JP2002520440A - Additive for printing ink that gives releasability - Google Patents

Abstract

(57) Abstract: (a) UV-curable or air-curable printing ink, and (b) methacrylate-terminated poly (dimethylsiloxane) having a number average molecular weight of 5,000 to 50,000, or general Formula (I), wherein y accounts for 0.5 to about 80% of (x + y), R ₁ , R ₂ and R ₃ may be independently the same or different, and alkyl, aryl Alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen, fluoroalkyl and a divalent linking group, wherein R ₄ , R ₅ and R ₆ are independently the same or different And a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen and fluoroalkyl; From about 16 to about 16 wherein x and y are at least 1 and the sum of x + y is an integer of 10 or more). A product printed with a printing ink mixed with an ink composition and a releasable additive.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing ink, and more particularly to a printing ink that provides a low energy surface and a product using a printing ink containing an additive.

BACKGROUND OF THE INVENTION Generally, re-stickable notepads, tapes and linerless labels have a pressure-sensitive adhesive (PSA) (and optionally a primer) applied to one side and a peel-off on the other side. It is composed of stacked sheets (paper, film, etc.) to which a coating (also referred to as “low adhesion back size (LAB)”) is applied. The release coating, whether in notepad (stacked sheet) or roll form, is in contact with the adhesive. In the form of a notepad, this release coating facilitates removal by reducing the force required to release the adhesive from adjacent sheets, and minimizes distortion and twisting of the notepad body. Used to keep In the form of a roll, this release coating is used to facilitate unrolling during processing and removal.

[0003] Lithographic, flexographic or gravure printing methods are often used to make printed, re-stickable notes, tapes and linerless labels. The printing step is often performed independently after the steps of applying the adhesive and release coating. In such a case, the adhesive and the release material are sent to a printing press in advance of a roll-shaped raw material that has been applied, and immediately after printing the ink on the release coating, the printed material is rewound, or Stack the cut pieces on separate sheets. Printing ink on this release coating results in the loss of release coating effect. Also, undesired interactions occur between the adhesive and the ink, resulting in poor release (faster unwinding, tearing, and difficulty in removing), and the printing of raw materials to the adhesive. Ink is transferred. Such "ink transfer" can damage printed images and contaminate the adhesive.

[0004] In general, common release materials used in conjunction with pressure sensitive adhesives (PSAs) are based on low surface energy parts such as aliphatics, silicones and fluorochemicals. Conventional ink additives used to lower the "stickiness" of the printed ink include polyethylene particles or waxes, polypropylene particles or waxes, or polytetrafluoroethylene (such as Teflon®) Particles or wax. These have been found to be relatively ineffective in mitigating the interaction between the pressure sensitive adhesive and the ink. Silicone additives are generally avoided because they can cause problems with ink wetting on printing rollers and printing plates and can adversely affect the transfer of ink from the printing plate to the support and print quality. ing.

[0005] Recently, the addition of an organopolysiloxane containing a mercapto group to an ultraviolet (UV) curable lithographic ink used for printing paper coated with polyethylene or polypropylene has been reported (Japanese Patent Application Laid-Open No. 56-118472). The addition of this mercapto-containing silicone reduces the tendency of printed sheets to fuse together after exposure to excessive heat and pressure. In contrast, the addition of the mercapto-containing silicone to the air-curable lithographic ink did not show any desired improvement.

[0006] At present, the addition of organopolysiloxanes containing mercapto groups to lithographic inks has been described to improve the properties of reprintable notepads, tapes and printed PSA products such as linerless labels. It is believed that no references exist. It would be advantageous to have an ink that does not create unwanted interactions between the adhesive and the ink, and that preferably acts as a release material. Such inks eliminate the aforementioned problems of poor releasability and high "ink transfer", and are improved (good releasability, low ink transfer) printed re-pasteable It supports the production of simple notepads, tapes and linerless labels.

SUMMARY OF THE INVENTION In summary, in one aspect of the invention, a printable ink containing (a) an ultraviolet-curable or air-curable printing ink and (b) a release additive is provided in a printable ink. The present invention provides a lithographic printing ink that imparts a stencil. A preferred additive for the UV-curable or air-curable ink is a mercaptopolydiorganosiloxane copolymer.

[0008] Inks containing additives, such as mercaptopolydiorganosiloxane copolymers, have been used to reduce unwanted interactions between PSAs and inks, and to print inks with PSAs. Can be advantageously used for products in contact with Undesirable interactions between the pressure sensitive adhesive and the ink that are avoided by the present invention include, from the printed image to the adhesive, damage to the printed image and contamination of the adhesive. High transfer force during "ink transfer" and unrolling or peeling of the sheet which would damage the backing or create an unusable product.

[0009] Another type of additive that imparts good properties to UV curable inks is acrylate terminated silicone ("silicone macromer"). Examples of such materials include 3M Company, St. And Silicone "Plus" HG-10 Siloxane, commercially available from Paul, MN. Silicone "Plus" HG-10 has a number average molecular weight of 10,0.
No. 00, a poly (dimethylsilicone) polymer terminated with methacrylate.

In another aspect of the present invention, (a) a backing support having a front surface and a back surface;
(B) a layer of a pressure-sensitive adhesive covering at least a part of the back surface of the backing support;
A) a mark printed on the surface of the backing support using a lithographic ink having releasability.

In yet another aspect of the present invention, a flexible adhesive having a pressure-sensitive adhesive applied to the back surface, a mark printed on the front surface, and a body portion having substantially the same size. Provided is a pad assembly composed of multiplexed flexible sheets. The indicia is such that the sheet can be easily peeled off when the sheet is peeled from the pad assembly, and the second mark on the first sheet from the surface of the first sheet.
In order to prevent the lithographic printing ink from being transferred to the back surface of the sheet, printing is performed with lithographic printing ink having releasability. Although the sheets are multiplexed, a pressure-sensitive adhesive is applied to the back surface of each sheet. These sheets are aligned to the corresponding peripheral edge of each body portion, and are stacked with the pressure sensitive adhesive of each sheet bonding that sheet to an adjacent sheet. Such products include printed and re-pastable notepads (eg, 3M Company's Post-
it® Notes), linerless labels, printed pressure-sensitive tape,
Adhesive coupons and the like.

Advantageously, the use of a lithographic ink having releasability provides a structure that does not require the application of a release coating to the sheet having the indicia printed on the surface.

[0013] In a further aspect of the present invention, there are provided: (a) combining an ultraviolet-curable or air-curable printing ink with an appropriate weight percent of an additive that acts as a release coating; Printing the mixed ink on the support such that printing is performed on the front surface of the support so as to match an adhesive coating applied to the back surface of the support having a back surface; (c) Stacking the printed support in a pad shape or wrapping it around a mandrel, using the lithographic ink having releasability.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, an ink additive has been discovered that eliminates the aforementioned problem of poor releasability and the problem of high "ink transfer". The additives can be combined with commercially available UV-curable or air-curable lithographic inks, and the resulting inks can be printed on a standard lithographic printing press.

Without being bound by a hypothesis, the mercapto group of the additive penetrates during the curing process of the air-curable lithographic ink and the ultraviolet-curable lithographic ink and forms a covalent bond with the cured ink. Is believed. The bound additive does not transfer to or contaminate the pressure sensitive adhesive that can come into contact with the ink.

Types of Additives A preferred additive is a mercaptopolydiorganosiloxane copolymer represented by the following general formula.

Embedded image Wherein y may occupy 0.5 to about 80%, preferably 1 to 20%, most preferably 3.5 to 14% of (x + y); R ₁ , R ₂ and R ₃ are Independently is the same or different and is a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen, fluoroalkyl and divalent linking groups. R ₄ , R ₅ and R ₆ are independently the same or different and are independently alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen and fluoroalkyl A monovalent moiety selected from the group consisting of: most preferably an alkyl moiety; z is 1 to about 16, preferably 1 to 5, most preferably 3 Ri, x and y are integers of at least 1, and x + y is an integer of at least 10.

The molecular weight of the additive is from about 1,000 to about 200,000, preferably about 50,000
00 to about 50,000. In these preferred ranges, the additive is
It has a desirable viscosity to be formulated into the ink. Molecular weight can also affect the effect of the additive. The optimum molecular weight depends on the additive and the type of ink.

Most preferred additives are Shin-Etsu, Inc. (1150 Damer
Drive, Akron, OH 44305) under the trade name “X-22-980”, in which case R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are CH ₃ And y accounts for 3.5-4.5% of (x + y), z is 3, and its number average molecular weight (Mn) is 8,000. Under high temperature vacuum (for example, 150 ° C.,
Most preferably, any cyclic material that may be present is removed prior to use by a method such as evaporation at 200 mmHg). Other most preferred additives with different values of R, x, y and z are Huls America Inc. (Piscata
Way, NJ).

The additives are added to the ink in an amount of 0.1 to 15% by weight of the ink, most preferably 1 to 5% by weight. The optimal amount of additive depends on the strength of the pressure sensitive adhesive and the desired release value on the printed product. If the additive is added too much, the printing roller or blanket may have a wetting problem, which may adversely affect the printing process. The upper limit for the amount of additives is about 5-15%, but depends on the type of press, roller and blanket materials, and ink formulation.

The content of mercapto in the additive (% by weight of SH part based on the weight of the additive) is from about 0.1 to about 20% by weight, most preferably from 0.35 to about 4% by weight. The effect of the additive appears to decrease when the amount of SH is very high. For example, poly (mercaptopropylmethylsiloxane) (26% by weight SH) is not a very effective additive.

Another type of additive that imparts good properties to UV-curable inks is acrylate-terminated silicone (“silicone macromer”). Examples of such materials include 3M Company, St. And Silicone "Plus" HG-10 Siloxane, commercially available from Paul, MN. Silicone "Plus" HG-10 has a number average molecular weight of 10,0.
No. 00, a poly (dimethylsilicone) polymer terminated with methacrylate.

Conventional ink additives such as polyolefins and polytetrafluoroethylene waxes (such as Teflon®) or particles have proven ineffective. Also, 3M Company, St. Fluorad ^™ FX-189, Fluorad ^™ FX-13 and Flu, commercially available from Paul, MN.
Fluoroacrylate compounds such as orad ^™ FX-14 also have no effect.

Kinds of Inks Preferred lithographic printing inks are those that cure by irradiation with ultraviolet light, but lithographic printing inks that cure by air oxidation can also be used. Common lithographic inks commercially available from common ink manufacturers can be used.

Suitable UV-curable lithographic printing inks include Kohl and Madd
En Corporation (Minneapolis, MN) UV1
/ D Process Ink and Zeller Interchem Corp.
ation (2205 Tomlyn Street, Richmond, V
A 23230) UVALUX process ink.

Suitable air-curable lithographic inks include Lithographic S
oy ABDT Black MSP-4200-D-STG-5 (adhesion =
16), PMS-185-ABD (OFF-ABD-STD-RED), and MSP-4200-D-STG-S (OFF-SOY-ABDT-BLACK)
). Another example of a suitable ink is Central Ink C
No. commercially available from the corporation (Plymouth, MN)
te Pad Process Black K52-3444-22.

Printing Method A standard lithographic printing press can be used. Examples of such a printer for air-curable inks include Webco by Didde's (Emporia, Kansas).
man and Apollo printing press and Stevens International
nal (Fort Worth, Texas). As a laboratory printing machine, Little Joe Proving Pre
ss (Little Joe Color Switcher, Somervi
lle, NJ). As an ultraviolet printer, Sanden (Camb
Ridge, Ontario) and Mueller Martini (New
Printing press available from J. York.

The present invention is further described by the following examples, which do not limit the scope of the invention. In the following examples, all parts, ratios and percentages are by weight unless otherwise indicated. The following test methods were used to evaluate and characterize printing inks containing the additive compositions prepared in the following examples. Unless stated otherwise, all materials are, for example, Al
It is commercially available from Drich Chemicals (Milwaukee, Wis.).

Examples Test Methods Mixing of Additives and Inks Additives were added to the base ink and mixed with a wood applicator until homogenous. The amount of the additive is indicated in% by mass based on the mass of the base ink used.

[0029] Little Joe Lithographic Proving Pres
Printing method using s Little Joe Lithographic Pr according to the following procedure.
oving Press (Little Joe Joe Color Swatch)
r, Somerville, NJ). Hand-printed rollers and printing blankets made exclusively for air-curable inks or UV-curable inks were used. 1) 28 x 25 cm stainless steel "ink plate" with 0.6 cc of ink
Was applied. 2) Next, this ink was uniformly spread over the entire ink plate using a hand-printing roller (rubber roller). 3) Next, the hand-printing roller containing plenty of ink was set to 10 × 15 cm.
Was rolled only once over the entire surface of the "printing plate" to transfer the ink to the printing plate. 4) The ink was once again spread evenly on the ink plate using the roller for manual printing. 5) The ink was again applied to the printing plate using a hand-printing roller containing a large amount of ink. 6) After rolling the printing “blanket” on the surface of the printing plate,
Rolls were made on the non-adhesive side of it (registered trademark) Note paper (yellow ashdown paper) to produce print # 1. 7) Print # 1 was peeled off. 8) Steps 4 to 6 were repeated to produce prints # 2 to # 6. 9) Print # 2 was peeled off. Prints # 3 to # 6 were evaluated with leaving them. 10a) For air-curable inks, print these prints at least 2
Hanged on the wall for 4 hours to dry. 10b) In the case of UV curable ink, each print sample is immediately attached to a piece of cardboard and a UV curing device (Fusion UV Curing Sys).
tems, Rockville, MD, F300 UV lamp unit, MC-6R
Conveyor) at a speed of about 15 ft (4.57 m) / min.

The proofing press was thoroughly cleaned before printing another sample.

The samples were tested for at least 24 hours after equilibration in a temperature and humidity controlled room.

“Peeling Adhesion” of 3M 810 Magic ^™ Tape to Support This test is similar to TAPPI test method UM-504. 3M 810 M
A 25 mm wide strip of Agic ^™ Tape was applied to the support. A 2 kg roller was rolled over the tape on the support (twice) to adhere the tape to the support. A tensile tester was attached to one end of the tape. The tape was peeled from the support at a 90 ° angle at a speed of 12 ″ (30.48 cm) / min. g / 1
The force in '' (2.54 cm) was recorded. The tape was set aside and used for the re-adhesion test. The test was performed on prints 3-6. The average of these tests was recorded. This average is referred to as "peel adhesion" throughout the examples.

Re-adhesion force Re-adhesion force is a qualitative measure of the amount of adhesive contamination that occurs when a 3M 810 Magic ^™ Tape is peeled from a support. In this test, the tape used in the peeling adhesion test was used to print unprinted Post-it (registered trademark) Note paper (
(Yellow ash down paper) on the non-adhesive side. The tape strip after measuring the peel adhesion was set aside for evaluation of ink transfer. The test was performed on prints 3-6. Record the average of these tests. This “re-adhesion value” is calculated using Post-it (registered trademark) Note paper (not printed).
Unused 3M 81 on the non-adhesive side of yellow ashdown paper)
0 Magic ^™ Tape was compared with the peel adhesion (Table 1, C1). Approximately the same values as C1 indicated little or no contamination, while values significantly lower than C1 indicated that adhesion was reduced due to contamination of the adhesive by the ink or ink additive. .

Transfer of Ink The transfer of the ink was performed using the 3M 810 Magic used in the peel adhesion test. ^TM This is the amount of ink to be transferred to Tape. The amount of ink transferred is white on the tape.
After bonding to the bond paper, it was evaluated with the naked eye. The evaluation was 0 = “no ink transfer
1 ”,“ very slight ”, 2 =“ slight ”, 3 =“ more ”from 0 to 3
Went on the floor.

Print Quality Print quality was evaluated visually. Rating scales of "good" (uniform image of desired color density) and "poor" (uneven image of low color density) were used.

Sheet Peeling Force The sheet peeling force is the force required to peel off the topmost sheet of a re-attachable notepad such as Post-it (registered trademark) Note. The test was performed by cutting the top sheet of the notepad to 1 inch (2.54 cm) wide so that the cut strip was perpendicular to the adhesive stripe. A tensile tester was attached to the non-adhesive end of the strip. The tape was peeled off the surface at a 90 ° angle at a rate of 12 ″ (30.48 cm) / min. The force in g / 1 '' (2.54 cm) was recorded. Repeat this test several times,
The average of the repeated tests was recorded.

Examples Using Air-Curable Inks The following examples illustrate the improved properties obtained with the present invention when using air-curable inks.

Comparative Examples C1 to C3 Comparative Examples C1 to C3 show that there is a deleterious effect when printing ordinary air-curable lithographic inks on paper coated with a release coating.

In Comparative Examples C1 to C3, standard Post-it, printed and unprinted (coated with adhesive, primer and release coating)
The peel adhesion of 3M 810 Magic ^™ Tape to ®Note paper was measured. Further, the "re-adhesion" of the 3M 810 Magic ^™ Tape was measured to see if the adhesive was contaminated by the printed surface. The print quality and the amount of ink transferred to the Magic ^™ Tape are shown.

The results for C1 and C2 (Table 1) show that the red ink is Post-it®
When printed on the top surface of Note paper, the peel adhesion is 140 g / 1.25 ″ (3
. 175 cm) to 242 g / 1.25 ″ (3.175 cm). When the black ink was used (C3), the peel adhesion value was 317.
g / 1.25 '' (3.175 cm). Re-adhesion value is 1
Much lower than 40 g / 1.25 ″ (3,175 cm) (117 g / 1
. 25 "(3.175 cm) and 105 g / 1.25" (3.175 cm)
)). This indicates severe contamination of the adhesive by the ink. Ink transfer was as high as (2.5) for both C2 and C3.

Comparative Examples C4 to C12 According to Comparative Examples C4 to C6 (Table 1), it is also possible to use common ink additives such as polyethylene wax or polytetrafluoroethylene wax (such as Teflon®). The peelability did not improve, and they were shown to cause contamination of the adhesive, as indicated by the high peel adhesion and low re-adhesion values. Comparative Examples C7-C12 showed that the results were also inadequate when using stearic acid, a fluorine-containing monomer, a silicone "silicone macromer" having methacrylate end groups, and polyethylene glycol monomethacrylate.

JM 410-9, 410-8 and 413-3 are common waxes used in lithographic printing inks. These are Kohl and Madden C
corporation, Minneapolis, Minn. JM4
10-9 is Lawer International, Pleasant,
It is commercially available from WI as "Super Poly 4". JM410-8
Is commercially available as "CC5510-D" and JM413-3 is commercially available as "PROTECH200" from Carroll Scientific, Countryside, IL.

Stearic acid is available from Aldrich Chemical Co. Obtained from.
Fluorad ^™ FX-13, Fluorad ^™ FX-189 and Fluor
ad ^™ FX-14 is available from 3M Company (Industrial Che
medical Products Division, St. Paul, MN). CW-750 is available from Polysciences, Inc. , War
Ringtone, a polyethylene glycol monomethacrylate containing 10 moles of EO obtained from PA (Cat. # 16713).

Comparative Examples C13 and C14 Comparative Examples C13 and C14 showed that using polydimethylsiloxane without a mercaptan functionality did not improve the properties. In these examples, polydimethylsiloxanes having different molecular weights (trimethylsiloxy-terminated, CAS No. [63148-62-9]) were evaluated. These are PS
041.2 (molecular weight = 9,430, viscosity = 200) and PS042 (molecular weight =
17,250, viscosity = 500) from Huls America. High peel adhesion, high ink transfer, and low re-adhesion values were observed.

Examples 1 to 10 According to Examples 1 to 8 (Table 1), 1 to 3% by weight of mercaptopolydiorganosiloxane (R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are CH ₃ And Z is 3;
Shi accounts for 3.5% to 4.5% of (x + y) and has a molecular weight of 8,000.
n-Etsu, Inc. The addition of "X-22-980", which is commercially available from Co., Ltd., reduces the interaction between the ink and the adhesive, as indicated by the reduced peel strength of the Magic ^™ Tape on the printed ink. It has been shown.
Very little adhesive contamination was observed, but the re-tack value was high. The amount of ink transferred was also greatly reduced. When X-22-980 was 2.5%, basically no ink was transferred.

Examples 9 and 10 showed that print quality was poor when using 3.75% or 5% X-22-980. Thereby, a relatively large amount of X-2
It has been shown that the use of 2-980 can affect print quality on certain printing presses. However, Didde Wabcom's stencil printing press is X-2
It should be noted that it has been found that an ink containing 5% 2-980 has been successfully printed and that the upper limit of the amount of X-22-980 depends on the printing press.

[0047]

[Table 1]

[0048] The ink was supplied by Kohl & Madden Printing Ink Cor.
p (Minneapolis, MN). The name of the red ink is P
MS-185-ABD (OFF-ABD-STD-RED).

The name of the black ink is MSP-4200-D-STG-S (OFF-SOY
-ABDT-BLACK).

Examples Using Ultraviolet-Curable Inks The following examples illustrate the improved properties obtained with the present invention when using ultraviolet-curable inks.

Comparative Examples C100 to C101 Comparative Examples C100 to C101 were carried out in the same manner as Examples C1 to C3. C10
The high peel adhesion value at 1 indicated that printing a conventional UV-curable lithographic ink on paper coated with a release coating resulted in deleterious interactions between the PSA and the ink. It was confirmed that, unlike the air-curable ink, when the ultraviolet-curable ink and appropriate curing conditions were used, the transfer of the ink was small and the contamination of the adhesive was small.

Comparative Examples C103-C109 The comparative examples C107-C109 (Table 2) show that with common ink additives such as polyethylene wax and polytetrofluoroethylene wax (such as Teflon®) the releasability is improved. No improvement was shown. Comparative Examples C103 to C
106 showed that the fluorine-containing monomer and polyethylene glycol monomethacrylate were also ineffective at reducing the interaction between the PSA and the ink.

JM 410-9, 410-8 and 413-3 are common waxes used in lithographic printing inks. These are Kohl & Madden Corpor
, Minneapolis, Minn. JM410-9 has been issued by Lawer International, Pleasant and WI.
It is commercially available as "Super Poly 4". JM410-8 is "CC5
510-D "as Carroll Scientific, Countries
commercially available from ide, IL. JM413-3 is "PROTECH 200
], As Carroll Scientific, Countryside, I
L is commercially available. Fluorad ^™ FX-13, Fluorad ^™ FX-
189 and Fluorad ^™ FX-14 are available from 3M Company (Ind.
usual chemical Products Division, S
t. Paul, MN). CW-750 is a Polyscience
es, Inc. Polyethylene glycol monomethacrylate containing 10 moles of EO obtained from Warrington, PA (Cat. # 16713).

Comparative Examples C110 and C111 Comparative Examples C110 and C111 show that using polydimethylsiloxane without a mercaptan functionality does not improve the properties. In these examples, polydimethylsiloxanes having different molecular weights (trimethylsiloxy-terminated, CAS No. [63148-62-9]) were evaluated. These are PS
041.2 (molecular weight = 9,430, viscosity = 200) and PS042 (molecular weight =
17,250, viscosity = 500) from Huls America. High peel adhesion values were confirmed. This indicates that the releasability is low when no mercaptan functional group is present.

Examples 100 to 108 The peel adhesion values of Examples 100 to 108 (Table 2) were as follows: X-22-980 was PSA.
It shows that the interaction between the ink and the ink is reduced. When the amount of X-22-980 is 1
When increasing from 6% by weight to 6% by weight, the peel adhesion decreases. High re-stick values indicate low adhesive contamination.

Examples 109 and 110 show that the print quality obtained when using 7.5% or 10% X-22-980 is low. This is because a relatively large amount of X
This indicates that the use of -22-980 may affect print quality on a particular printing press.

Examples 109-116 Examples 109-116 (Table 2) show the good effect of various additives with different mercapto content and polymer structure. With the exception of PS927 and PS405, these additives are dimethylsiloxy / 3-mercaptopropylmethylsiloxy copolymers with different comonomer ratios and molecular weights. PS927 is a homopolymer based on 3-mercaptopropylmethylsiloxy repeat units. PS405 is H
uls America by "Polydimethylsiloxane, branched-point t-
Structure of mercaptopropyl ". Table 3 details these additives.

[0058]

[Table 2]

Example 117 According to Example 117, methacrylate terminated poly (dimethylsiloxane) having a number average molecular weight of 10,000 (Silic available from 3M)
one Plus HG-10) has been shown to be an effective additive.

[0060]

[Table 3]

Comparative Example C200 and Examples 130-135 These examples are based on a Sanden Varic equipped with five UV curing units.
om printing machine. A roll of a plurality of 1.25 inch (3.175 cm) wide strips of adhesive and a release coated (over the paper) Post-it® Note paper is 500 ft (152 ft). .4m) / min and printed (2x9 inch (5.08x22.86cm) rectangular form at 100% ink coverage) with the UV curing device (UV luminous intensity = each light beam). Per 600 watts / inch (2.54 cm)), cut into 12 x 18 inch (30.48 x 45.72 cm) sheets and layered. A stack of 12 inch x 18 inch (30.48 x 45.72 cm) sheets is cut with a guillotine to make a 3 x 5 inch (7.62 x 12.70 cm) Post-i.
Several t (registered trademark) Note pads were prepared. The samples were tested for peel adhesion, re-adhesion, sheet peel, and ink transfer.

The ink used in these examples was Zeller Interchem
Obtained from Corporation. Black ink is UVALUX US48
26LD and the yellow ink was UVALUX US4825LD. The ink additive "X-22-980" was added to the inks in amounts of 1, 3 and 5% by weight based on the weight of these inks. The black ink was cured with four light beams, while the yellow ink was cured with one ultraviolet light.

The results in Table 4 show that in the case of the black ink and the yellow ink, the addition of X-22-980 reduced both the peeling adhesive force and the sheet peeling force (SRF). These improvements were more pronounced for black ink, which indicated that the type of ink could be important. The lower the SRF value, the smaller the deformation (twist) of the paper that occurs when the topmost sheet is peeled off.
RF reduction was an important quality improvement. Print quality was good for all samples. In these examples, no ink transfer was observed.

[0064]

[Table 4]

Examples when a product other than a re-stickable memo is used. Examples C200 to C203 and 201 and 202 Examples C200 to C203 and 201 and 202 show that the additives described in the present invention have a releasable property. It shows that it can be used to produce good printing tapes. Multiple 1 ″ (2.54 cm) wide Scotch ^™ Magic ^™ Ta
pe (810 commercially available from 3M company, St. Paul, MN)
The strip of tape) was printed on the non-adhesive side in the same way as C1 and C100. Prior to printing, these Scotch ^™ Magic ^™ Tap
A large area for printing was prepared by adhering the strips of e to bond paper with the strips adjacent to each other. The results shown in Table 5 show that the addition of 2.5% of X-22-980 reduces the transfer of the ink and decreases the peeling adhesive strength for both the ultraviolet curable ink and the air curable ink. Is shown.

[0066]

[Table 5]

Examples C210-C213 and 211 and 212 Examples C210-C213 and 211 and 212 show that the additives described in the present invention can be used in the production of printed labels with good releasability. . On the non-adhesive side of a 1 "x 25/8" (2.54 x 6.66cm) address label on an 8.5 "x 11" (21.59 x 2.54cm) liner, C1 and Printing was performed in the same manner as for C100. These labels are available from Avery Dennison Office Products (
Diamond Bar, CA) "Laser Labels" product # 51
60 is commercially available. The results shown in Table 6 show that the addition of 2.5% of X-22-980 reduces the transfer of the ink and reduces the peel adhesion for both the UV-curable ink and the air-curable ink. Is shown.

[0068]

[Table 6]

Various modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and principles of this invention, and the invention is unduly limited to the above-exemplified embodiments. It should be understood that this is not the case.
All documents and patents incorporated herein by reference are incorporated by reference to the same extent as if each document or patent was specifically and individually indicated to be incorporated by reference.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY , CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP , KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZW (72) Inventor Masuna, Charles A. United States, Minnesota 55133-3427, St. Paul, P. Oh. Box 33427 F term (reference) 4J004 AA10 AA11 AB01 AB06 CA01 CA02 CB02 CB03 CC04 CC05 DA04 FA01 4J039 AB12 AD10 AE11 BC57 BE01 EA02 EA06 EA15 EA19 EA42 FA02 FA07 GA02 GA03 GA04

Claims (20)

[Claims] 1. An air-curable printing ink comprising: (a) an air-curable printing ink; and (b) the following general formula: Wherein y is from 0.5 to about 80% of (x + y); R ₁ , R ₂ and R ₃ are independently the same or different and are alkyl, aryl, alkaryl, alkoxy A monovalent moiety selected from the group consisting of: alkylamino, hydroxyl, hydrogen, fluoroalkyl and a divalent linking group, wherein R ₄ , R ₅ and R ₆ may be independently the same or different And a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen and fluoroalkyl; z is 1 to about 16, x and y are at least 1 And the sum of x + y is an integer greater than or equal to 10. Exfoliation comprising a mercaptopolydiorganosiloxane copolymer additive represented by Ability of lithographic printing ink composition. 2. The method according to claim 1, wherein the proportion of y is 1 to 20% of (x + y).
3. The lithographic printing ink composition according to item 1. 3. The peelable lithographic printing ink composition according to claim 1, wherein the proportion of y is 3.5 to 14% of (x + y). 4. The exfoliable lithographic ink composition of claim 1, wherein the molecular weight of the additive is from about 1,000 to about 200,000. 5. The peelable lithographic ink composition according to claim 1, wherein the additive is present in the composition in an amount of 0.1 to 15% by weight of the ink. 6. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are CH ₃ and y is (
x + y) of 3.5 to 4.5%, z is 3 and the number average molecular weight (Mn)
The peelable lithographic printing ink composition according to claim 1, wherein) is 8,000. 7. A backing support having a front surface and a back surface, (b) a layer of a pressure-sensitive adhesive on at least a portion of the back surface of the backing support, and (c) the backing support. An adhesive-coated product comprising a mark on a surface of a backing support, wherein the mark comprises (a) an ultraviolet-curable printing ink or an air-curable printing ink, and (b) a general formula shown below. Wherein y is from 0.5 to about 80% of (x + y); R ₁ , R ₂ and R ₃ are independently the same or different and are alkyl, aryl, alkaryl, alkoxy A monovalent moiety selected from the group consisting of: alkylamino, hydroxyl, hydrogen, fluoroalkyl and a divalent linking group, wherein R ₄ , R ₅ and R ₆ may be independently the same or different And a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen and fluoroalkyl; z is 1 to about 16, x and y are at least 1 And the sum of x + y is an integer greater than or equal to 10. Exfoliation comprising a mercaptopolydiorganosiloxane copolymer additive represented by Adhesive coated products which are printed with a capacity of lithographic printing inks. 8. The adhesive-coated product of claim 7, wherein the molecular weight of the additive is from about 1,000 to about 200,000. 9. The adhesive-coated product according to claim 7, wherein the molecular weight of the additive is from about 1,000 to about 200,000. 10. The adhesive coated product according to claim 7, wherein said additive is present in said composition in an amount of 0.1 to 15% by weight of said ink. 11. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are CH ₃ , y accounts for 3.5-4.5% of (x + y) and z is 3. , And the number average molecular weight (M
The adhesive-coated product according to claim 7, wherein n) is 8,000. 12. A pad assembly comprising a multiplexed flexible sheet having substantially the same size as a main body portion on which a pressure-sensitive adhesive is applied to a back surface and a mark is printed on a front surface. The lithographic printing ink can be easily peeled off when the sheet is peeled off from the pad assembly, and the back surface of the second sheet above the first sheet from the surface of the first sheet. In a pad assembly in which the indicia is printed with a lithographic ink having a releasable property so that the lithographic ink is not transferred, the lithographic ink comprises: (a) an ultraviolet-curable printing ink or an air-curable printing ink; ) The following general formula: Wherein y is from 0.5 to about 80% of (x + y); R ₁ , R ₂ and R ₃ are independently the same or different and are alkyl, aryl, alkaryl, alkoxy A monovalent moiety selected from the group consisting of: alkylamino, hydroxyl, hydrogen, fluoroalkyl and a divalent linking group, wherein R ₄ , R ₅ and R ₆ may be independently the same or different And a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen and fluoroalkyl; z is 1 to about 16, x and y are at least 1 And the sum of x + y is an integer greater than or equal to 10. A pad acetate comprising a mercaptopolydiorganosiloxane copolymer represented by Yellowtail. 13. The pad assembly of claim 12, wherein said additive has a molecular weight of about 1,000 to about 200,000. 14. The pad assembly according to claim 12, wherein said additive has a molecular weight of about 1,000 to about 200,000. 15. The pad assembly according to claim 12, wherein said additive is present in said composition in an amount of 0.1 to 15% by weight of said ink. 16. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are CH ₃ , y accounts for 3.5-4.5% of (x + y) and z is 3. , And the number average molecular weight (M
13. The pad assembly according to claim 12, wherein n) is 8,000. 17. A roll of adhesive-coated material comprising a support having at least one portion of a back surface coated with a pressure-sensitive adhesive and having a surface printed with a mark on said one portion, When the material is unwound from the roll, the material can be easily peeled off, and the mark is printed with a lithographic ink having releasability so that the lithographic ink is not transferred from the surface of the support. In the roll of the adhesive coating material to be used, the lithographic printing ink includes (a) an ultraviolet-curable printing ink or an air-curable printing ink, and (b) the following general formula Wherein y is from 0.5 to about 80% of (x + y); R ₁ , R ₂ and R ₃ are independently the same or different and are alkyl, aryl, alkaryl, alkoxy A monovalent moiety selected from the group consisting of: alkylamino, hydroxyl, hydrogen, fluoroalkyl and a divalent linking group, wherein R ₄ , R ₅ and R ₆ may be independently the same or different And a monovalent moiety selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen and fluoroalkyl; z is 1 to about 16, x and y are at least 1 And the sum of x + y is an integer greater than or equal to 10. An adhesive coating comprising a mercaptopolydiorganosiloxane copolymer represented by Fee for the role. 18. A releasable lithograph containing (a) an ultraviolet-curable printing ink and (b) methacrylate-terminated poly (dimethylsiloxane) having a number average molecular weight of 5,000 to 50,000. Printing ink composition. 19. A pad assembly comprising a multiplexed flexible sheet having a back surface coated with a pressure-sensitive adhesive and a printed body having substantially the same size as a main body portion having a mark printed thereon. The sheet can be easily peeled off when the sheet is peeled off from the pad assembly, and the lithographic printing ink is applied from the front surface of the first sheet to the back surface of the second sheet above the first sheet. In a pad assembly wherein the indicia is printed with a releasable lithographic ink so that it is not transferred, the lithographic ink comprises (a) an ultraviolet curable printing ink and (b) a number average molecular weight of 5
A methacrylate-terminated poly (dimethylsiloxane) having a molecular weight of from 5,000 to 50,000. 20. A pressure-sensitive adhesive is applied to at least one part of the back surface,
A roll of adhesive-coated material comprising a support having a mark printed on the surface of the part, wherein the material can be easily peeled off when the material is unwound from the roll, and a lithographic ink Wherein the mark is printed with a lithographic ink having releasability so that the mark is not transferred from the surface of the support, wherein the lithographic ink comprises: (a) an ultraviolet curable printing ink; Or with air-curable ink, (
b) a roll of an adhesive coating material comprising methacrylate-terminated poly (dimethylsiloxane) having a number average molecular weight of 5,000 to 50,000.