JP3403067B2 - Pressure-sensitive pseudo adhesive sheet - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-cost, printed or printed information which can be used for delivery slips, confidential postcards, address labels and the like. The present invention relates to a peelable pressure-sensitive pseudo-adhesive sheet. 2. Description of the Related Art Conventionally, a general delivery slip has a configuration in which a plurality of delivery sections including at least a delivery section and a receiving section are stacked, cut and bound, and delivered to a higher-order slip. A copy structure is provided so that when information is entered, it is copied and entered in a lower order slip. As an information transmitting means having such delivery information, a device using a pressure-sensitive pseudo-adhesive sheet, which is exemplified in Japanese Patent Application No. 8-326355, has been invented and actively used. [0004] A pressure-sensitive pseudo-adhesive sheet has a so-called non-peelable pressure-sensitive adhesive base such as natural rubber or synthetic rubber and an adhesive force of the pressure-sensitive adhesive base on at least a part of one side of a base sheet. A layer of a pressure-sensitive adhesive composed of a fine particle filler that suppresses odor is provided, and generally has a function of temporarily adhering but easily peeling off when necessary. The pressure-sensitive adhesive deteriorates with time (hereinafter referred to as aging phenomenon) as represented by yellowing, a decrease in adhesive strength, and curing. Natural rubber, in particular, has a performance change due to the aging phenomenon. Remarkable. Generally, the aging phenomenon of the pressure-sensitive adhesive is mainly caused by oxidation due to contact with atmospheric oxygen and absorption of ultraviolet rays. In addition, the fine particle filler is usually compounded in the pressure-sensitive adhesive layer, but there is a problem that the bonding strength is not stable depending on the amount of the fine particle filler and the dispersion state. Further, the mechanical stability at the time of adjusting the pressure-sensitive adhesive is poor, and there is also a problem in suitability for application to the base sheet. Therefore, conventionally, in a pressure-sensitive pseudo-adhesive sheet, an antioxidant and an ultraviolet absorption inhibitor for preventing oxidation of the pressure-sensitive adhesive are added to the pressure-sensitive adhesive layer. Further, a tackifier, a surfactant, a thickener, a defoaming agent, a release agent, and the like are added to the same pressure-sensitive adhesive layer in order to improve the applicability of the pressure-sensitive adhesive. There is a disadvantage that the production cost is increased and the advantage of using inexpensive materials is lost. In recent years, with the rapid increase in demand for communication means requiring such delivery information, it has been required to print information on a high-efficiency and high-quality pressure-sensitive pseudo-adhesive sheet. The method of printing information on the pressure-sensitive pseudo-adhesive sheet has been shifting from printing with an impact printer, which was conventionally used in combination with a computer, to printing using an electrophotographic method or an inkjet recording method with a computer, and toner retransfer. In addition, problems such as ink bleeding have occurred. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a pressure-sensitive adhesive having a stable pressure-sensitive adhesive force, a non-sticky coating layer of a pressure-sensitive adhesive, and no blocking during processing. An object of the present invention is to provide a pressure-sensitive pseudo-adhesive sheet which has excellent printability and has removable pressure-sensitive pseudo-adhesive performance regardless of a material to be bonded. The inventors of the present invention have conducted intensive studies and as a result, the above-mentioned objects have been attained on at least one side of a support with a pressure-sensitive adhesive capable of printing or printing information. In a pressure-sensitive pseudo-adhesive sheet provided with an agent layer by coating having a drying step, the pressure-sensitive adhesive layer comprises an acrylic acid ester (A) , polyvinyl alcohol,
Lulose, polyvinylpyrrolidone, polyacrylic acid,
Liacrylamide, ethylene-maleic anhydride copolymer
Body, styrene-maleic anhydride copolymer, methyl vinyl
Ether-maleic anhydride copolymer, and isobutylene
One or two selected from the group of maleic anhydride copolymers
And water-soluble resin emulsion (B)
An acrylic emulsion pressure sensitive adhesive base agent obtained by mixing al, and a fine particle filler a layer containing as basic components, a glass transition point of the acrylic acid ester -9
In the range of 0 to 50 ° C., the acrylic acid ester 10
5 to 50 parts by weight of the water-soluble resin emulsion per 0 parts by weight.
0 parts by weight are mixed and dispersed, and the acrylate
The glass transition point when the water-soluble resin emulsion is mixed is in the range of -80~20 ℃, the acrylic Emma
The fine particles per 100 parts by weight of the pressure-sensitive adhesive
5 to 200 parts by weight of a filler, and the T-peel strength of the boundary surface where the pressure-sensitive adhesive layer of the pressure-sensitive pseudo-adhesive sheet is superimposed and re-peelable on the adhesive sheet is 2
The measurement based on JIS K6833 in an environment of 0 ° C. and 65% RH has revealed that the pressure-sensitive pseudo-adhesive sheet is characterized by having a peel strength of 10 to 120 g / 25 mm . In the present invention, an acrylic emulsion containing an acrylate ester and a water-soluble resin emulsion as main components is used as a pressure-sensitive adhesive base because a water-soluble resin emulsion formed into a protective colloid is dispersed in an acrylic resin ester. By causing the water-soluble resin to move to the surface of the coating layer in accordance with the evaporation of moisture and the like in the drying step during coating, the water-soluble resin component contains a large amount of the water-soluble resin component. The pressure-sensitive adhesive sheet coated with the pressure-sensitive adhesive of the present invention can prevent blocking or the like from occurring, or the pressure-sensitive adhesive This is for exhibiting the function of preventing the surface from being sticky. In the present invention, a pseudo-adhesive which can be re-peeled by adding a fine particle filler to a pressure-sensitive adhesive base comprising an acrylic emulsion containing an acrylic ester and a water-soluble resin emulsion as main components. Performance can be more effectively expressed. [0012] The mechanism is to use an acrylic resin in an emulsion state on the surface of the fine particle filler by using the fine particle filler, and in the drying step,
By developing a configuration in which the pressure-sensitive adhesive component is exposed on the surface of the fine-particle filler, and applying a pressure-sensitive adhesive containing the fine-particle filler with the adhesive component exposed on the surface, the surface of the coating layer becomes finer. Irregularities due to the particle filler are formed, the irregularities shift when a predetermined pressure is applied, the surface of the pressure-sensitive adhesive layer becomes flat, and the bonding surface changes from point bonding due to unevenness to surface bonding and it can be re-peeled Glue. Although the pseudo-adhesion mechanism in this case is not clear, self-diffusion of polymer resin, dipole force, hydrogen bonding,
Alternatively, it is considered to be due to an adhesion mechanism such as entanglement between the physical polymer resin and the substrate surface. The fine particle filler used in the present invention is preferably hydrophilic and has an average particle diameter in the range of 1 to 20 μm. When the average particle size is less than 1 μm, the fine particle filler tends to fall off from the pressure-sensitive adhesive applied layer, and when the average particle size is 20 μm or more, the protrusions of the pressure-sensitive adhesive applied surface become remarkable and sufficient feeling is obtained. There is a possibility that adverse effects such as a lack of pressure bonding force may be caused. The average particle size of the fine particle filler is generally represented by an average value of the size of one particle. For example, fine particles such as silica form a group, and When the particles behave like particles, the particle population (2
(Next particle). The compounding ratio of the water-soluble resin emulsion to be dispersed in the acrylate used in the present invention is preferably such that 5-500 parts by weight of the water-soluble resin emulsion is dispersed with respect to 100 parts by weight of the acrylate. . If the compounding ratio is less than 5 parts by weight or 500 parts by weight or more, there is a possibility of causing problems such as occurrence of blocking or insufficient expression of adhesive strength. More preferably, a water-soluble resin emulsion is dispersed in an amount of 5 to 200 parts by weight with respect to 100 parts by weight of an acrylate ester. Therefore, in the present invention, at least 5
It is preferred that about 500 parts by weight of the water-soluble resin emulsion is dispersed in the acrylate. More preferably, the glass transition point is-
The glass transition point when the acrylate in the range of 90 to 50 ° C. is mixed with the water-soluble resin emulsion is −
It is preferably in the range of 80 to 20 ° C. The mixing ratio of the pressure-sensitive adhesive and the fine particle filler used in the present invention is 100
It is preferable that the fine particle filler is contained in an amount of 5 to 200 parts by weight based on parts by weight. If the compounding ratio is less than 5 parts by weight, printing or printability is insufficient, or 2
When the amount is more than 00 parts by weight, there is a possibility that the fine particle filler may be easily peeled off from the applied layer of the pressure-sensitive adhesive, or may cause adverse effects such as insufficient adhesive strength. Therefore, in the present invention, at least 5
It is preferred to use the fine particle filler in the pressure-sensitive adhesive in an amount of up to 200 parts by weight. The fine particle filler used in the pressure-sensitive adhesive of the present invention includes silica, charcoal, kaolin, clay, talc, aluminum hydroxide, titanium oxide, zinc oxide, activated clay, starch particles, cellulose particles, styrene. It can be appropriately selected and used from inorganic or organic known fine particle fillers such as resin particles, acrylic resin particles, urea resin particles, microcapsules, oil capsules, polyethylene, and vinyl chloride. I can do it. These fine particle fillers may be used alone or in combination of two or more. When two or more kinds are used in combination, irregularities due to the fine particle filler on the pressure-sensitive adhesive applied surface can be made discontinuous, and the pressure-sensitive adhesive property can be easily adjusted. In the present invention, it is preferred that a hydrophilic, more preferably non-thermoplastic, fine particle filler is contained in the acrylic emulsion. The water-soluble resin emulsion to be dispersed in the acrylate used in the acrylic emulsion of the present invention includes polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, polyacrylic acid,
From among known water-soluble polymers such as polyacrylamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, etc. Can be appropriately selected and used. These resins may be used alone or
More than one type may be used in combination. By using two or more types of water-soluble resins, it becomes easy to adjust the glass transition point in the range of −80 to 20 ° C. when the acrylate and the water-soluble resin emulsion are mixed. In the present invention, UV resistance, printability,
It is most preferable to use a styrene-maleic anhydride copolymer excellent in blocking resistance and the like for stabilizing quality. The pressure-sensitive adhesive may further include a surfactant, an antifoaming agent, a thickener, a water-proofing agent, a dispersant, an ultraviolet absorber, an antioxidant, an antistatic agent, and an ink fixing agent, if necessary. Auxiliary agents such as a dye fixing agent, a fluorescent dye, a colored dye, a lubricant, a deodorant, a deodorant, and an antibacterial agent can also be added. The pressure-sensitive adhesive property of the pressure-sensitive adhesive layer according to the present invention is such that the T-peel strength at the boundary where the pressure-sensitive adhesive layer and the sheet to be bonded are superimposed and re-peelable is 300.
mm / min, JIS under the environment of 20 ° C and 65% RH
When measured based on K6833, the peel strength is preferably 10 g / 25 mm or more, particularly preferably 20 to 120 g / 25 mm. When the T-type peel strength is 10 g / 25 mm or less, spontaneous peeling may occur and 120 g / 25 mm In the above case, the printed or printed information may be damaged at the time of re-peeling, or peeling may not be possible. It is difficult to adjust the re-peeling strength only by the mixing ratio of the water-soluble resin emulsion to be dispersed in the acrylate, the mixing ratio of the fine particles, and the addition of the auxiliary. The combination ratio of the water-soluble resin emulsion to be dispersed, the combination ratio of the fine particles, and the addition of an auxiliary are combined, and the glass transition point when the water-soluble resin emulsion is dispersed in the acrylate is in the range of -80 to 30 ° C. It becomes easy by adjusting to. By the way, when the glass transition point is out of this range, the stability with time is inferior, and the stress absorption under pressure is greatly reduced, so that it may be difficult to achieve both peelability and adhesiveness. As the base material used in the present invention, for example, high quality paper, medium quality paper, recycled paper, art paper, coated paper, lightly coated paper, synthetic paper, film, laminated paper, metallized paper and the like are used. I can do it. In the present invention, the pressure-sensitive adhesive is applied to the substrate by using a conventionally known coating machine or printing machine such as a blade coater, an air knife coater, a bar coater, a roll coater, a gravure printing machine or a screen printing machine. Can be used. In the present invention, the amount of the pressure-sensitive adhesive to be applied to the substrate is usually preferably about ² to ²⁰ g / m ^{2 in} order to develop an appropriate adhesive force. DESCRIPTION OF THE PREFERRED EMBODIMENTS The pressure-sensitive adhesive of the present invention is obtained by mixing an acrylic emulsion pressure-sensitive adhesive base containing an acrylate ester and a water-soluble resin emulsion as main components, and preferably fine particles. The adhesive force is easily adjusted by mixing and containing an auxiliary as a basic component and adjusting the glass transition point when the water-soluble resin emulsion is dispersed in the acrylate ester within the range of -80 to 30 ° C. be able to. After the pressure-sensitive adhesive of the present invention is applied to a predetermined portion of the base material and dried, the portion to which the pressure-sensitive adhesive is applied and the portion to be bonded are opposed to each other, and a predetermined pressure is applied to the pseudo-adhesive. Can be glued. Further, since the surface of the coating layer of the pressure-sensitive pseudo-adhesive has good information recording suitability such as printing and printing, it becomes a pressure-sensitive pseudo-adhesive sheet on which information can be recorded. The pressure-sensitive pseudo-adhesive sheet of the present invention has a stable adhesive force and suppresses the stickiness of the surface of the adhesive layer. Since the material to be bonded is excellent and the material to be bonded is not selected, the range of selection of the material to be bonded is increased and the range of application is expanded. Further, the pressure-sensitive pseudo-adhesive sheet of the present invention is a heat-sensitive paper,
Inkjet paper, thermal transfer paper, no-carbon paper,
It can be used as coated paper, high-quality paper, or the like, or can be combined with these papers, or can be coated with an adhesive or the like on the back surface, and can be used in combination with various base materials. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” and “%” described below mean “parts by weight” and “% by weight”, respectively. Embodiment 1 100 parts (dry weight) of an acrylate ester (glass transition point is -50 ° C.) as an adhesive base and 100 parts (dry weight) of a styrene-maleic anhydride copolymer were mixed, and the glass transition point was -30 ° C. Was adjusted. 50 parts of synthetic silica (Carplex 80D: manufactured by Shionogi & Co., Ltd.) having an average particle diameter of 7 μm was mixed to obtain a target pressure-sensitive pseudo-adhesive. Next, this pressure-sensitive adhesive composition was prepared using 127.
9 g / m ² of high-quality paper was applied so that the application amount was 10 g / m ² (dry weight) to obtain a pressure-sensitive pseudo-adhesive sheet.
Using this sheet, adhesive strength, printability,
Table 1 shows the results of evaluating non-impact printing suitability (hereinafter referred to as NIP suitability) and blocking property. Adhesive force: After the sample was left in an environment of 20 ° C. and 50% RH for 12 hours or more, a mail sealer (MS) was used.
-9100: manufactured by Dai Nippon Printing Co., Ltd.) under pressure with a roll gap of 14 (140 μm).
A mold release test was performed based on JIS K6833. UV deterioration test: The sample was forcibly irradiated with ultraviolet light for a predetermined time using a UV irradiator, and was irradiated at 20 ° C. and 50% R.
After being left in an environment of H for 12 hours or more, evaluation was performed in the same manner as in the case of the adhesive strength. Printing suitability test: Using an offset printing machine, ink bleeding and image reproducibility when printed on the adhesive layer of the pseudo-adhesive sheet were visually observed and evaluated. -Good image reproducibility, etc.---Good image reproducibility-X: Non-impact printing suitability test:
Using a non-impact printer (F-6762D: manufactured by Fujitsu Ltd.), the transferability of the image and the like were visually observed and evaluated.・ Those with good image reproducibility and running performance without blurring etc. →
○-No problem in image reproducibility, but poor runnability → △-Poor image reproducibility and runnability, faint, dirty, etc. → × [0042] Blocking evaluation test: stacking 50 samples , 20 ° C., 65% RH, a predetermined load was applied and left for 24 hours, and then evaluated by hand peeling. -No occurrence of blocking etc.---Some blocking occurs, but it can be easily removed by hand---Blocking-> Example 2 As an adhesive base, 100 parts (dry weight) of an acrylate ester (glass transition point is −50 ° C.) and 100 parts (dry weight) of an ethylene-maleic anhydride copolymer are mixed, and the glass transition point is −30 ° C. Was adjusted. Forty parts of synthetic silica (Carplex 80D: manufactured by Shionogi & Co., Ltd.) having an average particle diameter of 7 μm were mixed to obtain a target pressure-sensitive pseudo-adhesive. The obtained pressure-sensitive adhesive was applied to high quality paper in exactly the same manner as in Example 1 to obtain a pressure-sensitive pseudo-adhesive sheet. Table 1 shows the results of evaluating the adhesive strength, printability, NIP suitability, and blocking property of the obtained sheet. Comparative Example 1 100 parts (dry weight) of an acrylate (glass transition point is −50 ° C.) as an adhesive base and 300 parts (dry weight) of a styrene-maleic anhydride copolymer were mixed, and the glass transition point was adjusted to 60 ° C. It was adjusted. Forty parts of synthetic silica (Carplex 80D: manufactured by Shionogi & Co., Ltd.) having an average particle diameter of 7 μm were mixed to obtain a target pressure-sensitive pseudo-adhesive. The obtained pressure-sensitive adhesive was applied to high quality paper in exactly the same manner as in Example 1 to obtain a pressure-sensitive pseudo-adhesive sheet. With respect to the obtained sheet, the results of evaluating the adhesive strength, printability, NIP suitability, and blocking property are as shown in Table 1. Comparative Example 2 Synthetic silica (Carplex 80D: Shionogi Pharmaceutical Co., Ltd.) having an average particle size of 7 μm without adding a water-soluble resin emulsion to 100 parts (dry weight) of an acrylate ester (glass transition point is −50 ° C.) as an adhesive base Was mixed together to obtain a pressure-sensitive pseudo-adhesive having an intended glass transition point of -50 ° C. The obtained pressure-sensitive adhesive was applied to high quality paper in exactly the same manner as in Example 1 to obtain a pressure-sensitive pseudo-adhesive sheet. About the obtained sheet, adhesive strength, printability, NI
Table 1 shows the results of evaluating the suitability for P and the blocking properties. Comparative Example 3 As an adhesive base, 100 parts (dry weight) of a styrene-maleic anhydride copolymer are mixed with 100 parts (dry weight) of an acrylate ester (glass transition point is −50 ° C.), and a fine particle filler is added. Target glass transition point is -50
A pressure-sensitive pseudo-adhesive at ° C was obtained. The obtained pressure-sensitive adhesive composition was applied to high quality paper in exactly the same manner as in Example 1 to obtain a pressure-sensitive pseudo-adhesive sheet. For the obtained sheet, the adhesive strength,
Table 1 shows the results of evaluating printability, NIP suitability, and blocking properties. Comparative Example 4 As an adhesive base, 100 parts (dry weight) of a styrene-maleic anhydride copolymer was used.
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 2 except that the amount was changed to parts (dry weight). The obtained pressure-sensitive adhesive composition was applied to high quality paper in exactly the same manner as in Example 1 to obtain a pressure-sensitive pseudo-adhesive sheet. For the obtained sheet, the results of evaluating the adhesive strength, printability, NIP suitability, and blocking property are shown below.
It is shown in Table 1. [Table 1]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a delivery slip according to one embodiment of the present invention. FIG. 2 is a sectional view taken along line AA ′ of FIG. [Description of Signs] 1 delivery slip, 2 base material, 3 pseudo adhesive, 4 delivery section, 5 receiving section, 6 perforations, 7 pressure sensitive pseudo adhesive sheet.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Yuji Takechi 5-1 Kamiyacho, Iyo Mishima City, Ehime Prefecture Daio Paper Co., Ltd. (56) References JP-A-9-263743 (JP, A) JP-A-8 -118560 (JP, A) JP-A-6-65547 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 7/02 B42D 11/00 B42D 15/02 501

Claims (1)

(57) [Claim 1] At least one surface of a support has a drying step of drying a pressure-sensitive adhesive layer capable of printing or printing information.
That in sensitive圧疑similar adhesive sheet provided by the coating, the pressure-sensitive adhesive layer is an acrylic acid ester (A), poly
Vinyl alcohol, carboxymethyl cellulose, poly
Vinylpyrrolidone, polyacrylic acid, polyacrylamide
, Ethylene-maleic anhydride copolymer, styrene-free
Water maleic acid copolymer, methyl vinyl ether-anhydride
Maleic acid copolymer and isobutylene-maleic anhydride
One or two water-soluble resins selected from the group of copolymers
Marjon (B) as a main component and obtained by mixing them.
A layer containing, as basic components, an acrylic emulsion pressure-sensitive adhesive base and a fine particle filler, wherein the glass transition point of the acrylate is in the range of −90 to 50 ° C., and the acrylate 100 parts by weight
And the water-soluble resin emulsion is mixed in an amount of 5 to 500 parts by weight.
Is dispersed and the water-soluble resin
Glass transition point when mixed with marjon is -80 to
Acrylic emulsion pressure sensitivity in the range of 20 ° C
The fine particle filler is 5 to 100 parts by weight of the adhesive.
200 parts by weight of the pressure-sensitive adhesive layer of the pressure-sensitive pseudo-adhesive sheet and the T of the boundary surface in which the adhesive sheet is superimposed and pseudo-adhered removably.
Mold peel strength is 20 ° C, 65% RH in an environment of J
10 to 120 g / 25 as measured according to ISK6833
A pressure-sensitive pseudo-adhesive sheet having a peel strength of 1 mm .