KR19990044418A - Articles coated with release coatings that contain electrophotographic toner - Google Patents

Abstract

The present invention relates to articles that can receive and adhere printed indicia and maintain good peeling properties. Articles of the invention are coated with a release agent on a substrate such as paper. A release coating capable of containing toner particles released by an electrophotographic device includes a polymer having at least one vinyl polymer segment and a at least one siloxane polymer segment having a T _g of −10 ° C. to 65 ° C.

Description

Articles coated with release coatings that contain electrophotographic toner

Known note pads include a large amount of paper sheets, each of which is a small, low-tack pressure adjoining one edge of the back surface that allows the sheet to be temporarily attached to a substrate, such as a document or other item (often for letter delivery purposes). Having an adhesive strip, the sheets are attached together to the pad by the adhesive strip. In one pad structure all the strips of adhesive are present along one side of the note pad, while in the other pad structure the adhesive strip is along the opposite side of the pad as disclosed in US Pat. No. 4,416,392 on each successive sheet in the pad. exist. Both note pads are currently sold under the trademark "Post-it" of the Minnesota Mining and Manufacturing Company (St. Paul, Minnesota).

Many conventional electrophotographic devices, such as printers and copiers, use dry toner. These printers and / or copiers use toner to form latent images on substrates such as paper, tags or label stock that can be delivered from an imaging device. The latent image treated with the toner is then heat melted to obtain the best print quality and tonerized image density.

Although the generated images often have good quality, there are problems associated with the imaging process using printers and / or copiers. For example, a problem arises in which various unwanted substances such as toner particles accumulate on a substrate.

Another common apparatus for office and commercial printing uses inks or inks containing pigments with carrier excipients. Examples of such printing devices include ink jets, offsets, flexographic, copiers or electrophotographic printers. The image is applied to the substrate and the excipient is absorbed into the substrate and then evaporated. Occasionally, the substrate is heated to improve the evaporation of the ink excipients.

Problems with such printers include "ghosting", in which ink delivery to the substrate is unstable. Typically, the residual ink is transferred to another roller of the printer and then to the substrate outside the register. This results in an easily colored image. Another problem with ink jet printing is the tendency of the ink to dewet from the substrate and not absorb or dry in the substrate. In each case, the ink stains when the continuous sheet contacts the image.

When the printed sheet is formed into a note pad, a release coating is typically used to easily remove the sheet from the pad. This release coating should accommodate the release coating in general writing implements and printing inks (lines 1 and 2 related to the background art of U.W. Patent No. 5,154,962). Peel coatings are selected to provide high quality images using specific printing techniques and to prepare for separation from the adhesive.

Commercial printing using offset printing apparatus, a centralized production facility, has long been practiced in the industry. However, the small publishing industry and the electronics industry are rapidly changing the print industry from centralized production by simple printing technology to decentralized production using various printing technologies. For example, the need for printing may require both offset printing (eg, company logo) followed by zero graphics production (eg, personal business cards).

In any case, the peel-coated substrate should be water soluble so that the markings can be firmly fixed. Coated substrates must first receive indicia without "backgrounding" in electrophotographic devices, "ghosting" in some printers, or staining in liquid ink printers. In addition, when formed into a pad, the printed mark should be firmly adhered to the substrate without transferring from the pad to the adhesive of the aforementioned notebook.

Coating is carried out to increase the water solubility of the ink or toner particles. International patent application US / 90/03286 (Joseph et al.) Discloses a toner water-soluble coating that can be applied to paper. U. S. Patent No. 5,154, 962 discloses an indication water soluble release coating that is particularly useful for writing with pens containing water soluble inks. However, there is no reference that teaches release coatings that accept and firmly adhere marks from various alignment devices including offset, ink jet, and zero graphics printers. Often customizations were made using sheet feeders such as laser printers, ink jet printers, and zeroographic copiers. This printing is useful when using a printed notepad. This pad can be made using the structures and methods disclosed in US Pat. No. 5,382,055. Accordingly, there is a need for a release coating that can receive and adhere toner particles, offset inks, and other liquid inks and toner at present.

The present invention relates to a release coating and to articles coated with the release coating. In particular, the present invention relates to a release coating having a printed mark, even when contacted with a repositionable pressure sensitive adhesive.

1 is a representative of one embodiment of the present invention tested according to the procedures described herein.

2 is a representative of Avery 30-up stock # 5160 tested according to the procedures described herein.

3 is an edge view of the sheet assembly according to the present invention.

4 is a simplified cross-sectional view taken along line 4-4 of FIG. 3.

Summary of the Invention

The present invention includes an article coated with a release coating capable of accepting and securing printed marks, which also maintain good peeling properties. The release coating of the present invention is applied onto a substrate such as paper. The article is in the form disclosed in US Pat. No. 5,382,055 and is useful for making small amounts of notes or note pads. The release coating includes a polymer having at least one vinyl polymer segment and at least one siloxane polymer segment having a T _g of −10 ° C. to 65 ° C. It is preferable that the T _g of the vinyl polymer segment is 200 ° C to 450 ° C.

In one aspect of the invention, the coating is a copolymer comprising the following formula:

Where

Each R ₁ may be the same or different and is a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxy, hydrogen and fluoroalkyl;

Each R ₂ is a divalent linking group which may be the same or different;

Each R ₃ may be the same or different and is a monovalent moiety selected from the group consisting of alkyl, aryl, alkylaryl, alkoxy, alkylamino, hydroxy, hydrogen and fluoroalkyl;

Each R ₄ is a divalent linking group which may be the same or different;

x is an integer from 0 to 3;

y is an integer of at least 10;

q is an integer from 0 to 3;

G ₅ and G ₆ are the same or different monovalent moieties each selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and -WSA, wherein W is a divalent linking group, A Is defined as follows;

G ₂ and G ₄ are A and A is a vinyl polymer segment or block consisting essentially of polymerized free radically polymerized monomers.

In another aspect of the invention, the coating comprises a copolymer of D and E monomers copolymerized to form a polymer backbone and F monomers grafted thereto, wherein:

D is at least one free radical polymerizable vinyl monomer;

E is at least one polar monomer copolymerizable with D, the amount of E being no more than 30% of the total weight of all monomers;

F is a monomer having the formula

X- (Y) _n SiR _(3-m) Z _m

In the above formula,

X is a vinyl group copolymerizable with D and E monomers;

Y is a divalent linking group where n is 0 or 1;

m is an integer from 1 to 3;

R is hydrogen, lower alkyl (eg methyl, ethyl or propyl), aryl (eg phenyl or substituted phenyl), or an alkoxy group;

Z is a monovalent siloxane polymer part having a number average molecular weight of about 1,000 or more and hardly reacts under copolymerization reaction conditions.

The present invention also includes a toner water-soluble article comprising a substrate such as a liner, a release coating and a label installed on the liner.

Detailed Description of the Preferred Aspects

The present invention includes an article coated with a release coating capable of fixing the toner. The release coating has at least one siloxane polymer segment and at least one vinyl polymer segment having a T _g of −10 ° C. to 65 ° C. Due to the chemical composition and structure and production characteristics, the release coating is suitable for adjusting the application to which the toner is fixed. In particular, it is believed that the silicon segment exhibits low energy, and the "siliconed" release surface and the high energy vinyl polymer segment provide adhesion to toner particles.

In one aspect of the invention, the coating is a copolymer comprising the following formula:

Formula 1

Where

R ₁ is a monovalent moiety which may be the same or different, each selected from the group consisting of alkyl, aryl, alkylaryl, alkoxy, alkylamino, hydroxy, fluoroalkyl and hydrogen. Preferably R ₁ is the same or different _monovalent moiety each selected from the group consisting of C _1-4 alkyl and hydroxy. Most preferably R ₁ is selected from the group consisting of methyl and butyl.

R ₂ is a divalent linking group which may be the same or different, respectively. Suitable divalent linking groups include but are not limited to: C ₁ to C ₁₀ alkylene, arylene, alkyl arylene and alkoxyalkylene. Preferably R ₂ is selected from the group consisting of C _1-3 alkylene and C ₇ -C ₁₀ alkylarylene to facilitate synthesis of the compound. Most preferably R ₂ is —CH ₂ —; 1,3-propylene; And It is selected from the group consisting of.

R ₃ is the same or different monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxy and fluoroalkyl and hydrogen, respectively. Preferably R ₃ is a _monovalent moiety which may be the same or different, respectively, selected from the group consisting of C _1-4 alkyl and hydroxy. Most preferably R ₃ is selected from the group consisting of methyl and butyl.

R ₄ is a divalent linking group which may be the same or different, respectively. Suitable divalent crosslinking groups include, but are not limited to: C ₁ to C ₁₀ alkylene, arylene, alkylarylene and alkoxyalkylene. Preferably R ₄ is selected from the group consisting of C _1-3 alkylene and C ₇ -C ₁₀ alkylene to facilitate synthesis. Most preferably R ₄ is —CH ₂ —; 1,3-propylene; And It is selected from the group consisting of.

G ₅ and G ₆ are the same or different monovalent moieties selected from the group consisting of alkyl, aryl, alkylaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and -WSA, wherein W is a divalent linking group, A Is defined below.

W is a divalent linking group. Suitable divalent linking groups include, but are not limited to, C ₁ to C ₁₀ alkylene, alkylene, arylene and alkoxyalkylene. Preferably W is selected from the group consisting of methylene and propylene.

G ₂ and G ₄ are the same or different and comprise A. A is a vinyl polymer segment consisting essentially of polymerized free radical polymerizable monomers. A includes homopolymer segments or blocks or copolymer segments or blocks. Toner sticking properties of the coating are determined by the vinyl polymer segment content. The chemical properties or composition of the vinyl polymer segments can be varied regardless of the peeling properties that improve the adhesion and adhesion of the toner to the substrate. Thus, the release coating can be chemically fabricated to provide a specific level of toner fixation. Typically composition A is selected based on the intended use of the release coating and the properties that the release coating must possess to achieve the intended purpose.

A includes, but is not limited to, free radically polymerizable monomer (s) selected such that the vinyl segment has a T _g or T _m of at least about −20 ° C. Preferred free radically polymerizable monomers are styrene, methyl methacrylate, methyl acrylate, acrylic acid, methacrylic acid, acrylonitrile, isobornyl acrylate, isobornyl methacrylate, N-vinyl pyrrolidone, butyl Methacrylate, isopropyl methacrylate, vinyl acetate, hydroxy propyl acrylate, hydroxy ethyl acrylate and mixtures thereof.

The amount and composition of the vinyl segment relative to the silicone ranges from about 98 to about 2 parts by weight, preferably from about 40 to 60 parts by weight. The vinyl polymer segment preferably has a molecular weight of 2,000 to 80,000, more preferably 5,000 to 50,000.

The peeling properties of the coating are determined by the silicone content (weight percent) present in the copolymer and the molecular weight of the silicone segment, with higher silicone content and / or higher molecular weight being more easily peeled off. The copolymer or copolymer mixture may therefore be chemically prepared to provide a consistent level of reproducibility that is consistently reproducible, thereby varying the peeling properties of the liner in a range of controlled types of values.

The silicone polymerizable segment should have an average molecular weight of at least about 1000 for the release coating to function properly. The silicone polymer segment preferably has a number average molecular weight of about 1,000 to about 20,000. Most preferably, the silicone polymer segment has a number average molecular weight of about 2,000 to 15,000. The silicone polymer segment may comprise about 2 to 60 weight percent of the peel coating for a wide range of peel performance.

In another aspect of the invention, the release coating comprises a copolymer of D and E monomers copolymerized to form a polymer backbone. F monomer is grafted to the backbone. D and E monomers provide toner sticking properties of the coating and F monomers provide peeling properties.

The D monomer or monomers (which may be one or more) are selected such that the T _g or T _m of the backbone is at least about −20 ° C. Representative examples of D monomers are styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, and methanol, ethanol, propanol, isopropanol, butanol, isobutanol, cyclohexanol, benzyl alcohol dodecanol, hexadecanol and octa Non-tertiary or tertiary alcohols such as decanol and esters of acrylic acid or methacrylic acid, the alcohols having from 1 to about 18 carbon atoms.

Particularly preferred D monomers include methyl methacrylate, butyl methacrylate, vinyl acetate, partially hydrolyzed vinyl acetate, methyl acrylate and octadecyl acrylate.

Representative E monomers useful in the present invention and that can be used individually or in combination are carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and 2-carboxyethyl acrylate and ammonium thereof Or metal salts; Sulfonic or phosphonic acids and ammonium salts or metal salts thereof such as 2-sulfoethyl methacrylate, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, strene sulfonic acid, and vinyl benzyl phosphonic acid; Amides such as acrylamide, methacrylamide, N, N-dimethyl acrylamide, and N-vinyl pyrrolidone; And monomers, alkylating agents or proton acids and amine-containing monomers having hydroxy functional groups (e.g., 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate and dihydroxypropyl acrylate). Eg, ammonium functionality induced in the reaction of N, N-dimethylaminoethyl methacrylate and vinyl pyridine) or zwitterionic functionality such as induced by the reaction of hydrogen peroxide or propane sulfone with an amine monomer. .

F monomers are compounds having Formula 2:

Formula 2

X- (Y) _n SiR _(3-m) Z _m

Where

X is a vinyl group copolymerizable with D and E monomers;

Y is a divalent linking group;

R is hydrogen, lower alkyl group (eg methyl, ethyl, or propyl), aryl group (eg phenyl, or substituted phenyl) and alkoxy groups (eg methoxy and ethoxy groups);

Z is a monovalent siloxane polymer moiety having a number molecular weight of at least about 1,000 and rarely reacts under copolymerizable reaction conditions.

Preferred F monomers can also be defined as having the X group of the formula:

In the above formula, R ¹ is a hydrogen atom or a COOH group, and R ² is a hydrogen atom, a methyl group or a CH ₂ COOH group.

The Z group of the F monomer has the formula

Wherein R ³ and R ⁵ are each lower alkyl, aryl, or fluoroalkyl, lower alkyl and fluoroalkyl both mean an alkyl group having 1 to 3 carbon atoms and aryl means phenyl or substituted phenyl do. R ⁴ is alkyl, alkoxy, alkylamino, aryl, hydroxy, or fluoroalkyl, r is an integer from 5 to 700. The F monomer has a formula selected from the group consisting of the following formulas 5 to 10; m is 1, 2, or 3; p is 0 or 1; R ″ is alkyl or hydrogen; and X, R and Z are as above:

(q is an integer from 2 to 6)

(q is an integer of 0 to 2)

(q is an integer from 2 to 6)

And

(q is an integer from 2 to 6)

The release coating of the present invention may comprise a copolymer of two embodiments alone, or may include a copolymer mixed with other compatible homopolymers and / or copolymers. If the proportion of silicone included in the copolymer is low, the copolymer can be readily compatible with polymers of composition similar to vinyl polymer blocks or segments. There are also several pairs of dissimilar polymers that yield compatible mixtures by specific interactions, as disclosed in S. Krause et al. (Polymer Blends, Academic Press, New York, 1978). Introducing low concentrations of silicon blocks onto one of these polymers does not affect compatibility.

In addition, additives, fillers or pigments such as alumina, silica, titanate, or calcium carbonate can be added to the copolymer composition.

The release coating of the present invention can provide a sufficient fixation spot for securing at least about 50% of the toner. "Substantially" is considered to mean 50% or more. It is more preferable to fix at least 70% of the toner.

In addition, the release coating should have a surface peel value of less than about 10 oz./in (11 N / dm). This upper limit applies when using strong pressure-sensitive adhesives (PSAs) having a peel adhesion value of 45 N / dm or more. PSAs are widely available in three categories: (1) low peel adhesion (5-15 N / dm), (2) medium peel adhesion (25-50 N / dm), and (3) high peel adhesion (60-100 N / dm). ) Into the range. The degree of peeling is selected according to the adhesion of the PSA to be contacted, and a high peeling value such as 10 oz / in (11 N / dm) is selected only for the PSA having the strongest adhesion. Peel coatings of PSAs with less strong adhesion are selected correspondingly low.

The release composition does not require curing or crosslinking; However, if solvent resistance is required for a particular application, the crosslinking can be carried out by standard methods known in the art such as radiation curing (electron beam or ultraviolet) or chemical crosslinking.

The release coating composition can be applied to any suitable backing or liner with conventional coating techniques such as wire-wound rods, direct gravure, offset gravure, reversing rolls, air-knife and trading braid coating. have. Suitable liners include paper, nonwovens, and films of thermoplastics such as polyesters, polyamides, polyolefins, polycarbonates, and polyvinyl chlorides.

It is also possible to use any substrate that can be applied to the liner by pressure sensitive adhesive. For example, paper is a suitable substrate.

In a preferred embodiment, the release coating of the present invention is used as a component of a label stock. In this preferred embodiment, one or more non-continuous substrates, such as labels, are attached to the protective liner with a suitable adhesive. The release coating of the present invention is coated on the liner so that the substrate is removed from the liner.

A particularly useful structure is the sheet assembly, as described below and in FIGS. 3 and 4. Sheet assembly 10 is illustrated with release coating 40 on one or more unbonded areas of back surface 15 of sheets 12 and 13. The release coating 40 can be applied to the strip, slightly wider than the strip 16 of the adhesive, and extends across the sheets 12 and 13 parallel to the edges 30, 36 and 37 and each strip release coating. 40 is adjacent to and extends along the edges of portions 34 of sheets 12 and 13 formed by separating sheets 12 and 13 along weak portions 31 and 33, the back surface of the sheet ( When 15) is laid face-to-face as illustrated in FIG. 3, the strip layer 16 of each adhesive is in contact with and generally positioned at the center of the strip release coating 40. As also illustrated, this coating is not necessary, but the entire front surface 14 of each sheet 12 and 13 is coated with a release coating 41. For example, the illustrated release coating 40 on the back surface 15 and the release coating 41 on the front surface 14 of the sheets 12 and 13 may be a low adhesive or repositionable adhesive layer 16 of the adhesive. Is not required (e.g., a low-tack adhesive based primarily on cohesive, elastomeric copolymer microspheres disclosed in US Pat. Nos. 3,961,140 and 3,857,731). The release coatings 40 and 41 allow the use of a more cohesive and permanent pressure sensitive adhesive layer 16 than the repositionable adhesive. Suitable release coatings 40 and 41 are materials and treatments of the present invention. When the sheets 12 and 13 are of a specific material or impregnated with a peeling material to easily peel off the adhesive layer 16 therefrom, the peel coatings 40 and 41 together with the adhesive pressure-sensitive adhesive layer 16 are applied. It may not be necessary.

3 and 4 show a specific arrangement of sheet assembly, this example and description are merely illustrative of the invention and other aspects are within the scope of the invention.

The following examples are exemplary features and are not intended to limit the invention.

Test sample

The polymer solutions of Examples 1 to 19 described below were diluted to 15% solids in distilled water. The solution was then coated onto commercial roll base paper using a gravure roll having a pyramid structure of 200 cells per inch. Two roll directional gravure coatings were applied to each sample. Two different roll base papers were used. Glossy paper CIS paper from Simpson Paper Company was coated with the dilute polymerization solution of Examples 1-4 and Akrosil's mechanical gloss base paper was coated with the dilute polymer solution of Examples 4-19. After coating, the base paper was dried at 77 ° C.

Test method

Peeling properties

Peeling properties of an adhesive means that the adhesive is easy to separate from other surfaces. The force required to remove the flexible adhesive tape from the test sample at a particular angle and removal rate. Measured in Newtons per decimeter (N / dm). Two sample methods are used to evaluate the peeling and marking fixation properties of the coated flexible sheet material. Two tests are modified versions of the industry standard peel adhesion test ASTM D3330-78 PSTC 1 and 3 used to evaluate PSA coated materials. Two modified peeling property tests were performed as follows.

1. Peel value

Each test sample was set overnight at constant temperature (22 ° C.) and humidity (50% RH) conditions. A 5.08 cm × 25.4 cm strip of test sample was then laminated with a double coated tape to a constant 90 ° jig of a commercial Deltron Ball Slide (J.R. Brass Co., Eden Prairie, Minn.). Subsequently, a 2.54 cm strip of PSA coated (# 810 tape, commercial assignee of the present application) was rolled onto the laminate using a 1.82 kg rubber roller. Subsequently, the force required to remove this tape at 90 ° and 30.5 cm / min was determined by the commercial Sintech / Instron Tensile Tester from SYNTEC Corporation, a division of MTS Systems Corp., Research Triangle Park, North Carolina. Measured by System.

2. Toner Soluble Test

Toner acceptability of the test samples was evaluated by printing an asterisk pattern (ie, ****) on a strip of 21.6 cm by 27.9 cm in a Hewlett Packard Laser Jet II printer. The imaged coating sheet was then left overnight in an environment controlled at 21 ° C. and 50% RH. Thereafter, a 2.54 cm × 25.4 cm strip of Scotch ^™ Brand 810 ^™ tape made by the Minnesota Mining and Manufacturing Company was rolled onto the test sample imaged in two passes of a 1.82 kg rubber roller. After two passes, the test sample was placed for 24 hours at controlled conditions of 21 ° C. and 50% RH. The Scotch ^™ Brand 810 ^™ tape is laminated with double coated tape to the image of the side of the stage in the TIMI Peel and Adhesion Tester from Testing Machines Inc. (Mitiville, NY). The 810 ^™ tape was then removed at 3048 cm / min, 180 ° peel angle. Image analysis is used to determine the amount of marking that is stuck to the coating sheet.

Abbreviation

AA- acrylic acid

AIBN-2-21-azobisbutyronitrile

BMA-Butyl Methacrylate

EMA-ethyl methacrylate

IPA- Isopropyl Alcohol

KF2001- Mercapto-functional dimethyl siloxane using commercially available mercapto-functional 4-5 mol% by Shin-Etsu

MA- methacrylic acid

MAA-methyl acrylate

MEK-methyl ethyl ketone

MMA-Methyl Methacrylate

ODA- Octadecyl Acrylate

Example 1

The composition of Example 1 was prepared as follows:

First, 45 g of mercapto functional dimethyl siloxane, 169 g of methyl acrylate, 11 g of acrylic acid, 335 g of methyl ethyl ketone in a 32 oz reaction bottle having 4-5 molar mercapto functionality of Shin-Etsu's commercial KF-2001. MEK) and 0.56 g of 2,2'-azobisisobutyronitrile (AIBN) were charged to prepare a solvent-based sample. Thereafter, the solution mixture was rinsed with nitrogen gas at 1 L / min for 2 minutes and then the bottle was sealed. The sealed bottle containing the clear solution was then placed in a constant temperature bath at 55 ° C. for 20 hours to give a viscous cloudy white solution.

Thereafter, 860 g of deionized (DI) water and 9 g of NH ₄ OH were charged into a 1 gallon bottle to prepare an aqueous solution. 537 g of solvent-based solution (40.0% solids) was then added to the solution in 1 gallon bottle. The resulting solution was placed in a shaker and shaken for 1 hour 30 to complete neutralization. MEK was then stripped from the resulting viscous solution in a rotary evaporator at 40 ° C. using an aspirator vacuum to obtain a 19.0% solids solution. Additional amount of DI water was added to give a 15.0% solids solution. This component was used to form a solvent-based solution, and the amounts of components used are shown in Tables 1 and 2, respectively. The components of the release coating, weight percent of the components and the test results are shown in Table 3.

Example 2-20

The copolymer of Examples 2-20 was prepared following the procedure outlined in Example 1. The components were used to prepare the solvent based solution and the aqueous solution, and the amounts of the components used are shown in Tables 1 and 2, respectively. The components of the release coating, weight percent of the components and the test results are shown in Table 3.

Example Components Used for Polymerization Reaction Amount of ingredient used in grams One KF2001 / MA / AA / MEK / AIBN 45/169/11/335 / 0.56 2 KF2001 / MA / AA / MEK / AIBN 25/70/10 / 157.5 / 0.52 3 KF2001 / MA / AA / MEK / AIBN 50/140/20/315 / 0.53 4 KF2001 / MA / MAA / MEK / AIBN 50/140/10/300 / 0.5 5 KF2001 / MA / MAA / MEK / AIBN 52/182/26/390 / 0.65 6 KF2001 / MA / MAA / MEK / AIBN 62/173/25/390 / 0.65 7 KF2001 / MA / MAA / MEK / AIBN 60/140/20/330 / 0.55 8 KF2001 / MA / MAA / MEK / AIBN 60/140/10/315 / 0.53 9 KF2001 / MA / MAA / MEK / AIBN 50/120/10/300 / 0.5 10 KF2001 / MA / MAA / MMA / MEK / AIBN 65/130/13/52/390 / 0.65 11 KF2001 / MA / MAA / MMA / MEK / AIBN 30/75 / 7.5 / 37.5 / 225 / 0.38 12 KF2001 / MA / MAA / MMA / MEK / AIBN 37.5 / 60 / 7.5 / 45/225 / 0.38 13 KF2001 / MA / MAA / MMA / MEK / AIBN 37.5 / 45 / 7.5 / 60/225 / 0.38 14 KF2001 / MA / MAA / MMA / MEK / AIBN 37.5 / 30 / 7.5 / 75/225 / 0.38 15 KF2001 / MA / MAA / MMA / MEK / AIBN 39.5 / 71 / 7.9 / 31.6 / 225 / 0.38 16 KF2001 / MA / MAA / MMA / MEK / AIBN 35.7 / 78.6 / 7.1 / 28.6 / 225 / 0.38 17 KF2001 / MA / MAA / MMA / MEK / AIBN 34.1 / 81.8 / 6.8 / 27.3 / 225 / 0.38 18 KF2001 / MA / MAA / MMA / MEK / AIBN 32.6 / 84.8 / 6.5 / 26.1 / 225 / 0.38 19 KF2001 / MA / MAA / MMA / MEK / AIBN 31.2 / 87.5 / 6.2 / 25/225 / 0.38 20 KF2001 / MA / MAA / MMA / MEK / AIBN 50/100/10/40/300 / 1.0

Example Ingredients Used to Prepare Aqueous Solutions Amount of ingredient used in grams One Polymer ¹ / NH ₄ OH / H ₂ O 537/9/860 2 Polymer / NH ₄ OH / H ₂ O 537 / 9.0 / 645 3 Polymer / NH ₄ OH / H ₂ O 520 / 8.8 / 650 4 Polymer / NH ₄ OH / H ₂ O 326/5/540 5 Polymer / NH ₄ OH / H ₂ O 320/9/500 6 Polymer / NH ₄ OH / H ₂ O 320/8/500 7 Polymer / NH ₄ OH / H ₂ O 321/540/9 8 Polymer / NH ₄ OH / H ₂ O 325/5/540 9 Polymer / NH ₄ OH / H ₂ O 317/5/540 10 Polymer / NH ₄ OH / H ₂ O 320 / 4.3 / 500 11 Polymer / NH ₄ OH / H ₂ O 360 / 7.5 / 576 12 Polymer / NH ₄ OH / H ₂ O 345 / 4.6 / 530 13 Polymer / NH ₄ OH / H ₂ O 345 / 4.7 / 530 14 Polymer / NH ₄ OH / H ₂ O 345 / 4.6 / 520 15 Polymer / NH ₄ OH / H ₂ O 340/5/530 16 Polymer / NH ₄ OH / H ₂ O 340 / 4.4 / 530 17 Polymer / NH ₄ OH / H ₂ O 340 / 4.2 / 530 18 Polymer / NH ₄ OH / H ₂ O 340/4/530 19 Polymer / NH ₄ OH / H ₂ O 340/4/530 20 Polymer / NH ₄ OH / H ₂ O 480/5/760 ^One polymer is the reaction product of KF2001, MA and AA and / or MAA or MMA.

Example ingredient Weight percent components T _g ℃ tape Peel g / inch Surface Acceptance% Early One MA / KF2001 / AA 70/20/5 11 A 51 8 2 MA / KF2001 / AA 70/25/10 16 A 10 75 3 MA / KF2001 / AA 70/25/5 20 A 15 68 4 MA / KF2001 / MAA 70/25/5 18 A 8 88 5 MA / KF2001 / MAA 70/20/10 26 A 10 56 6 MA / KF2001 / MAA 70/25/10 26 A 9 38 7 MA / KF2001 / MAA 70/30/10 26 A - 25 8 MA / KF2001 / MAA 70/30/5 ? A - 22 9 MA / KF2001 / MAA / MAA 60/25/10/5 ? A - 58 10 MA / KF2001 / MAA / MAA 50/25/20/5 40 A 14 92 11 MA / KF2001 / MAA / MAA 50/20/25/5 44 A 23 78 12 MA / KF2001 / MAA / MAA 40/25/30/5 18 A 34 75 13 MA / KF2001 / MAA / MAA 30/25/40/5 22 A 88 64 14 MA / KF2001 / MAA / MAA 20/25/50/5 30 A 157 50 15 MA / KF2001 / MAA / MAA 45/25/20/5 42 A 23 84 16 MA / KF2001 / MAA / MAA 55/25/20/5 38 A 15 88 17 MA / KF2001 / MAA / MAA 60/25/20/5 36 A 37 88 18 MA / KF2001 / MAA / MAA 70/25/20/5 34 A 31 90 19 MA / KF2001 / MAA / MAA 70/25/20/5 33 A 58 85 20 MA / KF2001 / MAA / MAA 50/25/20/5 40 B 27 92 A = acrylic B = rubber

Example 21

The composition of Example 21 was prepared in the following manner:

First in a 4 ounce glass bottle, 4 g of 15K silicon macromer (SiMac), 16 g of ethyl methacrylate (EMA), 30 g of methyl ethyl ketone (MEK) and 0.06 g of 2 prepared by the method disclosed in US Pat. No. 7,728,571. A solvent-based sample was prepared by charging 2,2'-azobisbutyronitrile (AIBN). Thereafter, the contents of the bottle were washed with nitrogen gas for 2 minutes. The bottle is then sealed and placed in a 55 ° C. water bath for 48 hours.

The sample was then diluted to 10% solids for coating. 40 g of 40% solids polymer solution, 96 g of toluene and 24 g of isopropanol (IPA) were added to a 16 ounce wide bottle. The mixture was shaken to obtain a homogeneous mixture. This component was used to form a solvent-based solution, and the amounts of components used are shown in Tables 4 and 5, respectively. The components of the release coating, weight percent of the components and the test results are shown in Table 6.

Example 22-27

The copolymers of Examples 22-27 were prepared following the procedure outlined in Example 21. The components were used to prepare solvent based solutions, the amounts used are shown in Tables 4 and 5, respectively.

Example Components Used in Polymerization Reaction Amount of Ingredient Used (g) 21 15KSIMAC / EMA / MEK / AIBN 4/16/30 / 0.06 22 15KSIMAC / EMA / MMA / MEK / AIBN 5 / 7.5 / 7.5 / 30 / 0.06 23 15KSIMAC / EMA / BMA / MEK / AIBN 5 / 7.5 / 7.5 / 30 / 0.06 24 15KSIMAC / EMA / MA / MEK / AIBN 5 / 7.5 / 7.5 / 30 / 0.06 25 15KSIMAC / MMA / BMA / MEK / AIBN 5 / 7.5 / 7.5 / 30 / 0.06 26 15KSIMAC / EMA / ODA / MEK / AIBN 5/11/4/30 / 0.06 27 15KSIMAC / EMA / MEK / AIBN 5 / 7.5 / 7.5 / 30 / 0.06

Example Ingredients Used to Prepare Solvent-Based Solutions Amount of Ingredient Used (g) 21 Polymer ² / Toluene / IPA 40/96/24 22 Polymer / Toluene / IPA 40/96/24 23 Polymer / Toluene / IPA 40/96/24 24 Polymer / Toluene / IPA 40/96/24 25 Polymer / Toluene / IPA 40/96/24 26 Polymer / Toluene / IPA 40/96/24 27 Polymer / Toluene / IPA 40/96/24 ^{The second} polymer is the reaction product of the components listed in Table 5 for each example.

Example ingredient Weight percent components Tg ℃ tape Peel g / inch Indicator% Toner Acceptance Early 21 EMA / 15KSiMac 80/20 47 A 34 88 22 EMA / MMA / 15KSiMAC 37.5 / 37.5 / 25 84 A 70 88 23 EMA / BMA / 15KSiMac 37.5 / 37.5 / 25 41 A 61 90 24 EMA / MA / 15KSiMac 37.5 / 37.5 / 25 35 A 23 87 25 MMA / BMA / 15KSiMaC 37.5 / 37.5 / 25 57 A 32 88 26 EMA / ODA / 15KSiMac 55/20/25 - A 91 96 27 EMA / AA / 15KSiMac 37.5 / 37.5 / 25 85 A 34 99 A = acrylic

Example 28

In particular, sheet assemblies that can be adapted to be printed on both sides in a printer of the type described above are used in addition to the use of four instead of two layers 16 of pressure sensitive adhesives positioned in spaced relation to each sheet 12 and 13. It has the structure illustrated in 1. Sheets 12 and 13 are each 20 pound bond paper, each about 8.5 x 11 inches, and sheet 13 is slightly longer and protrudes about 1 inch from edge 37. The pressure sensitive adhesive layer 16 was a copolymerized adhesive structured with microspheres disclosed in US Pat. No. 3,691,140 (Silver), dispersed at 8% solids in n-heptane. The release coating layer 40 was crosslinked to Syl Off7676 coated with 20% solids in 2-butanone. First, the paper was coated with a vinyl solution containing zinc oxide. The release coating 41 is U. S.S.N. except that the composition is KF2001 / MA / MAA / MMA 25/50/20/5 dispersed in 2-butanone at 1.5% solids (Example 20). 08/040876 is the polymer disclosed in Example 1. The adhesive is coated to extend the overall width of the sheets 12 and 13 to compare the 0.75-inch (1.9 cm) wide strips 16 with the trademark post-it notes (ie about 0.6 N / dm adhesion to glass). Can provide a suitable adhesive. Opposing strips of release coating 40 may be coated with a gravure cylinder to provide a 1.25-inch (3.2 cm) wide strip that extends the overall width of sheets 12 and 13. The material was coated on a wide web and then transformed and superimposed to form the sheet assembly 10.

Initial peeling of the sheet was 166 g / in. The sheet was then printed using an ink jet, zero graphic, and offset printer. In each case, the test form was a solid block of black ink or toner. The ink jet printer was a HP 1200C color ink jet printer, commercially available from Hewlett-Packard (Palo Alto, Calif.). The zero graphic printer was a Lanier 6540 copier, commercially available from Lanier Worldwide, Inc. (Atlanta, GA).

The indication acceptability% is as follows:

HP 1200 C 100%

Lanier 6540 92%

The test results show that the peel coating of the present invention can fix the marks more effectively than the peel coating used in the comparative example. This can be confirmed by comparing FIGS. 1 and 2 tested according to the toner acceptance test described above. The * pattern of FIG. 2 did not substantially adhere as compared to Applicant's release coating shown in FIG. 1. Applicant's composition used in FIG. 1 comprises MA / MAA / MMA / KF2001 comprised in an amount of 50/5/20/25.

Thus, the coating of the present invention significantly reduces the accompanying problems associated with display when used as a pressure sensitive note pile after being printed.

In summary, the present invention discloses a novel article applied with a unique toner water soluble release coating. Although specific aspects and embodiments of the invention are disclosed herein, the description and illustration are not intended to limit the invention. In particular, modifications within the general description herein are within the scope of the invention as defined by the following claims, including all equivalents.

Claims (12)

Particles released by an electrophotographic device comprising a polymer having at least one vinyl polymer segment having a T _g of −10 ° C. to 65 ° C. and a polymer having at least one siloxane polymer segment may be accommodated and substantially freeze particles. That peel off the coating. The release coating of claim 1 wherein the polymer is a copolymer comprising Formula 1: Formula 1 Where Each R ₁ may be the same or different and is a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxy, hydrogen and fluoroalkyl; Each R ₂ may be the same or different and is a divalent linking group; R ₃ is a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxy, hydrogen and fluoroalkyl, which may each be the same or different; Each R ₄ is a divalent linking group which may be the same or different; x is an integer from 0 to 3; y is an integer of at least 10; q is an integer from 0 to 3; G ₅ is a monovalent moiety which may be the same or different, respectively, selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and -WSA; A is a vinyl polymer segment or block consisting essentially of polymerized free radical polymerized monomers; G ₆ is a monovalent moiety which may be the same or different, respectively, selected from the group consisting of alkyl, aryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and -WSA; G ₂ and G ₄ are A. The copolymer of claim 1 wherein the polymer is a copolymer of D and E monomers copolymerized to form a polymer backbone and F monomers grafted thereto, D is one or more free radically polymerizable vinyl monomers; E is at least one polar monomer copolymerizable with D and the amount of E is 30% or less of the total weight of all monomers; F is a release coating which is a monomer having the formula Formula 2 X- (Y) _n SiR _(3-m) Z _m In the above formula, X is a vinyl group copolymerizable with D and E monomers; Y is a divalent linking group where n is 0 or 1; m is an integer from 1 to 3; R is hydrogen, lower alkyl (eg methyl, ethyl or propyl), aryl (eg phenyl or substituted phenyl), or an alkoxy group; Z is a monovalent siloxane polymer part having a number average molecular weight of about 1,000 or more and hardly reacts under copolymerization reaction conditions. The acrylic or methacrylic acid esters of styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, non-tertiary alcohols having 1 to about 18 carbon atoms and tertiary alcohols. And a release coating selected from the group consisting of: and mixtures thereof. 4. The release coating of claim 3 wherein said E monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, acrylamide, methacrylamide, N, N-dimethylacrylamide, methacrylonitrile and maleic anhydride. (a) a liner having a front side and a back side; (b) a release coating layer coated on a portion of the front side of the liner, the release coating being present in an amount sufficient by weight to provide a copolymer capable of substantially fixing the toner particles released by the electrophotographic conductive device; At least one vinyl polymer segment having a T _g of −10 ° C. to 65 ° C .; And a release coating layer comprising a polymer having at least one siloxane polymer segment present in a weight percent sufficient to provide a copolymer having a number average molecular weight of at least about 100 and a surface peel value of about 11 N / dm or less; (c) pressure sensitive adhesive layer; And (d) at least one substrate layer having a front side and a back side. The image water-soluble article of claim 6, wherein the polymer of the release coating is a copolymer comprising Formula 1: Formula 1 Where Each R ₁ may be the same or different and is a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxy, hydrogen and fluoroalkyl; Each R ₂ is a divalent linking group which may be the same or different; Each R ₃ may be the same or different and is a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxy, hydrogen and fluoroalkyl; Each R ₄ is a divalent linking group which may be the same or different; x is an integer from 0 to 3; y is an integer of at least 10; q is an integer from 0 to 3; G ₅ is a monovalent moiety which may be the same or different, respectively, selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and -WSA; A is a vinyl polymer segment or block consisting essentially of polymerized free radically polymerized monomers; G ₆ is a monovalent moiety which may be the same or different, respectively, selected from the group consisting of alkyl, aryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and -WSA; G ₂ and G ₄ are A. The copolymer of claim 6, wherein the polymer of the release coating is a copolymer of D and E monomers copolymerized to form a polymer backbone and F monomers grafted thereto, D is one or more free radically polymerizable vinyl monomers; E is at least one polar monomer copolymerizable with D and the amount of E is 30% or less of the total weight of all monomers; F is a monomer having the formula (2) Formula 2 X- (Y) _n SiR _(3-m) Z _m In the above formula, X is a vinyl group copolymerizable with D and E monomers; Y is a divalent linking group where n is 0 or 1; m is an integer from 1 to 3; R is hydrogen, lower alkyl (eg methyl, ethyl or propyl), aryl (eg phenyl or substituted phenyl), or an alkoxy group; Z is a monovalent siloxane polymer part having a number average molecular weight of about 1,000 or more and hardly reacts under copolymerization reaction conditions. 9. The acrylic or methacrylic acid ester of non-tertiary alcohol of claim 8, wherein the D monomer of the release coating polymer is styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, having from 1 to about 18 carbon atoms. And an image soluble article selected from the group consisting of: The method of claim 8, wherein the E monomer of the peel coating polymer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, acrylamide, methacrylamide, N, N-dimethylacrylamide, methacrylonitrile and maleic anhydride. Selected image soluble article. 7. The image soluble article of claim 6, wherein said substrate is a labelstock. A sheet assembly comprising a release coating of formula 1 on at least one non-adhesive containing region of the back surface of the sheet: Formula 1 Where Each R ₁ may be the same or different and is a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxy, hydrogen and fluoroalkyl; Each R ₂ is a divalent linking group which may be the same or different; Each R ₃ may be the same or different and is a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxy, hydrogen and fluoroalkyl; Each R ₄ is a divalent linking group which may be the same or different; x is an integer from 0 to 3; y is an integer of at least 10; q is an integer from 0 to 3; G ₅ is a monovalent moiety which may be the same or different, respectively, selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and -WSA; A is a vinyl polymer segment or block consisting essentially of polymerized free radical polymerized monomers; G ₆ is a monovalent moiety which may be the same or different, respectively, selected from the group consisting of alkyl, aryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and -WSA; G ₂ and G ₄ are A.