the fat-sensitive component or the like in which the phosphate has entered the anodized film formed on the aluminum support, It is thought that it is easy to dissolve and remove together with a part of. On the other hand, when the amount of the phosphoric acid compound is as large as 0.04 mol or more, it easily becomes dirty.

  Also, if it is within this range, the non-image area due to on-press development is less likely to be smudged with a fat-sensitive component (sufficient on-press development is performed), not only the initial ink setting, but also the subsequent printing, especially many Even when printing is performed, a high-quality image can be obtained without deterioration of the print image quality. There is little deterioration in the quality of halftone images.

  In a printing plate material having a photosensitive layer formed on a substrate having a hydrophilic surface used for so-called processless printing in which on-press development is performed, this is achieved by adjusting the phosphate concentration in the fountain solution to the above range. In this way, it is possible to improve the initial ink fillability and the quality of the printed image.

The fountain solution used in the present invention is preferably combined with a plurality of the following.
(A) pH adjuster (b) Auxiliary agent for improving wettability (c) Water-soluble polymer compound (d) Odor masking agent (e) Preservative (f) Chelating agent (g) Colorant (h) Antirust agent (i) Antifoaming agent As the (a) pH adjusting agent used in the fountain solution according to the present invention, at least one selected from water-soluble organic acids, inorganic acids and salts thereof can be used. These compounds are effective in adjusting the pH of the fountain solution or buffering the pH and appropriately etching or preventing corrosion of the lithographic printing plate support. Examples of preferable organic acids include citric acid, ascorbic acid, malic acid, tartaric acid, lactic acid, acetic acid, gluconic acid, hydroxyacetic acid, succinic acid, malonic acid, levulinic acid, sulfanilic acid, p-toluenesulfonic acid, and the like. Examples of inorganic acids include nitric acid and sulfuric acid. Furthermore, alkali metal salts, alkaline earth metal salts or ammonium salts of these organic acids and / or inorganic acids, and organic amine salts are also preferably used. One of these organic acids, inorganic acids and salts thereof may be used alone, or a mixture of two or more thereof may be used.

  The addition amount of these pH adjusting agents to the fountain solution is suitably in the range of 0.001% by mass or more and 0.1% by mass or less in combination of the organic acid, inorganic acid and salts thereof. When it is 0.001% by mass or more, the stain at the time of printing is good due to the etching force of aluminum which is the support of the lithographic printing plate. On the other hand, if it is 0.1 mass% or less, it is preferable at the point of the rust of a printing press.

  The pH value of the fountain solution according to the present invention is preferably used in the range of 4.5-8.

  (B) A surfactant or other solvent can be used as an aid for improving wettability. Among the surfactants, for example, anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, linear alkyl benzene sulfonic acid salts, branched alkyl benzene sulfonic acid. Acid salts, alkylnaphthalene sulfonates, alkylphenoxy polyoxyethylenepropyl sulfonates, polyoxyethylene alkylsulfenyl ether salts, N-methyl-N-oleyl taurine sodium salts, N-alkylsulfosuccinic acid monoamide disodium salts, Petroleum sulfonates, sulfated castor oil, sulfated beef tallow oil, sulfate esters of fatty acid alkyl esters, alkyl sulfate esters, polyoxyethylene alkyl ether sulfate esters, fatty acids Noglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, styrene -Partially saponified products of maleic anhydride copolymer, partial saponified products of olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensate and the like. Among these, dialkyl sulfosuccinates, alkyl sulfates and alkyl naphthalene sulfonates are particularly preferably used.

  Cationic surfactants include primary amine salts, acylaminoethylamine salts, N-alkyl polyalkylene polyamine salts, fatty acid polyethylene polyamides, amides, and salts thereof, alkylamines such as amine salts, and acylamine salts. Alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, alkylpyridium salt, acylaminoethylmethyldiethylammonium salt, acylaminopropyldimethylbenzylammonium salt, acylaminopropyl diethylhydroxyethylammonium salt, acylamino Quaternary ammonium salts such as ethyl pyridium salt, diacylaminoethyl ammonium salt or ammonium salts having an amide bond; diacyloxyethyl methyl Esters such as hydroxyethylammonium salts and alkyloxymethylpyridium salts; ammonium salts having an ether bond; imidazolines such as alkylimidazolines, 1-hydroxyethyl-2-alkylimidazolines, 1-acylaminoethyl-2-alkylimidazolium salts , Imidazolium salts; amine derivatives such as alkylpolyoxyethyleneamine, N-alkylaminopropylamine, N-acylpolyethylenepolyamine, acylpolyethylenepolyamine, fatty acid triethanolamine ester; and other fatty compounds, biosurfactants, oligo soaps At least one of these can be used.

  Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan Fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, poly Glycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid die Examples include olamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, polyoxyethylene-polyoxypropylene block polymers, and trialkylamine oxides. . In addition, fluorine-based surfactants and silicon-based surfactants can also be used. In the case of using a surfactant, the content thereof is 1% by mass or less, preferably 0.001 to 0.5% by mass in consideration of foaming. Two or more kinds can be used in combination.

  Other auxiliaries include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol mono Ethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, tetraethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl ether, Tetra Tylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monoisobutyl ether, tetraethylene glycol mono Isobutyl ether, ethylene glycol monotertiary butyl ether, diethylene glycol monotertiary butyl ether, triethylene glycol monotertiary butyl ether, tetraethylene glycol monotertiary butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether Ter, tripropylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, tetrapropylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, tripropylene Glycol monopropyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monoisopropyl ether, tripropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoisobutyl ether Ether, tripropylene glycol monoisobutyl ether, propylene glycol monotertiary butyl ether, dipropylene glycol monotertiary butyl ether, tripropylene glycol monotertiary butyl ether, polypropylene glycol having a molecular weight of 200 to 1000 and their monomethyl ether, monoethyl ether, mono Propyl ether, monoisopropyl ether and monobutyl ether, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and pentapropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, butylene glycol, hexylene glycol, 2-ethyl-1 , 3-hexanediol, 3-metho Ci-3-methyl-1-butanol, 1-butoxy-2-propanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, 2-pyrrolidone substituted at the 1-position with an alkyl group having 1 to 8 carbon atoms Derivatives, 3,5-dimethyl-1-hexyn-3-ol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, propargyl alcohol (2-propyn-1-ol), 3 -Butyn-1-ol, 1-butyn-3-ol, 2-butyne-1,4-diol, 3,6-dimethyl-4-octyne-3,6-diol, and the like. Among these, ethylene glycol monotertiary butyl ether, 3-methoxy-3-methyl-1-butanol and 1-butoxy-2-propanol are particularly preferable. These solvents may be used alone or in combination of two or more. In general, these solvents are suitably used in the range of 0.002 to 1% by mass, preferably 0.005 to 0.5% by mass, based on the total mass of the fountain solution.

  Examples of the water-soluble polymer compound (c) used in the fountain solution used in the present invention include gum arabic, starch derivatives (for example, dextrin, enzymatically degraded dextrin, hydroxypropylated enzymatically degraded dextrin, carboxymethylated starch, phosphoric acid Starch, octenyl succinylated starch), alginate, fibrin derivatives (for example, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, hydroxyethylcellulose) and other natural products and modified products thereof, polyethylene glycol and copolymers thereof, polyvinyl alcohol and derivatives thereof, Polyacrylamide and its copolymer, polyacrylic acid and its copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, polystyrene sulfonic acid and its copolymer Synthesis of polymer, polyvinylpyrrolidone, and the like. Among these, carboxymethyl cellulose and hydroxyethyl cellulose are particularly preferable. 0.001-0.5 mass% is suitable with respect to dampening water, and, as for content of a water-soluble polymer compound, More preferably, it is 0.005-0.2 mass%.

  (D) As an odor masking agent, the ester conventionally used as a fragrance | flavor is included. For example, there is one represented by the following general formula (I).

R ₁ -COOR ₂ (I)
In the compound of the general formula (I), R ₁ is an alkyl group having 1 to 15 carbon atoms, an alkenyl group, an aralkyl group, or a phenyl group. In the case of an alkyl group or an alkenyl group, the number of carbon atoms is preferably 4-8. When R ₁ represents an alkyl group, an alkenyl group or an aralkyl group, they may be linear or branched. An alkenyl group having one double bond is particularly suitable. Examples of the aralkyl group include a benzyl group and a phenylethyl group. One or more hydrogen atoms of the alkyl group, alkenyl group, aralkyl group, or phenyl group represented by R ₁ may be substituted with a hydroxyl group or an acetyl group. R ₂ is an alkyl group having 3 to 10 carbon atoms, an aralkyl group, or a phenyl group, which may be linear or branched. In the case of an alkyl group, the number of carbon atoms is preferably 3 to 9. Examples of the aralkyl group include a benzyl group and a phenylethyl group.

  Specific examples of (d) odor masking agents that can be used include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, 2-ethylbutyric acid, valeric acid, isovaleric acid, 2-methylvaleric acid, hexanoic acid (caproic acid), 4-methylpentanoic acid (isohexanoic acid), 2-hexenoic acid, 4-pentenoic acid, heptanoic acid, 2-methylheptanoic acid, octanoic acid (caprylic acid), nonanoic acid, decanoic acid (capric acid), 2-decenoic acid , Esters of lauric acid or myristic acid. In addition, there are acetoacetate esters such as benzyl phenylacetate, ethyl acetoacetate and 2-hexyl acetoacetate. Among them, preferred are n-pentyl acetate, isopentyl acetate, n-butyl butyrate, n-pentyl butyrate and isopentyl butyrate, and n-butyl butyrate, n-pentyl butyrate and isopentyl butyrate are particularly preferable. The content of these odor masking agents (d) in the fountain solution is suitably 0.001 to 0.5% by mass, more preferably 0.002 to 0.2% by mass, based on the total mass of the fountain solution. %. By using these, the work environment can be further improved. Also. Vanillin, ethyl vanillin or the like may be used in combination.

  (E) Preservatives used in the fountain solution according to the present invention include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benztriazole derivatives, derivatives of amidine or guanidine. , Quaternary ammonium salts, pyridine, quinoline or guanidine derivatives, diazine or triazole derivatives, oxazole or oxazine derivatives, bromonitroalcohol-based bromonitropropanol, 1,1-dibromo-1-nitro-2-ethanol, 3 -Bromo-3-nitropentane-2,4-diol and the like. A preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeasts, etc., and varies depending on the types of bacteria, molds, yeasts, etc. The range of mass% is preferable, and it is preferable to use two or more preservatives that are effective against various molds, bacteria and yeasts.

  The fountain solution according to the present invention may further contain (f) a chelating agent. The fountain solution is usually prepared by adding tap water, well water, etc. to the fountain solution concentrated composition and diluting it at the time of use. At this time, calcium ions contained in the tap water or well water to be diluted are prepared. It may have an adverse effect on printing and may cause the printed material to become dirty easily. In such a case, the above disadvantages can be eliminated by adding a chelating agent. Preferred chelating agents include, for example, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt, hydroxyethylethylenediaminetriacetic acid Nitrilotriacetic acid, sodium salt; 1-hydroxyethane-1,1-diphosphonic acid, potassium salt, sodium salt; aminotri (methylenephosphonic acid), potassium salt, sodium salt And organic phosphonic acids and phosphonoalkanetricarboxylic acids. Instead of the sodium salt or potassium salt of the chelating agent, an organic amine salt is also effective. These chelating agents are selected so that they are stably present in the dampening water during use and do not impair the printability. As content of the chelate compound in dampening water at the time of use, 0.0001-0.5 mass% is suitable, Preferably it is 0.0005-0.2 mass%.

  As the colorant (g) used in the fountain solution according to the present invention, food colorants can be preferably used. For example, CINo. 19140, 15985 and CI No. 16185, 45430, 16255, 45380, 45100, and purple pigments such as CI No. 42640, as a blue pigment, CI No. 42090 and 73015, CINo. 42095, and the like. As content of the coloring agent in the dampening water to be used, 0.0001-0.5 mass% is preferable. Examples of the rust inhibitor used in the fountain solution used in the present invention include benzotriazole, 5-methylbenzotriazole, thiosalicylic acid, benzimidazole, and derivatives thereof. As the antifoaming agent (i) used in the fountain solution used in the present invention, a silicon antifoaming agent is preferable, and any of emulsifying dispersion type and solubilizing type can be used. When used, the content of the rust inhibitor in the fountain solution is preferably 0.0001 to 0.5% by mass.

  Furthermore, the fountain solution of the present invention may be added with alcohols in order to improve the printability by adjusting the surface tension and viscosity. Examples of the alcohol that can be added include methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol.

  The balance is water as a component of the fountain solution composition according to the present invention. The fountain solution composition is generally concentrated and commercialized when it is usually commercialized. Accordingly, a concentrated fountain solution composition can be obtained as an aqueous solution in which the above various components are dissolved using water, preferably demineralized water, that is, pure water. When such a concentrated solution is used, it is diluted about 10 to 200 times with tap water, well water, etc. during normal use to obtain a fountain solution composition during use.

  The dampening water according to the present invention can be used in either a dampening water supply system or a continuous water supply dampening water supply apparatus, but is particularly preferably used in a continuous water supply dampening water supply apparatus. It can also be used in printing presses such as Mitsubishi Diamatic Dumpner, Comorimatic, Darleng Dampner and Heidelberg Alcolor Dumpner.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this.

Example 1
(Preparation of temperature-responsive material having lower critical solution temperature (LCST): specific structure urethane)
In a 50 ml autoclave, 8.8 mol of 2-methylaziridine and carbon dioxide (conditions shown in Table 1 below) are reacted for 24 hours to produce a temperature-responsive material (1-1-2-5) PU-5 having a different urethane ratio. , (1-1-2-2) PU-2, (1-1-2-6) PU-6 (lower critical solution temperature: described in Table 1 below).

  Separately, (1-1-1-1) isopropylacrylamide polymer (lower critical temperature: 32 ° C.) was prepared as temperature-responsive material A.

(Production of temperature-responsive material microcapsules)
As water phase components, the temperature-responsive materials (1-1-2-5) PU-5, (1-1-2-2) PU-2, and (1-1-2-6) PU-6 produced above. Alternatively, 10 g of (1-1-1-1) A (isopropylacrylamide polymer) and 0.1 g of Pionein A41C (manufactured by Takemoto Yushi) were dissolved in 60 g of water.

  As an oil phase component, 120 g of a 4 mass% cyclohexanone / dipropylene glycol monomethyl ether = 2/3 solution of Heimer ST95 (polystyrene: manufactured by Sanyo Chemical Co., Ltd.) was prepared.

  The oil phase component and the aqueous phase component were emulsified at 10,000 rpm using a homogenizer. To this, 40 g of ethyl acetate was added and stirred for 30 minutes at room temperature to prepare dispersions 1 to 4 of microcapsules of temperature-responsive material. The solid content concentration of the microcapsule dispersion of the temperature-responsive material thus obtained was 20% by mass, and the average particle size was 0.5 μm.

(Production of support)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by immersing it in a 10% sulfuric acid aqueous solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, this aluminum plate was subjected to an electrolytic surface roughening treatment for 20 seconds in an alternating current having a hydrochloric acid concentration of 11 g / L, a temperature of 25 ° C., a frequency of 50 Hz, and 50 A / dm ² . After electrolytic surface roughening, it was washed with water, desmutted for 10 seconds in a 1% aqueous sodium hydroxide solution maintained at 50 ° C., washed with water, and then washed in 30% sulfuric acid maintained at 50 ° C. for 30 seconds. Neutralization treatment was performed and washed with water. Subsequently, anodizing treatment was performed for 40 seconds in a 20% sulfuric acid solution under conditions of 25 ° C., a current density of 5 A / dm ² , and a voltage of 15 V, and washed with water. Further, a 0.44% polyvinylphosphonic acid aqueous solution was dipped at 75 ° C. for 30 seconds, then washed with distilled water and dried with cold air at 25 ° C. to obtain a support for a photosensitive lithographic printing plate material. . At this time, the center line average roughness (Ra) of the surface was 0.65 μm.

(Synthesis of polymer binder A (water-insoluble resin))
In a three-necked flask under a nitrogen stream, 58.0 parts (0.58 mol) of methyl methacrylate, 35.0 parts (0.41 mol) of methacrylic acid, 6.0 parts (0.05 mol) of ethyl methacrylate, ethanol 100 parts and 1.23 parts of α, α′-azobisisobutyronitrile were added and reacted in an oil bath at 80 ° C. in a nitrogen stream for 6 hours to obtain a polymer. Thereafter, 1 part of triethylbenzylammonium chloride and 28.0 parts (0.2 mol) of glycidyl methacrylate were added to the polymer and reacted at a temperature of 25 ° C. for 3 hours to obtain a polymer binder A (water-insoluble resin). Obtained. The weight average molecular weight measured using GPC was about 70,000 and the acid value was 95.

(Preparation of lithographic printing plate materials)
On the surface-treated support, an image forming layer coating solution having the following composition was applied with a wire bar so as to be 1.0 g / m ² when dried, and dried with cold air for 2.0 minutes. Thus, lithographic printing plate materials 1 to 5 were prepared.

(Image forming layer coating solution)
Synthetic polymer binder A 45.0 parts by mass Dispersion of microcapsules of temperature-responsive material [solid content: 20% by mass, cyclohexanone / dipropylene glycol monomethyl ether / ethyl acetate dispersion] (described in Table 2) 300.0 Mass parts Infrared absorbing dye CY-10 (manufactured by Nippon Kayaku Co., Ltd.) 4.0 parts by mass Fluorine-based surfactant (F178K: manufactured by Dainippon Ink & Chemicals, Inc.) 0.5 parts by mass Cyclohexanone (boiling point = 155 ° C.) 620 Mass (image formation by infrared laser method)
The lithographic printing plate material produced above was subjected to image exposure using an infrared laser exposure apparatus.

For the exposure, a laser beam having a wavelength of 808 nm and a spot diameter of about 18 μm is used, and the exposure energy is changed stepwise from 50 to 100 mJ / cm ² every 50 mJ, and 2,400 dpi (dpi is a dot per 2.54 cm) An image was formed with 175 lines, and an imaged lithographic printing plate material sample was prepared.

  The developed lithographic printing plate material sample after the above exposure is placed on a printing press (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.) and coated paper, printing ink (Toyo Ink Co., Ltd. Toyo King High) Echo M Red) and fountain solution (Tokyo Ink Co., Ltd. H liquid SG-51 concentration 1.5%), printing is started, and the number of lost paper and a good image until a good printed matter is obtained. The lowest exposure energy obtained was determined and evaluated.

  The results are shown in Table 2.

  From Table 2, it can be seen that the lithographic printing plate material of the present invention, that is, the positive lithographic printing plate material of the present invention is excellent in sensitivity and the number of printing wastes.

  Moreover, the negative lithographic printing plate obtained using the same was excellent in high printing durability.

Example 2
(Preparation of temperature responsive material having upper critical eutectic temperature (UCST))
According to JP 2000-319335, acrylamide (0.85 mmol), 3-acrylamidoacetanilide (0.15 mmol), N, N′-methylenebisacrylamide (0.01 mmol) and 2,2′-azobis (2-amidinopropane) A dihydrochloride (0.05 mmol) is dissolved in water (10 ml) and subjected to radical polymerization at 70 ° C. to obtain a cross-linked product (2-1-13) containing poly (acrylamide-co-3-acrylamidoacetanilide). It was.

  It was observed whether the aqueous solution of the cross-linked product caused turbidity change with temperature. It was confirmed to be a crosslinked product exhibiting temperature responsiveness having UCST that dissolves at 70 ° C. when it is ice-cooled.

(Preparation of temperature-responsive material microcapsule dispersion)
As an aqueous phase component, 10 g of the temperature-responsive material (2-1-13) prepared above and 0.1 g of Pionein A41C (manufactured by Takemoto Yushi Co., Ltd.) were dissolved in 60 g of 70 ° C. warm water.

  As an oil phase component, 120 g of a 4 mass% cyclohexanone / dipropylene glycol monomethyl ether = 2/3 solution of Heimer ST95 (polystyrene: manufactured by Sanyo Chemical Co., Ltd.) was prepared.

  The oil phase component and the aqueous phase component were emulsified at 10,000 rpm using a homogenizer. To this, 40 g of ethyl acetate was added and stirred at room temperature for 30 minutes to prepare a microcapsule dispersion 11 of a temperature-responsive material. The solid content concentration of the microcapsule dispersion of the temperature-responsive material thus obtained was 20% by mass, and the average particle size was 0.5 μm.

(Preparation of lithographic printing plate materials)
On the surface-treated support, an image forming layer coating solution having the following composition was applied with a wire bar so as to be 1.0 g / m ² when dried, and dried with cold air for 2.0 minutes. A lithographic printing plate material was prepared as described above.

(Image forming layer coating solution)
Polymer binder (polyvinylpyrrolidone K-30: manufactured by BASF) 45.0 parts by mass Dispersion of microcapsules of temperature-responsive material (2-1-13) [solid content: 20% by mass, cyclohexanone / dipropylene glycol monomethyl Ether / ethyl acetate dispersion] (described in Table 2) 300.0 parts by mass Infrared absorbing dye IR-1 4.0 parts by mass Fluorosurfactant (F178K: manufactured by Dainippon Ink & Chemicals, Inc.) 0.5 mass Part cyclohexanone (boiling point = 155 ° C.) 620 parts by mass

The lithographic printing plate material produced above was evaluated in the same manner as in Example 1 by performing image formation using an infrared laser system. That is,
(Image formation by infrared laser method)
The lithographic printing plate material produced above was subjected to image exposure using an infrared laser exposure apparatus.

For the exposure, a laser beam having a wavelength of 808 nm and a spot diameter of about 18 μm is used, and the exposure energy is changed stepwise from 50 to 100 mJ / cm ² every 50 mJ, and 2,400 dpi (dpi is a dot per 2.54 cm) An image was formed with 175 lines, and an imaged lithographic printing plate material sample was prepared.

  The developed lithographic printing plate material sample after the above exposure is placed on a printing press (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.) and coated paper, printing ink (Toyo Ink Co., Ltd. Toyo King High) Echo M Red) and fountain solution (Tokyo Ink Co., Ltd. H liquid SG-51 concentration 1.5%), printing is started, and the number of lost paper and a good image until a good printed matter is obtained. The lowest exposure energy obtained was determined and evaluated.

  The results are shown in Table 3.

  From Table 3, it can be seen that the lithographic printing plate material of the present invention, that is, the negative lithographic printing plate material of the present invention, is excellent in sensitivity and the number of lost printing sheets.

  Moreover, the negative lithographic printing plate obtained using the same was excellent in high printing durability.

Claims (11)

In a lithographic printing plate material comprising an image forming layer containing a microcapsule and a hydrophilic support, the microcapsule contains a compound that reversibly changes its polarity with temperature. A planographic printing plate material. 2. The lithographic printing plate material according to claim 1, wherein the compound that reversibly changes its polarity with temperature is water-soluble at room temperature. The lithographic printing plate material according to claim 1 or 2, wherein the microcapsule comprises a shell having a thermoplastic resin as a main component and a core containing a compound that reversibly changes its polarity depending on temperature. The lithographic printing plate material according to any one of claims 1 to 3, wherein the image forming layer contains at least a photothermal conversion agent, a water-insoluble resin, and the microcapsules. 2. The lithographic printing plate material according to claim 1, wherein the compound that reversibly changes polarity with temperature is insoluble in water at room temperature. 6. The lithographic printing plate material according to claim 5, wherein the microcapsule comprises a shell having a thermoplastic resin as a main component and a core containing a compound that reversibly changes its polarity depending on temperature. The lithographic printing plate material according to claim 5 or 6, wherein the image forming layer contains at least a photothermal conversion agent, a water-soluble resin, and microcapsules. A method for producing a positive lithographic printing plate, comprising: exposing the lithographic printing plate material according to any one of claims 2 to 4 to a lithographic printing plate by removing an exposed portion after image exposure with a high-power laser; . The lithographic printing plate material according to any one of claims 2 to 4, wherein after image exposure with a high-power laser, the image portion (exposed portion) is removed processlessly on a printing machine to form a lithographic printing plate. A processless positive type lithographic printing plate production method. A lithographic printing plate material according to any one of claims 5 to 7, wherein the lithographic printing plate is formed by removing an unexposed portion after image exposure with a high-power laser and forming a lithographic printing plate. Method. A lithographic printing plate material according to any one of claims 5 to 7 is formed by removing a non-image area (unexposed area) processlessly on a printing machine after image exposure with a high-power laser. A processless negative lithographic printing plate production method characterized by the above.