Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/016—Diazonium salts or compounds
  • G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders

Definitions

• the present invention relates to screen printing, and more particularly to a reinforcing agent for a screen printing screen and a method of applying the same, and a screen printing printing plate after application.
• the printing plate for screen printing is formed by coating a film layer of a photosensitive resin composition on a polyester or stainless steel wire mesh fixed by a frame, and on the above, a latent image of a desired pattern is drawn by the presence or absence of light. Then, the difference in solubility between the exposed portion and the unexposed portion is processed by the developer to complete the fabrication process.
• the developer used at this time is mostly neutral water, and an aqueous photosensitive resin composition is also used at the time of production.
• an aqueous photosensitive resin composition is used for screen printing, it is suitable to use polyvinyl alcohol, partially alkalized polyvinyl alcohol or a copolymer of polyvinyl alcohol and other monomers which are excellent in film formability and film strength.
• a diazo resin is added for compounding.
• the diazo resin is decomposed and reacts with polyvinyl alcohol or a derivative thereof to form a bridging structure, which becomes water-insoluble.
• the unexposed portion is removed by water development to form an image of the negative film. Since the photosensitive resin composition to which the diazo resin is added cannot be stored in a dark place for a long period of time, it is generally a two-liquid type (mixed before use).
• a photosensitive composition obtained by previously combining a photodimerization-type photosensitive group represented by a styrylpyridinium salt with polyvinyl alcohol or a derivative thereof is also widely used. Since the object can be stored in a dark place for a long period of time, it is used in the form of a one-liquid type photosensitive resin composition. Further, a photosensitive composition obtained by combining a residue containing an unsaturated bond such as a methacrylic group or an acrylic group with polyvinyl alcohol or a derivative thereof has also been proposed.
• the above-mentioned photosensitive material obtained from polyvinyl alcohol or a derivative thereof exhibits high hydrophilicity because it contains a large amount of hydroxyl groups, and although the exposed portion becomes water-insoluble by a photo-bridge reaction, since most of the hydroxyl groups remain, Water swelling (water swelling) is liable to occur, and the resolution (fineness) of the formed image is lowered. Thus, it is difficult to use it as a screen printing plate.
• a non-hydrophilic emulsion resin and a non-polar powder are generally added to the formulation, so that the polyvinyl alcohol or a derivative thereof can be relatively reduced as a main component.
• the water of the photosensitive material is swollen (water swelling).
• Patent Document 1 polyacetic acid having no hydrophilicity
• An emulsified resin of a hydrophobic high molecular polymer represented by vinyl ester is added to the formulation.
• a polyvinyl alcohol or a derivative thereof obtained by sensitizing a dichromate, a diazo resin or a styryl pyridinium salt is used as an emulsifier in combination with a photopolymerizable emulsion resin, and is produced in a photosensitive polyvinyl alcohol or a derivative thereof.
• a method in which an emulsion resin forms a solid particle by photopolymerization is also widely used. (for example, Patent Documents 2 to 9).
• the photosensitive polyvinyl alcohol or a derivative thereof is used as a protective colloidal light-initiating cationically polymerizable monomer and an emulsion resin of a photoacid generator (Patent Document 10), and a photoinitiated radical polymerizable monomer and a photoinitiated cationic polymerizable single A photosensitive emulsion resin in which a body coexists (Patent Document 11) has also been proposed.
• Patent Document 1 JP-A-53-51004
• Patent Document 2 Japanese Patent Publication No. 59-107343
• Patent Document 3 Japanese Patent Publication No. 60-10245
• Patent Document 4 Japanese Patent Publication No. 04-19542
• Patent Document 5 Japanese Patent Publication No. 06-67429
• Patent Document 6 Japanese Patent Publication No. 07-146549
• Patent Document 7 JP-A-2005-292780
• Patent Document 8 JP-A-2005-221990
• Patent Document 9 JP-A-2012-215862
• Patent Document 10 JP-A-2007-25723
• Patent Document 11 JP-A-2005-208070
• the reinforcing treatment is carried out using a polyurethane reinforcing agent prepared from a polyester resin and an isocyanate compound.
• a urethane resin is applied to both sides of the prepared printing plate, and then the urethane resin in the opening other than the image is removed, and then dried by heating to obtain a printing plate suitable for printing and dyeing.
• Still another method is to achieve a strengthening effect by thermochemical reaction of polyvinyl alcohol or a derivative thereof, which is a main constituent material of the photosensitive resin composition, by an acid catalyst.
• Patent Document 12 proposes a production method in which a water-soluble resin is treated with an aldehyde in the presence of a volatile acid such as hydrochloric acid or hydrofluoric acid, whereby a printing plate having enhanced printing durability can be obtained.
• the aldehydes mentioned therein include monoaldehydes - acetaldehyde, benzaldehyde, cinnamaldehyde; dialdehydes - glyoxal and glutaraldehyde.
• Patent Document 13 proposes a tempering treatment agent for a screen printing plate composed of a fluorine-containing resin, a dialdehyde, and an electrode or an organic acid.
• the dialdehyde compound used together with the fluorine-containing resin includes glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, maleic aldehyde, phthalaldehyde, isophthalaldehyde, and benzene. Formaldehyde and the like.
• a strengthening treatment agent can exert a hydrophobic effect of the fluorine-containing resin.
• Patent Document 14 proposes a fortifier formulation containing glutaraldehyde, hydrochloric acid, and water as main components, and an alcohol or a diol as an essential additive component.
• Patent Document 15 also proposes a formulation of a strengthening treatment agent for a screen printing plate which is characterized by containing a silane compound.
• Patent Document 12 Japanese Laid-Open Patent Publication No. Hei 6-202340
• Patent Document 13 Japanese Laid-Open Patent Publication No. Hei 8-262745
• Patent Document 14 JP-A-2013-52560
• Patent Document 15 JP-A-2006-347062
• an acidic aqueous solution of glutaraldehyde or glyoxal is widely used.
• An aqueous solution of such a dialdehyde or an acidic aqueous solution such as hydrochloric acid needs to be separately prepared, and when the user needs to strengthen the printing plate, it is mixed before use.
• Glutaraldehyde in several hydration in aqueous solution The physical form exists, and on the other hand, an oligomer is gradually formed by an aldol condensation reaction (Non-Patent Document 1: PSZhu, CG Roberts and MS Pavero, Current Organic Chemistry, No. 9, pp.
• the object of the present invention is to provide a wire which can be stored for a long period of time and which is not wasted after use (single liquid type), and which is greatly reduced in odor (irritating odor) during use, in order to overcome the drawbacks of the prior art described above. Reinforcing agent for printing plates for web printing and its application method.
• the present invention provides a screen printing printing plate which is characterized by being formed by a mixture of phthalic acid and 1,3-dihydroxy-phthalimone in a chemically balanced state. Reinforce the treatment agent. Further, according to the present invention, there is provided a method of treating a single-liquid type reinforcing treatment agent, which is applied to a surface of a printing plate produced by exposure and development, and dried. Further, according to the present invention, a printing plate for screen printing characterized by being processed by the above-described processing method is further included.
• the object of the present invention can be achieved by the following technical solutions: a reinforcing agent for printing plates for screen printing, characterized in that the reinforcing agent dissolves o-phthalaldehyde in water and adjusts the pH to below 3 A mixture in which phthalic acid and 1,3-dihydroxy-phthalic acid ether are in a chemical equilibrium state is obtained, and the concentration of the mixture is 0.3 to 10% by weight in terms of o-phthalaldehyde.
• the concentration of the mixture in which the o-phthalaldehyde and the 1,3-dihydroxy-phthalimone are in a chemical equilibrium state in the aqueous solution should be converted to o-phthalaldehyde. From 0.3% to 10% by weight, preferably from 0.5% to 7% by weight. Below this concentration range, sufficient bridging cannot be obtained, and above this concentration, a better reinforcement effect cannot be obtained.
• the pH of the aqueous solution of phthalaldehyde should be below 3, and if the pH is high, it cannot be reached. Fully reinforcing effect.
• the pH is adjusted by an organic or inorganic acid.
• the organic acid comprises benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid or ethylsulfonic acid; the inorganic acid is hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid. These acids are used to adjust the pH to the above-mentioned desired pH range.
• the printing plate reinforcing agent of the present invention can be adjusted to a desired pH range after dissolving orthophthalaldehyde, or can be prepared by adding acidic water to the alcohol solution of o-phthalaldehyde while stirring.
• the reinforcing agent further comprises glyoxal, and the amount thereof is added in an amount of 1 to 10% by weight in terms of glyoxal.
• glyoxal Under the premise of not compromising the effect of the mixture of phthalaldehyde and 1,3-dihydroxy-phthalimone in a chemical equilibrium state as a reinforcing agent, glyoxal, isophthalaldehyde, and benzene may be added. Dialdehyde, a dialdehyde or a monoaldehyde is blended. In particular, glyoxal having a high water solubility is preferred.
• Glyoxal can be obtained as an aqueous solution, but the aqueous solution is present in the form of a mixture of its hydrate or oligomer. Thus, like phthalaldehyde, it can reduce the odor.
• the amount added is in the range of 1 to 10% by weight in terms of glyoxal.
• the reinforcing agent further contains an alcohol having 1 to 3 carbon atoms or a diol having 2 to 3 carbon atoms, and the amount thereof is such that the concentration in the acidic aqueous solution is 1% by weight to 10% by weight.
• it may be methanol, ethanol, isopropanol, ethylene glycol or propylene glycol, and these alcohols may be used alone or in combination of two or more.
• the amount of these alcohols or diols to be added in the acidic aqueous solution should be from 1% to 10% by weight, and preferably from 2% to 5%.
• an antioxidant may be added.
• catechol, resorcinol, hydroquinone, 4-methoxyphenol, ascorbic acid, cysteine, cysteamine and the like are not limited thereto.
• a water-soluble emulsifier such as a hydrophobic resin or a silica resin may be added.
• an anticorrosive agent, a surfactant, and other water-soluble solvents, colorants, and the like may be added.
• a use of a reinforcing agent for a printing plate for screen printing characterized in that a reinforcing agent is used for screen printing printing made of an aqueous photosensitive resin composition composed of polyvinyl alcohol and or a derivative thereof
• the specific method is: after the water-soluble photosensitive resin composition is coated and dried on a screen, exposed for the purpose of forming a latent image, and then developed with water to obtain a printing plate, and a reinforcing agent is coated on the printing plate. After both sides, it is dried at room temperature to 80 ° C for 10 minutes to 2 hours.
• the aqueous photosensitive resin composition comprising the polyvinyl alcohol or a derivative thereof is an aqueous photosensitive resin composition composed of polyvinyl alcohol or a derivative thereof and a diazo resin and a diazide compound.
• an aqueous photosensitive resin composition comprising a light-bridged water-soluble polymer formed by combining a polyvinyl alcohol and a derivative thereof with a photosensitive group represented by a styrylpyridinium salt, or It is a photosensitive resin composition formed by dispersing or dissolving a photoacid generator and an acid bridging agent of polyvinyl alcohol and its derivative.
• the reinforcing agent is also coated with a sponge, a rag or a brush, or coated by a dip coating method or a spray method, and the drying temperature is room temperature to 60 ° C.
• the present invention is a reinforcing method for enhancing the strength of a screen printing plate by an aldehyde, it is indispensable for the aldehyde to be effectively impregnated into the interior of the printing plate. For this reason, the solvent of the reinforcing agent, water, needs to be dissolved within the specified concentration.
• the solubility of terephthalaldehyde and isophthalaldehyde in water alone is low, and even the plate reinforcing performance of the saturated aqueous solution does not achieve a significant effect.
• o-phthalaldehyde exhibits a higher water solubility than the above two isomers.
• phthalaldehyde solid After the phthalaldehyde solid is dissolved in water, as shown in the following chemical formula 1, two formaldehyde groups are additionally combined with water molecules to form a cyclic structure of 1,3-dihydroxy-phthalic ether. In water, about 90% is in the form of 1,3-dihydroxy-phthalic ether, forming a chemically balanced mixture with the dialdehyde form.
• O-phthalaldehyde introduces two hydroxyl groups by hydration reaction, so that it has higher water solubility than terephthalaldehyde and isophthalaldehyde which hardly undergo hydration reaction in an aqueous solution. Further, the volatility is remarkably lowered due to the hydrogen bonding of the hydroxyl group of the 1,3-dihydroxy-phthalic ether. Thus, the odor of the aqueous solution is remarkably lowered as compared with glutaraldehyde or the like. This is the reason why the medical cleaning agent and the industrial sterilizing agent described later use o-phthalaldehyde.
• o-phthalaldehyde and 1,3-dihydroxy-phthalic acid ether have no active methylene group, and a dehydration condensation reaction of an aliphatic dialdehyde represented by glutaraldehyde does not occur.
• O-phthalaldehyde is generally not found to be carcinogenic, and has excellent chemical properties as compared with glutaraldehyde, and is widely used in medical cleaning agents, industrial insecticides, and the like. way.
• phthalaldehyde and ethanol are reacted under acidic conditions, and as shown in Chemical Formula 3, the product is 1,3-dialkoxydihydroisobenzofuran, which is not a cyclic acetal. Therefore, a bridging structure in which a mixture of phthalaldehyde and 1,3-dihydroxy-phthalimone in a chemical equilibrium state and a 1,3-dihydroxyl position of polyvinyl alcohol are reacted under acidic conditions can be provided. Effective reinforcement, can also be stored for a long time. Glutaraldehyde has no such effect.
• the strength and water resistance of the printing plate made of the aqueous photosensitive resin composition are remarkably enhanced, and it is presumed that this is due to the bridging structure formed by the bridge bridging reaction.
• phthalaldehyde is reacted with an alcohol under acidic conditions to form a 1,3-dialkoxy group.
• Hydrogen isobenzofuran as shown in Chemical Formula 4, is a bridge between polyvinyl alcohol chains composed of 1,3-dialkoxydihydroisobenzofuran. This structure is different from the cyclic acetal structure of glutaraldehyde shown in Chemical Formula 2.
• the bridging is mainly composed of a straight and hydrophobic benzene ring, so it is expected to have excellent water resistance.
• the reinforcing treatment agent of the present invention can be mixed for a long time in an acidic solution, so that it can be mixed before use without any effort, and the reinforcement which is not used after mixing does not occur.
• phthalaldehyde is mainly present in the form of nonvolatile 1,3-dihydroxy-phthalic ether, and the odor is remarkably lowered.
• the bridging with polyvinyl alcohol or a derivative thereof is not a cyclic acetal structure represented by Chemical Formula 2, but a rigid and hydrophobic 1,3-dialkoxy group represented by Chemical Formula 4.
• the bridging structure formed by the intervention of the dihydroisobenzofuran structure has an excellent reinforcing effect on the printing plate for screen printing.
• the screen printing plate subjected to the reinforcing treatment was cut out into a 30 ⁇ 30 mm slice, and after drying at 40° C. for 24 hours, the weight was weighed as W 0 .
• the slice was immersed in water for 24 hours, and then taken out, and the surface moisture was wiped off. Weigh the weight to W 1
• each weight here is a value obtained by subtracting the weight of the polyester mesh.
• the moisture of the immersed slice is taken out, and the weight of the residue is weighed as W 2 , and the dissolution rate is calculated as (W 0 -W 2 /W 0 ) ⁇ 100%.
• the front of the experimental device was hung with a load for friction, and a rag was placed on the friction portion of the device to allow the solvent to penetrate the rag, and the friction plate was repeatedly tested in the same cycle.
• a 150 mesh polyester material screen was placed on an aluminum frame, and an SBQ type photosensitive resin composition (AQUASOL TS) was entirely coated on the screen to obtain a photosensitive film layer for screen printing having a film thickness of 15 ⁇ 1 ⁇ m.
• the screen plate was exposed to a fluorescent lamp in a vacuum exposure apparatus. After exposure, it was developed by water and dried to obtain a printing plate for screen printing.
• plate A Hereinafter referred to as plate A.
• the SBQ type photosensitive resin composition of Example 11 was replaced with a diazo resin type photosensitive resin composition (SP-1400), and after full-coating on a screen, the screen printing thickness of 15 ⁇ 1 micrometer was obtained.
• plate B a printing plate for screen printing.
• the SBQ type photosensitive resin composition of Example 11 was replaced with a diazo and a monomer type photosensitive resin composition (ADVANCE 50), and the screen layer was fully coated to obtain a screen printing thickness of 15 ⁇ 1 ⁇ m.
• plate C a printing plate for screen printing.
• the OPA-based reinforcing treatment agent was prepared, and the printing plate A was reinforced on the day of preparation and storage at 40 ° C for 4 weeks.
• the test results of the obtained water swelling filter, water dissolution rate and abrasion resistance are summarized in Table 5. After 4 weeks of storage, it still has the same degree of reinforcing effect as the day of modulation.
• the glutaraldehyde-based reinforcing agent prepared in Comparative Examples 1 to 3 was stored at 40 ° C for 4 weeks and then applied to the printing plate A. Line reinforcement processing. However, each type of insoluble matter is generated to cause contamination during reinforcement, and it cannot be applied to the reinforcing treatment of screen printing plates.
• the plate A was replaced by the printing plate B, and the test was carried out in the same manner as in the examples 14 to 17.
• the OPA-based reinforcing treatment agents of the examples 3, 5, 7 and 8 were stored at 40 ° C for 4 weeks, and then subjected to a reinforcing treatment.
• the test results of the obtained water swelling filter, water dissolution rate and abrasion resistance are summarized in Table 6.
• the glutaraldehyde-based reinforcing agent prepared in Comparative Examples 1 to 3 was subjected to a reinforcing treatment on the plate B after being stored at 40 ° C for 4 weeks.
• each type of insoluble matter is generated to cause contamination during reinforcement, and it cannot be applied to the reinforcing treatment of screen printing plates.
• the printing plate C was replaced by the printing plate C in the same manner as in Examples 14 to 17, and the OPA-based reinforcing treatment agents of Examples 3, 5, 7, and 8 were stored at 40 ° C for 4 weeks, and then subjected to reinforcing treatment.
• the test results of the obtained water swelling filter, water dissolution rate and abrasion resistance are summarized in Table 7.
• the glutaraldehyde-based reinforcing treatment agents prepared in Comparative Examples 1 to 3 were subjected to a reinforcing treatment on the printing plate C after storage at 40 ° C for 4 weeks.
• each type of insoluble matter is generated to cause contamination during reinforcement, and it cannot be applied to the reinforcing treatment of screen printing plates.
• the invention relates to a reinforcing agent for screen printing, wherein the reinforcing agent dissolves o-phthalaldehyde in water and adjusts the pH of the aqueous solution of phthalic acid phthalic acid to 3 or less to obtain phthalaldehyde and
• the mixture in which the 1,3-dihydroxy-phthalimone is in a chemical equilibrium state is a reinforcing agent, and the concentration by weight of the mixture is 0.3% in terms of o-phthalaldehyde.
• the above-mentioned reinforcing agent is used for a screen printing plate made of an aqueous photosensitive resin composition composed of polyvinyl alcohol or a derivative thereof by a method of: coating a water-soluble photosensitive resin composition on a wire mesh After coating and drying, exposure was carried out for the purpose of forming a latent image, and then a printing plate was prepared by water development, and the reinforcing agent was applied to both sides of the printing plate by dip coating, and then dried at room temperature for 2 hours.
• the printing plate for screen printing treated by the above method has good abrasion resistance, water swelling and water dissolution rate after being stored for 4 weeks.
• the invention relates to a reinforcing agent for screen printing, wherein the reinforcing agent dissolves o-phthalaldehyde in water and adjusts the pH of the aqueous solution of phthalic acid phthalic acid to 3.0 or less to obtain phthalaldehyde and
• the mixture in which the 1,3-dihydroxy-phthalimone is in a chemical equilibrium state is a reinforcing agent, and the concentration of the mixture is 10% by weight in terms of o-phthalaldehyde.
• the above-mentioned reinforcing agent is used for a screen printing plate made of an aqueous photosensitive resin composition composed of polyvinyl alcohol or a derivative thereof by a method of: coating a water-soluble photosensitive resin composition on a wire mesh After the coating was dried, exposure was carried out for the purpose of forming a latent image, and then a printing plate was prepared by water development, and the reinforcing agent was spray-coated on both sides of the printing plate and dried at 80 ° C for 10 minutes.
• the printing plate for screen printing treated by the above method has good abrasion resistance, water swelling and water dissolution rate after being stored for 4 weeks.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Printing Plates And Materials Therefor (AREA)

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• 2014
  • 2014-09-22 CN CN201410487661.1A patent/CN104317165B/zh active Active
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