CN106459650B

CN106459650B - The substrate of latex primer composition and latex proofing priming paint

Info

Publication number: CN106459650B
Application number: CN201580034029.4A
Authority: CN
Inventors: B.A.谢尔; R.T.凯恩; J.S.霍南; C.J.兰里-康特赖恩; C.L.鲍尔
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 2014-06-23
Filing date: 2015-06-11
Publication date: 2019-05-10
Anticipated expiration: 2035-06-11
Also published as: WO2015199988A1; CN106459650A; TW201615772A; TWI665270B

Abstract

First polymer latex and second polymer latex can be mixed dry bottom paint layer is formed on the substrate, to adhere to the patterning materials with filament.The first polymer latex includes first polymer and first surface activating agent, so that the dry coating of the first polymer latex has at least 50% surface polarity.The second polymer latex includes second polymer and second surface activating agent, so that the dry coating of the second polymer latex has the surface polarity less than or equal to 27%.In addition, the dry coating of mixture has at least 15% and at most and including 50% surface polarity.The substrate primed can be used for by will be patterned into material be applied to substrate prepare directly on dry bottom paint layer with conductive yarn conductive articles.This based article can be used as the touch-screen display in various electronic equipments.

Description

The substrate of latex primer composition and latex proofing priming paint

Invention field

The present invention relates to coating composition and there is the coating composition being coated on supporter (such as transparent supporting body) Substrate.The coating composition is adhered in substrate as prime coat with will be patterned into material, and includes two different poly- The mixture of object latex is closed, every kind of polymer emulsion contains polymer beads and surfactant.Resulting patterned article can For numerous purposes, and when pattern is conductive material, which can be used as in such as equipment containing touch screen Conductive film.

Background of invention

(primed) substrate primed is used in many industry, preferably to bond overlying strata, pattern or text.Art Language " priming " typically refers to the coating using usually dry polymeric coating, for required smoothness and composition Lower substrate and there is good bonding to material is above covered both.

For example, patternable materials can be used in various industry to provide conductive or non-conductive line, solid area, text Word, grid, circuit or other shapes of pattern.Letterpress component can be used for for these patterns being applied to various substrates, and Resulting pattern can provide after further treatment is used for electronics industry, display industry or the electric conductivity or other in energy industry Property.For example, conductive pattern can be designed and prepared on a transparent substrate for various display equipment, such as touch screen.

For decades, polyester and other polymer films have been as the useful substrate for applying layer or pattern has been applied with thereon It is well-known.Such polymer film (or product) is usually more suitable for due to its intensity, flexibility and potential transparency In various purposes, including print-member, image-forming component and display equipment.However, in the painting for attempting in polymeric substrates and above to cover During being generated between layer or pattern and keeping strong adhesive power, according to the material to be applied, it will usually occur actual tired Difficulty because polymeric substrates are usually very hydrophobic, and on the painting layer or pattern covered may be less hydrophobic in nature.Or Person, polymeric substrates are less hydrophobic than the painting layer or pattern above covered.

Many problems result from the bonding of the difference in various industry.It touches sensibility panel or display is needed in predetermined figure The very thin line (width is approximately less than 20 μm) of case, to realize desired electric conductivity while have high visual clarity (or high comprehensive It closes transmissivity (integrated transmittance)).

When unrealized during the filament for manufacturing and using the conductive material including conductive metal or metal precursor or holding When enough bondings, required electric conductivity or capacitor can not achieve.2007/0170403 (Conaghan of U.S. Patent Application Publication Et al.) describe these adhesion problems and by using various adhesives or prime coat in substrate or by adhesion promoting compound The some of the recommendations solution being incorporated in the conduction " ink " (composition) of application.

For example, flexible and transparent substrates can be improved using the polymeric primer for the support surface for being applied to polymer film Bond property and various surface naturies.It is expected that the material applied later is preferably bonded, especially when those materials are with uniform Mode when applying.The example of primer layer composition for the purpose is described in such as 6,162,597 (Bauer of United States Patent (USP) Et al.) and 6,165,699 (Bauer et al.) in.

In addition, U.S. Patent Application Publication 2013/0319275 (Fohrenkamm et al.) describe it is a kind of by by substrate It is designed as improving the means of flexographic plate printed circuit cable with unique polar relationship with printing ink.

Using for depositing " additional process " that provides the conductive pattern of function of sensor in flexible and transparent substrates Touch panel sensor is produced with roll-to-roll production method and other transparent conductive articles have become the theme of latest developments in industry. Particularly importantly production has suitable in the visible part (touch area) of desired electric property and touch panel sensor When both optical properties (transmissivity) touch panel sensor ability.It is non-in order to obtain necessary conductive and optical property Often the average line width of the conductor wire in expectation conductive grid is less than 10 μm.

The flexibility used in such method and transparent substrates should be optically transparent (the comprehensive transmissivity of height) and colourless And show low haze.Use the flexographic plate of additional process such as conductive material or seed metal (seed metal) composition Printing applies conductive pattern and needs flexible and transparent substrates with consistent with the scale of the minutiae to be applied (for example, filament) Surface appropriate can and roughness.Paying sizable effort in the electronics industry to realize these necessary features.

WO 2013063188 (Petcavich et al.) describes a kind of mutual capacitance touching for producing comprising dielectric substrate The method for touching sensor, by using the flexible version printing at least the first mother matrix (master plate) and the first ink Technique prints the first pattern on the first side of dielectric substrate；With solidify printed dielectric article.Similarly it can apply and consolidate Change the second ink to form the second pattern on the second surface of substrate.Both patterns then can conductive material in electroless plating. Resulting dielectric article is described as having 1 μm to the thickness of 1mm and the preferred surface of 20 dynes per centimeters to 90 dynes per centimeters Energy.

Ongoing effort is intended to find that a kind of cost-effective mode to show for such as touch panel sensor and other optics The various electronic equipments of device provide the flexibility and transparent substrates with required surface nature and optical property.The special needle of these effort Such substrate is manufactured and used in the roll-to-roll manufacturing operation of high efficiency, the substrate described in the operation is through various chemicals And mechanically actuated.

Particularly, need following flexible and transparent substrates in the art: it shows low haze, low color (low Color) and surface uniformity, and therefore more suitable for bonding minutiae such as filament, text or small shape, and especially It is suitable for conductive filament.It is also expected to flexible and transparent substrates, show strong bonding to " printing " pattern, the pattern is for example Conductive those of metalliferous composition application can further be become by flexible version printing intrinsic conduction or through handling.

Summary of the invention

The present invention solve the problems, such as to encounter in this field with coating composition it is various, the coating composition include first The mixture of polymer emulsion and second polymer latex,

Wherein the first polymer latex includes first polymer and first surface activating agent, so that first polymerization The dry coating of object latex has at least 50% surface polarity, and

Wherein the second polymer latex includes second polymer and second surface activating agent, so that second polymerization The dry coating of object latex has the surface polarity less than or equal to 27%, and

Wherein the dry coating of the mixture of the first polymer latex and the second polymer latex has at least 15% and at most and including 50% surface polarity.

In addition, the present invention provides comprising supporter and be arranged in dry at least one support surface of the supporter The substrate of prime coat, the dry bottom paint layer include the mixture of following substance:

First polymer latex, it includes first polymers and first surface activating agent, so that the first polymer glue The dry coating of cream has at least 50% surface polarity, and

Second polymer latex, it includes second polymer and different from the second surface activity of first surface activating agent Agent, so that the dry coating of second polymer latex has the surface polarity less than or equal to 27%,

Wherein the dry bottom paint layer has at least 15% and at most and including 50% surface polarity.

In specific embodiment of the invention, substrate includes transparent polyester supporter and is directly arranged at Dry bottom paint layer at least one support surface of the transparent polyester supporter,

Wherein:

(i) substrate has at least 88% synthesis transmissivity；

(ii) the dry bottom paint layer has at least 0.05 μm and at most and including 0.2 μm of average thickness, and include with The mixture of lower substance:

First polymer latex, it includes first polymers and first surface activating agent, wherein total based on first polymer Weight, the first polymer include at least 75 weight % and contracting derived from (methyl) acrylic acid at most and including 90 weight % The repetitive unit of water glyceride and at least 10 weight % and at most and including 25 weight % be derived from the positive fourth of (methyl) acrylic acid The repetitive unit of ester, the first polymer have at least 20 DEG C and at most and including 75 DEG C of glass transition temperature, and described First surface activating agent is alpha-olefin (C₁₄-C₁₆) sodium sulfonate；

Second polymer latex, it includes second polymer and different from the second surface activity of first surface activating agent Agent, wherein being based on second polymer total weight, the second polymer is comprising at least 75 weight % and at most and including 90 weights Measure the repetitive unit derived from (methyl) glycidyl acrylate and at least 10 weight % and at most and including 25 weights of % Measure % the repetitive unit derived from (methyl) n-butyl acrylate, the second polymer at least 25 DEG C and at most and including 75 DEG C of glass transition temperature, and the second surface activating agent is the ammonium salt of sulphation polyethoxy nonyl phenol；

(iii) the dry bottom paint layer has at least 28% and at most and including 50% surface polarity；

(iv) weight ratio of the first polymer latex and the second polymer latex is 1:1 and to and including 2.5: 1；

(v) it is based on dry bottom paint total weight, the first surface activating agent is at least 1 weight % and at most and including 3 weights The amount of amount % is present in the dry bottom paint layer；

(vi) it is based on total dry bottom paint layer, the second surface activating agent is at least 0.35 weight % and at most and including 1.1 The amount of weight % is present in the dry bottom paint layer；With

(vii) it is based on dry bottom paint layer total weight, the total amount of the first and second surfactants in the dry bottom paint layer is small In 3.35 weight %.

Various embodiments of the present invention provide many advantages.Most of all, the composition provided through the invention It is shown with the substrate primed for surface needed for applying in the pattern containing fine-feature and bonding various compositions Characteristic, the fine-feature include but is not limited to the line less than 15 μm or be more likely to the average line width less than 15 μm.For example, The photocurable containing metal seeds particle or heat-setting composition can be used to provide such pattern, and the pattern Electroless plating can be carried out, suitably to provide the conductive pattern with desired fine-feature.The substrate and system containing them Product show low haze, low color, required surface uniformity (appearance of coat) and high synthesis transmissivity (at least 88%).These Advantage passes through the bottom with the mixture comprising the first polymer latex and second polymer latex that have the following properties and form Coating compositions " are primed " on suitable support body material (such as transparent support material) and are realized.

Brief description

Fig. 1 is the flexographic plate Department of Printing that roll-to-roll printing (or imaging) is carried out on the two sides that can be used in substrate of the invention The schematic side elevation of system, wherein using representative Photocurable composition (patterning materials) and method of the invention.

Fig. 2 is the device (equipment) comprising the touch screen for preparing the touch sensor of (printing) with the usable present invention High-level system diagram.

Fig. 3 is the side view of the touch sensor of Fig. 2.

Fig. 4 is the top for the conductive metal pattern having been formed in the first support-side of the substrate in the touch sensor of Fig. 3 View.

Fig. 5 is the conductive metal pattern on second (opposite) side for the substrate being printed in the touch sensor of Fig. 3 Top view.

Detailed description of the invention

Following discussion is directed to various embodiments of the present invention, although and for special-purpose, some embodiment party Case may be desirable, but disclosed embodiment is not necessarily to be construed as or is additionally considered to be the following required guarantor of limitation The scope of the present invention of shield.In addition, it will be appreciated by those skilled in the art that following disclosure is with more extensive than what is be expressly recited Application.

Definition

Unless otherwise noted, otherwise as herein to define primer coating compositions, dry bottom paint layer, photocurable and Ke Re The singular " one " (" a ", " an ") and " institute of solidification composition filling and the various components of other composition characteristics as described herein State " (" the ") be intended to include one of described component or more (that is, include plural object).

Each term not clearly defined in this application should be understood usually to receive with those skilled in the art Meaning.If the construction of a term will make it hereinafter meaningless or substantially meaningless on it, the definition of the term Normal dictionary should be obtained from.

Unless in addition clearly it is further noted that otherwise the use of the numerical value in specified various ranges is recognized herein To be approximation, as there is word " about " before the minimum value and maximum value in the range.In this way, the model Enclosing slightly changing for above and below can be used for realizing the result essentially identical with the value in the range.In addition, these ranges Disclosure be intended as the successive range including each value between minimum value and maximum value.

As it is used herein, unless otherwise noted, otherwise molecular weight is weight average molecular weight, known step can be used And measuring apparatus, if the value is talked about from known in the literature.

Unless otherwise noted, term " photocurable or heat-setting composition " refers to Chemical composition that, can be used for It practices various methods of the invention and may be provided in product of the invention.Such composition have can consolidate under certain conditions Change, the required chemicals of polymerization or crosslinking.

Term " solidification " and " polymerization " be used herein to mean that in the presence of suitable catalyst or initiator, such as It is combined by covalent bonding largely compared with small molecule such as monomer or oligomer to form very big molecule, i.e. macromolecular or polymerization Object.Solidification or polymerization can form linear macromolecule or commonly referred to as the cross-linked polymer three-dimensional macromolecular that includes branched chain materials, or Person can be formed simultaneously both line style and crosslinking (or branch) material.The a type of polymerization that can be carried out in the practice of the invention It is acid catalysis (cation) polymerization.Free radical polymerization can also carry out in the practice of the invention.Alternatively, in some embodiments In, both acid catalyzed polymerisation and free radical polymerization can carry out simultaneously.

Term " photocurable " and it is " curable " be used for definition material (such as epoxy material), in photoinitiator appropriate It will when irradiating in the presence of composition when with suitable radiation, such as being irradiated with radiation such as ultraviolet (UV), visible or infra-red radiation Polymerization.

The average dry thickness of layer as described herein can for for example using electron microscope or optical microscopy dried layer not With the average value for the independent measurement two or more times that position carries out.In certain embodiments, it obtains and is individually surveyed more than 2 times Amount may be desirable.

Similarly, the average dry thickness or width of line as described herein, grid lines or other pattern characteristics can be for example to make With the average value for the independent measurement two or more times that electron microscope carries out.

Term " polymerizable epoxy material " is intended to include having one or more oxirane rings that can undergo polymerization Any material or compound.The term includes the monomer containing epoxy, the oligomer containing epoxy and the crosslinking agent containing epoxy.The art The singular of language is intended to include the plural form of the term.Oligomeric and multi-functional epoxy's material is also useful polymerizable epoxy Material.

Term " electron donor photosensitizer " means the light-absorbing compound for inducing photocuring.It is described after light excitation Electron donor photosensitizer leads to the one-electron reduction of salt.

Term " photoinitiator " means to resolve into free radical or Chemical moiety when exposed to light to cause further reaction Any compound (chemical compound).In some embodiments, the photoinitiator is " salt " or " changes Close object " or other photo-acid agents, the electronics from excited electron donor photosensitizer can be received, this is that one kind causes salt broken It splits to provide the process for the Taide Bu Langsi sour (Br nsted acid) for causing epoxy material polymerization.In other embodiments, The photoinitiator resolves into free radical, continues (proceed) to cause the solidification, polymerization or crosslinking of vinyl.

" actinic radiation " is for referring to generate photochemistry according to the present invention or light polymerization and having at least 150 Nm and at most and including 750 nm, or even at least 190 nm and at most and any electromagnetic radiation of the wavelength including 700 nm. Term " exposing radiation " also refers to such actinic radiation.

Term " visible light " is greater than 400 nm extremely and at most and the wave including 750 nanometers (nm) for referring to have herein Length is (for example, λ_max) electromagnetic radiation.

Term " UV light " herein for refers to have at least 150 nm and at most and the wavelength including 400 nm (for example, λ_max) electromagnetic radiation.

Term " near-infrared " and " infrared " are herein for referring to there is at least 750 nm and higher, and typically at least 750 nm and at most and the wavelength including 1400 nm is (for example, λ_max) electromagnetic radiation.

Term " comprehensive transmissivity " is the parameter for measuring " transparency ".Therefore, when supporter, substrate and product are claimed When being transparent, electromagnetic spectrum visibility region (such as the synthesis transmissivity on 400 nm to 750 nm) is 80% or bigger, Or be more likely to be at least 88%, or even 93% or bigger, as example using measured by spectrophotometer and known technology.It is logical Often, the touch area in conductive articles or film will have this high comprehensive transmissivity.However, electrode connector region or the area BUS The transparency in domain is usually much smaller, and can be typically below 68% using above-mentioned identical equipment and step, or be less than 50%, or even less than 40% synthesis transmissivity.

Alternatively, comprehensive transmissivity can be with the transparent article, supporter or the base that are not covered by conductive pattern in touch area The calculating percentage in bottom region is associated.

Term " average line width " about various patterns as described herein or patterning materials refers to using art technology Personnel by the measuring technique and equipment appropriate that know by identical or different line different location line it is single two or more times The solely determining size of measurement.In certain embodiments, measurement such more than 2 times may be desirable.

" touch area " in conductive surface, part, film or other structures refers to the product with patterning materials Region, such conductive pattern is designed to touch to manipulate image in the display device, " application program (apps) " or other Digital information.Therefore, touch area is different from " conductive electrode connector area ", " BUS line " and " region BUS ".

It is defined described in surface polarity embodiment as follows.

Purposes

Coating composition, substrate, product and method as described herein can be used for various purposes, wherein needing to have the property The substrate of matter is for further applying material or forming pattern.For example, (priming paint) coating composition, substrate and system as described herein Product are particularly useful for providing the conductive metal pattern (such as using electroless plating step) with fine-feature, can be coupled to various In equipment, the equipment includes but is not limited to touch screen or the other display equipment that can be used for numerous industry and commercial product.

For example, touch screen technology may include different touch sensor configurations, including capacitive touch sensors and resistance Formula touch sensor.Resistive touch sensor includes several layers, these layer is facing with each other, has gap between adjacent layers, It can be kept by the spacer (spacer) formed during manufacture.Resistive touch screen panel may include several layers, including Two thin metal conducting layers that the gap that can be formed by spacer separates.When such as object of contact pilotage, palm or finger tip is downward Pressing is in the point on the outer surface of panel, two metal layer contacts, and forms the connection for leading to curent change.The touch event It is sent to controller for further processing.

Capacitive touch sensors can be used for the electronic equipment for touching sensivity feature.These electronic equipments may include But it is not limited to may be adapted to show that image includes text, figure, video image, film, static image and PowerPoint (presentation) TV, monitor and projector.The vision facilities that can be used for these display equipment may include that cathode is penetrated Spool (CRT), projector, plate of flat liquid crystal display (LCD), LED information display system, OLED system, plasma system, electroluminescent are aobvious Show device (ELD) and Field Emission Display (FED).For example, the present invention can be used for preparing capacitive touch sensors, can be combined Equipment, computer display, portable media player are calculated to having in the electronic equipment for touching sensivity feature to provide Including electronic reader, mobile phone and other communications or digital storage equipment.

The manufacture in the roll-to-roll manufacturing process of high volume (can wherein generate micro conductive feature in one way) using the present invention Flexible and optics compatibility touch sensor system and method are possible.Photocurable or heat-setting composition can be with Letterpress component such as flexographic printing plates are used together, to form multiple high-resolution conductive patterns by scheduled design Picture.Multiple patterns can print in one or two support-side of substrate of the present invention, as described in more detail below.For example, one A predetermined pattern can print in a support-side of substrate, and different predetermined patterns can print the opposite support-side in substrate On.Then such as, such as the print of photocurable or heat-setting composition can be further processed using electroless metal coating technology Map brushing case, to provide the conductive metal pattern containing fine-feature.

Polymer emulsion

It provides for unique composition of the invention, the composition can be used for providing any of advantage of the present invention Suitable means deposition is on the surface.This composition is usually also referred to as " coating composition ", " primer layer composition " or " bottom Coating compositions ".The coating composition includes the mixture of at least first polymer latex and at least one second polymer latex. By using modifier " first " and " second ", it is not intended to infer in any given performance a kind of (or the polymerization of polymer emulsion Object) more preferably than another polymer emulsion (or polymer), and the modifier is only used for distinguishing two different polymer latexs Newborn composition.If desired, polymer emulsion in addition may be present in mixture, (retouch herein as long as obtaining required property It states).

First and second polymer:

First and second polymer emulsion separately includes first polymer and second polymer.When in latex form or When polymeric dispersions, first and second polymer is usually to be formed in micella using known emulsion polymerization technology In particle form exist.Although the first and second polymer can respectively be separated, they are in the present invention with the first He The mixture of second latex uses, and therefore, and separation will likely make it harder to use them in coating.

At least one of first and second polymer as described herein includes polyvinyl, and it includes at least partly Derived from (methyl) glycidyl acrylate (indicating glycidyl acrylate, glycidyl methacrylate or both) Repetitive unit, and in most of embodiments, first and second polymer is respectively at least partly derived from (first Base) glycidyl acrylate.In addition, at least one of the first polymer and second polymer are crosslinkable, and And can be for example after being applied on suitable supporter, such as be crosslinked during the drying or various heat treatments of substrate. Those skilled in the art will know how and the wise selection in the design in polymer repeat unit and reactive group Crosslinking ability is provided in given polymer.

It include one or more of first polymers and one or more of for first polymer latex of the invention One surfactant (described below), so that the dry coating of the first polymer latex has at least 50% (50% or more It is more), or the surface polarity of even at least 55% (55% or more).In most of embodiments, the first polymer glue Cream is substantially made of two kinds of required components: one or more of first polymers and one or more of first surface activity Agent.

Particularly useful first polymer is the ethylene linkage at least partly derived from one or more of glycidyl functionals Formula unsaturated polymerizable monomer, such as the polyvinyl of glycidyl acrylate and glycidyl methacrylate. Therefore, the first polymer can be the homopolymer derived from (methyl) glycidyl acrylate, but be more likely to it to derive From the copolymer of (methyl) glycidyl acrylate and one or more of other ethylenic bond unsaturated polymerizable monomers.Term " glycidyl " refers to (can also further substituted linear chain or branched chain comprising being connected to alkyl with 1 to 4 carbon atoms Alkyl), for example, methyl, ethyl, isopropyl and tert-butyl oxirane ring group.

For example, the total weight based on the first polymer, which may include at least 75 weight % and at most And including 100 weight % or at least 75 weight % and at most and the amount including 90 weight % contracts derived from (methyl) acrylic acid The repetitive unit of water glyceride.Therefore, especially desirable first polymer is derived from (methyl) glycidyl acrylate and one Kind or more other ethylenic bond unsaturated polymerizable monomers (comonomer), will during emulsion polymerization substantially with (first Base) copolymerization of glycidyl acrylate monomer, rather than reacted with glycidyl, and it will promote all ethylenic bond insatiable hungers Disperse intracorporal emulsion polymerization in reaction with polymerisable monomer.Suitable vinyl comonomer includes but is not limited to acrylic acid Arrcostab and alkyl methacrylate, wherein ester alkyl has a carbon atom of 1 to 4 (four)；Other substituted acrylic acid alkyls Ester and alkyl methacrylate；Acrylamide and Methacrylamide；Vinyl halide such as vinyl chloride；Ethenylidene halogen Compound such as vinylidene chloride；Vinyl pyrrolidone；Other N- vinylamides；Vinylpyridine；Styrene and styrene Derivative such as α-methylstyrene；Butadiene；Isoprene；Acrylonitrile；Methacrylonitrile；It will hold with those skilled in the art It is easily obvious other.If desired, the mixture of comonomer can be used.Those skilled in the art will enable with conventional real It tests to determine and will provide the appropriate amount of the various comonomers of required film-forming quality as described herein and surface polarity value.

The first polymer particularly by make one or more of (methyl) glycidyl acrylates and it is a kind of or More kinds of (methyl) alkyl acrylate copolymers design, and wherein ester alkyl has at least two carbon atom, including but not limited to, Ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-BMA, cyclohexyl acrylate, metering system Sour cyclohexyl, lauryl acrylate, lauryl methacrylate, allyl methacrylate, hydroxyethyl methacrylate, third Olefin(e) acid hydroxy methacrylate and those skilled in the art are other by what is be readily apparent.Particularly useful comonomer is wherein ester alkane Base has (methyl) alkyl acrylate of at least four carbon atom, including but not limited to n-butyl acrylate, methacrylic acid just Butyl ester, the just own ester of acrylic acid, the just own ester of methacrylic acid and cyclohexyl methacrylate.

Second polymer latex for use in the present invention includes one or more of second polymers and one or more Second surface activating agent (described below), so that the dry coating of the second polymer latex, which has, is less than or equal to 28% or small In or equal to 27% surface polarity.In most of embodiments, the second polymer latex is substantially required by two kinds Group is grouped as: one or more of second polymers and one or more of second surface activating agents.

Particularly useful second polymer is the ethylene linkage at least partly derived from one or more of glycidyl functionals Formula unsaturated polymerizable monomer, such as (methyl) glycidyl acrylate, such as glycidyl acrylate and metering system Acid glycidyl ester, the polyvinyl as described in above for first polymer.Therefore, the second polymer can be to spread out It is born from the homopolymer of (methyl) glycidyl acrylate, or is derived from (methyl) glycidyl acrylate and one or more The copolymer of the other ethylenic bond unsaturated polymerizable monomers of kind.Term " glycidyl " is as defined above.

Therefore, the total weight based on the second polymer, the second polymer may include at least 75 weight % and at most And including 100 weight % or at least 75 weight % and at most and the amount including 90 weight % contracts derived from (methyl) acrylic acid The repetitive unit of water glyceride.Therefore, especially desirable second polymer is derived from (methyl) glycidyl acrylate and one Kind or more other ethylenic bond unsaturated polymerizable monomers (comonomer), will during emulsion polymerization substantially with (first Base) copolymerization of glycidyl acrylate monomer, rather than reacted with glycidyl, and it will promote all ethylenic bond insatiable hungers Disperse intracorporal emulsion polymerization in reaction with polymerisable monomer.Suitable vinyl comonomer includes but is not limited to acrylic acid Arrcostab and alkyl methacrylate, wherein ester alkyl has a carbon atom of 1 to 4 (four)；Other substituted acrylic acid alkyls Ester and methacrylate；Acrylamide and Methacrylamide；Vinyl halide such as vinyl chloride；Vinylidene halide Such as vinylidene chloride；Vinyl pyrrolidone；Other N- vinylamides；Vinylpyridine；Styrene and styrene derived Object such as α-methylstyrene；Butadiene；Isoprene；Acrylonitrile；Methacrylonitrile；With those skilled in the art will be easy it is aobvious and What is be clear to is other.If desired, the mixture of comonomer can be used.As first polymer, those skilled in the art will Enough being determined using routine experiment will be provided herein for required film-forming quality and surface polarity described in second polymer latex The appropriate amount of the various comonomers of value.

The second polymer particularly by make one or more of (methyl) glycidyl acrylates and it is a kind of or More kinds of comonomers for example one or more of (methyl) alkyl acrylate copolymers design, and wherein ester alkyl has at least 2 carbon atoms, including but not limited to, the positive fourth of ethyl acrylate, ethyl methacrylate, n-butyl acrylate, methacrylic acid Ester, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, methacrylic acid allyl Ester, hydroxyethyl methacrylate, Hydroxyethyl Acrylate and those skilled in the art are other by what is be readily apparent.It is special Not useful comonomer is that wherein ester alkyl has at least four carbon atom (methyl) alkyl acrylate, such as acrylic acid N-butyl, n-BMA, the just own ester of acrylic acid, the just own ester of methacrylic acid and cyclohexyl methacrylate.

It is particularly pointed out in the embodiment of the present invention as described below, although first and second polymer can be difference Material, but the first and second polymer composition (repetitive unit of identical glycidyl functional having the same With the repetitive unit from comonomer) or with similar or identical molecular weight may be useful.

Although the molecular weight of first and second polymer cannot be always accurately determined, because this quasi polymer can have There is the bridged linkage obtained from glycidyl, but usually each polymer independently has at least 10,000 or is more likely at least 50,000 molecular weight.

In addition, first and second polymer respectively can independently have at least 25 DEG C or more typically at least 40 DEG C, And at most and including 75 DEG C of glass transition temperature (T_g), such as measured by differential scanning calorimetry (DSC).

The second polymerization in the amount of first polymer in the first polymer latex and the second polymer latex The amount of object may be the same or different.In most of embodiments, based on total first polymer latex solid, first polymerization The amount of first polymer in object latex is at least 10 weight % and at most and including 40 weight %；And it is poly- based on total second Object latex solid is closed, the amount of the second polymer in the second polymer latex is at least 20 weight % and at most and including 30 Weight %.

First and second surfactants:

The first polymer latex includes one or more of first surface activating agents, is individually sodium alkyl sulfonate Salt, wherein the alkyl has at least ten carbon atom.For example, the first surface activating agent can be alpha-olefin (C₁₄-C₁₆) sulphur Sour sodium or the first surface activating agent can be for by R-CH₂-CH=CH-CH₂-S(=O)₂O^-Na⁺The compound of representative, wherein R It is C₁₀、C₁₁Or C₁₂Alkyl, or the mixture of such compound with different R groups, the R group are C₁₀To C₁₂In alkyl Any kind.A kind of useful commodity containing first surface activating agent are Rhodacal^®A246L (such as available from Rhodia).If desired, the mixture of such first surface activating agent can be used.

The total amount of one of described first polymer latex or more first surface activating agent is adjusted, so that when by the (as priming paint when one polymer emulsion and the mixture of second polymer latex (described below) are applied in substrate and dry Layer), one of dry bottom paint layer or more first surface activating agent total amount be based on dry bottom paint layer total weight extremely Lack 1 weight % and at most and including 3 weight % or typically at least 1.6 weight % and at most and including 2.8 weight %.It considers The mixed weight of first polymer latex and second polymer latex ratio, those skilled in the art will know how many first surface Activating agent is incorporated in the lotion for being used to prepare first polymer latex, so that the amount needed is present in dry bottom paint layer.

The second polymer latex includes one or more of second surface activating agents, is individually to have at least three The alkyl phenol ammonium sulfate of ethylene oxide unit.For example, the second surface activating agent can be sulfuric acid polyethoxy nonyl phenol The ammonium salt or the second surface activating agent of (sulfate polyethoxy nonylphenol) can be by R'- phenyl-(O- CH₂CH₂)_n-S(=O)O₂ ^-NH₄ ⁺It represents, wherein R ' is C₈To C₁₂Alkyl, and n is at least 3 and at most and including 10, or is more likely to n It is at least 3 and at most and including 6.The useful commodity of one kind containing second surface activating agent are Rhodapex^®CO-436 (example Such as available from Rhodia).If desired, the mixture of such second surface activating agent can be used.

The total amount of one of described second polymer latex or more second surface activating agent is adjusted, so that when by the (as priming paint when one polymer emulsion and the mixture of second polymer latex (described below) are applied in substrate and dry Layer), it is at least 0.35 weight % and at most simultaneously in the total amount of one of dry bottom paint layer or more second surface activating agent Including 1.1 weight % or typically at least 0.45 weight % and at most and including 0.9 weight %, it is based on dry bottom paint layer total weight.It examines Consider the mixed weight ratio of first polymer latex and second polymer latex, those skilled in the art will know how many second Surfactant is incorporated in lotion to prepare second polymer latex, so that the amount needed is present in dry bottom paint layer.

The first polymer and the second polymer are dispersed in usually as fine particle separately includes first and In the independent water-borne dispersions of dimerization object latex.It, can be with any suitable when mixing these polymer emulsions according to the present invention Mode be applied to suitable substrate for them as coating formulation.Some water in every kind of polymer emulsion can use water miscibility Organic solvent (such as methanol or acetone) replacement.

It is generally desirable to use individually and independently have less than 200 μm, be more likely to less than 150 μm and even more desirably First and second polymer emulsions of the average first and second polymer partial sizes less than 100 μm.In order to obtain small and narrow gather Object particle diameter distribution is closed, in emulsion polymerization, any one of first polymer latex and second polymer latex or two kinds include The first and second amount of surfactant more than amount described in aforementioned paragraphs may be necessary.However, by using dialysis To remove excessive first and second surfactant, the total amount of the first and second surfactants can be reduced to for this hair Below the bright maximum.

Emulsion polymerization can be used respectively to prepare or conduct in the first polymer latex and the second polymer latex The water-borne dispersions of grain emulsion polymer (polymerizate) obtain.Emulsion polymerization including useful condition and reactant Step is known in the art, and representative details provides in United States Patent (USP) 6,162,597 (5-7 column).Above-mentioned One and second surface activating agent be respectively included in the preparation of the first polymer latex and the second polymer latex, example Such as at least one anionic surfactant.However, the preparation of first and second polymer emulsion is not limited to only divide It Shi Yong not first and second surfactant.Hereafter representative preparation method is provided with embodiment.

Coating composition

The first polymer latex and second polymer latex respectively can be independently miscible comprising one or more of water Property organic solvent, amount be based on latex total weight be at most and including 10 weight %；One or more of surfactants；It is a kind of Or more inorganic flatting agent (as long as mist degree does not dramatically increase and transparency does not significantly reduce)；Antistatic agent；To adjust The acid or alkali of pH；And buffer.

The one or more of crosslinking agents that it may also be desirable to be incorporated to known quantity (are alternatively referred to as " hardening in the art Agent "), in the friendship for further promoting polymer latex particle Yi Dan polymer latex particle is applied to supporter and dried Connection.Useful crosslinking agent includes but is not limited to that aldehyde-containing compounds such as formaldehyde and glyoxal, the compound containing aziridine are for example Ester such as the trimethylene double A sulphonate, active vinyl-compound example of tetramethylene -1,4- bis- (ethylidene-ureas), methanesulfonic acid As double acryloyl group ureas (bisacroyl urea) and methylene divinyl sulfonic acid, the compound containing glycidyl are for example double Phenol glycidol ether and isocyanates.

It is desirable, however, that first polymer latex and second polymer latex all do not contain a large amount of coalescing aid, Such as resorcinol and for this purpose in the 6th column of United States Patent (USP) 6,162,597 (above-mentioned), the 53rd row arranges in the 3rd row to the 7th and retouches The other compounds stated.Being especially desired to the first and second polymer emulsions includes the gross weight based on dry bottom paint layer (described below) Such coalescing aid such as resorcinol less than 1 weight % of amount, when described two polymer emulsions are mixture and are applied When being added to supporter.

Therefore, in some embodiments of composition as described herein, the dry bottom lacquer coat of the composition has extremely Lack 28% and at most and including 50% surface polarity.In addition, such composition can have the property that

Based on first polymer total weight, the first polymer is comprising at least 75 weight % and at most and including 90 weights Measure the repetitive unit derived from (methyl) glycidyl acrylate and at least 10 weight % and at most and including 25 weights of % Measure % the repetitive unit derived from (methyl) n-butyl acrylate, the first polymer at least 50 DEG C and at most and including 70 DEG C of glass transition temperature, and the first surface activating agent is alpha-olefin (C₁₄-C₁₆) sodium sulfonate；

Based on second polymer total weight, the second polymer is comprising at least 75 weight % and at most and including 90 weights Measure the repetitive unit derived from (methyl) glycidyl acrylate and at least 10 weight % and at most and including 25 weights of % Measure % the repetitive unit derived from (methyl) n-butyl acrylate, the second polymer at least 50 DEG C and at most and including 70 DEG C of glass transition temperature, and the second surface activating agent is the ammonium salt of sulphation polyethoxy nonyl phenol；

The dry coating of the composition has at least 28% and at most and including 50% surface polarity；

In the mixture the weight ratio of the first polymer latex and the second polymer latex be 1:1 and to and wrap Include 2.5:1；

Based on dry coating total weight, the first surface activating agent is at least 1 weight % and at most and including 3 weight %'s Amount is present in the dry coating of the mixture；

Based on dry coating total weight, the second surface activating agent is at least 0.35 weight % and at most and including 1.1 weights The amount of amount % is present in the dry coating of the mixture；With

Based on dry coating total weight, the total amount of the first and second surfactants in the dry coating of the mixture is less than 3.35 weight %.

Substrate

Above-mentioned composition (" priming paint " composition) can be applied to any suitable supporter in an appropriate manner, for into The processing of one step or processing are for given industrial purpose, to form substrate of the invention.Gained substrate can be opaque, transparent Or translucent or its combination with opaque section and transparent part.

For example, dry bottom paint layer can be formed on any suitable support body material, as long as it does not inhibit setting for resulting product Count purpose.For example, supporter can be by including but is not limited to that polymer film, metal, glass are (untreated or for example with tetrafluoro carbon (tetrafluorocarbon) plasma, hydrophobicity fluorine or the hydrophobic material processing of siloxanes), silicon wafer or potsherd, fabric, Paper and combinations thereof (such as various films laminated material or paper and film laminated material) material formed.Gained substrate can be rigid It is property or flexible.Particularly useful support body material be polyester, polycarbonate, polystyrene, polyimides, polyamide and its Composite material.

The supporter used in the substrate can have any desired average dry thickness, it typically is at least 50 μm and at most And including 3,000 μm.Most of continuous coiled materials (continuous web) used in the present invention will have average dry thickness (dry Prime coat and supporter), the final use by its product formed is depended on, such as be incorporated into various products or optics In equipment or display equipment.For example, substrate dry thickness (including dry bottom paint layer, supporter and any optional layer or coating) can be At least 50 μm and at most and including 250 μm, and particularly with polymer film for, the substrate dry thickness can be at least 80 μ M and at most and including 175 μm or at least 100 μm and at most and including 125 μm.

Substrate of the invention can be provided in a variety of manners, such as, such as the independent thin slice of any size or shape, and it is continuous Coiled material is for example adapted for the continuous coiled material of the transparent substrates including transparent polyester supporter of roll-to-roll operation.Such continuous volume Material can be divided into or be formed as individual first, second and other part, can be used to form the pattern of identical or different pattern Change material (described below).

Before or after forming dry bottom paint layer in one or two support-side of supporter, it can handle in an appropriate manner Support body material (if especially if polymer material), to improve the bonding of dry bottom coating compositions, to reduce substrate below Contraction during manufacture, coating or the other operation of description.Often, for example, it is desirable to before or after forming dry bottom paint layer, Stretched polyester or other polymer supports on one or two in-plane (vertical and horizontal).However, in most of realities It applies in scheme, after dry bottom paint layer is formed in one or two support-side of supporter, uses known step and condition Carry out horizontal and vertical stretching.After these stretching steps, it is being greater than 100 DEG C and at most and including 150 DEG C of temperature Continuing the heat treatment (or hot wire-CVD) of a few minutes down can provide the first and second polymer beads being enough to coalesce in dry bottom paint layer Thermal energy, to form relatively uniform dry bottom paint layer film, and one or both of be crosslinked first and second polymer (if They have required crosslinkable groups).

Other useful supporter processing include Corona discharge Treatment, flame treatment and various cleanings and washing step.

Above-mentioned paint base composition is usually applied to suitable supporter described herein with enough coverage rates (such as to wrap Include the polyester support of continuous polyester coiled material), to provide the required dry thickness of dry bottom paint layer described herein, such as at least 30 mg solids/m²And at most and including 300 mg solids/m²Coverage rate, applied using any technology described herein.It applies Cloth process can occur in any time during the manufacture of substrate of the invention, for example, it is as described above it is biaxial stretch-formed before, Or after longitudinal stretching and before cross directional stretch, or after biaxial stretch-formed.

Those skilled in the art will also be apparent that the required dry thickness of given dry bottom paint layer can be by according to this Multiple coatings of the identical or different paint base composition of invention realize so that final dry bottom paint layer can for identical or The composite material of multiple sublayers of different chemical compositions and dry thickness.If foring the composite material of this multilayer, according to definition, The surface polarity of final dry bottom paint layer by be composite dry prime coat outermost surface evaluation.

As described above, particularly useful substrate includes that can directly arrange to be done by what compositions described herein formed on it The supporter of prime coat (the one or more material described in aforementioned paragraphs forms).The dry bottom paint layer includes as above fixed The first polymer latex of justice and the mixture (for example, mixture of coalescence) of second polymer latex.In addition, the dry bottom paint Layer has at least 15% and at most and including 50% or at least 22% and at most and including 45% surface polarity.It is especially desirable , supporter is by one or more of transparent polymer materials such as mixture of polyester, polyester or polyester and another polymerization The mixture of object forms, and resulting substrate can have at least 88% and be more likely at least 93% synthesis transmissivity.For example, Particularly useful transparent support material can be made of poly- (ethylene glycol terephthalate) and poly- ((ethylene naphthalate)).

Although the dry bottom paint layer, which is directly arranged on supporter, (have been implied the absence of in most of embodiments Meaning forms or provides middle layer between dry bottom paint layer and supporter), but may also the supporter can be coated with it is a kind of or The mixture of more kinds of different priming paint polymer or polymer, to form one or more " intermediate basecoat layers ", (use exists Usual material known for this purpose in photographic art), and then dry bottom paint layer according to the present invention can be applied directly to institute State one or more intermediate basecoat layers.Such intermediate basecoat layer may be formed in one or two support-side of the supporter, It can be formed directly in the intermediate basecoat layer in one or two support-side of supporter with then dry bottom paint layer according to the present invention On.

Therefore, the dry bottom paint layer may be arranged at least one support-side of supporter, and in many embodiments In, identical or different (on composition, thickness or surface polarity) dry bottom paint layer can be directly arranged at two supports of supporter On side (that is, the first support-side and second opposite support-side)." support-side " refers to the planar side of supporter, rather than supporter material The edge of material.For example, dry bottom coating compositions according to the present invention may be arranged in a support-side of supporter, and it is other (non- It is of the invention) polymer (or priming paint) layer may be arranged in the opposite support-side of supporter.

The mixture (composition) of above-mentioned latex can be applied by using any suitable way at least the one of supporter Dry bottom paint layer is formed in a support-side, for example dip-coating, roller coating, hopper coating, spraying, spin coating or offer can be any for the mode The dry usual uniform coating of suitable mode (such as using step and equipment known in photographic supports field) is appointed What its method.Alternatively, can for example be imprinted using ink-jet, photolithography, use for example flexible version printing structure of letterpress component Part (such as flexographic printing plates and flexographic printing elements) " flexographic plate " printing, using lithographic printing plate lithographic printing and It is printed using the intaglio plate (gravure or intaglio) of print-member appropriate and the pattern of paint base composition is applied to supporter (or to any intermediate basecoat layer thereon).

The dry bottom paint layer being arranged on supporter can have several desirable properties.For example, dry in dry bottom paint layer The weight ratio of one polymer emulsion and dry second polymer latex is 1:3 and to and including 3:1 or is 1:1 and to and including 2.5:1。

In addition, be based on dry bottom paint layer total weight, the first surface activating agent (above description) can at least 1 weight % and At most and including 3 weight % and more generally at least 1.6 weight % and at most and the amount including 2.8 weight % be present in it is described dry In prime coat.

In addition, be based on dry bottom paint layer total weight, the second surface activating agent at least 0.35 weight % and at most and is wrapped Include 1.1 weight % or typically at least 0.45 weight % and at most and the amount including 0.9 weight % is present in the dry bottom paint layer In.

Based on dry bottom paint layer total weight, the total amount of the first and second surfactants in the dry bottom paint layer is at least 1.35 weight % and at most and including 3.35 weight %.

Also usefully, the dry bottom paint layer (or composite material of sublayer as described above) has at least 0.05 μm and extremely It is more and including 0.4 μm or typically at least 0.05 μm and at most and including 0.2 μm or even at least 0.07 μm and at most and including 0.2 μm of average dry thickness.Technical staff will know how to determine the density of specific primer composition prepared in accordance with the present invention, The required dry thickness of gained dry bottom paint layer is obtained with the wet coverage rate to be applied then is calculated.

When will include that the coating of mixture of the first and second polymer emulsion as described above is applied to suitable support Body and after drying, the mixture of latex particle usually " coalescence " usually has to be formed in be applied on its entire support surface The polymer film uniformly formed.In many embodiments, latex particle can be also crosslinked among their own, with provide more resistant to Long surface, more tolerant to the degradation of organic solvent.Then such durable uniform dry Primer Layer Coatings can provide for applying Add the more suitable surface of curable compositions.

Product

Above-mentioned substrate can be used for providing product, and wherein patterning materials are directly arranged on dry bottom paint layer, the dry bottom paint layer Directly arrangement (in most of embodiments) is on supporter (such as transparent polymeric support) again.It is especially useful that, Even if the product can still have at least 88% or typically at least 95% synthesis transmissivity there are patterning materials.Such system Product may include dry bottom paint layer, have the property that describe above with respect to substrate, including average dry thickness, first polymer latex and The weight ratio of second polymer latex, the specific composition of the first and second polyvinyls in the latex and vitrifying Transition temperature and specific first and second surfactant (and their amount).

It is also desirable that such dry bottom paint layer in the product is substantially free of resorcinol, such as based on dry bottom paint Layer total weight, resorcinol is less than 1 weight % or even less than 0.5 weight %.

Can patterning be provided in a manner of according to pattern (patternwise) in product of the invention in any suitable manner Material, such as including but not limited to flexographic plate print-member is used using the above-mentioned means and technology for being used to form dry bottom paint layer Such as flexographic printing plates, flexographic print cylinder and flexographic printing elements, use intaglio printing (intaglio Printing) and intaglio printing (gravure printing) is used.Ink jet printing method and equipment can also be used will be patterned into Material is applied to substrate.Once applying, at least part of patterning materials may include having less than 15 μm or even less than 10 μ The filament of the average line width of m.Certainly, patterning materials do not need to be made of this class filament completely, because if desired, can also wrap Containing big region, text and various shape.But in most of embodiments, at least part of patterning materials is main Comprising filament, to form the grid or pattern of filament.In some embodiments, the entire patterning materials on dry bottom paint layer It is made of this class filament.

Useful patterning materials, which are generally comprised, can be applied to substrate according to patterned fashion and can be used for spy in this manner Determine any suitable composition or " ink " of purpose.

In some embodiments, term " patterning materials " is conductive or can further become conductive through handling " conductive printing material ".Such material can be organic, inorganic, or include both organic component and inorganic component.Useful Conductive printing material usually responds at least current potential (although such material can also respond other stimulations) and shows scheduled activity. The example of conductive printing material includes but is not limited to, conductive organic or inorganic polymer (or its composite material), tin indium oxide Particle, particle, thin slice or the long filament of metal (such as gold, silver, copper, platinum, nickel, iron, aluminium and palladium), metal complex particle, gold Belong to alloy and metal precursor, and combinations thereof.Alternatively, conductive printing material can be conductive material precursor, such as metal salt (such as silver Salt, such as silver halide or organic silver salts) or electroless metallising catalyst such as palladium particle.It is particularly useful conduction printing material include Silver and silver salt, gold, copper, palladium, platinum, nickel, iron, tin indium oxide, carbon black and combinations thereof.

In addition, useful conductive printing material can include for any form or composition particle (or any needed for shape), Polymer material or nonpolymer molecules.For example, useful particle or film forming polymer conduction printing material includes but unlimited In polythiophene class, polyaniline compound, multi-metal polypyrrole, polycarbazole class, polybenzazole class, poly- azepineClass (polyazepines), poly- Asia Ethylenedioxy thiophene-based, poly- (3- alkylthrophene) class, poly- (to phenylene vinylidene) class, poly- (to phenylene) class, poly- (benzene second Alkene sulfonic acid) (PSS), poly- (to phenylene sulfoether), polyacetylene, poly- (3,4- Ethylenedioxy Thiophene) (PEDOT) and poly- (styrene Sulfonic acid) and poly- (3,4- Ethylenedioxy Thiophene) mixture (PSS:PEDOT).

In some embodiments, the patterning materials or conductive printing material may include the nano particle of conductive material Or be made from it completely, and therefore its size is measured with nanometer (nm), for example, the size at least one less than 200 nm, And in some embodiments, at least 3 nm to and including 100 nm average diameter.Nano particle can be with the shape of cluster Formula is provided or is used.The shape of nano particle is unrestricted, and including nanosphere, nanometer rods and nanometer cup (nanocup).Example Such as, useful conductive printing material may include carbon, such as carbon black, carbon nanotube, the nanometer of graphene and equivalent carbonaceous material Grain.Gold, silver, palladium, platinum and copper metal nanoparticle and dispersion can also be used for patterning materials.

More particularly, printing material used in the present invention includes particle (such as the nanometer of conductive metal (or its precursor) Particle), such as the particle of any one of silver, gold, copper, palladium, platinum, nickel and iron, or combinations thereof, the metallic particles be dispersed in as In the lower photocurable or heat-setting composition.The precursor of this metalloid, such as the salt of every kind of metal can also be used Or metal-ligand complex.In addition, tin indium oxide can be coupled in patterning materials.

In general, the solid material of patterning materials is prepared by dispersing, being dissolved or suspended in suitable carrier liquid, To form the liquid composition (" ink ") for being applied to substrate as described herein, and especially using as described herein Flexographic plate print-member.Carrier liquid for this purpose may include organic solvent and water, as long as them and patterning materials Solid component is compatible and does not react with it (for inertia).For example, the carrier liquid can be that can will be sufficient for the present invention The solid component of method such as metallic particles is dispersed or suspended in one of solution or more organic solvent.As described below Some embodiments in, the carrier liquid may be the photocurable for patterning materials a part or can be thermally cured combination The reactive component of object.

Patternable materials preparation can should at least soak at least uppermost relief surface of flexographic plate print-member (relief surface), because this is during the method for the present invention for will be patterned into the dry bottom paint that material is applied to substrate The desirable method of layer.The carrier liquid can have some volatility, and can also lead to one in flexographic plate print-member Quantitative swelling, this depends on the type for preparing the composition of flexographic plate print-member.Therefore, use will not destroy (attack) Or negatively affect the stability of elastomer relief surface of flexographic plate print-member and the carrier liquid of size is advantageous 's.Provides the art the abundant introductions about the suitable carrier liquid for specific pattern material.It is representative useful Carrier liquid solvent include but is not limited to alcohols (such as isopropanol, 2-Ethylhexyl Alcohol and α-terpenol), acetate esters (example Such as ethyl acetate), the combination of water, hydro carbons (such as toluene and hexamethylene) and miscible solvent.

In general, being in application to before substrate, patterning materials usually have at least 1 cps and at most and including 1500 Cps or typically at least 100 cps and at most and the viscosity including 1000 cps.If desired, more highly viscous patterning can be used Material.Conventional means and equipment such as Brookfield viscosimeter DV-II+Pro (Brookfield can be used in viscosity Engineering Laboratories) it measures.

Some useful patterning materials include but is not limited to the conduction containing conductive particle such as sheet metal or particle Ink.Electrically conductive ink include it is conductive containing silver ink (such as ink comprising silver nano-grain), containing bronze ink, cupric ink, Plating or electroless other ink are used for containing carbon printing ink, ink containing palladium and containing " crystal seed " material.Some such ink can From such as InkTec (California), Flint Ink Corporation (Michigan), Method Development The source of Company (Chicago) and Novacentrix (Austin, Texas) are commercially-available.One in these " ink " It can be used as carrier liquid, and other ink include both carrier liquid and one or more of conductive components.

In some embodiments, the patterning materials can further include colorant, including but not limited to dyestuff, light Absorbent, pigment, opacifier are learned, and changes the transmission or reflection of patterning materials at any time during the method for the present invention Any material of property.

As described above, the patterning materials can be photo curable or heat-setting." photo curable " refers to It is exposed to polymerizable or crosslinking composition when the radiation of suitable photocuring.For example, photocuring can use, such as at least 150 nm and at most and the λ including 750 nm_maxSuitable radiation, or be more likely to using having at least 150 nm and at most And the λ including 400 nm_maxRadiation when exposing the patterning materials comprising suitable photocurable component.It can be used Suitable such radiation source continues the suitable time and is exposed (photoexposure), with the solidification energy needed for providing.Skill Art personnel will know how optimal conditions to realize required polymerization or crosslinking.

Useful curing process can also by using suitable heat source for example electric hot plate, baking oven, infrared heating (for example, Be exposed to near-infrared or infrared emission laser) or other heating devices will be patterned into material and be heated at least 110 DEG C and at most And including 150 DEG C of temperature, continue time enough to obtain required polymerization or crosslinking, for example, at least 10 minutes and at most simultaneously It was carried out including 30 minutes.Those skilled in the art can easily determine realize desired polymerization or crosslinking by required best plus Hot temperature and time condition.

More particularly, the patterning materials can be Photocurable composition, it includes metallic particles as described above and The composition of the composition of free-radical curable, the composition of theobromine catalytic curing or free-radical curable and can acid catalysis it is solid The mixture of both compositions of change.

The composition of free-radical curable generally comprises one or more of materials, the production when being exposed to suitable radiation Raw free radical, free radical lead to the polymerization or crosslinking of the reactive monomer equally existed, oligomer or polymer again.Needed for various It usually being carried in one or more of solvents (carrier solvent) with optional component, the solvent can be different compound, Or they can also for for free radical be reactive compound (for example, free-radical reactive monomer, such as acrylate, It also functions as carrier solvent).The composition of many such free-radical curables is described in periodical and patent document.

Similarly, theobromine catalytic curing composition is also known in the art, and is generally comprised within and is exposed to conjunction One or more of compounds of acid moieties are generated when suitable radiation, then catalytic design is used for this chemical environment to the acid moieties Suitable compound polymerization or crosslinking.

There are also in other patterning materials, Photocurable composition may include free-radical curable and can acid catalysis it is solid Change the mixture of the chemicals of the two.When using two kinds of curing chemistry process (curing chemistries), institute The crosslinked matrix obtained may make up the interpenetrating polymer networks (IPN) including cross-linked material.This increased crosslink density can be into one Step increases chemical resistance and hardness, and provides excellent performance for the final conductive metal pattern comprising conductive yarn.

(a) photo polymerization epoxy material

The epoxy material (" epoxy resin ") of cationically polymerizable is the organic compound at least one oxirane ring Object, the oxirane ring are shown in following formula:

, can be polymerize by ring open mechanism.Such epoxy material, also referred to as " epoxides ", including The epoxides of monomeric epoxide compound and polymer type and can be aliphatic series, cyclic aliphatic, aromatics or heterocycle.It is average and Speech, these materials usually have at least one polymerizable epoxy groups per molecule, or typically at least about 1.5 and even at least about 2 polymerizable epoxy groups per molecules.Polymer epoxy material includes having epoxy-terminated linear polymer (for example, polyoxy Change the diglycidyl ether of aklylene glycol), with skeleton (skeletal) (main chain (backbone)) ethylene oxide unit Polymer (for example, polybutadiene polyepoxide) and polymer with pendant epoxy are (for example, methyl propenoic acid glycidyl Ester polymer or copolymer).

Polymerizable epoxy material can be single compound or they can be different epoxy materials mixture, contain one A, two or more epoxide groups/molecules." average " quantity of the epoxy group of per molecule passes through in epoxy material The total quantity of epoxy group is determined divided by the total quantity of the existing molecule containing epoxy.

Epoxy material can be from low molecular weight monomers changes in material to heavy polymer, and they main chain and can take The variation in nature of Dai Ji (or side group) is very big.For example, main chain can be any type and substituent group on it can be basic On do not interfere any group of expectation cation photocuring process at room temperature.The illustration of admissible substituent group includes but not It is limited to halogen, ester group, ether, sulfonate group, siloxy group, nitro and phosphate-based.The molecular weight of epoxy material can be at least 58 And at most and including 100,000 or even higher.

Useful epoxy material includes such as the epoxycyclohexane carboxylate those of containing cyclohexene oxide group, such as 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylate, 3,4- epoxy -2- methylcyclohexylmethyl -3,4- epoxy -2- Methylcyclohexanecarboxylic acid ester and bis- (3,4- epoxy -6- methylcyclohexylmethyl) adipate esters.With the useful of this property The more detailed inventory of epoxy material is provided in United States Patent (USP) 3,117,099 (Proops et al.).There are also other useful rings Oxygen material includes glycidyl ether monomers, for by the way that polyphenol is reacted the polynary of acquisition with excessive chlorethanol such as epichlorohydrin The glycidol ether [for example, diglycidyl ether of 2,2- bis--(2,3- epoxypropoxyphenol)-propane] of phenol.

Many commercially available epoxy materials are available, including glycidol ether such as bisphenol-A-diglycidyl ether (DGEBA), glycidol ether, benzene that bisphenol S and the glycidol ether of Bisphenol F, butanediol diglycidyl ether, bisphenol-A extend Phenol-formaldehyde glycidol ether (novolac epoxy resin (epoxy novolac)) and cresol/formaldehyde glycidol ether (cresols Formaldehyde epoxy resin (epoxy cresol novolac)), epoxidation of olefins such as 1,2- octylene oxide, 1,2,13,14- 14 Alkane dicyclic oxide, 1,2,7,8- octane dicyclic oxide, oxidation octadecylene, epichlorohydrin, styrene oxide, vinylcyclohexene Cyclohexene oxide oxide (vinyl cyclohexene oxicyclohexene oxide), glycidol, methacrylic acid Ethylene oxidic ester, bisphenol-A diglycidyl ether (for example, from Momentive with EPON trade mark such as Epon^TM 828, Epon^TM 825, Epon^TM1004 and Epon^TM1010 it is obtainable those, the DER-331 from Dow Chemical Co., DER-332 and DER-334 resin), vinyl cyclohexene dioxide is (for example, the ERL-4206 tree from Polyscience Rouge), 3,4- epoxycyclohexyl-methyl -3,4- epoxy hexane carboxylate is (for example, from Dow Chemical Company's 6105 resin of ERL-4221, UVR 6110 or UVR), 3,4- epoxy -6- methylcyclohexylmethyl -3,4- epoxy -6- methyl-ring Hexene carboxylate (coming from Pfalz and Bauer), bis- (3,4- epoxy -6- methylcyclohexylmethyl) adipate esters, bis- (2,3- rings Oxygen-cyclopenta) ether, with the aliphatic epoxy, Dipentenedioxide, epoxidized polybutadiene of polypropylene glycol modified (for example, coming from 2001 resin of Oxiron of FMC Corp.), the silicone resin containing epoxy-functional, fire-retarded epoxy resin is (for example, DER- 580 resins, brominated bisphenol type of epoxy resin can be obtained by Dow Chemical Co.), phenol formaldehyde (PF) phenolic resin The 1,4-butanediol diglycidyl ether of (phenol formaldehyde novolak) is (for example, come from Dow Chemical Co. DEN-431 and DEN-438 resin), resorcinolformaldehyde resin is (for example, from Dow Corning Corp.'s CYRACURE^TMResin), 2- (3,4- epoxycyclohexyl -5,5- spiral shell -3,4- epoxy) hexamethylene-dioxane, 2- (3,4- ring Oxygen cyclohexyl -5,5- spiral shell -3,4- epoxy) hexamethylene-dioxane, vinylcyclohexene monoxide, 1,2- epoxy 16 Alkane is (for example, the CYRACURE from Dow Corning Corp.^TMResin), alkyl glycidyl ether such as HELOXY^TM Modifier 7 and HELOXY^TMModifier 8 (coming from Momentive), butyl glycidyl ether are (for example, come from The HELOXY of Momentive^TMModifier 61), cresylglycidylether is (for example, the HELOXY from Momentive^TM Modifier 62), to tert-butyl-phenyl glycidol ether (for example, the HELOXY from Momentive^TM Modifier 65)、 The diglycidyl ether of polyfunctional glycidyl ether's such as 1,4-butanediol is (for example, the HELOXY from Momentive^TM Modifier 67), the diglycidyl ether of neopentyl glycol is (for example, the HELOXY from Momentive^TM Modifier 68)、 The diglycidyl ether of cyclohexanedimethanol is (for example, the HELOXY from Momentive^TMModifier 107), trihydroxy methyl Ethane triglycidyl ether is (for example, the HELOXY from Momentive^TMModifier 44), trimethylolpropane tris shrink Glycerin ether is (for example, the HELOXY from Momentive^TMModifier 48), the polyglycidyl ether (example of aliphatic polyol Such as, from the HELOXY of Momentive^TMModifier 84), polyglycol diepoxide (for example, come from Momentive HELOXY^TMModifier 32), Bisphenol F epoxy is (for example, from Huntman Advanced Materials's EPN-1138 or GY-281 resin) and 9,9- is bis- > and 4- (2,3- glycidoxy)-phenylfluorone is (for example, come from Momentive Epon^TM1079 resins).

It is resin there are also other useful epoxy materials, such as derived from the acrylate reacted with glycidol such as third Olefin(e) acid ethylene oxidic ester and glycidyl methacrylate are copolymerized with one or more of ethylenic bond unsaturated polymerizable monomers Copolymer.Other useful epoxy materials are epichlorohydrin class such as epichlorohydrin, alkylene oxide such as propylene oxide and Oxybenzene second Alkene, alkylene oxides (alkenyl oxide) such as oxygenated butadiene and ethylene oxidic ester such as glycidol acetoacetic ester.Also Having other useful epoxy materials is the silicone with epoxy-functional or group such as cyclohexyl ring oxygen groups, is especially had Those of silicone backbone epoxy material.The commercial embodiments of such epoxy material include UV 9300, the UV available from Momentive 9315, UV 9400,9425 silicone material of UV.

Polymer epoxy material optionally contains the cation for not interfering photopolymerization composite substantially at room temperature Other functional groups of photocuring.For example, the photo polymerization epoxy material may also include the functional group of free redical polymerization.

The photo polymerization epoxy material may include the blend or mixture of two or more different epoxy materials.This The example of class blend includes the photo polymerization epoxy material with two or more molecular weight distributions, such as one or more of Kind low molecular weight (200 or less) epoxy material and one or more of intermediate molecular weight (200 to 10,000) photo polymerization epoxies The blend of material, or one or more of such photo polymerization epoxy material and one or more of higher molecular weights (about 10, 000 or more) blend of epoxy material.

If desired for specifying effectiveness, the photo polymerization epoxy material can be used for providing adhesive function.In addition, thus Purpose, if desired, may include non-photocurable polymer or resin.Alternatively, following photocurable acrylate can be used for mentioning For adhesive function.

Can suitably measure one or more of photo polymerization epoxy materials includes in photopolymerization composite, to mention For required effective photocuring or photopolymerization.For example, based on all four (a) to (d) component in Photocurable composition Total weight, one or more of photo polymerization epoxy materials are at least 10 weight % and at most and including the presence of the amount of 95 weight %.

(b) photo-acid agent

Various compounds can be used to generate suitable acid to participate in the photocuring of photopolymerization composite described herein. Some in these " photo-acid agents " are acid and others are nonionics.In view of introduction provided herein, in addition to Other than those of following, other useful photo-acid agents will be readily apparent to those skilled in the art.It can Various compounds as photo-acid agent are purchased from various commercial sources or are made using known synthetic method and starting material It is standby.

(i) salt

The raw sour agent of salt includes but is not limited to diazonium salt, microcosmic salt, salt compounded of iodine or sulfonium salt, including polyaryl diazonium salt, Microcosmic salt, salt compounded of iodine and sulfonium salt.Salt compounded of iodine or sulfonium salt include but is not limited to diaryl iodonium salt and triarylsulfonium salt.Useful Counter anion includes but is not limited to halide metal compound, for example, tetrafluoroborate, hexafluoro antimonate, fluoroform sulphonate, Hexafluoro arsenate, hexafluorophosphate and arene sulfonate.Salt can also for multiple salt parts oligomer compounds or Polymer compound and molecule with single salt part.

The example of useful aromatic iodonium salts includes but is not limited to diphenyl iodine tetrafluoroborate；Two (4- methylbenzenes Base) iodine tetrafluoroborate；Phenyl -4- aminomethyl phenyl iodine tetrafluoroborate；Two (4- heptyl phenyl) iodine tetrafluoroborates； Two (3- nitrobenzophenone) iodine hexafluorophosphates；Two (4- chlorphenyl) iodine hexafluorophosphates；Two (naphthalene) iodine tetrafluoro boric acids Salt；Two (4- trifluoromethyl) iodine tetrafluoroborates；Diphenyl iodine hexafluorophosphate；Two (4- aminomethyl phenyl) iodine six Fluorophosphate；Diphenyl iodine hexafluoro arsenate；Two (4- Phenoxyphenyl) iodine tetrafluoroborates；Phenyl -2- thienyl iodine Hexafluorophosphate；3,5- dimethyl pyrazole oxazolyl -4- phenyl-iodide hexafluorophosphate；Diphenyl iodine hexafluoro antimonate；2,2'- Diphenyl iodine tetrafluoroborate；Two (2,4- dichlorophenyl) iodine hexafluorophosphates, two (4- bromophenyl) iodine hexafluorophosphoric acids Salt；Two (4- methoxyphenyl) iodine hexafluorophosphates；Two (3- carboxy phenyl) iodine hexafluorophosphates；Two (3- methoxycarbonyls Phenyl) iodine hexafluorophosphate；Two (3- methoxysulfonyl phenyl) iodine hexafluorophosphates；Two (4- acetylamino phenyl) iodine Hexafluorophosphate；Two (2- benzothienyl) iodine hexafluorophosphates；With diphenyl iodine hexafluoro antimonate；And its mixing Object.Such compound can be according to Beringer et al., J. Am. Chem. Soc. The introduction of 81,342 (1959) passes through phase It is prepared by the double decompositions of the aromatic iodonium simple salts (such as, such as diphenyliodonium bisulfate) answered.

Useful salt compounded of iodine can for simple salt (for example, containing anion for example chloride ion, bromide ion, iodide ion or C₄H₅SO₃ ^-) or metal double salt (for example, containing SbF₆ ^-、PF₆ ^-、BF₄ ^-, four (perfluorophenyl) borates or SbF₅OH₃₁ AsF₆ ^-)。 If desired, any kind of mixture in these salt compounded of iodine of identical or different classification can be used.

Useful sulfonium salt includes but is not limited to the triaryl matte hexafluoro antimonate (example for the salt such as mixing that triaryl replaces Such as, commercially available as the UVI-6974 from Dow Chemical Company), mixing triaryl matte hexafluorophosphate (for example, commercially available as the UVI-6990 from Dow Chemical Company) and aryl sulfonium hexafluorophosphate (example Such as, as the SarCa from Sartomer Company^TMKI85 is commercially available).

Based on the total weight of all four (a) to (d) component, one or more of salt (such as salt compounded of iodine or sulfonium salt) are logical Often at least 0.05 weight % and at most and including 10 weight %, or typically at least 0.1 weight % and at most and including 10 weight %'s Amount is present in the photopolymerization composite.

(ii) Nonionic photo-acid agent

In addition to the above-described salts, nonionic photo-acid agent is also useful.Such compound includes but is not limited to weight N-formyl sarcolysine alkane derivatives such as, such as bis- (benzenesulfonyl)-diazomethanes, bis- (p-toluenesulfonyl) diazomethanes, bis- (dimethylbenzene Sulfonyl)-diazomethane, bis- (cyclohexylsulfonyl)-diazomethanes, bis- (Cyclopentylsulfonyl) diazomethanes, bis- (normal-butyls Sulfonyl) diazomethane, bis- (iso-butylsulfonyl)-diazomethanes, bis- (sec-butylsulfonyl) diazomethanes, bis- (n-propyls Sulfonyl) diazomethane, bis- (isopropelsulfonyl)-diazomethanes, bis- (tert. butylsulfonyl) diazomethanes, bis- (n-pentyls Sulfonyl) diazomethane, bis- (isopentyl sulfonyl)-diazomethanes, bis- (sec-amyl sulfonyl) diazomethanes, bis- (tertiary pentyls Sulfonyl) diazomethane, 1- cyclohexylsulfonyl -1- (tert. butylsulfonyl) diazomethane, 1- cyclohexylsulfonyl -1- (uncle Pentylsulfonyl) diazomethane and 1- tertiary pentyl sulfonyl -1- (tert. butylsulfonyl) diazomethane.

Nonionic photo-acid agent may also include glyoxime derivative such as, such as double-o- (p-toluenesulfonyl)-α-two Dimethylglyoxime (bis-o-(p- toluenesulfonyl)-α-dimethylglyoxime), double-o- (tolysulfonyl Base)-α-diphenyl glyoxime, double-o- (p-toluenesulfonyl)-α-dicyclohexyl glyoximes, double-o- (tolysulfonyl Base) -2,3- pentanedione-glyoxime, the amyl- diketone glyoxime of double-o- (p-toluenesulfonyl) -2- methyl -3,4-, it is double-o- (just Fourth sulfonyl)-alpha-alpha-dimethyl glyoxime, double-o- (positive fourth sulfonyl)-α-diphenyl glyoximes, double-o- (positive fourth sulphonyl Base)-α-dicyclohexyl glyoxime, double-o- (positive fourth sulfonyl) -2,3- pentanedione glyoximes, double-o- (positive fourth sulfonyls) - 2- methyl -3,4- pentanedione glyoxime, double-o- (mesyl)-alpha-alpha-dimethyl glyoximes, double-o- (trifyls) - Alpha-alpha-dimethyl glyoxime, double-o- (1,1,1- trifluoro ethylsulfonyl)-alpha-alpha-dimethyl glyoximes, double-o- (tertiary fourth sulfonyls)- Alpha-alpha-dimethyl glyoxime, double-o- (the pungent sulfonyl of perfluor)-alpha-alpha-dimethyl glyoximes, double-o- (hexamethylene sulfonyl)-alpha, alpha-dimethyls Base glyoxime, double-o- (benzenesulfonyl)-alpha-alpha-dimethyl glyoximes, double-o- (to fluorophenylsulphonyl)-alpha-alpha-dimethyl glyoximes, Double-o- (to tert-butyl benzene sulfonyl)-alpha-alpha-dimethyl glyoximes, double-o- (ditosyl)-alpha-alpha-dimethyl glyoximes, Or double-o- (camphor sulfonyl)-alpha-alpha-dimethyl glyoximes.

Such photo-acid agent further comprise bis sulfone derivative such as, such as double Naphthylsulfonyl methane, bis trifluoromethyl Sulfonyl methane, double methyl sulfonyl methanes, double ethylsulfonyl methane, double sulfonyl propyl methylmethanes, double isopropyl-sulfonyls Methane, double-tolysulfonyl methylmethane, double benzenesulfonyl methane, 2- cyclohexyl-carbonyl -2- (p-toluenesulfonyl) propane (β - Ketone sulfone derivative) and 2- isopropyl-carbonyl -2- (p-toluenesulfonyl) propane (β -one sulfone derivative).

The useful nonionic photo-acid agent of other classifications include two sulfones (disulfono) derivative such as, such as hexichol Two sulfone of two sulfone of base and dicyclohexyl；Sulfonic acid p-Nitrobenzyl derivative such as, such as p-methyl benzenesulfonic acid 2,6- dinitro benzyl ester and right Toluenesulfonic acid 2,4- dinitro benzyl ester；Sulfonate derivatives such as, such as 1,2,3- tri- (mesyl-oxygroup) benzene, 1,2,3- Three (three fluoro- mesyl oxygroups) benzene and 1,2,3- tri- (p-toluenesulfonyl oxygroup) benzene；With the sulphonic acid ester of N- hydroxy imide Such as, such as n-hydroxysuccinimide methanesulfonates, N- hydroxy-succinimide triflate, N- hydroxysuccinimidyl acyl Imines esilate, n-hydroxysuccinimide 1- propane sulfonic acid ester, n-hydroxysuccinimide 2- propane sulfonic acid ester, N- hydroxysuccinimidyl Penta sulphonic acid ester of acid imide 1-, the pungent sulphonic acid ester of n-hydroxysuccinimide 1-, n-hydroxysuccinimide p-methyl benzenesulfonic acid ester, N- hydroxyl Base succinimide is to methoxy benzenesulfonic acid ester, n-hydroxysuccinimide 2- chloroethene sulphonic acid ester, n-hydroxysuccinimide benzene Sulphonic acid ester, the fluoro- benzene sulfonate of n-hydroxysuccinimide 2,4,6- tri-, n-hydroxysuccinimide 2,4,6- trimethyl-benzene sulphur Acid esters, the chloro- benzene sulfonate of n-hydroxysuccinimide 2,4,6- tri-, n-hydroxysuccinimide 4- cyano-benzene sulfonate, N- hydroxyl Base succinimide 1-naphthalene sulfonic aicd ester, n-hydroxysuccinimide 2- napsylate, N- hydroxyl -2- phenyl succinimide methylsulphur Acid esters, N- hydroxy maleimide methanesulfonates, N- hydroxy maleimide esilate, N- hydroxyl -2- benzyl maleimide Amine methanesulfonates, N- glutarimide methanesulfonates, N- glutarimide benzene sulfonate, N- hydroxyl phthalyl Imines methanesulfonates, n-Hydroxyphthalimide benzene sulfonate, n-Hydroxyphthalimide triflate, N- Hydroxyphthalimide p-methyl benzenesulfonic acid ester, N- hydroxyl naphthalimide methanesulfonates, N- hydroxyl naphthalimide Benzene sulfonate, N- hydroxyl -5- norbornene -2,3- dicarboximide methanesulfonates, N- hydroxyl -5- norbornene -2,3- diformazan Acid imide triflate, N- hydroxyl -5- norbornene -2,3- dicarboximide p-methyl benzenesulfonic acid ester, N- hydroxyl naphthalene diformazan Acid imide triflate and N- hydroxyl -5- norbornene -2,3- dicarboximide perfluor -1- fourth sulphonic acid ester.

Based on the total weight of all four (a) to (d) component, one or more of nonionic photo-acid agents can be at least 0.05 weight % and at most and including 10 weight %, or typically at least 0.1 weight % and at most and the amount including 10 weight % is present in In the photopolymerization composite.

(c) electron donor photosensitizer

Useful electron donor photosensitizer should dissolve in photo curable composition, without will substantially interfere cation The functional group of Light Curing, and light can be carried out at least 150 nm and at most and in the wave-length coverage including 1000 nm It absorbs (sensitivity).

Suitable electron donor photosensitizer response causes salt (or other photo-acid agents) by the photon of irradiation absorption Chemical transformation.Electron donor photosensitizer should also be able to after electron donor photosensitizer has absorbed light reduce photo-acid agent (that is, Photo-induced electron transfer).Therefore, electron donor photosensitizer, usually can be to photogenerated acid after absorbing the photon from irradiation Agent is for electron.

For wherein needing quickly to solidify very much photo curable group of (such as solidification of the thin application film of composition) The use of object is closed, the electron donor photosensitizer under required illumination wavelength using Light Curing there can be at least 1000 L- mol^-1 cm^-1And typically at least 50,000 L-mol^-1 cm^-1Extinction coefficient.

For example, each electron donor photosensitizer usually has at least 0.4 V and at most and including 3 V vs. SCE (saturation is sweet Mercury electrode), or more generally at least 0.8 V and at most and the oxidizing potential including 2 V vs. SCE.

Generally, many different classes of compounds can be used as the electron donor photosensitizer of various reactants.Useful electricity Sub- donor photosensitizer includes but is not limited to aromatic compounds such as naphthalene, 1- methyl naphthalene, anthracene, 9,10- dimethoxy anthracene, benzo [a] Anthracene, pyrene, phenanthrene, benzo [c] phenanthrene and fluoranthene.

The other useful electron donor photosensitizers for being related to triplet excited state are carbonyls such as thioxanthones and xanthene Ketone.Ketone and coumarine dye such as coumarin ketone including aromatic ketone such as Fluorenone for example with strong power supply subdivision (such as Dialkyl amido) those of also be used as electron donor photosensitizer.Other suitable electron donor photosensitizers are it is believed that include xanthene Dyestuff, acridine dye, thiazole dye, thiazine dye, oxazine dye, azine dye, aminoketone dye, porphyrin, aromatics are polycyclic Hydrocarbon, the aminostyryl ketone compounds of contraposition substitution, aminotriaryl methanes, part cyanines, sour cyanines (squarylium) dyestuff in side And pyridine dye.

It is also possible to the mixture using the electron donor photosensitizer selected from identical or different classification material.

Various useful electron donor photosensitizers are available from various commercial sources and can easily be found to be used for this hair It is bright.

Based on the total weight of component (a) to (d), the one or more electron donor photosensitizer can be at least 0.0001 Weight % and at most and including 5 weight %, and typically at least 0.001 weight % and at most and the amount including 2 weight % be present in can light In cured composition.In some embodiments, the electron donor photosensitizer is pyrene, BaP or benzo, Total weight based on component (a), (b) and (d), at least 0.05 weight % and at most and including the presence of the amount of 2 weight %.

(d) metallic particles

Metallic particles is present in photo curable composition.A type of metallic particles is usually used only, but It may include the mixture of the metallic particles of the metal from the identical or different classification not interfered with one another.These metallic particles are logical Often with there is net neutral charge.

Useful metallic particles can be selected from the noble metals of one or more of classifications, semi-precious metal, Group IV metal or its Combination.Useful noble metal granule includes but is not limited to, gold, silver, palladium, platinum, rhodium, iridium, rhenium, mercury, ruthenium and osmium particle.Useful The particle of semi-precious metal includes but is not limited to, iron, cobalt, nickel, copper, carbon, aluminium, zinc and tungsten particle.Useful Group IV metal Particle includes but is not limited to the particle of tin, titanium and germanium.The noble metal granule such as particle of gold, silver, palladium and platinum be it is particularly useful, And the particle of semi-precious metal nickel and copper is also particularly useful.In Group IV metal classification, tin particles are particularly useful. In many embodiments, silver-colored or copper particle is used for photo curable composition as " crystal seed " metallic particles of electroless process In.

Metallic particles for use in the present invention can be coated with surfactant, polymer or carbon.For coated metal powder Carbon can be amorphous, sp2 hydridization or class graphene property.Such carbon can be used for preventing the aggregation of metallic particles and provide can Improved dispersibility in the composition of photocuring.

Metallic particles is dispersed in various organic solvents and in other necessary component (examples of photo curable composition Such as multifunctional polymer epoxy material) in the presence of or optional component (example polyfunctional acrylic ester resin described as follows) In the presence of can have improved dispersibility.Method for dispersed metal particle includes but is not limited to ball milling, magnetic agitation, height Speed homogenizes, high pressure homogenizing and ultrasonication.

Metallic particles can be used as individual particle and be present in photopolymerization composite, but in many embodiments, Metallic particles exists as the agglomerate of two or more metallic particles.Such metallic particles can be deposited with any geometry In including but not limited to spherical, rodlike, prismatic, cube, taper, pyramid, threadiness, flake (flake), small pieces Shape (platelet) and combinations thereof, and they can be uniform or heterogeneous in shape and size.Individual metallic particles Average grain diameter with the metallic particles of agglomeration can be at least 0.01 μm and at most and including 25 μm, or is more likely at least 0.02 μ M and at most and including in the range of 5 μm.Although being not particularly limited the size of metallic particles, using have at least 0.02 μm and Best benefit can be realized as the metallic particles of individual particle or agglomerate at most and including 10 μm of average grain diameter.Phase Hope particle diameter distribution it is narrow to as defined below that: be wherein greater than 50%, or typically at least 75% particle in average grain diameter 0.2 to 2 times within the scope of partial size.Average grain diameter (average particle size) is (with average grain diameter (mean Particle size) identical) can be determined by particle diameter distribution, any suitable step and equipment can be used in the particle diameter distribution It is determined including the equipment available from Coulter or Horiba and the mathematical computations appropriate being used together with that equipment.

Useful metallic particles available from various commercial sources or they can derived from various metal salts or compound and For the known reduction and separation process before practice of the invention.Some commercial metals particles are available from for example Novacentrix。

Based on the total weight of component (a) to (d), the metallic particles is usually at least 0.1 weight % and at most and including 50 Weight % or more generally at least 1 weight % and at most and the amount including 30 weight % is present in photo curable composition.

(e) compound of free redical polymerization

Compound of the photo curable composition also containing one or more of free redical polymerizations can to provide The functional group of free radical polymerization, including the unsaturated polymerisable monomer of ethylenic bond, oligomer or polymer, for example, simple function or Polyfunctional acrylic ester (also including methacrylate).The compound of such free redical polymerization includes at least one ethylenic bond Unsaturated polymerizable key, and they may include these two or more unsaturated parts, can undergo addition (or from By base) polymerization.The material of such free redical polymerization includes mono-, two- or poly- acrylate and methacrylate, including but It is not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, the just own ester of acrylic acid、Third Olefin(e) acid stearyl ester, allyl acrylate, glycerol diacrylate, three glycerol acrylates, ethylene glycol diacrylate, two propylene Sour diethylene glycol (DEG) ester, dimethacrylate triethyleneglycol ester, diacrylate 1,3- propylene glycol ester, dimethacrylate 1,3- propylene glycol Ester, diacrylate 1,4- butanediol ester, diacrylate 1,6-HD ester, diacrylic acid pentyl diol ester, dimethacrylate Neopentyl glycol ester, trimethylolpropane trimethacrylate, trimethacrylate acid 1,2,4- butantriol ester, diacrylate 1,4- hexamethylene Diol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, pentaerythritol tetramethacrylate, six acrylic acid Dipentaerythritol ester, six acrylic acid sorbitol esters, bis- [1- (2- acryloxies)]-are to ethoxyl phenenyl dimethylmethane、 Bis- [1- (3- acryloxy -2- hydroxyls)]-are to propoxyphenyl dimethylmethane and three-ethoxys-chlorinated isocyanurates front three Base acrylate；With 200 to and including 500 molecular weight polyethylene glycol double methacrylate and double methyl methacrylate, Such as it the acrylate monomer that those of is described in United States Patent (USP) 4,652,274 (Boettcher et al.) and is for example described in The copolymerizable mixture of acrylate oligomer those of in United States Patent (USP) 4,642,126 (Zader et al.)；And ethylene Based compound such as styrene and styrene derivative, diallyl phthalate, divinyl succinate ester, adipic acid diethyl Enester and phthalic acid diethyl enester.If desired, two or more in the material of these free redical polymerizations can be used Mixture.

Such material is purchased from numerous commercial sources or is prepared using known synthetic method and starting material.

Although the amount of the material of the one or more free redical polymerization is not particularly limited, they can be based on can At least 20 weight % of all components total weight of the composition of photocuring and at most and including 75 weight % or typically at least 40 weights % and at most and the amount including 60 weight % is present in photopolymerization composite is measured, and can be based on the combination of Photocurable composition The required property of object solubility and mechanical strength optimizes.

(f) free radical photo-initiation

(e) component if it exists, then one or more of free radical photo-initiations exist in photo curable composition To generate free radical in the presence of the compound of free redical polymerization.Such free radical photo-initiation, which is included in be exposed to, to be used for Any compound that can be generated free radicals after the photopolymerization radiation (such as ultraviolet or visible radiation) that the present invention practices.Example Such as, free radical photo-initiation can be selected from triaizine compounds, thioxanthones (thioxantone) compound, benzoin compound, carbazole Compound, dione compounds, sulfonium borate compound, diazonium compound and united imidazole and those skilled in the art It is other by what is be readily apparent.The mixture of such compound can be selected from identical or different classification.

Equally usefully benzophenone cpd such as benzophenone, benzoylbenzoic acid ester, benzoylbenzoic acid first Ester, 4- phenyl benzophenone, dihydroxy benaophenonel, propylene are acidified (acrylated) benzophenone, the bis- (dimethylaminos of 4,4'- Base) benzophenone and bis- (diethylamino) benzophenone of 4,4'-, anthraquinone compounds and acetophenone compound such as 2,2'- bis- Acetophenone, 2,2'- dibutoxy acetophenone, 2- hydroxy-2-methyl propiophenone, to tert-butyl trichloroacetophenone, to uncle Butyl dichloroacetophenone, benzophenone, 4- chloro-acetophenone, 4,4'- dimethylamino benzophenone, 4,4'- dichloro benzophenone, 3,3'- dimethyl-2- methoxy benzophenone, the chloro- 4- metaphenoxy acetophenone of 2,2'- bis-, 2- methyl-1-(4- (methyl mercapto) benzene Base) -2- morpholinyl propyl- 1- ketone and 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl)-butyl- 1- ketone.The type its Its useful compound is described in such as United States Patent (USP) 7,875,416 (Park et al.).

Many kinds in such free radical photo-initiation are available from various commercial sources.

Such free radical photo-initiation is usually at least 0.1 of all components total weight based on photo curable composition Weight % and at most and including 10 weight %, or typically at least 1 weight % and at most and the amount including 5 weight % is present in photocurable Composition in.

It is also possible that electrical-conductive nanometer oxide and electrical-conductive nanometer carbon material such as nanotube, nano-graphene and bucky-ball (bucky ball).Electrical-conductive nanometer oxide includes but is not limited to tin indium oxide, antimony oxide, antimony tin, indium oxide, oxidation Zinc, zinc oxide aluminum and its mixture.

It include the material (including polyalcohol) of one or more of hydroxyls in photo curable composition as charge Transfer agent may be useful to assist photo-polymerization process.Term " polyol " refer in the molecule have two or more primary Or the organic compound of secondary aliphatic hydroxide radical.Each hydroxyl (hydroxy) (or hydroxyl (hydroxyl)) in the material of hydroxyl Directly it is connect with the non-aromatic carbon atom in molecule.In use, the material of the hydroxyl can be liquid or solid form and have There is organic nature.Any hydroxyl can be located at homopolymer or copolymer chain end or pendency on it.

Vinyl ether compound is added in photo curable composition as chain-transferring agent can also desirably further Increase photopolymerization rate or ensures the required physical property in the cured patterning materials of final light.Useful vinyl ethers chemical combination The example of object includes but is not limited to Rapi-Cure^TMDVE-3 (triethylene glycol divinyl ether), Rapi-Cure^TM CHVE (1, 4- cyclohexanedimethanol divinyl base ether) and Rapi-Cure^TMHBVE (butanediol mono vinyl ether), it is all available from Ashland Inc.)。

Photo curable composition can also contain suitable adjuvant (or additive), such as accelerator, inhibitor, absorption Agent, stabilizer, pigment, dyestuff, UV absorbent, viscosity modifier, flow improver (flow improver), surface tension Inhibitor and wetting aid, antioxidant, surfactant and other ingredients well known to the skilled person.

Usually under the conditions of " safety light ", have in the suitable inertia not with any component significant reaction being incorporated in In solvent, photo curable composition is prepared by being simply mixed as patterning materials for being coated with, printing or other Applying means is to substrate of the invention.The example of suitable atent solvent includes but is not limited to, acetone, methylene chloride, isopropanol, Dowanol PM, 1- methoxy-2-propanol, ethylene glycol and its mixture.When one or more of groups to be used are divided into liquid When form, those components may act as " solvent " of photo curable composition, or with one or more of inert organic solvents groups It closes and uses.Not solvent-laden photo curable composition can by simply dissolving, dispersion and mix necessary component (a) to (d) and Any optional components are prepared with or without the use of mild heating with promoting to dissolve or disperse.

When using inert organic solvents, they can be based on at least 1 weight % of above-mentioned component (a) to (d) total weight And at most and including 70 weight % or at least 20 weight % and at most and including the presence of the amount of 50 weight %.

Under the conditions of suitable photocuring or heat cure, said products may include patterning materials, and it includes conductive metals With photocuring or heat-curing composition, all to be arranged according to patterned fashion on the dry bottom paint layer of substrate.Patternable materials At least part of pattern includes the line with the average line width less than 15 μm.Therefore such patterning materials may include dispersion Gold, silver, copper, palladium in photocuring or heat-curing composition derived from corresponding photocurable or heat-setting composition Or the particle of platinum.

Method for manufacturing the pattern including conductive pattern

First method is used to provide the product primed with patterning materials, including providing includes transparent polymer The substrate of supporter (as described above) and dry bottom paint layer (as described above), and then by patternable materials (such as It is upper described) pattern be directly provided on dry bottom paint layer.As described above, can be printed by dry bottom paint layer and relief printing plate as described herein To provide the pattern, which will be patterned into material fortune for the direct contact of brush member (such as flexographic plate print-member) It is downloaded on the upper surface of relief image, which is usually formed with elastomeric material.Intaglio printing (gravure printing and Intaglio printing) it is other means for being applied to the pattern of patternable materials on dry bottom paint layer.

Furthermore, it is also desirable to which at least part of the pattern of as provided patterning materials includes to have less than 15 μm The line of average line width, and such part of patterning materials will be present in finally by be the product primed touch screen areas The place in domain (opposite with electrode zone or the region BUS).This patterning materials may include conductive metal as described above or lead Electric metal precursor, and the patterning materials may include photocurable or heat-setting composition, wherein one of both packet Containing conductive metal or conductive metal precursor.

It should also understand in the description of specific manufacture embodiment especially from the description below, it can be by identical or different pattern Change the opposite support-side that material is applied to substrate, if especially the substrate includes dry bottom paint in two support-sides of supporter Layer.Such prime can be considered as " duplex (duplex) " with patterned product because they supporter (including Transparent polymeric support) two sides on all have dry bottom paint layer and pattern material.

In the especially desirable embodiment that wherein patterning materials include photocurable or heat curable composition, so Patterning materials are made to be subjected to condition of cure and device on the one or both sides of substrate afterwards.

For example, can be by realizing that light is solid with the radiation energy irradiation patterns material of ultraviolet light such as described above Change.Desirable photocuring can be used at least 184.5 nm to and including 700 nm wavelength and at least 1 mJ/cm²And at most And including 1000 mJ/cm²Or more generally at least 1 mJ/cm²And at most and including 800 mJ/cm²Intensity UV irradiation or can Irradiation is seen to realize.

At least part of the gained cured pattern of patterning materials (for example, precursor conductive material) may include in the part In the curing materials with average line width less than 15 μm filament.In many embodiments, solidification is entire in this way Pattern.

It can be completely converted by least part of the cured pattern of precursor conductive material and usually comprising as described above Conductive yarn conductive material pattern." precursor conductive material " refer to can through chemistry, physically or electrically processing so that the material Expect conductive composition.Some embodiments of such " precursor " material are the combinations comprising " crystal seed " metal described below Object.

When the patterning materials in such embodiment include conductive metal or conductive metal precursor, for example, wherein institute Stating conductive metal includes seed metal particle, and ability can be used in the seed metal particle in the pattern of the patterning materials in substrate Condition known to domain and electroless plating reagent carry out electroless metal plating, and some of details are described below.It can generate in this way Multiple patterns containing seed metal particle, especially when the substrate containing dry bottom paint layer is following illustrates and such as When continuous coiled material shown in FIG. 1.

In such embodiment, multiple independent patterns of photocurable or heat-setting composition are provided in company On the substrate of continuous web form, the photocurable or heat-setting composition are containing seed metal particle Precursor conductive material is applied directly on the dry bottom paint layer in multiple unitary parts of the continuous coiled material.Such continuous volume Material can have at least 88% or at least 95% synthesis transmissivity, and being included in can be transparent polyester supporter (as described above) Transparent polymeric support on dry bottom paint layer (as described above).

In this way, multiple precursor articles as described herein can be prepared, for using immediately after manufacture or later Time use.For example, multiple precursor articles can provide in roll form, and then to contain first, second and optionally Other multiple cured patterns the continuous coiled material of the substrate primed of the invention rolled of roll form on formed.Institute as above Each of multiple independent patterns of the photocurable or heat-setting composition in cured pattern material are stated, even Multiple individual cured patterns are formed in multiple unitary parts on continuous coiled material, which contains seed metal Grain.

It then can be after hardening immediately or after a period of time and optionally in different positions, using identical or different Electroless plating bath and condition carry out the electroless plating of such multiple individual cured patterns as described below.

Products obtained therefrom (product article) contains one or more conductive patterns on the one or both sides of substrate Case, the conductive pattern may include the filament with the average line width less than 15 μm, and can be placed in conductive articles or show and set In standby touch area.The particularly useful equipment of the type includes the electrically conducting transparent of the synthesis transmissivity at least 88% Film, and the dry bottom paint layer (as described above) of substrate is directly arranged on transparent polymeric support such as polyester support.

Consider now about the product primed is manufactured and used on a large scale with provide conductive articles and equipment it is more carefully Section.

The product primed of the invention can be used alone as discrete component, or as continuous coiled material (for example, for roll-to-roll Method), there is the pattern for the multiple portions being directly arranged in dry bottom paint layer (in one or two support-side of substrate) Change the pattern of material.This continuous coiled material may be machined to apply patterning materials in coating station (coating station), It stands with then exposure (solidification) is advanced through, or exposure (solidification) equipment can be in multiple patterns of the patterning materials of continuous coiled material Top passes through.Identical or different photo curable composition can be used for (for example, printing) in two support-sides of substrate In patterning materials, no matter the substrate is single element form or continuous coiled material form.It in many embodiments, will be different Conductive metal pattern be formed in the opposite support-side of substrate (or continuous coiled material).

As described above, can be used any suitable applying means to apply patterning materials according to patterned fashion, but use The flexible version printing of flexographic plate print-member is particularly useful.

It, can be by that can not adversely influence remaining ingredient or cause too early after it will be patterned into material and be applied in substrate The drying of polymerization or pre-bake step remove any inert organic solvents.Useful drying condition can down to room temperature it is low continue down to 5 seconds and at most and including several hours, this depended on manufacturing method.In most methods, for example, it is described below roll-to-roll In method, drying condition can remove at least 90% inert organic solvents at least 1 second at sufficiently high temperature.

The pattern of any application of patterning materials may include that (or other shapes include round or irregular net to grid lines Network), there is at least 0.2 μm and at most and including 20 μm, or typically at least 2 μm and at most and including 15 μm of average thickness (or width), and can adjust best dry thickness (or width) with the desired use for the uniform photocurable layers of gained, the net Ruling usually has the dry thickness about the same with the grid lines of the patterning materials of non-photocuring (or width).

Therefore, the present invention provides the product of the pattern comprising substrate and patterning materials, wherein it is believed that this based article is " precursor " product, it means that they are with the first product of the method production for providing conductive articles.

It in some embodiments, can be in an appropriate manner by identical or different photocurable or heat-setting combination Object is applied in two support-sides of substrate, to form each curable pattern on " duplex " or two-sided precursor article Various features, and multiple cured patterns can have identical or different seed metal particle, be gold particle, Argent grain, Copper particle, palladium particle or platinum grain.

In many embodiments, the pattern of photocurable or heat-setting composition is applied using letterpress component It adds in one or two (opposite) support-side of substrate (such as roll-to-roll continuous coiled material), the letterpress component example The elastomer print-member such as obtained by flexographic printing plates precursor, many is known in the art, and some is city Sell it is available, such as the Cyrel from DuPont^®Flexographic plate photopolymer plate (Flexographic Photopolymer Plates) and Flexcel SR and NX flexographic printing plates from Eastman Kodak Company (Flexographic plates)。

Particularly useful letterpress component is obtained from flexographic printing plates precursor and flexographic printing elements precursor, respectively It can suitably be imaged and (and if desired, develop) to provide for " printing " or apply the relief image of suitable pattern.

For example, useful flexographic plate print-member precursor is described in United States Patent (USP) 7,799,504 (Zwadlo et al.) and 8, In 142,987 (Ali et al.) and U.S. Patent Application Publication 2012/0237871 (Zwadlo).Relief image layer can not Together, the different pattern of patterning materials is provided for based identical or opposite support-side.In other embodiments, elastic The elastomer relief printing plate element precursor that body relief printing plate element can be carved by direct (or ablation) laser with or without the use of complete mask It provides, is such as example described in United States Patent (USP) 5,719,009 (Fan), 5,798,202 (Cushner et al.), 5,804,353 (Cushner et al.), 6,090,529 (Gelbart), 6,159,659 (Gelbart), 6,511,784 (Hiller et al.), 7,811,744 (Figov), 7,947,426 (Figov et al.), 8,114,572 (Landry-Coltrain et al.), 8, 153,347 (Veres et al.), 8,187,793 (Regan et al.) and U.S. Patent Application Publication 2002/0136969 (Hiller et al.), 2003/0129530 (Leinenback et al.), 2003/0136285 (Telser et al.), 2003/ In 0180636 (Kanga et al.) and 2012/0240802 (Landry-Coltrain et al.).

When the elastomer relief printing plate element is used in the present invention, material can be will be patterned into an appropriate manner and be applied to Uppermost relief surface (convex surfaces) in letterpress component.Several suitable means can be used to complete to apply, And it is desirably coated on as few as possible on side (slope) or the recess of relief printing plate recess (relief depression). Therefore, it is also desirable to which patterning materials as much as possible are only applied to uppermost relief surface.Anilox roller can be used (63.5 hundred million cubes micro- per square inch for (Anilox roller) system or other roller application systems, especially 2,500,000,000 cu μ ms Rice is every square centimeter) low volume anilox roller below and relevant slicer (skive knives).It can be viscous by controlling Degree or thickness, or applying means appropriate is selected to realize the best metering on patterning materials to uppermost relief surface.

It can will be patterned into material from anilox roller inking system or other rollers for the measured quantity of each printed patterns Inking system charging.In one embodiment, the first roller can be used for will be patterned into material from " ink " disk or metering system turn Move to metering roll or anilox roller.When will be patterned into material from anilox roller be transferred to printing plate cylinder when, usually by it Metering is uniform thickness.When by substrate (such as continuous coiled material) by roll-to-roll processing system from printing plate cylinder be moved to pressure When printing roller, which applies pressure to printing plate cylinder, and image is transferred to substrate from letterpress component.

After it will be patterned into material and be applied to the uppermost relief surface (or convex surfaces) of letterpress component, It might be useful that at least any inert organic solvents of 25 weight % for including in patterning materials are removed, in relief image Uppermost relief surface on form more sticky deposit.It can achieve in any way going for the inert organic solvents Remove, for example, using heated air jets, at room temperature evaporation or baking oven at elevated temperatures in heat or it is known in the art For removing other means of solvent.

Once one or more patterns are arranged on the dry bottom paint layer of substrate (for example, as continuous coiled material), before gained Patterning materials in system product can be for example by with as described above from the suitable of suitable source such as fluorescent lamp or LED Radiation irradiation is to solidify, to provide one or more cured patterns in substrate.For generating the irradiation system of appropriate radiation It can be made of one or more ultraviolet lamps, such as in the form of 1 to 50 discharge lamp, such as xenon, metal halide, metal arc (such as with from several millimeters to the required operating pressure of about 10 atmospheric pressure it is low, in or high-pressure mercury vapour discharge lamp).Institute Stating lamp may include being transmissive at least 190 nm and up to and including 700 nm or typically at least 240 nm and up to and including 450 The shell (envelop) of the light of nm wavelength.The typical lamp that can be used for providing ultraviolet radioactive is such as the GE for example, middle pressure mercury arc H3T7 arc lamp and Hanovia 450W arc lamp.The combination of various lamps can be used to carry out in photocuring, some or complete in the lamp Portion can operate in an inert atmosphere.When using UV lamp, the irradiation flux of impact basement (or the layer or pattern applied) can be for extremely Few 0.01 watt/inch²(0.00155 watt/centimetre²), with realized for example in roll-to-roll operation applied patterning materials with Abundant quick photocuring of the continuation mode in 1 to 20 second.

LED illumination equipment to be used can have 350 nm or bigger emission peak wavelength in photocuring station.LED is set Standby may include the element with the different emission peak wavelengths more than or equal to 350 nm of two or more seed types.Have 350 nm or bigger emission peak wavelength and the commercial embodiments of LED device with UV LED (UV-LED) are Available from the NCCU-033 of Nichia Corporation.

This irradiation of precursor article the result is that comprising substrate (for example, individually thin slice or continuous coiled material) and on it With one or more cured patterns in one or two support-side of the substrate (for example, respectively containing suitable Seed metal particle) intermediate.In some embodiments of the precursor article, multiple curable patterns and solidification Identical photocurable or heat-setting composition can be used to be formed for pattern.This photo curable composition may include can be certainly By the composition of the cured composition of base, acid catalysis composition or free-radical curable and the composition two of theobromine catalytic curing Person, all as described above.

Gained intermediate can be used for some applications in this form, but in most of embodiments, they are further It is processed to be incorporated to conductive metal in one or more (multiple) cured patterns, each cured pattern may include seed metal Particle is to plate step for electroless metal.For example, the seed metal particle can be the metal that above-identified is component (d) Or mixtures thereof grain, such as gold particle, Argent grain, copper particle, palladium particle or platinum grain,.

The useful method of one kind according to the present invention in printing station using multiple flexographic printing plates in heaps (for example, Preparation as described above), wherein each heap has the printing plate cylinder of their own, so that each flexographic printing plates in substrate for printing The unitary part of brush patterning materials, such as using galley heap at one of substrate web (such as polymer continuous coiled material) Or in the multiple portions in two support-sides printed patterns material pattern.Can be used multiple flexographic printing plates by identical or On different photopolymerization composites " printing " or these multiple portions being applied in the substrate.

In other embodiments, common impression cylinder can be together with the single impression cylinder being mounted on press rack It uses.When the substrate enters press rack, and impression cylinder contact, and with patterning materials such as photocurable Composition print pattern appropriate.Alternatively, wherein printing station is with water using series connection (in-line) flexographic printing process Horizontal line placement is simultaneously driven by common line shaft.The printing station may be connected to exposure station, cutting station, folding machine (folder) and its Its downstream equipment.The usable available information in this field of technical staff is readily determined equipment and the other useful of station is matched It sets.For example, describing a kind of (in-the-round) imaging method comprehensively in WO 2013/063084 (Jin et al.).

It will can prepare cured pattern (or portion containing one or more containing seed metal particle at this stage immediately Point) intermediate immerse in water base electroless metal plating bath or plating solution, or can by the intermediate only with cured pattern one Storage is played to use in later time.

The accessible electroless plated metal identical or different with above-mentioned corresponding seed metal particle of the intermediate.Big In most embodiments, the electroless plated metal is the metal different with corresponding seed metal particle.

At this time can be used will likely without any metal of electric " plating " in the cured pattern of corresponding seed metal particle, But in most of embodiments, electroless plated metal can be such as copper (II), silver (I), gold (IV), palladium (II), platinum (II), nickel (II), chromium (II) and combinations thereof.Copper (II), silver-colored (I) and nickel (II) are particularly useful electroless plated metals.

The one or more electroless plated metal can at least 0.01 weight % based on total solution weight and at most simultaneously Amount including 20 weight % is present in water base electroless plating bath or plating solution.

Known temperature and time condition can be used to carry out electroless plating, because such condition is in various textbooks and science text It is well-known in offering.It is known that include various additives, such as metal chelating agent or stabilizer in water base electroless plating liquid. Variation on up time and temperature changes metal electroless plating thickness or electroless deposition of metals rate.

Useful water base electroless plating liquid or plating bath are to contain formaldehyde as reducing agent without electrolytic copper (II) plating bath.Ethylenediamine tetraacetic Acetic acid (EDTA) or its salt can be used as the presence of copper complexing agent.For example, depending on required deposition rate and plating rate and plating Metal thickness is covered, copper electroless plating can carry out several seconds and up to a few houres at room temperature.

Other useful water base electroless plating liquid or plating bath include the silver (I) with EDTA and sodium tartrate, have ammonia and Portugal The silver (I) of grape sugar, the copper (II) with EDTA and dimethyamine borane, the copper (II) with citrate and hypophosphites, tool There are the nickel (II) and the water base electroless plating bath of other industrial standards or plating solution of lactic acid, acetic acid and hypophosphites, such as by Mallory et al. existsElectroless Plating:Fundamentals and ApplicationsDescribed in 1990 that A bit.

Carrying out electroless plating step with one at one of substrate (such as continuous coiled material) or in opposite support-side or more After providing conductive metal pattern in multiple cured portions, resulting product is removed from water base electroless plating bath or plating solution, and Can reuse distilled water or deionized water or another group water solution washing to remove the electroless plating chemicals of any remnants (chemistry).At this time, electroless plated metal is usually stable and can be used for its expected purpose.

In some embodiments, products obtained therefrom can be rinsed with water or clean at room temperature, such as such as WO 2013/ Described in [0048] section of 063183 (Petcavich), or less than 70 DEG C at a temperature of rinsed with deionized water or clear It is clean, as described in [0027] section of WO 2009/169345 (Ramakrishnan et al.).

Therefore, this method provides the product comprising substrate, the substrate includes dry bottom paint layer as described above and has There is the conductive pattern arranged on it, the conductive pattern includes having less than 15 in one or two support-side of substrate μm average line width at least some filaments.

In order to which vision or durability reason change the surface of electroless plated metal, various post-processings may can be used, including At least still another (third or more) metal such as nickel, palladium or silver surface it will be plated on electroless plated metal that (step is sometimes Referred to as " capped "), or generate metal oxide, metal sulfide or metal selenide layer, be enough to change surface color and Electric conductivity of the scattering nature without reducing electroless plating (second) metal.Depending on used in the various capped steps in this method Metal may desirably be used in another seed metal catalyst in water base seed metal catalyst solution to handle electroless plating Metal is to promote the deposition of other metal.

In addition, identical or different condition can be used successively to carry out a variety of processing with water base electroless metal plating solution.Suitable In the case of, can also room temperature or lower than 70 DEG C at a temperature of sequentially washed or rinsing step.

In addition, identical or different electroless plated metal and identical or different electroless plating condition can be used successively to carry out repeatedly Electroless plating step.

Therefore, in some embodiments of the method for providing product of the invention, which comprises

The continuous coiled material of the substrate of above-mentioned any embodiment is provided,

Using photocurable as described above or heat-setting composition, such as using flexographic plate print-member, even Photocurable or heat-setting pattern are formed (directly on dry bottom paint layer) in at least first part of continuous coiled material,

Solidification photocurable (as described above) or heat-setting pattern in an appropriate manner, in the first part Photocuring or heat cure pattern are formed, and

Using above-mentioned electroless plating step make in the first part photocuring or heat cure pattern electroless plating on it is conductive Metal.

The embodiment of this method can be implemented in the single support-side of substrate or in the opposite support-side of substrate, to mention For identical or different conductive pattern.

There are also in other embodiments, method of the invention can be used for providing multiple conductive metal patterns, the method Include:

There is provided it is according to the present invention in respective part include multiple photocuring patterns continuous coiled material, each photocuring figure Case is provided by irradiating photocurable as described above or heat-setting composition,

The continuous coiled material comprising multiple photocurings or heat cure pattern is handled with electroless metal plating solution, on continuous coiled material Multiple electroless gold plating metal patterns are provided in respective part, and

Optionally, multiple electroless gold plating metal patterns are further processed with capped metal, it is multiple to be provided on continuous coiled material Capped conductive pattern.

This method can pass through following steps further progress:

Individual conductive articles are formed by the continuous coiled material comprising multiple capped conductive patterns, and

Individual conductive articles are assembled into identical or different individual equipment, such as aobvious with touch-screen display Show equipment.

Such method embodiment can be used identical or different photocurable or heat-setting composition in substrate It is carried out in two support-sides.

Capacitive touch screen sensor especially can be made in useful product prepared in accordance with the present invention, it includes suitable Conductive mesh ruling, electrode (or the region BUS), electrical lead and electric connector.For example, electrode and lead (tail) can be schemed by printing Pattern printed by case material and electroless plating is formed.

Some datail descriptions of useful method and apparatus for carrying out the present invention are in such as WO 2013/063183 (Petcavich), in WO 2013/169345 (Ramakrishnan et al.).Conductive articles are used to prepare (especially with roll-to-roll Mode) other details of useful manufacture system be provided in PCT/US/062366 (by Petcavich and Jin in 2012 October 29 submitted) in.

It can be used for implementing other device systems and steps characteristic of the invention and be described in United States serial 14/146,867 In (being submitted by Shifley on January 3rd, 2014).

With reference to Fig. 1, it illustrates the schematic side elevations of flexographic printing system 100, can be used for the method for the present invention In embodiment, for the roll-to-roll printing photocurable in two (opposite) support-sides of substrate 150 or heat-setting group Object is closed, the substrate 150 may include the dry bottom paint layer being directly arranged on supporter.Substrate 150 is used as continuous coiled material from supply Roller 102 is supplied to take-up roller 104 by flexographic printing system 100.Substrate 150 has the first support-side 151 and the second support Side 152.

Flexographic printing system 100 includes two printings for being configured as printing in the first support-side 151 of substrate 150 Module 120 and 140, and it is configured as two printing modules printed in second (opposite) support-side 152 of substrate 150 110 and 130.The continuous coiled material of substrate 150 is overall to be advanced with roll-to-roll direction 105 (in Fig. 1 from left to right).However, various rollers 106 and 107 for locally changing the direction of the continuous coiled material of substrate according to the requirement for adjusting web tension, to provide buffering And support-side is inverted for printing.Particularly, 120 roller 107 of printing module is used to invert the part side of the continuous coiled material of substrate 150 To so that it is substantially mobile with direction from right to left.

Each printing module 110,120,130,140 may include some similar device features, including the rolling of respective printing plate Cylinder 111,121,131,141, is separately installed with respective flexographic printing plates 112,122,132,142 thereon.Each flexographic plate Print-member (flexographic printing plates) 112,122,132,142 has protruding features 113, limits to be printed in substrate 150 Picture pattern.Each printing module 110,120,130,140 further includes respective impression cylinder 114,124,134,144, It is configured to that the support-side of substrate 150 is forced to contact with corresponding flexographic plate print-member 112,122,132,142.

With reference to the direction of rotation of the different components of printing module 110,120,130,140, it is noted that 120 He of printing module Inverse time in the impression cylinder 124 and 144 of 140 (for being printed on the first side 151 of substrate 150) view shown in Fig. 1 Needle direction rotates, and 114 He of impression cylinder of printing module 110 and 130 (for printing in second side 152 of substrate 150) 134 are rotated clockwise in this view.

Each printing module 110,120,130,140 further includes respective anilox roller 115,125,135,145, is used for It will be patterned into material and be provided to corresponding flexographic plate print-member (flexographic printing plates) 112,122,132,142.Such as printing Well known in the industry, anilox roller is a kind of hard roller, is usually built by steel or aluminium core, is had containing millions of The outer surface of a very tiny scrobicula (referred to as ink hole (cell)).Hold the transfer of patterning materials using anilox roller It is easily feasible.In some embodiments, some or all of printing module 110,120,130,140 further includes respective UV solid Change station 116,126,136,146, for the patternable materials of printing to be solidificated in substrate 150.

Can embodiment preparation through the invention product and some embodiments of equipment be shown in Fig. 2-5.

Fig. 2 shows the high-level system diagram of the device (or equipment) 300 with touch screen 310, which includes Show the touch sensor 330 of at least part visibility region of equipment 320 and covering display equipment 320.Touch sensor 330 Perception touches and electric signal corresponding to the touch perceived (for example, related with capacitance) is transmitted to controller 380.Touching Touch the example that sensor 330 is the product that can be printed in two support-sides by flexographic printing system 100, the flexographic plate print Brush system 100 includes the printing module in conjunction with the embodiment of above-mentioned flexible version printing (inking) system.

Fig. 3 shows the schematic side elevation of touch sensor 330.Transparent substrates 340 of the invention, for example, it is transparent poly- Ester, such as transparent poly- (ethylene glycol terephthalate) have the first conductive pattern being printed in the first support-side 341 350, and the second conductive pattern 360 being printed in second (opposite) support-side 342.It is cut from take-up roller 104 (Fig. 1) saturating The length and width of bright substrate 340 is no more than the flexographic printing plates of flexographic printing system 100 (Fig. 1) (or flexible version printing Component) 112,122,132,142, but its be likely less than flexographic printing plates (or flexographic plate print-member) 112,122,132, 142.Optionally, the first conductive pattern 350 and the second conductive pattern 360 can be in flexible version printing and cured pattern or patterning materials It is plated using coating method after material coated with improvement electric conductivity.According to the method for the present invention, patterning materials can be used for providing institute State conductive pattern 350 and 360.

Fig. 4 shows the printing module that one or more printing modules such as flexographic printing system (Fig. 1) can be used 120 and 140 examples for being printed on the conductive pattern 350 in the first support-side 341 (Fig. 3) of substrate 340 (Fig. 3).Conductive pattern Case 350 includes grid 352, which includes the mesh column 355 that the filament 351 and 353 intersected is formed, with a row channel Pad (channel pad) 354 connects.Interconnection line 356 is by channel pads 354 and the connector for being connected to controller 380 (Fig. 2) Pad (connector pad) 358 connects.In some embodiments, conductive pattern 350 can be printed by single printing module 120 Brush.However, because the best printing condition for filament 351 and 353 (for example, with about 4 to 8 μm line width) is typically different In the printing condition for printing broader channel pads 354, connector pad 358 and interconnection line 356, it is possible that advantageous It is to carry out printing fine line 351 and 353 using a printing module 120 and print broader spy using the second printing module 140 Sign.In addition, for the clean intersection of filament 351 and 353, it is also possible to advantageously be printed using a printing module 120 With one group of filament 351 of solidification, and second group of filament 353 is printed and solidified using the second printing module 140, and use and printing The third printing module (not shown in figure 1) of the similar configuration of module 120 and 140 prints broader feature.

Fig. 5 shows the printing that one or more printing modules such as flexographic printing system 100 (Fig. 1) can be used The example that module 110 and 130 is printed on the conductive pattern 360 in the second support-side 342 (Fig. 3) of substrate 340 (Fig. 3).It leads Electrical pattern 360 includes grid 362, which includes the mesh row 365 that the filament 361 and 363 intersected is formed, with a row Channel pads 364 connect.Interconnection line 366 connects channel pads 364 with the connector pad 368 for being connected to controller 380 (Fig. 2) It connects.In some embodiments, conductive pattern 360 can be printed by single printing module 110 (Fig. 1).However, because for thin The best printing condition of line 361 and 363 (for example, with about 4 to 8 μm line width) is usually different from that for broader channel weldering The printing condition of disk 364, connector pad 368 and interconnection line 366, it is possible that advantageously using a printing module 110 (Fig. 1) carrys out printing fine line 361 and 363 and prints broader feature using the second printing module 130 (Fig. 1).In addition, in order to The clean intersection of filament 361 and 363, it is also possible to advantageously be printed using a printing module 110 (Fig. 1) and solidify one Group filament 361, and second group of filament 363 is printed and solidified using the second printing module 130 (Fig. 1), and use and printing die The third printing module (not shown in figure 1) of block 110 and 130 (Fig. 1) similar configuration prints broader feature.

Alternatively, in some embodiments, one for being configured similar to printing module 110 and 130 (Fig. 1) can be used Or more printing module come printed conductive patterns 350 (Fig. 4), and can be used be configured similar to 120 He of printing module One or more printing modules of 140 (Fig. 1) come printed conductive patterns 360 (Fig. 5).

With reference to Fig. 2-5, in operation touch-screen 310, controller 380 can be via the sequentially electric drive net of connector pad 358 Lattice column 355, and the electric signal on mesh row 365 can be sequentially perceived via connector pad 368.In other embodiments, net Driving and the perception effect of lattice column 355 and mesh row 365 can overturn.

The present invention provides at least following embodiments and combinations thereof, but as those skilled in the art will be from the religion of the disclosure Lead middle understanding, it is believed that other combinations of feature within the scope of the present invention:

1. a kind of composition, it includes the mixture of first polymer latex and second polymer latex,

Wherein the dry coating of the composition has at least 15% and at most and including 50% surface polarity.

2. composition described in embodiment 1, wherein the dry coating of the composition has at least 28% and at most and wraps Include 50% surface polarity.

3. composition described in embodiment 1 or 2, in which:

Based on the first polymer total weight, the first polymer is comprising at least 75 weight % and at most and including 90 The repetitive unit derived from (methyl) glycidyl acrylate and at least 10 weight % of weight % and at most and including 25 weights Measure % the repetitive unit derived from (methyl) n-butyl acrylate, the first polymer at least 25 DEG C and at most and including 75 DEG C of glass transition temperature, and the first surface activating agent is alpha-olefin (C₁₄-C₁₆) sodium sulfonate;

Based on the second polymer total weight, the second polymer is comprising at least 75 weight % and at most and including 90 The repetitive unit derived from (methyl) glycidyl acrylate and at least 10 weight % of weight % and at most and including 25 weights Measure % the repetitive unit derived from (methyl) n-butyl acrylate, the second polymer at least 25 DEG C and at most and including 75 DEG C of glass transition temperature, and the second surface activating agent is the ammonium salt of sulphation polyethoxy nonyl phenol；

The weight ratio of the first polymer latex in the mixture and the second polymer latex is 1:1 and extremely And including 2.5:1；

The first surface activating agent is at least 1 weight % based on dry coating total weight and at most and including 3 weight % Amount be present in the dry coating of the mixture；

The second surface activating agent is at least 0.35 weight % based on dry coating total weight and at most and including 1.1 weights The amount of amount % is present in the dry coating of the mixture；With

Based on dry coating total weight, the total amount of first and second surfactant in the dry coating of the mixture At most and including 3.35 weight %.

4. composition described in any of embodiment 1 to 3, wherein the first surface activating agent is by R-CH₂- CH=CH-CH₂-S(=O)₂O^-Na⁺The compound of representative, wherein R is C₁₀、C₁₁Or C₁₂Alkyl；Or this with different R groups The mixture of class compound, the R group are C₁₀To C₁₂Any kind in alkyl；And the second surface activating agent is by R '- Phenyl-(O-CH₂CH₂)_n-S(=O)O₂ ^-NH₄ ⁺It represents, wherein R' is C₈To C₁₂Alkyl, and n is 3 to 10.

5. composition described in any of embodiment 1 to 4, wherein the first polymer latex and described second At least one of polymer emulsion includes polyvinyl, and the polyvinyl also includes derived from containing extremely The repetitive unit of (methyl) alkyl acrylate of the ester alkyl of few 2 carbon atoms.

6. composition described in any of embodiment 1 to 5, wherein the first polymer and second polymerization At least one of object is crosslinking.

7. a kind of substrate, it includes supporters and the dry bottom being arranged at least one support surface of the supporter Paint layer, the dry bottom paint layer include composition described in any of embodiment 1 to 6.

8. substrate described in embodiment 7, at least 88% synthesis transmissivity.

9. substrate described in embodiment 7 or 8, it includes transparent polymeric support and described with being directly arranged at The dry bottom paint layer on transparent polymeric support.

10. substrate described in any of embodiment 7 to 9, wherein the first polymer in the dry bottom paint layer The weight ratio of latex and the second polymer latex is 1:3 and to and including 3:1.

11. substrate described in any of embodiment 7 to 10, wherein the dry bottom paint layer have at least 0.05 μm and At most and including 0.4 μm of average thickness.

12. substrate described in any of embodiment 7 to 11, it includes poly- (ethylene glycol terephthalates) or poly- ((ethylene naphthalate)) supporter.

13. substrate described in any of embodiment 7 to 12 is continuous flexible substrates.

14. a kind of product, it includes the substrates of any of embodiment 7 to 13, and include: transparent polymeric support With the dry bottom paint layer at least one support surface for being arranged in the transparent supporting body, and comprising have less than 15 μ The patterning materials of the line of the average line width of m, the patterning materials are directly arranged on the dry bottom paint layer.

15. product described in embodiment 14, wherein the patterning materials include to be selected from gold, silver, copper, palladium, platinum, nickel And its conductive metal or its precursor of precursor.

16. product described in embodiment 14 or 15, wherein the patterning materials include the combination of free-radical curable Both compositions of object, the composition of the composition of theobromine catalytic curing or free-radical curable and theobromine catalytic curing mix Close object.

17. product described in embodiment 14 or 15, wherein the patterning materials include to be dispersed in photocuring or thermosetting Change the metallic particles in composition.

18. product described in any of embodiment 14,15 and 17, wherein the patterning materials include to be dispersed in The particle of gold, silver, copper, palladium or platinum in photocuring or heat-curing composition, the photocuring or heat-curing composition are derived from Both composition and the composition of theobromine catalytic curing of free-radical curable.

19. a kind of method is used to provide product described in any of embodiment 14 to 18, which comprises

Substrate described in any of embodiment 7 to 13 is provided, and

The pattern of patterning materials is provided directly on the dry bottom paint layer.

20. method described in embodiment 19, wherein at least part of the pattern of the patterning materials includes to have The line of average line width less than 15 μm.

21. method described in embodiment 19 or 20, wherein described at least part of the pattern of the patterning materials It is present in the touch screen zone of the product primed.

22. method described in any of embodiment 19 to 21 comprising:

It is contacted by the dry bottom paint layer with the direct of the letterpress component for carrying the patterning materials, directly in institute It states and the patterning materials is provided on dry bottom paint layer.

23. method described in any of embodiment 19 to 22, wherein the patterning materials include conductive metal or Its precursor.

24. method described in any of embodiment 19 to 23, further include:

Solidify the photocurable or heat-setting composition in the patterning materials.

25. method described in any of embodiment 19 to 24, wherein the patterning materials include metallic particles, And the method also includes:

Electroless metal plating is carried out to the pattern of the patterning materials.

26. a kind of product, the method as described in any of embodiment 19 to 25 is obtained, wherein the product includes At least one pattern of conductive material, wherein at least part of the pattern of the conductive material includes to have less than 15 μm The conductor wire of average line width, the part of the pattern of the conductive material is directly arranged at the described of the substrate On dry bottom paint layer.

27. method described in any of embodiment 19 to 25 comprising:

The substrate is provided as continuous coiled material,

Directly providing on the dry bottom paint layer in one or more unitary parts of the continuous coiled material respectively can One or more independent patterns of photocuring or heat-setting composition are as the precursor conductive material, the photocurable Or heat-setting composition includes metal seeds particle,

By solidifying in one or more independent patterns for converting the photocurable or heat-setting composition Each, it is one to form one or more individual cured patterns in one or more unitary part Or more individually each of cured pattern include the metal seeds particle, and

The metal seeds particle of the electroless plating in each of one or more individually cured pattern, with One or more individual conductive patterns are provided.

28. a kind of method is used to provide multiple products, which comprises

There is provided any of such as embodiment 7 to 13 substrate claimed,

The dry bottom paint layer in first part by making the continuous coiled material, which directly contacts, carries the photocurable Or the flexographic plate print-member of hot (thermally) composition, it is described dry in the first part of the continuous coiled material Directly form the first curable pattern on prime coat, the described first curable pattern include containing seed metal particle can Photocuring or heat-setting composition,

Make include the first part of the described first curable pattern the continuous coiled material advance (advancing) close to curing station and the described first curable pattern is solidified, thus to form the in the first part One cured pattern, first cured pattern include the seed metal particle,

Flexographic plate print-member by the photocurable or heat-setting composition identical or different with carrying is direct It contacts, directly forms the second curable pattern on the dry bottom paint layer in the second part of the continuous coiled material, it is described Second curable pattern includes the identical or different photocurable comprising identical or different seed metal particle or can thermosetting The composition of change,

Make include the second part of the described second curable pattern the continuous coiled material advance with close Curing station simultaneously solidifies the described second curable pattern, the second cured pattern is thus formed on the second part, this second Cured pattern includes identical or different seed metal particle,

Optionally, it is printed using identical or different curable or heat-setting composition and identical or different flexographic plate Brush member respectively partially implements the formation and advance feature one or more times for the other of the continuous coiled material, with Other cured pattern is formed on the other respective part, and

Roll comprising first, second and optional other cured pattern the continuous coiled material to provide multiple preceding systems The volume of product.

29. method described in embodiment 28, wherein identical seed metal particle is present in the multiple cured pattern Each of in, which is gold particle, Argent grain, copper particle, palladium particle or platinum grain.

30. method described in embodiment 28 or 29, wherein in each formation feature for each curable pattern It is middle to use identical photocurable or heat-setting composition.

31. method described in any of embodiment 28 to 30, wherein for each curable each of pattern It is formed and uses identical photo curable composition in feature, which includes the combination of free-radical curable Both object, the composition of the composition of theobromine catalytic curing or free-radical curable and composition of theobromine catalytic curing.

32. a kind of equipment of the product comprising any of embodiment 14 to 18 and 26, it includes being directly arranged at One or more conductive metal patterns on dry bottom paint layer are stated,

Wherein each of one or more conductive metal pattern includes touch area, the touch area packet Containing the conductor wire with the average line width less than 15 μm.

33. equipment described in embodiment 32 is touch panel device.

Following embodiment is provided to illustrate practice of the invention, and is not intended to limit in any way.

Embodiment 1: the preparation of the mixture of composition-polymers latex

The preparation of first polymer latex (latex A):

Poly- (glycidyl methacrylate -co- third is synthesized by the way that 652 g softened waters are added in 2 liters of glass reactors Olefin(e) acid butyl ester).Other 651 g softened water is added in 2 liters of glass head tanks.Blender on two containers is set in 150 Under RPM.Nitrogen atmosphere is established in systems, and the Rhodacal of 30.9 g is added into each container^®A246L anion table Face activating agent (" first surface activating agent ").Reactor content temperature is risen to 60 DEG C, and by 526 g Glycidyl methacrylates Glyceride and 92.3 g n-butyl acrylates are added in head tank.It is 60 when having prepared monomer emulsions and temperature in head tank DEG C when, bis- (4- cyano) valeric acids (75%) of 6.16 g azos are added into reactor.The content of head tank was counted through 240 minutes Amount is added in reactor, and reactor content is stirred 2 hours at 60 DEG C, and being dissolved in 9 g water for 0.48 g is then added Arabo-ascorbic acid.Then, the 30 weight % hydrogen peroxide of 1.35 g being dissolved in 47 g water are added instead in a manner of dropwise It answers in device.Then reactor content is stirred for 1 hour at 60 DEG C.Then resulting first polymer latex is cooled to 25 DEG C, and filtered by 30 μm of cloth.The prepared product (preparation), which obtains the filtered of 1900 g, has 32% to consolidate The first polymer latex of body.Measuring first polymer median particle diameter by UPA is 53.1 nm.

The preparation of second polymer latex (latex B):

Poly- (glycidyl methacrylate -co- is synthesized by the way that 675.2 g softened waters are added in 2 liters of glass reactors Butyl acrylate).674 g softened waters are added into 2 liters of glass head tanks.Blender on two containers is set in 150 Under RPM.Nitrogen atmosphere is established in systems, and the Rhodapex of 7.72 g is added into each container^®CO-436 anion table Face activating agent (" second surface activating agent ").Reactor content temperature is risen to 60 DEG C, and by 526 g Glycidyl methacrylates Glyceride and 92.3 g n-butyl acrylates are added in head tank.When having been prepared in head tank in monomer emulsions and reactor When tolerant temperature is at 60 DEG C, 28% ammonia spirit of bis- (4- cyano) valeric acids (75%) of 6.16 g azos and 2.66 g are added Reactor.By the content of head tank through in 240 minutes metered reactors, and reactor content is stirred at 60 DEG C 2 hours, the arabo-ascorbic acid of 0.48 g being dissolved in 9 g water is then added.Then, by 30 be dissolved in 47 g water of 1.35 g Weight % hydrogen peroxide is added in reactor in a manner of dropwise.Reactor content is stirred for 1 hour at 60 DEG C.Then Resulting first polymer latex is cooled to 25 DEG C, and is filtered by 30 μm of cloth.The prepared product obtains the process of 1900 g The first polymer latex with 30.6% solid of filter.Measuring first polymer median particle diameter by UPA is 87.1 nm.

Use the glass transition for the various polymer that emulsion polymerization as described above and different monomer weight ratios obtain Temperature obtains as follows:

The weight ratio of glycidyl methacrylate and n-butyl acrylate	T_g(as using dsc measurement)
		100:0	70°C
85:15	43°C
		75:25	28°C

Embodiment 2: the preparation of substrate and product

Poly- (ethylene glycol terephthalate) substrate primed is prepared in the following manner.

By squeezing out and being cast (casting) to suitable for obtaining 125 μ m thicks after stretching on both vertical and horizontal The thickness of Biaxially oriented film forms the sample of transparent poly- (ethylene glycol terephthalate) (PET) film (or supporter).? Before stretched operation, apply paint base composition and drying, to provide dry bottom paint in two opposite support-sides of PET supporter Layer.The paint base composition tested contains any one of above-mentioned latex A and latex B or two kinds.Then as obtained by the stretching The substrate primed comprising transparent supporting body and dry bottom paint layer, with reduce shrink and mist degree.It is various resulting to prime The average dry thickness of substrate A to N and gained dry bottom paint layer is described in lower Table II.

Using the first polymer latex (latex A) and second polymer latex (latex B) of equivalent, in 50 weight % solution 0.2 weight % saponin(e (Saponin) and 0.033 weight % Aerodisp^®W7512S pyrogenic silica particle is (average Having a size of 0.1 μm), it prepares under the concentration of 20% total latex polymer and is identified as priming for sample B described in Table II Substrate.The substrate primed for being identified as sample A, C and D to N is prepared in a similar way, wherein the first polymer latex Change as shown in Table II with the amount of second polymer latex.The substrate of sample D primed is identified as also containing 1 weight %'s Resorcinol.The substrate primed for being identified as sample N is prepared in a manner of identical with the paint base composition for being identified as sample A, In addition to will be with the Rhodacal of the amount of the 2 weight % relative to the second polymer total weight in latex B^®A246L anion Surfactant (" first surface activating agent ") is added in dispersion (is incorporated with first surface activating agent and the second table as a result, Both face activating agents, but first surface activating agent is incorporated to not as a part of different polymer emulsions).

Embodiment 3:

Mixture and the various substrates primed using above-mentioned first and second polymer emulsion, provide in the following manner The printed patterns of patterning materials including conductive pattern.

% surface polarity:

Based on known Fowkes ENERGY METHOD, by measuring a drop water and a drop two on given drying surface first The respective 2 minutes contact angles (θ) of iodomethane determine given drying surface (for example, the drying of dry bottom paint layer or polymer emulsion Layer) % surface polarity.Surface tension of liquid (the γ of known every kind of fluid_L) dispersive component (γ^d _L) and polar component (γ^P _L) (referring to lower Table I) calculates the polar component and dispersive component on given drying surface using equation 1 shown below.Then make With calculating % surface polarity shown in the equation 2 and Table I being illustrated below.

Table I

。

Photo curable composition (" ink ")

Photo curable composition1 (ink 1):

The photo curable composition (or patterning materials) is similar to United States serial 14/174,879 (above-mentioned) It described in the inventive embodiments 1 of inventive embodiments 1 and United States serial 14/197,293 (same above-mentioned), and include to be formed At least following components of 100 g aliquots:

14.4 g epoxy acrylates (CN 153 from Sartomer), 9.9 g poly(ethylene glycol) diacrylate (M_n Be 258, Sigma-Aldrich), 2.1 g poly(ethylene glycol) diacrylate (M_nBe 575, Sigma-Aldrich), 10.8 g The triarylsulfonium salt six of pentaerythritol tetraacrylate (Sigma-Aldrich), 0.8 g being blended in 50% propene carbonate The triarylsulfonium salt hexafluoro antimonate of fluorophosphate (Sigma-Aldrich), 0.8 g being blended in 50% propene carbonate (Sigma-Aldrich), 2.4 g free radical photo-initiation hydroxycyclohexylphenylketones (Sigma-Aldrich), 1.2 g are free Base photoinitiator methyl -4 '-(methyl mercapto) -2- raorpholino propiophenone (Sigma-Aldrich), 19.5 g silver nano-grains (Novacentrix, 20-25 nm average grain diameter, Ag-25-ST3), 1.1 g carbon nano-particles are (from US Nano's US1074), the 9-Fluorenone (Sigma-Aldrich) of 0.001 g and the 1- methoxyl group isopropanol (Sigma-Aldrich) of 35 g are molten Agent.

Photo curable composition 2 (ink 2):

The photo curable composition (or patterning materials) is prepared similar to ink 1, but is free of 9-Fluorenone.

Print photo curable composition:

Use the desk-top test for coming from IGT Testing Systems Inc., Arlington Heights, IL " IGT F1 Printability Tester " obtains above-mentioned in the various PET bases primed with flexographic plate mode can light The sample of the printed patterns of cured composition.Reticulate pattern for photo curable composition to be applied to flexographic printing plates passes Ink roller system has the value by IGT 1.3 BCMI specified and 1803 lpi.Printed patterns use 20 N's at ambient temperature It is prepared by the print speed printing speed of anilox roller power (Anilox force), the print force of 10 N and 0.20 m/s.

Flexographic printing plates for printing photo curable composition are that commercially available Kodak Flexcel NX is photosensitive The sample of property resin plate (photopolymer plate) precursor (Eastman Kodak Company), has used mask Imaging, the mask, which has, to be made a reservation for using Kodak Square Spot laser technology with what the resolution ratio of 12,800 dpi was written Pattern.The flexographic printing plates precursor of exposure exposes through UV and uses the known item by manufacturer to these letterpress component suggestions Part is processed (development).It is thick (including PET) that resulting flexographic printing plates are respectively 1.14 mm.For by flexographic printing plates The backing adhesive tape for being installed to printing form roller is the 1120 cream-coloured adhesive tapes from 3M company, is 20 mils (0.051 cm) Thickness, and with 55 Xiao A hardness.Relief image design in flexographic printing plates includes having to have at the relief surface of top There is the lattice of the filament of 7 μm of width.The average line width of printing in the PET base primed as shown below is from printing There is the pattern of the lattice to obtain.

After the printing, using provide 190-1500 nm between illumination wavelength 300 WPI medium pressure mercury lamp of Fusion, With about 298 mJ/cm²Light exposure (exposure) each printed patterns for irradiating photo curable composition are radiated with UV, With each printed patterns of cured pattern material.Using Olympus BH-2 optical microscopy in both transmission and reflective-mode The average line width of the printing of lower measurement cured pattern.

Electroless metal plating:

It include the intermediate of the cured pattern in the various substrates primed by containing Enplate at 45 DEG C Submergence carrys out electroless copper in intermediate 7 minutes with cured pattern m in the beaker of Cu-406 electroless plating liquid (Enthone), so It is afterwards with distilled water flushing and dry with nitrogen, to form the product with the conductive pattern being arranged in the substrate primed.

Adhesiveness test (" adhesive tape removal test "):

Immediately by a piece of Scotch from 3M company after electroless plating^®810 Magic Tape adhesive tapes are applied to On electroless plating pattern in each product, and then tear from the surface of the product.Record the amount of the copper removed by the operation Instruction as electroless plating pattern and the adhesiveness for the PET base primed.As a result it is shown in lower Table II.

The appearance of coat of every kind of substrate is evaluated with the scale of 0 to 5 grade, wherein " 0 " grade indicates on surface uniformity There is no visible difference, " 1 " grade indicates that hardly apparent surface heterogeneity, " 2 " grade indicate smaller but apparent table Face inhomogeneities, " 3 " grade indicate that clearly evident surface heterogeneity, " 4 " grade indicate significant surface heterogeneity, packet Haze and iris are included, and " 5 " grade indicates serious surface heterogeneity, including haze and iris.

Equally in lower Table II, Hazegard Plus haze meter (BYK Gardner) measurement mist degree (%) and " % are used T ", wherein " mist degree " is the measurement scattered by the light of substrate, and biggish number influences its clarity；And " %T " is logical Cross the measurement of the synthesis transmissivity of substrate, and the higher transparency of biggish digital representation.

Colourimetric number (the colorimetry of each substrate is measured using Ultrascan XE colorimeter (Hunter) Value), and with standard CIELAB title report as a result, wherein the b * in Table II represents the color of the substrate on blue-yellow axis, And the b * value corrected indicates appearance more yellow in substrate.

In table ii, " YI " represents yellowness index (E313 standard), is the calculated value in conjunction with CIELAB measurement result, makes Obtain the appearance that increased YI value indicates more yellow in substrate.

Grid lines evaluation is carried out in two support-sides of substrate.Observe the basic phase of line width result of two support-sides Together.

In table ii, " ink " refers to any one in ink 1 or ink 2 as identified above.

。

The printed matter for being identified as Comparative examples A, C and D shows similar total surface energy, but different % surface polarities, Lead to the printing difference of patterning materials.Comparative examples A, which generates, has the printing system that inventive embodiments B and E to M is identified as than using The printing conductor wire of the bigger average line width of the average line width that product obtain.The printed matter for being identified as comparative example C and D, which is shown, goes on business Track quality.

It is prepared using dry bottom paint layer according to the present invention (mixtures of the first and second polymer emulsions) to provide 19 And the conductor wire that the printed matter for being identified as inventive embodiments B and E to M of the % surface polarity between 44 generates has less than 10 μm average line width and good quality, and show good electroless plating performance and electroless copper to the viscous of the substrate primed Conjunction property.The printed matter for being identified as inventive embodiments E-G and I-L shows particularly good appearance of coat, low haze and low color It is color.

The printed matter for being identified as comparative example N shows individually to single polymers latex (" second " polymer emulsion or glue Newborn B) in only add a kind of other surfactant (" first surface activating agent ") and be not enough to provide necessary coating uniformity. On the contrary, according to the present invention, needing to provide the first and second surfactants via individual first and second polymer emulsion To dry bottom paint layer.

The printed matter for being identified as inventive embodiments H does not show best appearance of coat, but has desirable conductor wire product Matter.

Embodiment 4:

The precursor article containing the substrate primed is formed by following steps: using similar to described in embodiment 1 Photo curable composition, using Mark-Andy press with 20 ft/m (6.06 m/min) and similar to side described in Fig. 1 Method in two support-sides of PET supporter to provide the pattern as the photo curable composition of narrow line.

Parts list

100 flexographic printing systems

102 feed rolls

104 take-up rollers

105 roll-to-roll directions

106 rollers

107 rollers

110 printing modules

111 plate cylinders

112 flexographic printing plates (or flexographic plate print-member)

113 protruding features

114 impression cylinders

115 anilox rollers

116 UV curing stations

120 printing modules

121 plate cylinders

122 flexographic printing plates (or flexographic plate print-member)

124 impression cylinders

125 anilox rollers

126 UV curing stations

130 printing modules

131 plate cylinders

132 flexographic printing plates (or flexographic plate print-member)

134 impression cylinders

135 anilox rollers

136 UV curing stations

140 printing modules

141 plate cylinders

142 flexographic printing plates (or flexographic plate print-member)

144 impression cylinders

145 anilox rollers

146 UV curing stations

Parts List-is continuous

150 substrates (or continuous coiled material)

151 first support-sides

152 second (opposite) support-sides

300 devices (or equipment)

310 touch screens

320 display equipment

330 touch sensors

340 transparent substrates

341 first support-sides

342 second support-sides

350 conductive patterns

351 filaments

352 grids

353 filaments

354 channel pads

355 mesh columns

356 interconnection lines

358 connector pads

360 conductive patterns

361 filaments

362 grids

363 filaments

364 channel pads

365 mesh rows

366 interconnection lines

368 connector pads

380 controllers

Claims

Wherein the first polymer latex includes first polymer and first surface activating agent, so that the first polymer glue The dry coating of cream has at least 50% surface polarity, and

Wherein the second polymer latex includes second polymer and second surface activating agent, so that the second polymer glue The dry coating of cream has the surface polarity less than or equal to 27%, and

Wherein the dry coating of the composition has at least 15% and at most 50% surface polarity.

2. composition described in claim 1, wherein the dry coating of the composition has at least 28% and at most 50% table Face polarity.

3. composition of any of claims 1 or 2, in which:

Based on the first polymer total weight, the first polymer includes spreading out at least 75 weight % and at most 90 weight % Be born from (methyl) glycidyl acrylate repetitive unit and at least 10 weight % and at most 25 weight % derived from (first Base) n-butyl acrylate repetitive unit, the first polymer has at least 25 DEG C and at most 75 DEG C of glass transition temperature Degree, and the first surface activating agent is alpha-olefin (C₁₄-C₁₆) sodium sulfonate；

Based on the second polymer total weight, the second polymer includes spreading out at least 75 weight % and at most 90 weight % Be born from (methyl) glycidyl acrylate repetitive unit and at least 10 weight % and at most 25 weight % derived from (first Base) n-butyl acrylate repetitive unit, the second polymer has at least 25 DEG C and at most 75 DEG C of glass transition temperature Degree, and the second surface activating agent is the ammonium salt of sulphation polyethoxy nonyl phenol；

The weight ratio of the first polymer latex and the second polymer latex in the mixture is 1:1 to 2.5:1；

The first surface activating agent is present in at least amount of 1 weight % and at most 3 weight % based on dry coating total weight In the dry coating of the mixture；

The second surface activating agent is at least 0.35 weight % based on the dry coating total weight and at most 1.1 weight % Amount is present in the dry coating of the mixture；With

Based on the dry coating total weight, the total amount of first and second surfactant in the dry coating of the mixture At most 3.35 weight %.

4. composition of any of claims 1 or 2, wherein the first surface activating agent is by R-CH₂-CH=CH-CH₂-S(= O)₂O^-Na⁺The compound of representative, wherein R is C₁₀、C₁₁Or C₁₂Alkyl, or the mixing of such compound with different R groups Object, the R group are C₁₀To C₁₂Any kind in alkyl；And the second surface activating agent is by R '-phenyl-(O- CH₂CH₂)_n-S(=O)O₂ ^-NH₄ ⁺It represents, wherein R ' is C₈To C₁₂Alkyl, and n is 3 to 10.

5. composition of any of claims 1 or 2, wherein in the first polymer latex and the second polymer latex At least one includes polyvinyl, and the polyvinyl also includes derived from containing at least two carbon atom The repetitive unit of (methyl) alkyl acrylate of ester alkyl.

6. composition of any of claims 1 or 2, wherein at least one of the first polymer and the second polymer It is crosslinking.

7. a kind of substrate, it includes supporter and the dry bottom paint layer being arranged at least one support surface of the supporter, The dry bottom paint layer includes composition described in any one of claims 1 to 6.

8. substrate as claimed in claim 7, at least 88% synthesis transmissivity.

9. substrate described in claim 7 or 8, it includes transparent polymeric support and described transparent poly- with being directly arranged at Close the dry bottom paint layer on object supporter.

10. substrate described in claim 7 or 8, wherein the first polymer latex in the dry bottom paint layer and described the The weight ratio of dimerization object latex is 1:3 to 3:1.

11. substrate described in claim 7 or 8, wherein the dry bottom paint layer is flat at least 0.05 μm and at most 0.4 μm Equal thickness.

12. substrate described in claim 7 or 8, it includes poly- (ethylene glycol terephthalate) or poly- (naphthalenedicarboxylic acid ethylene glycol Ester) supporter.

13. substrate described in claim 7 or 8 is continuous flexible substrates.

14. a kind of product comprising substrate described in any one of claim 7 to 13, and include: transparent polymeric support With the dry bottom paint layer at least one support surface for being arranged in the transparent supporting body, and comprising have less than 15 μ The patterning materials of the line of the average line width of m, the patterning materials are directly arranged on the dry bottom paint layer.

15. product described in claim 14, wherein the patterning materials include selected from gold, silver, copper, palladium, platinum, nickel and its preceding The conductive metal of body or its precursor.

16. product described in claims 14 or 15, wherein the patterning materials include free-radical curable composition, can The mixture of both compositions of composition and theobromine catalytic curing of the cured composition of acid catalysis or free-radical curable.

17. product described in claims 14 or 15, wherein the patterning materials include to be dispersed in photocuring or heat cure group Close the metallic particles in object.

18. product described in claims 14 or 15, wherein the patterning materials include to be dispersed in photocuring or heat cure group The particle of gold, silver, copper, palladium or platinum in conjunction object, the photocuring or heat-curing composition are derived from the group of free-radical curable Close both object and the composition of theobromine catalytic curing.

19. a kind of method is used to provide product described in any one of claim 14 to 18, which comprises

Substrate described in any one of claim 7 to 13 is provided, and

20. method described in claim 19, wherein at least part of the pattern of the patterning materials includes to have to be less than The line of 15 μm of average line width.

21. method described in claim 19 or 20, wherein described at least part of the pattern of the patterning materials exists In the touch screen zone for the product primed.

22. method described in claim 19 or 20 comprising:

It is contacted by the dry bottom paint layer with the direct of the letterpress component for carrying the patterning materials, directly described dry The patterning materials are provided on prime coat.

23. method described in claim 19 or 20, wherein the patterning materials include conductive metal or its precursor.

24. method described in claim 19 or 20, further include:

The photocurable or heat-setting composition being solidificated in the patterning materials.

25. method described in claim 19 or 20, wherein the patterning materials include metallic particles, and the method is also Include:

26. method described in claim 19 or 20 comprising:

The substrate is provided as continuous coiled material,

There is provided on the dry bottom paint layer directly in one or more unitary parts of the continuous coiled material respectively can light it is solid Change or one or more independent patterns of heat-setting composition are used as precursor conductive material, the photocurable or can be hot Cured composition includes metal seeds particle,

It is each in one or more independent patterns for converting the photocurable or heat-setting composition by solidifying It is a, it is one or more to form one or more individual cured patterns in one or more unitary part Each of multiple individual cured patterns include the metal seeds particle, and

The metal seeds particle of the electroless plating in each of one or more individually cured pattern, to provide One or more individual conductive patterns.

27. a kind of product, the method as described in any one of claim 19 to 26 is obtained, wherein the product includes conduction At least one pattern of material, wherein at least part of the pattern of the conductive material includes to have being averaged less than 15 μm The conductor wire of line width, the part of the pattern of the conductive material are directly arranged at the described dry of the substrate On prime coat.

28. a kind of method is used to provide multiple products, which comprises

It provides if any one of claim 7 to 13 substrate claimed is as continuous coiled material,

The dry bottom paint layer in first part by making the continuous coiled material directly contacts the carrying photocurable or can The flexographic plate print-member of the composition of heat cure, on the dry bottom paint layer in the first part of the continuous coiled material Directly formed the first curable pattern, the described first curable pattern include the photocurable containing seed metal particle or Heat-setting composition,

Make include the first part of the described first curable pattern the continuous coiled material advance with close to solidification It stands and solidifies the described first curable pattern, thus form the first cured pattern in the first part, described first is solid Changing pattern includes the seed metal particle,

By directly being contacted with the flexographic plate print-member for carrying identical or different photocurable or heat-setting composition, The second curable pattern is directly formed on the dry bottom paint layer in the second part of the continuous coiled material, described second can Cured pattern includes the identical or different photocurable comprising identical or different seed metal particle or heat-setting group Object is closed,

Make include the second part of the described second curable pattern the continuous coiled material advance with close to solidification It stands and solidifies the described second curable pattern, thus form the second cured pattern on the second part, described second is solid Changing pattern includes identical or different seed metal particle,

Optionally, using identical or different curable or heat-setting composition and identical or different flexible version printing structure Part respectively partially implements the formation and advance feature one or more times for the other of the continuous coiled material, described In addition other cured pattern is formed on respective part, and

Roll comprising first, second and optional other cured pattern the continuous coiled material to provide multiple precursor articles Volume.

29. method described in claim 28, wherein identical seed metal particle is present in the multiple cured pattern In each, the seed metal particle is gold particle, Argent grain, copper particle, palladium particle or platinum grain.

30. method described in claim 28 or 29, wherein making in each formation feature for each curable pattern With identical photocurable or heat-setting composition.

31. method described in claim 28 or 29, wherein making in each formation feature for each curable pattern With identical photo curable composition, the photo curable composition includes that composition, the theobromine of free-radical curable are urged Change both composition and the composition of theobromine catalytic curing of cured composition or free-radical curable.

32. the equipment of a kind of product comprising any one of claim 14 to 18 or the product of claim 27, it includes straight One or more conductive metal patterns being arranged on the dry bottom paint layer are connect,

Wherein each of one or more conductive metal pattern includes touch area, and the touch area includes tool There is the conductor wire of the average line width less than 15 μm.

33. equipment described in claim 32 is touch panel device.