CN1717630A - Positive photosensitive composition - Google Patents

Abstract

There is provided a positive photosensitive composition which requires no burning, makes it possible to obtain necessary and sufficient adhesion when it is applied under a humidity of 25 to 60%, can be developed at a low alkali intensity, makes it possible to carry out development with keeping high sensitivity while forming no residue, ensures sharp edges, can provide a very hard resist film and is improved in scratch resistance in the handling before development. The positive photosensitive composition comprises, as essential components, (A) a high molecular substance having at least one carboxyl group in a molecule and (B) a photo-thermal conversion material that absorbs infrared rays from an image exposure light source to convert them into heat.

Description

Positive light sensitivity composition

Technical field

The present invention relates to a kind of positive light sensitivity composition, more specifically say, relate to a kind of to wavelength 700-1, the alkali-soluble positive light sensitivity composition alkaline soluble developer solution of induction part after the laser explosure of the 100nm induction, that have the laser induced property in infrared wavelength zone.Positive light sensitivity composition of the present invention can effectively be applied to photofabrication manufacturing (photo-fabrication) field, and the photofabrication that manufacturing was suitable for that is particularly suitable for being applied in the associated components etc. of galley, electronic unit, exact instrument parts, false proof usefulness is made the field.

Background technology

As everyone knows, contained novolac resin in the ancient in the past positive type light sensitive type lithographic plate and be o-quinone two triazo-compounds the material of white light sensitization, shown in (I), owing to the make a mistake rearrangement of special type (Arndt-Eistert) of Arndt-Ace takes place for the photolysis (chemical change) of o-quinone two triazo-compounds, form the ketenes structure, and 5 Yuans of generations encircle carboxylic acids in the presence of water, in addition, shown in (II), the naphthoquinones two triazo-compounds reaction of the ketenes on the photographic layer top of photographic department and photographic layer bottom forms lactone, when developing with aqueous alkali, lactonic ring is opened, form carboxylic acid sodium, and because the novolac resin of coexistence also is alkali-soluble, therefore dissolving is separated out together, on the other hand, novolaks with coexistence under the effect of the alkali of the photographic layer of unexposed portion when developing take place to become alkali slightly solubility material, and left behind (with reference to non-patent literature 1) as the resist pattern picture as shown in the formula the coupling reaction shown in (III).As mentioned above, when containing o-quinone two triazo-compounds, can obtain big development tolerance (latitude).

In addition, said state with development tolerance is meant in this instructions, in development, there are not the variation (film shrinks few) of thickness, the area of site in certain development time, not to have to change, can not take place to stablize the state of plate-making under the situation of the emergent phenomenon of residue.

Relative therewith, for mask-making technology also can be carried out under white lamps, someone has invented the positive light sensitivity composition that utilizes chemical change variation in addition, having developed the laser that utilizes the infrared wavelength zone shines into the eurymeric image and increases the solubleness of exposure portion to developer solution, thereby form the method for eurymeric image, and adopt offset plate making and aniline plate-making to implement this scheme (with reference to as patent documentation 1-10 etc.).

In the positive light sensitivity lithographic plate described in each above-mentioned document, with absorption infrared light such as infrared absorption pigment and be converted into the material of heat and alkali soluble resinss such as novolac resin are main photographic layer composition, and utilize the heat that produces by infrared laser exposure, make resin that the structure variation take place and wait physical change, thereby increase solubleness developer solution.

But, utilize the laser in infrared wavelength zone to shine into to make behind the eurymeric image with regard to not containing o-quinone two triazo-compounds resin physical change such as structure variations grade to take place to increase for the deliquescent positive type light sensitive type lithographic plate, also there are the following problems at present, promptly, must bake version (burning after filming, heating operation), even bake version, the dissolution velocity difference of exposure portion and unexposed portion still is less, the key property of galleys such as light sensitivity, development tolerance is relatively poor, is difficult to satisfy the stability of development treatment when increasing the development treatment number.

Opposite with said circumstances, situation is different fully in photogravure plate-making.In the Japan that photogravure plate-making, printing are popularized the most, the positive-working, thermally sensitive resist that can develop under non-heating condition after in the past at all not implementing to use formation to film carries out the photogravure method for platemaking of photogravure plate-making, and does not also have patent documentation, test document.

In the past, adopt the photogravure plate-making process of the cylinder of being made a plate of etch/laser plate-making method, for example may further comprise the steps charging-degreasing-washing-pickling-washing-バ ラ-De processing-water Xian-バ ラ-De copper facing-washing-abrasion wheel grinding-washing-coating emulsion-coating antioxidant-utilize the image solarization system-development-washing-decorations quarter-washing-resist of infrared laser exposure device to peel off-wash-chromium plating-washing-grinding-washing-discharging.As disclose employing etch/laser plate-making method by the technical literature of photogravure plate-making process of plate-making cylinder, patent documentation 11-29 is for example arranged.

In the photogravure plate-making process described in the above-mentioned document, all light-sensitive surfaces of coating for constituting by negative photosensitive composition, rather than be coated with the light-sensitive surface that constitutes by positive light sensitivity composition.In the etch in the past, be on by the plate-making cylinder, to be coated with the light-sensitive surface of minus and coated film is parched, make the negative photosensitive film, utilize the argon laser technology of making a blueprint then, and be not to be implemented in to be formed the positive type light sensitive film on the plate-making cylinder, utilize the laser of infrared wavelength to shine into positive type light sensitive agent image then.

The high-power semiconductor laser head of Canadian Network レ ォ サ イ テ ッ Network ス company can be launched the laser in infrared wavelength zone, can be installed on the offset machine and and shine to positive light sensitivity composition, thereby carry out good development, therefore just worldwide be applied.

If the beam diameter of argon laser size and wavelength are 700-1, the beam diameter of the laser of 100nm is identical, and then with regard to the resolution of laser, eurymeric is higher than minus, and can significantly shorten the processing time.

Have, when the laser that utilizes the infrared wavelength zone shines into the eurymeric image with the light-sensitive surface of positive light sensitivity composition, compare when shining into the minus image with the light-sensitive surface that utilizes argon laser with negative photosensitive composition, the sharpness of its pattern is better.This may be by causing because of differing from of the sharpness of the different patterns of forming that produce of positive light sensitivity composition and negative photosensitive composition.

In the past, positive light sensitivity composition was used to offset plate making and aniline plate-making always, and was not used in gravure plate-making, and its reason is that the negative photosensitive agent can be used in photogravure plate-making.The negative photosensitive agent can guarantee the degree of polymerization of the resin of exposed portion when irradiation ultraviolet radiation, and therefore no matter which kind of material applied face is, can both fully guarantee the tolerance of developing.

On the other hand, do not occur as yet so far having and to satisfy and the positive light sensitivity composition of the development tolerance of the relation of the copper sulphate plating of photogravure cylinder.Do not bake the photosensitive composite of version after particularly also occurring being coated with.Even with offset plate making and aniline make a plate that employed positive light sensitivity composition is coated on that photogravure uses by on the plate-making cylinder, almost do not have yet can film forming condition.What in most cases, photogravure was used can all be washed away by alkaline developer by filming of the positive light sensitivity composition on the plate-making cylinder.Even it also is like this baking version after the coating.

Use can be with the laser in infrared wavelength zone with the semiconductor laser of high power output and YAG laser instrument etc. and with the high-resolution photogravure forme-producing system of positive type light sensitive film, compare with the situation of using Argon ion laser, the aspects such as sharpness of the surround lighting when the miniaturization of installing, plate-making operation, resolution, pattern are good, so the urgent hope of industry can realize this technology.

Patent documentation 1: the spy opens flat 10-268512 communique

Patent documentation 2: the spy opens flat 11-194504 communique

Patent documentation 3: the spy opens flat 11-223936 communique

Patent documentation 4: the spy opens flat 11-84657 communique

Patent documentation 5: the spy opens flat 11-174681 communique

Patent documentation 6: the spy opens flat 11-231515 communique

Patent documentation 7: international disclosing No. 97/39894

Patent documentation 8: international disclosing No. 98/42507

Patent documentation 9: the spy opens the 2002-189293 communique

Patent documentation 10: the spy opens the 2002-189294 communique

Patent documentation 11: the flat 10-193551 communique of special hope

Patent documentation 12: the flat 10-193552 communique of special hope

Patent documentation 13: the spy opens the 2000-062342 communique

Patent documentation 14: the spy opens the 2000-062343 communique

Patent documentation 15: the spy opens the 2000-062344 communique

Patent documentation 16: the spy opens the 2001-179923 communique

Patent documentation 17: the spy opens the 2001-179924 communique

Patent documentation 18: the spy opens the 2001-187440 communique

Patent documentation 19: the spy opens the 2001-187441 communique

Patent documentation 20: the spy opens the 2001-191475 communique

Patent documentation 21: the spy opens the 2001-191476 communique

Patent documentation 22: the spy opens the 2001-260304 communique

Patent documentation 23: the spy opens the 2002-127369 communique

Patent documentation 24: the spy opens the 2002-187249 communique

Patent documentation 25: the spy opens the 2002-187250 communique

Patent documentation 26: the spy opens the 2002-200728 communique

Patent documentation 27: the spy opens the 2002-200729 communique

Patent documentation 28: the spy opens the 2002-307640 communique

Patent documentation 29: the spy opens the 2002-307641 communique

Patent documentation 30: special fair 07-109511 communique

Patent documentation 31: the spy opens the 2004-133025 communique

Patent documentation 32: special public clear 47-25470 communique

Patent documentation 33: special public clear 48-85679 communique

Patent documentation 34: special public clear 51-21572 communique

Non-patent literature: loose forever unit is the youth too, and universe English husband work " photosensitive composite " talk society publishes, on September 1st, 1978, p.104-122

The inventor etc. In view of the foregoing, the exploitation that begins one's study is a kind of is fastening with the pass of the sulfuric acid ketone plating of photogravure cylinder, not bake an edition positive light sensitivity composition that also has sufficient development tolerance after the coating.

In the etch of one of method for platemaking of photogravure cylinder, made a kind of stoste that has cooperated the positive light sensitivity composition of novolac resin and the peaceful pigment of match earlier, then being coated on the positive type light sensitive agent that obtains after this stoste of solvent dilution on the copper sulphate plating face of photogravure with the cylinder of being made a plate.Used the light-sensitive surface apparatus for coating (シ of Co., Ltd. Application Network ラ ボ ラ ト リ-system) in the patent documentation 30 in the coating of positive type light sensitive agent.Utilization is equipped with the laser in infrared laser exposure device (シ of Co., Ltd. Application Network ラ ボ ラ ト リ-system) the irradiation infrared wavelength zone of the high-power semiconductor laser head of Network レ ォ サ イ テ Star Network ス company, shine into the eurymeric image, develop afterwards, the test findings light-sensitive surface all comes off, and the resist pattern picture of a satisfaction also fails to obtain.

Afterwards, the film forming that the light-sensitive surface apparatus for coating that utilizes in the patent documentation 30 obtains is estimated, we think in this method owing to after adopting in the emulsion in painting drum be impregnated in jar coated face is carried out repeatedly the spiral scan mode of the contact coating method of emulsion coating, so air can be blended in the light-sensitive surface.But also find that because jar is open structure, therefore the solvent that is stored in the jar can be captured evaporation latent heat by evaporation, causes painting drum to turn cold, thereby is attended by whiting in the coating.Also have,, can not be coated with into uniform thickness because of the continuous minimizing of solvent strength, the rising gradually of viscosity.Its result can draw to draw a conclusion: utilize the light-sensitive surface apparatus for coating in the patent documentation 30 can suitably carry out coating, the film forming of negative photosensitive agent, but eurymeric emulsion film extremely is not suitable for.

So, the device of the light-sensitive surface apparatus for coating in the patent documentation 30 has instead been developed solvent in the emulsion in a kind of jar and has been in the air-tight state that can not evaporate and can be to the light-sensitive surface apparatus for coating of the whiting that be carried out the noncontact coating by the plate-making cylinder, occur when can avoid being coated with.

The general formation of this light-sensitive surface apparatus for coating below is described.As on by the plate-making cylinder, being coated with the method for positive type light sensitive agent with the system film, upper end as the emulsion effuser of longitudinal tubule (L tubule) is clamped by level near two ends and rotate by below the end of plate-making cylinder, make the emulsion of supply little by little swarm from the upper end of emulsion effuser to come and overflow, and with the emulsion effuser from by plate-making cylinder an end move to the other end, in the rotation sweep mode coating fluid is applied to by on the plate-making cylinder thus, and the continuation swing roller, up to the coated film air dry.

So continue to discover, this method can not obtain the firm adhesiveness of positive light sensitivity composition to copper sulphate plating face, during development, does not have the difference of image portion and non-image portion, all can be washed away by alkaline developer at once.Therefore, we think that the roasting version that must implement face is heated to high temperature after filming handles, to give adhesion.

Why think and to bake version, be because we think that the reason that produces the state that can't make film is the adhesiveness extreme difference of positive light sensitivity composition to copper sulphate plating face, if and bake behind the film edition in system, the hydrogen bond that then has the alkali solubility organic polymer material of phenol hydroxyl can be led enhancing, thereby can improve adhesiveness.

So, decision is implemented roasting version and is handled and proceeded research, but will be by the cooperation of above-mentioned making the positive light sensitivity composition of novolac resin and the peaceful pigment of match be coated on by on the plate-making cylinder and implement 30 ℃ of minutes roasting versions so that the face temperature is carried out laser explosure after becoming 60 ℃ and when developing, it is undesirable to find to develop.

So, implement 30 ℃ of minutes roasting versions so that the face temperature becomes 130 ℃, even if the poor visualization phenomenon that comprises that non-image portion all comes off has also still taken place like this.Therefore drawn such conclusion, poor visualization also still takes place is too low to the adhesiveness of copper sulphate plating face because of positive light sensitivity composition even if bake version.

Therefore, the auxiliary agent as improving adhesion has added silane coupling agent in positive light sensitivity composition, attempt to increase the adhesion of light-sensitive surface, and result's exposure, development become good a little.Concrete example as, make being rotated with the low velocity of 25r.p.m of 200 Φ mm by the plate-making cylinder, thereby coating positive type light sensitive agent, and constantly rotation is in order to avoid liquid drips, and drying is 5 minutes under natural drying condition, and the formation solvent gasifies to the light-sensitive surface of the drying of the state of following of liquid that can not, afterwards, 130 ℃ of roasting versions of carrying out 30 minutes, this moment, dissolvent residual concentration was lower than 2%, at this moment can utilize the laser blueprint and developed.

But, do not reached the best to the adhesiveness of film is talkative, but be that exposure, development become good slightly.And when making the face temperature reach 130 ℃, roasting version and cooling afterwards need the time more than 100 minutes, need lot of energy, and operating cost is higher, lacks practicality.In addition, when making the face temperature reach 130 ℃, the hydrogen bond with alkali solubility organic polymer material of phenol hydroxyl can strengthen, thereby become and be difficult to develop, cause the peaceful pigmental degeneration of match simultaneously, light sensitivity descends, and this point just can be found out from the relatively poor characteristics of the sharpness of pattern.

So examined the resist pattern picture, found that to have produced a lot of apertures.In minus resist pattern picture, can not produce above-mentioned aperture.Hence one can see that, if with only washing behind the emery wheel precise finiss, then can not wash off fully attached to the lapping powder on the quilt plate-making cylinder; If the plate-making chamber is not arranged to the decontamination chamber of height, then in by the conveyance of plate-making cylinder, dust can be attached on the quilt plate-making cylinder; And look like to compare with negative resist pattern, the positive resist pattern picture is responsive more to film forming condition.So carried out various researchs again, found that (wipingcloth) fully cleans with cloth for wiping or dusting, then can suppress the generation of aperture if before coating emulsion on the cylinder of being made a plate.

Photogravure with by plate-making cylinder the cylinder base material have aluminum with made of iron, in addition, diameter of cylinder is different, simultaneously diameter of cylinder not simultaneously, thickness is also different fully, therefore because the difference of specific heat capacity, promptly use the identical time of heater heats, the heat that is passed to the cylinder base material also can not make the face temperature reach 130 ℃ all the time, can be heated to the temperature that has nothing in common with each other and produces deviation, therefore we think, key is to reduce the problem that temperature solves specific heat capacity.By the composition of selecting to optimize, also can finish separated from solvent significantly to reduce the roasting version operation that solvent strength is a purpose to the face temperature even under being set at far below the condition of 130 ℃ of temperature, carry out.

In addition, also carried out the test of shortening heat time heating time,, can confirm that solvent strength becomes below 6%, but it has been undesirable to develop when the roasting version temperature that makes face drops to 80 ℃-100 ℃ and when carrying out 50 minutes roasting versions.We think that the reason that produces this result is can not obtain sufficient adhesion with above-mentioned silane coupling agent.

Then, as adhesive, try to add curing accelerator imidazoles (comprising imidazoles silane) and replaced silane coupling agent, the result compares the roasting version temperature that does not change face especially, and also the situation with silane coupling agent is identical with the situation of silane coupling agent.

Next, to by alkali solubility organic polymer material with phenol hydroxyl, with the infrared ray that absorbs the image exposure light source and be converted into the stoste of the positive light sensitivity composition that the photo-thermal conversion material of heat constitutes, various adhesives have been added respectively, under 25 ℃ of room temperatures, on copper sulphate plating cylinder, formed light-sensitive surface then, and utilize above-mentioned infrared laser exposure device (シ of Co., Ltd. Application Network ラ ボ ラ ト リ-system) that trial image has been carried out exposure imaging, the result has added the light-sensitive surface of the positive light sensitivity composition of titanium organic compound, can make roasting version temperature significantly reduce (with reference to patent documentation 31).

Added under the situation of light-sensitive surface of positive light sensitivity composition of titanium organic compound, even a roasting version temperature is 46 ℃ of also film forming well, light sensitivity is good, develops and also carries out easily., in not baking the test that version handles, film forming well, and it is also undesirable to develop.

Even if can make roasting version temperature drop near the characteristics that also still need to bake the version operation 50 ℃, it is following unfavorable to bring: must cool off after the roasting version, roasting version and cooling afterwards are with spended time and energy, the device line is equivalent to this part length of roasting version device with prolongation, and installation cost and cost of operation uprise.Therefore we think this problem that must solution need bake edition.

When baking version, cylinder is different from light sheet material, and thermal load is big, be heated to needed temperature and need 30-60 minute, and cool to room temperature needed more than 50-100 minute, and the above-mentioned time is according to the difference of cylinder size and therefore difference can not be controlled equably.Also have, roasting version is a reason that causes following phenomenon: cause the sex change of the peaceful pigment of match, light sensitivity descends, the sharpness variation of pattern, and resist attenuation when developing simultaneously, soft edge produces aperture.Therefore, a kind of positive type light sensitive film that does not need roasting version of strong request exploitation.

The repetition test of many times is learnt, when total dissolvent residual concentration such as the MEK when film forming, IPA, PM is higher, can not utilize laser blueprint (light-sensitive surface that can not cut off exposed portion form the main chain of molecule of resin or pendant moiety and make it to become alkali solubility higher low molecular form the latent image that has suitably produced the state that photographic layer splashes simultaneously).

On the copper sulphate plating plate the above-mentioned interpolation of coating the positive type light sensitive agent of titanium organic compound, be 11% in 25 ℃ of dissolvent residual concentration after under the natural drying condition of not blowing dry 15 minutes of room temperature, be 9% through the dissolvent residual concentration after 25 hours.With 45r.p.m. rotating speed rotation by the plate-making cylinder on the agent of coating positive type light sensitive, after 10 minutes, measure, its as a result dissolvent residual concentration only drop to 7%.Therefore, we judge if will carry out modification and make it to contain the auxiliary agent that increases adherence the eurymeric emulsion, thereby make the stoste of the positive type light sensitive film that does not need roasting version again, confirm its result by exposure, development afterwards, then need at first to work out a kind of technology that can significantly reduce dissolvent residual concentration.

Therefore, the first time such as the inventor a kind of practicability of the positive type light sensitive film that does not need roasting version as the exploitation theme, from the conceptive basis of distinguishing, carry out to bake after the film forming version respectively and utilized additive method can easily significantly reduce the exploitation of the film forming dry technology of dissolvent residual concentration at short notice, improve the exploitation of the big positive type light sensitive film of the adhesiveness of positive type light sensitive film self and development tolerance greatly with the auxiliary agent that increases adherence by interpolation, to solve the above-mentioned problem that first-selection will overcome.

When solvent volatilized from coated film, coated film contacted the back and begins drying from the surface with air, and hardness increases, and tissue becomes closely, and As time goes on, the diffusivity of the solvent that the dry more internal layer in surface exists is low more.On the other hand, we think that solvent is different because of the difference of the pressure of atmosphere from the degree of coated film volatilization, if negative pressure, solvent is big from the degree of coated film volatilization, can effectively reduce residual solvent.But, can not be put into the cylinder after the film forming with in the evacuated case of vacuum pump.So the inventor after the liquid that can not of coated film drips by the time, makes by the plate-making cylinder and carried out high speed rotating, found that at short notice can be with below the dissolvent residual density loss to 3%.

On this basis, to be supported on the light-sensitive surface apparatus for coating in the patent documentation 30 by the both ends horizontal of plate-making cylinder, and with required low velocity make it the rotation, to test sensitization liquid with spiral scan mode noncontact coating method evenly is coated with, continue rotation afterwards, form the gasify light-sensitive surface of drying of the state that can not drip to drop of solvent, then, even if also can significantly reduce the technology of solvent strength in the short time as not roasting version at the utmost point, adopted and made this cylinder of being made a plate in the required high-speed method of rotation required time down, make the residual solvent in the film be subjected to action of centrifugal force and make film surface and windage, make the residual solvent in the film in air, spread disengaging thus, thereby set up a kind of technology that can utilize laser to embody the blueprint property and can form the film of low solvent residue concentration.

Even painting photosensitive liquid on the drum to test of 200 Φ mm, finishing the coating back with 25r.p.m. rotating speed rotation 5 minutes, stop the rotation afterwards, whether wait for 5 minutes, observing has liquid to drip, and with the naked eye confirms not have after liquid drips, with 100r.p.m. rotating speed rotation test cylinder 20 minutes, stop then, measure the dissolvent residual concentration in the light-sensitive surface, the result is 2.3%.

In addition, even if also can significantly reduce in the short time on the basis of technology of solvent strength at the utmost point in the roasting version of exploitation, further studied add the various auxiliary agents that increase adherence and the eurymeric emulsion exposed, develops after whether have the development tolerance.

Its result; when to by alkali solubility organic polymer material with absorb the infrared ray of image exposure light source and be converted in the stoste of the positive light sensitivity composition that the photo-thermal conversion material of heat constitutes with phenol hydroxyl; when adding cellulose derivative and being selected from any titanium organic compound at least in alkoxytitanium, acidylate titanium or the titanium chelate; if baking version handles; develop and become bad; if do not handle and do not bake version, developing becomes good, can obtain best resist pattern.At this moment room temperature is 25-27 ℃, and humidity is about 50-55%.

But, when the highest temperature by day is about 16 ℃, when testing under the very low condition that is 21-23% of humidity, light-sensitive surface can all come off after developing.We know that the positive type light sensitive agent generally has the humidity dependence that can whiting take place and can not make film under the high humidity more than 60%.But, can determine according to above-mentioned result, at temperature low and humidity extremely low in, the positive type light sensitive agent can not show adhesion yet.Also have, why whiting takes place and can not to make the film this point not clear.

Then, the matrix resin with development tolerance that can substitute the alkali solubility organic polymer material with phenol hydroxyl is studied.Replace having the alkali solubility organic polymer material of phenol hydroxyl, styrene/maleic acid half ester resin after using phenylethylene/maleic anhydride copolymer by ethyl esterification, making contains the infrared ray that absorbs the image exposure light source and is transformed into the positive light sensitivity composition of the photo-thermal conversion material of heat, film forming on cylinder, expose then, develop, test findings has obtained bigger development tolerance.

Be specially, room temperature in the laboratory is set at 25 ℃, humidity in the case of light-sensitive surface apparatus for coating is set at 25%, 30%, 55%, 60% respectively, being supported on the light-sensitive surface apparatus for coating of 200 Φ mm of copper sulphate that made plating by plate-making cylinder two ends, rotate with the 25r.p.m. rotating speed, clean and and then be coated with above-mentioned positive type light sensitive agent with cloth for wiping or dusting, after finishing, coating also continues rotation to avoid liquid to drip, drying is 5 minutes under natural drying condition, reduced residual solvent in 10 minutes with the rotation of 100r.p.m. rotating speed after the film forming, stop the rotation afterwards.

From the light-sensitive surface apparatus for coating take out by on the plate-making cylinder, all be coated with and formed glossy and very strong adhering extremely hard light-sensitive surface is arranged.The thickness of resist is 3.5-3.8 μ m.Measure the dissolvent residual concentration result and show that all drum to test are all about 2.3%.Utilize above-mentioned infrared laser exposure device (シ of Co., Ltd. Application Network ラ ボ ラ ト リ-system) then, (with the exposure of image portion) exposes trial image under the laser in infrared wavelength zone, then carried out the alkali development, non-image portion has taken place and has also dissolved the film shrinkage phenomenon of separating out in the result, but all samples flooded in alkaline developer in 60-70 second, had all obtained extremely clear and did not have the resist pattern of residue.Therefore can determine that if it is back through after a while to develop, it is extremely hard that the resist pattern of air dry will become.Resist thickness after the development is 1.8-2.5 μ m.Do not generate and shrink caused aperture by film.On above-mentioned basis, finished the present invention.

Summary of the invention

The present invention relates to wavelength 700-1, after the laser explosure induction of 100nm, this induction part becomes the positive light sensitivity composition of the state of alkaline soluble developer solution, its purpose is to provide the positive light sensitivity composition with following feature: when 1) being coated with under the humidity of coating in the work-room is the condition of 25-60%, after on applied object, being coated with, version need not be baked and just sufficient adhesiveness can be obtained aluminium, especially for the adhesion of needs copper or copper sulphate plating face, also can obtain sufficient adhesiveness much larger than aluminium; 2) can carry out good alkali in the 60-70 reasonable time of second and develop and do not produce residue, also can develop even if the base strength of developer solution is low, therefore operation and the liquid waste processing ratio that develops is easier to; 3) handle owing to not baking version, therefore can keep ISO, edge of image against corrosion can be carried out extremely good development according to the irradiation pattern that exposes with profile disconnection clearly; 4) contraction of the film after the development is little, and it is less to shrink caused aperture by film, can carry out extremely good development; 5) can obtain such resist pattern picture, glossy in this resist pattern picture, even if be directly used in printing, also have and can print about thousands of printability resistance, and the mar resistance in the processing after forming light-sensitive surface, before developing is improved; 6) utilize the tolerance of the blueprint of laser and development good.

In order to solve the problems of the technologies described above, positive light sensitivity composition of the present invention is characterised in that, contains the photo-thermal conversion material that the polymer substance, (B) that have at least 1 carboxyl in (A) molecule absorb the infrared ray of image exposure light source and be converted into heat.

Described polymer substance (A) preferably is selected from the polymkeric substance that obtained by the unsaturated compound with at least 1 carboxyl and/or acid anhydride (a1) and by at least a kind of polymer substance in the described unsaturated compound (a1) and the multipolymer that can obtain with the compound (a2) of this unsaturated compound copolymerization.

Described unsaturated compound (a1) preferably is selected from least a kind of compound in maleic acid, (methyl) acrylic acid and their derivant.Among the present invention, acrylic and methacrylic acid group one are called (methyl) acrylic in the lump.

Described polymer substance (A) is preferably selected from least a kind of multipolymer in maleic acid polymkeric substance, (methyl) acrylate copolymer, styrene/maleic acid based copolymer and the derivant thereof.

Described polymer substance (A) preferably makes the reaction of compound with hydroxyl and phenylethylene/maleic anhydride based copolymer and styrene/maleic acid based copolymer of obtaining.Described compound with hydroxyl is preferably alcohol.

Described polymer substance (A) is preferably the multipolymer shown in the following general formula (1).

In the formula (1), R ¹And R ²Represent hydrogen atom or replacement or unsubstituted alkyl respectively independently, a is the integer of 1-3, and b is the integer of 6-8.

In the positive light sensitivity composition of the present invention, preferably also contain (C) resistance solvent.

Described resistance solvent (C), the compound shown in the preferred following structural formula (2).

Described photo-thermal conversion material (B), the compound shown in the preferred following general formula (3).

In the formula (3), R ³-R ⁸Represent the alkyl of hydrogen atom, carbon number 1-3 or the alkoxy of carbon number 1-3 respectively independently, X represents halogen atom, ClO ₄, BF ₄, right-CH ₃C ₆H ₄SO ₃Or PF ₆

Described photo-thermal conversion material (B), the compound shown in the preferred following general formula (4).

In the formula (4), R ⁹-R ¹²Represent independently respectively hydrogen atom, methoxyl ,-N (CH ₃) ₂Or-N (C ₂H ₅) ₂, Y represents C ₄H ₉-B (C ₆H ₅) ₃, right-CH ₃C ₆H ₄SO ₃Or CF ₃SO ₃

In the positive light sensitivity composition of the present invention, preferably also contain (D) light acid propellant.Compound shown in the preferred following formula (5) of described light acid propellant (D).

In the positive light sensitivity composition of the present invention, preferably also contain at least a kind of resin (E) that is selected from the following resin: (1) vinyl pyrrolidone/vinyl acetate co-polymer, (2) vinyl pyrrolidone/dimethylaminoethyl methacrylate multipolymer, (3) vinyl pyrrolidone/caprolactam/dimethylaminoethyl methacrylate multipolymer, (4) polyvinyl acetate (PVA), (5) polyvinyl butyral, (6) polyvinyl formal, (7) terpene phenolic resin, (8) alkyl phenol resin, (9) melamine/formaldehyde resin and (10) ketone resin.

In the positive light sensitivity composition of the present invention, preferably also contain (F) triarylmethane dye.

Photofabrication manufacture method of the present invention is characterised in that, uses positive light sensitivity composition of the present invention.Preferably this photofabrication manufacture method is applicable to the manufacturing of the member etc. of printed matter, electronic unit, exact instrument parts and relevant false proof usefulness.

Method for platemaking of the present invention is characterised in that, uses positive light sensitivity composition of the present invention.Utilize method for platemaking of the present invention can make the galley of intaglio plate (photogravure), lithographic plate, relief printing plate, hole version etc.

Use positive light sensitivity composition of the present invention as described below as the general plate-making process of the photogravure of sensitization liquid:

1. painting photosensitive liquid (the preferred 2-5 μ of dry film thickness m on cylinder.Some are better in order to remove the aperture thickness, but thinnerly can reduce consumption, correspondingly save cost) → 2. drying (to touch dry 15 minutes → to finishing 15-20 minute) → 3. exposure (light source: semiconductor laser 830nm, 220mJ/cm ²) → 4. develop (60-90 second/25 ℃) 5. washing (spraying 30 seconds) → 6. etching (degree of depth 10-30 μ m, etching copper chloride solution, copper conversion amount are 60g/L) → 7. resist peel off (alkali is peeled off) → 8. washing → 9. chromium plating (with respect to water, chromic acid 250g/L, sulfuric acid 2.5g/L) → 10. and wash → 11. and print.

As described below positive light sensitivity composition of the present invention as the general plate-making process of the lithographic plate (PS version) of sensitization liquid:

(1.CTP PS version) (aluminium grinding → painting photosensitive liquid → drying) → 2. exposure (light source: semiconductor laser 830nm, 220mJ/cm ²) → are 3. developed → 4. printing.

The invention effect

Positive light sensitivity composition of the present invention is that the laser to the infrared wavelength zone exposes that this induction part dissolves in alkali-soluble positive light sensitivity composition developer solution, that have the laser induced property in infrared wavelength zone after the induction, has following excellent results.

(1) not only aluminium and copper to the applied object of the poor adhesion of copper facing face of glossiness mirror-like and so on, also can obtain sufficient adhesiveness under the condition of roasting version.Also have, can under roasting edition condition, obtain to have and baked in the past the light-sensitive surface of the equal gloss of situation of version.

(2) even under the condition of humidity 25-60%, also can obtain sufficient adhesiveness.

(3) can in reasonable time, there be the good alkali development that residue produces.Although the photographic layer composition can satisfy the key property of the galley of printability resistance, light sensitivity, development tolerance etc. fully basically not because of chemical change takes place in exposure.In addition, owing to use polymer substance, also can develop even the base strength of developer solution is low with carboxyl.Because at the pH of developer solution is also can develop between the 10-12 time, therefore the dissolving of airborne carbonic acid gas is less, and the decline that alkaline developer is passed in time is also correspondingly less.On the other hand, the developer solution of phenol resin system has the decline of pH because of the influence of carbonic acid gas behind the formation developing bath immediately, if be not made into buffer solution, then can not develop continuously, and 2-3 day, the decline of alkali concn will take place at most.Under described situation, compare with the phenol resin type of developing with the developer solution more than the pH13.0, the present invention is for easier the managing of decline of alkali concn.Have, the intensity of alkali wasteliquid was low when the range of choice of alkali host was wide, thereby liquid waste processing is easy again.Form developing bath and be meant dilute with water developer solution stoste in developing trough, make developer solution.

(4) carry out image exposure even use than the high exposure energy exposure energy still less that sends excessive heat by the photo-thermal conversion material in the photographic layer, also can obtain wide development tolerance, therefore, can must be lower the extent control that photographic layer splashes, thus can not produce because of photographic layer splash (ablation) pollute the problem of the optics system of exposure device.

(5) handle owing to not baking version, therefore can keep ISO, edge of image against corrosion can be carried out extremely good development according to the irradiation pattern that exposes with profile disconnection clearly.Also have, end face part does not exist the deviation by the caused thermal capacitance of roasting version, the uniform thickness after can keeping developing yet.

(6) the film contraction is few, glossy in the resist pattern picture, even if directly corrosion can not produce aperture yet, can carry out photogravure plate-making.Also have, the resist pattern of acquisition looks like to be used for printing when waiting, and has the printability resistance that can print more than thousands of, and can avoid after the light-sensitive surface drying, the generation of the aperture in the processing before the development, or raising mar resistance;

(7) rate of change to the blueprint that utilizes laser is few, and the tolerance of developing is good.

(8) because the contraction of the film after developing is few, so the generation of aperture is less.

Description of drawings

Fig. 1 is the synoptic diagram at expression embodiment 1 employed sensitization liquid test pattern and mensuration place, (a) is test pattern, (b) is the expanded view of the circle part of (a).

Embodiment

The specific embodiment of the present invention below is described, described embodiment is the example of enumerating, so long as in technological thought scope of the present invention, can carry out various changes.

Positive light sensitivity composition of the present invention contains and has the polymer substance of at least 1 carboxyl in (A) molecule as neccessary composition and (B) absorb the infrared ray of image exposure light source and be transformed into the photo-thermal conversion material of heat, as required, preferably also be combined with (C) resistance solvent, (D) light acid propellant, (E) be selected from least a kind of resin and (F) triarylmethane based dye in the following resin: (1) vinyl pyrrolidone/vinyl acetate co-polymer, (2) vinyl pyrrolidone/dimethylaminoethyl methacrylate multipolymer, (3) vinyl pyrrolidone/caprolactam/dimethylaminoethyl methacrylate multipolymer, (4) polyvinyl acetate (PVA), (5) polyvinyl butyral, (6) polyvinyl formal, (7) terpene phenolic resin, (8) alkyl phenol resin, (9) melamine/formaldehyde resin and (10) ketone resin.

As described polymer substance (A), get final product so long as have the polymer substance of at least 1 carboxyl in the molecule, do not have particular determination, suitable example as for the polymkeric substance of unsaturated compound (a1) with at least 1 carboxyl and/or acid anhydride and as described in unsaturated compound (a1) and can with the multipolymer of the compound (a2) of this unsaturated compound copolymerization.The content of the carboxyl in the described polymer substance (A) is preferably the amount that makes acid number reach 30-500, and special preferred acid number reaches the amount of 200-250.Weight-average molecular weight is with 1,500-100, and 000 is advisable, and 7,000-10, about 000 is desirable more.

The preferred maleic acid of described unsaturated compound (a1), (methyl) acrylic acid, fumaric acid, itaconic acid and their derivant, above-claimed cpd can use more than 2 kinds alone or in combination.

As maleic acid and derivant (being called maleic acid is monomer) thereof, suitable example is if any maleic acid, maleic anhydride, maleic acid monoesters (as: monomethyl maleate, ethyl maleate, maleic acid list n-propyl, maleic acid list isopropyl ester, the positive butyl ester of maleic acid list, maleic acid list isobutyl ester and the maleic acid list tert-butyl ester etc.), maleic acid diester etc.

As (methyl) acrylic acid and derivant [being called (methyl) propylene base system monomer] thereof, suitable example is if any (methyl) acrylic acid or (methyl) acrylate (for example being: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) hydroxy-ethyl acrylate etc.).

As can with the compound (a2) of described unsaturated compound (a1) copolymerization, the compound that preferably has unsaturated double-bond, special optimization styrene, α-Jia Jibenyixi, or to methoxy styrene, p-methylstyrene, para hydroxybenzene ethene, 3-hydroxymethyl-styrene and derivants (being called styrenic monomers) thereof such as 4-hydroxyl-styrene.Above-claimed cpd can use more than 2 kinds alone or in combination.

As described polymer substance (A), preferred described maleic acid is polymer of monomers or is that monomer is the multipolymer of major component with maleic acid, the polymkeric substance of described (methyl) acrylic monomer or be the multipolymer of major component with (methyl) acrylic monomer, maleic acid is the multipolymer of monomer and other monomers such as (methyl) acrylic monomer and styrenic monomers, the copolymerization maleic acid is styrene/maleic acid based copolymer (hereinafter referred to as multipolymer (b1)) that monomer and styrenic monomers obtain, the multipolymer of acrylic monomer and styrenic monomers, the derivant of above-mentioned polymkeric substance or modifier; Be more preferably maleic acid polymkeric substance, (methyl) acrylate copolymer, have the multipolymer of the structure shown in structure shown in following general formula (6) and/or (7) and the following general formula (8) or the multipolymer of (methyl) acrylic acid and (methyl) acrylate and styrene monomer; Multipolymer shown in the further preferred following general formula (1).

In the formula (6), R ¹³And R ¹⁴The substituting group of representing hydrogen atom or 1 valency respectively independently, preferred hydrogen atom, low alkyl group or have the group of reactive double bond.

In the formula (8), R ¹⁵And R ¹⁶The substituting group of representing hydrogen atom or 1 valency respectively independently, preferred hydrogen atom or methyl, R ¹⁷The substituting group of expression hydrogen atom or 1 valency, preferred hydrogen atom, hydroxyl, alkyl or alkoxy, R ¹⁸The substituting group of expression hydrogen atom or 1 valency, preferred hydrogen atom or hydroxyalkyl.

In the formula (1), R ¹And R ²The substituting group of representing hydrogen atom or 1 valency respectively independently, preferred hydrogen atom or replacement or unsubstituted alkyl, more preferably there are a plurality of R in hydrogen atom, low alkyl group or alkoxyalkyl ¹And R ²The time, they can be identical or different.R ¹And R ²In preferably have at least 1 to be hydrogen atom, a is the integer more than 0 or 1, preferred 1-3, b is the integer 1 or more, preferably 6-8.

The manufacture method of described styrene/maleic acid based copolymer does not have particular determination, can be according to the known method manufacturing, it is desirable to make compound with hydroxyl and phenylethylene/maleic anhydride based copolymer (being the multipolymer of styrenic monomers and maleic anhydride) to react and finish esterification and obtain.

As described compound with hydroxyl, there is not particular determination, for example have: diglycol ethers such as glycol ethers such as alcohol, ethylene glycol butyl ether, diethylene glycol monoethyl ethers such as isopropyl alcohol, n-propanol, isopropyl alcohol/cyclohexanol, butanols, isooctyl alcohol, ethylene glycol etc.

In addition, as described polymer substance (A), can also use the material [hereinafter referred to as multipolymer (b2)] after described multipolymer (b1) is had reactive double bond compound modified.At this moment, the ratio of the structure shown in structure shown in formula (6) and (7) and the formula (8) preferably is about 1.Described multipolymer (b2) specifically can make compound with reactive double bond and the anhydride group in the multipolymer (b1) or carboxyl reaction and makes.At this moment be necessary in the multipolymer residual have carry out the alkali required carboxyl that develops.

Described compound with reactive double bond is preferably the compound with carbon-to-carbon double bond, suitable example if any: unsaturated alcohol (for example has: allyl alcohol, 2-butene-1-2-alcohol, furfuryl alcohol, oleyl alcohol, styron, acrylic acid 2-hydroxy methacrylate, methacrylic acid hydroxyl ethyl ester, N hydroxymethyl acrylamide etc.), (methyl) alkyl acrylate (for example has: methyl methacrylate, metering system tert-butyl acrylate etc.), the epoxy compound that has 1 oxirane ring and reactive double bond respectively (for example has glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, acrylic acid α-ethyl ethylene oxidic ester, the crotyl glycidol ether, itaconic acid monoalkyl list ethylene oxidic ester etc.) etc.

In addition, as described multipolymer (b2), can also use above-mentioned epoxy compound that has 1 oxirane ring and reactive double bond respectively and the material that utilizes unsaturated alcohol to introduce reactive double bond to react so that the material that reactive double bond concentration has increased.

Described multipolymer (b1) and manufacture method (b2) do not have particular determination, can carry out according to known method (for example having: with reference to patent documentation 32-34 etc.).The polymer substance with carboxyl beyond styrene/maleic acid based polymer also can be introduced reactive double bond as described above.Give reactive double bond to polymer substance and help the increase of degree of cure and the raising of printability resistance.

The content of the polymer substance in the positive light sensitivity composition of the present invention (A) does not have particular determination, with respect to (A) composition, (B) composition, (C) composition, (D) composition, (E) composition and (F) the solid constituent total amount of composition, be preferably 80-98 weight %, more preferably 90-95 weight %.Above-mentioned polymer substance (A) can be used alone, and also can more than 2 kinds and use.

As described photo-thermal conversion material (B), get final product so long as can change the light that absorbs into hot compound, there is not particular determination, for example can enumerate and have wavelength 700-1, the pigment of the organic or inorganic of the absorption band of part or all of the infrared spectral range of 100nm and dyestuff, organic pigment, metal, metal oxide, metal carbide, metal boride etc., preferably can absorb the light of described wavelength region may expeditiously, even and if absorb the light of ultraviolet range hardly or absorb the optical absorption pigment of also not responding to basically, compound and the derivant thereof shown in following general formula (3) or (4) is more suitable.

In the formula (3), R ³-R ⁸Represent hydrogen atom, low alkyl group (alkyl of preferred carbon number 1-3) or lower alkoxy (alkoxy of preferred carbon number 1-3) respectively independently.X ^-The expression balance anion, X for example is halogen atom, ClO ₄, BF ₄, right-CH ₃C ₆H ₄SO ₃, or PF ₆Deng.

In the formula (4), R ⁹-R ¹²Represent independently respectively hydrogen atom, methoxyl ,-N (CH ₃) ₂Or-N (C ₂H ₅) ₂, Y ^-The expression balance anion, Y for example is C ₄H ₉-B (C ₆H ₅) ₃, BF ₄, right-CH ₃C ₆H ₄₈O ₃, or CF ₃SO ₃Deng.

Compound shown in the above-mentioned general formula (4), more preferably its maximum absorption wavelength is in the near infrared absorbing coloring matter shown in following structural formula (9)-(12) of near infrared region.

In addition, as other optical absorption pigment, for example be: (CH=) n what is called match that connect, broad sense peacefulness is the material of pigment representative to the heterocycle that contains nitrogen-atoms, oxygen atom or sulphur atom etc. described in patent documentation 6 etc. by polymethine, concrete example is as being: quinoline system (the peaceful system of so-called match), indoles system (the peaceful system of so-called indoles match), benzothiazole system (the peaceful system of so-called sulphur match), imino group cyclohexadiene system (so-called polymethine system), pyrans system, sulphur pyrans system, ス Network ア リ リ ウ system system, Network ロ コ ニ ウ system system, ア ズ レ ニ ウ system system etc.Wherein preferably quinoline system, indoles system, benzothiazole are, the imino group cyclohexadiene is, pyrans is or thiopyridines is muttered is, preferred especially phthalocyanine or match peacefulness.

Described photo-thermal conversion material (B) is that part or all of infrared wavelength zone of 700 to 1100 nanometers has absorption band to wavelength, and have laser that absorbs this infrared wavelength zone and the characteristic of carrying out thermal decomposition, relate to the mol ht fracture that utilizes described polymer substance (A) with carboxyl alkali-soluble degraded-melt (ablation).

What of the addition of photo-thermal conversion material concerning the too much or not enough of heat that exposure is produced, and in addition, the strong or weak relation of infrared laser thermal decomposition too much and not enough of the existing organic polymer material of exposed portion, therefore will set suitable amount.The content of the photo-thermal conversion material in the positive light sensitivity composition of the present invention (B), with respect to (A) composition, (B) composition, (C) composition, (D) composition, (E) composition and (F) the solid constituent total amount of composition, preferred 0.1-10 weight %, more preferably 1-4 weight %.

Described resistance solvent (C), in order to increase exposure portion and non-exposure portion deliquescent mistiming of alkaline developer is cooperated, the material that uses is to have and polymer substance (A) forms hydrogen bond and reduces the deliquescent function of this polymer substance, and absorb the light of region of ultra-red hardly, can be by the material of the photolysis of region of ultra-red.

Described resistance solvent (C), preferably use the compound shown in the following formula (2) (4,4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethylidene] bis-phenol).

In addition, resistance solvent (C) can also use known resistance solvent.Concrete example is as being: sulphonic acid ester, phosphate, aromatic carboxylic acid esters, aromatic series two sulfones, carboxylic acid anhydrides, aromatic ketone, aromatic aldehyde, aromatic amine, aromatic ether etc. and have lactone skeleton, thiolactone skeleton, N, the sour color emissivity pigment of N-diaryl amide backbone or diaryl methylene imine skeleton, the alkali color emissivity pigment with lactone skeleton, thiolactone skeleton or sulfo group lactone skeleton, nonionic surfactant etc. wherein preferably have the sour color emissivity pigment of lactone skeleton.

The content of the resistance solvent in the positive light sensitivity composition of the present invention (C) is with respect to (A) composition, (B) composition, (C) composition, (D) composition, (E) composition and (F) the solid constituent total amount of composition, preferred 0.5-8 weight %, more preferably 1-5 weight %.Above-mentioned resistance solvent may be used alone, two or more kinds can also be used.

Described light acid propellant (D) is because of the acidic material of light, can play the effect of sensitizer.As described light acid propellant (D), for example be: diphenyl iodnium, triphenyl sulfonium salt, aromatic sulfonic acid ester, triaizine compounds, diazonium two sulfone based compounds etc., preferred following general formula (13)-(47)

Shown compound, the compound shown in the preferred especially following formula (5).

In the formula (13), R ¹⁹And R ²⁰Represent hydrogen atom, alkyl or alkoxy respectively independently, preferred hydrogen atom, methyl, the tert-butyl group, methyl-propyl or methoxyl.Z ^-The expression balance anion, Z for example is PF ₆, CF ₃SO ₃, C ₄F ₉SO ₃, SbF ₆, BF ₄Deng organic anions such as inorganic acid radical, right-toluenesulfonic acid, camphor-β-sulfonic acid etc.

In the formula (14), R ²¹Expression hydrogen atom, alkyl, alkoxy or-SC ₆H ₅Base, preferred hydrogen atom, methyl, the tert-butyl group, methyl-propyl or methoxyl.Z ^-Definition identical with formula (13).

In the formula (16), R ²²The organic group of representing 1 valency for example is: trichloromethyl, phenyl, right-methoxyphenyl, Dimethoxyphenyl, right-CH ₃SC ₆H ₄Base, rubigan, methoxyl-styrene, dimethoxy-styryl, trimethoxy styryl, propoxyl group styryl, butyl phenyl ether vinyl, amyl phenyl ether vinyl, right-methoxyl--chlorostyrene base, 4 '-methoxyl-1 '-naphthyl etc.

In the formula (21), R ²³Organic group for hydrogen atom or 1 valency for example is: hydrogen atom, the tert-butyl group etc.

In the formula (24), R ²⁴And R ²⁵Represent the organic group of hydrogen atom or 1 valency respectively independently, for example be: hydrogen atom, methyl, the tert-butyl group etc.

In the formula (25), R ²⁶And R ²⁷Represent the substituting group of hydrogen atom or 1 valency respectively independently, for example be: hydrogen atom, chlorine atom, methyl, the tert-butyl group etc.R ²⁸And R ²⁹Represent hydrogen atom or methyl respectively independently.

Z in the formula (31) ^-Definition identical with formula (13).

Z in the formula (32) ^-Definition identical with formula (13).A is hydrogen atom or hydroxyl.

Z in the formula (33) ^-Definition identical with formula (13).

In the formula (34), R ³⁰The expression hydrogen atom or-SCH ₃Base.

In the formula (36), R ³¹-R ³³The organic group of representing 1 valency respectively independently, alkyl such as preferable methyl or ethyl.

In the formula (37), R ³⁴And R ³⁵Represent hydrogen atom or NO respectively independently ₂Base.

In the formula (38), R ³⁶Expression hydrogen atom or NO ₂Base.

In the formula (39), R ³⁷Expression methyl, CF ₃Base, phenyl or right-ethylphenyl.

In the formula (41), R ³⁷Definition identical with formula (39).

In the formula (43), R ³⁷Definition identical with formula (39).

In the formula (47), Z ^-Definition identical with formula (13).

As light acid propellant, specifically can be extensive use of product BDE, Anisil by name, BBI-102, TAZ-101, TAZ-104, the TAZ-106 of IRGACURE series, the ミ De リ KCC of チ バ ス ペ シ ヤ Le テ ィ Network ミ カ Le ズ (strain), the light acid propellant of TAZ-110, BC etc.Also have, can use the diazonium two sulfones system of Wako Pure Chemical Industries, Ltd., the light acid propellant of triphenylsulfonium system.

The content of the light acid propellant in the positive light sensitivity composition of the present invention (D), with respect to (A) composition, (B) composition, (C) composition, (D) composition, (E) composition and (F) the solid constituent total amount of composition, preferred 0.5-10 weight %, more preferably 1-5 weight %.Above-mentioned light acid propellant may be used alone, two or more kinds can also be used.In addition, can also be used in combination with other sensitizer.

Described resin (E) is at least a kind of alkali soluble resins that is selected from the following resin, and can play the effect of adhesiveness modifying agent: (1) vinyl pyrrolidone/vinyl acetate co-polymer, (2) vinyl pyrrolidone/dimethylaminoethyl methacrylate multipolymer, (3) vinyl pyrrolidone/caprolactam/dimethylaminoethyl methacrylate multipolymer, (4) polyvinyl acetate (PVA), (5) polyvinyl butyral, (6) polyvinyl formal, (7) terpene phenolic resin, (8) alkyl phenol resin, (9) melamine/formaldehyde resin, (10) ketone resin.

Described (1) vinyl pyrrolidone/vinyl acetate co-polymer (hereinafter referred to as the PVP/VA multipolymer) is to make vinyl pyrrolidone and the vinyl acetate copolymerized thermoplastic resin that obtains, and has the structure shown in the following general formula (48).

In the formula (48), n, m are respectively the integer more than 1.The vinyl pyrrolidone in the PVP/VA multipolymer and the ratio of vinyl acetate do not have particular determination, but the preferred 70/30-30/70 of the ratio of vinyl pyrrolidone and vinyl acetate, more preferably 70/30-50/50.

The manufacture method of PVP/VA multipolymer does not have particular determination, preferably makes vinyl pyrrolidone and vinyl acetate carry out the random copolymers of the line style that free radical polymerization obtains.The molecular weight of PVP/VA multipolymer does not have particular determination yet, and is preferred 10,00-60,000, more preferably 20,000-50,000.

Described (2) vinyl pyrrolidone/dimethylaminoethyl methacrylate multipolymer has the structure shown in the following general formula (49).

In the formula (49), n, m are respectively the integer more than 1.

Described (3) vinyl pyrrolidone/caprolactam/dimethylaminoethyl methacrylate multipolymer, be the multipolymer of vinyl pyrrolidone and caprolactam and dimethylaminoethyl methacrylate, have the structure shown in the following general formula (50).

In the formula (50), n, m, l are respectively the integer more than 1.

Described (4) polyvinyl acetate (PVA) is the homopolymer of vinyl acetate or is the multipolymer of major component with the vinyl acetate to have the structure shown in the following general formula (51).

In the formula (51), n is the integer more than 1.As polyvinyl acetate (PVA), for example can be suitable for the サ Network ノ-Le SN-09T (trade name) of Deuki Kagaku Kogyo Co., Ltd.

Described (5) polyvinyl butyral (be called for short PVB) is butyraldehyde and polyvinyl alcohol (PVA) to be reacted and resin that butyralization obtains, has the structure shown in the following general formula (52).

In the formula (52), n, m, l are respectively the integer more than 1.As polyvinyl butyral, the example that is fit to is specially: the product of Deuki Kagaku Kogyo Co., Ltd, デ Application カ Block チ ラ-Le 5000A and 6000EP, BH-3, the BH-S of BM-1, the BM-2 of the BL-1 of the product of Sekisui Chemical Co., Ltd, low polymerization degree type, BL-2, BL-2, BL-S, BX-L, middle degree of polymerization type, BM-5, BM-S, high polymerization degree type, BX-1, BX-2, BX-5, BX-55 etc. especially preferably can be dissolved in BL-S, BM-S, the BH-S of multiple solvent.

Described (6) polyvinyl formal (PVFM) are the good resins of electrical insulating property with the structure shown in the following general formula (53).

In the formula (53), n, m, l are respectively the integer more than 1.The manufacture method of polyvinyl formal does not have particular determination, for example, polyvinyl acetate (PVA) is dissolved in the acetic acid, add formaldehyde and sulfuric acid then, carry out saponification and dimethoxym ethane reaction simultaneously, in this reactant liquor, add dilute sulfuric acid and make the polyvinyl formal precipitation, obtain product through solvent recovery, washing, drying process then.

Described (7) terpene phenolic resin can be extensive use of known in the past material.The example that is fit to is specially: マ ノ Le 803L and 901 (trade name of Arakawa Chemical Industries, Ltd.'s system).

Described (8) alkyl phenol resin can be extensive use of known in the past material.The example that is fit to concrete as: マ ノ Le 520S, 521,526,586 and 572S (trade name of Arakawa Chemical Industries, Ltd.'s system).

Described (9) melamine/formaldehyde resin is the resin that utilizes the addition condensation reaction of melamine and formaldehyde to obtain, and can be extensive use of known melamine/formaldehyde resin.The concrete preferred バ Application セ リ Application SM-960 (trade name) that uses Ha リ マ to change into Co., Ltd..

Described (10) ketone resin can use known ketone resin, does not have particular determination.For example, can make ketone and formaldehyde reaction with known method and obtain.Ketone for example is: MEK, methyl isobutyl ketone, acetophenone, cyclohexanone, methyl cyclohexanone etc., preferred especially cyclohexanone and acetophenone.As ketone resin, the cyclohexanone shown in the preferred following formula (54) is that ketone resin and the acetophenone with structure shown in the following formula (55) are ketone resin.

In formula (54) and the formula (55), m, n are respectively the integer more than 1.

The content of the resin in the positive light sensitivity composition of the present invention (E) is with respect to (A) composition, (B) composition, (C) composition, (D) composition, (E) composition and (F) the solid constituent total amount of composition, preferred 1-40 weight %, more preferably 5-30 weight %.

As described (F) triarylmethane based dye, can be extensive use of the illuminating colour that known in the past triarylmethane is, concrete preferable methyl purple, crystal violet, victoria blue B, oil blue 613 (trade name of ォ リ エ Application ト chemical industry (strain) system) and their derivant.Above-mentioned triarylmethane is that pigment may be used alone, two or more kinds can also be used in combination.

By using illuminating colour can obtain following effect, that is,, carry out overlapping operation with opaquing fluid easily at the aperture that just can know identification light-sensitive surface surface through development when forming pattern, foul etc.The high more easy more resolution of the concentration of dyestuff, thus more satisfactory.In addition, owing to can not revise, therefore make in the semiconductor industry, need revise in order to regenerate waste product and print in industry, the electronic unit association area in the decontamination chamber.

The content of the dyestuff in the positive light sensitivity composition of the present invention (F) is with respect to (A) composition, (B) composition, (C) composition, (D) composition, (E) composition and (F) the solid constituent total amount of composition, preferred 0.1-10 weight %, more preferably 1-4 weight %.

Positive light sensitivity composition of the present invention except above-mentioned composition, can also cooperate other the pigment or the various adjuvants of colorant, sensitizer, development accelerant, adhesiveness improver, coating modifying agent etc. such as dyestuff as required.Development accelerant preferably trace adds as dicarboxylic acid or amine or glycols.

The state of the solution that positive light sensitivity composition of the present invention obtains to be dissolved in solvent usually uses.The usage ratio of solvent with respect to the solid constituent total amount of photosensitive composite, represents to be generally 1-20 scope doubly with weight ratio.

As solvent, as long as, can give good filming property and get final product, there is not particular restriction to using composition to have sufficient solubleness, can use cellosolve series solvent, propylene glycol series solvent, ester series solvent, pure series solvent, ketone series solvent, intensive polar solvent.The cellosolve series solvent for example is: methyl Cellosolve, ethyl Cellosolve, methyl glycol acetate, ethyl cellosolve acetate etc.The propylene glycol series solvent for example is: propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol single-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol list ethylether acetate, propylene glycol single-butyl ether acetate, dipropylene glycol dimethyl ether etc.The ester series solvent for example is: butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethy-aceto oxalate, ethyl pyruvate, 2-hydroxybutyric acid ethyl ester, ethyl acetoacetate, methyl lactate, ethyl lactate, 3-methoxypropionic acid methyl esters etc.The alcohol series solvent for example is: enanthol, hexanol, diacetone alcohol, furfuryl alcohol etc.Intensive polar solvent for example is: ketone series solvent such as cyclohexanone, methyl amyl ketone or dimethyl formamide, dimethyl acetamide, N-Methyl pyrrolidone etc.Other also have: the mixed solvent of acetic acid or above-mentioned solvent, and add the solvent that obtains behind the aromatic hydrocarbon in the above-mentioned solvent.

Positive light sensitivity composition of the present invention, usually form described each composition is dissolved in the cellosolve series solvent, propylene glycol series solvent equal solvent and the solution that obtains, be coated on the copper plating face or the copper sulphate plating face of the cylinder of using as the photogravure on support surface of being made a plate, high speed rotating after the air dry, make the state that is in rotation at full speed by the surface of plate-making cylinder, and utilization becomes the characteristics of certain negative pressure state because of mass action that centrifugal force produced in the light-sensitive surface and near surface, and dissolvent residual concentration is reduced to below 6%, make the positive type light sensitive film that has formed the photosensitive composite layer on the support surface thus.

As coating process, can use meniscus coating, spraying coating, dip coated, rotary coating, cylinder coating, wire bar coating, airblade coating, scraper plate coating and the coating of curtain formula etc.The preferred 1-6 μ of the thickness of coated film m, more preferably 3-5 μ m.

Light source as the positive light sensitivity composition layer being carried out image exposure preferably sends wavelength 700-1, the semiconductor agent laser instrument of the infrared laser light of 100nm or YAG laser instrument.Can use the solid state laser of ruby laser, LED etc. in addition.The light intensity of LASER Light Source preferred 2.0 * 10 ⁶MJ/scm ²More than, preferred especially 1.0 * 10 ⁷MJ/scm ²More than.

The salt of Na, K etc.) or the developer of the inorganic or organic alkali formation that waits of organic base (for example being: TMAH (hydrogen-gasified tetramethyl-ammonium) or choline etc.) as the employed developer solution of light-sensitive surface, preferably (for example be: by inorganic base to using positive light sensitivity composition of the present invention to form.

During development,, 15-45 ℃ temperature, preferably carry out under 22-32 ℃ the temperature usually by immersion development, spray developing, brushing development, ultrasound wave development etc.

Embodiment

Below further specify the present invention with embodiment, described embodiment is used for illustrationally, obviously is not limitation of the invention.

Embodiment 1

According to cooperation material shown in the table 1 and cooperation ratio modulation positive light sensitivity composition, as test sensitization liquid.

Table 1

	Cooperate material	Use level (weight portion)
			Composition (A)	Resin A 1	100
Composition (B)	Infrared ray absorbing pigment B1	3
			Composition (C)	Resistance solvent 1	2
Composition (D)	Light acid propellant 1	2
			Composition (E)	Resin E1	8
Composition (F)	Colored pigments F1	2
			Solvent	PM IPA MEK	590 737 589

Each composition in the table 1 is as described below.

Resin A 1:SMA 1440 (SARTOMER corporate system, phenylethylene/maleic anhydride copolymer is by the partial esterification thing of butyl cellosolve partial esterification).

Infrared ray absorbing pigment B1: the infrared ray absorbing pigment shown in the described formula (3).

Resistance solvent: TrisP-PA (Honshu chemical industry (strain) system, the compound shown in the described formula (2)).

Light acid propellant: IRGACURE 250 (チ バ ス ペ シ ヤ Le テ ィ Network ミ カ Le ズ (strain) system, the compound shown in the described formula (5))

Resin E1:PVP/VA multipolymer (vinyl pyrrolidone that molecular weight 46,000, glass transition temperature are 96 ℃ and multipolymer, vinyl pyrrolidone/vinyl acetate=50/50 of vinyl acetate)

Colored pigments F1: oil blue 613 (ォ リ エ Application ト chemical industry (strain) system, ColorIndex (C.I.) No.42595)

PM: propylene glycol monomethyl ether

IPA: isopropyl alcohol

MEK: MEK

Use resulting test sensitization liquid to carry out following test.In addition, the experiment indoor temperature is 25 ℃, and tests under the damp condition shown in the table 2.With the cylinder mother metal be iron and through copper sulphate plating and minute surface 200 Φ mm through grinding by the plate-making cylinder, (dehydrating unit and damping device are installed with spraying (fountain coating) device, can be controlled to be the device of desired moisture level) clamp its two ends, rotate with the 25r.p.m rotating speed, and clean fully with cloth for wiping or dusting.Also have, this spray equipment can avoid the solvent in the positive light sensitivity composition to change because of evaporation causes the ratio of solvent in coating.

Afterwards, make the pipe of the test sensitization liquid of gushing out from its upper end be in distance is had 500 μ m gaps approximately by an end of plate-making cylinder position, and make sensitization liquid only gush out the coating needed amount, make this pipe from being moved to the other end by an end of plate-making cylinder, with the even coated test sensitization of spiral scan mode liquid, finish to begin to calculate from coating, continue rotation with the 25r.p.m rotating speed and stop the rotation after 5 minutes.

Left standstill 5 minutes, and observed the situation that drop drips, with the naked eye do not observed drop and dripped.Measured thickness then, the lower part of cylinder and upper part do not have difference as a result.Therefore, can confirm to form the light-sensitive surface that is dried to the state that liquid do not drip.

Then, making drum to test with 100r.p.m rotating speed rotation 20 minutes, stop then, measure the dissolvent residual concentration of light-sensitive surface clock, is 2.9%.

Then, drum to test is installed on the exposure device (シ of Co., Ltd. Application Network ラ ボ ラ ト リ-system) of the high-power semiconductor laser head that Network レ ォ サ イ テ Star Network ス company is housed, laser to this drum to test irradiation infrared wavelength zone, shine into the eurymeric image, then, be installed on the developing apparatus drum to test and rotation, developing trough is risen, developing disappears up to residue, afterwards washing.Also have, use KOH4.2% (25 ℃) as developer solution.The resist pattern picture that obtains with microscopic evaluation.The result is as shown in table 2.

Table 2

	Humidity (%)	Adhesiveness	Light sensitivity (mJ/cm 2)	Develop (second)	Residual film ratio (%)	Image	The resolving power at edge	The development tolerance
									Embodiment 1-1	35	◎	180	75	71	◎	◎	◎
Embodiment 1-2	45	◎	180	75	73	◎	◎	◎
									Embodiment 1-3	55	◎	180	75	72	◎	◎	◎

Evaluation method in the table 2 is as described below.

1) resolving power at edge

Use resolving power test pattern shown in Figure 1, whether the edge of the line of 7.9 μ m of mensuration check design, clathrate line (grating) is clear.The ◎ ecbatic is good in the table, and resolving power is qualified, and * expression does not have image, can not make a plate, and resolving power is defective.

2) development tolerance

Use the セ Le Tibetan (can measure the device of the numerical aperture of site automatically) of Janpanese Printing Co., Ltd to measure.According to the exposure of the test of carrying out multidevelopment (being 3 times in the present embodiment), fall into 60-75 μ m when calculating with cellar area by 7.9 μ m * 7.9 μ m ²Scope the time, fallen into the permissible range of printing concentration, thereby be well, represent with ◎ in the table.When dropping on outside the printing permissible range, usefulness * expression in the table.

3) adhesiveness

Tesa test: in the reticulate pattern adhesiveness test that utilizes DIN EN ISO 2409 adhesive tapes, use ◎ when all staying for 100, usefulness * expression when peeling off more than zero, 20% when in being lower than 20% scope, peeling off.

4) light sensitivity

Regulate exposure, determine light sensitivity near the picture pattern person with repeatability.Exposure machine uses the thermal imagery head of company.

5) develop

Mensuration was developed to the required time of residue disappearance.

6) residual film ratio

The device FILMETRICS Thin Film AnalyzerF20 (Filmetrics Co system) of the thickness of filming is measured in use, measures the thickness before developing, the thickness after the development, calculates residual film ratio.

7) image

Whether estimate has the repeatability that approaches original image.◎: very good, *: non-constant ,-: the back picture drop-out of developing.

Sensitization liquid test pattern and mensuration place are as shown in Figure 1.Test event and assay method to the mensuration place among Fig. 1 are as shown in table 3.

Table 3

The mensuration place	Test event	Take a picture and photograph	Area estimation (セ Le Tibetan)
				①	Having or not of development residue	-	-
②	1 pixel grid	○	-
				③	1 pixel bright spot (high light)	○	○
④	7 μ m grid	○	○

As shown in table 2, the positive light sensitivity composition of embodiment 1 can obtain not having the figure clearly of residue through 70 seconds under the condition of 25 ℃ room temperature, humidity 35-55%, can carry out good development.The development tolerance is also good.

In addition, also use copper face or aluminium face to replace copper sulphate plating face to test, the result has similarly obtained good result with embodiment 1.Obtained wide especially development tolerance under the situation of aluminium face.

Embodiment 2-6

Except changing composition (B) in the composition and composition (F) as shown in table 4ly and embodiment 1-2 similarly test.In addition, mensuration is to carry out under the condition of humidity 45%.The result is summarised in the table 4.

Table 4

	Composition (B) use level	Composition (F) use level	Adhesiveness	Light sensitivity (mJ/cm 2)	Develop (second)	Residual film ratio (%)	Image	The resolving power at edge	The development tolerance
										Embodiment
2	Pigment B2 1	Pigment F2 6	◎	180	75	70	◎	◎	◎
										Embodiment 3	Pigment B3 3	Pigment F3 3	◎	180	75	69	◎	◎	◎
Embodiment 4	Pigment B4 4	Pigment F4 4	◎	180	75	72	◎	◎	◎
										Embodiment 5	Pigment B5 6	Pigment F1 1	◎	180	75	73	◎	◎	◎
Embodiment 6	Pigment B6 2	Pigment F2 2	◎	180	75	71	◎	◎	◎

In the table 4, pigment B2-B6 and pigment F2-F4 are as described below.In addition, composition (B) and use level (F) are the weight portions when being 100 weight portions with the use level of composition (A) respectively.

Pigment B2:IR-B (the infrared ray absorbing pigment shown in clear and electrician's (strain) system, the described formula (9))

Pigment B3:IR-T (the infrared ray absorbing pigment shown in clear and electrician's (strain) system, the described formula (10))

Pigment B4:IR-2MF (the infrared ray absorbing pigment shown in clear and electrician's (strain) system, the described formula (11))

Pigment B5:IR-13F (the infrared ray absorbing pigment shown in clear and electrician's (strain) system, the described formula (12))

Pigment B6:NK-2014 (the infrared ray absorbing pigment shown in (strain) woods protobiochemistry institute system, the following formula (56))

Pigment F2: iron methyl violet BB ス ペ シ セ Le (hodogaya chemical industry (strain) system, C.I.BasicViolet 1, No.42535)

Pigment F3: iron crystal violet (hodogaya chemical industry (strain) system, C.I.Basic Violet3, No.42555)

Pigment F4: iron victoria blue B H (hodogaya chemical industry (strain) system, C.I.Basic Blue26, No.44045)

Embodiment 7-15

Except changing the composition (A) in the composition as shown in table 5ly and embodiment 1-2 similarly test.The result is summarised in the table 5.

Table 5

	Composition (A)	Adhesiveness	Light sensitivity (mJ/cm 2)	Develop (second)	Residual film ratio (%)	Image	The resolving power at edge	The development tolerance
									Embodiment 7	Resin A 2	◎	180	75	73	◎	◎	◎
Embodiment 8	Resin A 3	◎	180	75	72	◎	◎	◎
									Embodiment 9	Resin A 4	◎	180	75	75	◎	◎	◎
Embodiment 10	Resin A 5	◎	180	75	70	◎	◎	◎
									Embodiment 11	Resin A 6	◎	180	75	72	◎	◎	◎
Embodiment 12	Resin A 7	◎	180	75	69	◎	◎	◎
									Embodiment 13	Resin A 8	◎	180	75	73	◎	◎	◎
Embodiment 14	Resin A 9	◎	180	75	72	◎	◎	◎
									Embodiment 15	Resin A 10	◎	180	75	71	◎	◎	◎

In the table 5, the use level of composition (A) is identical with embodiment 1, and Resin A 2-A10 is as described below.

Resin A 2:SMA 17352 (SARTOMER corporate system, phenylethylene/maleic anhydride copolymer are by the partial esterification thing of isopropyl alcohol/cyclohexanol partial esterification).

Resin A 3:SMA 2624 (SARTOMER corporate system, phenylethylene/maleic anhydride copolymer are by the partial esterification thing of n-propanol partial esterification).

Resin A 4:SMA 3840 (SARTOMER corporate system, phenylethylene/maleic anhydride copolymer are by the partial esterification thing of isooctyl alcohol partial esterification).

Resin A 5: ォ キ シ ラ Star Network SH-101 (Japanese catalyst chemical industry (strain) system, styrene/maleic acid half ester multipolymer).

Resin A 6: (acid number 98, weight-average molecular weight 21000, base monomer are than acrylic acid: methyl methacrylate: styrene=1: 1: 1) for acrylic acid, methyl methacrylate and cinnamic multipolymer.

Resin A 7: maleic acid polymkeric substance (acid number 300, weight-average molecular weight 10000)

Resin A 8: acrylate copolymer (acid number 100, weight-average molecular weight 25000)

Resin A 9: ォ キ シ ラ Star Network SH-101 derivant (addition the styrene of glycidyl methacrylate/maleic acid based copolymer, acid number 80)

Resin A 10: addition the Resin A 6 of glycidyl methacrylate

Embodiment 16-25

Except using each resin shown in the table 6 to replace resin E1 as composition (E) and embodiment 1-2 similarly tests.The result is summarised in the table 6.

Table 6

The embodiment sequence number	Composition (E) weight portion	Adhesiveness	Light sensitivity (mJ/cm 2)	Develop (second)	Residual film ratio (%)	Image	The resolving power at edge	The development tolerance
									16	Resin E2 2	◎	180	75	69	◎	◎	◎
17	Resin E3 5	◎	180	75	73	◎	◎	◎
									18	Resin E4 10	◎	180	75	75	◎	◎	◎
19	Resin E5 8	◎	180	75	72	◎	◎	◎
									20	Resin E6 20	◎	180	75	70	◎	◎	◎
21	Resin E7 30	◎	180	75	71	◎	◎	◎
									22	Resin E8 10	◎	180	75	77	◎	◎	◎
23	Resin E9 10	◎	180	75	76	◎	◎	◎
									24	Resin E10 10	◎	180	75	73	◎	◎	◎
25	Resin E11 8	◎	180	75	75	◎	◎	◎

In the table 6, resin E2-E11 is as described below.

Resin E2:GAFQUAT 734 (ISP society system, vinyl pyrrolidone/dimethylaminoethyl methacrylate multipolymer)

Resin E3:GAFFIX VC-713 (ISP society system, vinyl pyrrolidone/caprolactam/dimethylaminoethyl methacrylate multipolymer)

Resin E4: サ Network ノ-Le SN-09T (electrochemical industry (strain) system, polyvinyl acetate (PVA))

Resin E5: デ Application カ Block チ ラ-Le #3000 (electrochemical industry (strain) system, polyvinyl butyral)

Resin E6: PVC ニ レ Star Network-K type (チ Star ソ society system, polyvinyl formal)

Resin E7: マ ノ Le 803L (waste river chemical industry (strain) system, terpene phenolic resin)

Resin E8: マ ノ Le 520S (waste river chemical industry (strain) system, alkyl phenol resin)

Resin E9: バ Application セ リ Application SM-960 (Ha リ マ changes into (strain) system, melamine/formaldehyde resin)

Resin E10: Ha イ ラ Star Network 111 (Hitachi changes into (strain) system, cyclohexane resin)

Resin E11: Ha イ ラ Star Network 110H (Hitachi changes into (strain) system, acetophenone resin)

Embodiment 26

Except mismatching composition (C) and embodiment 1-2 similarly test.The result is as shown in table 7.

Embodiment 27

Except mismatching composition (D) and embodiment 1-2 similarly test: the result is as shown in table 7.

Embodiment 28

Except mismatching composition (E) and embodiment 1-2 similarly test.The result is as shown in table 7.

Embodiment 29

Except mismatch composition (C), (D) and (E) and embodiment 1-2 similarly test.The result is as shown in table 7.

Table 7

The embodiment sequence number	Adhesiveness	Light sensitivity (mJ/cm 2)	Develop (second)	Residual film ratio (%)	Image	The resolving power at edge	The development tolerance
								26	◎	180	75	73	◎	◎	◎
27	◎	180	75	71	◎	◎	◎
								28	◎	180	75	76	◎	◎	◎
29	◎	180	75	75	◎	◎	◎

Comparative example 1-3

Except the composition that changes positive light sensitivity composition as shown in table 8ly and embodiment 1-2 similarly test.The result is as shown in table 9.

Table 8

	Comparative example 1	Comparative example 2	Comparative example 3
				Novolac resin	100	100	100
Infrared ray absorbing pigment B1	1	1	1
				The titanium organic compound	-	2	-
Imidazoles silane	-	-	2
				Solvent PM IPA MEK	800 800 600	800 800 600	800 800 600

In the table 8, infrared ray absorbing pigment B1 is identical with table 1 with solvent, and other compositions are as described below.Novolac resin: PR-NMD-100 (Sumitomo ベ one Network ラ イ ト society system)

Titanium organic compound: ォ Le ガ チ Star Network ス-10 (alkyl titanium oxide) the imidazoles silane of this industrial pharmacy (strain) system of pine: silane coupling agent with structure of following formula (57).In its Chinese style (57), R ⁴¹-R ⁴⁴Be respectively alkyl, n is the integer of 1-3.

Table 9

	Adhesiveness	Light sensitivity (mJ/cm 2)	Develop (second)	Residual film ratio (%)	Image	The resolving power at edge	The development tolerance
								Comparative example 1	○	150	60	0	-	×	×
Comparative example 2	○	150	60	0	-	×	×
								Comparative example 3	○	150	60	0	-	×	×

As shown in table 9, comparative example 1-3 is after development, and image all disappears, and can not obtain the tolerance of developing fully.

The possibility of using on the industry

Positive light sensitivity composition of the present invention, be conducive to be formed the positive type light sensitive film what photogravure was used by the copper sulphate plating face of plate-making roller, moreover, when the plastic sheeting after the metallic plate of aluminium, zinc, copper, iron, chromium, nickel etc. that has been applicable to the metallic plates such as aluminium, zinc, steel, plating or evaporation, the paper that has been coated with resin, the paper of having pasted the metal formings such as aluminium, plastic sheeting, the hydrophilicity-imparting treatment and glass plate etc. are upper, also have at low temperatures good adhesiveness, and can obtain ISO.

Therefore, positive light sensitivity composition of the present invention can be applicable to photosensitive lithographic plate, simple and easy correction printing and makes with photoresist with the colour filter of copper etching resist, flat-panel monitor manufacturing usefulness with resist, LSI with proof, distributing board and heliogravure etc.

Claims (18)

1. a positive light sensitivity composition is characterized in that, contains to have the polymer substance of at least 1 carboxyl in (A) molecule and (B) absorb the infrared ray of image exposure light source and be transformed into the photo-thermal conversion material of heat.

2. positive light sensitivity composition as claimed in claim 1, it is characterized in that described polymer substance (A) is to be selected from the polymkeric substance that obtained by the unsaturated compound with at least 1 carboxyl and/or acid anhydride (a1) and by at least a kind of macromolecular compound in the described unsaturated compound (a1) and the multipolymer that can obtain with the compound (a2) of this unsaturated compound copolymerization.

3. positive light sensitivity composition as claimed in claim 2 is characterized in that, described unsaturated compound (a1) is at least a kind of compound that is selected from maleic acid, (methyl) acrylic acid and their derivant.

4. as each the described positive light sensitivity composition among the claim 1-3, it is characterized in that described polymer substance (A) is at least a kind of polymkeric substance that is selected from maleic acid polymkeric substance, (methyl) acrylate copolymer, styrene/maleic acid based copolymer and the derivant thereof.

5. positive light sensitivity composition as claimed in claim 4 is characterized in that, described polymer substance (A) is to make compound with hydroxyl and the reaction of phenylethylene/maleic anhydride based copolymer and styrene/maleic acid based copolymer of obtaining.

6. as each the described positive light sensitivity composition among the claim 1-5, it is characterized in that described polymer substance (A) is the multipolymer shown in the following general formula (1),

In the formula (1), R ¹And R ²Represent hydrogen atom or replacement or unsubstituted alkyl respectively independently, a is the integer of 1-3, and b is the integer of 6-8.

7. as claim 5 or 6 described positive light sensitivity compositions, it is characterized in that described compound with hydroxyl is an alcohol.

8. as each the described positive light sensitivity composition among the claim 1-7, it is characterized in that said composition also contains (C) resistance solvent.

9. positive light sensitivity composition as claimed in claim 8 is characterized in that, described resistance solvent (C) is the compound shown in the following chemical formula (2).

10. as each the described positive light sensitivity composition among the claim 1-9, it is characterized in that described photo-thermal conversion material (B) is the compound shown in the following general formula (3),

In the formula (3), R ³-R ⁸Represent the alkyl of hydrogen atom, carbon number 1-3 or the alkoxy of carbon number 1-3 respectively independently, X represents halogen atom, ClO ₄, BF ₄, right-CH ₃C ₆H ₄SO ₃Or PF ₆

11. each the described positive light sensitivity composition as among the claim 1-9 is characterized in that, described photo-thermal conversion material (B) is the compound shown in the following general formula (4),

In the formula (4), R ⁹-R ¹²Represent independently respectively hydrogen atom, methoxyl ,-N (CH ₃) ₂Or-N (C ₂H ₅) ₂, Y represents C ₄H ₉-B (C ₆H ₅) ₃, right-CH ₃C ₆H ₄SO ₃Or CF ₃SO ₃

12. each the described positive light sensitivity composition as among the claim 1-11 is characterized in that said composition also contains (D) light acid propellant.

13. positive light sensitivity composition as claimed in claim 12 is characterized in that, described light acid propellant (D) is the compound shown in the following formula (5).

14. as each the described positive light sensitivity composition among the claim 1-13, it is characterized in that said composition also contains at least a kind of resin (E) that is selected from the following resin: (1) vinyl pyrrolidone/vinyl acetate co-polymer, (2) vinyl pyrrolidone/dimethylaminoethyl methacrylate multipolymer, (3) vinyl pyrrolidone/caprolactam/dimethylaminoethyl methacrylate multipolymer, (4) polyvinyl acetate (PVA), (5) polyvinyl butyral, (6) polyvinyl formal, (7) terpene phenolic resin, (8) alkyl phenol resin, (9) melamine/formaldehyde resin, (10) ketone resin.

15. each the described positive light sensitivity composition as among the claim 1-14 is characterized in that, said composition also contains (F) triarylmethane based dye.

16. a photofabrication manufacture method is characterized in that, uses each the described positive light sensitivity composition among the claim 1-15.

17. photofabrication manufacture method as claimed in claim 16 is characterized in that, it is applicable to the manufacturing of the associated components etc. of galley, electronic unit, exact instrument parts and false proof usefulness.

18. a method for platemaking is characterized in that, uses each the described positive light sensitivity composition among the claim 1-15.

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