JPH06506709A - Photosensitive composition containing comb polymer binder - Google Patents

Abstract

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

Description

[Detailed description of the invention] name of invention Cross-reference to applications related to photosensitive compositions containing comb polymer binders This patent application is pending patent application No. 07/6 filed on February 28, 1991. This is a continuation-in-part of No. 62.540.

Background of the invention The present invention is considered a type of comb polymer. The present invention relates to novel compositions of substances. The present invention relates to liquids containing such polymeric products. and solid imaging and photosensitive compositions, and also relates to solid imaging and photosensitive compositions, and Including use as photoresist and solder mask.

Polymeric products are used as components of imaging and photosensitive systems, and in particular in J. Ko. sar, r photosensitive systems - Chemistry and applications of non-silver halide photographic processing methods J (John Viley & 5ons, Inc.

1965), and more recently J, Sturge, V, Walworth. and^.

Edited by 5hepp, [Methods and materials for image formation - Nebulette edition, 8th edition (V An No. 5 trand (Re1nhold, 1989) Used in image forming systems. In such systems, actinic radiation Collisions with materials containing substances, causing physical or chemical changes in the materials. Useful images A latent image is thus created that can be processed into a useful image. . Typical actinic radiation useful for imaging spans the near-ultraviolet to visible spectral range. Light, and if so, may also include infrared rays, deep ultraviolet rays, X-rays, and electron beams. There is.

Although the polymeric product itself can be photoactive, generally the photosensitive composition is - Contains one or more photoactive components in addition to the product. exposure to actinic radiation The photoactive components act to modify the rheological state, solubility, surface properties, refractive index, color, electromagnetic properties or photosensitive compositions as described in the Neblett publication above. Other physical or chemical properties of the thing change.

The polymer product is exposed to light as described in Chapter 7 of the Neblett publication cited above. Particularly useful in polymerizable systems. Such photopolymerizable systems typically contain 1 as a binder. one or more linear polymers, and one or more terminal ethylenic polymers. Contains at least one addition-polymerizable monomer component having a saturated site. often ends A combination is a simple blend of polymers, i.e. a homogeneous mixture of two or more polymers. A quality mixture that has no covalent chemical bonds between different types of polymer chains. be. During imaging exposure, the heptamer component polymerizes and/or crosslinks to form a polymer or form a polymer network within which at least some of the polymer binder is trapped. The exposed portions are thereby photocured or insolubilized.

Comb polymers have a large number of branched polymer segments that form the main chain segment of a linear polymer. A particular type of branched polymer that is bonded along the Comb polymer is It can be said to be a linear polymer with polymer arms. Such polymers are They are usually made by copolymerizing conventional monomers with macromers. Ma Chromer is a term used by Kavaka i as a term for polymer chemistry and engineering. 9, pp. 195-204 (John filey & 5ons.

New York, 1987), it has a molecular weight of several hundred to several hundred, and has a Functional groups that can be further polymerized, such as ethylene, epoxy, dicarboxylic acids, It is defined as a polymer with diol or diamino groups. European Patent Application No. 28 No. 0,979 is a printing plate for such a polymer. or as a binder in photopolymerizable materials suitable for the production of resist patterns. is disclosed. The disclosed polymer binder consists of a film-forming copolymer, which those in which at least one phase has a glass transition temperature below room temperature and less than Both are multiphase forms in which one other phase has a glass transition temperature above room temperature. This The polymer has an average molecular weight (weight average) greater than 10.000, and Ethylenically unsaturated monomers with an average molecular weight (weight average) of 00 to 100.000 made using

Although the physical and chemical properties of existing comb polymers are desirable for some photosensitive systems, The branch polymer segments of the comb polymers used are highly polydisperse and commonly They usually have high molecular weights and are relatively expensive to manufacture. It has a clearly outlined structure, They are cheap to manufacture and process well in photoimaging systems to be tough, flexible, and dense. Create comb polymer binders with hydrophilic functionality that is useful for adhesion or other purposes. , and their end use performance needs to be reduced while process steps are improved. , cannot be addressed with current technology.

Summary of the invention The present invention provides one or more chemically bonded along a linear polymer backbone segment. branched polymer products containing hydrophilic groups consisting of many branched polymer segments. in which the branched polymer product contains at least one ethylenically unsaturated macromer. - formed during the addition polymerization of the component and at least one ethylenically unsaturated comonomer. and in that (a) The ethylenically unsaturated macromer component is thicker than 40.000 (no weight average) (b) The linear polymer backbone segment has an average molecular weight (Iv) of approximately 10.00 having a weight average molecular weight ( ) of 0 to about 500,000, (C) a linear polymer; The weight ratio of main chain segment to branch polymer segment(s) is approximately 2 00/1 to about 1/4; and (d) a branched polymer segment. The component(s) contain about 35% to 100% hydrophilic groups.

More particularly, the present invention provides branched polymeric products containing hydrophilic groups and at least It relates to sensitive compositions consisting of one photoactive or thermally active component. Specific devices of the present invention The example is (a) Numerous branch polymers chemically bonded along a linear polymer backbone segment -branched polymer products consisting of segments (in which branched polymer segments is at least one ethylenically unsaturated containing one or more hydrophilic functional groups Formed during addition polymerization of branched polymer products from macromer components; The ethylenically unsaturated macromer component is thicker than 30,000 (no weight average molecular volume (ml, ) and polydispersity (11,/l1n) not greater than about 5), and Beauty (b) A sensitive composition comprising at least one photoactive or thermally active component.

detailed description of the invention The sensitive compositions of the present invention contain branched polymer segments known as polymer arms. Contains a novel branched polymer product known as a comb polymer with Branched polymer segments have limited molecular weight and linear polymer backbone segments. hydrophilic acid that has a limited weight ratio and is typically present in the polymer product Contains most of the sexual groups. The composition also contains components such as catalysts and photoinitiators; makes the composition responsive to heat and/or radiant energy.

Polymer raw grilled food The branched polymer product contains hydrophilic groups and linear polymer backbone segments consisting of one or more branched polymer segments joined along. branch poly The mer product comprises at least one ethylenically unsaturated macromer component and at least Formed during free radical addition polymerization of one ethylenically unsaturated comonomer. Echire The functionally unsaturated macromer component has a weight average molecular weight not greater than 40,000. ), and the linear polymer main chain segment produced by polymerization is approximately 10.0 00 to about 500.000. Linear polymer main chain The weight ratio of segment to branch polymer segment is from about 2θ0/1 to about 1/4. range, preferably from about 80/20 to about 60/40. good Preferably, the macromer component ranges from several hundred to about 40,000, and even more preferably about It has a weight average molecular weight (Ml) of 6.000 to about 15.000. Typically that Ethylenically unsaturated macromer components such as 2 to about 500 monomer units used, and preferably 30 to 200 monomer units. It can have a weight average molecular weight (1,) equivalent to the molecular weight of the mer unit.

The branch polymer segment comprises about 35 to 35 of the total hydrophilic groups present in the branch polymer product. 100% by weight, and preferably from about 50% to 100%. Preferred hydrophilic group is a protic group such as hydroxy, amino, ammonium, amide, imide, or Rethane, ureido, or mercapto; or carboxylic acid, sulfonic acid, sulfine acid, phosphoric acid, or phosphonic acid, or a salt thereof. Preferably, the hydrophilic group is Acid groups and especially carboxylic acid groups, but other groups such as hydroxy are also present. be able to. The acid-containing branched polymer products of this invention typically have about 3 to about 2 0% by weight and preferably from about 5% to about 10% acid groups. Such acid-containing branches The branched polymer segments of the split polymer product typically contain 35 of the acid groups present. % to 100%. When the hydrophilic group is an acid group, such branched polymer products are preferred. preferably has an acid value of about 20 to about 90, more preferably about 40 to about 70; and the ethylenically unsaturated macromer component preferably has a molecular weight of about 50 to about 650, and even more Preferably, it has an acid value of about 90 to about 300.

Alternatively, the branched polymer product may contain basic groups, e.g. It can contain a mino group.

In this case, the ethylenically unsaturated macromer component preferably has a molecular weight of from about 20 to about 90%. so preferably has an amine value of about 40 to about 70 and an ethylenically unsaturated macromolecule. The Roman component preferably has a molecular weight of about 50 to about 650, more preferably about 90 to about 30. It has an amine value of 0.

In certain embodiments, the branched polymer product comprises linear polymer backbone segments. It consists of a large number of branched polymer segments chemically bonded along the The polymer segment has a weight average molecular weight (W) of about 30,000 and a weight average molecular weight of about 5 or less. has a polydispersity (11,/m1n) lower than that of also has one hydrophilic group. Polydispersity, in its conventional sense, refers to the weight average molecular weight (M , ) to the number average molecular weight (Mo), that is, l1w/In.

The branched polymer products of this invention have one or more hydrophilic functional groups thereon. is a copolymer of at least one ethylenically unsaturated macromer component attached . Generally the total polymer molecular weight is up to about 500,000, but higher molecular weights are also possible. It is possible.

The branched polymer product contains at least 0.5% by weight of branched linear segments.

Branch linear segments are also known as polymer arms and are typically Evenly distributed along the chain segment. “Polymer arm” or branch polymer segment The ment can be a polymer or oligomer (both of two repeating monomer units). , which is covalently attached to the linear polymer. branch polymer seg Ment or polymer arms are polymerized during the addition polymerization process of macromers and comonomers. Incorporated into the branched polymer product as a chromer component. Purpose of the invention A "macromer" for use in polymers contains from several hundred to about 40. Polymers, copolymers or oligomers with molecular weights up to 0.000. Preferably Macromers are linear polymers or copolymers end-capped with ethylene groups. be. Typically, branched polymer products include one or more polymer atom(s). and preferably a copolymer having at least two polymer arms. , and about 0.5 to about 80% by weight of the monomer components used in the polymerization process are macromolecules. It is characterized by being a mer. Typically used with macromers in the polymerization process. The comonomer component likewise contains a single ethylene group, which is an ethylenically unsaturated polymer. Can be copolymerized with chromer.

Branched polymers of ethylenically unsaturated macromers and resulting branched polymer products One or more hydrophilic functional groups are attached to the segment. Eyes of the invention For purposes of this, a "hydrophilic group" refers to a macromer and/or a branched polyester to which it is attached. refers to a functional group that increases the solubility, swelling, or dispersibility of the mer product in an aqueous environment. shall be tasted. Preferred hydrophilic groups are protic functional groups such as hydroxy, carbon, etc. Rubonic acid, amino, ammonium, amide, imide, urethane, ureido, sulfuric acid Phonic acid, sulfinic acid, phosphoric acid, phosphonic acid, mercaptan or a salt thereof.

Functional groups may be incorporated into the ethylenically unsaturated macromer during or after its formation. however, typically assembly is performed prior to formation of the branched polymer product. engulf it.

Branched polymer segments attached to linear polymer backbone segments are U.S. patented 4.680.352 and the general description of U.S. Pat. No. 4,694.054. or any of those derived from ethylenically unsaturated macromers, as disclosed above. is incorporated herein by reference. Macromers are cobalt compounds, especially cobalt (If) produced by free radical polymerization using the compound as a catalytic chain transfer agent . Cobalt (n) compounds are pentacyanocobalt (■) compounds or vicinal imitations. dihydroxyimino compounds, dihydroxyimino compounds, diazadihydroxyimino compounds Minodialkyldecadiene, diazadihydroxyiminodialkylundecadiene Tetraazatetraalkylcyclotetradecatetraene, Tetraazatetraene Alkyl cyfurotide decatetraene, bis(difluoroboryl) diphenylglycium Oxymato, bis(difluoroboryl)dimethylglyoximato, N, N'- Bis(salicylidene)ethylenediamine, dialkyldiaza-dioxodialkyl of rudodecadiene or dialkyldiazadioxodialkyl-tridecadiene It can be a cobalt(n) chelate.

A low molecular weight methacrylate macromer as disclosed in U.S. Pat. No. 4,722,984. It can also be made using a pentacyanocobalt (n) catalyzed chain transfer agent, as described above. The disclosure is incorporated herein by reference.

Examples of macromers are vinyl polymers, acrylic polymers, and acrylic monomers and vinyl polymers. In this case, the polymer or copolymer has a terminal polymer. It has a non group and a hydrophilic functional group. Preferred models that can be used to produce macromers Nomer components are methyl methacrylate (IIIA); ethyl methacrylate ( EIA), butyl methacrylate (Bll^); 2-ethylhexyl methacrylate Rate: Methyl acrylate (薖＾): Ethyl rare acrylate (EA).

Butyl acrylate (BA); 2-ethylhexyl acrylate: 2-hydroxy Ethyl methacrylate (HIJA); 2-hydroxyethyl acrylate ( tlE^); Methacrylic acid (薖^A) Niacrylic acid (A^); Ester group is 1~ Acrylic and methacrylic acid esters containing 18 carbon atoms; acrylic and methacrylic acid esters containing 18 carbon atoms; Nitriles and amidonigrindyl methacrylates and acrylates of acrylic acid; Itaconic acid (IA) and itaconic anhydride, half esters and imides: maleic acid and and maleic anhydride, half esters and imides: aminoethyl methacrylate; t- Butylaminoethyl methacrylate, dimethylaminoethyl methacrylate: Di Ethylaminoethyl methacrylate; aminoethyl acrylate dimethylamine Noethyl acrylate; Diethylaminoethyl acrylate; Acrylamide; N-t-octylacrylamide; vinyl methyl ether; styrene (S): a Contains rufer methyl styrene; vinyl acetate; vinyl chloride, etc.

In contrast to prior art comb polymers, the branched polymer products of the present invention The polymer segment is a macromolecule from which the branched polymer product is created. It has a limited molecular weight, polydispersity and hydrophilicity determined by the mer components.

The macromers useful in this invention have a limited molecular weight and a limited polydispersity. Sometimes there are degrees. Preferably, the macromer has about 40,000 to several hundred It has a weight average molecular weight (11). In certain embodiments, the macromer has about 5 or It has a polydispersity (if, /wn) smaller than that. Low molecular weight limit of macromers A field is a molecule of two, three or four heptad units used in macromer formation. It is equivalent to quantity. Preferably the macromer component used in its formation is from 2 to about 50 0 monomer units, and preferably 30 to 200 monomer units It has a weight average molecular weight (Iv) equivalent to the molecular weight. Typically macromer components are branched from about 0.5% to about 80% by weight of the ingredients used in making the polymeric product, and preferably Preferably, it comprises about 5 to about 50% by weight.

Branched polymer products may be prepared by any conventional addition polymerization method. Can be done. one or more branched polymer products or comb polymers a compatible ethylenically unsaturated macromer component and one or more compatible conventions; can be prepared from commercially available ethylenically unsaturated comonomer components. preferred attachment The polymerizable ethylenically unsaturated comonomer component is methyl methacrylate (■^) : Ethyl methacrylate (EIA); Butyl methacrylate (BIA); 2-Ethylhexyl methacrylate: Methyl acrylate (MA), ethyla Acrylate (EA), butyl acrylate (BA): 2-ethylhexyl ac Lylate; 2-hydroxyethyl methacrylate (tlEso^): 2-hydroxy Ethyl acrylate (HE^); methacrylic acid (IAA), acrylic acid (^ ^); Itaconic acid (IA) and itaconic anhydride, half esters and imides: Malay amino acid and maleic anhydride, half esters and imides; aminoethyl methacrylate :t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate G; Diethylaminoethyl methacrylate; Aminoethyl acrylate dimethacrylate Diethylaminoethyl acrylate; Diethylaminoethyl acrylate: Acrylic acid Mid; Nt-octylacrylamide; Vinyl methyl ether: Styrene (S ); alpha methylstyrene; vinyl acetate; vinyl chloride, etc.

The linear polymer backbone segments and components of each component of the branched polymer products of this invention and/or branch polymer segments may contain various functional groups, including the hydrophilic functional groups described above. be able to. "Functional group" refers to polymers or Let be any moiety that can be attached to a branch polymer segment. polymer main Examples of functional groups that chain segments or branched polymer segments can have are -CO OR, -OR, -3R (wherein R is hydrogen, alkyl of 1 to 12 carbon atoms, or loalkyl, aryl, alkaryl or aralkyl, heterocyclic, or -OR, where R1 is alkyl, aryl, alkyl of 1 to 12 carbon atoms. Can be karyl or aralkyl ): -CN; -NRlR, or -C-1tR2R8 (wherein R3 and R8 are water alkyl or cycloalkyl of 1 to 12 carbon atoms, aryl, alkali Aralkyl, -CIl*0R4 (wherein R4 is hydrogen, aralkyl of 1 to 12 carbon atoms) or cycloalkyl, aryl, alkaryl, aralkyl or R1 and R3 together form a heterocyclic ring. ); -C-CRsRt (wherein 5, R6 and R7 are hydrogen, 1 to Alkyl or cycloalkyl, aryl, alkaryl, ara of 12 carbon atoms or -COOR, or R8, Ro and/or R7 are ring 80,5 urethane group; isocyanate or Blocked isocyanate group; Urea group; Oxirane group Niasiridine group; Nondiazide group; azo group, niasito group; diazonium group, niacetylacetoxy group; -5iR@R@R,. (In the formula, R8, R9 and I?to are 1 to 12 carbon atoms or cycloalkyl or -OR, where R11 is 1 Alkyl or cycloalkyl, aryl, alkaryl, alkyl of ~12 carbon atoms ralkyl): or -03O3R,, -0POtR+t, -PO,R,! , -PR+ tR+ sR+ <, -0POR+ t, -3R+ J + s, or -N 14 groups (wherein R11, R13 and R14 are water alkyl or cycloalkyl of 1 to 12 carbon atoms, aryl, alkali aralkyl, aralkyl); or a salt or onium salt of any of the foregoing. It is. Preferred functional groups are -COOH, -0■, -NFIm, amide group, vinyl group, urethane group, isocyanate group, blocked isocyanate group or It is a combination of these.

The functional group may be located at any position on the branched polymer product. However, there are In order to impart bulky polymer properties to the linear polymer backbone segments of the polymer product, Physical and chemical functionality other than hydrophilicity in comonomers and branched polymer segments For example, it is desirable to select a macromer that imparts solubility, reactivity, etc.

The present invention utilizes multiple branches chemically linked along a single linear polymer backbone segment. Dispersions, solvents and melts of branched polymer products consisting of polymer segments , coatings and molded articles, in which case the technical polymer segment is one or more contains fewer (and one ethylenically unsaturated) macromers containing more hydrophilic functional groups. - formed during the addition polymerization of branched polymer products from components, in which ethylene The unsaturated macromer component has a weight average molecular weight (weight average molecular weight) greater than about 40,000. ,)have. The polydispersity (MW/an) is not greater than about 5. The present invention particularly and further comprises at least one photoactive or thermally active component. Regarding scattering.

Dispersions or solutions of polymer products can be used in industrial and chemical applications with or without the addition of pigments. Can be used to create coatings for cosmetic and automotive purposes . They are especially used for surface abrasion-resistant finishes, coatings, and plastics on automobile and truck parts. Useful as a coating for plastic auto parts and as a pigment dispersant. this minute The powder or solution may be mixed with nail polish remover or other such cosmetic coatings or materials. It is also useful.

The residue after removing the organic liquid from the dispersion or solution is used in water purification and electrolyzers. As a semi-permeable membrane for automotive structural parts and building panels, as a release film, as an adhesive film, e.g. for the production of multilayer printed circuits. as a photoresist, as a solder mask, and as an aircraft and automatic A useful filler for making curved panels of various plastic materials in car manufacturing. Can be used to create lums.

Branched polymer products can also be extruded or molded into a variety of useful shapes. Can be used as an elastomer, gasket, hose, belt and It can be used in the manufacture of bushings and bushings and as an adhesive.

Excellent toughness-flexibility balance and solvent resistance in one branched polymer product or higher polymer components with epoxy, isocyanate and aminoblasts. Branched polymers can be created by cross-linking with cross-linking agents such as resins. The compositions are particularly suitable for sensitive compositions containing only a small amount (both containing one photoactive or thermally active ingredient, and It is particularly useful for photosensitive compositions such as photoresists, solder masks, etc. These will be further described to illustrate the invention. “Photosensitivity” and “photoactivity” are synonymous. ``Sensitivity'' means that its chemical or physical properties change or change when exposed to actinic radiation. directly, e.g. to form an image, or a precursor e.g. refers to a substance that forms a latent image that is further processed to produce the desired change It is. ``Thermal activation'' is when the temperature is increased or when a substance is added or removed. In other words, it refers to a substance that changes or causes a change in its chemical or physical properties. So Examples of photoactive or thermally active components such as cyclizing, dimerizing, polymerizing, crosslinking, produce ionic species or dissociate when exposed to actinic radiation or heated It is a substance that The photoactive or photosensitive component is a photoinitiator, a photosensitizer, or a combination thereof. : Solubilizer; Photodesensitizer: Photoinhibitor: Phototackifier; Photodetackifier: Or photo Disintegrability; Photochromic: Photoreducibility; Photooxidation; Photoadhesion: Photopeelability; Photomagnetism ; photodemagnetizing; containing photoconductive or photoinsulating components; or refractive index by exposure to actinic radiation; A substance that changes or causes a change to occur. The sensitive composition of the present invention a substance that binds component (b) to component (a) in (i) Polymerizable monomer, and (if) Contains a substance consisting of an initiation system that can be activated by actinic radiation.

The branched polymer products are useful for photosensitive systems and especially for photosensitive systems, J. Kosar, r. Chemistry and Applications of Non-Silver Halide Photographic Processing Methods J (John 1iley & 5o ns, Inc., 1965), and more recently J. Sturge, V. Wa. lworth and^, edited by 5hepp, [Methods and materials for image formation-Neb "letter version, 8th edition" (Van No5trand Re1nhold, 19 It is useful as a component of photoimaging systems such as those described in 89). Such a system In , actinic radiation impinges on a material containing a photoactive component and causes physical or causes chemical changes. A useful image or one that can be processed into a useful image. This is how a latent image is created. The typical actinic radiation useful for image formation is near violet. Light from outside that spans the visible spectrum, including infrared and deep violet It may also include external radiation, x-rays and electron beams.

Although the polymeric product can itself be photoactive, generally the photosensitive composition is - Contains one or more photoactive components in addition to the product. When exposed to actinic radiation, Photoactive components act to modify rheological state, solubility, surface properties, refractive index, color, and electromagnetic properties. photosensitive compositions such as those described in the Neblett publication above. The physical or chemical properties of the substance change.

Typically, the photosensitive compositions of the invention are used in the form of a supported film or layer. However, unsupported solid articles can also be made. Applying the photosensitive composition to a suitable substrate a continuous film or layer is formed thereon, which is directly image-wise exposed to actinic radiation. forming an image or latent image. Alternatively, this layer can be uniformly exposed to actinic radiation to harden the layer. or cure or harden, at which time the photosensitive composition can be continuously or is a patterned layer, either in the form of a protective finish, paint or ink, e.g. It can be applied with. Any conventional actinic radiation source can be used; lamps, discharge lamps and incandescent lamps, as well as laser, X-ray and electron beam equipment. child The layer can be applied as a pure solvent-free photosensitive liquid or as a solution and dried to solidify. body layer, in which any conventional coating or printing method can be used. can be used. Alternatively, this layer or film can be used as a supported solid photosensitive layer. can be applied by laminating it to a substrate and then optionally removing the support. Ru.

Applications that do not require additional processing steps after exposure to actinic radiation are those in which the image is formed directly. , for example, Laugh, U.S. Pat. No. 3,658., whose refractive index changes upon exposure to actinic radiation. 526, a photosensitive polymer hologram disclosed in Gervay and tal ker, a penetrating resist disclosed in U.S. Pat. No. 3,718,473, Ce5con a ndDessaurer, color-forming systems disclosed in U.S. Pat. No. 3,445,234 or others. including photochromic systems. Color-forming systems based on photooxidizing or photoreducing agents are 1 IacLachlan, as disclosed in US Pat. No. 3,390,996. decoration apply a protective coating and photocure or apply a patterned layer. and photocuring applications, such as Lipson et al.

Photoresist screen printing ink disclosed in U.S. Pat. No. 4.003.877. Ki is also included.

When forming a latent image, the exposed or unexposed portions of the layer containing the latent image are then exposed or unexposed. The material is deposited or removed on or in the exposed or unexposed areas, except for the exposed areas. The imaging layer is modified by processing the layer and developing the imaging layer.

Deep-lead the exposed or unexposed parts of the layer using a solvent or aqueous alkaline developer. Leaf images or thin stencil images can be formed or they can be attached to the substrate. It can be peeled off from any remaining unexposed or exposed areas that adhere to it. of relief Deep relief images that taper on the sides and do not extend into the substrate are typically letterpress Used as a printing plate for printing or flexographic printing, eg Plabeck.

U.S. Patent 2.760.863 and Brennen and Chen, U.S. Patent 4, 323.637. In contrast, stencil images A thin relief with side walls that fall perpendicular to the plate, thereby allowing the remaining uncoated forming a thin substrate surface portion. Stencil images have many uses, for example Ce1 este, as a resist disclosed in U.S. Pat. No. 3,469,982,^1ie s, as a lithographic printing plate disclosed in U.S. Pat. No. 3,458,311, by Bratt and Cohen, photosensitive polymer resin disclosed in U.S. Pat. No. 4.229.517. Colgrove, U.S. Pat. No. 3,353,955, discloses As a release drafting film, or Cohen and Fan, U.S. Pat. No. 4.2 47.619. form a stencil image, When using this as a resist, it forms an unprotected substrate area and further Modifying unprotected surface areas by etching or depositing materials onto them Can be done.

The exposed and unexposed parts of the layer containing the latent image are modified by depositing material onto them. For example, a powder material can be deposited on the unexposed areas, e.g. d　Cohen, optical sharp tackification method in the processing method of U.S. Patent 3.649.268 , or applying a powdered material to the exposed portions of the layer, e.g. Chu et al., USA. Patent No. 4.243.741 and processing of Grossa, U.S. Pat. No. 4,604.340 By phototackification or photoadhesion method in the Act. Riesenfeld et al. In the photoconductive or photoinsulating method disclosed in U.S. Pat. No. 4,732,831, liquid A toner is used to develop the latent image in an electrostatic system. Gorondy.

U.S. Pat. No. 4.105.572, Nacci, U.S. Pat. No. 4.292.120 and N. acci et al., U.S. Patents 4.338.391 and 4.359.516 magneto-optical to apply dyes to textiles and resists to circuit boards as disclosed in Both magnetic and optical demagnetizing systems are used. The photosensitive composition containing the latent image must be treated with a reagent. or by further treatment with actinic radiation or heat. can. Ordinary silver halide or diazo type systems form a latent image upon exposure, which is When treated with a developing reagent, it is developed into a visible image. Some silver halide direct records In direct writing systems, to the visible image Development is achieved by homogeneous exposure to actinic radiation. (In the reversal image forming method) In some cases, processing steps are used to complete the formation of the latent image before or during development. the Such systems are photopolymer systems, such as Pazos, U.S. Pat. No. 4,198.242. or Doeber et al., U.S. Pat. No. 4,477,556. This includes a photoinhibitor, and the image-forming exposure produces an inhibitor in the exposed portions of the layer. , and subsequent uniform exposure to actinic radiation or, in some cases, uniform heating, to produce light A latent image is created in the remaining area without the inhibitor.

Such reversal systems are desensitizing systems, such as Roos, U.S. Pat. No. 3,778,270. and that disclosed in US Pat. The component is decomposed or desensitized to an inactive form and 1 is added to the unexposed areas. Subsequent treatment with reagents develops the components into an image or latent image.

Examples of such photosensitive systems can be found on pages 226-262 of the Neblett publication cited above. Chapter 7 of the page, ^, B, Cohen and P, talker.

It is described in ``Polymer Imaging,'' where photocrosslinking, photodimerization, photocyclization, presolubilization, and ionic and free radical photopolymerization, as well as electrostatic photopolymerization. mer imaging and solid state imaging are discussed. Pages 263-278, No. 8 Chapter, R, Dessauer and C, E, Looney, I” Low amplification image Image-forming systems discussed in "Color-forming free radicals, diazo, and vesicle-forming systems" vesicular systems, photochromism, photoadhesion and Includes optical tackification and thermal and photothermal systems.

photosensitive composition The branched polymer product is added to a photopolymerizable composition containing a monomer material and a photoinitiator system. Particularly useful. In such systems, the branched polymer product is exposed to light and Dispersibility imparting desired physical and chemical characteristics to unexposed photopolymerizable compositions Functions as a polymer binding ingredient. Upon exposure to actinic radiation, the photoinitiator system becomes mole Chain growth polymerization of nomeric materials occurs either by a condensation mechanism or by free radical addition polymerization. vinegar. Although all photopolymerization mechanisms are possible, the compositions and methods of the present invention are unique in that they are Relationship to free radical-initiated addition polymerization of hepatomers with more terminal ethylenically unsaturated groups Described in. In this context, photoinitiator systems exhibit monotony when exposed to chemical 7 radiation. act as a source of reverse-opening radicals necessary to initiate polymerization of the mer. The light initiation of this system The initiator can be activated by a photosensitizer, which increases the absorption spectrum of the initiator itself. It absorbs possible actinic radiation outside the scope of the radiation spectrum to provide more practical radiation spectral regions, e.g. Sensitizes addition polymerization in the near-ultraviolet, visible, and near-infrared regions.

In the narrower sense of the term, the photoactive component of the compositions of the present invention refers to substances that absorb actinic radiation. photoactive substances, such as photoinitiators or photosensitizers, but in a broader sense the term Contains any or all of the essential substances necessary for the component, i.e. photoinitiation system and monomer. Point.

A photopolymerizable composition is a branched polymer product, an initiator system activated by actinic radiation. , and at least one non-gas ethylene having a boiling point higher than 100°C at normal pressure. contains a functionally unsaturated compound and forms a high molecular weight polymer by photoinitiated addition polymerization. can be done. Preferred photopolymerizable compositions include monofunctional or polyfunctional acrylates or contains methacrylate, and particularly preferred two, three or more Contains acrylate or methacrylate groups and can also be crosslinked simultaneously during the photopolymerization process It is a composition.

Addition polymerizable monomer Suitable monomers that can be used as single monomers or in combination with others is t-butyl acrylate, 1,5-bentanediol diacrylate, N, N -diethylaminoethyl acrylate, ethylene glycol diacrylate, 1 ．． 4-butanediol diacrylate, diethylene glycol diacrylate, Hexamethylene glycol diacrylate, 1,3-propanediol diacrylate rate, decamethylene glycol diacrylate, decamethylene glycol diacrylate Tacrylate, 1,4-cyclohexanediol diacrylate, 2,2-dime Tyrolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethylol Propane triacrylate, pentaerythritol triacrylate, polyoxy ethylated trimethylolpropane triacrylate and trimethacrylate and Similar compounds disclosed in U.S. Pat. No. 3,380,831, Droxyphenyl)-propane diacrylate, pentaerythritol tetraa acrylate, 2,2-di(p-hydroxyphenyl)-propane dimethacrylate triethylene glycol diacrylate, polyoxyethyl-2,2-di -(p-hydroxyphenyl)-propane dimethacrylate, bisphenol- A di(3-methacryloxy-2-hydroxypropyl)ether, bisph Di(2-methacryloxyethyl)ether of phenol-A, bisphenol -A di(3-acryloxy-2-hydroxypropyl)ether, bisph di(2-acryloxyethyl)ether of phenol-A, tetrachloro-bi Di(3-methacryloxy-2-hydroxypropyl) ester of sphenol-A ether, tetrachloro-bisphenol-A di(2-methacryloxyethyl di(3-methacryloyl)ether, tetrabromo-bisphenol-A (2-hydroxypropyl) ether, tetrabromo-bisphenol-A di(2-methacryloxyethyl)ether, 1,4-butanediol (3 -methacryloxy-2-hydroxypropyl) ether, diphenolic acid -(3-methacryloxy-2-hydroxypropyl)ether, triethylene Glycol dimethacrylate, polyoxypropyl on trimethylol propane Triacrylate (462), ethylene glycol dimethacrylate, butyle glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1.2.4-butanetriol trimethacrylate, 2,2.4-1-samethyl -1,3-bentanediol dimethacrylate, pentaerythritol trimeta acrylate, 1-phenylethylene-1,2-dimethacrylate, pentaeri Tritol tetramethacrylate, trimethylolpropane trimethacrylate , 1,5-bentanediol dimethacrylate, diallyl fumarate, styrene , 1,4-benzenediol dimethacrylate, 1,4-diisopropenylben zene, and 1,3.5-triisopropenylbenzene.

The type of monomer is an alkylene glycol of 2 to 15 carbons or an ether of 1 to 10 carbons. alkylene or polyalkylene made from polyalkylene ether glycol with alkylene glycol diacrylate and U.S. Patent 2,927.02 2, and these are numerous, especially when present as terminal bonds. It has an addition-polymerizable ethylene bond. at least one and preferably most of them. carbon in which such bonds are double bonded to carbon and heteroatoms such as nitrogen, oxygen and sulfur Preferably, it is conjugated with a double-bonded carbon containing an element. ethylenically unsaturated groups, especially Also preferred are substances in which the vinylidene group is conjugated with an ester or amide structure.

Particularly preferred types of monomers are t-butyl acrylate, cyclohexyl acrylate. ester, hydroxyCl-C1,0-alkyl acrylate, butanediol di Acrylate, hexamethylene glycol diacrylate, triethylene glyco diacrylate, tripropylene glycol diacrylate, pentaeryth litol triacrylate, trimethylolpropane triacrylate, polio xyethylated trimethylolpropane triacrylate, bisphenol-A Di(3-acryloxy-2-hydroxypropyl)ether, tetrabromo Di(3-acryloxy-2-hydroxypropyl) to -bisphenol- ethers, or their methacrylate analogues.

photoinitiator system A photoinitiator system has one or more molecules that directly give free radicals when activated with actinic radiation. have a compound. This system is activated by actinic radiation to produce compounds that give free radicals A sensitizer may also be included. Useful photoinitiator systems typically have close spectral responses. Contains sensitizers that extend into the ultraviolet, visible, and near-infrared regions.

Polymers containing redox systems such as rose bengal/2-dibutylaminoethanol A number of free radical generating compounds can be conveniently selected. Examples of photoreducible dyes and reducing agents For example, US Patent 2.850.445; 2.875.047; 3.097. 096.

3,074.974: 3.097.097: 3.145.104; and and that disclosed in U.S. Patent No. 3.579.339; and U.S. Patent No. 3.427.161 ;3.479.185;3,549.367;4.311.783: 4.622.286: and phenazine described in 3.784.557, Dyes of xazine and quinone compounds; ketones, quinones; 2.4. with hydrogen donors; 5-) Using liphenylimidazolyl dimers and mixtures thereof as initiators can be used. Other initiators are the dyes disclosed in U.S. Pat. No. 4,772,541. Boric acid complex: and disclosed in U.S. Pat. The indicated trichloromethyltriazine. Useful discussion on dye-sensitized photopolymerization Discussion, B., Volman, G., S. Hammond, and K.G. Edited by Ollinick, ^dv, in Photochemistry, Vol. , 13 (Wiley-Interscience, New York, 1 986), pages 427-487, or with F, Eaton, r dye. Sensitized photopolymerization". Similarly, U.S. Patent 4,341.860 Lohexagenone compounds are useful as initiators.

A preferred photoinitiator is CDl-HABI, i.e. 2-(0-chlorophenyl)- 4,5-bis(m-methoxyphenyl)-imidazole dimer; o-CI -HABI, i.e. 1.1'-biimidazole, 2.2'-bis(0-k) lorophenyl)-4,4',5,5'-tetraphenyl-; and TCTI1 4^BI, i.e. IH-imidazole, 2,5-bis(0-chlorophenyl) -4-[3,4-dimethoxyphenyl]-, including dimers, each of which is commonly Use with normal hydrogen donor.

Sensitizers useful in combination with photoinitiators include methylene blue and U.S. Pat. 53; 3.563.750; 3.563.751.

3,647.467; 3.652.275; 4.162.162; 4.268.667.

4,351.893; 4.454.218; 4.535.052; and and that disclosed in 4.565.769. A preferred group of sensitizers is Bau■ etal, bis(p-dialkylar) disclosed in U.S. Pat. minobenzylidene) ketone, and Dueber, U.S. Pat. No. 4,162,162. including the disclosed acrylidene aryl ketones. A preferred sensitizer is DBC, such as Cyclopentanone; 2,5-bis-IC4-Cdiethylamino)-2-methy [luphenyl]-methylene 1. DE^1, i.e. cyclopentanone, 2,5-bi Su-1[4-(diethylamino)-phenyl]methylene) Nidimethoxy JDI , i.e. tn-inden-1-one, 2,3-dihydro-5,6-simethoxy -2- ((2,3,6,7-titrahydrol■, 511-benzo(i, D -quinolidin-9-yl)methylene]-: and JAW, i.e. cyclopentano 2,5-bis((2,3,6,7-titrahydroIn, 5H-benzo(i , D-quinolidin-1-yl)methylene], each of which has the following structure. One.

D.B.C. EAF Dimethoxy-JDI Other particularly useful sensitizers are cyclopentanone, 2,5-bis[2-(],,]3- dihydro1.3.3-1-dimethyl-2H-indole-2-ylidene)ethyl Liden], CAS 27713-85-5; and cyclopentanone, 2,5- Bis(2-(1-ethylnaphtho(1,2-d)thiazol-2(III)-yli) ethylidene), CAS, 27714-25-6.

The hydrogen donor compound that acts as a chain transfer agent in the photopolymer composition is 2 -Mercaptobenzoxazole, 2-mercaptobenzothiazole, 4-methy -4tl-1,2,4-triazole-3-thiol, etc.; and various types compounds, such as those of 1IacLachlan, U.S. Pat. (a) ether, (b) ester, (c ) alcohols, (d) compounds containing allyl or benzyl hydrogen, (e) acetals , (f) aldehydes, and (g) amides. Benzimidazole type initiators and Hydrogen donor compounds suitable for use in systems containing both N-vinyl carbazole and 5-chloro-2-mercaptobenzothiazole; 2-mercaptobenzothia Sol; 1n-1,2,4-triazole-3-thiol: 6-ethoxy 2 -mercaptobenzothiazole; 4-methyl-411-1,2,4-triazo -3-thiol: 1-dodecanethiol; and mixtures thereof. Especially good Preferred types of photoinitiators and photosensitizers include benzophenone, Michler's ketone, and ethyl chloride. Lumichler's ketone, p-dialkylaminobenzaldehyde, p-dialkyl Aminobenzoic acid alkyl ester, polynuclear quinone, thioxanthone, hexaary rubiimidazole, cyclohexagenone, benzoin, benzoin dialkyl ether, or a combination thereof, where alkyl contains 1 to 4 carbon atoms. Including children.

Optional ingredients Other compounds conventionally added to photopolymer compositions may be added to the filter for certain uses. can be present to modify the physical properties of the membrane. Other such ingredients Polymer binders, fillers, thermal stabilizers, hydrogen donors, thermal crosslinkers, optical brighteners , ultraviolet radiation material als), adhesion modifiers, coating aids and mold release agents.

crosslinking agent When using the photopolymerizable composition as a permanent coating, e.g. a solder mask, Chemically or thermally activated crosslinkers can be used to improve high temperature properties, chemical resistance or end-use products. Can be blended to improve other mechanical or chemical properties required for Wear. A suitable crosslinking agent is Gervay.

U.S. Patent 4.621.043 and Gelssler et at, U.S. Pat. , 438.189, such as melamine, urea, benzoguanami Including.

Examples of suitable crosslinking compounds are organic carboxamide N-methylol compounds such as N , N'-dimethylolurea, N, N'-dimethyloloxamide, N, N'-dimethylol malonamide, N, N'-dimethylol succinimide, N, N'-dimethylol ureamide, N, N', N'-1-dimethylol site Lamid, 1,3-dimethylol imidazolidin-2-one, 1,3-dimethylo -4,5-dihydroxyimidarizin-2-one, 1,3-dimethylolper Hydropyrimidin-2-one, trimethylolmelamine, tetramethylolmelamine amine, hexamethylolmelamine, 1,3-dimethylol-5-methylperhydride rho-1,3,5-triazin-2-one, 1,3-dimethylol-5-allylpe 1,3,5-1-riazin-2-one, 1,3-dimethylol-5- Butyl perhydro-1,3,5-triazin-2-one, 1,2-bis-[1, 3-dimethylolperhydro-1,3,5-)riazin-2-one-5-yl] -ethane, tetramethylolhydrazinedicarboxamide, N,N'-dimethylo luterephthalamide, N,N'-dimethylolbenzene-1,3-disulfo amide and tetramethylic glycoluril; and phenol, phenol - C-methylol compounds of ethers and aromatic hydrocarbons 2.4.6-dorimethy Lorphenol, 2,6-simethylo-4-methyloanisole, 2,6-simethylo-4-methyloanisole Methylol-4-methylphenol, ■, 3-dimethylol-4,6-ditube lobilbenzene, 2,2-bis-(4-hydroxy-3,5-dimethylolphene) propane), and 3,3'-dimethylol-4,4'-dihydroxydife Contains nil sulfone. Instead of the methylol compounds mentioned above, e.g. using ethyl, ethyl or butyl ethers, or esters of acetic or propionic acid. It can also be used. A suitable example is 4,4'-bismethoxymethyl diphenyl ether. ter, tris-methoxymethyl-diphenyl ether, tetrakis-methoxymethane Chylhydrazine dicarpoxamide, tetrakis-methoxymethyl-glycol uril, tetrakis-hydroxyethoxymethylglycoluril, bis-acetyl Contains toxymethyl diphenyl ether, hexamethoxymethyl-melamine. child A preferred crosslinking agent of the type is hexamethoxymethylmelamine.

Compounds containing two or more epoxy groups such as Ervig et al. ,, bisepoxides disclosed in U.S. Pat. No. 4,485,166 are also useful as crosslinking agents. It is for use. Suitable bisepoxides include dihydric alcohols and phenols such as bisepoxides. Bis-glycidyl ether of phenol-A, polyethylene of bisphenol-A that with glycol and polypropylene glycol ether, butane-1,4- Diol, hexane-1,6-diol, polyethylene glycol, propylene including that of glycol or polytetrahydrofuran. Trihydric alcohols such as Bis-glycidyl ether of lycerol or halogenated bisphenol-A example For example, that of tetra-bromobisphenol-A can also be used. this species A preferred crosslinking agent of the class is 2,2-bis-(4-glycidoxy-phenyl)-propyl 2,2-bis-(4-epoxyethoxy-phenyl)-propane, tetra- Bis-glycidyl ether of chloro-bisphenol-A, tetra-bromo-bi Bis-glycidyl ether of spphenol-A, tetra-chloro-bisphenol bis-oxiranyl ether of Ru-A, and tetra-bromo-bisphenol- A bis-oxiranyl ether.

Blocked polyisocyanates are also useful as crosslinking agents. Blocked polyiso When cyanate is heated, the capping groups cleave to create free reactive polyisocyanate. Jiru.

Useful polyisocyanates are toluene diisocyanate; isophorone diisocyanate nate: 1,4-naphthalene diisocyanate, 1,6-hexamethylene diiso Cyanate; Tetramethylxylene diisocyanate: Bis(4-isocyanato cyclohexyl)methane, etc. Useful blocking groups are caprolactam: diethyl malonate: alcohol: phenol; oxime, e.g. methyl ethyl ketoxy It is guided from the system, etc.

polymer modifier The photopolymerizable composition has adhesion, flexibility, hardness, oxygen permeability, moisture sensitivity, and its processing properties. or to modify other mechanical or chemical properties required for end use. A polymeric binder may be included. Branched polymer production of the present invention A suitable polymeric binder that can be used in combination with esters and alpha-alkyl polyacrylate esters, such as polymethyl esters. Tacrylate and polyethyl methacrylate, polyvinyl esters, e.g. Vinyl acetate, BoI) Vinyl acetate 7/acrylate, polyvinyl acetate tate//methacrylate and hydrolyzed polyvinyl acetate, ethylene /vinyl acetate copolymers: polystyrene polymers and copolymers, e.g. That with maleic anhydride and esters, vinylidene chloride copolymers, e.g. vinylidene chloride/acrylonitrile; vinylidene chloride/methacrylate and vinylidene chloride/vinyl acetate copolymer: polyvinyl chloride and copolymers such as poly(vinyl chloride/vinyl acetate); polyvinyl chloride/vinyl acetate; Lupyrrolidone and copolymers such as poly(vinylpyrrolidone/vinyl acetate) g) Saturated and unsaturated polyurethanes; synthetic rubbers such as butadiene/acrylonite Lyle, acrylonitrile/butanoene/styrene, methacrylate/acryloni Tolyl/butadiene/styrene copolymer, 2-chlorobutadiene-1,3 poly mer, chlorinated rubber, and styrene/butadiene/steoneone, styrene/isopropylene Ren/styrene block copolymer: about 4,000 to i, ooo, ooo High molecular weight polyethylene oxide of polyglycol with average molecular weight; epoxide; Copolyesters, such as those of the formula [0(CL). oll (in the formula, n is an integer from 2 to 1O) (1) polymethyone glycol, and (1) hexahydroterephthalic acid, sepa (2) terephthalic acid, isophthalic acid and cepatic acid; (3) Terephthalic acid and sepatic acid, (4) Terephthalic acid and isophthalic acid, and and (5) the glycol and (i) terephthalic acid, isophthalic acid and cepatic acid. and (u) derived from terephthalic acid, isophthalic acid, sepatic acid and adipic acid It is made from the reaction product of a mixture of copolyesters: nylon or Polyamides, such as N-methoxymethylbolyhexamethyleneazibacod: cellulose cellulose esters, such as cellulose acetate-1, cellulose acetate fucine -1 and cellulose acetate butyrate; cellulose ethers, e.g. cellulose, ethylcellulose and benzylcellulose: polycarbonate; Polyvinyl acetals, such as polyvinyl butyral, polyvinyl formal; Contains polyformaldehyde.

If aqueous development of the photosensitive composition is desired, branched polymer products and/or buffers may be used. The inder contains sufficient acidic groups or its like to make the composition processable in an aqueous developer. Must contain other groups. Useful water-based processable binders are No. 3,458,311 and that disclosed in U.S. Pat. No. 4,273,857. . Useful amphoteric polymers include N-alkyl acrylamide or methacrylamide, acid Derived from film-forming comonomers and alkyl or hydroxyalkyl acrylates interpolymers, such as those described in U.S. Pat. No. 4.293. Including that disclosed in No. 635. Sensitivity without exposure to radiation for aqueous development The layers are removed little by little, but a liquid such as an all-aqueous solution containing 1% by weight of sodium carbonate is Virtually unaffected during development by the body.

A particularly preferred type of polymer binder modifier is polyvinylpyrrolidone polymer. and copolymers and amphoteric polymers and copolymers.

plasticizer Photopolymerizable compositions are characterized by adhesion, flexibility, hardness, solubility and their properties during processing or final use. Inclusion of plasticizers to modify other required mechanical or chemical properties Can be done.

Suitable plasticizers are triethylene glycol and triethylene glycol diacetate. , triethylene glycol dipropionate, triethylene glycol shikari triethylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylene glycol dimethyl ether, (2-ethylhexanoate), tetraethylene glycol dihebutanoate , poly(ethylene glycol), poly(ethylene glycol) methyl ether, Isopropylnaphthalene, diisopropylnaphthalene, poly(propylene glyco) ), glyceryl tributyrate, diethyl adipate, diethyl sebacate , dibutyl suberate, dioctyl phthalate, tricresyl phosphate, Butyl phosphate, tris(2-ethylhexyl) phosphate, Br1 j■3゜[C+Jzs(OCF12CHt)<Ot[) and Br1j@35 Contains [CI Jti(OCRl-CHt)z*OH).

Oiokuno The photopolymerizable composition has the mechanical or chemical properties required during its processing or for its end use. Particulate matter, such as organic or inorganic fillers, can be included to modify the material. suitable Fillers are essentially transparent organic fillers such as those disclosed in U.S. Pat. No. 2,760,863. or inorganic reinforcements such as organophilic silica bentonite, silica, and 0.4 mil Powdered glasses with smaller particle sizes, such as those disclosed in U.S. Pat. No. 3,525,615, Inorganic thixotropic materials such as boehmite alumina, highly thixotropic of silicate oxide such as bentonite and 99.5% silica and 0.5% Clay mixture of finely ground thixotropic gels containing mixed metal oxides: Microcrystalline thickeners such as microcrystalline cellulose as disclosed in US Pat. and microcrystalline silica, clay, alumina, bentonite, chironite, attaburta and montmorillonite; as disclosed in U.S. Pat. No. 3,891,441. Finely ground powder with a particle size of 5 millimicrons to 50 microns, e.g. silicon oxide, oxidized Titanium, carbon black, zinc oxide, and other commercially available pigments; and European patents Binder-added transparent inorganic particles as disclosed in Application No. 87113013, 4 Magnesium silicate (talc), aluminum silicate (clay), calcicarbonate Contains aluminum and alumina. Typically this filler is transparent to actinic radiation; Eliminate adverse effects during imaging exposure. Its function in photopolymerizable compositions Depending on the capacity, the filler may be colloidal or have a diameter of 50 microns or more. can have a fine average particle size.

adhesion promoter Photopolymerizable compositions can be used as coatings on metal surfaces, e.g. as photoresists. If a heterocyclic or mercaptan compound is required during processing or in the end-use product, It can be added to improve the adhesion of coated coatings to metals. suitable Suitable adhesion promoters are heterocyclic compounds such as those described by Rurley et al., U.S. Pat. 3.622.334, Jones, U.S. Pat. No. 3.645.772, and Weed , including that disclosed in U.S. Pat. No. 4,710,262. Examples of useful adhesion promoters is benzotriazole, 5-chloro-benzotriazole, 1-chloro-benzo Triazole, 1-carboxy-benzotriazole, 1-hydroxy-benzo Triazole, 1,2-naphthotriazole, benzimidazole, mercapto Benzimidazole, 5-nitro-2-mercaptobenzimidazole, 5-a Mino-2-mercaptobenzimidazole, 2-amino-benzimidazole, 5-methyl-benzimidazole, 4.5-diphenyl-benzimidazole, 2-guanidino-benzimidazole, benzothiazole, 2-amino-6-methane Tyl-benzothiazole, 2-mercaptobenzothiazole, 2-methyl-ben Zothiazole, benzoxazole, 2-mercaptobenzoxazole, 2- Mercaptothiazoline, benzotriazole, 3-amino-1,2,4-)ria sol, IH-1,2,4-triazole-3-thiol, 5-amino-1,3 , 4-thiodiazole-2-thiol, 4-mercapto-IH-pyrazolo[3, 4-d] pyrimidine, 4-hydroxy-virazolo(3,4-d)pyrimidine, 5-amino-tetrazole-hydrate, tolutriazole, 1-phenyl-3-methane Contains captotetrazole, 2-amino-thiazole, and thiobenzanilide. nothing. The preferred adhesion promoter for use in photoresists and solder masks is base. benzotriazole, 5-chloro-benzotriazole, 1-chloro-benzotriazole Azole, 1-carboxy-benzotriazole, 1-hydroxy-benzotriazole Azole, 2-mercaptobenzoxazole, 1■-1,2,4-triazo -3-thiol, 5-amino-1,3,4-thiodiazole-2-thiol, and mercaptobenzimidazole.

Other ingredients The photopolymerizable composition contains other ingredients such as thermal polymerization inhibitors, dyes and pigments, and fluorescent bleaching agents. may be included to stabilize the color or otherwise enhance the composition. I can do that.

A thermal polymerization inhibitor that can be used in the photopolymerizable composition is p-methoxyphenol. , hydroquinone, and alkyl and aryl substituted hydroxynes and quinones, te rt-butylcatechol, pyrogallol, copper resinate, naphthylamine, base Turnaphthol, cuprous chloride, 2,6-tert-butyl-p-cresol , phenothiazine, pyridine, nitrobenzene and dinitrobenzene, p-tolu quinone and chloranil. Nitro as disclosed in U.S. Patent 4.168.982 The compositions are also useful as thermal polymerization inhibitors.

Various dyes and pigments can be added to increase the visibility of the resist image . However, any colorant used must be transparent to the actinic radiation used. Must be.

Useful fluorescent bleaches include those disclosed in Held, U.S. Pat. No. 3,854,950. include. A preferred fluorescent bleach is 7-(4'-chloro-6-dinithylamino-1', 3',5'-triazin-4'-yl)amino-3-phenylcoumarin . The same ultraviolet absorbing materials useful in the present invention (Iled, U.S. Pat. No. 3,854.9 50.

Application to photoresist The photopolymerizable compositions of the invention are particularly useful as photoresists for making printed circuit boards. Useful. Generally, the use of resist for making printed circuits began in 1979 at 1cG. raw-Hill.

Edited by C. F. Coombs, Jr., published by Inc. 2nd edition, which uses screen-printed resists and and photoresist. Photocircuit manufacturing The use of conventional photoresists was introduced in 1975 for cGraw-Bi11. ．． “Photoresist” by W. S. DeForest, published by Inc. - described in Materials and Methods J, which is a negative photopolymerizable and photocrosslinkable or dimeric positive-acting photosolubilizable systems as well as positive-acting photosolubilizable systems. Photoresist is a primary image For temporary coatings to create printed circuits in imaging processes, or as secondary images. Protects the circuit from environmental influences during subsequent processing in the imaging process or during use. A permanent protective coating, for example used to create a solder mask. I can do that. Permanent coatings are used as intermediate insulating layers in the production of multilayer printed circuits. can also be used.

In practice, the photopolymerizable layer is typically 2.5 to 125 micrometers thick. - a printed circuit board, usually a copper-clad glass fiber epoxy board for subsequent imaging; or applied to printed circuit relief patterns on boards for secondary imaging. next The applied photopolymerizable layer is imagewise exposed to actinic radiation to harden or insolubilize the exposed areas. let The unexposed areas are then removed completely, typically using a developer solution; The developer solution can be applied to unexposed areas without adversely affecting the integrity or adhesion of exposed areas. selectively dissolve, strip, or otherwise disperse the components. Coated during development process The surface area of the substrate except for the material is then etched or the material is removed. Or modify it by attaching material to it.

For primary imaging to create printed circuit boards, etching the copper surface area excluding the coating. Add or remove etchants to create printed circuits directly or add resistance to etching agents. of copper or other metals such as gold, tin/lead etc. can be plated thereon. . In the first case, the cured exposed resist is usually removed from the remaining copper surface by a stripping method. directly to create a circuit board. In the second case, the hardened resist is plated first strip the untreated copper surface and then etch the surface or remove it from the substrate. Create a stripped and plated printed circuit board.

When creating a permanent resist or solder mask on a printed circuit board, the developed solder The derma resist image is first baked at elevated temperatures or exposed to actinic radiation. or a combination thereof. Allow to harden and harden to cover all parts except the pad or through-hole area. Create a circuit board with a solder mask layer. Next, insert the electrical components into the through holes. , and then solder them directly to create packaged electrical components. multilayer stamp If a printed circuit is to be printed, a permanent resist is applied to the catalyzed substrate, imaged, and coated. The non-catalyzed portions are developed and then typically electroless plated to create the first circuit layer. . The entire surface of the first circuit layer is then catalyzed and this process is repeated one or more times. Repeat to create a multilayer printed circuit board.

A particularly preferred embodiment of the invention is (1) Apply a photopolymerizable composition to the surface of a substrate with a circuit pattern and photopolymerize it on top. (2) imagewise exposure to actinic radiation to form exposed and unexposed areas; height, (3) Remove the unexposed parts of the layer and apply the stencil solder mask image to the exposed parts. Form the unexposed parts of the remaining circuit pattern on a printed circuit board with an embossed conductive circuit pattern on its surface consisting of steps This is a method of forming a solder mask on the photopolymerizable composition. (A) one or more chemically bonded along a linear polymer backbone segment; A branched polymer product containing hydrophilic groups consisting of many branched polymer segments ( wherein the branched polymer product has at least one ethylenically unsaturated macromer component and at least one ethylenically unsaturated comonomer, Therein, (a) the ethylenically unsaturated macromer component is not greater than 40,000; (b) the linear polymer main segment has a weight average molecular weight of about io, It has a weight average molecular weight (Iris) of ooo to about 500.000, and (C) linear polyester. The weight ratio of polymer backbone segment to branch polymer segment(s) is in the range of about 200/1 to about 174; and (d) the branched polymer se component(s) containing about 35% to 100% hydrophilic groups): and (B) Additional polymerizable monomer containing at least one terminal, ethylenically unsaturated group -: and (C) Consists of an initiation system activated by actinic radiation.

In a particular embodiment of this method, (A) is is a branched polymer product consisting of many chemically bonded branched polymer segments. composition, in which the branch polymer segment has one or more hydrophilic functionalities. a polymer branched from at least one ethylenically unsaturated macromer component containing groups - formed during the addition polymerization of the product, in which the ethylenically unsaturated macromer component is a number average molecular weight (ml, ) not greater than 30,000 and not greater than about 5 It has polydispersity (If/1ln).

The photopolymerizable composition typically includes a heat-activated crosslinking component and step (C) After this, the resist area is exposed to a chemical reagent, usually by heating and by uniform exposure to actinic radiation. Cured by treatment with drugs or a combination thereof.

Particularly preferred for use in permanent coating compositions are branched polymer formations. and this branched polymer product is B^/S/HE^/macromer. copolymer (in this case, the macromer is B/I/HEIA/A copolymer) mer, BIA/HIJA/Iris ^^ copolymer or BIA/Shija AA copolymer. each with a single terminal ethylene group), resulting in a branched polymer product. The weight ratio of each monomer in is approximately 48/15/15/22. The respective ratios in chromer are approximately 43/2/30/25.45/ 30/25 or 75/25. In the branched polymer products shown, B ^ is butyl acrylate, BIA is butyl methacrylate, IIEI^ is 2 -Hydroxyethyl methacrylate; A^ is methacrylic acid; Iris is methyl methacrylate; Tacrylate: and S is styrene.

Applying resist Photopolymerizable resists are applied to printed circuit boards as a liquid and as a preformed dry film. It can be applied as a liquid or as a combination of liquid and dry film.

coating liquid Photopolymerizable resists print as liquids using any conventional coating method Can be coated onto circuit boards. This liquid is a resist solution; If the solvent is removed after coating to create a dry solid resist layer, or The liquid is a pure, solvent-free resist that is directly imaged after coating. A hardened resist layer can be created by exposure to actinic radiation. The liquid is Coosbs above, DeForest above, Lipson etal, USA Patent No. 4.064.287, or Oddi et al., U.S. Pat. No. 4.376. Roller coating, spin coating, screen coating as disclosed in 81.5. It can be printed or screen printed. Loser this liquid as a normal solution. t et al.

It is also possible to flow coat as disclosed in US Pat. No. 4,230,793. H e1art, US Patent 4.548.884, Hauser, US Patent BI 4 ．． 528,261, or 5ullivan, U.S. Patent 4,424.089 and 4 ．． 591.265 using a method such as that disclosed in 591.265 and By forming an image, Celeste described in U.S. Pat. No. 3,469,982. Typically, the photopolymerizable resist layer is preformed using a lamination method. It is usually applied from multilayer plates and transfer resist elements. Multilayer plate resist The elements in turn are actinically transparent temporary support films, such as polyethylene terephthalate. a thin photopolymerizable resist layer made of Consists of a removable covering sheet for It is described in Ce1este above. If there is a coating sheet, remove it and remove the coating from the photoreceptor. For example, by applying heat and/or pressure to a copper-clad printed circuit board, Laminate using a commercial hot roll laminating machine. The photoresist phase is If not sensitive to surrounding elements, the laminate is usually exposed to actinic radiation through a temporary support film. Image-forming exposure but temporary support to improve resolution and other such properties can be removed before imaging. In some cases, the adhesion of the resist to the substrate may be This can be improved by treating the surface of the substrate with a liquid during or immediately before lamination. typical This liquid is sensitive to actinic radiation (see Jones).

Solution of adhesion promoter disclosed in U.S. Pat. No. 3,645,772, Fickes, USA Resist phase solvent or swelling agent disclosed in National Patent No. 4.069.076, Cohe n, US Patent 4.405.394 and European Patent 0041639. Pilett e et at, U.S. Patent 4.378.764, and fej, ner et al, the non-solvent disclosed in European Patent 0040842, or Lau et al. , is a liquid component of the resist layer disclosed in U.S. Pat. No. 4,698,294. Can be done. This liquid may optionally be photosensitive (e.g. l5aacson, Photoresist solution disclosed in U.S. Pat. No. 3,629.036, O'Ne1l etal, the photosensitive liquid disclosed in European Patent Application No. 87113176, 9, or 5ullivan, a pure photoresist disclosed in U.S. Patent 4.506.004. It is a strike liquid.

Dry film for example solder masks on substrates with low relief such as circuit boards If laminated to a have to take a stand. The trapped air is Fr1e1. U.S. Patent 4.12 7.436 by the vacuum lamination method of Colier et al.

The grooved roll lamination method of U.S. Patent 4.071.367 or by Fickes, supra, supra. Lau et al., 0'Net1 et al., supra, or 5ullivan's °004 patent, supra. Removed by using the liquid treatment agents described.

Example 1 The macromer solution (1) used for subsequent branched polymer product formation is prepared in the following manner. Create using the order.

The following compounds were added to a clean reaction vessel.

amount Methacrylic acid (Seal A^) 3.31 Hydroxyethyl methacrylate) (IIEIIA) 7.93 Butyl methacrylate Rate (B) 11.89 Methyl ethyl ketone 15.50 The resulting solution was heated to reflux temperature and kept there with stirring. Next oh The next solution, previously mixed for 15 minutes under nitrogen, was immediately added.

amount Methyl ethyl ketone 1.56 Bis(difluoroboryl)diphenyl 0.004 gloximatocobalt ■Hydration Product (SCT) Vazo■52 catalyst 0.023 2.2'-Azobis(2,4-dimethylpentanenitrile) then preliminarily charged with nitrogen The next solution, which had been heated for 15 minutes under a = , was simultaneously added to the reaction vessel.

Solution (A) amount Methyl ethyl ketone 8.79 SCT　0.007 Vazo■52 0.252 Solution (B) amount Methacrylic acid (Iris ^^) 7.68 Hydroxyethyl methacrylate (Osho^) 5.29 Butyl methacrylate ( BIA) 7.93 Methyl ethyl ketone 0.55 54.8% of solution (A) was added over 90 minutes, and the remaining 45.2% was added. The mixture was further added and supplied over a period of 240 minutes. Apply solution (B) at 67% for 120 minutes. and the remaining 33% was added and fed over an additional 120 minutes.

The reaction was held at reflux temperature for 45 minutes with stirring, then 6.9 parts of methyl ethyl Ketones were added. The reaction was then held at reflux temperature for an additional 30 minutes and cooled to 50°C. The solution was then filtered to obtain a macromer solution (1). Conventional gel permeation of molecular weight Measured using chromatography (GPC) method. The weight average molecular weight (11) is 4618, and the number average molecular weight is 2152, thus the polydispersity (1,/In ) was 2.15.

The branched polymer product (A) was made using the following procedure.

The following materials were added to the reaction vessel.

amount Macromer solution (1’>16.00 Butyl acrylate (BA) 20.94 Styrene (S) 6.54 Hydroxyethyl methacrylate (HEIIIA) 6.54 methyl ethyl keto N 10.83 Heat the reaction to reflux temperature and keep it there with stirring while simultaneously adding The quality solution was added over 5 minutes.

amount Methyl ethyl ketone 2.18 Vazo@67 (2,2'-azobis(2-methyl 0.96bentanonitri) ) This was flooded with additional methyl ethyl ketone (+,,03), then the reaction was The temperature was kept at reflux for 120 minutes with stirring.

The next solution was then added to the reaction.

amount Methyl ethyl ketone 1.31 Vazo@67 0.57 This was flushed with additional methyl ethyl ketone (0,33), then the reaction was stirred. The temperature was kept at reflux for 120 minutes with stirring.

Then the next solution was added.

amount Methyl ethyl ketone 0.87 Vazo@67 0.22 This was flushed with additional methyl ethyl ketone (0,33), then the reaction was stirred. The branched polymer product (A) is obtained by keeping it at reflux temperature for 120 minutes with stirring. is BA/S/tlEIl^/macromer, while macromer is 81^/BE Seal^/IIA^ − is.

For simplicity, we will now use a linear polymer without arms (not that of the present invention). Polymerization was carried out as described below in a solution of

Add the following solution to the above solution, amount Methacrylic acid 0.58 Methyl methacrylate 4.27 Methyl ethyl ketone 7.06 A solution containing the following was then added:

amount Methyl ethyl ketone 0,34 Vazo[F]67 0.13 This was flushed with additional methyl ethyl ketone (0,24). Stir the reaction again. It was kept at reflux temperature for 120 minutes with stirring and then the next solution was added.

amount Methyl ethyl ketone 0.145 Vazo@34 0.068 This was flushed with additional methyl ethyl ketone (0,04). Then the reactants The polymer product (B) was obtained by keeping it at reflux temperature for 240 minutes with stirring. Iris ＾ / Iris A ＾ This mixture was dried in an extrusion devolatilizer and formed into pellets with a weight of 24.658 It had a weight average molecular weight ( ).

Glass transition MIX is -11.1°C and 28.4°C as measured by differential scanning calorimetry. It was.

Example 2 Dry film, following the photosensitive solder mask elements with pentaerythritol trichloride Acrylate 450.0 Trimethylolpropane triacrylate 450. Hexamethylene blocked with 0' methyl ethyl ketoquine 817.8 diiso Cyanate homopolymer (75% solids) diethylhydroxylamine 1.5 Benzophenone 120.0 Michler's Ketone 3.0 3-mercapto-IFI-1,2,4-) lyazole 6.0 glycol colorant ( Dayglo@122-9655) 90. Or’VP K-90 (polyviny Lupiroride:/) 180.0 composition with 90% methylene chloride and 10% methanol The solution was dissolved for coating in 5365 parts by weight of a solvent consisting of

This solution was then transferred to a 92D polyethylene terephthalate film (E, 1. du Pant de Nemours and Company). The photosensitive layer was coated and air dried at 150°F to form a 2 mil thick dry photosensitive layer. Coat the smooth side of the matte 1 mil polyethylene film over the layer of A dry film and a photosensitive solder mask element were obtained.

A set of printed circuit board panels measuring 12 inches by 18 inches and having a diameter of 17 mm. Approximately 3.5 mil relief floating on both panel surfaces with approximately 1200 holes of ~35 mil. In addition, tripropylene glycol diacrylate (at 25℃) (having a viscosity of 14.5 centipoise) was coated using a wetting sponge.

While keeping this monomer-wetted panel in a vertical position, the gap between the two rolls is adjusted horizontally. At the same time, pass the polyethylene film over the wet panel, from which the polyethylene film is first removed. After drying, a dry photosensitive layer was laminated. Adjust the pore pressure to approximately 35 psi with a pneumatic cylinder. The temperature of the roll was brought to about 140°F while kneading. Each roll is VALU” 5y ste■ It is a type used for lamination, but it is covered with a normal rubber coating. It was equipped with a Teflon@polytetrafluoroethylene sleeve.

During the lamination procedure, the monomer of the liquid coating is measured from the run-off relief of the panel. The coating is present at a constant thickness of approximately 0.2 mil and is directly adjacent to the raised relief. It spans about 3.5 mils abutting and about 0.2 mils above the raised relief.

The edges of the panel were trimmed and the remaining monomer liquid was removed by spraying with water.

The panels were laminated for 130 minutes, then a DuPont PC-130 exposure system was used. After exposure, MYlar@Poly Remove the ethylene terephthalate film and transfer the sample to 1% in a S processing apparatus. Developed at 105°F using sodium carbonate solution. Development time is approximately 180 seconds. It was. After development, each side of each plate was first exposed to 2 Joules/C in a rgus ultraviolet unit. 2, then cooled the plate, then exposed to 6 joules/cw” to harden. I set it. The board was then baked at 150°C for 1 hour. The resulting solder mask is It was permanently attached to each printed circuit board.

This board has solder mask properties such as soldering resistance, solvent resistance, electrical properties, and adhesion. As a solder mask, when evaluated using typical methods including thermal shock resistance and flammability. showed successful results. Inspection of ink connecting and packaging electronics Institute for Interco-necting and Packaging Electronic C1rcuits) is recommended. Subsequent branches of the standard method described in its publication IPC-8l-840 are recommended. Separate the macromer solution (2) used to form the polymer product using the following steps: I made it.

The following compounds were added to a clean reaction vessel.

Methacrylic acid (l[A^) 3.21 Hydroxyethyl methacrylate (HEIA) 7.70 Butyl methacrylate (BIIA) 11.04 methyl methacrylate (l[1IA) 0.51 acetate Ton 15.05 The resulting solution was heated to reflux temperature and kept there with stirring. Next oh The next solution, previously mixed for 15 minutes under nitrogen, was immediately added.

Acetone 3.04 Bis(difluoroboryl)diphenyl 0.0008 gloximatocobalt■Water Sumitomo (SCT) Va @52 catalyst 0.0084 2.2'-Azobis(2,4-dimethylpentanenitrile) then preliminarily charged with nitrogen The next solution was added simultaneously, mixed for 15 minutes under .

Acetone 8.53 SCT　O,0014 Vazo@52 0.0918 spoon! ■ Methacrylic acid (IIAA) 7.46 Hydroxyethyl methacrylate (HEIA) 5.14 Butyl methacrylate (BIA) 7.36 Methyl methacrylate (I) 0.34 Acetone 0 ．． 53 54.8% of solution (A) was added over 90 minutes and the remaining 45.2% The addition was continued for an additional 240 minutes. Solution (B) at 67% for 120 minutes and the remaining 33% was added and fed over an additional 120 minutes. . After the addition is complete, add 0.35 and 0.53 parts of solutions (A) and (B) to the containers, respectively. Fluid with acetone and added to reaction vessel.

The reaction was held at reflux temperature for 45 minutes with stirring and then 6.71 parts of acetone was added. Added. The reaction was then held at reflux temperature for an additional 30 minutes, cooled to 50°C and After filtration, a macromer solution (2) was obtained. Conventional gel permeation chromatography to determine molecular weight It was measured using the GPC method. Weight average molecular weight (WW) is 7562 , and the number average molecular weight is 4409, so the polydispersity (llv/l1n) is It was 1.72. The calculated acid value of macromer in macromer solution (2) is 16 It was 2.

A branched polymer product (B) was made using the following procedure.

The following materials were added to the reaction vessel.

Stage V Macromer solution (2') 22.34 Butyl acrylate (B^) 15.94 Hydroxyethyl methacrylate (O Iris A) 6.26 methyl methacrylate (IIIA) 6.26 styrene (S ) 0.102 Methacrylic acid (I^^) 0.102 Acetone 1.81 Heat the reaction to reflux temperature and keep it there with stirring while simultaneously adding The quality solution was added over 5 minutes.

Acetone 1.05 Vazo@52 0.1253 This was flushed with additional acetone (1,0) and the reaction was then refluxed with stirring. It was held at flow temperature for 120 minutes.

The next solution was then added to the reaction.

Acetone 0.42 Vazo[F]52 0.0205 This was flushed with additional acetone (0,4) and the reaction was then refluxed with stirring. It was held at flow temperature for 120 minutes.

The next solution was then added to the reaction.

Vazo@67 (2,2'-azobis(2-methyl 0.0102 pentani) trill) This was flushed with additional acetone (0,4), then the reaction was stirred and It was kept at reflux temperature for 180 minutes. This polymer solution was then diluted with acetone to 1 1.79, step ■), cooled to 50°C and filtered to obtain the branched polymer product ( B), this thing is B^/HE Seal^/IIA/S/I^^/Macromer 38, 92/15.2 9/15.29/0.25/0.25/30, while the macromer It is B ＾ / HEM ＾ / IIIA / IIAA.

The molecular weight of the branched polymer product (B) was determined by gel permeation chromatography (GPC). ) method. The weight average molecular weight ( ) is 140.386, and the number is The average molecular weight (an) is 28,728, so the polydispersity (11/lid n) is 4. It was 89. The branched polymer separator of the main chain segment of the branched polymer product (B) The weight ratio to the component was 70/30.

The calculated acid number of the branched polymer product (B) was 49. branch polymer seg ment is 60.5% by weight of the hydrophilic groups present in the branched polymer product (B). including.

Example 4 Dry film, photosensitive solder mask element prepared as described in Example 2 and processed. However, the composition of the solder mask was as shown in the table below.

Solder mask composition amount Pentaerythritol triacrylate 6.768 trimethylol proppant Reacrylate 6.768 Hexamethyl blocked with methyl ethyl ketoxime Ren 4.500 Diisocyanate homopolymer (75% solids) diethyl hydride Roxylamine 18 Benzophenone 1.260 Ethyl Michler's Ketone 108 3-mercapto-111-1,2,4-1-lyazole 72 colorant (Penn color 9G5) 360 Green colorant (Dayglo 122-965 5) Branched polymer product (B) of 540 Example 3 (60% solids) 23 , 836 5.400 dispersed in a solution of the branched polymer product (B) of Example 3 Treated talc (Cyprabond @) 40% N-t-octyl Acrylamide, 34% methyl 990 methacrylate, 16% acrylic acid, 6% Hydroxypropyl methacrylate and 4% t-butylaminoethyl methacrylate ampholytic copolymer formed from carbonate; molecular weight approximately 50,000 PVP K-90 (polyvinylpyrrolidone) 1.440 This composition is 16.3 Dissolved in 41 parts by weight of additional acetone and 27,000 parts by weight of methanol.

This solution was coated and evaluated in a manner similar to that described in Example 2, and the plates were Solder mask properties include soldering resistance, solvent resistance, electrical properties, adhesion, and heat shock resistance. It has been successfully used as a solder mask when evaluated using typical methods including flammability and flammability. The results were shown. Inspection by Ink Connecting and Packaging Electronic Circuits Association according to the standard method described in its publication IPC-3l-840 recommended by .

Example 5 Macromer solutions (3) and (4) used in subsequent branched polymer product formation ) using the procedure of Example 3.

The following materials were added to a clean reaction vessel.

Stage ■ Macromer (3) (4) Quantity Quantity Methacrylic acid (Ayu^) 3.21 3.21 Hydroxyethyl methacrylate ( ITEIIA) 7.69 7.69 Butyl methacrylate (BIIA) 11 ．． 02 11.02 Methyl methacrylate (MIIIA) 0.51 0.51 Acetone 15.03 - Methyl ethyl ketone Each resulting solution was heated to reflux temperature and kept there with stirring. Next The next solution, previously mixed for 15 minutes under nitrogen, was immediately added.

Stage ■ Macromer (3) (4) Quantity Quantity Acetone 3.03 - IE[-2.96 SCT O. 0008 0.0034 Vazo@52 catalyst 0.1105 0.0224 then 1 under nitrogen in advance The next solution mixed for 5 minutes was added at the same time.

Stage■ Macromer (3) (4) Solution (A) amount amount Acetone 8.52 - 11EI [-8.52 SCT O. 0014 0.0064 Vazo■52 0.0917 0.2445 level■ Macromer (3) (4) Solution (B) amount amount Methacrylic acid (MAA) 7.45 7.45 hydroxyethyl methacrylate (1'[EI[A) 5. 13 5. 13-butyl methacrylate) (BIA ) 7.35 7.35 Methyl methacrylate (IIIA) 0.34 0. 34 Acetone 0.53 - IIEK - 0.53 Macromer (3)-solution (A) was added at 67% over 60 minutes and the remainder 33% of the total amount was added and fed over a further 120 minutes. Solution (B), 67% Added over 60 minutes and added the remaining 33% over an additional 120 minutes. I supplied it.

Macromer (4)-solution (A) was added at 54.8% over 90 minutes and The remaining 45.2% was added and fed over an additional 240 minutes. Solution (B), 67% was added over 120 minutes and the remaining 33% was added over an additional 120 minutes. was added and supplied.

After the addition is complete, add 0.35 and 0.53 parts of solution (A) and (B) to the containers, respectively. agent (acetone for macromer (3) and ME for macromer (4)) K) and added to the reaction vessel. Reflux temperature while stirring the reactants. for 45 minutes, then 6.71 parts of solvent were added. The reactants are then brought to reflux temperature. Hold for an additional 30 minutes, cool to 50°C and filter to remove macromer solution (3) and (4) was obtained. Molecular weight was determined by conventional gel permeation chromatography (GPC) method. Measured using

For macromer (3), the weight average molecular weight (I,) is 28, 165, and The number average molecular weight (11) is 8.415 and therefore the polydispersity (1./I.) was 3.34.

For macromer (4), the weight average molecular weight (I,) is 4, 570, and the number The average molecular weight (In) is 3,030, so the polydispersity (1./mln) is It was 1.51.

Branched polymer products (C) and (D) were made using the following procedure.

The following materials were added to each reaction vessel.

Stage V Branched polymer product (C) (D) amount amount Macromer solution (3) 22.34 - Macromer solution (4) - 22.36 Butyl acrylate (B^) 15.94 15.96 Hydroxyethylmethac Relate (FIEIA) 6.26 6.27 Methyl methacrylate (IImA ) 6.26 6.27 Styrene (S) 0.102 0.102 Methacrylic acid (Iris A^) 0.102 0.102 Acetone 1.81 - Heat each reactant to reflux temperature and keep it there with stirring while simultaneously adding the next solution was added over 5 minutes.

Stage ■ Branch polymer product (C) (D) Quantity Quantity Acetone 1.05 - n[-1.05 Vazo ■ 52 0.1253 0.0627 Product (C) Reactant is added to t (1.0) and then bring the reaction to reflux temperature with stirring for 120 min. I paused. Product (D) The reactant was flooded with additional IEK (1,0) and its The post-reaction was kept at 80-84° C. for 180 minutes with stirring.

The following solutions were then each added to their respective reactions.

Stage ■ Branch polymer product (C) (D) Quantity Quantity Acetone 0.42 - Iris EK -0,42 Vazo052 0.0205 0.0102 Product (C) Reactant added to t (0,4) and then bring the reaction to reflux temperature with stirring for 120 min. I paused. Product (D) Reactant was flooded with additional IEK(0,4), then The reaction was held at 80-84°C for 180 minutes with stirring.

The following solutions were then each added to their respective reactions.

Stage ■ Branch polymer product (C) (D) Quantity Quantity Acetone 0.42 - 111EK -0,42 Vazo[F]67 (2,2'-azobis(2-methyl 0.0102 0.0 102 pentanenitrile) Product (C) Fludge the reactant with additional acetone (0,4), then add the reactant to The temperature was kept at reflux for 180 minutes with stirring. This polymer solution was then heated to 11.7 Dilute with 9 parts acetone, cool to 50°C and filter to form branched polymer. Product (C) was obtained. This product (D) reactant was flushed with additional IIEK (0,4). The reaction was then kept at 80-84° C. for 180 minutes with stirring. Next of polymer solution was diluted with -13.62 parts of IIEK, cooled to 50°C and filtered. A branched polymer product (B) was obtained.

Each branched polymer product has the same composition, which is BA/IIIIIA/Iris/S/IAA/Macromer 38, 92/1 5.29/15.29/0.25/0.25/30, while macro Ma is B lid ^/TIEIIA/IIA/IAA.

Measuring the molecular weight of branched polymer products using gel permeation chromatography did.

For the branched polymer product (C), the weight average molecular weight (Iris V) is 399.0 00, and the number average molecular weight (n) is 44.700, thus the polydispersity (I f/　I. ) was 8.93.

For the branched polymer product (D) the weight average molecular weight (V) is 34.50 0, and the number average molecular weight (In) is 9.200, thus the polydispersity (mwz 'In) was 3.75.

Each of the branched polymer products (C) and (D) can be used for the manufacture of printed circuit boards etc. , in alkaline water-based photoresists and photosensitive solder mask formulations. It can be used as a polymer binder component.

Example 6 Macromer solution used to produce branched polymer products with amino functionality (5 ) was created using the following steps.

The following materials were added to a clean reaction vessel.

Dimethylaminoethyl methacrylate (DilAEllA) 4.71 methyl methacrylate Tacrylate (M Ayu) 17.73MEN 15.03 The resulting solution was heated to reflux temperature and kept there with stirring. Next oh The next solution, previously mixed for 15 minutes under nitrogen, was quickly added.

IF4 2.95 SCT　0.0013 Vazo@52 catalyst 0.0224 The next solution, previously mixed for 15 minutes under nitrogen, was then simultaneously added.

”! ! Solution (A) I IEK 8.52 SCT　0.0021 Vazo (1520, 2445 Stage ■ DIIAE irises ＾ 4.26 M1^　16.01 Lid EK 0.53 54.8% of solution (A) was added over 90 minutes and the remaining 45.2% The addition was continued for an additional 240 minutes. Solution (B) at 67% for 120 minutes and the remaining 33% was added and fed over an additional 120 minutes. . After the addition is complete, add 0.35 and 0.53 parts of solutions (A) and (B) to the containers, respectively. Fluid with IIEK and added to reaction vessel. Return each reactant to reflux with stirring. It was held at flow temperature for 45 minutes and then 6.71 parts of IEK was added. The reactants are then reduced. The macromer solution ( 5), this thing is 11mA/D 菖＾El＾ Molecular weight was determined using conventional gel permeation chromatography (GPC') method. . The weight average molecular weight (ml, ) is 7.778, and the number average molecular weight (an) is 3. 089, and therefore the polydispersity (mvz”In) was 2.51. -(5) has a calculated amine value of 42.

Macromer (5) containing an amino group is an acidic aqueous processing type for the production of printed circuit boards, etc. Can be used as a polymer binder component in photoresist formulations It can be used to store flexible branched polymer products.

Such formulations are prepared using aqueous solutions containing lactic, acetic, formic, or phosphoric acids. can be constructed.

international search report 1″--”””””-””MT/II<QC! /n+1)R front page Continued (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, MC, NL, SE), AU, CA, JP, KR (72) Inventors Shart Thesad, Frank Leonard Praue State, USA 19806. wilmington, west sevente 2305 Vince Street

Claims (1)

[Claims] 1. one or more chemically bonded along the linear polymer backbone segment. a branched polymer product comprising hydrophilic groups consisting of branched polymer segments, wherein the technical polymer product comprises at least one ethylenically unsaturated macromer component; and at least one ethylenically unsaturated comonomer, wherein (a) the ethylenically unsaturated macromer component has a weight average molecular weight (Mw) of no greater than 40,000; (c) the linear polymer backbone segment has a weight average molecular weight (Mw) of about 10,000 to about 500,000; The weight ratio of segment to branch polymer segment(s) is approximately 200/ and (d) the branched polymer segment(s) contains about 35% to 100% hydrophilic groups. 2. A branched polymer product according to claim 1, wherein the hydrophilic groups are protic groups. 3. The hydrophilic group is hydroxy, amino, ammonium, amide, imide, uretano, ureido, or mercapto; or carboxylic acid, sulfonic acid, sulfinic acid, 2. The branched polymer product of claim 1, which is a phosphonic acid or a phosphonic acid or a salt thereof. 4. 2. The branched product of claim 1, wherein the hydrophilic group is an acid group, the ethylenically unsaturated macromer component has an acid number of about 50 to about 650, and the branched polymer product has an acid number of about 20 to about 90. Polymer products. 5. The branched polymer of claim 1, wherein the hydrophilic group is an amine group, the ethylenically unsaturated macromer component has an amine number of about 35 to about 650, and the branched polymer product has an amine number of about 20 to about 90. product. 6. The branched polymer product of claim 1, wherein the macromer component has a weight average molecular weight (Mw) from several hundred to about 40,000. 7. The branched polymer product of claim 1, wherein the ethylenically unsaturated macromer component has a weight average molecular weight (Mw) of from about 6,000 to about 15,000. 8. The branched polymer product of claim 1, wherein the ethylenically unsaturated macromer component has a weight average molecular weight (Mw) equivalent to the molecular weight of from 2 to about 500 monomer units used to form the macromer component. 9. The branched polymer product of claim 1, wherein the ethylenically unsaturated macromer component comprises from 30 to 200 monomer units. 10. The branched polymer product of claim 1, wherein the ethylenically unsaturated macromer component comprises at least 0.5% by weight of the components used to form the branched polymer product. 11. The branched polymer product of claim 1, wherein the ethylenically unsaturated macromer component comprises at least about 0.5% to about 80% by weight of the components used to form the branched polymer product. 12. the ethylenically unsaturated macromer component is a linear polymer, copolymer or oligomer containing terminal ethylene groups, and the macromer component is one or more The branched polymer of claim 1 formed by free radical polymerization of vinyl monomers. -Product. 13. The macromer component is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, or maleic acid, and their anhydrides, esters, amides, imides, or nitriles. 13. The branched polymer product of claim 12, wherein the branched polymer product is formed from at least one or more vinyl monomers. 14. Vinyl monomer component is methyl methacrylate (MMA); ethyl methacrylate rate (EMA); butyl methacrylate (BMA); 2-ethylhexyl methacrylate Acrylate; Methyl acrylate (MA); Ethyl acrylate (EA); acrylate (BA); 2-ethylhexyl acrylate; 2-hydroxyethyl acrylate methyl methacrylate (HEMA); 2-hydroxyethyl acrylate (HEA); methacrylic acid (MAA); acrylic acid (AA); itaconic acid (IA) and itaconic acid, half esters and imides; maleic acid and maleic anhydride, half esters ter and imide; aminoethyl methacrylate; t-butylaminoethyl methacrylate rylate, dimethylaminoethyl methacrylate; diethylaminoethyl methacrylate rylate; aminoethyl acrylate; dimethylaminoethyl acrylate; Ethylaminoethyl acrylate; acrylamide; Nt-octyl acrylate The branched polymer product of claim 12 selected from the group consisting of amide; vinyl methyl ether; styrene (S); alpha methyl styrene; vinyl acetate; and vinyl chloride. 15. The ethylenically unsaturated comonomer component is a free radical polymerizable vinyl monomer. A branched polymer product according to claim 1. 16. The vinyl monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid or maleic acid and their anhydrides, esters, amides, imides or nitriles. 16. The branched polymer product of claim 15, wherein the branched polymer product is 17. Vinyl monomer component is methyl methacrylate (MMA); ethyl methacrylate rate (EMA); butyl methacrylate (BMA); 2-ethylhexyl methacrylate Acrylate; Methyl acrylate (MA); Ethyl acrylate (EA); Acrylate (BA): 2-ethylhexyl acrylate; 2-hydroxyethyl acrylate methyl methacrylate (HEMA); 2-hydroxyethyl acrylate (HEA): methacrylic acid (MAA); acrylic acid (AA); itaconic acid (IA) and anhydrous itaconic acid, half esters and imides; maleic acid and maleic anhydride, half esters ter and imide; aminoethyl methacrylate; t-butylaminoethyl methacrylate rylate, dimethylaminoethyl methacrylate; diethylaminoethyl methacrylate Lylate: Aminoethyl acrylate: Dimethylaminoethyl acrylate; Ethylaminoethyl acrylate; acrylamide; Nt-octyl acrylate The branched polymer product of claim 15 selected from the group consisting of amide; vinyl methyl ether; styrene (S); alpha methyl styrene; vinyl acetate; and vinyl chloride. 18. At least one of the branched polymer segment, linear polymer backbone segment, ethylenically unsaturated macromer component, or ethylenically unsaturated comonomer component has a functional group of -COOR; -OR; -SR (wherein R is hydrogen, 1 to alkyl of 12 carbon atoms or cycloalkyl, aryl, alkaryl or aralkyl, heterocyclic, or can be -OR1, where R1 is alkyl of 1 to 12 carbon atoms, ali -CN; halogen; -NR2R3 or -■-NR2R3 (wherein R2 and R3 are hydrogen, alkyl or cycloalkyl of 1 to 12 carbon atoms, aryl, alkyl; Ryl, aralkyl, -CH2OR4 (wherein R4 is hydrogen, alkyl or cycloalkyl of 1 to 12 carbon atoms) or R2 and R3 together can form a heterocyclic ring); -=CR6R7 where R5, R6 and R7 is hydrogen, alkyl of 1 to 12 carbon atoms or is cycloalkyl, aryl, alkaryl, aralkyl, or -COOR or R5, R, and/or R7 can form a cyclic group); -SO3H; urethane group; isocyanate or blocked isocyanate to group; urea group; oxirane group; aziridine group; quinonediazide group; azo group; dido group; diazonium group; acetylacetoxy group; -SiR8R9R10 (wherein R6, R9 and R10 can be alkyl or cycloalkyl of 1 to 12 carbon atoms or -OR11, where R11 is 1 to 12 carbon atoms); Alkyl or carbon atom or -OSO3R12, -OPO2R12, -PO2R12, -PR12R13R14, -OPOR12, -SR12R13, or -N+R12R13R14 group (wherein 12, R13 and R14 can be cycloalkyl, aryl, alkaryl, aralkyl); hydrogen, alkyl or silyl of 1 to 12 carbon atoms; (can be chloroalkyl, aryl, alkaryl, aralkyl): or The branched polymer product of claim 1, wherein has one or more functional groups which are any of the foregoing salts or onium salts. 19. Functional groups include carboxy, hydroxy, amino, amide, vinyl, and urethane groups. 19. The branched polymer product of claim 18, which is a tan group, an isocyanate group, a blocked isocyanate group, or a combination thereof. 20. Few branched polymer segments or ethylenically unsaturated macromer components 19. The branched polymer product of claim 18, wherein at least one has one or more carboxy, hydroxy, amino, amide, vinyl, urethane, isocyanate, blocked isocyanate groups or combinations thereof. 21. The branched polymer product of claim 1, wherein the macromer component is formed by a free radical polymerization process using a cobalt compound as a catalytic chain transfer agent. 22. The branch according to claim 21, wherein the cobalt compound is a cobalt (II) compound. polymer product. 23. The cobalt(II) compound is a pentacyanocobalt(II) compound, a vicinaliminohydroxyimino compound, a dihydroxyimino compound, a diazazihydride Roxyiminodialkyldecadiene, diazadihydroxyiminodialkylundecadiene, tetraazatetraalkylcyclotetradecatetraene, tetraaza Zatetraalkyl cyclotedodecatetraene, bis(difluoroboryl) diphene Nylglyoximato, bis(difluoroboryl)dimethylglyoximato, N,N'-bis(salicylidene)ethylenediamine, dialkyldiazadioxodia 23. The branched polymer product of claim 22, which is a cobalt(II) chelate of alkyl dodecadiene or a dialkyl diazadioxodialkyl tridecadiene. 24. (A) one or more chemically bonded along a linear polymer backbone segment; A branched polymer product containing hydrophilic groups consisting of more than one branched polymer segment, in which the branched polymer product is formed during the addition polymerization of at least one ethylenically unsaturated macromer component and at least one ethylenically unsaturated comonomer. formed (a) the ethylenically unsaturated macromer component has a weight average molecular weight (Mw) of no greater than 40,000; and (b) the linear polymer backbone segment has a weight of from about 10,000 to about 500,000. average molecular weight (Mw); (c) linear polymer main chain separator; The weight ratio of segment to branch polymer segment(s) is approximately 200/ and (d) the technical polymer segment(s) comprises from about 35% to about 100% hydrophilic groups); and (B) at least one photoactive group. or sensitive compositions comprising thermally active ingredients. 25. 25. The sensitive composition of claim 24, wherein component (B) cyclizes, dimerizes, crosslinks, generates free radicals, generates ionic species, or dissociates upon exposure to actinic radiation. 26. 25. The sensitive composition of claim 24, wherein component (B) is a photoinitiator, a photosensitizer, or a combination thereof. 27. 25. A sensitive composition according to claim 24, wherein component (B) is a photosolubilizer. 28. 25. The sensitive composition according to claim 24, wherein component (B) is a photodesensitizer. 29. 25. A sensitive composition according to claim 24, wherein component (B) is a photoinhibitor. 30. 25. The sensitive composition according to claim 24, wherein component (B) is a photodegradable component. 31. 25. A sensitive composition according to claim 24, wherein component (B) is photochromic. 32. 25. The sensitive composition according to claim 24, wherein component (B) is photoreducible or photooxidizable. 33. 25. The sensitive composition according to claim 24, wherein component (B) is photoadhesive or photopeelable. 34. The sensitive composition according to claim 24, wherein component (B) is a phototackifying agent or a photodetackifying agent. 35. Component (B) changes or does not undergo a change in refractive index upon exposure to actinic radiation; 25. The sensitive composition according to claim 24, which is a substance that causes sensitization. 36. 25. A sensitive composition according to claim 24, wherein component (B) is photomagnetic or photodemagnetized. 37. 25. The sensitive composition of claim 24, wherein component (B) is photoconductive or photoinsulating. 38. 25. A sensitive composition according to claim 24, wherein component (B) binds component (a). 39. 25. The sensitive composition of claim 24, wherein component (B) comprises: (i) a polymerizable monomer; and (ii) an initiation system that can be activated by actinic radiation. 40. 40. The sensitive composition of claim 39, wherein the polymerizable monomer contains one or more ethylenically unsaturated groups. 41. 40. A sensitive composition according to claim 39, wherein the polymerizable monomer is at least one vinyl or acrylic compound or a combination thereof. 42. 25. The susceptible composition of claim 24, further comprising linear, branched or steel-like structural polymers, inorganic particulate materials, or combinations thereof. 43. 25. A sensitive composition according to claim 24 having a coloring agent dispersed therein. 44. 25. The sensitive set of claim 24, comprising at least one heat-activated curing agent. A product. 45. ( 1) applying a photosensitive composition to a substrate to form a photosensitive layer thereon; (2) imagewise exposing the layer to actinic radiation to form exposed and unexposed areas; and (3) exposing or unexposed areas. forming an image-forming layer by removing a portion, depositing material on or into the surface of the exposed or unexposed portion, or treating the surface with a reagent to develop an image in the exposed or unexposed portion. modifying the exposed or unexposed portions of the layer by (A) a hydrophilic composition comprising one or more branched polymer segments chemically bonded along a linear polymer backbone segment; Branched polymer products containing functional groups (such as The branched polymer product contains at least one ethylenically unsaturated macromer component and and at least one ethylenically unsaturated comonomer; (a) the ethylenically unsaturated macromer component has a weight not greater than 40,000; (b) the linear polymer backbone segment has a weight average molecular weight (Mw) of about 10,000 to about 500,000; and (c) the branches of the linear polymer backbone segment The weight ratio to polymer segment(s) is within the range of about 200/1 to about 1/4, and (d) the branch polymer segment(s) is about 35% to 100% a hydrophilic group); and (B) at least one photoactive component. 46. 46. The method of claim 45, wherein the photosensitive composition is applied as a pure solvent-free photosensitive liquid. 47. 45. The method of claim 44, wherein the photosensitive composition is applied as a coating solution and dried into a solid photosensitive layer. 48. Applying a photosensitive composition by laminating a supported solid photosensitive layer thereof 45. The method of claim 44. 49. 45. The method of claim 44, wherein at least a portion of the exposed or unexposed portions of the layer are removed after step (3) to form a relief image. 50. All exposed or unexposed portions of the layer are removed from the substrate surface after step (3) to form stenciled resist portions and remaining unprotected substrate surface portions. 50. The method of claim 49. 51. 51. The method of claim 50, wherein after step (3) the unprotected substrate surface portions are permanently modified by etching or depositing material thereon. 52. 52. The method of claim 51, wherein the resist portion is removed from the substrate after modifying the substrate surface. 53. Plating or soldering metal over unprotected board surfaces 52. The method of claim 51, wherein the modification is carried out by depositing by brushing. 54. After step (3), the resist area is uniformly exposed to actinic radiation by heating. 51. The method of claim 50, wherein the method is cured by treatment with a chemical reagent, or a combination thereof. 55. 50. The method of claim 49, wherein the exposed or unexposed portions of the layer are removed with an aqueous alkaline or acid developer therefor. 56. 50. The method of claim 49, wherein exposed or unexposed portions of the layer are removed with an organic solvent developer therefor. 57. 50. The method of claim 49, wherein the exposed or unexposed portions of the layer are peeled away from the remaining unexposed or exposed portions adhering to the substrate. 58. A colorant or powder material is deposited on an exposed or unexposed surface to form a visible surface image. 45. The method of claim 44. 59. 59. The method of claims 44 and 58, wherein steps (1), (2) and (3) are repeated one or more times after step 3 to form a multilayer image. 60. 57. The method of claim 56, wherein the photoactive component comprises: (a) an additional polymerizable ethylenically unsaturated monomer; and (b) an actinic radiation activated initiation system. 61. (1) Applying a photopolymerizable composition to the surface of a substrate having a circuit pattern to form a photopolymerizable layer thereon; (2) Image-forming exposure of the layer to actinic radiation to expose exposed and unexposed areas; (3) removing the unexposed portions of the layer to form the exposed portions the stencil solder mask image and the remaining unprotected portions of the circuit pattern; (A) forming the linear polymer backbone segments; Branched polymer products containing hydrophilic groups consisting of one or more branched polymer segments chemically bonded along the The branched polymer product contains at least one ethylenically unsaturated macromer component and and at least one ethylenically unsaturated comonomer; (a) the ethylenically unsaturated macromer component has a weight not greater than 40,000; (b) the linear polymer backbone segment has a weight average molecular weight (Mw) of about 10,000 to about 500,000; and (c) the branches of the linear polymer backbone segment The weight ratio to polymer segment(s) is within the range of about 200/1 to about 1/4, and (d) the branch polymer segment(s) is about 35% to 100% (B) an additional polymerizable monomer comprising at least two terminal ethylenically unsaturated groups; and (C) an actinic radiation-activated initiation system; A method of forming a solder mask on a printed circuit board with a raised conductive circuit pattern. Law. 62. After step (3), the resist area is uniformly exposed to actinic radiation by heating. cured by treatment with chemical reagents, or by a combination thereof. 62. The method according to claim 61. 63. 62. The method of claim 61, wherein the photopolymerizable composition comprises a heat-activated crosslinking moiety. 64. (a) Numerous branch points chemically linked along a linear polymer backbone segment. A branched polymer product consisting of remer segments, in which branched polymer segments The agent is formed during the addition polymerization of a branched polymer product from at least one ethylenically unsaturated macromer component containing one or more hydrophilic functional groups; (b) at least one photoactive or Sensitive compositions consisting of thermally active ingredients. 65. Branched polymer products containing hydrophilic groups consisting of one or more branched polymer segments chemically bonded along a linear polymer backbone segment A coating composition comprising a dispersion or solution, wherein the branched polymer product comprises at least one ethylenically unsaturated macromer component and at least one ethylenically unsaturated macromer component. formed during the addition polymerization of an ethylenically unsaturated comonomer, wherein (a) the ethylenically unsaturated macromer component has a weight average molecular weight (Mw) not greater than 40,000, and (b) the linear polymeric backbone segment has a weight average molecular weight (Mw) of about 10,000 to about 500,000; The weight ratio of segment to branch polymer segment(s) is approximately 200/ and (d) the branched polymer segment(s) comprises about 35% to 100% hydrophilic groups. 66. 66. The coating composition of claim 65, comprising a crosslinking agent. 67. A dry fill of a dispersion or solution of a branched polymer product according to claim 65. Substrate coated with Lum. 68. A dry film obtained from a dispersion or solution of a branched polymer product according to claim 65. 69. A product obtained from a dispersion or solution of a branched polymer product according to claim 1. shaped articles.