CN106459650A

CN106459650A - Latex primer composition and latex primed substrates

Info

Publication number: CN106459650A
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: 2017-02-22
Anticipated expiration: 2035-06-11
Also published as: TWI665270B; TW201615772A; CN106459650B; WO2015199988A1

Abstract

A first polymer latex and second polymer latex can be mixed to form a dried primer layer on a substrate to adhere patterned materials having fine lines. The first polymer latex comprises a first polymer and a first surfactant such that a dried coating of the first polymer latex has a surface polarity of at least 50%. The second polymer latex comprises a second polymer and a second surfactant such that a dried coating of the second polymer latex has a surface polarity of less than or equal to 27%. Moreover, a dried coating of the mixture has a surface polarity of at least 15% and up to and including 50%. Primed substrates are useful for preparing electrically- conductive articles having electrically-conductive fine lines directly on a dried primer layer by applying a patterned material to a substrate. Such articles can be used as touch screen displays in various electronic devices.

Description

Latex primer compositionss and the substrate of latex proofing priming paint

Invention field

The present invention relates to coating composition and the base with the coating composition being coated on supporter (such as transparent supporting body) Bottom.This coating composition is adhered in substrate with will be patterned into material as prime coat, and comprises two kinds of different polymer The mixture of latex, every kind of polymer emulsion contains polymer beads and surfactant.The patterned article of gained can be used for Various purposes, and when pattern is conductive material, this patterned article can be used as leading in the such as equipment containing touch screen Electrolemma.

Background of invention

(primed) substrate primed is used in many industry, so that preferably bonding overlying strata, pattern or word.Term " priming " typically refers to the coating using usually dry polymeric coating, under it is for having required smoothness and forming Layer substrate and both there is good bonding to overlying material.

For example, patternable materials can be used in various industry to provide conductive or non-conductive line, solid area, literary composition Word, grid, circuit or other shapes of pattern.Letterpress component can be used for applying these patterns to various substrates, and The pattern of gained can be after further treatment to provide for the electric conductivity in electronics industry, display industry or energy industry or other Property.For example, can design on a transparent substrate and prepare conductive pattern for various display devices, such as touch screen.

Recent decades, polyester and other polymeric film as the useful substrate being applied with coating or pattern are thereon Well-known.Such polymeric film (or product) due to its intensity, flexible and potential transparency and be generally more suitable for In various purposes, including print-member, image-forming component and display device.However, attempting the painting in polymeric substrates and overlying During producing between layer or pattern and keeping strong adhesive power, according to material to be applied it will usually the tired of reality occurs Difficulty, because polymeric substrates are typically very hydrophobic, and the coating of overlying or pattern may be less hydrophobic in nature.Or Person, polymeric substrates are less hydrophobic than the coating of overlying or pattern.

Many problems result from the bonding of the difference in various industry.Touch sensitivity panel or display needs in predetermined figure The very thin line (width is approximately less than 20 μm) of case, to realize desired electric conductivity, to have high visual clarity (or high comprehensive simultaneously Close absorbance (integrated transmittance)).

Unrealized or holding during the fine rule in the conductive material that manufacture and use include conducting metal or metal precursor It is impossible to realize required electric conductivity or electric capacity during enough bondings.U.S. Patent Application Publication 2007/0170403 (Conaghan Et al.) describe these adhesion problem and by substrate using various binding agents or prime coat or by adhesion promoting compound It is incorporated to some of the recommendations solution in the conduction " ink " (compositionss) of applying.

For example, using the polymeric primer of the stayed surface being applied to polymeric film, flexibility and transparent substrates can be improved Bond property and various surface nature.Expect preferably to bond the material applying later, particularly when those materials are with uniform Mode when applying.The example of primer layer composition for the purpose is described in such as United States Patent (USP) 6,162,597 (Bauer Et al.) and 6,165,699 (Bauer et al.) in.

Additionally, U.S. Patent Application Publication 2013/0319275 (Fohrenkamm et al.) describes a kind of passing through substrate It is designed as that there are the means that unique polar relationship to improve flexographic plate printed circuit cable with printing-ink.

Using the function that sensor is provided for deposition conductive pattern " additional process " in flexible and transparent substrates Touch panel sensor is produced with volume to volume production method and other transparent conductive article has become the theme of latest developments in industry. Particularly importantly produce and there is fitting in desired electric property and the visible part (touch area) of touch panel sensor When optical property (absorbance) both touch panel sensors ability.In order to obtain necessary conductive and optical property, non- Often the average live width of the conductor wire in expectation conductive grid is less than 10 μm.

Flexible used in such method should be optically transparent (high synthesis absorbance) and colourless with transparent substrates And show low haze.Flexographic plate using additional process such as conductive material or seed metal (seed metal) compositionss It is consistent with the yardstick of minutiae (for example, fine rule) to be applied that printing applying conductive pattern needs flexibility and transparent substrates to have Suitable surface energy and roughness.Paying sizable effort in the electronics industry to realize these necessary features.

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

It is that such as touch panel sensor shows with other optics that ongoing effort is intended to find that a kind of cost-effective mode is come The various electronic equipments of device provide the flexibility with required surface nature and optical property and transparent substrates.The special pin of these effort To manufacturing in high efficiency volume to volume manufacture operation and using such substrate, described in described operation, substrate is through various chemicals And mechanically actuated.

Especially, following flexible and transparent substrates are needed in the art：Its display low haze, low color (low Color) and surface uniformity, and therefore more suitable for bonding minutiae such as fine rule, word or little shape, and especially It is suitable for the fine rule of conduction.It is also expected to flexible and transparent substrates, it shows strong bonding to " printing " pattern, and described pattern is for example By flexible version printing intrinsic conduction or can those becoming the conductive compositionss containing metal and applying treated further.

Content of the invention

Present invention coating composition solves the various problems running in this area, and described coating composition comprises first Polymer emulsion and the mixture of second polymer latex,

Wherein said first polymer latex comprises first polymer and first surface activating agent so that described first polymer glue The dry coating of breast has at least 50% surface polarity, and

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

The dry coating of the mixture of wherein said first polymer latex and described second polymer latex have at least 15% and At most and include 50% surface polarity.

Additionally, the invention provides comprising supporter and be arranged in dry at least one stayed surface of described supporter The substrate of prime coat, described dry bottom enamelled coating comprises the mixture of following material：

First polymer latex, it comprises first polymer and first surface activating agent so that described first polymer latex Dry coating has at least 50% surface polarity, and

Second polymer latex, it comprises second polymer and the second surface activating agent different from first surface activating agent, makes The dry coating of second polymer latex has surface polarity less than or equal to 27%,

Wherein said dry bottom enamelled coating have at least 15% and at most and include 50% surface polarity.

In the particular of the present invention, substrate comprises transparent polyester supporter and is directly arranged at Dry bottom enamelled coating at least one stayed surface of this transparent polyester supporter,

Wherein：

I () described substrate has at least 88% comprehensive absorbance；

(ii) described dry bottom enamelled coating has at least 0.05 μm and at most and include 0.2 μm of average thickness, and comprises following thing The mixture of matter：

First polymer latex, it comprises first polymer and first surface activating agent, is wherein based on first polymer gross weight, Described first polymer comprise at least 75 weight % and at most and include 90 weight % derived from (methyl) acrylic acid shrink sweet The repetitives of grease and at least 10 weight % and at most and include 25 weight % derived from (methyl) n-butyl acrylate Repetitives, this first polymer has at least 20 DEG C and at most and include 75 DEG C of glass transition temperature, and described first Surfactant is alpha-olefin (C₁₄-C₁₆) sodium sulfonate；

Second polymer latex, it comprises second polymer and the second surface activating agent different from first surface activating agent, its In be based on second polymer gross weight, described second polymer comprises at least 75 weight % and at most and include spreading out of 90 weight % It is conigenous the repetitives of (methyl) glycidyl acrylate and at least 10 weight % and at most and include the derivative of 25 weight % From the repetitives of (methyl) n-butyl acrylate, this second polymer has at least 25 DEG C and at most and include 75 DEG C of glass Change transition temperature, and described second surface activating agent is the ammonium salt of sulphation polyethoxy nonyl phenol；

(iii) described dry bottom enamelled coating have at least 28% and at most and include 50% surface polarity；

(iv) weight of described first polymer latex and described second polymer latex is than for 1:1 and to and include 2.5:1；

V () is based on dry bottom paint gross weight, described first surface activating agent with least 1 weight % and at most and includes 3 weight % Amount is present in described dry bottom enamelled coating；

(vi) it is based on total dry bottom enamelled coating, described second surface activating agent with least 0.35 weight % and at most and includes 1.1 weights The amount of amount % is present in described dry bottom enamelled coating；With

(vii) it is based on dry bottom enamelled coating gross weight, the total amount of the first and second surfactants in described dry bottom enamelled coating is less than 3.35 weight %.

Various embodiments of the present invention provide many advantages.Most of all, the compositionss being provided by the present invention Show for applying in the pattern containing fine-feature and bonding the surface needed for various compositionss with the substrate primed Characteristic, described fine-feature including but not limited to has the line less than 15 μm or being more likely less than 15 μm of average live width.For example, Such pattern can be provided using the photocurable containing metal seeds granule or heat-setting compositionss, and described pattern Electroless plating can suitably be carried out, to provide the conductive pattern with desired fine-feature.Described substrate and the system containing them Product show low haze, low color, required surface uniformity (appearance of coat) and high synthesis absorbance (at least 88%).These Advantage passes through the bottom with comprising the mixture with following properties and the first polymer latex forming and second polymer latex Coating compositions are realized in suitable support body material (such as transparent support material) upper " priming ".

Brief description

Fig. 1 is the flexographic printing system that can be used for carrying out volume to volume printing (or imaging) on the both sides of the substrate of the present invention Schematic side elevation, wherein using representational Photocurable composition (patterning materials) and the method for the present invention.

Fig. 2 is the device (equipment) comprising to have the touch screen of touch sensor that can prepare (printing) using the present invention High-level system diagram.

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

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

Fig. 5 is the conductive metal pattern on second (relative) side of 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 embodiments can Can be desirable, but disclosed embodiment is not necessarily to be construed as or is additionally considered to being that restriction is as claimed below The scope of the present invention.In addition, it will be appreciated by those skilled in the art that disclosure below has widely should than be expressly recited With.

Definition

Unless otherwise noted, otherwise if this paper is in order to define primer coating compositions, dry bottom enamelled coating, photocurable and thermal curable The singulative " one " (" a ", " an ") of various components of compositionss and other composition characteristic as herein described and " described " (" the ") was intended to including one of described component or more kinds of (that is, including plural thing).

Each term not clearly defined in this application should be understood generally to accept with those skilled in the art Implication.If the construction of a term will make it hereinafter meaningless thereon or substantially free of meaning, the definition of this term Should be available from normal dictionary.

In addition unless clearly it is further noted that the use of numerical value in otherwise herein specified various scopes is recognized For being approximation, as there being word " about " before the minima in described scope and maximum.By this way, described model Enclose slightly changing of above and below to can be used for realizing the result essentially identical with the value in described scope.Additionally, these scopes Disclosure be intended to the successive range as each value including between minima and maximum.

As it is used herein, unless otherwise noted, otherwise molecular weight is weight average molecular weight, and it can use known step And measuring apparatus, if this value is not from known in the literature words.

Unless otherwise noted, term " photocurable or heat-setting compositionss " refers to Chemical composition that, and it can be used for In the various methods putting into practice the present invention and the product that may be provided in the present invention.Such composition has can be consolidated under certain conditions The necessary chemicals of change, polymerization or crosslinking.

Term " solidification " and " polymerization " are used herein to mean that in the presence of suitable catalyst or initiator, for example Very big molecule is formed with reference to substantial amounts of compared with small molecule such as monomer or oligomer by covalent bonding, i.e. macromole or polymerization Thing.Solidify or polymerization can form linear macromolecule or commonly referred to cross linked polymer includes the three-dimensional macromolecular of branched chain materials, or Person can form line style and crosslinked (or side chain) material simultaneously.The a type of polymerization that can carry out in the practice of the invention It is acid catalysiss (cation) polymerization.Radical polymerization also can be carried out in the practice of the invention.Or, in some embodiments In, acid catalyzed polymerisation and radical polymerization can be carried out simultaneously.

Term " photocurable " and " curable " be used for definition material (such as epoxy material), it is in suitable light trigger When using suitable radiation exposure in the presence of compositionss, for example with radiation as ultraviolet (UV), visible or infra-red radiation irradiate when will Polymerization.

The average dry thickness of layer as herein described can be for for example using ultramicroscope or optical microscope in dried layer not The meansigma methodss of the two or more times independent measurement carrying out with position.In certain embodiments, obtain and individually survey more than 2 times Amount is probably desirable.

Similarly, the average dry thickness of line as herein described, grid lines or other pattern characteristics or width can be for for example making The meansigma methodss of the two or more times independent measurement being carried out with ultramicroscope.

Term " polymerizable epoxy material " is intended to including having one or more oxirane rings that can experience polymerization Any material or compound.This term includes the monomer containing epoxy, the oligomer containing epoxy and containing epoxy cross-linking agent.This art The singulative of language is intended to the plural form including this 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.After light excites, described Electron donor photosensitizer leads to the one-electron reduction of salt.

Term " light trigger " means that resolving into free radical or Chemical moiety when exposed to light reacts further to cause Any compound (chemical compound).In some embodiments, described light trigger is " salt " or " change Compound " or other photo-acid agent, it can accept the electronics from excited electron donor photosensitizer, and this is that one kind leads to salt broken Split to provide the process of Bu Langsi Taide acid (Br nsted acid) causing epoxy material polymerization.In other embodiments, Described light trigger resolves into free radical, and it proceeds (proceed) to cause solidification, polymerization or the crosslinking of vinyl.

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

Term " visible ray " is herein used for finger and has extremely and at most and including the ripple of 750 nanometers (nm) more than 400 nm Long (for example, λ_max) electromagnetic radiation.

Term " UV light " is herein used for referring to having at least 150 nm and at most and include the wavelength of 400 nm (for example, λ_max) electromagnetic radiation.

Term " near-infrared " and " infrared " herein have at least 750 nm and Geng Gao for finger, and typically at least 750 nm and at most and include wavelength (for example, the λ of 1400 nm_max) electromagnetic radiation.

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

Or, comprehensive absorbance can be with transparent article, supporter or the base not covered by conductive pattern in touch area The calculating percentage ratio in bottom region is associated.

Term " average live width " with regard to various patterns as herein described or patterning materials refers to use art technology Personnel by the suitable e measurement technology knowing and equipment by identical or different line diverse location line two or more times list The size that solely measurement determines.In certain embodiments, measurement such more than 2 times is probably desirable.

The product referring in conductive surface, " touch area " partly, in film or other structures there are 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 " BUS region ".

It is defined described in surface polarity following article embodiment.

Purposes

Coating composition as herein described, substrate, product and method can be used for various purposes, wherein need there is described property Substrate is used for applying material further or forms pattern.For example, (priming paint) as herein described coating composition, substrate and product are special Not can be used for providing the conductive metal pattern (for example using electroless plating step) with fine-feature, it can be coupled to various equipment In, other display devices that described equipment includes but is not limited to touch screen or can be used for numerous industry and commercial product.

For example, touch screen technology can comprise different touch sensor configurations, including capacitive touch sensors and resistance Formula touch sensor.If resistive touch sensor comprises dried layer, these layer is facing with each other, has gap between adjacent layers, It can be kept by the sept (spacer) being formed during manufacture.If resistive touch screen panel can comprise dried layer, including The two thin metal conducting layers that can be separated by the gap that sept is formed.When the object of such as contact pilotage, palm or finger tip is downward When being pressed against the point on the outer surface of panel, two metal level contacts, and form the connection leading to curent change.This touch event It is sent to controller for processing further.

Capacitive touch sensors can be used for thering is the electronic equipment touching sensivity feature.These electronic equipments may include But it is not limited to may be adapted to display image include word, figure, video image, film, rest image and PowerPoint (presentation) TV, monitor and projector.The vision facilitiess that can be used for these display devices may include negative electrode and penetrate Spool (CRT), projector, plate of flat liquid crystal display (LCD), LED information display system, OLED system, plasma system, electroluminescent show Show device (ELD) and Field Emission Display (FED).For example, the present invention can be used for preparing capacitive touch sensors, and it can be combined To in the electronic equipment have touch sensivity feature to provide computing device, computer display, portable electronic device Including electronic reader, mobile phone and other communication or digital storage equipment.

Manufactured in high volume volume to volume manufacture process (wherein can produce 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 compositionss can be with Letterpress component such as flexographic printing plates are used together, to form multiple high-resolution conductive patterns by predetermined 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 Individual predetermined pattern can print in a support-side of substrate, and different predetermined patterns can print the relative support side in substrate On.Then such as example photocurable or the print of heat-setting compositionss can be processed further using electroless metal coating technology Map brushing case, to provide the conductive metal pattern containing fine-feature.

Polymer emulsion

Provide the compositionss of the uniqueness for the present invention, said composition can be using for providing any suitable of advantage of the present invention Means deposit from the teeth outwards.This compositionss are generally also referred to as " coating composition ", " primer layer composition " or " priming paint group Compound ".This coating composition comprises the mixture of at least first polymer latex and at least one second polymer latex.Pass through Using modifier " first " and " second ", it is not intended to infer a kind of polymer emulsion (or polymer) ratio in any given performance Another kind of polymer emulsion (or polymer) is more preferable, and described modifier is only used for distinguishing two kinds of different polymer emulsions combinations Thing.If desired, polymer emulsion in addition may be present in mixture, as long as obtaining required property (described herein).

First and second polymer：

Described first and second polymer emulsions comprise first polymer and second polymer respectively.When in latex form or polymerization During thing dispersion, described first and second polymer are generally to be formed in micelle using known emulsion polymerization technology Presented in granule.Although the first and second polymer each can be separated, they are in the present invention with first and second The mixture of latex uses, and therefore, separate may make it harder to in coating using them.

At least one in first and second polymer as herein described comprises polyvinyl, and it comprises at least partly Derived from (methyl) glycidyl acrylate (represent glycidyl acrylate, glycidyl methacrylate or both) Repetitives, and in most of embodiments, described first and second polymer are each at least partly derived from (first Base) glycidyl acrylate.Additionally, at least one in described first polymer and second polymer is crosslinkable, and And for example can carry out crosslinking during the drying of substrate or various heat treatment for example after being applied on suitable supporter. Those skilled in the art will know how by the wise selection in the design of polymer repeat unit and reactive group Crosslinking ability is provided in given polymer.

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

Useful especially first polymer is at least part of ethylene linkage derived from one or more of glycidyl functional The polyvinyl of formula unsaturated polymerizable monomer, such as glycidyl acrylate and glycidyl methacrylate. Therefore, described first polymer can be the homopolymer derived from (methyl) glycidyl acrylate, but more likely it is derivative Copolymer from (methyl) glycidyl acrylate and one or more of other ethylenic unsaturated polymerizable monomer.Term " glycidyl " refers to comprise to connect to the alkyl (straight or branched also being substituted further with 1 to 4 carbon atom Alkyl), the group of the oxirane ring of such as methyl, ethyl, isopropyl and the tert-butyl group.

For example, the gross weight based on described first polymer, this first polymer can comprise at least 75 weight % and at most And include 100 weight % or at least 75 weight % and at most and include 90 weight % amount derived from (methyl) acrylic acid contracting The repetitives of water glyceride.Therefore, especially desirable first polymer is derived from (methyl) glycidyl acrylate and one Kind or more kinds of other ethylenic unsaturated polymerizable monomer (comonomer), its will during emulsion polymerization substantially with (first Base) glycidyl acrylate monomer copolymerization, rather than react with glycidyl, and it will promote all ethylenic insatiable hungers With polymerisable monomer in the internal emulsion polymerization of reaction dispersion.Suitable vinyl comonomer includes but is not limited to, acrylic acid Arrcostab and alkyl methacrylate, wherein ester alkyl have 1 to 4 (four) individual carbon atom；Other acrylic acid alkyls replacing 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 Derivant such as α-methyl styrene；Butadiene；Isoprene；Acrylonitrile；Methacrylonitrile；To hold with those skilled in the art Easily obviously other.If desired, the mixture of comonomer can be used.Those skilled in the art will enable real with routine Test the appropriate amount to determine the various comonomers by providing required film-forming quality as herein described and surface polarity value.

Described first polymer especially by make one or more of (methyl) glycidyl acrylate with a kind of or Designing, wherein ester alkyl has at least 2 carbon atoms to more kinds of (methyl) alkyl acrylate copolymer, 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 by the other being readily apparent.Particularly useful comonomer is wherein ester alkane Base just has (methyl) alkyl acrylate of at least 4 carbon atoms, including but not limited to n-butyl acrylate, methacrylic acid Butyl ester, the just own ester of acrylic acid, the just own ester of methacrylic acid and cyclohexyl methacrylate.

The second polymer latex that can be used for the present invention comprises one or more of second polymers and one or more of Second surface activating agent (described below) so that the dry coating of described second polymer latex have less than or equal to 28% or little In or be equal to 27% surface polarity.In most of embodiments, described second polymer latex is substantially required by two kinds Group is grouped into：One or more of second polymers and one or more of second surface activating agent.

Useful especially second polymer is at least part of ethylene linkage derived from one or more of glycidyl functional 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, described second polymer can be for spreading out Be conigenous the homopolymer of (methyl) glycidyl acrylate, or derived from (methyl) glycidyl acrylate and one or more Plant the copolymer of other ethylenic unsaturated polymerizable monomers.Term " glycidyl " is as defined above.

Therefore, the gross weight based on described second polymer, this second polymer can comprise at least 75 weight % and at most And include 100 weight % or at least 75 weight % and at most and include 90 weight % amount derived from (methyl) acrylic acid contracting The repetitives of water glyceride.Therefore, especially desirable second polymer is derived from (methyl) glycidyl acrylate and one Kind or more kinds of other ethylenic unsaturated polymerizable monomer (comonomer), its will during emulsion polymerization substantially with (first Base) glycidyl acrylate monomer copolymerization, rather than react with glycidyl, and it will promote all ethylenic insatiable hungers With polymerisable monomer in the internal emulsion polymerization of reaction dispersion.Suitable vinyl comonomer includes but is not limited to, acrylic acid Arrcostab and alkyl methacrylate, wherein ester alkyl have 1 to 4 (four) individual carbon atom；Other acrylic acid alkyls replacing 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 Thing such as α-methyl styrene；Butadiene；Isoprene；Acrylonitrile；Methacrylonitrile；To easily show with those skilled in the art and The other being clear to.If desired, the mixture of comonomer can be used.As first polymer, those skilled in the art are by energy Enough determined using normal experiment and will provide herein for the required film-forming quality described in second polymer latex and surface polarity The appropriate amount of the various comonomers of value.

Described second polymer especially by make one or more of (methyl) glycidyl acrylate with a kind of or Designing, wherein ester alkyl has at least more kinds of comonomers for example one or more of (methyl) alkyl acrylate copolymer 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 by the other being readily apparent.Special Not useful comonomer is that wherein ester alkyl has at least 4 carbon atom (methyl) alkyl acrylates, 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.

Particularly pointing out in the embodiment of the present invention as described below although described first and second polymer can be difference Material, but described first and second polymer have identical composition the (repetitives of identical glycidyl functional With the repetitives from comonomer) or have similar or identical molecular weight be probably useful.

Although the molecular weight of described first and second polymer can not always be accurately determined, because such polymer can have There is the bridged linkage obtaining from glycidyl, but generally each polymer independently has at least 10,000 or more likely at least 50,000 molecular weight.

Additionally, described first and second polymer each can independently have at least 25 DEG C or more typically at least 40 DEG C, And at most and include 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 and described second polymer latex in described first polymer latex The amount of thing may be the same or different.In most of embodiments, based on total first polymer latex solid, described first polymerization The amount of the first polymer in thing latex is at least 10 weight % and at most and include 40 weight %；And it is poly- based on total second Compound latex solid, the amount of the second polymer in described second polymer latex is at least 20 weight % and at most and include 30 Weight %.

First and second surfactants：

Described first polymer latex comprises one or more of first surface activating agents, and it is individually mersolates, its Described in alkyl there are at least 10 carbon atoms.For example, described first surface activating agent can be alpha-olefin (C₁₄-C₁₆) sodium sulfonate, Or described first surface activating agent can be by R-CH₂-CH=CH-CH₂-S(=O)₂O^-Na⁺The compound representing, wherein R is C₁₀、 C₁₁Or C₁₂Alkyl, or there is the mixture of such compound of different R group, described R group is C₁₀To C₁₂Any in alkyl Kind.A kind of useful commodity containing first surface activating agent are Rhodacal^®A246L (for example available from Rhodia).If needing Will, the mixture of such first surface activating agent can be used.

Adjust the total amount of one of described first polymer latex or more kinds of first surface activating agent so that when by the The mixture of one polymer emulsion and second polymer latex (described below) is applied in substrate and when being dried (as priming paint Layer), it is based on dry bottom enamelled coating gross weight extremely in the total amount of one of this dry bottom enamelled coating or more kinds of first surface activating agent Few 1 weight % and at most and include 3 weight % or typically at least 1.6 weight % and at most and include 2.8 weight %.Consider The mixed weight ratio of first polymer latex and second polymer latex, those skilled in the art will know how many first surfaces Activating agent be incorporated to for prepare first polymer latex emulsion in so that the amount of needs is present in dry bottom enamelled coating.

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

Adjust the total amount of one of described second polymer latex or more kinds of second surface activating agent so that when by the The mixture of one polymer emulsion and second polymer latex (described below) is applied in substrate and when being dried (as priming paint Layer), it is at least 0.35 weight % and at most simultaneously in the total amount of one of this dry bottom enamelled coating or more kinds of second surface activating agent Including 1.1 weight % or typically at least 0.45 weight % and at most and include 0.9 weight %, based on dry bottom enamelled coating gross weight.Examine 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 emulsion to prepare second polymer latex so that the amount needing is present in dry bottom enamelled coating.

Described first polymer and described second polymer are dispersed in usually as fine particle and comprise first and respectively In the independent aqueous dispersion of dimerization compound latex.When these polymer emulsions are mixed according to the present invention, can be with any suitable Mode they are applied to suitable substrate as coating formulation.Some water in every kind of polymer emulsion can use water miscibility Organic solvent (such as methanol or acetone) is replaced.

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

Described first polymer latex and described second polymer latex each can be used emulsion polymerization to prepare or conduct The aqueous dispersion of grain emulsion polymer (polymerizate) obtains.The condition including and the emulsion polymerization of reactant Step is known in the art, and representational details provides in United States Patent (USP) 6,162,597 (5-7 row).Above-mentioned One and second surface activating agent be respectively included in described first polymer latex and the preparation of described second polymer latex, example As at least one anion surfactant.However, the preparation of described first and second polymer emulsions is not limited to only divide Not using described first and second surfactants.Hereafter provide representational preparation method with embodiment.

Coating composition

Described first polymer latex and second polymer latex each can independently comprise one or more of water miscibilities and have Machine solvent, its amount is at most based on latex gross weight and includes 10 weight %；One or more of surfactants；A kind of or more Multiple inorganic flatting agents (as long as mist degree does not dramatically increase and transparency does not significantly reduce)；Antistatic additive；In order to adjust pH's Acid or alkali；And buffer agent.

The one or more of cross-linking agent that it may also be desirable to be incorporated to known quantity (are alternatively referred to as " hardening in the art Agent "), with the friendship promoting polymer latex particle after polymer latex particle is put on supporter drying further Connection.Useful cross-linking agent includes but is not limited to, and aldehyde-containing compounds such as formaldehyde and Biformyl, the compound containing aziridine are for example Tetramethylene -1,4- double (ethylidene-urea), ester such as the trimethylene double A sulphonate, active vinyl-compound example of methanesulfonic acid As for example double in double acryloyl group ureas (bisacroyl urea) and methylene divinyl sulfonic acid, the compound containing glycidyl Phenol glycidyl ether, and isocyanates.

It is desirable, however, that first polymer latex and second polymer latex all do not contain substantial amounts of coalescing aid, For example resorcinol and for this purpose United States Patent (USP) 6,162,597 (above-mentioned) the 6th row, the 53rd row arranges in the 3rd row to the 7th and retouches The other compounds stated.It is especially desired to the first and second polymer emulsions and all comprise the gross weight based on dry bottom enamelled coating (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 compositionss as herein described, the dry bottom lacquer coat of described compositionss have to Few 28% and at most and include 50% surface polarity.Additionally, such composition can have the following properties that：

Based on first polymer gross weight, described first polymer comprises at least 75 weight % and at most and include 90 weight % Repetitives derived from (methyl) glycidyl acrylate and at least 10 weight % and at most and include spreading out of 25 weight % It is conigenous the repetitives of (methyl) n-butyl acrylate, this first polymer has at least 50 DEG C and at most and include 70 DEG C of glass Glass transition temperature, and described first surface activating agent is alpha-olefin (C₁₄-C₁₆) sodium sulfonate；

Based on second polymer gross weight, described second polymer comprises at least 75 weight % and at most and include 90 weight % Repetitives derived from (methyl) glycidyl acrylate and at least 10 weight % and at most and include spreading out of 25 weight % It is conigenous the repetitives of (methyl) n-butyl acrylate, this second polymer has at least 50 DEG C and at most and include 70 DEG C of glass Glass transition temperature, and described second surface activating agent is the ammonium salt of sulphation polyethoxy nonyl phenol；

The dry coating of described compositionss have at least 28% and at most and include 50% surface polarity；

The weight of described first polymer latex and described second polymer latex is than for 1 in the mixture:1 and to and include 2.5:1；

Based on dry coating gross weight, described first surface activating agent with least 1 weight % and at most and includes the amount of 3 weight % and deposits It is in the dry coating of described mixture；

Based on dry coating gross weight, described second surface activating agent with least 0.35 weight % and at most and includes 1.1 weight % Amount be present in the dry coating of described mixture；With

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

Substrate

In an appropriate manner above-mentioned composition (" priming paint " compositionss) can be applied to any suitable supporter, for further Process or process for given industrial purpose, to form the substrate of the present invention.Gained substrate can for opaque, transparent or Translucent, or it has opaque section and the combination of transparent part.

For example, dry bottom enamelled coating can be formed on any suitable support body material, as long as it does not suppress setting of resulting product Meter purpose.For example, supporter can be (untreated or for example use tetrafluoro carbon by including but not limited to polymeric film, metal, glass (tetrafluorocarbon) plasma, hydrophobicity fluorine or siloxanes scold water material process), silicon chip or potsherd, fabric, The material of paper and combinations thereof (laminated material of for example various films, or the laminated material of paper and film) is formed.Gained substrate can be firm Property or flexibility.Useful especially support body material be polyester, Merlon, polystyrene, polyimides, polyamide and its Composite.

The supporter using in the substrate can have any required average dry thickness, it typically is at least 50 μm and at most And include 3,000 μm.Used in the present invention, most of continuous coiled materials (continuous web) will have average dry thickness and (do Prime coat and supporter), it depending on the final use of the product being formed by it, for example, is incorporated into various products or optics In equipment or display device.For example, substrate dry thickness (including dry bottom enamelled coating, supporter and any optional layer or coating) can be At least 50 μm and at most and include 250 μm, and particularly with polymeric film for, described substrate dry thickness can be at least 80 μ M and at most and include 175 μm or at least 100 μm and at most and include 125 μm.

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

Before or after one or two support-side of supporter forms dry bottom enamelled coating, can process in an appropriate manner Support body material (if if special polymeric material), to improve the bonding of dry bottom coating compositions, to reduce substrate below The contraction of the manufacture, coating or other during the operation of description.Often, for example, it is desirable to before or after forming dry bottom enamelled coating, In the upper stretched polyester of one or two in-plane (vertical and horizontal) or other polymer supports.However, in most of realities Apply in scheme, after dry bottom enamelled coating is formed in one or two support-side of supporter, using known step and condition Carry out horizontal and vertical stretching.After these stretching step, it is being greater than 100 DEG C and at most and include 150 DEG C of temperature Continuing down the heat treatment (or hot wire-CVD) of a few minutes can be provided enough to coalesce the first and second polymer beads in dry bottom enamelled coating Heat energy, to form relatively uniform dry bottom enamelled coating film, and one of crosslinked described first and second polymer or two kinds (if They have necessary crosslinkable groups).

Other useful supporters process and include Corona discharge Treatment, flame treatment and various cleaning and washing step.

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

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

As described above, useful especially substrate comprises can directly arrange thereon by doing that compositions described herein forms The supporter (the one or more of materials described in aforementioned paragraphs form) of prime coat.Described dry bottom enamelled coating comprises as above fixed The first polymer latex of justice and the mixture (for example, the mixture of coalescence) of second polymer latex.Additionally, described dry bottom paint Layer have at least 15% and at most and include 50% or at least 22% and at most and include 45% surface polarity.Especially desirable , supporter is by one or more of the transparent polymer materials such as mixture of polyester, polyester or polyester and another polymerization The mixture composition of thing, and the substrate of gained can have at least 88% and more likely at least 93% comprehensive absorbance.For example, Useful especially transparent support material can be made up of poly- (ethylene glycol terephthalate) and poly- ((ethylene naphthalate)).

Although in most of embodiments, described dry bottom enamelled coating is directly arranged at and (has implied the absence of on supporter Meaning forms or provides intermediate layer between dry bottom enamelled coating and supporter), but be likely to this supporter can be coated with one kind or More kinds of different priming paint polymer or the mixture of polymer, with formed one or more " intermediate basecoat layer " (using Usual known for this purpose material in photographic art), and and then the dry bottom enamelled coating according to the present invention can be applied directly to institute State one or more intermediate basecoat layer.Such intermediate basecoat layer may be formed in one or two support-side of this supporter, With the intermediate basecoat layer that then be can be formed directly according to the dry bottom enamelled coating of the present invention in one or two support-side of supporter On.

Therefore, described dry bottom enamelled coating 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 enamelled coating can be directly arranged at two supports of supporter On side (that is, the first support-side and the second relative support side)." support-side " refers to the planar side of supporter, rather than supporter material The edge of material.For example, be may be arranged in a support-side of supporter according to the dry bottom coating compositions of the present invention, and other (non- The present invention's) polymer (or priming paint) layer may be arranged on the relative support side of supporter.

The mixture (compositionss) of above-mentioned latex can be applied by using any suitable mode at least the one of supporter Dry bottom enamelled coating is formed on individual support-side, for example dip-coating, roller coat, hopper coating, spraying, spin coating or offer can be any for described mode The appointing of the generally uniform coating that suitable mode (for example using known step and equipment in photographic supports field) is dried What its method.Or, can for example be imprinted using ink-jet, photolithography, using for example flexible version printing structure of letterpress component Part (such as flexographic printing plates and flexographic printing elements) " flexographic plate " printing, using lithographic plate lithographic printing and Intaglio plate (gravure or intaglio) printing using suitable print-member applies the pattern of paint base composition to supporter (or to any intermediate basecoat layer thereon).

The dry bottom enamelled coating being arranged on supporter can have several desirable properties.For example, dry in dry bottom enamelled coating The weight of one polymer emulsion and dry second polymer latex is than for 1:3 and to and include 3:1 or be 1:1 and to and include 2.5:1.

Additionally, be based on dry bottom enamelled coating gross weight, described first surface activating agent (being described above) can at least 1 weight % and At most and include 3 weight % and more generally at least 1.6 weight % and at most and include 2.8 weight % amount be present in described dry In prime coat.

In addition, being based on dry bottom enamelled coating gross weight, described second surface activating agent with least 0.35 weight % and at most and wraps Include 1.1 weight % or typically at least 0.45 weight % and at most and include the amount of 0.9 weight % and be present in described dry bottom enamelled coating In.

Based on dry bottom enamelled coating gross weight, the total amount of the first and second surfactants in described dry bottom enamelled coating is at least 1.35 weight % and at most and include 3.35 weight %.

Also usefully, described dry bottom enamelled coating (or composite of sublayer as above) has at least 0.05 μm and extremely Many and include 0.4 μm or typically at least 0.05 μm and at most and include 0.2 μm or even at least 0.07 μm and at most and include 0.2 μm of average dry thickness.Technical staff will know how to determine the density of specific primer compositionss prepared in accordance with the present invention, The required dry thickness to obtain gained dry bottom enamelled coating for the wet coverage rate to be applied with then calculating.

When the coating of the mixture comprising the first and second polymer emulsions as above is applied to suitable to support After body drying, the mixture generally " coalescence " of latex particle is generally had with being formed to be applied with its whole stayed surface The uniformly polymeric film of composition.In many embodiments, latex particle also can be crosslinked among their own, with provide more resistant to Long surface, it is more tolerant to the degraded of organic solvent.Then such durable uniformly dry Primer Layer Coatings can provide for applying Plus the more suitably surface of curable compositions.

Product

Above-mentioned substrate can be used for providing product, and wherein patterning materials are directly arranged on dry bottom enamelled coating, and this dry bottom enamelled coating is again straight Connect arrangement (in most of embodiments) on supporter (such as transparent polymeric support).It is especially useful that, even if There are patterning materials, described product still can have at least 88% or typically at least 95% comprehensive absorbance.This based article can Comprise dry bottom enamelled coating, it has the property above with respect to substrate description, including average dry thickness, first polymer latex and second The weight ratio of polymer emulsion, the specific composition of the first and second polyvinyls in described latex and glass transition Temperature and specific first and second surfactants (and their amount).

It is also desirable that the such dry bottom enamelled coating in described product is substantially free of resorcinol, for example, it is based on dry bottom paint Layer gross weight, resorcinol is less than 1 weight % or even less than 0.5 weight %.

Can in any suitable manner in the product of the present invention to provide patterning according to pattern (patternwise) mode Material, such as using the above-mentioned means for forming dry bottom enamelled coating and technology, including but not limited to, using flexographic plate print-member Such as flexographic printing plates, flexographic print cylinder and flexographic printing elements, using intaglio printing (intaglio Printing) with using intaglio printing (gravure printing).Also can be will be patterned into using ink jet printing method and equipment Material applies to substrate.Once applying, at least a portion of patterning materials can comprise have less than 15 μm or even less than 10 μ The fine rule of the average live width of m.Certainly, patterning materials do not need to be made up of this class fine rule completely, because if desired, it also can wrap Containing big region, word and variously-shaped.But, in most of embodiments, at least a portion of patterning materials is main Comprise fine rule, to form grid or the pattern of fine rule.In some embodiments, the whole patterning materials on dry bottom enamelled coating It is made up of this class fine rule.

Useful patterning materials generally comprise and can apply to substrate according to patterned fashion and can be used for spy in this manner Determine any suitable compositionss or " ink " of purpose.

In some embodiments, term " patterning materials " be conductive or can further treated to become conductive " conductive printing material ".Such material can be organic, inorganic, or comprises organic component and inorganic component.Useful Conductive printing material generally response at least current potential (although such material also can respond other stimulations) and show predetermined activity. The example of conductive printing material includes but is not limited to, conductive organic or inorganic polymer (or its composite), tin indium oxide Granule, the granule of metal (such as gold, silver, copper, platinum, nickel, ferrum, aluminum and palladium), thin slice or long filament, the granule of metal complex, gold Belong to alloy and metal precursor, and combinations thereof.Or, conductive printing material can be conductive material precursor, for example slaine (such as silver Salt, such as silver halide or organic silver salts), or electroless metallising catalyst such as palladium granule.Useful especially conduction printing material includes Silver and silver salt, gold, copper, palladium, platinum, nickel, ferrum, tin indium oxide, white carbon black and combinations thereof.

Additionally, useful conductive printing material can for any form or compositionss include granule (or any required form), Polymeric material, or nonpolymer molecules.For example, useful granule or film forming polymer conduction printing material include but do not limit 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 ethenylidene) 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, described patterning materials or conductive printing material can comprise the nano-particle of conductive material Or completely consisting of, and therefore its size is weighed with nanometer (nm), for example, has size that at least one is less than 200 nm, And in some embodiments, have at least 3 nm to and include the average diameter of 100 nm.Nano-particle can be with the shape of cluster Formula provides or uses.The shape of nano-particle is unrestricted, and includes nanosphere, nanometer rods and nanometer cup (nanocup).Example As useful conductive printing material may include carbon, such as white carbon black, the nanometer of CNT, Graphene and equivalent carbonaceous material Grain.The metal nanoparticle of gold, silver, palladium, platinum and copper and dispersion can also be used for patterning materials.

More particularly, used in the present invention, printing material comprises granule (the such as nanometer of conducting metal (or its precursor) Granule), such as the granule of any one in silver, gold, copper, palladium, platinum, nickel and ferrum, or a combination thereof, this metallic particles be dispersed in as In lower described photocurable or heat-setting compositionss.Also the precursor of this metalloid, the salt of for example every kind of metal can be used Or metal-ligand complex.Additionally, tin indium oxide can be coupled in patterning materials.

Generally, the solid material of patterning materials by dispersion, be dissolved or suspended in and to prepare in suitable carrier liquid, Thus formed for applying to the fluid composition (" ink ") of 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 constituent is compatible and does not react (for inertia).For example, described carrier liquid can be for being sufficient for the present invention The solid constituent of method such as metallic particles is dispersed or suspended in one of solution or more kinds of organic solvent.As described below Some embodiments in, described carrier liquid be probably be patterning materials a part photocurable or thermal curable combination The reactive component of thing.

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

Generally, before being in application to substrate, patterning materials generally have at least 1 cps and at most and include 1500 Cps or typically at least 100 cps and at most and include the viscosity of 1000 cps.If desired, more high-viscosity patterning can be used Material.Viscosity can use conventional meanses and equipment such as Brookfield viscometer DV-II+Pro (Brookfield Engineering Laboratories) measuring.

Some useful patterning materials include but is not limited to the conduction containing conductive particle such as foil or granule Ink.Electrically conductive ink include conduction argentiferous ink (for example comprising the ink of silver nano-grain), containing bronze ink, cupric ink, Containing carbon printing ink, ink containing palladium and containing " crystal seed " material for plating or electroless other ink.Some such ink can From such as InkTec (California), Flint Ink Corporation (Michigan), Method Development The source of Company (Chicago) and Novacentrix (Austin, Texas) is commercially-available.In these " ink " one Can be used as carrier liquid, and other ink comprises carrier liquid and one or more of conductive component.

In some embodiments, described patterning materials can further include coloring agent, including but not limited to dyestuff, light Learn absorbent, pigment, opacifier, and the transmission or reflection changing patterning materials during the method for the present invention at any time Any material of property.

As described above, described patterning materials can be photo curable or heat-setting." photo curable " refers to The compositionss of polymerizable or crosslinking when being exposed to suitable photocuring radiation.For example, photocuring can use, for example, have at least 150 nm and at most and include the λ of 750 nm_maxSuitable radiation, or more likely using having at least 150 nm and at most And include the λ of 400 nm_maxThe radiation patterning materials that make to comprise suitable photocurable component occur when exposing.Can use Suitably such radiation source continues the suitable time and is exposed (photoexposure), to provide required solidification energy.Skill Art personnel will know how optimal conditions to realize required polymerization or crosslinking.

Useful curing process also can by using suitable thermal source such as electric hot plate, baking oven, Infrared Heating (for example, Be exposed to near-infrared or infrared emission laser instrument) or other heater will be patterned into material and be heated at least 110 DEG C and at most And include 150 DEG C of temperature, and continue time enough to obtain required polymerization or crosslinking, for example, at least 10 minutes and at most simultaneously To carry out including 30 minutes.Those skilled in the art be readily determined realize desired polymerization or crosslinking by required optimal plus Hot temperature and time condition.

More particularly, described patterning materials can be Photocurable composition, its comprise metallic particles as above and The compositionss of free-radical curable, the compositionss of theobromine catalytic curing, or the compositionss of free-radical curable and can acid catalysiss solid The mixture of the both compositions changed.

The compositionss of free-radical curable generally comprise one or more of materials, and it produces when being exposed to suitable radiation Raw free radical, free radical leads to the polymerization of reactive monomer, oligomer or polymer equally existing or crosslinking again.Various required Generally carry in one or more of solvents (carrier solvent) with optional component, described solvent can be different compounds, Or they be alternatively for free radical be reactivity compound (for example, free-radical reactive monomer, such as acrylate, It also functions as carrier solvent).The compositionss of many such free-radical curables are described in periodical and patent documentation.

Similarly, theobromine catalytic curing compositionss are also known in the art, and are generally comprised within and are exposed to conjunction The one or more of compounds of acid moieties are produced, this acid moieties and then catalytic design is used for this chemical environment during suitable radiation The polymerization of suitable compound or crosslinking.

In also other patterning materials, Photocurable composition may include free-radical curable and can acid catalysiss consolidate Change the mixture of both chemicals.When using two kinds of curing chemistry process (curing chemistries), institute The crosslinked matrix obtaining may make up the interpenetrating polymer networks (IPN) including cross-linked material.The crosslink density of this increase can enter one Step increases chemical resistance and hardness, and the final conductive metal pattern for comprising conductive yarn provides excellent performance.

(a) photo polymerization epoxy material

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

, it can be polymerized by ring open mechanism.Such epoxy material, also referred to as " epoxide ", including monomer The epoxide of epoxide and polymer type and can be aliphatic series, cyclic aliphatic, aromatics or heterocycle.On average, this A little materials generally have at least one polymerizable epoxy groups per molecule, or typically at least about 1.5 and even at least about 2 can Polymerization epoxide groups/molecule.Polymer epoxy material includes thering is epoxy-terminated linear polymer (for example, polyoxyalkyl The diglycidyl ether of base glycol), there is the polymer of skeleton (skeletal) (main chain (backbone)) ethylene oxide unit (for example, polybutadiene polyepoxide) and polymer (for example, the glycidyl methacrylate polymerization with pendant epoxy Thing or copolymer).

Polymerisable epoxy material can for single compound or they can be the mixture of different epoxy materials, it contains one Individual, two or more epoxide groups/molecule." average " quantity of the epoxide group of per molecule is passed through with epoxy material The total quantity of epoxide group to determine divided by the total quantity of the molecule containing epoxy existing.

Epoxy material can be from low molecular weight monomers changes in material to heavy polymer, and they in main chain and can take The change in nature of Dai Ji (or side base) is very big.For example, main chain can be any types and substituent group thereon can be basic On do not interfere any group of expectation cation photocuring process at room temperature.The illustration of admissible substituent group include 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 include 100,000, or even more high.

Useful epoxy material includes those containing cyclohexene oxide group, such as epoxycyclohexane carboxylate, for example 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylate, 3,4- epoxy -2- methylcyclohexylmethyl -3,4- epoxy -2- Methylcyclohexanecarboxylic acid ester and double (3,4- epoxy -6- methylcyclohexylmethyl) adipate ester.There is 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.).Also have other useful rings Oxygen material includes glycidyl ether monomers, and it is by polyhydric phenols and excessive 2-chloroethyl alcohol such as epichlorohydrin are reacted the polynary of acquisition The glycidyl ether [for example, the diglycidyl ether of 2,2- pair-(2,3- epoxypropoxyphenol)-propane] of phenol.

Much commercially available epoxy material is available, including glycidyl ether such as bisphenol-A-diglycidyl ether (DGEBA), the glycidyl ether of bisphenol S and Bisphenol F, butanediol diglycidyl ether, the glycidyl ether of bisphenol-A extension, benzene Phenol-formaldehyde glycidyl ether (novolac epoxy resin (epoxy novolac)) and cresol/formaldehyde glycidyl ether (cresol Formaldehyde epoxy resin (epoxy cresol novolac)), epoxidation of olefins such as 1,2- octylene oxide, 1,2,13,14- 14 Alkane diepoxide, 1,2,7,8- octane diepoxide, oxidation octadecylene, epichlorohydrin, styrene oxide, VCH Cyclohexene oxide oxide (vinyl cyclohexene oxicyclohexene oxide), (+)-2,3-Epoxy-1-propanol, methacrylic acid Ethylene oxidic ester, the diglycidyl ether of bisphenol-A are (for example, from Momentive with EPON trade mark such as Epon^TM828, Epon^TM825, Epon^TM1004 and Epon^TM1010 obtainable those, from Dow Chemical Co. DER-331, DER-332 and DER-334 resin), vinyl cyclohexene dioxide is (for example, from the ERL-4206 tree of Polyscience Fat), 3,4- epoxycyclohexyl-methyl -3,4- epoxy hexane carboxylate is (for example, from Dow Chemical Company's ERL-4221, UVR 6110 or UVR 6105 resin), 3,4- epoxy -6- methylcyclohexylmethyl -3,4- epoxy -6- methyl-ring Hexene carboxylate (from Pfalz and Bauer), double (3,4- epoxy -6- methylcyclohexylmethyl) adipate ester, double (2,3- ring Oxygen-cyclopenta) ether, (for example, it is derived from the aliphatic epoxy of polypropylene glycol modified, Dipentenedioxide, epoxidized polybutadiene Oxiron 2001 resin of FMC Corp.), the silicones containing epoxy-functional, fire-retarded epoxy resin (for example, DER- 580 resins, brominated bisphenol type of epoxy resin, can be obtained by Dow Chemical Co.), phenol formaldehyde (PF) phenolic resin The BDDE of (phenol formaldehyde novolak) is (for example, 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) a hexamethylene-dioxane, vinylcyclohexene monoxide, 1,2- epoxy 16 Alkane is (for example, from the CYRACURE of Dow Corning Corp.^TMResin), alkyl glycidyl ether such as HELOXY^TM Modifier 7 and HELOXY^TMModifier 8 (from Momentive), butyl glycidyl ether (for example, are derived from The HELOXY of Momentive^TMModifier 61), cresylglycidylether is (for example, from the HELOXY of Momentive^TM Modifier 62), to tert-butyl-phenyl glycidyl ether (for example, from the HELOXY of Momentive^TMModifier 65)、 The diglycidyl ether of polyfunctional glycidyl ether's such as BDO is (for example, from the HELOXY of Momentive^TM Modifier 67), the diglycidyl ether of neopentyl glycol is (for example, from the HELOXY of Momentive^TMModifier 68)、 The diglycidyl ether of cyclohexanedimethanol is (for example, from the HELOXY of Momentive^TMModifier 107), trihydroxy methyl Ethane triglycidyl ether is (for example, from the HELOXY of Momentive^TMModifier 44), trimethylolpropane tris shrink Glycerin ether is (for example, from the HELOXY of Momentive^TMModifier 48), the polyglycidyl ether (example of aliphatic polyol As from the HELOXY of Momentive^TMModifier 84), polyglycol diepoxide is (for example, 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- pair>4- (2,3- glycidoxy)-phenylfluorone is (for example, from Momentive Epon^TM1079 resins).

Other useful epoxy materials are also had to be resin, such as derived from the acrylate reacting with (+)-2,3-Epoxy-1-propanol such as third Olefin(e) acid ethylene oxidic ester and glycidyl methacrylate, with one or more of ethylenic unsaturated polymerizable monomer copolymerization 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 (+)-2,3-Epoxy-1-propanol acetoacetic ester.Also There are other useful epoxy materials to be the silicone with epoxy-functional or group such as cyclohexyl ring oxygen groups, particularly have Those epoxy materials of silicone backbone.The commercial embodiments of such epoxy material include UV 9300, the UV available from Momentive 9315th, UV 9400, UV 9425 silicone material.

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

Described photo polymerization epoxy material can comprise blend or the 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 distribution, for example one or more Plant low-molecular-weight (less than 200) 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, More than 000) blend of epoxy material.

If desired it is used for specifying effectiveness, described photo polymerization epoxy material can be used for providing binding agent function.In addition, being this Purpose, if desired, may include non-photocurable polymer or resin.Or, following photocurable acrylate can be used for carrying For binding agent function.

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

(b) photo-acid agent

The photocuring that suitably acid participates in photopolymerization composite described herein can be produced using various compounds.These Some in " photo-acid agent " be acid and other be nonionic.In view of teaching provided herein, except following Those beyond, other useful photo-acid agents will be readily apparent to those skilled in the art.Can be used as The various compounds of photo-acid agent are purchased from various commercial source or are prepared using known synthetic method and parent material.

(i) salt

Salt raw acid agent includes but is not limited to, and diazol, microcosmic salt, iodine salt, or sulfonium salt, including polyaryl diazol, phosphorus Salt, iodine salt and sulfonium salt.Iodine salt or sulfonium salt include but is not limited to, diaryl group iodized salt and triarylsulfonium salt.Useful contends with Anion includes but is not limited to halide metal compound, such as tetrafluoroborate, hexafluoro antimonate, fluoroform sulphonate, hexafluoro Arsenate, hexafluorophosphate and arene sulfonate.Salt can be also oligomer compounds or the polymerization with multiple salt parts Compounds and the molecule with single salt part.

The example of useful aromatic iodonium salts includes but is not limited to, diphenyl iodine tetrafluoroborate；Two (4- methylbenzene Base) iodine tetrafluoroborate；Phenyl -4- aminomethyl phenyl iodine tetrafluoroborate；Two (4- heptyl phenyl) iodine tetrafluoroborate； Two (3- nitrobenzophenone) iodine hexafluorophosphate；Two (4- chlorphenyl) iodine hexafluorophosphate；Two (naphthyl) iodine Tetrafluoroboric acid Salt；Two (4- trifluoromethyl) iodine tetrafluoroborate；Diphenyl iodine hexafluorophosphate；Two (4- aminomethyl phenyl) iodine six Fluorophosphate；Diphenyl iodine hexafluoro arsenate；Two (4- Phenoxyphenyl) iodine tetrafluoroborate；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- Dichlorobenzene base) iodine hexafluorophosphate, two (4- bromophenyl) iodine hexafluorophosphoric acid Salt；Two (4- methoxyphenyl) iodine hexafluorophosphate；Two (3- carboxy phenyl) iodine hexafluorophosphate；Two (3- methoxycarbonyl Phenyl) iodine hexafluorophosphate；Two (3- methoxysulfonyl phenyl) iodine hexafluorophosphate；Two (4- acetylamino phenyl) iodine Hexafluorophosphate；Two (2- benzothienyl) iodine hexafluorophosphate；With diphenyl iodine hexafluoro antimonate；And its mixing Thing.Such compound can be according to Beringer et al., J. Am. Chem. Soc.Phase is passed through in 81,342 (1959) teaching The double decomposition of the aromatic iodonium simple salts (such as, such as diphenyliodonium bisulfate) answered is preparing.

Useful iodine salt 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 SbF₅OH₃₁AsF₆ ^-). If desired, the mixture of any kind in these iodine salt of identical or different classification can be used.

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

Based on the gross weight of all four (a) to (d) component, one or more of salt (such as iodine salt or sulfonium salt) are led to Often with least 0.05 weight % and at most and include 10 weight %, or typically at least 0.1 weight % and at most and include 10 weight % Amount is present in described 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, diazonium first Alkane derivatives such as, for example double (benzenesulfonyl)-Azimethylene .s, double (p-toluenesulfonyl) Azimethylene., double (diformazan benzene sulfonyl Base)-Azimethylene., double (cyclohexylsulfonyl)-Azimethylene., double (Cyclopentylsulfonyl) Azimethylene., double (normal-butyl sulphonyl Base) Azimethylene., double (iso-butylsulfonyl)-Azimethylene., double (sec-butylsulfonyl) Azimethylene., double (n-pro-pyl sulphonyl Base) Azimethylene., double (isopropelsulfonyl)-Azimethylene., double (tert. butylsulfonyl) Azimethylene., double (n-pentyl sulphonyl Base) Azimethylene., double (isopentyl sulfonyl)-Azimethylene., double (sec-amyl sulfonyl) Azimethylene., double (tertiary pentyl sulphonyl Base) Azimethylene., 1- cyclohexylsulfonyl -1- (tert. butylsulfonyl) Azimethylene., 1- cyclohexylsulfonyl -1- (tertiary pentyl Sulfonyl) Azimethylene., and 1- tertiary pentyl sulfonyl -1- (tert. butylsulfonyl) Azimethylene..

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

Such photo-acid agent further includes bis sulfone derivant such as, for example double Naphthylsulfonyl methane, bis trifluoromethyl Sulfonyl methane, double methyl sulfonyl methane, double ethylsulfonyl methane, double sulfonyl propyl methylmethane, double isopropyl-sulfonyl 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 includes disulfone (disulfono) derivant such as, such as hexichol Base disulfone and dicyclohexyl disulfone；Sulfonic acid p-Nitrobenzyl derivant 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-epoxide) benzene, 1,2,3- Three (three fluoro- mesyl epoxides) benzene, and 1,2,3- tri- (p-toluenesulfonyl epoxide) benzene；Sulphonic acid ester with N- hydroxy imide Such as, such as N-hydroxy-succinamide methanesulfonates, N- hydroxy-succinimide triflate, N- hydroxysuccinimidyl acyl Imines esilate, N-hydroxy-succinamide 1- propane sulfonic acid ester, N-hydroxy-succinamide 2- propane sulfonic acid ester, N- hydroxysuccinimidyl Acid imide 1- penta sulphonic acid ester, the pungent sulphonic acid ester of N-hydroxy-succinamide 1-, N-hydroxy-succinamide p-toluenesulfonic esters, N- hydroxyl Base butanimide is to methoxy benzenesulfonic acid ester, N-hydroxy-succinamide 2- chloroethene sulphonic acid ester, N-hydroxy-succinamide benzene Sulphonic acid ester, the fluoro- benzene sulfonate of N-hydroxy-succinamide 2,4,6- tri-, N-hydroxy-succinamide 2,4,6- trimethyl-benzene sulphur Acid esters, the chloro- benzene sulfonate of N-hydroxy-succinamide 2,4,6- tri-, N-hydroxy-succinamide 4- cyano group-benzene sulfonate, N- hydroxyl Base butanimide 1-naphthalene sulfonic aicd ester, N-hydroxy-succinamide 2- napsylate, N- hydroxyl -2- phenyl succinimide first sulphur 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, HP benzene sulfonate, HP triflate, N- Hydroxyphthalimide p-toluenesulfonic esters, N- hydroxyl naphthalimide methanesulfonates, N- hydroxyl naphthalimide Benzene sulfonate, N- hydroxyl -5- norborene -2,3- dicarboximide methanesulfonates, N- hydroxyl -5- norborene -2,3- diformazan Acid imide triflate, N- hydroxyl -5- norborene -2,3- dicarboximide p-toluenesulfonic esters, N- hydroxyl naphthalene diformazan Acid imide triflate, and N- hydroxyl -5- norborene -2,3- dicarboximide perfluor -1- fourth sulphonic acid ester.

Based on the gross 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 include 10 weight %, or typically at least 0.1 weight % and at most and include the amount of 10 weight % and be present in In described photopolymerization composite.

(c) electron donor photosensitizer

Useful electron donor photosensitizer should dissolve in photo curable compositionss, solid without will substantially interfere cationic photopolymerization The functional group of change process, and can at least 150 nm and at most and include carrying out light absorbs in the wave-length coverage of 1000 nm (light sensitivitys).

Suitable electron donor photosensitizer response is caused salt (or other photo-acid agent) by the photon of irradiation absorption Chemical transformation.Electron donor photosensitizer should also be able to reduce photo-acid agent (i.e., after electron donor photosensitizer absorbing light Photo-induced electron transfer).Therefore, electron donor photosensitizer, usually can be to photogenerated acid after absorbing the photon being derived from irradiation Agent supplies electron.

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

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

Usually, 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 useful electron donor photosensitizer of other being related to triplet excited state is carbonyl compound such as thiaxanthone and ton Ketone.Including the ketone of aromatic ketone such as Fluorenone, and coumarine dye such as coumarin ketone for example has strong power supply subdivision (for example Dialkyl amido) those also be used as electron donor photosensitizer.Other suitable electron donor photosensitizer are it is believed that include ton Dyestuff, acridine dye, thiazole dye, thiazine dye, piperazine dyestuff, azine dye, aminoketone dye, porphyrin, aromatics are multi-ring Hydrocarbon, the aminostyryl ketone compounds of para-orientation, aminotriaryl methanes, part cyanines, side's acid cyanines (squarylium) dyestuff 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 photosensitizer be found can for this available from various commercial source and easily Bright.

Based on the gross weight of component (a) to (d), described one or more of electron donor photosensitizer can at least 0.0001 Weight % and at most and include 5 weight %, and typically at least 0.001 weight % and at most and include the amount of 2 weight % be present in can light In the compositionss of solidification.In some embodiments, described electron donor photosensitizer is pyrene, benzopyrene, or benzo, its Based on the gross weight of component (a), (b) and (d), with least 0.05 weight % and at most and include the amount of 2 weight % and exist.

(d) metallic particles

Metallic particles is present in photo curable compositionss.Generally only using a type of metallic particles, but it is likely to Mixture including the metallic particles of the metal from the identical or different classification not interfered with one another.These metallic particles generally have There is net neutral charge.

Useful metallic particles be selected from the noble metal 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, the granule of gold, silver, palladium, platinum, rhodium, iridium, rhenium, hydrargyrum, ruthenium and osmium.Useful The granule of semi-precious metal includes but is not limited to, the granule of ferrum, cobalt, nickel, copper, carbon, aluminum, zinc and tungsten.Useful Group IV metal Granule includes but is not limited to the granule of stannum, titanium and germanium.The granule of noble metal granule such as gold, silver, palladium and platinum is useful especially, And the granule of semi-precious metal nickel and copper is also useful especially.In Group IV metal classification, tin particles are useful especially. In many embodiments, silver or copper granule are used for photo curable compositionss as " crystal seed " metallic particles of electroless process In.

The metallic particles that can be used for 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 assembling and providing can of metallic particles The dispersibility of the improvement in the compositionss of photocuring.

Metallic particles is dispersed in various organic solvents and other necessary component (example in photo curable compositionss As multifunctional polymer epoxy material) in the presence of or in optional component (example polyfunctional acrylic ester described as follows resin) In the presence of can have the dispersibility of improvement.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 present in photopolymerization composite as single granule, 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, bar-shaped, prismatic, cube, taper, pyramid, wire, flake (flake), small pieces Shape (platelet) and combinations thereof, and they can be uniform or heterogeneous in shape and size.Individually metallic particles With the mean diameter of the metallic particles of agglomeration can at least 0.01 m and at most and include 25 m, or more likely at least 0.02 M and at most and include in the range of 5 m.Although being not particularly limited the size of metallic particles, using have at least 0.02 m and At most and include 10 m mean diameter the metallic particles as single granule or agglomerate can achieve best benefit.Phase Hope narrow diameter distribution to as defined below that：Wherein it is more than 50%, or typically at least 75% granule has in mean diameter 0.2 to 2 times in the range of particle diameter.Mean diameter (average particle size) is (with mean diameter (mean Particle size) identical) can be determined by particle diameter distribution, described particle diameter distribution can use any suitable step and equipment The suitable mathematical calculation be used together including the equipment available from Coulter or Horiba and with that equipment to be determined.

Useful metallic particles available from various commercial source, or they can derived from various slaines or complex and For the known reduction before the practice of the present invention and separation process.Some commercial metals granules are available from for example Novacentrix.

Based on the gross weight of component (a) to (d), described metallic particles generally with least 0.1 weight % and at most and includes 50 Weight % or more generally at least 1 weight % and at most and include the amount of 30 weight % and be present in photo curable compositionss.

The compound of (e) free redical polymerization

The compound that described photo curable compositionss also can contain one or more of free redical polymerizations can be free to provide The functional group of base polymerization, including the undersaturated polymerisable monomer of ethylenic, oligomer or polymer, such as simple function or many officials Can acrylate (also including methacrylate).The compound of such free redical polymerization comprises at least one ethylenic insatiable hunger With polymerizable key, and they can comprise two or more these unsaturated parts, and it can experience addition (or freely Base) polymerization.The material of such free redical polymerization includes single-, two- or poly- acrylate and methacrylate, including but not It is limited to, acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, isopropyl methacrylate, the just own ester of acrylic acid、Propylene Sour stearyl ester, allyl acrylate, glycerol diacrylate, three glycerol acrylate, ethylene glycol diacrylate, diacrylate Diethylene glycol 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 new penta Diol ester, trimethylolpropane trimethacrylate, trimethacrylate acid 1,2,4- butantriol ester, diacrylate 1,4- cyclohexanediol Ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, pentaerythritol tetramethacrylate, six acrylic acid two season Doutrate, six acrylic acid sorbitol esters, double [1- (2- acryloxies)]-to ethoxyl phenenyl dimethylmethane、Double [1- (3- acryloxy -2- hydroxyl)]-to propoxyphenyl dimethylmethane and three-ethoxy-chlorinated isocyanurates trimethacrylate Acid esters；Have 200 to and include 500 double methacrylate of Polyethylene Glycol of molecular weight and double methyl methacrylate, for example retouch The acrylate monomer of those that is set forth in United States Patent (USP) 4,652,274 (Boettcher et al.) and to be for example described in the U.S. special The copolymerizable mixture of the acrylate oligomer of those in sharp 4,642,126 (Zader et al.)；With vinyl chemical combination Thing such as styrene and styrene derivative, diallyl phthalate, divinyl succinate ester, vinyl hexanediacetate and Phthalic acid divinyl ester.If desired, the mixing of two or more in the material of these free redical polymerizations can be used Thing.

Such material is purchased from numerous commercial source or is prepared using known synthetic method and parent material.

Although the amount of the material of described one or more of free redical polymerization is not particularly limited, they can be based on can At least 20 weight % of all components gross weight of the compositionss of photocuring and at most and include 75 weight % or typically at least 40 weights Amount % and at most and include the amount of 60 weight % and be present in photopolymerization composite, and can combination based on Photocurable composition The required property of thing dissolubility and mechanical strength is optimizing.

(f) free radical photo-initiation

If exist (e) component, one or more of free radical photo-initiations exist in photo curable compositionss with Free radical is generated in the presence of the compound of free redical polymerization.Such free radical photo-initiation includes being exposed to for this Any compound of free radical can be produced after photopolymerization radiation (such as ultraviolet or visible radiation) of bright practice.For example, certainly Triaizine compounds, thiaxanthone (thioxantone) compound, benzoin compound, carbazole chemical combination are selected from by base light trigger Thing, dione compounds, sulfonium borate compound, diazonium compound and united imidazole, and those skilled in the art will hold Easily obviously other.The mixture of such compound is selected from identical or different classification.

Equally usefully benzophenone cpd such as benzophenone, benzoylbenzoic acid ester, benzoylbenzoic acid first Double (the dimethylamino of ester, 4- phenyl benzophenone, dihydroxy benaophenonel, acrylated (acrylated) benzophenone, 4,4'- Base) double (diethylamino) benzophenone of benzophenone and 4,4'-, anthraquinone compounds and acetophenone compound such as 2,2'- bis- Acetophenone, 2,2'- dibutoxy 1-Phenylethanone., 2- hydroxy-2-methyl propiophenone, to tert-butyl group 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 isophthalic acid-(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 source.

Such free radical photo-initiation is generally with least 0.1 of all components gross weight based on photo curable compositionss Weight % and at most and include 10 weight %, or typically at least 1 weight % and at most and include the amount of 5 weight % and be present in photocurable Compositionss in.

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

Include the material (inclusion polyhydric alcohol) of one or more of hydroxyls in photo curable compositionss as electric charge Transfer agent is probably useful to assist photo-polymerization process.Term " polyol " refer to have in the molecule 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 connected with the non-aromatic carbon atom in molecule.During use, the material of described hydroxyl for liquid or solid form and can have There is organic nature.Any hydroxyl can be located at homopolymer or copolymer chain end or dangles thereon.

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

Photo curable compositionss also can 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 composition well known to the skilled person.

Generally under the conditions of " safety light ", do not having with the suitable inertia of any component significant reaction being incorporated in In machine solvent, it is used for being coated with, prints or other by being simply mixed to prepare photo curable compositionss and be used as patterning materials Applying means to the present invention substrate.The example of suitable atent solvent includes but is not limited to, acetone, dichloromethane, isopropanol, Dowanol PM, 1- methoxy-2-propanol, ethylene glycol and its mixture.When to be used one or more of groups are divided into liquid During form, those components may act as " solvent " of photo curable compositionss, or with one or more of inert organic solvents groups Close and use.Not solvent-laden photo curable compositionss can by simply dissolving, dispersion and the necessary component of mixing (a) to (d) and Any optional components, using or do not promote to dissolve using gentle heating or disperse preparing.

When using inert organic solvents, they can at least 1 weight % based on above-mentioned component (a) to (d) gross weight And at most and include 70 weight % or at least 20 weight % and at most and include 50 weight % amount exist.

Under the conditions of suitable photocuring or heat cure, said products can comprise patterning materials, and it comprises conducting metal With photocuring or heat-curing composition, all to be arranged on the dry bottom enamelled coating of substrate according to patterned fashion.Patternable materials At least a portion of pattern comprises the line with the average live width less than 15 μm.Such patterning materials therefore can comprise to disperse Gold, silver in the photocuring derived from corresponding photocurable or heat-setting compositionss or heat-curing composition, copper, palladium Or the granule of platinum.

Method for manufacturing the pattern including conductive pattern

First method is used for providing the product primed with patterning materials, comprises transparent polymer support including offer Body (as described above) and the substrate of dry bottom enamelled coating (as described above), and then by patternable materials (as above institute State) pattern be directly provided on dry bottom enamelled coating.As described above, can be by dry bottom enamelled coating and letterpress structure as described herein Providing this pattern, this letterpress component will be patterned into material and is carried to the directly contact of part (such as flexographic plate print-member) On the upper surface of relief image, this image is generally 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 enamelled coating.

In addition it is also desirable at least a portion of the pattern of so provided patterning materials comprises to have less than 15 μm The line of average live width, and such part of patterning materials will be present in being the touch screen areas of the product primed the most at last The place in domain (relative with electrode zone or BUS region).This patterning materials can comprise conducting metal as above or lead Electric metal precursor, and described patterning materials can comprise photocurable or heat-setting compositionss, wherein one of both bag Containing conducting metal or conducting metal precursor.

Also should understand in the description of specific manufacture embodiment especially from the description below, can be by identical or different pattern Change material to apply to the relative support side of substrate, if particularly this substrate all comprises dry bottom paint in two support-side of supporter Layer.Such product primed and pattern can be considered as " duplex (duplex) ", because they (include in supporter Transparent polymeric support) both sides on be respectively provided with dry bottom enamelled coating and pattern material.

Patterning materials comprise in photocurable or the especially desirable embodiment of heat curable composition wherein, so Make patterning materials that condition of cure and device are stood on the one or both sides of substrate afterwards.

For example, can be solid by realizing light with the emittance irradiation patterns material of ultraviolet light such as above Change.Desirable photocuring can using have at least 184.5 nm to and include wavelength and at least 1 mJ/cm of 700 nm²And at most And include 1000 mJ/cm²Or more generally at least 1 mJ/cm²And at most and include 800 mJ/cm²Intensity UV irradiate or can See irradiation to realize.

At least a portion of the gained cured pattern of patterning materials (for example, precursor conductive material) can be included in this part In the curing materials of average live width having less than 15 μm fine rule.In many embodiments, solidify in like fashion entirely Pattern.

Can be completely converted into by least a portion of the cured pattern of precursor conductive material and generally and comprise as mentioned above The conductive material of conductive yarn pattern." precursor conductive material " refers to can be through chemistry, physically or electrically process so that this material The conductive compositionss of material.Some embodiments of such " precursor " material are to comprise the combination of " crystal seed " described below metal Thing.

When the patterning materials in such embodiment comprise conducting metal or conducting metal precursor, for example, wherein institute State conducting metal and comprise seed metal granule, the seed metal granule in the pattern of suprabasil patterning materials can use ability Condition known to domain and electroless plating reagent carry out electroless metal plating, and some of them details is described below.Can produce in like fashion Multiple patterns containing seed metal granule, particularly when the substrate containing dry bottom enamelled coating is following illustrates and such as During continuous coiled material shown in Fig. 1.

In such embodiment, the multiple independent pattern of photocurable or heat-setting compositionss is provided in even On the substrate of continuous web form, this photocurable or heat-setting compositionss are containing seed metal granule Precursor conductive material, it is applied directly on the dry bottom enamelled coating in multiple unitary part of this continuous coiled material.Such continuous volume Material can have at least 88% or at least 95% comprehensive absorbance, and to be included in can be transparent polyester supporter (as described above) Transparent polymeric support on dry bottom enamelled coating (as described above).

By this way, multiple precursor article as herein described can be prepared, for after manufacture immediately using or after a while Time use.For example, multiple precursor article can provide in roll form, and and then with containing first, second and optionally The continuous coiled material of the substrate primed of the present invention rolled of roll form of other multiple cured pattern on formed.As above institute State each of multiple independent pattern of photocurable in cured pattern material or heat-setting compositionss, with even Form multiple single cured pattern, this single cured pattern contains seed metal in multiple unitary part on continuous coiled material Grain.

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, proceed as described below the electroless plating of such multiple single cured pattern.

Products obtained therefrom (product article) contains one or more conductive patterns on the one or both sides of substrate Case, this conductive pattern can comprise the fine rule with the average live width less than 15 μm, and can be placed in conductive articles or display set In standby touch area.The useful especially equipment of the type comprises the electrically conducting transparent with least 88% comprehensive absorbance Film, and the dry bottom enamelled coating (as described above) of substrate is directly arranged on transparent polymeric support such as polyester support.

Consider now with regard to extensive manufacture and using the product primed provide conductive articles and equipment more carefully Section.

The product primed of the present invention can be used alone as discrete component, or as continuous coiled material (for example, for volume to volume Method), it has the pattern of some being directly arranged on dry bottom enamelled coating (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), Stand with then advancing through exposure (solidification), or exposure (solidification) equipment can be in multiple patterns of the patterning materials of continuous coiled material Top is passed through.Identical or different photo curable compositionss can be used for (for example, printing) in two support-side of substrate In patterning materials, no matter this substrate is single element form or continuous coiled material form.In many embodiments, by difference Conductive metal pattern be formed on the relative support side of substrate (or continuous coiled material).

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

After will be patterned into material and being applied in substrate, can be by remaining ingredient can not adversely be affected or causes too early The drying of polymerization or pre-bake step remove any inert organic solvents.Useful drying condition can as little as room temperature be low continues as little as 5 seconds and at most and include some hours, this depended on manufacture method.In most methods, volume to volume for example described below In method, drying condition can be at sufficiently high temperature to remove at least 90% inert organic solvents at least 1 second.

The pattern of any applying of patterning materials can comprise grid lines, and (or other shapes include circle or irregular net Network), it has at least 0.2 μm and at most and include 20 μm, or typically at least 2 μm and at most and include 15 μm of average thickness (or width), and adjustable optimal dry thickness (or width) is for the desired use of the uniform photocurable layers of gained, this net Ruling generally has the dry thickness (or width) about the same with the grid lines of the patterning materials of non-photocuring.

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 is it means that they are the first products for providing the method for conductive articles to produce.

In some embodiments, can be in an appropriate manner by identical or different photocurable or heat-setting combination Thing applies to two support-side of substrate, to form each curable pattern on " duplex " or two-sided precursor article Various features, and the pattern of multiple solidification can have identical or different seed metal granule, it is gold grain, Argent grain, Copper granule, palladium granule or platinum grain.

In many embodiments, using letterpress component, the pattern of photocurable or heat-setting compositionss is applied Add in one or two (relative) support-side of substrate (for example as volume to volume continuous coiled material), described letterpress component example As the elastomer print-member being obtained by flexographic printing plates precursor, many of which is known in the art, and some are cities Sell available, such as the Cyrel from DuPont^®Flexographic plate photopolymer plate (Flexographic Photopolymer Plates) and the Flexcel SR from Eastman Kodak Company and NX flexographic printing plates (Flexographic plates).

, available from flexographic printing plates precursor and flexographic printing elements precursor, it is each for useful especially letterpress component The relief image that (and if desired, being developed) can be suitably imaged to provide for " printing " or apply 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 With for based identical or relative support side offer patterning materials different patterns.In other embodiments, elasticity Body relief printing plate element is by the elastomer relief printing plate element precursor using or not using direct (or ablation) laser of complete mask can carve There is provided, be 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 in the present invention using described elastomer relief printing plate element, can will be patterned in an appropriate manner material apply to Uppermost relief surface (convex surfaces) in letterpress component.Can complete to apply using several suitable means, And desirably it is coated on as few as possible on side (slope) or the recess of relief printing plate depression (relief depression). Therefore it is also desirable to patterning materials as much as possible are only applied to uppermost relief surface.Anilox roller can be used (Anilox roller) system or other roller application system, (63.5 hundred million cubes micro- per square inch for particularly 2,500,000,000 cu μ ms Rice is every square centimeter) following low volume anilox roller, and the microtome knife (skive knives) of correlation.Can be viscous by controlling Degree or thickness, or select suitable applying means to realize the optimal metering to uppermost relief surface for the patterning materials.

The measured quantity that each printed patterns can be directed to will be patterned into material from anilox roller inking system or other roller Inking system feeds.In one embodiment, the first roller can be used for will be patterned into material turning from " ink " disk or metering system Move to metering roll or anilox roller.When will be patterned into material from anilox roller be transferred to printing plate cylinder when, generally by it Measure as uniform thickness.When by substrate (such as continuous coiled material) pass through volume to volume processing system from printing plate cylinder movement to pressure During print cylinder, this impression cylinder applies pressure to printing plate cylinder, and image is transferred to substrate from letterpress component by it.

Will be patterned into after material applies to the uppermost relief surface (or convex surfaces) of letterpress component, It might be useful that any inert organic solvents of at least 25 weight % that removing patterning materials include, with relief image Uppermost relief surface on form the deposit of more viscosity.Can achieve in any way going of this inert organic solvents Remove, such as using heating or known in the art in heated air jets, at room temperature evaporation or baking oven at elevated temperatures The other means for removing solvent.

Once one or more patterns are arranged on the dry bottom enamelled coating of substrate (for example, as continuous coiled material), before gained Patterning materials in system product can for example pass through with being derived from the suitable of suitable source such as fluorescent lamp or LED as described above Radiation exposure solidifying, so that one or more cured pattern to be provided on substrate.For producing the irradiation system of appropriate radiation Can be made up of one or more uviol lamps, such as in the form of 1 to 50 discharge lamp, such as xenon, metal halide, metal arc (for example have from some millimeters to the action required pressure of about 10 atmospheric pressure low, or high-pressure mercury vapour discharge lamp).Institute State lamp and may include and be transmissive at least 190 nm and be up to and include 700 nm or typically at least 240 nm and be up to and include 450 The shell (envelop) of the light of nm wavelength.The typical lamp that can be used for providing ultraviolet radioactive is for example middle pressure mercury arc, such as GE H3T7 arc lamp and Hanovia 450W arc lamp.Photocuring can be carried out using the combination of various lamps, some in described lamp or complete Portion can operate in an inert atmosphere.When using UV lamp, impact basement (apply layer or pattern) irradiation flux can be to Few 0.01 watt/inch²(0.00155 watt/centimetre²), with for example realize in volume to volume operation applied patterning materials with Fully quick photocuring in 1 to 20 second for the continuation mode.

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

The result of this irradiation of precursor article is to comprise substrate (for example, single thin slice or continuous coiled material) and thereon There are the one or more cured pattern in one or two support-side of described substrate (for example, each contain suitably Seed metal granule) intermediate.In some embodiments of described precursor article, multiple curable patterns and solidification Pattern can be formed using identical photocurable or heat-setting compositionss.This photo curable compositionss can comprise can be certainly The compositionss that solidified by base, acid catalysiss compositionss, or the compositionss of free-radical curable and the compositionss two of theobromine catalytic curing Person, all as mentioned above.

Gained intermediate can be used for some applications in this form, but in most of embodiments, they are further Processed to be incorporated to conducting metal in one or more (multiple) cured pattern, each cured pattern may include seed metal Granule plates step for electroless metal.For example, described seed metal granule can be the metal of component (d) for above-identified Grain, such as gold grain, Argent grain, copper granule, palladium granule or platinum grain or its mixture.

A kind of useful method according to the present invention in printing station using multiple flexographic printing plates in heaps (for example, Prepared as described above), wherein each heap has the printing plate cylinder of their own so that each flexographic printing plates are used for printing in substrate 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 some in two support-side printed patterns material pattern.Can using multiple flexographic printing plates by identical or Different photopolymerization composite " printing " or be applied in described these some suprabasil.

In other embodiments, common impression cylinder can be together with the single impression cylinder being arranged on press rack Use.When described substrate enters press rack, itself and impression cylinder contact, and with patterning materials such as photocurable The compositionss suitable pattern of printing.Or, series connection (in-line) flexographic printing process can be utilized, wherein printing station is with water Horizontal line disposes and is driven by common line shaft.Described printing station may be connected to exposure station, cutting station, folding machine (folder) and its Its downstream equipment.Technical staff can be readily determined equipment and useful the joining of other at station using the available information in this area Put.For example, WO 2013/063084 (Jin et al.) describes a kind of (in-the-round) imaging method comprehensively.

Can will prepare in this stage containing one or more cured pattern containing seed metal granule (or portion immediately Point) intermediate immerse in water base electroless metal plating bath or plating solution, or can by this intermediate only with cured pattern one Play storage to use in later time.

Described intermediate can contact the electroless plated metal identical or different with above-mentioned corresponding seed metal granule.Big In most embodiments, described electroless plated metal is the metals different with corresponding seed metal granule.

At this time can use by may no electric " plating " any metal in the cured pattern of corresponding seed metal granule, But in most of embodiments, electroless plated metal can be such as copper (II), silver-colored (I), golden (IV), palladium (II), platinum (II), nickel (II), chromium (II) and combinations thereof.Copper (II), silver-colored (I) and nickel (II) are useful especially electroless plated metals.

Described one or more of 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.

Electroless plating can be carried out using known temperature and time condition, because such condition is in various textbooks and science literary composition It is well-known in offering.It is known that and include various additives, such as metal chelating agent or stabilizer in water base electroless plating liquid. Change on up time and temperature is changing metal electroless plating thickness or electroless deposition of metals speed.

Useful water base electroless plating liquid or plating bath are no electrolytic copper (II) plating bath as reducing agent containing formaldehyde.Ethylenediamine tetraacetic Acetic acid (EDTA) or its salt can exist as copper chelating agent.For example, depending on required sedimentation rate and plating rate and plating Cover metal thickness, copper electroless plating can carry out several seconds at room temperature and be up to a few houres.

Other useful water base electroless plating liquid or plating bath comprise the silver (I) with EDTA and sodium tartrate, have ammonia and Portugal The silver (I) of grape sugar, has the copper (II) of EDTA and dimethyamine borane, has the copper (II) of citrate and hypophosphites, tool Have the nickel (II) of lactic acid, acetic acid and hypophosphites, and other water base electroless plating bath of industrial standard or a plating solution, for example by Mallory et al. existsElectroless Plating：Fundamentals and ApplicationsThat described in 1990 A bit.

Carrying out electroless plating step with of substrate (such as continuous coiled material) or relative support side or more After providing conductive metal pattern in multiple cured portion, the product of gained is removed from water base electroless plating bath or plating solution, and The electroless plating chemicals with any remnants of removing of distilled water or deionized water or another group water solution washing can be reused (chemistry).At this time, electroless plated metal is typically stable and can be used for its expected purpose.

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

Therefore, this method provide the product comprising substrate, described substrate comprises dry bottom enamelled coating as above and has There is the conductive pattern arranged thereon, described conductive pattern is included in having less than 15 in one or two support-side of substrate μm average live width at least some fine rule.

For the surface of vision or durability reason change electroless plated metal, various post processings may can be adopted, including At least will be plated on electroless plated metal that (this step is sometimes by still other (the 3rd or more kinds of) metal such as nickel, palladium or silver surface Referred to as " capping "), or produce metal-oxide, metal sulfide or metal selenide layer, its be enough to change surface color and Scattering nature and do not reduce the electric conductivity of electroless plating (second) metal.Depending on the method various cap step used in Metal, may desirably be used in another seed metal catalyst in water base seed metal catalyst solution processing electroless plating Metal is to promote the deposition of other metal.

In addition, the multiple process with water base electroless metal plating solution can be carried out successively using identical or different condition.Suitable When in the case of, also can be in room temperature or less than sequentially being washed or rinsing step at a temperature of 70 DEG C.

Additionally, can be carried out successively repeatedly using identical or different electroless plated metal and identical or different electroless plating condition Electroless plating step.

Therefore, in some embodiments of the method for the product for providing the present invention, methods described includes：

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

Using photocurable as above or heat-setting compositionss, such as using flexographic plate print-member, roll up continuous Form photocurable or heat-setting pattern (directly on dry bottom enamelled coating) at least Part I of material,

Solidification photocurable (as described above) or heat-setting pattern in an appropriate manner, to form on described Part I Photocuring or heat cure pattern, and

Make conducting metal on the photocuring on described Part I or heat cure pattern electroless plating using above-mentioned electroless plating step.

The embodiment of the method can be implemented in the single support-side of substrate or on the relative support side of substrate, to carry For identical or different conductive pattern.

In also having other embodiments, the method for the present invention can be used for providing multiple conductive metal pattern, methods described Including：

There is provided the continuous coiled material that multiple photocuring patterns are comprised in each partly according to the present invention, each photocuring pattern leads to Cross and irradiate photocurable as above or heat-setting compositionss to provide,

With electroless metal plating solution process comprise multiple photocurings or the continuous coiled material of heat cure pattern, with continuous coiled material each From the partly multiple electroless gold plating metal patterns of middle offer, and

Optionally, multiple electroless gold plating metal patterns are processed further with capping metal, so that multiple capping to be provided on continuous coiled material Conductive pattern.

The method can be carried out further by following steps：

Single conductive articles are formed by the continuous coiled material comprising multiple conductive patterns capping, and

Single conductive articles are assembled into identical or different single equipment, the display for example with touch-screen display sets Standby.

Such method embodiment can be using identical or different photocurable or heat-setting compositionss in substrate Carry out in two support-side.

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

For implement the present invention useful method and apparatus some detailed descriptions in such as WO 2013/063183 (Petcavich), in WO 2013/169345 (Ramakrishnan et al.).For preparing conductive articles (especially with volume to volume Mode) other details of useful manufacture system be provided in PCT/US/062366 (by Petcavich and Jin in 2012 October 29 submitted to) in.

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

With reference to Fig. 1, it illustrates the schematic side elevation of flexographic printing system 100, it can be used for the inventive method In embodiment, print photocurable or heat-setting group for volume to volume in two (relative) support-side of substrate 150 Compound, described substrate 150 can comprise the dry bottom enamelled coating being directly arranged on supporter.Substrate 150 is 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 being configured to two printings of printing in the first support-side 151 of substrate 150 Module 120 and 140, and it is configured to two printing modules of printing in second (relative) support-side 152 of substrate 150 110 and 130.The continuous coiled material of substrate 150 is totally advanced with volume to volume direction 105 () in Fig. 1 from left to right.However, various rollers 106 and 107 for the direction locally to change the continuous coiled material of substrate according to the requirement of regulation web tension, thus providing buffering And invert support-side and be used for printing.Especially, printing module 120 roller 107 is used for inverting the local side of the continuous coiled material of substrate 150 To so that it is substantially moved with direction from right to left.

Each printing module 110,120,130,140 may include some similar device features, including the rolling of respective forme 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, its limit to be printed in substrate 150 Picture pattern.Each printing module 110,120,130,140 also includes respective impression cylinder 114,124,134,144, its It is configured to force the support-side of substrate 150 to contact with corresponding flexographic plate print-member 112,122,132,142.

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

Each printing module 110,120,130,140 also includes respective anilox roller 115,125,135,145, is used for Will be patterned into material is provided to corresponding flexographic plate print-member (flexographic printing plates) 112,122,132,142.As in printing Well known in the industry, anilox roller is a kind of hard cylinder, is generally built by iron and steel or aluminium core, has containing millions of The outer surface of individual very tiny scrobicula (referred to as ink hole (cell)).Using anilox roller, the transfer making patterning materials is held Easily feasible.In some embodiments, some or all in printing module 110,120,130,140 also include respective UV admittedly Change station 116,126,136,146, for the patternable materials of printing are solidificated in substrate 150.

The product that can be prepared by embodiment of the present invention and some embodiments of equipment are shown in Fig. 2-5.

Fig. 2 shows the high-level system diagram of the device (or equipment) 300 with touch screen 310, and this touch screen 310 includes The touch sensor 330 of at least a portion visibility region of display device 320 and covering display device 320.Touch sensor 330 Perception touches and the signal of telecommunication (for example, to capacitance related) corresponding with the touch perceiving is sent to controller 380.Touch Touch the example that sensor 330 is the product that can be printed in two support-side, described flexographic plate print by flexographic printing system 100 Brush system 100 includes the printing module of the embodiment with reference to above-mentioned flexibility version printing (inking) system.

Fig. 3 shows the schematic side elevation of touch sensor 330.The transparent substrates 340 of the present invention, for example transparent poly- Ester, such as transparent poly- (ethylene glycol terephthalate), there is the first conductive pattern being printed in the first support-side 341 350, with the second conductive pattern 360 being printed in second (relative) support-side 342.From take-up roller 104 (Fig. 1) cut saturating The length and width of bright substrate 340 is not more than flexographic printing plates (or the flexible version printing of flexographic printing system 100 (Fig. 1) 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 Carry out plating using coating method after material and improve electric conductivity.The method according to the invention, patterning materials can be used for providing institute State conductive pattern 350 and 360.

Fig. 4 shows the printing module that can use one or more printing modules such as flexographic printing system (Fig. 1) 120 and 140 examples 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, the mesh column 355 that the fine rule 351 and 353 that this grid 352 includes intersecting is formed, and it is with row's passage Pad (channel pad) 354 connects.Interconnection line 356 is by channel pads 354 and the adapter 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 optimal printing condition for fine rule 351 and 353 (for example, having about 4 to 8 μm of live width) is typically different In the printing condition for printing broader channel pads 354, adapter pad 358 and interconnection line 356, it is possible that favourable It is to come printing fine line 351 and 353 and print broader spy using the second printing module 140 using a printing module 120 Levy.Additionally, in order to the clean intersection of fine rule 351 and 353 is it is also possible to advantageously be printed using a printing module 120 With solidify one group of fine rule 351, and printed using the second printing module 140 and solidify second group of fine rule 353, and using and printing 3rd printing module (not shown in figure 1) of module 120 and 140 similar configuration is printing broader feature.

Fig. 5 shows the printing that can use one or more printing modules such as flexographic printing system 100 (Fig. 1) Module 110 and 130 is printed on the example of the conductive pattern 360 in the second support-side 342 (Fig. 3) of substrate 340 (Fig. 3).Lead Electrical pattern 360 includes grid 362, the mesh row 365 that the fine rule 361 and 363 that this grid 362 includes intersecting is formed, and it is with a row Channel pads 364 connect.Interconnection line 366 is by channel pads 364 with the adapter pad 368 being connected to controller 380 (Fig. 2) even Connect.In some embodiments, conductive pattern 360 can be printed by single printing module 110 (Fig. 1).However, because for thin The optimal printing condition of line 361 and 363 (for example, having about 4 to 8 μm of live width) is usually different from that for broader passage weldering The printing condition of disk 364, adapter pad 368 and interconnection line 366, it is possible that advantageously using a printing module 110 (Fig. 1) printing fine line 361 and 363 and print broader feature using the second printing module 130 (Fig. 1) are come.Additionally, in order to The clean intersection of fine rule 361 and 363 is it is also possible to advantageously being printed using a printing module 110 (Fig. 1) and solidifying one Group fine rule 361, and printed using the second printing module 130 (Fig. 1) and solidify second group of fine rule 363, and use and printing die 3rd printing module (not shown in figure 1) of block 110 and 130 (Fig. 1) similar configuration is printing broader feature.

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

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

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

1. a kind of compositionss, it comprises first polymer latex and the mixture of second polymer latex,

The dry coating of wherein said compositionss have at least 15% and at most and include 50% surface polarity.

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

3. the compositionss described in embodiment 1 or 2, wherein：

Based on described first polymer gross weight, described first polymer comprises at least 75 weight % and at most and include 90 weights The amount repetitives derived from (methyl) glycidyl acrylate of % and at least 10 weight % and at most and include 25 weights The repetitives derived from (methyl) n-butyl acrylate of amount %, this first polymer has at least 25 DEG C and at most and include 75 DEG C of glass transition temperature, and described first surface activating agent is alpha-olefin (C₁₄-C₁₆) sodium sulfonate;

Based on described second polymer gross weight, described second polymer comprises at least 75 weight % and at most and include 90 weights The amount repetitives derived from (methyl) glycidyl acrylate of % and at least 10 weight % and at most and include 25 weights The repetitives derived from (methyl) n-butyl acrylate of amount %, this second polymer has at least 25 DEG C and at most and include 75 DEG C of glass transition temperature, and described second surface activating agent is the ammonium salt of sulphation polyethoxy nonyl phenol；

The weight of the described first polymer latex in described mixture and described second polymer latex is than for 1:1 and to and wrap Include 2.5:1；

Described first surface activating agent with least 1 weight % based on dry coating gross weight and at most and includes the amount of 3 weight % It is present in the dry coating of described mixture；

Described second surface activating agent with least 0.35 weight % based on dry coating gross weight and at most and includes 1.1 weight % Amount be present in the dry coating of described mixture；With

Based on dry coating gross weight, the total amount of described first and second surfactants in the dry coating of described mixture be to Many and include 3.35 weight %.

4. any one described compositions in embodiment 1 to 3, wherein said first surface activating agent is by R-CH₂- CH=CH-CH₂-S(=O)₂O^-Na⁺The compound representing, wherein R is C₁₀、C₁₁Or C₁₂Alkyl；Or have different R group this The mixture of class compound, described R group is C₁₀To C₁₂In alkyl any kind；And described second surface activating agent by R '- Phenyl-(O-CH₂CH₂)_n-S(=O)O₂ ^-NH₄ ⁺Represent, wherein R' is C₈To C₁₂Alkyl, and n is 3 to 10.

5. any one described compositions in embodiment 1 to 4, wherein said first polymer latex and described second At least one in polymer emulsion comprises polyvinyl, and described polyvinyl also comprises derived from having containing extremely The repetitives of (methyl) alkyl acrylate of ester alkyl of few 2 carbon atoms.

6. any one described compositions in embodiment 1 to 5, wherein said first polymer and described second polymerization At least one in thing is crosslinked.

7. a kind of substrate, it comprises supporter and the dry bottom being arranged at least one stayed surface of described supporter Enamelled coating, described dry bottom enamelled coating comprises any one described compositions in embodiment 1 to 6.

8. the substrate described in embodiment 7, it has at least 88% comprehensive absorbance.

9. the substrate described in embodiment 7 or 8, its comprise transparent polymeric support having be directly arranged at described Described dry bottom enamelled coating on transparent polymeric support.

10. any one described substrate in embodiment 7 to 9, the described first polymer in wherein said dry bottom enamelled coating The weight of latex and described second polymer latex is than for 1:3 and to and include 3:1.

Any one described substrate in 11. embodiments 7 to 10, wherein said dry bottom enamelled coating have at least 0.05 μm and At most and include 0.4 μm of average thickness.

Any one described substrate in 12. embodiments 7 to 11, it comprises poly- (ethylene glycol terephthalate) or poly- ((ethylene naphthalate)) supporter.

Any one described substrate in 13. embodiments 7 to 12, it is continuous flexible substrates.

A kind of 14. products, it comprises the substrate of any one in embodiment 7 to 13, and comprises：Transparent polymeric support With the described dry bottom enamelled coating at least one stayed surface being arranged in described transparent supporting body, and comprise to have less than 15 μ The patterning materials of the line of average live width of m, this patterning materials is directly arranged on described dry bottom enamelled coating.

Product described in 15. embodiments 14, wherein said patterning materials comprise selected from gold, silver, copper, palladium, platinum, nickel And its conducting metal of precursor or its precursor.

Product described in 16. embodiments 14 or 15, wherein said patterning materials comprise the combination of free-radical curable Thing, the compositionss of theobromine catalytic curing, or the both compositions of the compositionss of free-radical curable and theobromine catalytic curing is mixed Compound.

Product described in 17. embodiments 14 or 15, wherein said patterning materials comprise to be dispersed in photocuring or thermosetting Change the metallic particles in compositionss.

Any one described product in 18. embodiments 14,15 and 17, wherein said patterning materials comprise to be dispersed in The granule of the gold, silver in photocuring or heat-curing composition, copper, palladium or platinum, described photocuring or heat-curing composition derived from The compositionss of free-radical curable and the both compositions of theobromine catalytic curing.

A kind of 19. methods, it is used for providing any one described product in embodiment 14 to 18, and methods described includes：

Any one described substrate in embodiment 7 to 13 is provided, and

The pattern of patterning materials is directly provided on described dry bottom enamelled coating.

Method described in 20. embodiments 19, at least a portion of the pattern of wherein said patterning materials comprises to have The line of the average live width less than 15 μm.

Method described in 21. embodiments 19 or 20, described at least a portion of the pattern of wherein said patterning materials In the touch screen zone of the product primed described in being present in.

Any one described method in 22. embodiments 19 to 21, it includes：

By the directly contact of described dry bottom enamelled coating and the letterpress component carrying described patterning materials, directly described dry Described patterning materials are provided on prime coat.

Any one described method in 23. embodiments 19 to 22, wherein said patterning materials comprise conducting metal or Its precursor.

Any one described method in 24. embodiments 19 to 23, it also includes：

Solidify the photocurable in described patterning materials or heat-setting compositionss.

Any one described method in 25. embodiments 19 to 24, wherein said patterning materials comprise metallic particles, And methods described also includes：

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

A kind of 26. products, it is obtained by the method that in embodiment 19 to 25, any one is described, and wherein said product comprises At least one pattern of conductive material, at least a portion of the pattern of wherein said conductive material comprises to have less than 15 μm The conductor wire of average live width, this part of the pattern of described conductive material is directly arranged at the described of described substrate On dry bottom enamelled coating.

Any one described method in 27. embodiments 19 to 25, it includes：

There is provided described substrate as continuous coiled material,

Directly provide on the described dry bottom enamelled coating in one or more unitary part of described continuous coiled material respectively and can consolidate light Change or heat-setting compositionss one or more independent pattern as described precursor conductive material, this photocurable or can The compositionss of heat cure comprise metal seeds granule,

Converted each in described photocurable or the one or more independent pattern of heat-setting compositionss by solidification Individual, to form one or more single cured pattern in one or more unitary part, one or more Each of multiple single cured pattern comprise described metal seeds granule, and

Described metal seeds granule in each of one or more single cured pattern for the electroless plating, to provide One or more single conductive patterns.

A kind of 28. methods, it is used for providing multiple products, and methods described includes：

Substrate as required for protection in any one in embodiment 7 to 13 is provided,

Carry described photocurable or heat by making the described dry bottom enamelled coating directly contact in the Part I of described continuous coiled material (thermally) the flexographic plate print-member of compositionss, the described dry bottom paint in the described Part I of described continuous coiled material First curable pattern is directly formed on layer, the described first curable pattern comprises can consolidate light containing seed metal granule Change or heat-setting compositionss,

The described continuous coiled material making to comprise the described Part I of the pattern curable including described first advances (advancing) Near curing station solidify the described first curable pattern, thus to form the first cured pattern on described Part I, This first cured pattern comprises described seed metal granule,

By with the flexographic plate print-member directly contact carrying identical or different photocurable or heat-setting compositionss, Described dry bottom enamelled coating in the Part II of described continuous coiled material directly forms the second curable pattern, described second can The pattern of solidification comprises the identical or different photocurable comprising identical or different seed metal granule or heat-setting group Compound,

The described continuous coiled material making to comprise the described Part II of the pattern curable including described second advances near solidification Stand and solidify the described second curable pattern, thus on described Part II, form the second cured pattern, this second solidification Pattern comprises identical or different seed metal granule,

Optionally, using identical or different curable or heat-setting compositionss and identical or different flexible version printing structure Part be directed to described continuous coiled material other each partly implement described formed and advance feature one or more times, with described Other each partly above forms other cured pattern, and

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

Method described in 29. embodiments 28, wherein identical seed metal granule are present in the plurality of cured pattern Each of in, this seed metal granule is gold grain, Argent grain, copper granule, palladium granule or platinum grain.

Method described in 30. embodiments 28 or 29, wherein in each the formation feature for each curable pattern Middle use identical photocurable or heat-setting compositionss.

Any one described method in 31. embodiments 28 to 30, wherein for each curable pattern each Formed in feature and comprise the combination of free-radical curable using the photo curable compositionss of identical, this photo curable compositions Thing, the compositionss of theobromine catalytic curing, or the compositionss of free-radical curable and the both compositions of theobromine catalytic curing.

A kind of 32. equipment comprising the product of any one in embodiment 14 to 18 and 26, it comprises to be directly arranged at institute State the one or more conductive metal pattern on dry bottom enamelled coating,

Each of wherein said one or more conductive metal pattern comprises touch area, and described touch area comprises tool There is the conductor wire of the average live width less than 15 μm.

Equipment described in 33. embodiments 32, it is touch panel device.

There is provided following examples so that the practice of the present invention to be described, and be not intended to limit by any way.

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

The preparation of first polymer latex (latex A)：

Synthesize poly- (glycidyl methacrylate -co- acrylic acid by adding 652 g softened waters in 2 liters of glass reactors Butyl ester).Other 651 g softened waters are added in 2 liters of glass head tanks.Agitator on two containers is set in 150 RPM Under.Set up nitrogen atmosphere in systems, and add the Rhodacal of 30.9 g in each container^®A246L anionic surface is lived Property agent (" first surface activating agent ").Reactor content temperature is risen to 60 DEG C, and by 526 g methyl propenoic acid glycidyls Ester and 92.3 g n-butyl acrylates add in head tank.It is 60 DEG C when having prepared monomer emulsions and temperature in head tank When, add double (4- cyano group) valeric acid (75%) of 6.16 g azos in reactor.The content of head tank was measured through 240 minutes Add in reactor, and reactor content is stirred 2 hours at 60 DEG C, be subsequently adding being dissolved in 9 g water of 0.48 g Arabo-ascorbic acid.Then, the 30 weight % hydrogen peroxide being dissolved in 47 g water of 1.35 g are added reaction in the way of dropwise In device.Then reactor content is stirred for 1 hour at 60 DEG C.Then the first polymer latex of gained is cooled to 25 DEG C, and filtered by 30 μm of cloth.This prepared product (preparation) obtains the filtered of 1900 g and has 32% solid First polymer latex.Measuring first polymer median particle diameter by UPA is 53.1 nm.

The preparation of second polymer latex (latex B)：

Synthesize poly- (glycidyl methacrylate -co- propylene by adding 675.2 g softened waters in 2 liters of glass reactors Acid butyl ester).Add 674 g softened waters in 2 liters of glass head tanks.Agitator on two containers is set under 150 RPM. Set up nitrogen atmosphere in systems, and add the Rhodapex of 7.72 g in each container^®CO-436 anion surface active Agent (" second surface activating agent ").Reactor content temperature is risen to 60 DEG C, and by 526 g glycidyl methacrylate Add in head tank with 92.3 g n-butyl acrylates.When having prepared monomer emulsions and reactor content temperature in head tank When degree is at 60 DEG C, 28% ammonia spirit of double for 6.16 g azos (4- cyano group) valeric acids (75%) and 2.66 g is added reaction Device.The content of head tank is added in reactor through metering in 240 minutes, and it is little reactor content to be stirred at 60 DEG C 2 When, it is subsequently adding the arabo-ascorbic acid being dissolved in 9 g water of 0.48 g.Then, by 30 weights being dissolved in 47 g water of 1.35 g Amount % hydrogen peroxide adds in reactor in the way of dropwise.Reactor content is stirred for 1 hour at 60 DEG C.Then will The first polymer latex of gained is cooled to 25 DEG C, and is filtered by 30 μm of cloth.This prepared product obtain 1900 g through filter The first polymer latex with 30.6% solid.Measuring first polymer median particle diameter by UPA is 87.1 nm.

The glass transition of the various polymer being obtained using emulsion polymerization as above and different monomer weight ratios 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：Substrate and the preparation of product

Prepare poly- (ethylene glycol terephthalate) substrate primed in the following manner.

Obtain 125 μ m thick by extruding and being cast (casting) to after be suitable to stretch on vertical and horizontal The thickness of Biaxially oriented film is forming the sample of transparent poly- (ethylene glycol terephthalate) (PET) film (or supporter).? Before stretched operation, apply paint base composition and be dried, so that dry bottom paint to be provided on two relative support sides of PET supporter Layer.The paint base composition tested contains any one or two kinds of in above-mentioned latex A and latex B.Then as described stretching gained The substrate primed comprising transparent supporting body and dry bottom enamelled coating, with reduce contraction and mist degree.The priming of various gained The average dry thickness of substrate A to N and gained dry bottom enamelled coating is described in lower Table II.

Using first polymer latex (latex A) and the second polymer latex (latex B) of equivalent, in 50 weight % solution 0.2 weight % saponin (Saponin) and 0.033 weight % Aerodisp^®W7512S pyrogenic silica granule is (average A size of 0.1 μm), it is identified as priming of sample B described in preparation Table II under the concentration of 20% total latex polymer Substrate.Prepare the substrate primed being identified as sample A, C and D to N, wherein said first polymer latex in a similar manner Change as shown in Table II with the amount of second polymer latex.The substrate primed being identified as sample D is also containing 1 weight % Resorcinol.To prepare, with the paint base composition identical mode being identified as sample A, the substrate primed being identified as sample N, Except by with the Rhodacal of the amount of 2 weight % with respect to the second polymer gross weight in latex B^®A246L anion Surfactant (" first surface activating agent ") is added in dispersion and (thus, is incorporated with first surface activating agent and the second table Both face activating agents, but first surface activating agent is incorporated to not as a part for different polymer emulsions).

Embodiment 3:

Using mixture and the various substrate primed of above-mentioned first and second polymer emulsions, provide in the following manner and include The printed patterns of the patterning materials of conductive pattern.

% surface polarity：

Based on known Fowkes ENERGY METHOD, by measuring given be dried on surface a water and a diiodo- first first Respective 2 minutes contact angles (θ) of alkane, determine that give is dried surface (for example, the drying layer of dry bottom enamelled coating or polymer emulsion) % 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) (ginseng See below Table I), calculate given polar component and dispersive component that surface is dried using equation 1 shown below.Then under using Shown calculating % surface polarity in equation 2 that face shows and Table I.

Table I

.

Photo curable compositionss (" ink ")

Photo curable compositionss1 (ink 1)：

This photo curable compositions (or patterning materials) is similar to the invention of United States serial 14/174,879 (above-mentioned) Described in the inventive embodiments 1 of embodiment 1 and United States serial 14/197,293 (equally above-mentioned), and comprise to form 100 At least following components of g aliquot：

14.4 g epoxy acrylates (from the CN 153 of Sartomer), 9.9 g PEG diacrylate (M_nFor 258, Sigma-Aldrich), 2.1 g PEG diacrylate (M_nFor 575, Sigma-Aldrich), 10.8 g seasons Penta tetra-acrylate (Sigma-Aldrich), the triarylsulfonium salt hexafluoro being blended in 50% Allyl carbonate of 0.8 g Phosphate (Sigma-Aldrich), the triarylsulfonium salt hexafluoro antimonate being blended in 50% Allyl carbonate of 0.8 g (Sigma-Aldrich), 2.4 g free radical photo-initiation hydroxycyclohexylphenylketone (Sigma-Aldrich), 1.2 g are free Base light trigger methyl -4 '-(methyl mercapto) -2- raorpholino propiophenone (Sigma-Aldrich), 19.5 g silver nano-grains (Novacentrix, 20-25 nm mean 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 1- methoxyl group isopropanol (Sigma-Aldrich) of 35 g are molten Agent.

Photo curable compositionss 2 (ink 2)：

Prepare this photo curable compositions (or patterning materials) similar to ink 1, but do not contain 9-Fluorenone.

Print photo curable compositionss：

Using from IGT Testing Systems Inc., the desk-top test " IGT of Arlington Heights, IL The above-mentioned photocurable that F1 Printability Tester " is obtained in the various PET base primed with flexographic plate pattern The printed patterns of compositionss sample.For photo curable compositionss being applied to the anilox roller of flexographic printing plates System has the value of 1.3 BCMI being specified by IGT and 1803 lpi.Printed patterns are at ambient temperature using the reticulate pattern of 20 N The print speed printing speed of distributor rollers power (Anilox force), the print force of 10 N and 0.20 m/s is preparing.

Flexographic printing plates for printing photo curable compositionss are that commercially available Kodak Flexcel NX is photosensitive The sample of property resin plate (photopolymer plate) precursor (Eastman Kodak Company), it is using mask Imaging, described mask has predetermined with the resolution write of 12,800 dpi using Kodak Square Spot laser technology Pattern.The flexographic printing plates precursor of exposure exposes through UV and uses the known bar these letterpress components advised by manufacturer Part is processed (development).The flexographic printing plates of gained are respectively 1.14 mm thick (including PET).For by flexographic printing plates The backing adhesive tape being installed to printing form cylinder is 1120 cream-coloured adhesive tapes from 3M company, and it is 20 mils (0.051 cm) Thickness, and there is 55 Xiao A hardness.Relief image design inclusion in flexographic printing plates has tool at the relief surface of top There is the lattice of the fine rule of 7 μm of width.The average live width of the printing in the shown below PET base primed is from printing The pattern having described lattice obtains.

After the printing, using the Fusion 300 WPI medium pressure mercury lamp of the illumination wavelength providing between 190-1500 nm, With about 298 mJ/cm²Light exposure (exposure) use the photo curable compositionss of UV radiation exposure each printed patterns, Each printed patterns with cured pattern material.Using Olympus BH-2 optical microscope in transmission and reflective-mode The average live width of the printing of lower measurement cured pattern.

Electroless metal is plated：

The intermediate being included in the various suprabasil cured pattern primed is passed through at 45 DEG C containing Enplate Cu- Submergence in the beaker of 406 electroless plating liquid (Enthone) has the intermediate of cured pattern m and comes electroless copper, Ran Houyong in 7 minutes Distilled water flushing is simultaneously dried with nitrogen, has, to be formed, the product being arranged in the suprabasil conductive pattern primed.

Cohesive test (" adhesive tape removes test ")：

Immediately by a piece of Scotch from 3M company after electroless plating^®810 Magic Tape adhesive tapes are applied to each On electroless plating pattern in product, and and then tear from the surface of this product.The amount recording the copper being removed by this operation is used as The instruction of electroless plating pattern and the cohesive of the PET base primed.Result is shown in lower Table II.

Evaluate the appearance of coat of every kind of substrate with the yardstick of 0 to 5 grade, wherein " 0 " grade represents on surface uniformity There is no visible difference, " 1 " grade represents hardly obvious surface heterogeneity, " 2 " grade represents less but obvious table Face inhomogeneities, " 3 " grade represents clearly evident surface heterogeneity, and " 4 " grade represents significant surface heterogeneity, bag Include haze and iris, and " 5 " grade represents serious surface heterogeneity, including haze and iris.

Equally in lower Table II, using Hazegard Plus haze meter (BYK Gardner) measurement mist degree (%) and " % T ", wherein " mist degree " are measuring of the light scattering by substrate, and larger numeral affects its definition；And " %T " is logical Cross the measuring of comprehensive absorbance of substrate, and larger numeral represents higher transparency.

Measure the colourimetric number (colorimetry of each substrate using Ultrascan XE tintometer (Hunter) Value), and with standard CIELAB title report result, the b * wherein in Table II represents the color of the substrate on blue-yellow axle, And the b * value corrected represents more yellow outward appearance in substrate.

In table ii, " YI " represents yellowness index (E313 standard), and it is the value of calculation with reference to CIELAB measurement result, makes The YI value that must increase represents more yellow outward appearance in substrate.

Two support-side of substrate carry out grid lines evaluation.Observe the basic phase of live width result of two support-side With.

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

.

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

There is provided 19 using dry bottom enamelled coating (mixture of the first and second polymer emulsions) preparation according to the present invention With the conductor wire of the printed matter generation being identified as inventive embodiments B and E to M of the % surface polarity between 44 has less than 10 μm average live width and good quality, and show that good electroless plating performance and electroless copper are viscous to the substrate primed Conjunction property.It is identified as inventive embodiments E-G and the printed matter of I-L shows especially good appearance of coat, low haze and low color Color.

The printed matter 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, need via single first and second polymer emulsions, the first and second surfactants to be provided To dry bottom enamelled coating.

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

Embodiment 4：

Form the precursor article containing the substrate primed by following steps：Using similar to described in embodiment 1 can light Solidification compositionss, using Mark-Andy press with 20 ft/m (6.06 m/min) and similar to the method described in Fig. 1 with The pattern of the photo curable compositionss as narrow line is provided on two support-side of PET supporter.

Parts list

100 flexographic printing system

102 feed rolls

104 take-up roller

105 volume to volume 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-continuous

150 substrates (or continuous coiled material)

151 first support-side

152 second (relative) support-side

300 devices (or equipment)

310 touch screens

320 display devices

330 touch sensors

340 transparent substrates

341 first support-side

342 second support-side

350 conductive patterns

351 fine rules

352 grids

353 fine rules

354 channel pads

355 mesh columns

356 interconnection lines

358 adapter pads

360 conductive patterns

361 fine rules

362 grids

363 fine rules

364 channel pads

365 mesh rows

366 interconnection lines

368 adapter pads

380 controllers

Claims

2. the compositionss described in claim 1, the dry coating of wherein said compositionss has at least 28% and at most and include 50% surface polarity.

3. the compositionss described in claim 1 or 2, wherein：

Based on described first polymer gross weight, described first polymer comprises at least 75 weight % and at most and include 90 weights The amount repetitives derived from (methyl) glycidyl acrylate of % and at least 10 weight % and at most and include 25 weights The repetitives derived from (methyl) n-butyl acrylate of amount %, described first polymer has at least 25 DEG C and at most and wrap Include 75 DEG C of glass transition temperature, and described first surface activating agent is alpha-olefin (C₁₄-C₁₆) sodium sulfonate；

Based on described second polymer gross weight, described second polymer comprises at least 75 weight % and at most and include 90 weights The amount repetitives derived from (methyl) glycidyl acrylate of % and at least 10 weight % and at most and include 25 weights The repetitives derived from (methyl) n-butyl acrylate of amount %, described second polymer has at least 25 DEG C and at most and wrap Include 75 DEG C of glass transition temperature, and described second surface activating agent is the ammonium salt of sulphation polyethoxy nonyl phenol；

Described second surface activating agent with least 0.35 weight % based on described dry coating gross weight and at most and includes 1.1 weights The amount of amount % is present in the dry coating of described mixture；With

Based on described dry coating gross weight, the total amount of described first and second surfactants in the dry coating of described mixture It is at most and includes 3.35 weight %.

4. the compositionss any one of claims 1 to 3, wherein said first surface activating agent is by R-CH₂-CH=CH- CH₂-S(=O)₂O^-Na⁺The compound representing, wherein R is C₁₀、C₁₁Or C₁₂Alkyl, or there is such compound of different R group Mixture, described R group is C₁₀To C₁₂In alkyl any kind；And described second surface activating agent is by R '-phenyl-(O- CH₂CH₂)_n-S(=O)O₂ ^-NH₄ ⁺Represent, wherein R ' is C₈To C₁₂Alkyl, and n is 3 to 10.

5. the compositionss any one of Claims 1-4, wherein said first polymer latex and described second polymer At least one in latex comprises polyvinyl, and described polyvinyl also comprises derived from having containing at least 2 The repetitives of (methyl) alkyl acrylate of the ester alkyl of carbon atom.

6. the compositionss any one of claim 1 to 5, in wherein said first polymer and described second polymer At least one is crosslinked.

7. a kind of substrate, it comprises supporter and the dry bottom enamelled coating being arranged at least one stayed surface of described supporter, Described dry bottom enamelled coating comprises the compositionss any one of claim 1 to 6.

8. the substrate described in claim 7, it has at least 88% comprehensive absorbance.

9. the substrate described in claim 7 or 8, its comprise transparent polymeric support having be directly arranged at described transparent poly- Described dry bottom enamelled coating on compound supporter.

10. the substrate any one of claim 7 to 9, the described first polymer latex in wherein said dry bottom enamelled coating With the weight of described second polymer latex than for 1:3 and to and include 3:1.

Substrate any one of 11. claim 7 to 10, wherein said dry bottom enamelled coating has at least 0.05 μm and at most And include 0.4 μm of average thickness.

Substrate any one of 12. claim 7 to 11, it comprises poly- (ethylene glycol terephthalate) or poly- (naphthalene two Formic acid glycol ester) supporter.

Substrate any one of 13. claim 7 to 12, it is continuous flexible substrates.

A kind of product of any one of 14. claim 7 to 13, and comprise：Transparent polymeric support and be arranged in described Described dry bottom enamelled coating at least one stayed surface of bright supporter, and the average live width comprising to have less than 15 μm The patterning materials of line, described patterning materials are directly arranged on described dry bottom enamelled coating.

Product described in 15. claim 14, wherein said patterning materials comprise selected from gold, silver, copper, palladium, platinum, nickel and its front The conducting metal of body or its precursor.

Product described in 16. claims 14 or 15, wherein said patterning materials comprise free-radical curable compositionss, can The mixture of the both compositions of the compositionss of the compositionss of acid catalysiss solidification or free-radical curable and theobromine catalytic curing.

Product described in 17. claims 14 or 15, wherein said patterning materials comprise to be dispersed in photocuring or heat cure group Metallic particles in compound.

Product any one of 18. claim 14,15 and 17, wherein said patterning materials comprise to be dispersed in photocuring Or the granule of the gold, silver in heat-curing composition, copper, palladium or platinum, described photocuring or heat-curing composition are derived from can be free The compositionss of base solidification and the both compositions of theobromine catalytic curing.

A kind of 19. methods, it is used for providing the product any one of claim 14 to 18, and methods described includes：

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

Method described in 20. claim 19, at least a portion of the pattern of wherein said patterning materials comprises to have and is less than 15

μm average live width line.

Method described in 21. claim 19 or 20, described at least a portion of the pattern of wherein said patterning materials exists In the touch screen zone of the described product primed.

Method any one of 22. claim 19 to 21, it includes：

Method any one of 23. claim 19 to 22, wherein said patterning materials comprise conducting metal or its before Body.

Method any one of 24. claim 19 to 23, it also includes：

It is solidificated in the photocurable in described patterning materials or heat-setting compositionss.

Method any one of 25. claim 19 to 24, wherein said patterning materials comprise metallic particles, and institute Method of stating also includes：

A kind of 26. products, it is obtained by the method any one of claim 19 to 25, and wherein said product comprises conduction At least one pattern of material, at least a portion of the pattern of wherein said conductive material comprises to have average less than 15 μm The conductor wire of live width, the described part of the pattern of described conductive material is directly arranged at the described dry of described substrate On prime coat.

Method any one of 27. claim 19 to 25, it includes：

There is provided described substrate as continuous coiled material,

Distinguish and directly provide on the described dry bottom enamelled coating in one or more unitary part of described continuous coiled material and can consolidate light Change or heat-setting compositionss one or more independent pattern as described precursor conductive material, described photocurable or Heat-setting compositionss comprise metal seeds granule,

Such as any one of claim 7 to 13 substrate required for protection is provided,

Carry described photocurable or heat by making the described dry bottom enamelled coating directly contact in the Part I of described continuous coiled material The flexographic plate print-member of compositionss, directly forms on the described dry bottom enamelled coating in the described Part I of described continuous coiled material First curable pattern, the described first curable pattern comprises the photocurable containing seed metal granule or thermal curable Compositionss,

The described continuous coiled material making to comprise the described Part I of the pattern curable including described first advances near solidification Stand and solidify the described first curable pattern, the first cured pattern is thus formed on described Part I, described first is solid Change pattern and comprise described seed metal granule,

The described continuous coiled material making to comprise the described Part II of the pattern curable including described second advances near solidification Stand and solidify the described second curable pattern, the second cured pattern is thus formed on described Part II, described second is solid Change pattern and comprise identical or different seed metal granule,

Method described in 29. claim 28, wherein identical seed metal granule are present in the plurality of cured pattern In each, described seed metal granule is gold grain, Argent grain, copper granule, palladium granule or platinum grain.

Method described in 30. claim 28 or 29, wherein makes in each formation feature of the pattern curable for each With identical photocurable or heat-setting compositionss.

Method any one of 31. claim 28 to 30, wherein in each formation for each curable pattern Using the photo curable compositionss of identical in feature, described photo curable compositionss comprise the combination of free-radical curable Thing, the compositionss of theobromine catalytic curing, or the compositionss of free-radical curable and the both compositions of theobromine catalytic curing.

A kind of 32. equipment of the product comprising any one of claim 14 to 18 and 26, it comprises to be directly arranged at described doing One or more conductive metal pattern on prime coat,

Equipment described in 33. claim 32, it is touch panel device.