TW573208B - Positive acting photoresist composition and imageable element - Google Patents

Description

573208 V. Description of the invention 1 Bright background 1 · Field of the invention The present invention relates to the field of imaging, particularly resist imaging, more specifically anti-corrosive imaging, and more particularly laser guided imaging. The present invention illustrates a new positive action anti-heat residue composition, a heat resistance structure, a heat resistance method, and a thermal erosion resistance system, as well as a novel synthetic procedure for forming a resist material. 2. Background of the Invention The effects of laser-directed imaging (LDI) have been known for a long time in the printing industry for the manufacture of lithographic printing boards and for the manufacture of printed circuit boards (PCBs). LDI provides better line quality, just-in-time processing, improved manufacturing yields, elimination of film costs, and other recognized benefits. In the direct imaging method, only a selected area of the heat-sensitive material is exposed by an appropriate energy effect focusing source, and the coating composition needs to be changed. See, for example, U.S. Patent No. 4,724,465 'U.S. Patent No. 5,641,608 (McDermid) and U.S. Patent No. 5,713,287 (Gelbert), the teachings of which are incorporated herein by reference. Thermal imaging elements are classified as compositions that undergo chemical transformation in response to exposure to and absorption of an appropriate amount of thermal energy. Thermally induced chemical transformation properties can erode the composition, or change the solubility of the composition in a particular developer, or change the surface adhesion, or change the hydrophilicity or hydrophobicity of the surface of the heat-sensitive layer. The selective exposure of a predetermined area of a thin film or thin layer formed by such a heat-sensitive composition to heat (such as image distribution thermal energy) has the ability to directly or indirectly produce a suitable imaging pattern of the composition, which can be used in PCB manufacturing as a resist Pattern, or used to make photolithographic printing plates. In a similar way to using photoresist, the heat-sensitive composition can be positive-acting. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). F Please read the precautions on the back before filling this page.)丨; r 4 573208 A7 ^ ___ B7_ 5. Description of the invention (2) or negative effect. Using a positive-acting heat-sensitive composition, the film is selectively exposed to an appropriately focused beam that produces the required thermal energy to (a) ablate the composition so exposed, in which case a predetermined pattern can be made directly, and the pattern is borrowed. Part of the remaining film that is exposed to focused heat and not etched is imaged; or (b) the exposed composition becomes more differentially soluble in a suitable solvent, in which case a latent image is mainly generated in the film. The latent image allows the film to dissolve in the heat-exposed area, and remains insoluble in the non-heat-exposed area and remains in it to obtain the desired pattern. Using a negative-acting heat-sensitive composition, the film is selectively exposed to an appropriately focused beam with the required thermal energy, causing the exposed area to become differentially less soluble in a suitable developer, so it is dissolved and removed when exposed to heat when exposed to the developer. Area, leaving the heat-exposed area as the desired pattern. Through the use of thermal imaging elements, the ability to produce patterns on the surface of a substrate by direct imaging without using optical tools has been greatly enhanced because the imaging beam only needs to be a focused source with the required thermal energy, such as from a low cost Lasers are made in a solid state, as opposed to a narrow-wavelength focused source of specific wavelengths required for direct photoresist imaging. Focused thermal energy sources such as infrared laser beams are more suitable for commercial scale operations than UV light in terms of cost, life, and reliability. UV light is required for direct imaging of a variety of photosensitive compositions. In addition, heat-sensitive compositions that undergo only thermally induced composition changes, rather than light-induced components or composition changes, are less complex than photosensitive compositions used for direct imaging processes. In this way, not only the heat-sensitive composition can be formulated in a cost-effective manner required for industrial applications such as PCB manufacturing, but its simpler operating mechanism can also be operated under indoor or daylight, and tends to obtain roughly better storage life. . This paper size applies Chinese National Standard (CNS) A4 Regulations (230X297). (Please read the precautions on the back before writing this page].! Order ----------- ♦ 573208 A7- -—-------_____— V. Description of the invention (3) The positive-acting photosensitive composition of resole novolac-azidoquinone resin is the main imaging material in the computer chip industry, (for example, see RR. Dammei, Γ "Azinaphthoquinone-based resists", teaching paper No. 丨 丨, SPIE Press, Burlingham, WA, 1993). Photosensitive A-step Panjun varnish-azide g-Kun resin composition is also widely used Used in the manufacture of printed boards. Photosensitized naphthoquinone derivatives (DNq) can be added to resole novolac resins (phenol-cresol novolac condensation polymers) to slow down the dissolution of the resin and expose the film (with light-induced decomposition of DNQ) Product) even faster than the pure resol novolac resin film. The molecular mechanism of resol novolac_DNq imaging materials was recently revealed (A. Reiser, Journal of Imaging Science and Technology, Vol. 42, No. 1, 1998 (January / February, pages 15-22) and teaching on resols and azides The basic feature of the imaging phenomenon of the composition is the observation of (resin) dissolution inhibition, which is based on the formation of phenolic strings through the interaction of a strong hydrogen acceptor (as a solubility inhibitor) with the OH groups of the resin. When exposed, the phenolic strings The thermal effect is the Wolff rearrangement reaction, which is cleaved by its anchors and then the azide portion of the photolysis inhibitor molecule. This rearrangement is not only extremely fast, but also highly exothermic (△ H. At least- 66 kcal / mol). A sudden thermal pulse appears at the location of the solubility inhibitor, and its amplitude causes the temperature peak to be not less than about 220 ° C. At the generated high temperature, the phenolic string is cleaved by its kDNq anchor to become inactive. (Dispersion) because it is no longer combined by the inducing effects of solubility inhibitors. It can be explained that a wide range of thermosensitive compositions based on resole novolac resins that combine different types of inhibitors appear in patent references and in commercial Published facts, such as explanations based on the application of the Chinese National Standard (CNS) A4 specification (230X297 mm) to the paper standards for ultraviolet, visible and / or infrared

-* Yes. (Tf read the precautions on the back before filling this page) -6-573208 A7 ----- B7_ V. Description of the invention (4) Direct work of direct radiation laser-addressable phenol resin for printing Form precursors (see, for example, U.S. Patent 4,708,925 (Newman, 3M); U.S. Patent 5,372,907 (Haley et al., Kodak Company); U.S. Patent 5,491,040 (DeBoer et al., Kodak Company). In U.S. Patent 4 In 708,925, phenol-based resins are dissolved in alkaline solutions and replaced by radiation-sensitive oxygen-drilling salts instead of DNQ. The natural solubility of the resin is restored when the oxonium salt is photo-decomposed. The characteristics of the oxonium salt composition against UV Radiation sensitive, and also sensitive to infrared radiation. U.S. Patent Nos. 5,372,907 and 5,491,064 utilize a direct positive action system based on radiation-induced latent Bronsted acid decomposition to increase the solubility of the resin matrix upon image-by-image exposure. All of these compositions are Additional use as a negative-acting system 'to undergo additional processing after imaging and pre-imaging. WO 97/39894 (Horsell) describes a thermosensitive composition and the use of laser-guided imaging (LDI) to make lithography Method for printing plate. The composition is based on a complex of a hope resin and a range of inhibitors containing a strong hydrogen acceptor, such as a nitrogen-containing heterocyclic ring and a compound containing at least one nitrogen atom undergoing fourth chemistry. Several groups of compounds that are widely known as inhibitors of UV-sensitive phenolic resin compositions can be used as inhibitors of heat-sensitive compositions. This is not surprising in terms of the aforementioned mode (A. Reiser). WO 97 / The composition described in 39894 (Horsell) is believed to be sensitive to ultraviolet and visible light, as opposed to the aforementioned oxonium salt or Bronsted acid decomposition composition. W0 97/39894 states that it can absorb incident radiation and convert it into thermal energy. Absorptive compositions. Horsell's references use, for example, dyes selected from the following categories: squalene iron, cyanine, cloth cyanine, pyrylium, and other known categories in the industry. Organic and inorganic pigments such as Carbon black or this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the note on the back before writing this page)

-7-573208 A7 B7 5. Description of the invention (5) Indigocyanine pigments can also be used as radiation absorbing materials that convert absorbed incident light into heat. WO99 / 08879 (Horsell) describes the application of radiation-sensitive compositions for the manufacture of printed boards and their electronic components and for the manufacture of covers. These coatings are based on phenolic resins, which are typically poor in mechanical properties. WO99 / 01795 (Horsell) describes a method for manufacturing a predetermined resist pattern such as a printed board, a circuit board or a cover. This method is characterized by the use of a novel polymeric material that becomes functionally functionalized to become insoluble in the developer but has the property of being exposed to light and becoming soluble in the developer. These groups are not azide anion groups as in the conventional system, but are groups that do not release nitrogen when exposed to radiation and have hydrogen bonding capabilities. Such groups are, for example, 2 · naphthyl fluorenyloxy, 2 ° secenyl% fluorenyloxy, danSyloxy, dansylsulfonyloxy, benzyloxy and n-butyl The group continues with fluorenyloxy. W099 / 21725 (Horsell) describes a composition based on a novolac novolac resin for use in the manufacture of photolithographic printing plates. The solubility of the composition in the aqueous developer is increased in the heating zone. The composition contains a compound which increases the resistance to development (dissolution) in an aqueous developer in a non-heated zone of the heat-sensitive composition. The composition includes a variety of compounds including A) poly (cycloalkoxy) units; B) silane units; and C) esters, ethers, and amines of polyols. WO 98/42507 (Kodak Multicolor Graphics Corporation) discloses a positive-acting thermal composition that can be imaged using infrared radiation lasers without a post-exposure baking step and without any overflow exposure step. This composition includes a phenol-based resin, an infrared radiation absorbing compound, and a non-photosensitive dissolution inhibitor. The dissolution inhibitor can provide hydrogen bonding with the phenolic position of the binder resin. ⑽) Shun grid (please read the notes on the back before filling out this page) Order —: Line · 573208 A7 £ 7_ V. Description of the invention (6) Knot position. WO 99/08157 (Kodak Multicolor Graphics Corporation) provides an infrared imaging composition containing two main components: a non-basic infrared radiation absorbing material (such as carbon black) and a phenol-based resin, a phenol-based resin mixture or a reactive azide Naphthol derivatives. These compositions can be used in positive- or negative-acting imaging modes such as photolithographic printing plates. WO 99/11458 (Kodak Multicolor Graphics Corporation) also describes a phenol-based resin (or other polymers with bypass groups, acid, ammonium, nitric acid, or a combination thereof) and an infrared Light absorbing compound. The imaging layer also contains a polymer with a bypass group with a bond, and the bypass group is 2-naphthoquinonediazide, a hydroxyl group, a carboxylic acid, a sulfonamide, a nitrile, and the like. The imaging layer also contains a solubility inhibitor, a visible light dye, or both. A wide variety of thermal sensing compositions that can be used as thermal mapping recording materials are disclosed in GB 1,245,924 (Agfa), so the solubility of a specified solvent in any specified area of the imageable layer can be increased by heating the layer. The heating method is indirectly Exposure to high-intensity visible light and / or infrared radiation for a short period of time, the visible light or infrared radiation is transmitted or reflected from the original background area of the pattern in contact with the recording material. The system can be modified and operated by a number of different mechanisms, as well as using different imaging materials from water to chlorinated organic solvents. Included within the scope of the disclosed compositions that can be developed by water are compositions that include resole novolac resins. The patent shows that the coating film of this resin shows increased insolubility when heated. The composition contains an endothermic compound such as carbon black or Milori Blue (C.I. Pigment Blue 27), which can be used as a recording medium in addition to coloring. (Please read the notes on the back before filling in this I)

JT line · This paper size is applicable to China National Standards (CNS) 8 4 specifications (2] 〇 \ 297 public 漦) 573208 A7 _ B7_ V. Description of the invention (7) As far as the inventors know, there are very few positive-acting thermosensitive combinations The objects are directly related to the manufacture of printed circuit boards using LDI and are described in patent references. Several compositions of this type are described in U.S. Patent No. 5,641,608 (McDermid), but the coating composition on the copper surface of the printed circuit board uses an ultraviolet laser beforehand, and is then scanned by an infrared laser. Another example of this patent is that the positive-acting thermal anti-agent does not contain any radiation-absorbing material that can convert infrared light into heat, so it is not clear how the composition that can transmit ultraviolet light can change its chemistry. The oxycarbonyl group undergoes acidic hydrolysis) and provides a difference in the developer solution. The exposure of the negative-acting composition to the infrared beam is also unknown. Here, the negative-acting composition does not contain a radiation-absorbing material on the coating film that is transparent to ultraviolet light over copper. The advantages of using a positive-acting photoresist over a negative-acting dry reactant as a single-layer dry film for the manufacture of printed circuit boards are described in Ep 0848290 (Morton) and ΤΑ · Koes and SH Wheeler, IPC Expo 98. Record, S12-3-1. The heat-sensitive negative-acting anti-surname agent composition is presented in, for example, US Patent No. 5,512,418 (Ma, DuPont). The energy required for the polymerization imaging area is in the range of 600 μJ / cm2, and the time required for imaging is extremely long. Addressing the need for high throughput in the printed circuit board industry. Polyvinyl acetal polymers, particularly polyvinyl butyrals, are used in a wide variety of products as adhesives because of their excellent film-forming properties and outstanding mechanical properties. These polymers are also known to have a chemical attack resistance. Very resistant material. One of the uses of these polymers is in the application of radiation-sensitive compositions' here they are used as binders for the manufacture of negative-acting printing plates, and the paper size is suitable for financial and domestic use (CNS) A4 specifications ⑵ϋχ297 公 幻 — -10- -------------------: ... fit! (Please read the precautions on the back before filling this page) Order: Line 573208 A7 B7_ V. Description of the invention (8) Manufacture of photoresist in the printed circuit board industry. Polyvinyl butyraldehydes or polyvinyl formaldehydes are described as materials that are insoluble in water-based developers used in the manufacture of printed boards or printed circuit boards. It has been proposed that a number of different polymers can be used for negative effects. The UV-sensitive composition can be used as a binder to provide the required aqueous solubility. 〇 Special advantages are achieved for polymers containing hydroxyl or carboxyl groups in the acetal moiety. These binder polymers are described in U.S. Patents 4,665,124; 4,940,646; 5,169,898; 5,169,897; 5,700,619. Photosensitive materials containing a resin binder, including an ethylene polymer having a phenolic hydroxyl group and an aromatic diazonium salt having only a single diazo group are disclosed in U.S. Patent No. 4,374,193, a polymer containing a p-hydroxybenzaldehyde moiety It is also described in U.S. Patent No. 5,792,823 as a polymer precursor of a chemically amplified positive-acting resist in lithography, but the hydroxybenzaldehyde acetal polymer itself is not used for the positive-acting resist layer as a composition. JP 09,328,519 teaches similar vinyl acetals for use as oxygen inhibitors. SUMMARY OF THE INVENTION The present invention provides novel positive-acting thermal imaging compositions and components. The positive-acting heat-activatable composition contains a heat-absorbing component, an adhesion promoter, and a special type of heat-sensitive acetal polymer as a resin binder component. It is preferable that the imaging element of the present invention is a heat-sensitive composition based on these polymers, and when it is irradiated with a wavelength of near-infrared light applied by a laser imaging device, it is thermally broadened to change its solubility in a weak alkaline solution. . Therefore, according to the first specific embodiment, the present invention includes an acidic polymer containing the following repeating units in the polymer main chain. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2) 0X297 male arrow. (Please first Read the notes on the back and then write this page again) * tr ·: r 11 573208 A7 __ B7 V. Description of the invention (9) I. Canton-Ca Canton "Shibuyibuyi, /, / ° 〇 \ / 0 { From rr > c 1 2 * 1 where

Ri is -CnH2n + i where n = M2; R2 is a phenol group, which contains no substituents or contains (preferably up to 3) additional substituents selected from -HO'-OCH3, Br- and -N02 or a group of _c〇CH; at least part of it can be expressed by the following formula:

Where R4 = -〇H; R5 = -OH or -OCH3 or Br- or -〇-CH2-C = CH; AR6 = Br or No 2 R3 =-(CH2) 2-COOH, -C tri-CH, or Here r7 = cooh,-(CH2) 3-COOH, -〇- (CH2) 2-COOH, and m = 5-40% mole ratio, preferably 15 to 35% mole ratio n = 10-60% Molar ratio, preferably 20 to 40% Molar ratio = 0 = 0-20% Molar ratio, preferably 0 to 10% Molar ratio p = 1-20% Molar ratio, preferably isio% Molar ratio q = 5-50% mole ratio, preferably 15 to 40% mole. As indicated in the above structural formula, the acetal polymer of the present invention may be a quaternary, wherein the repeating unit includes a vinyl acetate moiety and an ethylene An alcohol moiety, and a first and a second cyclic acetal group; or a pentad in which the repeating unit is the paper size

-12-573208 A7 ____B7__ 5. Description of the invention (10) Contains a vinyl alcohol moiety, a vinyl acetate moiety, and a first, second and third cyclic acetal group. All tricyclic acetal groups are six-membered cyclic acetal groups, one of which is substituted by an alkyl group and the other is substituted by a hydroxy group or a vial group and an alkoxy group, or a hydroxy group and a aryl group. -And bromo-based aromatic group substitution; and the third is substituted with an acid group, an acid-substituted alkyl group, or an acid-substituted aryl group. When R5 = -C = CH, a particularly advantageous advantage can be obtained on the copper surface. This specific base (detailed later) provides good adhesion to the copper surface. Providing the base inside the polymer itself can further reduce the need for compounds for use in the compositions of the present invention. DETAILED DESCRIPTION OF THE INVENTION One of the main components for implementing the present invention is to select a thermosensitive polymer component that can be used in a positive-acting resist layer. As outlined above, the acetal polymer must contain at least about 5 to about 60% of a Morbibene group (or a percentage of the number of units in the polymer chain): where: V. ▽. , Xi i. Heart rrr ^ 111 is-(: 1 ^ 211 + 1 where n = l-12; R2 is an age group 'which contains no substituents or contains 1 (preferably up to 3) additional substituents selected from -HO' -0CH3, Br- and · N02 or -C0CH group; at least part of it can be expressed by the following formula: This paper size applies the Chinese National Standard (CNS) Α4 specification (2) 0 × 297 mm) ------- ----------------- 装 —— (Please read the precautions on the back before filling this page) • Order · .. Line 丨 13 573208 A7 ^ __ B7_ 5. Description of the invention ( 11) where R4 = -OH; R5 = -〇h or -〇ch3 or Br- or -O-CHrOCH; & R6 = Br or No2 R3 =-(CH2) 2-CO〇H, -C ^ CH, or incense, where r7 = cooh,-(CH2) 3-COOH, · 0 · ((: Η2) 2 < 00Η, and a molar ratio of about 5-40 〇 / 〇, preferably 15 to 35% Mo Ear ratio n = about 5-60 or about 10-60% mole ratio, preferably 20 to 40% mole ratio 0 = 0-20% mole ratio, preferably 0 to 10% mole ratio p = 1-20% Morse ratio, preferably 1 to 10% Morse ratio q = 5-50% Morse ratio, preferably 15 to 40% Morse ratio The ratio of these bases is changed to allow the industry to modify Polymer properties combined with resist elements used in the practice of this invention Any specific needs required for resist processing. Using a lower percentage of the required phenolic substituents (for example, 5-40 / 0, 10-30%, 15-30%) can provide higher flexibility and lower brittleness. Polymers; and the use of souther percentages (such as 30-60%, 35-50%) can provide polymers that are easier to dissolve by thermal energy. Other linking groups provided in the polymer chain to further adjust the polymers are also within the scope of the present invention When using the term "polymer chain contains" or other language with illegal restrictions, the language allows other groups to exist in the polymer chain. When using "major composition of the polymer chain" or "composition of the polymer chain" The word 'in the words' means that it is limited to repeating units of the general type on the polymer chain, and this paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) 14 573208 A7 B7 V. Description of the invention Applied to the substitution of the polymer bond unit itself. As mentioned above, these polymers are described in patent references, and the inventors have provided a novel method described herein that is clearly excellent for controlling phenolic substitution in polymer manufacturing processes The amount of the base is as indicated by the structural formula of fluorene. The acid-condensation polymer of the present invention may be a desired quaternary polymer or a pentad polymer. In the quaternary polymer, the repeating unit includes vinyl acetate as defined above. Moieties and vinyl alcohol moieties and with first and second cyclic acetal groups. In the pentad, the repeating unit includes the aforementioned vinyl alcohol moiety, vinyl acetate moiety, and the first, second, and third cyclic acid groups. The aforementioned three acetal groups are all six-membered cyclic acetal groups, one of which is substituted by an alkyl group and the other by an aromatic group, and the aromatic group is hydroxy_, or hydroxy- and alkoxy- Or hydroxy · and optionally nitro-, bromo-, and ethynyl-OC- substitution; and the third acetal group is substituted with an acid group, an acid-substituted alkyl group, or an acid-substituted aryl group. The heat absorbing component of the present invention may be selected from any known material which can absorb infrared light and convert it into heat. Such materials include, for example, organic and inorganic dyes and pigments, which absorb infrared light and convert it into heat. Stone anti-black, certain cyanine pigments, SqUarine dyes, squalene dyes, cyanine dyes, cloth cyanine dyes, amaranth dyes, benzoin® diamond dyes, metal oxides, metals Sulfides and other types of materials known in the industry to absorb near and outer light areas. The amount of infrared light-absorbing thermal conversion material in the composition is based on the heat normally required for the system's addressing sensitivity, the intensity of the infrared light source, the exposure time (such as the pulse length from the laser), and other solutions to system sensitivity. Selection of factors for normal consideration. Usually A4 specifications (2) 0X297 public capital (please read the precautions on the back before filling out this page): line 丨 this paper size applies " Lao National Standard (CNS) 15 573208 A7 B7 V. Invention Description The amount of the heat-absorbing component is 0.00% of the composition; [to 20% by weight, 0.5 to 10% by weight of the composition, ο 'to 8% by weight of the composition, or 1 to 70/0 weight ratio. Higher content can be used, but higher amount will affect the physical properties of the anti-I insect layer. Lower content can be used, but the laser system which is the most ideal for this must be used. Based on this The thermosensitive composition of the inventive polymer can provide a photolithographic printing plate, which is characterized by improved abrasion resistance, extended compression properties, and another major advantage is that it can be processed in an alkaline imaging solution that does not contain organic solvents. It is believed that A photolithographic printing plate made of the optimized composition according to the present invention described later will be able to perform 500,000 printings. The heat-sensitive composition based on the polymer of the present invention also provides high resolution Density printed circuit board due to its excellent film Formation properties and improved adhesion, resulting in low-defect or non-defective resist coatings at relatively low thickness and low cost, which can clearly distinguish the solubility of light and unexposed areas, as well as good acid and alkaline etchant Etching resistance and good removal ability in aqueous alkaline solution. According to another characteristic aspect of the present invention, it also provides the advantages of such a composition, which can be applied by liquid or can be laminated on a dry monolayer film on a substrate for manufacturing The printed circuit board is because the composition of the present invention has optimal thermal and mechanical characteristics. In order to increase the sensitivity of the heat-sensitive composition of the present invention, a radiation absorber that can absorb incident infrared light and convert it into heat is combined. The radiation-absorbing material suitable for the heat-sensitive composition of the present invention can be selected from a wide range of organic and inorganic pigments such as carbon black 'metal oxides, cyanine, etc. Infrared light-absorbing dyes The paper dimensions are applicable to Chinese national standards (CNS ) People 4 rules (2) 0 × 297 Governor (please read the precautions on the back before filling this page) II --------. Line 丨 16 573208 A7 _ B7 " 11 Those with a wavelength of 1300 μm usually use near-infrared light absorbing materials (between about 700 and 1000 μm). The present invention also includes polyethylene-based acetal resin adducts, and polyethylene-acetal resin derivatives. Blends of the aforementioned lipids and uronic acids containing meridian and / or other functional groups with the following other polymers, such as hyaluronic acid, methacrylates, polyurethanes, benzene Ethylene-maleic anhydride copolymers, phenols, polyvinyl ketones, alkyl vinyl ethers, cellulose derivatives, epoxy resins and other resins. These other resins also provide additional physical properties that are advantageous for the particular use of the resist coatings of the present invention. For example, more lipophilic resins or polymers can be used to improve the ink properties of photoresist elements. A heat-softenable polymer with better adhesion to a specific surface can also be added to the primary polyethylene acetal resin used in the present invention to improve adhesion and especially improve dry film lamination. Here, dry film lamination is used. Agent. Another characteristic aspect of the present invention is to provide a method for synthesizing the aforementioned polymer. The method provided by the present invention facilitates the use of an acid having a high degree of conversion through an aromatic aldehyde containing a hydroxyl group to achieve a high shrinkage reaction of a polyethylene glycol radical. Another characteristic aspect of the present invention is to provide a novel type of adhesion promoter of the resist composition of the present invention for improving the adhesion property of the coating resist to at least the copper surface, because of the internal bond (acetylene) in the adhesion promoter. Bond) because of its affinity for copper. The heat-sensitive composition of the present invention is suitable for use as a heat-sensitive positive-acting resist when manufacturing printed circuit boards by thermal mold imaging, and is also applied to thermal paper cost. Paper standards are applicable to Chinese national standards (QsjS) from specifications (2) 〇χ297 mm)

.Order ----- • Take (Please read the precautions on the back before filling out this page) 17 573208 A7 —------- B7_ V. Description of the invention (15) As a precursor in positive printing form , Has the advantages outlined for positive action liquid thermal anti-money. (Proceedings of IPC Show 98, Εν · Halevy, Yossi-· Outfit—— (Please read the notes on the back before writing this page)

Atiya). Another advantage of the developed composition is that it can form a thin film with good mechanical properties, and it has improved adhesion to substrates such as anodized aluminum for printed board preparation and copper shields for printed circuit board manufacturing. Another advantage of this composition is that it can be applied as a liquid film or laminated by a heat roller to provide a dry film. The advantages of using a developer mainly composed of water and containing no organic solvent and having good solubility in the developer between the exposed and unexposed areas provide additional advantages of the heat-sensitive composition described below. Finally, the composition is not sensitive to white light ' so the coating product can be treated under white light. The anti- # agent element of the present invention is roughly described as a positive-acting thermal anti-depressant element, which includes a metal substrate, and a layer of positive-acting thermal anti-insectant is adhered to at least one side of the substrate.物 Contains 5-40. /. (Mole basis) lipid acetal group, and 10-60 / 100 (Mole basis) phenol-based acetal group, and infrared absorbing material, the content of which is 0.001 to 20 or 30% by weight of the positive-acting thermal erosion layer ratio. The thickness of the resist layer is preferably is% micrometer, but if applied as a dry film anti-corrosion layer, it is preferably thicker, such as 3 to 50 micrometers or 5 to 50 micrometers, or 10-50 micrometers. The solubility change performed in the polymer composition of the present invention is sufficiently long-lasting, so that no immediate development is required. The latent image formed by thermal imaging can last several days. The polyethylene acetal polymer of the present invention includes an acetal polymer carrying the following repeating units on the polymer main chain: This paper is sized to the Chinese National Standard (CNS) A4 (2Kj > < 297 public praise) 18 573208 V. Description of Invention (16

CH

CH ίΗι

Where Ri is -CnH2n + i where n = l-12; R2 is or

Where R4 = -OH; R5 = -OH or -OCH3 or Br- or -〇-CH2-CECH and R6 = -Br or No 2 R3 =-(CH2) 2-COOH or -C Ξ CH or --- --------------------- Install ...: (Please read the precautions on the back before filling this page}

., One bite: line 丨 here r7 = cooh,-(CH2) 4COOH, _0- (CH2) 3C00H and m = about 5-40% mole ratio, preferably 15 to 35% mole ratio n = about 10-60% mole ratio, preferably 20 to 40% mole ratio 0 = 0-20% mole ratio, preferably 0 to 10% mole ratio p = 1-20% mole ratio, preferably 1 To 10% Morse ratio q = 5-50% Morse ratio, preferably 15 to 40% Morse As indicated in the above structural formula, the acetal polymer of the present invention may be a quaternary, wherein the repeating unit includes vinyl acetate An ester moiety and an ethyl alcohol moiety, and a first and second cyclic acid group, or a pentad in which the repeating unit includes an ethyl acetate moiety, and a first, second, and third cyclic Reduced paper size applies to Chinese National Standard (CNS) A4 (230X297 mm) 19 573208

V. Description of the invention (17 A7

Aldehyde group. All tricyclic acid groups are six-membered cyclic mysteryl groups, one of which is substituted with an alkyl group, and the other is substituted with fluorene- or fluorene- and alkoxy group ... The aromatic group of the molyl group is substituted by &; and the third is substituted with an acid group, an acid-substituted alkyl group, or an acid-substituted aryl group. There are at least several reasons for choosing such a thermosensitive polymer polystructure because the polymers based on the polyethylene backbone are known to have excellent mechanical properties, excellent film formation characteristics, excellent abrasion resistance, and resistance to chemical attack. Sex is excellent. Modifications of polyvinyl alcohol are broad and easy to implement. The acetal unit containing a phenolic group is mainly responsible for imaging (heat sensitivity), that is, its function is similar to the aforementioned polymer mainly composed of resole novolac resin. Hydroxyl groups can accumulate acetal oxygen for intermolecular and intramolecular hydrogen bonding, or oxygen from the other radicals of the main chain polymer molecules. These hydrogen-bonding protective polymers are not easily soluble in diagnostic developers. When the material is exposed to incident energy, the radiation absorbing material converts the absorbed energy into heat and breaks the hydrogen bonds accumulated inside the coating film, thereby promoting the solubility of the exposed area. As a result of this type of bond breaking, the exposed and unexposed areas were screened for aqueous alkaline imaging agents. This type of solubility discrimination between exposed and unexposed areas is a peculiar property of polymer films, without the need to introduce dissolution inhibitors such as diazonaphthoquinone (DNQ) or heat-generating species in the formulation, which can attack the polymer chain. The various parts or bonds increase their solubility. Such compounds may be present, but their presence is not a preferred additive as it adds material components and combines with the resist layer. The substantial increase in solubility in the heated zone can be used for printed circuit board manufacturing or photolithographic printing board manufacturing. Due to the formation of thermally susceptible complexes with any endothermic pigments or dyes, the discrimination rate has only slightly increased, and the amount used in the formulation is extremely small, so only pigments or dyes are needed to convert light emission energy into heat. Please read the notes on the back before completing this page

The paper size of the edition is applicable to China National Standards () from the specifications (2) 0 × 297 public redundant) 20 573208 A7 I ---------— B7 __ V. Description of the invention (18) 1 ~ Side by side aliphatic The acetal part is responsible for thermal properties (butyl g), hydrophobicity_ink acceptability (for printed circuit board manufacturing), or anti-etching property (for photolithographic printed board manufacturing). A third acetal group containing a carboxylic acid by-product acetal or an aromatic group carrying a carboxylic acid functional group is believed to increase solubility in an aqueous developer and selectivity in polymer structure. Therefore, by optimizing or adjusting the ratio between the acetal of the main chain polymer and the remaining hydroxyl groups, it is possible to achieve a polymer with predetermined characteristics for a variety of specific applications. Sensitivity and thermal properties (for the lamination of dry resist films (Very important), mechanical properties, controlled solubility in aqueous imaging agents, anti-etching properties, and hydrophilic / hydrophobic balance properties can be changed individually by explaining their individual contributions to polymer properties based on previous teachings Group manipulation. Polyvinyl acetal polymer used as the main and sole binder resin for the heat-sensitive composition according to the present invention. The solubility of the polymer in water / alkaline developer can be changed thermally. The composition can be utilized. Novel synthetic methods begin with the preparation of inexpensive polymers available on a large scale. The starting materials for preparing the polymers according to the present invention are those containing at least about 80 ° /. Acetyl alcohol units and vinyl acetate-vinyl alcohol copolymers having an average molecular weight of about 2,000 to 120,000 or more, preferably about 8,000 to 50,000 (molecular weight is a number average or weight average molecular weight, and the changes therebetween affect the whole of the invention There are no relative restrictions on implementation). Suitable polyvinyl alcohols include, for example, a wide range of molecular weights available under the trade names MOWIOL 3-83, Mowell 3-98, Mowell 4-88, etc. from Clariant GMbH, others can be Trade names: AIRVOL 103, 203, 502, etc. are obtained from Air Products, and are obtained from Asia -------- _____________ This paper & standard suitable financial standards (⑽) A4 specifications (⑵ϋ297297) " -21-(Please read the notes on the back before filling this page). ^ Τ line 丨 573208 A7 _____ B7_— One. V. Description of the invention (19) Appropriate polyvinyl alcohol from ALDRICH and other suppliers class. Suitable aldehydes that can be used to prepare the first cyclic acetal group of the acetal polymer of the present invention include, for example, acetaldehyde, propanoic acid, n-butyraldehyde, n-valeric acid, n-hexanal, n-heptanyl isobutyraldehyde, isovaleric acid, mixtures thereof, and the like. Suitable aldehydes that can be used to prepare the second cyclic acetal group of the acetal polymer of the present invention include, for example: 2-hydroxybenzaldehyde 3-hydroxybenzaldehyde 4-hydroxybenzaldehyde 2-hydroxy-1-naphthoic acid 2,4 -Dihydroxybenzaldehyde 3,5 · dibromo-4-hydroxybenzaldehyde 4-oxopropynyl-3-hydroxybenzaldehyde vanillin isovanillin cinnamaldehyde, a mixture thereof, and the like. The third cyclic acetal group which can be used to prepare the acetal polymer of the present invention. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm).

22 573208 A7 B7 V. Description of the invention (Appropriate aldehydes of 20 include, for example: glyoxylic acid 2 · fluorenylphenoxyacetic acid 3-fluorenyl-4-fluorenylphenoxyacetic acid propynaldehyde, mixtures thereof, etc. Polyethylene The acetalization of an alcohol is performed according to a known standard method; for example, described in U.S. Patent No. 4,665,124; U.S. Patent No. 4,940,646; U.S. Patent No. 5,169,898; U.S. Patent No. 5,700,619; U.S. Patent No. 5,792,823; Japanese 09,328,519 No. etc. This acetalization reaction usually requires the addition of a strong inorganic or organic catalyst acid. The catalyst acid is, for example, hydrochloric acid, sulfuric acid, phosphoric acid or p-toluenesulfonic acid. Other strong acids can also be used, such as perfluoroalkylsulfonic acid and others Perfluorinated activated acid. The amount of acid must be effective to allow the protonation reaction, but it will not significantly change the final product by causing undesired hydrolysis of the acid group. The temperature of the acetalization reaction is determined according to the type of aldehyde and the predetermined degree of substitution. The reaction temperature is 0c> c, and the boiling point of the solvent used if applicable. Organic solvents and mixtures of water and organic solvents can also be used. Particularly suitable organic solvents are alcohols (for example Methanol, ethanol, propanol, butanol, or glycol ethers), cyclic ethers (such as 丨, ^ dioxane) or bipolar aprotic solvents (such as N, N • dimethylformamide, n_ If the methylation reaction is carried out in an organic solvent or a mixture of organic solvent and water, even if the raw material polyethylene glycol is not completely dissolved, the product still remains in the solution. Raw material Polyvinyl alcohol does not completely dissolve in organic solvents, which may lead to irreproducible degrees of conversion and different products. Water or organic solvents and water mixtures must be used to achieve the complete polyethylene standard. The standard applies to China National Standards ^-…… ------------------ Packing: ... (Please read the precautions on the back before filling this page) • Line 丨 23 573208 A7 ---- ___B7____ V. Description of the invention " ~ Material and reproducible products of the acidification reaction results. The order of adding different acidification agents is not important, and comparable products can be obtained through different preparation procedures. In order to separate the final product as a solid, Polymer solution is introduced under vigorous stirring, filtration and drying In a solvent. Water is particularly suitable as a non-solvent for polymers. Shen Jianren found that acetalization using hydroxy-substituted aromatic aldehydes was compared with aliphatic or unsubstituted aromatic aldehydes or from carboxylic acids under the same synthetic conditions. Some aldehydes establish acetals, which is far more prone to undesired hydrolysis of acetal groups. Even a small amount of water in the reaction mixture will lead to a reduction in acetalization, and the aromatic aldol used is not completely converted. It was found In the absence of water, the hydroxy-substituted aromatic aldehyde reacts immediately with the hydroxy group of the alcohol and obtains a conversion rate of almost 100%. Therefore, the desired polymerization according to the present invention is obtained by the process of substituting the aromatic aromatic polycondensation acid. Vinyl acetals are carried out in a different way than known from the prior art. The main difference in the present invention is the removal of water from the reaction mixture during the synthesis. The main amount of water can be removed by distillation under reduced pressure and replaced with an organic solvent. The applicant has found that the remaining water in the reaction mixture can be removed by adding a mixture of organic materials that are convenient to react with water, and the reaction results in volatile substances or inert compounds. These materials may be selected from carbonates, orthocarbonates of carbonic acid or carboxylic acids, such as diethyl carbonate, trimethyl orthoformate, tetraethyl carbonate, tetrasilicate Ethyl esters, etc. Adding these materials to the reaction mixture resulted in a 100/0 conversion of the used alcohol and, as far as the inventors know, no prior art was used as a water-removing agent in the manufacture of type polymer acetals. (The use of trimethyl orthoacetate when synthesizing 5-lactones is described in G. Saucy, R. Borer and DP. The paper size is applicable to China @ 家 标 华 （0 ^） 八 44⑵ > < 297g Magic-24-573208 kl ____ B7_ V. Description of the invention (22)

Trullinger; Journal of Organic Chemistry, Vol. 42, No. 19, p. 3206, 1977). The method for synthesizing a polyvinyl acetal polymer according to the present invention includes acetalizing a polyvinyl alcohol resin with a radical-containing aromatic aldehyde and a strong catalyst, and reacting with water and adding volatility to the water and / or Inert compounds whose speed is sufficient to effectively remove part of the water (reduced concentration but not completely removed) before the acetal reaction is completed and replace the water with polyvinyl alcohol and hydroxyl substituted aromatic aldehydes' by reducing polyvinyl alcohol and hydroxyl substituted aromatics The amount of water in the aldehyde is acetalized by replacing the aromatic aldehyde with a hydroxyl group to control the number of acetal groups to be hydrolyzed. In this method, for example, a material selected from the group consisting of organic carbonates, orthocarbonates of carbonic acid or carboxylic acid, and a group containing silicon compounds can be used as a material that reacts with water. Crude-containing compounds are, for example, selected from the group consisting of oxalates and syrups, such as orthosilicates, metasilicates, and ester-containing silanes. Preparation starts at 80_90. 〇The raw material polyvinyl alcohol is dissolved in water, and then the solution is rapidly cooled to 60 ° C, and an acidic catalyst is added to dissolve it in an organic solvent. The solvent used in the present invention is an alcohol or a glycol ether, such as n-propanol, 2-methyl Oxyethanol or 丨 methoxy · 2 · propanol Dowanol PM (hereinafter referred to as rPM ") and so on, and then the solution of aromatic hydroxy substituted aldehyde in the same solvent is added to the solution, just as adding aromatic After the family aldehydes, add a solution of aliphatic aldehydes and / or carboxylic acid substituted aldehydes or other aldehydes in the same solvent, and the reaction mixture is stirred at this temperature for 2 · 3 hours, and then water and water are removed by distillation and replacement with organic solvents. An azeotropic mixture of organic solvents. In these stages, the conversion of aromatic hydroxyaldehyde reached 95-98%. Then, the acid of the reaction mixture is neutralized, and the mixture is mixed with water to precipitate a polymer. The size of the polymer paper conforms to Chinese Standard (CNS) M Regulation (2) 〇 > < 297 Gongmeng) 25 573208 A7 B7 V. Description of the invention (23) Filtered, washed with water and dehydrated. The second way to achieve 100% conversion of aromatic aldol to benzyl alcohol is to add organic substances (such as carbonate, orthoformate, etc.) to remove water after adding acids to the reaction mixture. Radiation absorbing materials suitable for use in the heat-sensitive composition of the present invention are selected from a wide variety of organic and inorganic pigments such as carbon blacks, incyanines, or metal oxides. Green pigment: manufactured by Heliogen Green D8730, D9360 and Fanal Green D8830 BASF; manufactured by Predisol 64H-CAB678 by Sun Yang Chemical Co., and black pigment: Prediso CAB2604 , Prediso N1203, Prediso Black CB-C9558, made by Shengyang Chemical Co., Ltd., are examples of some effective endothermic pigments. These pigments and compositions are used in an amount of 3 to 20% or preferably 3 to 7% by weight of the composition. Infrared absorbing dyes are preferred heat absorbing agents and can be used in the composition of the present invention. In particular, infrared absorbing dyes can absorb infrared light having a wavelength longer than 700 nanometers, for example, in the range of about 700 to 1100 nanometers. These dyes are, for example, Epolight IV-62A, IV-62B, and IV-66X manufactured by Epolin Corporation; ADS 830, ADS 835, and ADS 840 manufactured by American Dye Source Corporation; Hayashibara) NK-2911 and NK-4432 manufactured by Biochemical Labs. The amount of the infrared light-absorbing dye in the composition is generally lower than that of the pigment, and the amount of the light-absorbing dye is 0.1 to 5% by weight of the composition ', or preferably 0.1 to 1% by weight of the composition. Known acetylene-containing reference compounds have copper affinity (Jukes AE ·, Advances in Organometallic Chemistry, No. 12, New York, 1974, pp. 215-322), prompting applicants to use such compounds as heat-sensitive compositions for copper Adhesion on the surface ---------------------- Installation-(Please read the precautions on the back before filling this page): Line 丨 This paper size applies to China Standard (CNS) A4 specification (210X297 mm) 26 573208 A7 ------ B7 V. Description of invention (24) Accelerator material. To the applicant's knowledge, no acetylenic compound is used for this purpose. The adhesion promoter of the present invention belongs to esters, sulfoesters, amidoamines, polyesters, polycarbonates, and polyurethanes containing a bond or a series of bonds: Ινχ-(:( Ι13 , I14)-(: Ξ (:-( :( I13, I14) -X · κ2, or Ri-XC (r3, r4)

-C Three CC (R3, R4) -X- (Y) mXC (R3, R4) _c ξ CC (R3, R4) _X-R2 or Ri-XC (R3, R4) -CeCH here ... Ι ^ & amp I12 =-(: ηΗ2η + 1, substituted aromatic or heterocyclic fragments; R3 and R4 = H or alkyl X = -0-C (0) -'- OS (O)-, -NH-C ( O)-; Y = -CnH2n4 substituted aromatic groups; and, for example, may be propynol or 2-butyne-1,4-diol, and chloro anhydride of an appropriate carboxylic acid or sulfonic acid, or an aliphatic or aromatic isocyanate Or diisocyanates; or by propyne bromide or propyne chloride or propyne chloroformate and appropriate polyols, or by any method known to those in the industry. Polycarbonates with reference bonds-(CH2Ce C-CH2 -0-C (0) -0-R-0-) m which can be obtained from 2-butyne-1,4-diol pirates and the corresponding glycol: HO-R-OH, here : RMCHOm-, n = 2-6; R = -CH2CH2 (OCH2CH2) n, n = 1, 4; R = -CH2-CH = CH-CHr, -CH2-C = C-CH2-, CH3 CHj Cft 0¾ CHj CHj

II I I I I • C-CHjCHa-C-, * C «CH-CH heart,,

II II CH3 Ob CH > CH, CH2CH (OCH2CH) ", n; M; II Oh CHj This paper size is applicable to China National Standard (CNS) A4 specification (2) 0X297 mm) ---------- -------------- ^ —— (Please read the notes on the back before writing this page)

， 可 I; Line 丨 27 ^ 3208 A7 ^^^ __ — B7__ 5. Description of the invention (25) " '-~~ R = aromatic group, for example = Ar-=-C6H4, -C1 () H6 and so on. From these non-limiting examples, it is understood that the acetylene bond may exist inside the molecular structure or at the terminal position of the molecule. In addition, colorants, plasticizers, surfactants, other metal adhesion promoters, extenders, labeling agents, further resin components, and the like may be added to the heat-sensitive composition. Useful colorants include resists and well-known dyes in printing plate coating formulations, i.e. methyl violet, ethyl violet, crystal violet, basic Sudan black, Victoria Blue R, methyl blue, aniline black, and others. The preferred amount of dye is from 0.01 to 2% by weight of the heat-sensitive composition. Useful coating aids include fluorocarbon surfactants such as the Zonyl series (DuPont) or FC-430 or FC-43 1 (3M) or other anionic, cationic nonionic or mixture interfaces Active agent. The preferred amount of surfactant is from about 0.01 to 10/0, based on the total weight of the composition. Specific plasticizing includes, for example, Tweens (e.g., available from ICI Corporation) 'polyoxyalkylene plasticizers (e.g., polyethylene oxide / polypropylene oxide co-monomer or copolymer) and the like. The amount of the plasticizer may be in a wide range, for example, 0.1 to 15% by weight of the heat-sensitive composition. Plasticizers are also known to aid the imaging properties of the thermosensitive polymer in the imaging step. Fillers and extenders can also be used in the thermal imageable composition of the present invention ', for example, to increase the solids content of the composition by using inertness or having improved properties such as the heat resistance or heat permeability of the composition. The filler can be used to accumulate the thickness of the thermally imageable layer after coating, or to adjust the strength and physical properties of the layer. It is inherently inert, granular, or film-forming. Non-limiting examples of particularly suitable inert fillers include starch, kaolin, titanium dioxide, silicon oxide, polytetrafluoro. This paper is sized to the Chinese National Standard (CNS) A4 (2) 0 × 297 mm. ------- ---------......... ^! (Please read the notes on the back before filling out this page) • Order · -line 丨 28 573208 A7 B7 V. Description of the invention (26 Ethylene and talc. The present invention The heat-sensitive composition can be used for manufacturing printed circuit boards, lithography printed boards, and other heat-sensitive elements suitable for laser guided imaging. The heat-sensitive (thermo-imageable) combination mainly composed of the composition of the present invention It can additionally provide highly polished, chemically ground metals. At least in part because of its excellent adhesion to a wide variety of metals and alloys, the addition of additives does not adversely affect the performance of the composition and improves the adhesion. The solubility of exposed and unexposed areas has good discrimination power, good etching resistance (good after-resistance to the widely used gasified iron surname solution), and easy removal of residual composition. This can be used for the industry's known Radiation exposure and washout imaging methods are used to make small medical component parts such as vascular stents and catheters, as described in US Patent No. 6,027,863. The heat-sensitive composition based on the composition of the present invention can also provide heat-activated resins. It can be used in the manufacture of printing plates such as gravure printing cylinders. The composition of the present invention can provide good film forming properties on the coating, good adhesion to the surface of the gravure printing cylinders, and the ability to develop water, and the remaining composition after development and etching Easy to remove. The heat-sensitive composition of the present invention also provides high sensitivity to infrared laser radiation and good adhesive removal properties for screen printing stencils. Suitable substrates include conventional copper pigs, back-treated copper cymbals, Drum-side processed copper cymbals and double-processed copper foil shields are used on plastic laminates used to make printed circuit boards; | Lu boards and sheets and anodized sheets are used to make printed boards. Substrates such as steel, polymer Materials (such as nylon, high-density polyolefins, polycarbonates, polyacrylates, polyethylene resins, etc.) can be used to make screen plates ----— — This paper size _ Zhongguanjia Standard (CNS) A4 specifications ⑵QX297 public magic (Please read the precautions on the back before filling this page)

29 573208 A7 B7 V. Description of the invention (27) Printed template. Chromium and copper substrates can also be used to form gravure printing plates. For final treatment, obtain a solution of the thermosensitive formulation in an appropriate solvent, filter to remove insoluble components, and apply from a liquid in a known manner such as doctor blade coating, line coating, square coating, stick coating or dip coating. The solvents used in the present invention are glycol ethers, that is, -PM or 2.methoxyethanol. The solid content of the polymer material in the solution is determined based on the predetermined dry thickness of the film and is in the range of 5 to 25% by weight. Another application method is to coat a suitable intermediate substrate (polyester or polyethylene) with a heat-sensitive composition solution, dry, and then apply a film to the final substrate (copper) by heat lamination. After the coating is properly dried, the printed board is imaged using a laser beam on the CREO PLATESETTER-3244, and the printed circuit board is exposed on a Creo Diamond 2028F imager. The exposed area is developed using an alkali metal salt solution or a weak alkali hydroxide solution. The invention is further illustrated by the following examples. Preparation Example 1 110 g of Mowell 3-98 polyvinyl alcohol (980000/0 hydrolyzed polyvinyl acetate with an average molecular weight of about 16,000) was added to a closed reaction container. The container was equipped with a water-cooled condenser, an addition funnel, and a thermometer. Contains 250 grams of demineralized water. With continuous stirring, the mixture was heated at 90 ° C for 1 hour until it became a clear solution. After Ik the temperature was adjusted to 60 ° C and 3 grams of concentrated sulfuric acid was added. Over a period of 15 minutes, a solution of 59.8 g of 4-hydroxybenzaldehyde and 4 g of 2,6-di-tert-butyl · 'cresol in 450 g of 2-methoxyethanol was added dropwise. The reaction mixture was diluted with 500 g of 2-methoxyethanol, and 35.3 g of n-butyraldehyde was added dropwise to 500 g of 2 • oxoethyl paper. The paper was scaled to the China® Standard (CNS) from the specifications. (2) 〇χ297 公 漦) (Please read the notes on the back before filling this page)

30 573208 A7 B7_ V. Description of the invention (28) Alcohol. When the addition of acids was completed, the reaction was continued at 50 ° C for another 3 hours. Water was distilled from the reaction mixture and replaced with 2-methoxyethanol (the remaining water in the solution was less than 0.30 / 0). The reaction mixture was neutralized with sodium bicarbonate to pH 7 ± 0.5, and then 15 liters of water · methanol (10: 1) were mixed. The precipitated polymer was washed with water, filtered and dehydrated in vacuo at 50 ° C. 178 g of polymer was obtained with a yield of 95.2% (calculated based on PVA) and a 4-benzaldehyde conversion of 92%. The polymer structure conforms to the structural formula, in which the Ri group is derived from n-butyraldehyde and the R2 group is derived from 4-hydroxybenzaldehyde. The 1Ώ value is 36% mole ratio, the η value is 37% mole ratio, and the p value. Molar ratio of 2% and q value of 25% Molar ratio (Tg63 ° C). Preparation Example 2 110 g of Mowell 3-83 polyvinyl alcohol (83% hydrolyzed polyacetic acid with a number average molecular weight of about 14,000) S purpose) is added to a closed reaction container, the container is equipped with a water-cooled condenser, an addition funnel and a thermometer, and contains 1 J g of demineralized water and 110 g of methanol. With continuous stirring, the mixture was heated at 80 ° C for 0.5 hours until it became a clear solution. The temperature was then adjusted to 6 ° C and 3 g of concentrated sulfuric acid was added to 100 g of PM. Over a period of 15 minutes, 65 g of 3-hydroxybenzaldehyde and 1.4 g of 2,6-di-tert-butyl-4 were added dropwise. • Phenol in 45 grams of pM2 solution. The reaction mixture was diluted by an additional 200 grams of PM, and 9.2 grams of n-butyl was brewed in 200 grams of PM in a dropwise manner. When the addition of the genus was complete, the reaction continued at 50 ° C and continued. It was carried out for 3 hours. At this stage, the conversion of butyraldehyde was completed, and the conversion rate of 3 · hydroxybenzyl was close to 50 ° / ρ. During the mixing, 500 g of trimethyl orthoacetate was added dropwise to the reaction mixture. After trimethyl acetic acid, the conversion rate of Hongjingjiejie acid reaches 100% (the water content of the reaction mixture is less than 0%). This paper size is applicable to China National Standard (CNS) A4 size (2WX297 mm) (Please read first (Notes on the back then fill out this page)

31 573208 A7 __B7_ V. Description of the invention (29) 158 grams of polymer was obtained with a yield of 96.8% (based on PVA calculation). The polymer structure conforms to the structural formula, in which the R group is derived from n-butyraldehyde, and the r2 group is derived from 3-hydroxybenzaldehyde, and the m value is 12 ° /. Molar ratio, η value is 49% Molar ratio, ρ value is 17% Molar ratio, and q value is 22% Molar ratio (Tg 59 ° C). Preparation Example 3 110 grams of Alfo 103 polyvinyl alcohol (98% hydrolyzed polyvinyl acetate with an average molecular weight of about 18,000) was added to a closed reaction container. The container was equipped with a water-cooled condenser, an addition funnel and a thermometer, and contained 250 grams Mineral water. With continuous stirring, the mixture was heated at 90 ° C. for 1 hour until it became a clear solution. The temperature was then adjusted to 60 ° C and 3 grams of concentrated sulfuric acid was added to 100 grams of pm. Over a period of 15 minutes, a solution of 61 g of 2-hydroxybenzaldehyde (salicylaldehyde) and 1 · 4 g of 2,6-di-tert-butyl-4-cresol in 450 g of PM was added dropwise. The reaction mixture was diluted with 500 g of PM, and 27 g of n-butyraldehyde and 10 g of glyoxylic acid were added dropwise to 500 g of PM. The reaction was completed at 50 when the addition of aldehydes was completed. (: Continue for another 3 hours. Distill the water from the reaction mixture and replace it with PM (10 g of water remains in the solution, ie less than 1.5%). 100 g of triethyl orthoacetate are added to the mixture with stirring. The reaction mixture. At this time, the water content of the reaction mixture was lower than 0 · P /, and the conversion rate of salicylaldehyde to benzaldehyde was quantified. The reaction mixture was neutralized to pH 7 ± 0.5 using sodium bicarbonate, and then mixed. 15 liters of water-methanol (10: 1). The precipitated polymer was washed with water, filtered, and dehydrated under vacuum at 50 eC. 185.8 g of polymer was obtained, yield 97.6% (calculated based on PVA), and 2-benzyl acid conversion 100%. The polymer structure conforms to the structural formula, where the & group is derived from n-butyraldehyde, and the & group is derived from 2-hydroxybenzaldehyde, and the r3 group is derived from glyoxylic acid; the m value is 30% Morse ratio, n value 41% Morse ratio This paper size is applicable to Chinese National Standard (CNS) into 4 specifications (2) 0X297 mm) (Please read the precautions on the back before composing this page) •, Stare; line · 32 573208 A7 _____B7 V. Description of the invention (30), p value is 2% Morse ratio, 0 value is 9% Morse ratio, and q It is 20% molar ratio (Tg68 ° C). Preparation Example 4 110 grams of Alfo 502 polyvinyl alcohol (88% hydrolyzed polyvinyl acetate with an average molecular weight of about 16,000) is added to a closed reaction container, and the container is equipped with a water-cooled type Condenser, addition funnel and thermometer containing 110 grams of demineralized water and 110 grams of methanol. The mixture was heated at 90 ° C for 1 hour to a clear solution by continuous stirring. The temperature was then adjusted to 60 ° C and 3 grams of concentrated Sulfuric acid at 100 g of PM. A solution of 61 g of 3-hydroxybenzaldehyde and 14 g of 2,6-di · tert-butyl-4-cresol in 450 g of PM was added dropwise over a period of 15 minutes. The reaction mixture was diluted with 200 g of PM, and 18.2 g of n-butyraldehyde and 8.1 g of propargaldehyde were added dropwise to 500 g of PM. The reaction of aldehydes was completed at 50. (3 continued for 3 hours. The reaction mixture was distilled off water and replaced with pm. At this time, the water content of the reaction mixture was less than 0.2%, and the conversion rate of m-hydroxybenzaldehyde to benzaldehyde was quantified. The reaction mixture was neutralized to pH 7 using sodium bicarbonate. ± 0.5, and then mix 15 liters of water-methanol (10: 1). The precipitated polymer was washed with water Filtration and vacuum dehydration at 50 ° C. 177 g of polymer was obtained with a yield of 97.6% (based on PVA calculation), and the conversion rate of benzaldehyde was 100%. The polymer structure conforms to the structural formula, where R] is derived from N-butyraldehyde, and R2 group are derived from 3-hydroxybenzaldehyde, and r3 group is derived from propyne S; m value is 21% mole ratio, η value is 43% mole ratio, p value is 2% mole The ear-to-earth 'value is 10% mole ratio, and the q-value is 24% to mole ratio (Tg65 ° C). Preparation Example 5 This paper is sized to Chinese National Standard (CNS) A4 (2) 0X297 mm) (Please read the precautions on the back before filling this page)

33 573208 A7

This paper size applies the Chinese National Standard (CNS) A4 Regulations (2) 0X297. 34 573208 A7 ----------- _______ V. Description of the invention (32) Cold condenser, adding funnel and thermometer and contains 110 grams of demineralized water and 110 grams of methanol. With continuous stirring, the mixture was heated at 800 c for 1 hour until it became a clear solution. Subsequently, the temperature was adjusted to 60 ° C and 3 g of concentrated sulfuric acid was added at 100 g PM ° for 15 minutes. 32 g of 4-hydroxybenzaldehyde, 30 g of 2-hydroxy-1-naphthaldehyde and L4 g of a solution of 2, ... di-tertiary-butyl-4-phenol in 500 * pM. The reaction mixture was diluted with 200 g of pm, and 21.4 g of n-butyraldehyde was added dropwise to 500 g of PM. When the addition of aldehydes was completed, the reaction was continued for 50 hours and continued for 3 hours. Water was distilled from the reaction mixture and αρΜ was replaced. The water content of the reaction mixture at this time was less than 0.21 0 / ❶, and the conversion of the aromatic aldehyde to benzaldehyde was quantitative. The reaction mixture was neutralized to pH 7 ± 0.5 using sodium bicarbonate, and then 15 liters of water · methanol (10: 1) were mixed. The precipitated polymer was washed with water, decanted and dried under vacuum at 50 ° C. 170 g of polymer was obtained with a yield of 96% (calculated based on pvA) and 4-hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde conversion of 100%. The polymer structure conforms to the structural formula, in which the R 丨 group is derived from n-butyraldehyde and the R2 group is derived from a mixture of 4 • hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde; the m value is 25% molar ratio , N value is a mole ratio, ρ value is 12% mole ratio, and q value is 26% mole ratio (Ding g74t :). Preparation Example 7: 110 g of Pulver 502 polyvinyl alcohol (average molecular weight of about 6,000 to 880/0 hydrolyzed polyvinyl acetate) was added to a closed reaction container. The container was equipped with a water-cooled condenser and an addition funnel. And a thermometer containing 20 grams of demineralized water and 100 grams of methanol. With continuous stirring, the mixture was heated at 9 ° C for 1 hour until it became a clear solution. The temperature was then adjusted to 60t and 12.4 grams of concentrated hydrochloric acid was added to 100 grams of PM. After 30 minutes, 40.3 was added dropwise. Gram 4 • Medium size This paper applies Chinese National Standard (CNS) Α4 specification (2) 〇χ297 公 梦

(Please read the precautions on the back before writing this page) Order. 35 573208 A7

___B7 V. Description of the invention (33) A solution of phenylphenoxyacetic acid and 30.8 g of 2-hydroxybenzaldehyde and 1.5 g of 2,6 · di-tert-butyl-4-methanol in 750 g of PM. The reaction mixture was diluted with 200 g of pm, and 34.2 g of isovaleraldehyde was added dropwise to 500 g of PM. When the addition of aldehydes was completed, the reaction was continued at 50 C for another 3 hours. Water was distilled from the reaction mixture and replaced with PM. At this time, the water content of the reaction mixture was less than 0.01%, and the conversion ratio of 2-to benzyl acid via 2-anosic acid and 4-methylfluorenylphenoxyacetic acid was quantitative. The reaction mixture was neutralized to pH 7 ± 0.5 using sodium bicarbonate, and then 15 liters of water-methanol (10: 1) were mixed. The precipitated polymer was washed with water, filtered and dehydrated under vacuum at 50 ° C. 194 g of polymer was obtained with a yield of 92.6% (calculated based on pva). The polymer structure conforms to the structural formula 'wherein the R1 group is derived from n-butyric acid, and the group is derived from 2-hydroxybenzaldehyde, and the R3 group is derived from 4-formamylphenoxyacetic acid, and the m value is 16%. Ear ratio, n value is 10% mole ratio, p value is 12% mole ratio, 0 value is 18% mole ratio, and q value is 44% mole ratio (Tg65 ° C). Preparation Example 8 110 g of Mowell 3-98 polyvinyl alcohol (having a number average molecular weight of about 16000 of 98 ° / 〇 hydrolyzed polyvinyl acetate) was added to a closed reaction container, and the container was equipped with a water-cooled condenser, an addition funnel, and a thermometer. And contains 25 grams of demineralized water. With continuous stirring, the mixture was heated at 900 c for 1 hour until it became a clear solution. Thereafter the temperature was adjusted to 6 ° C and 6 grams of p-toluenesulfonic acid was added. Over a period of 15 minutes, 152 grams of 3,5 • dibromohydroxyaldehyde and 1.4 grams of 2,6 · di · tertiary butyl were added dropwise. A solution of stilbeneol in 750 g? ^. The reaction mixture was diluted with an additional 500 g of PV [diluted, and 123 g of n-butyl fluorene was added in a dropwise manner to 500 g. Responds to A4 specification (210X297 mm) at 50 ° C. This paper size applies Chinese National Standard (CNS) 573208 A7 B7. 5. Description of the invention (34 for 3 hours. Water is distilled off from the reaction mixture and replaced with pM ( The amount of residual water in the solution was less than 1%). 100 g of triethyl orthoformate was added to the reaction mixture. The water content in the reaction mixture was detected to be less than 01%, and 3, the conversion rate of dibromohydroxybenzoic acid was quantitative. The reaction mixture was neutralized with ammonium carbonate to pH 7.5, and then mixed with 15 liters of water · methanol (10: 1). The precipitated polymer was washed with water, filtered and dehydrated under vacuum at 50 ° C. 248 g of polymer was obtained The yield is 95.2% (calculated based on PVA). The polymer structure conforms to the structural formula, of which the Ri-based system is derived from The butyric acid and r2 groups are derived from 3,5-dibromo-4-hydroxybenzaldehyde, with an m value of 14% mole ratio, an n value of mole ratio, a p value of 2% mole ratio, and q The value is 40% Molar ratio (Tg 73 ° C). Application Example 1 The polymer obtained from Preparation Example 1 was dissolved in PM and used to prepare a heat-sensitive composition having the following formula: Ingredient acid-acid polymer 1 13.2 Pigment ( Predisosol N1203 *) 0.8 Surfactant 0.05 Dovano PM 85.95 * The composition of Shengyang Chemical Co., Ltd. was ball-milled for 12 hours, filtered and coated on 0.5 ounces of conventional copper shield pre-cleaned and micro-etched 8 mil glass_epoxy laminate on the cover surface. After drying at 13CTC for 3 minutes, the resulting plate is coated with a dry thickness of 5.5 g / m2. The plate is imaged on a Clio diamond 2028F imaging machine. Good quality is required The energy density of the image is 200 millijoules per square centimeter. The flat plate is suitable for China National Standards (CNs) A4 specifications (2) 0 > < 297 mm) at this paper scale. (Please read the precautions on the back before writing on the wall Page), can ........ line — 37 573208 V. Description of the invention (35 5% denatured sodium hydroxide in aqueous solution for 60 seconds to obtain a band There is an image of 2 mil line-to-line ratio. The developed plate is etched with a conventional vaporized copper etchant, and the printed circuit with a sharp conductor edge and a 2 mil line-to-line ratio is obtained. ^ MΛM1 is obtained from the preparation example The polymer of 2 is dissolved in Dowa-PM, and is used to prepare a heat-sensitive composition having the following formula: ingredients. / + S .. / 〇W w acetal polymer 2 16 0 adhesion promoter-1, 3, 5-reference [propynyloxycarbonyl] benzene 〇 05 pigment Haili Golden Green D-8330 * i Surfactant 005 Dowano PM 82 9

* BASF ------------------------ install—— (Please read the precautions on the back before writing this page) • 、 一 -T 丨: Line 丨 The composition was ball-milled for 12 hours, filtered and coated on a 20-mil glass-epoxy laminate laminated to the surface of a 1-ounce pre-cleaned copper shield. After drying at 130 ° C for 4 minutes, the resulting plate was coated with a dry thickness of 9.5 g / m 2. The plate was imaged on a Clio Diamond 2028F imager. The energy density required to obtain a good image is 300 mJ / cm2. The plate was developed with 0.75% sodium hydroxide in aqueous solution for 50 seconds to obtain an image with a 2-mil line-to-line ratio. The developed plate was etched with a conventional vaporized copper etchant. As a result, a printed circuit with a sharp conductor edge and a 2-mil wire-to-wire ratio was obtained. Application Example 3 The polymer obtained from Preparation Example 3 was dissolved in Donovan PM and used to prepare a heat-sensitive composition having the following formula: This paper is in accordance with Chinese National Standard (CNS) A4 Regulation (230X297) 573208 A7 B7 V. Description of the invention (36, knife% weight ratio acetal polymer 3 15 〇 Guyan accelerator-2,4,6-ginseng (2 · two lack of certain gas 1,3,5-tri_ 0 〇 3 IR Dye-NK-2911 * * Colorant-Pyridyl Blue Surfactant Dovano PM * Lim Biochemical Laboratory Company

The ingredients of the composition were dissolved in PM ′, filtered and coated on an 8 mil glass-epoxy resin laminate of a copper shield surface that was previously cleaned and microscopically etched on a 25 mm plate. After drying at 13 ° C for 3 minutes, the resulting plate was coated with a dry thickness of 65 g / m 2. The plate was imaged on a Clio Diamond 2028F imager. The energy density required to obtain a good image was 250 mJ / cm 2. The plate was developed with 0.9% sodium hydroxide in an aqueous solution for 60 seconds to obtain an image with a 75.75 mil line-to-line ratio. The developed plate was engraved with a conventional alkaline etchant, and as a result, a sharp conductor edge and 〇 were obtained. · 75 mil line-to-line printed circuit. Application Example 4 The polymer obtained in Preparation Example 4 was dissolved in PM and used to prepare a heat-sensitive composition with the following formula: (Please read the precautions on the back first, and then Fill out this page]: Line · Ingredients: Acetal polymer 4 IR Dye · ΝΚ-4432 * Surfactant colorant · Crystal violet Dovano PM * Forest weight ratio 16.0 0.1 0.05 0.05 83.8 This paper size is applicable Chinese National Standard (CNS) μ Specification (2) 0 × 297 Public Key -39 573208 A7 B7 V. Description of the Invention (37 The components of the composition are dissolved in PM, filtered and coated in a 0.5-ounce unprotected copper shield Surface, 12 mil glass_ring Laminated on the resin. After drying at 130C for 3 minutes, the resulting plate was coated with a dry thickness of 6 g / m2. The plate was imaged on a Clio Diamond 2028F imager. The energy density required to obtain a good image was 250 mJ / square Cm. The plate was developed with 0.7 sodium hydroxide in aqueous solution for 60 seconds to obtain an image with 丨 mil line-to-line ratio. The plate after etching was etched with a conventional alkaline etchant to obtain a sharp conductor edge and 1 mil wire-to-line ratio printed circuit. Application Example 5 The polymer from Preparation Example 4 was dissolved in Donovan PM and used to prepare a thermosensitive composition having the following formula: -------- ---------------- 装 —— (Please read the precautions on the back before writing this page} 、 一 -Τ— Ingredients% by weight acetal polymer 4 15.0 Polyacetic acid Vinyl ester-copolymer-crotonic acid " 3 IR dye-ΝΚ-2911 * 0.08 colorant-crystal violet 0.05 surfactant surfactant 0.05 Dowano PM 81.82: line · ** Alich Corporation * Lin Biochemical Laboratory Company composition The ingredients are dissolved in PM, filtered and coated on 0.5 pans. The drum side is treated without prior cleaning. A 12 mil glass-epoxy laminate was laminated on the surface of the copper shield. After drying at 13 ° C for 4 minutes, the resulting plate was coated with a dry thickness of 9.5 g / m 2. The plate was imaged on a Clio Diamond 2028F imager The energy density required to obtain a good image is 300 mJ / cm2. 4. The paper size is applicable to China National Standard (0) M specifications (2) 0 x 297 mm. 40 573208 A7 ____ B7 5. Description of the invention (38). The plate was developed with 0.75 sodium hydroxide in aqueous solution for 60 seconds to obtain an image with i-mil line-to-line ratio. After the development, the plate was left in a conventional acid chloride steel etchant. As a result, the printed circuit composition and preparation of a sharp conductor edge and a 1 mil wire-to-line ratio were the same as those in Preparation Example 5, but polyvinyl acetate-copolymerization · The crotonic acid copolymer was replaced with a polymethyl methacrylate-co-methacrylic acid copolymer (Alirich). After drying at 13 ° C for 4 minutes, the resulting plate was coated with a dry thickness of 9.5 g / m 2. The plate was imaged on a Clio Diamond 2028F imager. The energy density required to obtain a good image was 250 mJ / square Cm. The plate was developed with 0.8 sodium hydroxide in aqueous solution for 60 seconds to obtain an image with a 1-mil line-to-line ratio. The plate after etching was etched with a conventional alkaline etchant to obtain a sharp conductor edge and a dense Printed circuit with ear-to-ear ratio. Application Example 7 The polymer obtained from Preparation Example 4 was dissolved in Donovan PM, and used to prepare a thermosensitive composition having the following formula: Ingredient% by weight to acetal polymer 4 20.0 IR Dye_ADS_830 * 0.1 Colorant-Crystal Violet 0.2 Surfactant 0.05 Dowano PM 79.65 * American Dye Source Company's paper standards are applicable to Chinese national standards (3) A4 size (2) 0X297 mm

Order ----- (Please read the precautions on the back before filling this page). Line 丨 41 573208 A7 B7 V. Description of the invention (39 solution coated on 1 mil thick polyester liner with arc treatment, And dried at 120 ° C for 5 minutes. The dry thickness of the resistive film after coating was 12 microns. The film was thermally laminated to 0.25 ounces of 8 mil glass on the drum side treated copper shield surface without pre-cleaning. Laminated with epoxy resin (roller heated to 100c). The polyester cover was removed and the plate was imaged on a Creo Diamond 202817 imager. The energy density required to obtain a good image was 300 mJ / square Cm. The plate was developed with 0.9% sodium hydroxide in an aqueous solution for 60 seconds to obtain an image with} mil line-to-line ratio. The plate after etching was etched with a conventional acid etchant to obtain a sharp conductor edge and dense. There was no sign of adhesion failure on the printed circuit of the ear-to-line ratio. Application Example 8 The polymer obtained in Preparation Example 5 was dissolved in PM and was used to prepare a heat-sensitive composition having the following formula:% by weight 15.0 Ingredient Acetal Polymer 5 Fish _ Accelerator-Polyurethane 0.35 IR Dye-NK-2911 ** 〇.08 Colorant-Methyl Blue 〇.05 Surfactant 005 Donovano PM 84.57 Natrium Labs Inc. Butyne-1 4-diol and 58 斿 肀 肀 兰 兰 兰 兰 孕 孕 杂 义 杂 杂 杂 杂 杂 杂 杂 杂 灭 ⑼ ⑼ ⑼ ⑼ ⑼ 克 ㉝ ㉝ ㉝ 之 The composition of the composition is dissolved in PM, filtered and coated in 0.5 ounces without prior 8 mil glass-epoxy laminate on a clean, double-treated copper shield surface. After drying at 130 ° C for 4 minutes, the resulting plate is coated with a dry thickness of 8 g / m2. The plate is a Clio diamond 2028F imager imaging. The energy density required to obtain a good image is 250 mJ / cm2. Flat plate at 573208 A7 B7 V. Description of the invention (405% sodium hydroxide was developed in aqueous solution for 60 seconds. Image of ear-to-line ratio. The developed plate was etched with a conventional alkaline etchant to obtain a printed circuit with a sharp conductor edge and a 1-mil line-to-line ratio. Also & MM1 Polymerization from Preparation Example 7 It dissolves MPM, and is used to prepare a heat-sensitive composition having the following formula: knife-to-weight% acetal polymer 7 18 〇Number ^ ASL-2,4,6-ginseng (2-propynyloxy) -ns · Sangen 002 IR dye-ADS-830 * 〇08 Colorant-methyl blue surfactant 〇 多Wano PM 81 8 * The ingredients of the American Dyestuffs Corporation composition are dissolved in PM, filtered and coated on a 0.5 ounce glass-epoxy laminate of a copper shield surface scratched with a wave of stone. After drying at 130C for 3 minutes, the resulting plate had a fen layer of 5 g / m 2 dry thickness. The plate was imaged on a Clio Diamond 2028F imaging machine. The energy density required to obtain a good image is 200 mJ / cm2. The plate was developed with 2% sodium hydroxide in aqueous solution for 40 seconds to obtain an image with a 1-mil line-to-line ratio. The developed plate was etched with a conventional alkaline etchant. As a result, a printed circuit with a sharp conductor edge and a 1-mil wire-to-line ratio was obtained. Application Example 10 The polymer obtained from Preparation Example 8 was dissolved in PM and used to prepare the paper with the applicable Chinese National Standard (CNS) A4 specification Ulx297 mm. (Please read the precautions on the back before filling this page ). One appeal 丨: Line 丨 43 573208 A7 __ _B7_ V. Description of the invention (41) The thermosensitive composition with the following formula: Ingredient% by weight acetal polymer 8 12 > 8 Adhesion promoter-2-6 (2-propynyl gas) -1.55 ^ ^ 〇〇3 IR dye-ADS-830 * 〇005 color agent · Crystal Violet 005

Surfactant 0.M Dovano PM 87 q2 * The ingredients of the American Dyestuffs Corporation composition are dissolved in PM, filtered and coated on 05 ounces. 12 mils of pre-cleaned and drum-side treated copper shield surface. Glass-epoxy laminate. After drying at 130 ° C for 3 minutes, the resulting plate was coated with a dry thickness of 9.5 g / m 2. The plate was imaged on a Creo Diamond 202817 imager. The energy density required to obtain a good image is 300 mJ / cm2. Plate at 2% sodium carbonate in water at 35. (^ Development is 60 seconds, and it is washed with hot (45 ° C) water to obtain an image with a 1 mil line-to-line ratio. After development, the plate is etched with a conventional acid vaporized copper etchant, and the result is sharp. Printed circuit with conductor edge and 1 mil line-to-line ratio. Application Example 11 The polymer obtained in Preparation Example 6 was dissolved in Donovan pM and used to prepare a thermosensitive composition having the following formula: Acetal polymer 6 This paper size applies Chinese National Standard (CNS)% weight ratio 12.0 (Please read the precautions on the back before writing this page) Order -----: Line 丨 44 573208 A7 B7 V. Description of the invention (42 IR dyes -ADS-830 * 0.12 Colorant · Crystal Violet 0.05 Surfactant 0.03 Donovan PM 87.8

S Note The components of the composition are dissolved in PM, filtered and coated on the anodized aluminum surface. After drying at 12CTC for 3 minutes, the resulting plate had a coating thickness of 2.5 g / m2 | dry thickness. Plates were imaged on the Creo Plate Setter 3244. The energy density required to obtain polar images is 250 mJ / cm². The plate was developed with a 5.5% sodium hydroxide solution in water for 80 seconds, washed with water and dried. Using a sheet feeding press and black ink in a commercially available process, the printing plate was subjected to a compression operation without any image wear. A 5% mark is acceptable on a 150 mesh / inch screen. The details of the present invention have been described with reference to certain preferred embodiments, but it should be understood that various changes and modifications can be made within the spirit and scope of the present invention. This paper size applies to China National Standard (CNS) Α4 size (2K) × 297 male and female 45

Claims (1)

573208 Bulletin VI. Scope of Patent Application Patent No. 89126927 claims for amendment of the scope of the patent. This revision date: April 1992 A positive action anti-corrosion element, including a metal sublayer, an alloy sublayer, or a printing board including a substrate with at least one metal surface and A positive heat-resisting agent is used to adhere to the at least one metal surface, and the positive-acting heat-resisting material contains an acetal polymer containing the general formula: Vy ° 0, > · \ / Ιο *-? Fr & 1 · CH \ R 1 where RA_CnH2n + 1 where n = l-12; R2 is Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy where R4OH; R5 = -0H or -OCH3 · or Br- or -O-CH2-C eCH; and R6 = Br- or N02 R3 =-(CH2) n-COOH or -C three CH or one ^^ ~% where R7 = COOH,-(CH2) 3COOH, -0- (CH2) 2-C00H, and m = 5-40% mole ratio, n = 10-60% mole Ear ratio, 〇 = 0-20% Morse ratio, p = 1- 10% Morse ratio, this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 g t) IIII If II-· 1111111 ^ · 111111 I Γ Jr. (Please read the notes on the back before filling out this page) 46 Patent application scope q = 5-50% Molar ratio; and an infrared light absorbing material whose content accounts for the positive action anti-corrosion layer 0.01 to 20% by weight. 2. The positive-acting anti-corrosion element according to item 1 of the scope of patent application, wherein the positive-acting anti-corrosion layer is a positive-acting anti-corrosion layer comprising: an acetal polymer containing 5-40% (Moore's reference) ) Aliphatic acetal group ', 10-60% (Mole basis) phenolic acetal group, and an infrared light absorbing material, the content of which is 0.01 to 20% by weight of the positive-acting thermal corrosion layer. 3. The positive-acting anti-corrosion element according to item 丨 or 2 of the scope of the patent application, wherein the metal is selected from the group consisting of chromium, inscription and copper. 4. The positive-acting anti-corrosion element according to item 1 or 2 of the scope of patent application, wherein the metal is selected from the group consisting of aluminum and copper; and the anti-corrosion layer contains an adhesion-promoting amount with an acetylene bond Of compounds. 5. The positive-acting heat-resistant money element according to item 1 or 2 of the scope of patent application, wherein at least one of the side groups of the side group acetal resin has an acetylenic bond based thereon. 6. The positive-acting heat-resistant element according to item 1 or 2 of the patent application scope, wherein the infrared light absorbing material includes an infrared light absorbing pigment. 7. The positive-acting heat-resistance element according to item 1 or 2 of the patent application scope, wherein the infrared light absorbing material comprises an infrared light absorbing dye. 8. If the positive-acting anti-corrosion element of item 1 or 2 of the patent application scope, wherein the heat-resistant # layer does not contain a photosensitive compound, its imaging ability can be changed when it is irradiated with ultraviolet or visible light radiation. The size of this paper is suitable— (2iq 297 mm) 573208 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and applied for a patent scope 9. If a positive-acting anti-corrosion element of the scope of patent application item 1 or 2, The layer has an average thickness of 1 to 30 micron. 10_ —A type of positive action anti-corrosion element comprising a copper-containing substrate bonded to at least one surface of the substrate and a positive-acting heat-resistant surname layer having a thickness of 1 to 30 microns, the layer comprising: a) — Acetal polymer, containing 5-40 ❶ / 〇 (Mole basis) aliphatic acetal group 'and 10-60% (Mole basis) hope system acetal group, and b) an infrared light absorbing material, which The content is 0.01 to 20% by weight of the positive-acting anti-corrosion layer. 11. A dry film buildable resist element comprising a removable carrier, a positive-acting heat-resistant layer having a thickness of about 3 to 50 microns is removably attached to a release surface thereof, and the layer comprises: An acetal polymer containing 5-40% (Mole-based) aliphatic acetal group 'and 10-60% (Mole-based) phenol-based acetal group, and an infrared light absorbing material, the content of which is positive 0.01 to 20% by weight of the anti-corrosion layer. 12 · —A method for synthesizing a polyvinyl acetal polymer such as the one in the scope of the patent application, comprising a) using a hydroxyl group to replace the aromatic aldehyde and a strong catalyst acid acetalizing polyvinyl alcohol, and controlling the use of a hydroxyl group to replace the aromatic The amount of acetal hydrolysis obtained by acetalization of aldehydes is controlled by removing water from polyvinyl alcohol and hydroxyl-substituted aromatic aldehydes by distillation before the acetal reaction is completed. Achieved by radically substituted aromatic water; or b) using hydroxyl substituted aromatic aldehydes and strong catalysts to acetalize polyvinyl alcohol 'and controlling the use of radically substituted aromatic acids for shrinking to reach paper costs Chinese National Standard (CNS) A4 Specification (2) 0 X 297 mm Order I 48 573208, the amount of shrinking base hydrolyzed in the scope of the patent application, the control method is through the completion of the acetal reaction 'with the addition of water and water The reaction produces volatile and / or inert materials. 13. The method of claim 12 in which the material capable of reacting with water is selected from the group consisting of organic carbonates, orthoesters of carbonic acid or carboxylic acids, and silicon-containing compounds. 14. A direct method for making an imaging pattern on the surface of a printing plate, the method comprising the steps of forming a positive-acting anti-corrosive printing plate as described in the scope of the patent application: a) guiding a focus with sufficient intensity flux The energy beam can reach a selected area of the film to perform a thermally induced transformation based on the solubility properties of the composition; and b) the film is contacted with an imaging agent which can effectively remove the composition from the impacted area of the energy beam. 15. The method of claim 14 in which the surface of the substrate comprises copper or copper. 16. The method according to item 14 of the patent application scope, wherein the positive-acting resist composition further includes an adhesion-promoting amount of a compound containing a fast-type bond (0 297 mm). Order & Application of Chinese National Standards (CNS) ) A4 specifications (2J0: 49