JPH02502312A - Image reversible dry film photoresist - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Image reversible dry film photoresist Background of the invention The present invention relates to the photoresist system Kfl@L, and more particularly to the post-imaging processing steps used. Dry film sensitivity that can be used to produce both positive and negative images depending on the Regarding photoresist.

Photoresist systems that produce positive resist images and photoresist systems that produce negative resist images. Resist systems are well known in the art. However, these two systems have the composition and generally very different in behavior. In other words, the positive resist system In general, base-soluble polymers such as novolac resins and benzonoid structures are located adjacent to each other. and a photosensitizer containing a diazo group and a keto group. of this composition to the chemoradial rim. Exposure converts the diazo-keto form of the photosensitizer into a carboxylic group to expose the exposed composition. It takes a lot of inspection to make it soluble in the Lucari developer. In contrast, negative resist systems are Polymers and chemical radiation in general! ! Photosensitization that initiates cross-linking of the polymer upon exposure consisting of a combination with an agent. The exposed image thereby becomes insoluble in the developer solvent; Then, by dissolving and removing the unexposed parts of this resist system, the original state is restored. It will be done.

More recently, photoresists have been developed that can be processed in negative as well as positive formats. A strike system has been announced. For example, in U.S. Pat. No. 4,007,047 to Kablan et al. is an alkali-compatible resin and a diazo-ketone sensitizer (usually used in positive mode). A method for producing negative images using the system based on 5 is described. Such a system Imagewise exposure of a layer of this composition to actinic radiation to produce a negative resist image using The diazo-keto photosensitizer is converted into an alkali-soluble carboxylic acid, and the Fujide image is heated to a hot temperature. This treatment clearly decarboxylates the alkali-soluble form of the photosensitizer. alkali-insoluble ff1K conversion by silation) and then treated in this manner. The layer is exposed to light to remove the photosensitizer from the previously unexposed areas of the layer. Convert it to r1km. This negative image is then developed using an alkaline developer. . This alkaline developer is applied to the part of the photosensitive layer where Kjl was not released at the beginning (this part (now alkali-labile) is removed by treatment.

A variation of the above method is disclosed in U.S. Pat. No. 4,581.321 to Stahlhoen. described in which the material in the exposed image is aluminized by post-exposure baking of the image. It becomes insoluble in the potash developer and then the previously unexposed parts of the photosensitive layer As mentioned above, the radiation edge is exposed to light, and the negative image is produced using an alkaline developer. Developed. Compositions in which hexamethylol melamine ether is used in this method It is contained in the machine, and the machine string is made of 8 as a bonding agent for the positive polymer resin of the braid. ! It is said that he is capable of Noh.

This cross-linking occurs during subsequent exposure, resulting in the release of light in the parts of the photosensitive layer exposed to actinic radiation. It is said that it is catalyzed by the IIK produced.

Chiong et al. IBM Techsic@l Diacloasra Bsl- Jstjs 27/l61j (June 1984) as a modification of the above method. Reports on how to avoid light. Image exposure is done using deep ultraviolet light, and then Immediately after the post-baking process, deep exposure using near ultraviolet light is carried out.

Spark et al 5aventh I%national Tea 5sfca JCasfarmsga as P*1yva, ars (New York, USA) Ellenville) lθ, 1985, pages 247-269, diazide photosensitizer and novolat A typical reversible system based on black resin (this system is commercially available under the name j2R5214) This paper describes the nature of the available materials and the theory behind their operation. Ne Spark et al.'s description of how to use this system in the negative image format The previous example does not specifically mention the need for a second dew point in the development @. This corresponds to that shown in US Pat. No. 1,321.

US patent application 11! Parent No. 67,732 (June 26, 1987) Treatment of unexposed areas of the system before image development in negative formats. Improvements that do not require the original A reversible photoresist system has been described. This result shows that the chemical radiation edge exposure 1 One or more organic solubilizers that make the entire iJK composition soluble in an alkaline developer. This is accomplished primarily by including sufficient amounts of the agent in the composition.

U.S. Pat. No. 4,093,464 to Lutzker et al. Watery and alkali-soluble phenolic resin and ortho-naphthoquinone diazide photosensitive Dry film photoresist using a mixture of agent and acrylic resin as a photosensitive layer are listed.

The present invention provides a dry film photoresist that can be used in both positive and negative image formats. It offers a wide range of benefits.

contract of invention One object of the present invention is to provide an image reversible photoresist system in the form of a dry film. There is a particular thing.

Another object of the invention is to require scratch exposure of unexposed portions of the system prior to viewing the negative style image. It is an object of the present invention to provide a photoresist system with image reversal properties of film that does not have the disadvantages of etiquette.

These objectives 8 and other objectives that become clear from the following description of T3A are the objectives of the present invention. M, achieved by things and methods.

That is, in one embodiment, the present invention provides a removable photosensitive image reversible photoresist. A dry film photoresist supported on a wearable backing sheet is provided. It is. Compositions that can be used to make this film are well known in the art (representative). The most common examples are the above-mentioned photosensitive compositions. It can be anything. That is, these compositions generally include at least one phenolic resin, l,2-quinonediazide sensitizer, and optionally organic solubilizer (phenolic group and/or carbon rR group) (including). Solubilizer (if used, in alkaline developer) Sufficient volume is used to promote dissolution of the composition. Dry film photo of the present invention The resist is also a light-sensitive image reversal photoresist composition that is otherwise exposed to light in the film. Includes a removable cover sheet that extends completely over all exposed surfaces. It's okay.

The present invention also provides positive or also relates to a method of producing any negative resist image. That is, 5 of the present invention Layer the dry film resist onto the substrate and apply this photo lettuce 1-chemical brain g! ! Dew Light the backing sheet from this photoresist, and then remove the exposed photoresist. Produce a positive resist image by dissolving the light area in an alkaline developer . The negative resist image is produced by laminating the dry film resist of the present invention on a substrate. The photoresist is imagewise exposed to actinic radiation in a piltt manner; temperature and time sufficient to render the 1stt portion of the stock insoluble in the alkaline developer. It is produced by heating. This negative image is then optionally exposed to chemical radiation Wi K After the cover exposure, the photoresist is dissolved in an alkaline developer. Develop with K. initially present on the dry film photoresist of the present invention. The backing sheet can be removed either before or after the heating process .

The term "image reversible photoresist composition" refers to either positive or negative image formats. means a photosensitive composition that can be used in

The dry film photoresists of this invention can be used to form resist images on a variety of substrates for a wide range of applications. It can be used to make. In other words, this resist uses a metal substrate analogy. It can be produced on zinc, aluminum, copper, etc. to make lithographic printing plates. or etch in gravure and/or photoengraving techniques. Can be used as a resist. These images are used in the production of printed circuit boards. In the manufacturing of semiconductors, reinforced epoxy resins, such as silicone Can be produced on non-metallic substrates.

detailed description of the invention Must be applied to the substrate as a liquid nuclide and then dried by solvent removal In contrast to the use of liquid photoresist systems, the use of dry film photoresists Chinese cabbage technology is characterized by well-known multi-recognized benefits. Avoidance of solvent removal is This is of course the main advantage. Another advantage is that liquid photoresists can be used to In contrast to the much larger thickness of photoresist films that can be used with It's there. This is, for example, one flea per l# in the production of printed circuit boards. . The large thickness of the resist image allows for the fabrication of circuits without any lateral length between the resist walls. This is because it allows the accumulation of large thicknesses such as electroless and tS copper. similarly , dry film resist in the manufacture of printed circuit boards with through holes. The use of resist allows the resist to be used to overlay holes, thereby The integrity of the through-holes in the copper plate during copper etching is ensured by the resist. It has the advantage of being kept away from unprotected areas of the circuit board. In contrast to this Generally, liquid photoresist cannot be used to cover through-holes. . In addition, the through hole became 7 latched while applying liquid resist. If so, subsequent removal of the resist from the 5 holes may pose a problem. 5ru.

The use of dry film resist means that the film of resist that is compatible with the substrate is substantially (Also ensures uniform thickness. In contrast, liquid photoresist is coated with applying it to the substrate and then removing the solvent will result in a film that does not have a uniform thickness. There may be variations in the thickness of images produced from the film.

The dry film photoresist of the present invention is manufactured using techniques well known in the Chinese cabbage art. It will be done. Its novel feature is the light-sensitive photoresist used to manufacture this film. The problem lies in the image reversibility of the composition. That is, for example, the dry film photoresist of the present invention The resist is produced by depositing a film of a photoresist composition on a backing sheet. Manufactured by The backing sheet is made of non-photoresist or photoresist on the edge of the film. Manufactured from materials that do not permanently bond with the composition. The most commonly used backing sheet Polyethylene terephthalate) (commercially available under the trade name MYLAR) Although other polyesters and the like can be used if desired.

Advantageously, the backing sheet has a thickness of about 2 to 10 mils and is sufficiently flexible. Suitable moment when producing photoresist images using the dry film of the present invention It can be easily removed from the photoresist film by peeling it off with a be.

The photosensitive photoresist composition is applied to the tiling sheet using a device such as a drawing rod. using conventional nuclide techniques such as roller coating, which allows for uniform thickness coatings. can be done. As discussed in more detail below, the photoresist composition is It is prepared by keeping the solvent content at the minimum value necessary for overturning to occur without difficulty. is advantageous.

When the coating operation is completed, a layer of photosensitive composition is deposited on the backing sheet. and remove the solvent in any conventional manner. Generally speaking, this process involves M acid below the temperature that results in the decomposition of the photosensitizer present (described in more detail below). This is achieved by heating the substrate to a temperature of Temperature of about 90-110℃ temperature is usually satisfactory and vacuum can be used to facilitate solvent removal if desired. You can also The actual photosensitive layer preferably produced as described above Thickness will vary depending on the final application to which the dry film photoresist is placed. one Generally, the thickness of the photoresist layer is on the order of about 0.05 to 2 mils; The thickness is not critical; larger or smaller thicknesses may be used in specific cases. I can do it.

Any of the dry film photoresists of the present invention! # sign, do as above The exposed side of the photoresist film produced on the backing sheet is a protective film. Contamination of the film during storage or handling prior to use of the dried film in sheets of can be prevented. The sheet of protective film creates a permanent bond with the photoresist material. materials such as polyolefins (examples include polyethylene and polypropylene) Manufactured from such materials as Ren). Such sheets are made using the techniques described below. Resist image raw JliEK dry film surface of photoresist material before using It can be peeled off from. The thickness of the protective cover sheet is advantageously about 2 to 10 mils. However, the actual thickness is not critical, and thicker or thinner ones may also be desired. Mule can be used.

As mentioned above, the novel features of the uninvented dry film photoresist are related to its manufacture. It depends on the nature of the photoresist composition used. That is, this photoresist composition The dried film produced from it is used in either positive or negative format. In other words, it has image reversal properties. As mentioned above, we are familiar with Chinese cabbage technology. Any of the image reversible photoresist compositions described can be used.

What is listed in U.S. National Register No. 4,581,321, the above-mentioned report by Chiong et al. and those described in the aforementioned paper by Spark et al. This is an example table. In a preferred embodiment, a dry film photoresist) is used. Photosensitive compositions are those described in the aforementioned U.S. FF 149 Application No. 67,732. It is a product. These compositions require covering and exposing unexposed areas before development. Because they don't.

In its broadest aspect, the dry film resists of the present invention are The photosensitive image reversible photoresist composition includes a phenolic resin, l,2-quinone diazide, a photosensitizer, and at least 12 as optional ingredients! of organic solubilizers. " ``Organic solubilizing agent'' refers to an organic solubilizing agent that is not exposed to chemical radiation, but is All components of the photosensitive composition, when present in the receiving area, are soluble in an alkaline developer. The passage of organic compounds and/or two or more such compounds into a tube Lazy things. The solubilizer used is miscible with the other components of the composition, i.e. The former does not chemically react with the latter, or the former does not react with the latter in an alkaline developer without exposing it to light. Other than making it soluble, it does not interfere with the desired manipulation of the photosensitive composition. Solubilizer misfires The degree to which the bright composition is made alkali-soluble is determined by However, after undergoing post-image baking, a reasonable length of time, i.e. up to about 5 minutes for compositions with an average thickness of up to about 50 microns. Preferably, the time is 1 to 2 minutes, which is considered appropriate if it is completely soluble. It will be done.

Examples of such organic solubilizers include phenolic groups and/or Mataha carbon fIRi It is a compound containing v. Such compounds contain at least L in the C6) benzonoid ring. preferably 2 or more 7-enolic groups, (&) at least 1 preferably 2@ or more carboxylic acid groups or (1) at least one phenolic group in the molecule and at least one carboxylic acid group. This kind of transformation Examples of compounds include phenolic compounds such as 7-, di-, and tri-hydroxybenzenes. Zophenone, resorcinol, 1,3.4-xylenol, hydroquinone, Catechol, pyrogallol, phloroglysitur, poly! −-like phenolic resin [ For example, poly(vinylphenol)], orcinol, 1,2,4-benzene Liol, 4-methylcathyl, 2-methylresorcinol% 212Z4. 4'-tetrahydroxybenzophenone, pic I) 7flk, coniferylal Cole, etc.; Weak carboxylic acids such as avidinic acid, cinnamic acid, 9-anthrone acid, 3-methyladipic acid, pimelic acid, 1-methyl-1-cyclohexanecal Contains both carboxylic acid groups and phenolic groups, such as linoleic acid and linoleic acid. Compounds such as salicylic acid, protocatetheenoic acid, hydroxybenzoic acid, Nilin 11, p-hydroxybenzoic acid, 2-hydroxy=3-su7tonic acid, Gallic acid, 3-hydroxy-4-methoxycinnamic acid, 4-hydroxy-3-methoxycinnamic acid Toxicinnamic acid, 3-hydroxy-4-methoxymandel, 4-hydroxy -3-methoxymandelic acid, homovanillic acid, hydroxymandelic acid, etc. It is.

A preferred compound for use in the compositions of the invention is poly(vinylphenol) , polyhydroxybenzophenone, vinyl acetate/crotonic acid copolymer, and It is a mixture of over 221 such compounds.

As mentioned above, the compounds used alone or in a mixture of 2181 or more in the compositions of the present invention The organic solubilizer used in films up to approximately 50 microns thick The entire composition without chemical radiation exposure is processed using a conventional alkaline developer such as hydroxide. Aqueous solution of sodium or iced potassium, sodium meta-silicate, ortho- Sodium phosphate, hydrogen/aI! complete in a reasonable length of time to sodium etc. It should at least be soluble in water.

Determine the desired solubilization rate of the composition! The details of the organic solubilizer required for L are , in a given case, in a particular manner 9, i.e. from the composition. It depends primarily on whether the dry film used is used with positive or negative images. Ru. That is, in the positive mode mechanism, as described in more detail below, Both the exposed image and the unexposed photoresist composition were subjected to aqueous alkaline development 4a to different extents. It is soluble in In order to develop the image 'It under these conditions, it is necessary to The rate of image dissolution is significantly greater than the rate of dissolution of unexposed material in the same developer. There is a clear need to do so. This speed difference is generally due to the development constellation. loss of film in the area that remains after the highly soluble area has been completely removed. 4b can be measured in any case by simply determining the % of Ru.

For compositions intended for use as positive modality dry film resists, Development contrast advantageously remains in the unexposed areas when the exposed areas are completely removed. The percentage of film thickness can be approximately 50% of the original thickness. . Preferably, the thickness of the film remaining in the unexposed areas is about 70% of the original thickness. It is. present in the above composition to achieve a 3JL contrast in the above range. The concentration of organic solubilizer used will naturally depend to some extent on the particular solubilizer used. Varies, but always a trial and error method can be easily established by law. Generally used in compositions such as The total amount of solubilizer is about 1 to 1 of the phenolic resin present in the composition. It is about 20%.

When the composition is used in a negative mode dry film resist, the development contrast The requirement that the As stated, the exposed image is rendered substantially insoluble in alkaline developers. Therefore , in this format KM, the organic solubilizer group is group 1. A normal aperture is placed in the non-exposed area 2 of *. A film of about 1.25 to 50 microns within a reasonable time Advantageously, the thickness is completely dissolved within a time period of about 600 to about 5 minutes, preferably about 1 minute. It only needs to be sufficient to cause necessary to achieve such solubility. The concentration of the above solubilizing agent required in any case is easily determined by trial and error. can be done. In general, the amount of solubilizer (when using two or more types of solubilizers) based on the weight of the phenolic resin present in the total composition. It is about 2 to 20% by weight.

Any of the phenolic fats commonly used in positive photoresist compositions. Can be used in compositions used to make dry film resists of the invention. Ru.

Such resins are generally formaldehyde and phenol or alkyl/1/Ii With converted phenols, e.g. iosof j'5-5alic Rem1ss (written by Kutsutubu et al.; US News Conditions set out in Chapter 4 of Spring in York County, published in 1996. It is produced by the following auto-combination. Particularly preferred for use in the compositions of the invention The types of resins are 1-cresol alone, 2-cresol, 2-cresol, and 2-cresol. (S-cresol is the main component; i.e. S-cresol or 50'j I! fJ (preferably present in an amount of at least 90% by weight) It is a novolac resin. Advantageously, the resin used is one of the preferred resins mentioned above. Average molecular weight in the range of about 600 to about 16,000, preferably about 800 to F+1500 have quantity.

1 and 2 used in the composition used in the production of the dry film resist of the present invention - Quinonediazide photosensitizers are commonly used in positive photoresist compositions utilized in the art. It is any one that is used. Such photosensitizers are 7-toquinone (1,2) -diazide-(21-4-sulfonic acid and 7-toquinone-(1,2)-diazide) Consists of esters and amides of do-(2)-5-sulfonic acid. The ester is one In general, polyhydric phenols such as 2,3°4-)IJ hydroxybenzo Phenone% 2.4-dihydroxybenzophenone, 4-decanoyl-resorsi alcohol, 4,4-bis(4-hydroxy)valeric acid butyl ester, etc. It is an ester derived from a mixture of these. The above two types used in the composition Amides of acids are those derived from long chain aliphatic-class amines or aromatic-class amines. It is de.

This compound used in the composition used to make the dry film resist of the present invention. The proportion of the photosensitizer is advantageously such that the Mt of all components of the group M, aikJ other than the solvent is monotonically set. The content is about 2 to 20% by weight, preferably about 1132 to 20% by weight.

The fraction of iIt error to use in a given case can be easily determined by trial and error. can do.

Similarly, the proportion of phenolic resin used in the above compositions is advantageously adjusted to About 2 to 20% by weight based on tt of all components of the composition, preferably about 2 to 20% Weight%.

The compositions generally also include a solvent or solvent mixture.

The solvent to be used is generally selected in consideration of the compatibility of the photoresist. present invention Examples of solvents used alone or in mixtures in the composition of Ruethyl ketone, methyl isopropyl ketone, diethyl ketone, etc.: Chlorinated carbonization Hydrogen such as trichlorethylene, 1, 1. , 1- Trichloroethane D: Aliphatic alcohol tatoeha ethanol, tai-probyl alcohol, ren-buchi alcohol, deaf-hexyl alcohol; Hft aliphatic ester, e.g. -Butyl acetate, gastric -hexyl acetate, seronulp acetate: Recall ace-f such as ethylene glycol monomethyl ether, propylene Glycol monomethyl ether and its esters such as acetate, propylene onates etc.: and aromatic hydrocarbons such as toluene, xylene etc. . Preferred solvents are aliphatic alcohols, aliphatic esters, glycol ether esters. 2a or more mixtures of solvents, aromatic hydrocarbons, and such solvents. solvent Advantageously, the amount of [The amount is limited to just that needed to be applied to the support sheet. In general, The weight of the medium ranges from about 35% to 85% by weight, based on the weight of the total composition.

The above compositions may contain conventional techniques such as star-forming agents, surfactants, adhesion promoters, finely divided pigments, etc. It may also contain other optional ingredients commonly used in. In certain embodiments, the composition is one or more cross-linking agents such as hexamethylol melamine alkyl ether, 2,6-bis(hydroxymethyl)-4-methylphenol, resol, epoxy Also includes resins. Such cross-linking agents may be used in combinations other than solvents present in the composition. At a concentration of about 0.5 to 20%, preferably about 1 to 1%, based on the weight of the component *K It can be used at a concentration of 0.03% by weight. The optimal concentration to use in a given case The degree can be easily determined by trial and error methods.

As previously mentioned, the dry film resist of the present invention can be used as either a positive or negative image. i.e. depending on the specific application employed in the production of photoresist images. ``'C shows reversibility.The first step in the generation of greatness is whether it is positive, negative, or K. Instead, IIj, dried film resin is applied to the substrate on which the photoresist is to be produced. Including laminating the resist. The surface of the substrate is generally cleaned using conventional methods. processed and preprocessed. The method used varies depending on the nature of the 2TiIJR used. Become. Lamination is a commonly used technique for applying dry film resist to a substrate. This is accomplished using methods and equipment that As an example, we attached a black sheet (cover If a sheet is used, remove the dry film resist. jl light surface '4! : applied to the substrate in contact with the substrate and using heat and pressure. Lamination is performed using Lamination is generally performed using any suitable equipment available in the art. Do it using An example of such a device is the one in Wilmington, Plateau, USA. DuPont HRL Lami available from Pont's Liston Products Division It's Neta. The temperature used for lamination is the temperature at which the gjt agent in the resist begins to decompose. temperature, preferably about 100-135°C. The pressure used for lamination is advantageous is approximately 5 to 20 psi. Dry film resist is applied to the substrate if desired. It can be applied to only one side, but for certain applications such as printed circuit board fabrication. In the process, resist is often applied to both sides of a substrate simultaneously or sequentially.

Laminated dry film resist and substrate with resist backing sheet still Then, imagewise exposure to the activating radiation edge is performed. Carry out this process One common means of obtaining either positive or negative images is through a photo exposure of the photoresist to actinic radiation, such as ultraviolet radiation. positive image To create the resist image, the backing material is then peeled off and the resist image is created using techniques such as immersion or tin spraying. Develop by exposure to the action of an alkaline developer using a technique. a The alkaline developer dissolves the exposed portions of the photoresist. used in the art Any alkaline developer can be used for this purpose. This kind of current situation Examples of image agents are sodium hydroxide or potassium hydroxide in water, sodium meta-silicate. sodium orthophosphate, sodium hydrogen phosphate, etc.

To make a negative image, K optionally leaves the backing sheet still on after the above exposure step. [While still in place, the photoresist is subjected to post-exposure baking. This is the photoresist heating at a temperature and time sufficient to render the exposed areas insoluble in the alkaline developer. It is done by.

The temperature required to achieve this is generally in the range of about 115-140°C, and is preferably Preferably, the temperature is within the range of about 120 to 135°C. This temperature is applied to the unexposed parts of the photosensitive layer. Preferably, the choice is made to avoid significant decomposition of the photosensitizer present. desired result That is, the time required to achieve insolubilization of the exposed image depends on the particular composition used and varies depending on the temperature and heating mode used. Generally, the time required for scraping is about 5 to 6 during open hours. The heating time is 0 minutes, and it takes about 1 to 3 minutes when using a hot plate. Optimal time is trial l&i error can be easily determined by law.

Kg=ft of photolayer during exposure and subsequent post-exposure baking.

It is believed that the process that occurs in the part is as follows. Exposure of M&light agent to actinic radiation edge Light causes the conversion of the diazoketo functional group of the photosensitizer into an indene carbon group. It is believed that the

During the post-exposure firing period, the indenecarboxylic acid produced in that case is heated as described above. The lupine dispersion group acts as a catalyst for the cross-linking of the novolak resin in the exposed image area of the photosensitive layer. You can trust that it will work. This cross-linking is due to the photosensitive nature of the dry film resist of the present invention. This is facilitated by the presence of a cross-linking agent in the composition. The unexposed parts of the photosensitive layer are Does not undergo differential coupling. During the imagewise exposure to the actinic radiation edge of the photosensitive layer, the unexposed areas are This is because carboxylic acid is not produced under such conditions.

Therefore, in the latter preferred embodiment, when a solubilizing agent is present in the composition, the photosensitive The unexposed parts of the transparent layer remain soluble in the alkaline developer, whereas the exposed parts The components become insoluble upon exposure and subsequent post-exposure calcination. Therefore, in this particular aspect For negative images, the unexposed areas of the photosensitive layer are processed using an alkaline developer as described above. The IEL is prepared by melting.

The photosensitive composition of the dry film resist of the present invention contains a solubilizer as described above. If not, or the weight of the solubilizer makes the non-I1 element easily soluble in the alkaline developer. If this is insufficient, the photosensitive layer is subjected to a 20th exposure to actinic radiation. The previously unexposed areas of the photoresist are made soluble in an alkaline developer. the Later the negative image was developed using an alkaline developer and made soluble by wax exposure. Unnecessary parts of the resist are removed.

For the production of negative images, exposure of the photoresist to actinic radiation through a photomask The process is the so-called direct manufacturing method of statues! Can be replaced. This direct manufacturing method The photoresist can optionally be exposed to ultraviolet rays while the irradiation sheet is still in place. diazo sensitizers as mentioned above to indenecarboxylic acid. A simple 7-land exposure is carried out long enough to cause a complete conversion. The required image pattern is The child beam is used to trace the heat generated by the beam. Cross-linking of the resist occurs in the areas to be raced. The negative image is a Sections of the resist that were developed using a caustic developer and were not exposed to the electron beam. area is dissolved. In another direct method of generating a negative image pattern, the negative image pattern The traces are traced directly into the resist layer using a thermal laser. thermal laser is Local heating and cross-linking of the initial 7 to perform the generation of indene carbo 7ai2 Achieved in a single process without the need for land light.

The following examples illustrate the uninvented dry film resist and its uses. and represents the best mode (to the knowledge of the invention) of carrying out the invention; It should not be construed as limiting the invention.

lol example 1゜ These nine practical examples describe the method for producing dry film photoresists according to the present invention and the method for producing a negative film. This is for specifically explaining the method of using the photoresist for producing a photoresist image. It is.

Photoresist) M acid is produced by mixing the following components in the following proportions. Ta.

Novolac resin (1j20.1 Photosensitizer (3) 6・O Tricresyl phosphate 4.4 Vinyl acetate/crotonic acid copoly-=r-4,2100,0 (1) Acid-catalyzed formaldehyde-Cresol-2-Cresol tin compound; average molecular weight = 1000 (2) Maruzen street oil; average molecular weight = sooo; Maruzen Oil (3) Naphthoquinone-(1,2)-diazide-(21-4-sulfonic acid and trihydric acid) Esters with droxybenzophenone (417/90n MFP-F: Synthron Incorporated; Wet/Flat lubricant (5) Mew41itk (:’t, 5: American Hoechst corporation A portion of the above composition was applied without pretreatment to electrical grade MYLAR [New Chassis, USA]. Cadillac Plastics and Chemical Company, Linden, State] A 1 mil thick sheet (6 inches x 6 inches) was coated. Make sure the thickness of the coating - Adjusted using the stretching rod of the film applicator. Hot air gas that produces nuclides The film was dried in a vacuum chamber to leave a film of photoresist of a substantially uniform thickness of 1 mil.

The dried film resist thus obtained is then pre-cleaned chemically. Copper clad reinforced epoxy resin matrix (6" x 6") K laminate.

This S [layer is DuPont ERL laminator (Dupont Noristone Tivision) ) using a logging temperature of 110 °C, a feed rate of 0, 5 wh 7 min and l 5 It was carried out at a pressure of paj.

Cool the ginger laminate to room temperature and place the MYLAR-backed sheet in one layer. The photoresist of Carrying Company Limited] is used to create a wide range of Rikko style (150 Image exposure was carried out on the outside of the s// side 2). After exposure, the plate to be laminated was heated to 125℃ for 25 minutes. commercially available aqueous alkaline developer (U.S., Connecticut, USA). McDermitt Incorporated of Waterbury Mp62A) in approx. It was immersed for 30 seconds. After washing this seed plate with water and drying it, the resulting negative image will be separated into sections. What's wrong with you! 5! It was noticed.

Example 2゜ This example describes a method for producing dry film photoresist using unexploded BAK and a positive Also for specifically explaining the method of using the photoresist for producing resist images. It is.

Using the same photoresist set Jii and method as described in Example IK [drying] A film photoresist was produced.

This dry film resist was prepared using the same method and equipment as described in Example 1. Copper-clad reinforced epoxy 1fIi fat matrix (6 in. x 6 inches) K laminated. Cool the resulting laminate to room temperature and apply the MYLAR backing. The photoresist layer with the sheet in place can be exposed to a wide range using an ORC exposure unit. Image exposure was carried out on the outer edge of the prefecture with a band exposure pattern (approximately 1000 s//i). Covered after exposure The image on the plate was prepared using a commercially available aqueous developer [JF/62: McDermit]. By immersing it in a 70% by volume bath solution of Developed. The generated plate was washed with water and dried. The positive comrades seen in this way are divided into sections. It was observed that it was bright.

Example 3゜ This example describes a method for producing iE dried film photoresist using unexploded BA and To specifically clarify the method of using the photoresist for producing a photoresist image It is something.

A photoresist composition is prepared by mixing the chain components listed below in the proportions listed below. Ta.

Part by weight Novolac ItMli” 3.6 poly(vinylphenol) (” 20.5 photosensitizer (312,6 Acrylic copolyff-(19 Vinyl acetate/crotonic acid copolymer +51 s, s Abietin Shun 2.1 Trihydroxybenzo 7e/7 3.1 Sudan Blue 0.4 (1) Acid catalyst Formaldehyde-2-cresol anchor compound: average molecular weight = lO00 (21 Same as Example 1.

(3) Same as Example 1.

(4) Same as Example 1.

(5) Same as Example 1.

Using the photoresist composition thus produced, the same method as that used in Example 1 was used. Using the same method and equipment, the dried film was deposited on the MYLAR:y illumination sheet. - Manufactured a photoresist. This dry film resist was described in Example 1. Using a method and equipment, a pre-chemical Kfi-cleaned copper clad reinforced epoxy resin base ! (6 inches x 6 inches) K laminated. The resulting laminate was cooled to room temperature and MYLA The photoresist layer with the R-shaped sheet still in place was as described in Example 1. Images were exposed in the ultraviolet range under the same conditions as . After exposure, the laminate was baked at 125°C for 25 minutes. and commercially available alkaline developer [D89: McDermitt I It was immersed for about 5 minutes in a 25 vol. This laminate is washed with water. Washed and dried. It has been found that the generated negative image has distinct sections. .

Implementation example 4゜ This example describes a process for making an IK, dry film photoresist according to the present invention and A method of using the photoresist for producing a negative resist image will be explained in detail. It is for.

A photoresist composition is manufactured by mixing the following string components in the following proportions. Ta.

Components Parts by weight Novolac resin (″ 15.7 Poly(vinylphenyl)” 3- 3 Photosensitizer i51 4.7 Tricresylphos 7e 11,4 acrylic copolymer ((trans)) 2.4 Vinyl acetate/crotonic acid copolymer” 10.1 Dipropylene Len glycol mether ether 5.0100.0 (1) LOL Same as example 1.

! 21 Same as Example 1.

(3) Same as FuM example 1.

(41 Same as Example 1.

(5) Same as Example 1.

Using the photoresist composition thus produced, the same method as that produced in Example 1 was used. * Using the same method and equipment, dry film powder was applied to YLAR film noodle sheet. Manufactured a tresist. Using the method and equipment described in Example 1, this dried filtrate was Copper clad reinforced epoxy mg+i substrate with pre-chemically cleaned Lum resist (6 inches x 6 inches) K’S layer, set and MYLAR backing sheet still The as-placed photoresist layer was exposed to ultraviolet fiK images. After exposure, this product The laminates were fired at 120° C. for 30 minutes and then the same set I as described in Example 1! t It was immersed in an alkaline bath. The laminate was washed with water and dried. generated negative image It was observed that the area was clearly divided. A method for producing a photoresist and using the photoresist for producing a positive resist image. This is to specifically explain the method used.

Made using the method and equipment described in Example 1, but with 5K as described in Example 4. A dry film photoresist was prepared using the prepared photoresist composition.

The resulting dry film resist was processed using the method described in Example 1 and y&wrinkle. , pre-chemically cleaned copper clad reinforced epoxy resin base negative (6" x 6" H) was used for well logging. This laminate is cooled and used in a wide range of applications using an ORC light unit. Ultraviolet ilK statue Fujimitsu in imperial contact formation style (approximately 1000 Ill // (3m”)) did. After exposure, this strong back plate was processed using a commercially available alkaline developer (D89: When immersed in an 8% by volume aqueous solution of Kudermit, Inc. for about 5 minutes, I'm sorry for the inconvenience. The wa board was then washed with water and dried. The generated positive image is It was observed that the image was clear.

This example describes a method for producing a dry film photoresist according to the present invention and a method for producing a positive photoresist. This is for specifically explaining the method of using the photoresist for producing a photoresist image. It is.

A photoresist composition is manufactured by mixing the following components in the following proportions. Ta.

Components Part by weight Novolac resin (1123,2 Photosensitizer (odor) 5.8 butylbenzyl 7 tala (sr) s, l acrylic copolymer ((trans)) 2.9 Vinegar Vinyl/LiE”)/lie!ff Polymer 153 4. a Suda/Blue 0.5100.0 note fil Same as Example 1.

(2) Same as Example 1.

(3) Santicizer 160 = Monsando Company (same as 41st implementation fvl) character.

(5) Same as Example 1.

Using the photoresist composition thus produced, a dry film according to the present invention is produced. - A photoresist was manufactured using the method and equipment described in Example IK. generated dry Example IK was described with the dried film resist MYLAR sheet attached. Using the method and apparatus, a pre-chemically cleaned copper clad reinforced epoxy resin base *(6 inches x 6 inches) K laminated. Cool this laminate and line it with MYLAR With the sheet still in place, use the 0RCz optical device to make a wide band connection. Imagewise exposure was carried out for 4 minutes to ultraviolet light in a deexposure mode (1000 ml 10N). exposure Afterwards, the laminate was washed with a commercially available alkaline developer (D89: MacDermid Inc.) in a 15% aqueous solution by volume. It was imaged by The laminate was finally washed and dried. The main statue is Ku-ga. The bulge was on the edge of the folds.

Example 7゜ This example describes a method for producing a dry film resist according to the present invention and a method for producing a negative resist. This is to specifically explain how to use the resist for producing a photo-image layer. .

A photoresist composition was prepared using the ingredients and proportions shown in Example 6. This group A dry film holder of the invention was prepared using the method and apparatus described in Example 1K. Manufactured a tresist. The dried film photoresist shown in Example 1K is A pre-cleaned copper clad reinforced epoxy resin matrix (6 inch x 6 inch] K laminated. The laminate is cooled and the MYLAR-backed sheet is Broadband connection using the ORCg optical unit while the light source is still in place An ultraviolet aK image was exposed in the jll light mode (approximately 300 s//wound 2). λYLΔ after exposure The R backing sheet was peeled off, and the coated plate was baked at 120° C. for 20 minutes.

This coated plate was cooled and a commercially available aqueous alkaline developer [MF62A Nima The sample was soaked for 30 minutes in "Kudermit Incorporated" for 30 minutes. This cover plate is Afterward, it was washed with water and dried. It was observed that the generated negative lines were clearly divided. It was done.

Repeat the method described in Example 7 to prepare a dry film photoresist according to the invention. A negative photoresist image layer Va was prepared using this method. However, next changes were made. Image exposure was carried out at approximately 150 w J/cx” for 36 seconds. The formation process was carried out at 120°C for 5 hours, followed by ultraviolet! l(approx. 14201-17/(is ) was used to conduct a 7-rad test. For development, use a commercially available developer [D8 9: Use McDermid Incorporated by diluting it with an equal volume of water. It was done by doing this. The image of the produced gas was clearly divided.

Example 9゜ Repeat the method described in Example 7 for a dry film photoresist according to the invention. and used to produce a negative photoresist image layer. However, next changes were made. Image exposure was carried out at approximately 150 m/7 cm for 36 seconds. The formation step was carried out at 120° C. for 5 minutes, and the development was carried out using a commercially available developer [D89: McDermid Incorporated] was used at full strength.

Example 10° Implementation of etiquette film photoresist according to the present invention with MYLARg stamping sheet Made using the same photoresist composition and the same method and equipment as described in Example IK. Ru. Add a cover sheet of l mil polyethylene film to the exposed side of the resist layer. The product is then stored until needed for use in the production of photoresist image layers. the At this point, the polyethylene cover sheet is peeled off from the photoresist layer and its vkK properties are The person who described the example IK with the photoresist layer and the klYLARk punching sheet placed. The method and equipment are used to deposit the substrate and produce the required photoresist image.

international search report ″″＠″′＠″′−−＾−−−−SF18B102676

Claims (26)

[Claims] 1. Film-removable backing sheet of photosensitive image reversible photoresist composition A dry film photoresist comprising: (a) a small amount of photoresist; at least one phenolic resin, (b) a 1,2-quinonediazide photosensitizer and ( c) Dry film photoresist characterized in that it comprises a cross-linking agent in a mixed state. Gist. 2. (c) at least one type containing a phenolic group and/or a carboxylic acid group It also includes an organic solubilizer, which solubilizer makes the composition soluble in an alkaline developer. A dry film photoresist according to claim 1, wherein the dry film photoresist is present in a sufficient amount. 3. A light-sensitive image-reversing photoresist composition is exposed without a film covering. Claim 1 also includes a removable cover sheet that extends substantially completely over the surface of the Dry film photoresist according to item 1. 4. Claim 2, wherein said component (c) comprises poly(vinylphenol). Dry film photoresist. 5. Claim 2, wherein said component (c) comprises a vinyl acetate/crotonic acid copolymer. Dry film photoresist as described in Section. 6. The component (a) is m-cresol or a combination of m-cresol and p-cresol. A drying film as claimed in claim 1 comprising a novolac resin derived from a mixture. Lum Photoresist. 7. The component (b) is naphthoquinone-(1,2)-diazo(2)-4-sulfone Acid or ester of naphthoquinone-(1,2)-diazo(2)-5-sulfonic acid 2. A dry film photoresist as claimed in claim 1, comprising a film or an amide. 8. Drying according to claim 7, wherein the ester is an ester of polyhydric phenol. Film photoresist. 9. Claim 8, wherein the polyhydric phenol is trihydroxybenzophenone. Dry film photoresist. 10. Claim 7, wherein said amide is derived from a primary amine or a secondary amine. Dry film photoresist as described. 11. The cross-linking agent is 2,6-bis(hydroxymethyl)-4-methylphenol. A dry film photoresist as claimed in claim 1, comprising: 12. Claim 1: The photosensitive image reversible photoresist composition also contains a plasticizer. Dry film photoresist as described. 13. Claim 12, wherein said plasticizer comprises tricresyl phosphate. Dry film photoresist. 14. Claims in which the removable backing sheet comprises a sheet of Mylar film The dry film photoresist according to item 1 above. 15. The removable cover sheet consists of a sheet of polyolefin film. A dry film photoresist according to claim 2. 16. The drying film according to claim 15, wherein the polyolefin is polyethylene. Lum Photoresist. 17. A film of a light-sensitive image-reversing photoresist composition is coated with a Mylar film. It is supported on a sheet and its exposed surface is covered with a sheet of polyolefin film. a dry film photoresist comprising: (a) m-cresol; or at least one derived from a mixture of m-cresol and p-cresol. Seed novolak resin, (b) naphthoquinone-(1,2)-diazo(2)-4- or an ester of -5-sulfonic acid, and (c) a cross-linking agent in admixture. A dry film photoresist characterized by comprising: 18. The component (b) is an ester of the acid and trihydroxybenzophenone. The dry film photoresist of claim 17. 19. The cross-linking agent is 2,6-bis(hydroxymethyl)-4-methylphenol. 18. The dry film photoresist of claim 17 comprising a film. 20. At least one organic group containing a phenolic group and/or a carboxylic acid group and a solubilizing agent, the solubilizing agent being sufficient to render the composition soluble in an alkaline developer. 18. The dry film photoresist of claim 17, wherein the dry film photoresist is present in an amount of 21. The solubilizer is poly(vinylphenol), vinyl acetate/crotonic acid copolymer, mer, polyhydroxybenzophenone, and mixtures thereof. Dry film photoresist according to claim 20. 22. Claim 17: The photosensitive image reversible photoresist composition also includes a plasticizer. Dry film photoresist as described in Section. 23. Claim 22, wherein said plasticizer comprises tricresyl phosphate. Dry film photoresist. 24. A method for producing a negative resist image on a substrate, comprising the following steps: Chi, Laminating the dry film photoresist according to claim 1 on the substrate; The photoresist is imagewise exposed to actinic radiation; after exposure, the dry film is the photoresist to make the exposed portions of the photoresist insoluble in the alkaline developer. heat to a temperature sufficient for a sufficient time; blanket exposing the thus treated photoresist to actinic radiation; removing the backing sheet before or after the heating and/or blanket exposure step; and Then, the unnecessary portions of this photoresist are dissolved in an alkaline developer; A method characterized by consisting of various steps. 25. A method for producing a positive resist image on a substrate, comprising the following steps: Chi, Laminating the dry film photoresist according to claim 1 on the substrate; The photoresist is imagewise exposed to actinic radiation; The exposed areas of the photoresist are then dissolved in an alkaline developer. make it understand; A method characterized by consisting of various steps. 26. A method for producing a negative resist image on a substrate, comprising the following steps: Chi, Laminating the dry film photoresist according to claim 2 on the substrate; The photoresist is imagewise exposed to actinic radiation; after exposure, the dry film is the photoresist to make the exposed portions of the photoresist insoluble in the alkaline developer. heat to a temperature sufficient for a sufficient time; Remove the backing sheet before or after the heating process; and then remove the photoresist. Dissolve the unnecessary part in an alkaline developer; A method characterized by consisting of various steps.