JPS63196679A - Pressure-sensitive adhesive layer - Google Patents

Abstract

PURPOSE:To obtain a pressure-sensitive adhesive sheet simply at a low cost, which has excellent sticking workability in registration and gives a good surface profile after bonding, by using a pressure-sensitive adhesive layer obtd. by forming a specified difficultly sticking solid layer on at least one surface of a flat pressure-sensitive adhesive layer. CONSTITUTION:This pressure-sensitive adhesive layer is obtd. by forming a difficultly sticking solid layer 2 thinner than a flat pressure-sensitive adhesive layer 1 on at least one surface or surface layer of said adhesive layer 1, said solid layer 2 being formed by coating said adhesive layer 1 directly or indirectly with a solidifiable flow material and then solidifying said material. A base material layer 3 is provided on one side of the adhesive layer 1 of the pressure- sensitive adhesive to obtain a pressure-sensitive adhesive sheet. The adhesive sheet is stuck on a substrate by sticking the sheet on the surface of a substrate 5 to be stuck, registering positions to be stuck and bonding them from the back of the base layer 3 under pressure.

Description

Detailed Description of the Invention (Field of Application of Ii Chestnut) The present invention relates to a pressure-sensitive adhesive layer, a pressure-sensitive adhesive sheet using the same, a pressure-sensitive adhesive sheet-like structure, and a method for manufacturing and using the same. More specifically, for example, when a pressure-sensitive adhesive sheet is used as a pressure-sensitive adhesive layer to adhere to the surface of an adherend, alignment of the adhesion position to a desired application site on the surface of the adherend is applied. The giant nails can be moved to the desired attachment site as necessary, or defects in attachment, such as wrinkles, bubbles, etc.
Initial adhesion is small enough to enable corrective movement to avoid bulges, etc. (adhesive force when brought into contact with the surface of the substrate to be adhered before the crimping operation).
...), and the rate of increase in adhesive force over time after crimping and the value of the increased adhesive force are significantly large, and the surface condition after crimping is flat and beautiful. The present invention relates to a pressure-sensitive adhesive layer that can exhibit unique improved performance such as being easy to manufacture.

[Prior art]

There are three known types of pressure-sensitive adhesive sheet-like structures that have a pressure-sensitive adhesive layer on the surface of a base material such as a tape, film, or sheet.
Display use.

It is used in fleet marking applications such as automobiles and containers, as well as in a wide range of other fields, by being attached to the surface of the substrate to which it is attached.

Since such a pressure-sensitive adhesive layer is required to have strong adhesive strength over a long period of time, its initial adhesive strength is generally large, and it requires skill to apply it to nine sides of the target/adherent substrate, making it difficult for even an experienced person to apply it. It is extremely difficult to accurately apply the adhesive to the desired application site in one go, and the application position is likely to shift.

For this purpose, it is often necessary to reapply or move the adhesive to the appropriate area, such as corrective movement to the desired application area or corrective movement to avoid adhesion failure, such as wrinkles and bubble bulges. This often causes problems such as deformation, breakage, and wrinkles of the base material. Such troubles are
Furthermore, it becomes a bigger problem when attaching a large-sized pressure-sensitive adhesive sheet-like structure. As a matter of fact, for large-sized pressure-sensitive adhesive sheets, it has been ideally desired to have an initial adhesive strength of 4N, even virtually zero.

In order to solve the above-mentioned technical problems with pressure-sensitive adhesive layers, it is attempted to reduce only the initial adhesive strength of the pressure-sensitive adhesive layer without substantially reducing the desired adhesive strength of the pressure-sensitive adhesive layer. Several attempts have been proposed and are known.

One such proposal, in Japanese Patent Publication No. 44-8110, is characterized in that the adhesive layer has small brittle or collapsible non-adhesive ribs uniformly distributed on at least one surface thereof. A tacky adhesive l- has been proposed. According to this proposal, a friable or collapsible non-adhesive hollow microballoon, such as a hollow microballoon of resin such as urea-formaldehyde resin or a hollow glass microballoon, is attached to at least one of the adhesive cocoon layers. By uniformly distributing it on the fitting surface, the initial adhesive force is reduced, and when the hollow microballoons are ruptured or crushed when pressed to the adhered substrate, the adhesive force of the adhesive layer is developed. The proposal also discloses that some variation in the diameter of the cough microballoon is acceptable, but that a range of about 40 to about 100 microns is best.

Another proposal, in Japanese Patent Publication No. 44-17040, is to provide a continuous, non-adhesive, brittle protective envelope over a height of at least about one quarter of the height of the protrusion having a height of at least 15 microns. The uniform pattern of small protrusions, each memorized by the individual, and the intervening flat adhesive surfaces that separate them, create a thin, continuous pattern with an outline similar to that of scattered pebbles. Adhesive sheets are known which contain an adhesive and which can be slid over an adhesive-receiving work surface to the proper position and thereupon adhered thereto by mere application of pressure.

However, in these conventional proposals, it is difficult to ideally reduce the initial adhesion force without having a substantial negative effect on the adhesion force during crimping, and it is also difficult to reduce it to a practically acceptable level. Therefore, it has been found that if the initial adhesive strength is reduced to a satisfactory level, there is a problem in that the pressure bonding strength is substantially adversely affected. Furthermore, the hollow microballoons that can shatter, tear, or collapse in the former case, and the non-adhesive, brittle protective envelope in the latter case, are relatively large and It was found that the particles tend to disperse into the adhesive layer and remain as fragments on the surface of the adhesive side (which has a significant adverse effect on the increase in adhesive strength after pressure bonding).

Furthermore, there is a problem in that these fragments deteriorate the different surface condition after crimping, give a smooth surface condition, and cause the balloons to come apart. In practice, it is difficult to distribute the agent so that part of it is buried in the surface of the layer and the rest of it is protruding, and there are defects that make it difficult to manufacture.In the latter case, it is even more difficult to manufacture.
This has the disadvantage of being complicated.

Furthermore, it is essential to use a support for the adhesive surface used in the latter case, and this support must have countless depressions of 15 microns or more, and its manufacture requires a special method. However, industrial manufacturing is generally difficult with IA. It has also been found that in the manufacturing process of the adhesive sheet disclosed in Japanese Patent Publication No. 44-17040, even slight irregularities in control can cause non-uniformity in the initial adhesive strength. Furthermore, this adhesive sheet theoretically cannot reduce the initial adhesion force to near zero, and in reality, it is possible to achieve a practically satisfactory initial adhesion force and pressure bonding using a wide range of desired adhesives. It has been found that it is extremely difficult to obtain a product that has both high adhesive strength.

Further, when the adhesive sheet of the invention having a transparent film as a base material is used for protecting photographs or attached to glass, a fatal drawback occurs. In other words, in this case, the adhesive j- can also be seen through, but small air bubbles originating from the protrusions on the adhesive surface remain in the adhesive layer, making the adhesive layer appear opaque and impractical. . In addition, when electrical appliance parts or motorcycle parts to which an adhesive sheet with an adhesive layer containing air bubbles is attached are heated in the process, the removable sheet may swell due to the expansion of the air bubbles. This can cause fatal accidents such as peeling.

Furthermore, if such an adhesive sheet containing air bubbles is attached to an outdoor structure, accidents may occur even when exposed to direct sunlight.

In addition, in the case of a general adhesive sheet and the adhesive having a cross-linked #4 structure, the viscous flow of the adhesive is restricted, so protrusions larger than is μ remain on the adhesive layer even after pasting, which adversely affects #I physical properties. 8 sometimes.

If the adherend has a rough surface with protrusions of 15 microns or more, there is also the disadvantage that these protrusions come into contact with the adhesive surface of the adhesive sheet, making it difficult to position the adhesive sheet.

These above-mentioned drawbacks also occur in the case of Japanese Patent Publication No. 44-811BO.

Further, in order to improve the above-mentioned drawbacks, JP-A No. 68-18582 discloses a non-hollow material having a particle size smaller than the thickness of the pressure-sensitive adhesive layer, an average particle size of less than 10μ, and a layer adhesive property. A pressure-sensitive adhesive layer has been proposed in which the solid particles have a dispersed layer of uniformly dispersed particles on at least one surface or six-sided layer of the pressure-sensitive adhesive layer. . According to this proposal.

A pressure-sensitive sheet M4 method is disclosed in which non-hollow solid particles are dispersed on a release paper using a flour mill or other suitable means, followed by applying a pressure-sensitive adhesive layer and laminating the paper to a base sheet.

However, in this proposal, it is difficult for the non-hollow solid particles to form a sufficient adhesive state with the release paper;
Therefore, due to shedding of non-hollow solid particles during the manufacturing process,
It has disadvantages in drying, such as difficulty in controlling the distribution of solid particles and furthermore, the amount of distribution.

[Problem to be solved by the invention]

The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and to easily produce a pressure-sensitive adhesive sheet that has excellent positioning and other adhering operations, and has a good surface condition after adhesion. The purpose is to provide it at low cost.

Another object of the present invention is to prevent air bubbles from being trapped in the adhesive layer of the pressure-sensitive adhesive sheet pasted, and to provide pressure-sensitive bonding 71f111 with good positioning properties. An object of the present invention is to provide a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive sheet-like structure.

[Means for solving problems]

The present invention has been made to solve the above-mentioned problems. (1) A fluid material that can be solidified is directly or indirectly coated on a flat pressure-sensitive adhesive layer +11 and then solidified. In addition, a flat pressure-sensitive adhesive layer (thinner than 11 tack-resistant solid layer (2) is placed on at least one surface of the flat pressure-sensitive adhesive layer (1) or 9Athi)-
A pressure-sensitive φ adhesive layer comprising:

(2) Having a base material layer (3) on one side of a flat pressure-sensitive YIl agent layer (1), and solidifying after directly or indirectly coating a fluid substance that can solidify on the other side. The adhesive solid layer (1), which is thinner than the flat pressure-sensitive adhesive layer (1), is removed from the flat pressure-sensitive adhesive layer (1).
1! ! ! A pressure-sensitive adhesive sheet-like structure having a peelable support layer (4) on the outside of a flat pressure-sensitive adhesive layer (11) on the surface or as a surface layer.

(3) Flat pressure sensitive adhesive layer (base material layer (on one side of 11)
3), which is thinner than the flat pressure-sensitive adhesive layer (1) and is produced by directly or indirectly coating one side with a fluid substance that can solidify and then solidifying it. The solid layer (2) is coated with a flat pressure-sensitive adhesive M (11
Pressure-sensitive adhesive 7 having a flat surface on the surface or surface layer of the
m (8) on a pressure-sensitive adhesive sheet-like structure carrying a peelable support layer (4) on the outside of 11;
Pressure-sensitive adhesive sheet soft structure with a coating of a flowable material that can be solidified and a release solid/I 121 of % [! Of course, how to send M.

(4) Flat pressure sensitive adhesive layer (base material layer (on one side of 11)
3), which is thinner than the flat pressure-sensitive adhesive layer (1) caused by directly or indirectly coating one side with a fluid substance that can solidify and then solidifying it. A pressure-sensitive adhesive sheet having the adhesive solid layer (2) on the second or surface side of the flat pressure-sensitive adhesive layer (11) is pasted on the surface of the substrate to be pasted (5), and then applied to the desired pasting site. Pressure-sensitive adhesive whose % value is the adhesive strength of the pressure-sensitive adhesive layer (1) that is exerted by pressing from the back side of the base layer (3) after alignment of the adhesive and the adhesive is attached to the substrate to be adhered. How to paste the sheet.

It provides:

In a preferred embodiment, the non-adhesive solid layer (2) is a pressure sensitive adhesive JIIB which is a printed layer, and the printed layer is a gravure printing layer, a screen printing layer, an offset printing layer, a letterpress printing layer, or a jet spray coating printing layer. layer, the pressure-sensitive adhesive layer is a roll-coated printing layer, the solidifying fluid substance is a resin liquid, and the Keyaki adhesive solid layer (2) is partially formed. The pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer in which the partially formed non-adhesive solid layer (2) occupies an area of 8 to 98% of the entire pressure-sensitive adhesive layer. Yes, the base material layer is a resin film,
The pressure-sensitive adhesive sheet-like structure is a paper, cloth, or metal sheet, and the base layer (2) has a thickness of 30 to 500 μm, and the resin film (2)
The pressure-sensitive adhesive sheet-like structure has a yield stress of 1 to 5/-, and the resin film (2) is a vinyl chloride-based resin, and the vinyl chloride-based resin is a pressure-sensitive adhesive sheet-like grooved material made of vinyl chloride resin for paste, and the flat pressure-sensitive adhesive layer (1) has a micro-rolling force of 0.4 after being attached to an aluminum plate and left for 34 hours or more. A pressure-sensitive adhesive sheet-like structure that is a (meth)acrylic acid ester adhesive having ~16~/Cat, and the flat pressure-sensitive adhesive layer (1) is a crosslinkable adhesive. It provides wood-shaped products.

According to the research conducted by the present inventors, the pressure-sensitive adhesive layer obtained by the present invention can be easily aligned to the desired attachment site on the surface of the substrate to be adhered, and can also be applied as needed. Accordingly, it exhibits an improved small initial adhesion property that is sufficiently satisfactory to enable positional correction movement to the desired adhesion site and correction movement to avoid adhesion failure, such as wrinkles and bubble bulges. It was discovered that.

Furthermore, as shown later in Examples and Comparative Examples, the rate of increase in adhesive strength over time after crimping and the value of adhesive strength become significantly thicker in a relatively short period of time (and the surface condition after crimping becomes It has been discovered that the unexpected effect of smoothness can be achieved at once.In addition, the above-mentioned excellent pressure-sensitive adhesive layer can be produced industrially and advantageously using easier and simpler means than conventional methods. I learned that I can do it.

The "fluid substance that can solidify" as used in the present invention may be any substance as long as it solidifies and forms a sticky solid layer, but generally, for example, molten resin, molten wax, etc. organic inks and paints that use a combination of materials, solutions such as resin solutions, latex such as resin latex, polymer precursors, monomers, resins and pigments or fillers, water glass-based inorganic paints, etc., and mixtures thereof. Can be mentioned.

In addition, considering the adhesive strength to the support layer and the pressure-sensitive adhesive layer (11), these fluid substances that can be solidified are used as the support layer (4).
, may be adjusted according to the constituent materials of the adhesive j-.Generally, examples of molten materials include wax and other 1! with an appropriate melting point. Resin such as machined smoke, low molecular weight nylon, low molecular weight polyethylene, polystyrene, polyester, R'
iIt, can you give examples of inorganic substances such as low melting point metals and low melting point salts? ! ! Examples of liquids include vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, styrene resin, (
Solutions of organic compounds such as methacrylic acid ester resins, (meth)acrylic ester copolymer resins, vinyl alcohol @ fats, acrylate polymers, acrylic acid polymers, fluorocarbon resins, gelatin, polysaccharides, glue, etc. Soluble natural polymers, mixtures of rubber and vulcanizing agents, solutions of polymer compounds such as polyethylene glycol, polypropylene glycol, polyesters, unryamides, alkyd resin solutions, polyurethane resin solutions, polyester resin solutions, phenolic resin solutions, melamine Examples include polymer precursor solutions such as resin solutions, linseed oil, and sumac solutions. The solvents used in these solutions are appropriately selected depending on the solute, but examples include toluene, xylene, acetone, methyl isobutyl ketone, Examples include methyl alcohol, butyl alcohol, propyl alcohol, isopropyl alcohol, and mixed solvents thereof. In addition, when a polymer precursor is used, it is best to polymerize it by an appropriate method after marking or printing. As the latex, latex particles that coalesce with each other to form a film after coating can be preferably used, examples of which include vinyl acetate polymer latex, stichine resin latex, (meth)acrylic acid ester (co)polymer latex, Styrene-acrylic copolymer latex, vinyl acetate-acrylic copolymer latex, mixed latex of rubber and vulcanizing agent,
Resin latex such as hot melt resin latex,
Examples include resin solution latex, linseed oil, sumac, epoxy resin, urethane resin, phenol resin, and polymer precursor latex such as a mixture of a polymer monomer and a polymerization accelerator.

Common +m colors include phenolic resins, epoxy resins, unsaturated polyester resins, polyurethane resins, UV-cured resins, other resins that cure resins, drying oils, and polymers such as uricium (meth)acrylic acid ester oligomers. Precursors are mentioned, each of which needs to be solidified by a suitable method.

As the monomer, the monomer of the resin used in the solution is generally used, and particularly preferred are (meth)acrylic acid, (methacrylate ester, vinyl acetate, styrene, etc.).

Organic inks and paints include acrylic paints, epoxy paints, and epoxy paints obtained from the resins and resin solutions and pigments.
Examples include vinyl chloride-vinyl acetate paints, alkyd paints and inks, and examples of inorganic paints include water glass inorganic paints.

Examples of mixtures include mixtures of the above-mentioned resins with mica, whiskers, etc., and mixtures of the aforementioned substances.

In addition, there are 7 other types of fluid vIJX that can be solidified, such as the melt, bath liquid, latex, etc. Ftil can contain various additives such as leveling agents, surfactants, antifoaming agents, inorganic fillers, and peeling AiI agents.

When the colored ink or paint, which is a fluid substance that can be solidified, is used, the homogeneity when applied or printed can be judged with the naked eye, and the pigment makes these material layers brittle, and the pressure-sensitive adhesive sheet of the present invention When pressed, the adhesive layer (1) can quickly exhibit adhesive force, which is very advantageous.

Further, in the case where the base material (3) of the pressure-sensitive adhesive sheet is a transparent material such as a transparent film, the pressure-sensitive adhesive layer (1) can be seen through with the naked eye even after the sheet is pasted. i
t (If 11 also needs to be transparent, the non-adhesive layer (2) must also be transparent. In this case, the refractive index of the material in 11 and the adhesive layer ( It is particularly preferable that the refractive indexes of 2) are the same or similar.

Another method for forming the adhesive layer (2) is to apply i! to the surface of the pressure sensitive adhesive layer (1). Special methods such as direct or indirect chemical plating or deposition of silver particles in a silver salt bath may also be employed.

The linear adhesive solid layer (2) of the present invention functions as a layer to achieve low adhesiveness that allows re-peelability and positional movement when the pressure-sensitive adhesive sheet is attached to an adherend, and After deciding where to put it, apply finger pressure from the back of the base layer (3).
Roll pressure.

Destroy, crush, deform, etc. the solid N (2) by pressure bonding such as squeegee pressure to enable contact between the pressure sensitive f & adhesive layer (1) and the adherend, or reduce the thickness of the solid layer (2). Pressure-sensitive welding from
The adhesive layer (1) and the adherend are brought into contact with each other by external pressure to exert the adhesive strength of the pressure-sensitive adhesive (1), but generally the adhesive solid layer (2) is preferably formed partially on the pressure sensitive adhesive layer.

The form (pattern, region, thickness, etc.) and area of the partially formed layer of the releasable solid layer (2) may be appropriately selected as desired, and are not particularly limited. When applying it to an adherend as an adhesive sheet, if high initial adhesion strength and free positioning are required, cover the entire surface of the adhesive layer discontinuously with the smallest possible solid layer + 21rkJ area. In general, the shape of I- formed partially in the J11 adhesive solid layer is dotted, linear, frame-like, or planar, and even if these are formed continuously or discontinuously. good.

For example, in the case of points, examples include round points, triangular points, star points, spots, side points, target points, non-target points, etc. In the case of lines, examples include straight lines, curves, broken lines, dotted lines, thread-like lines, target lines, etc. Examples include asymmetric lines, and in the case of planar surfaces, examples include planes, cut surfaces, circular surfaces, triangular surfaces, quadrilateral surfaces, and polygonal surfaces.

The preferred proportion of the area occupied by these hard-to-adhesive solid layers is about 8 to about 98 percent, particularly preferably about 85 to about 96 percent, of the entire pressure-sensitive adhesive layer, preferably about 40-90 percent.

In addition, it is thought that it is preferable that the hard-tack solid layer (2) is buried in the pressure-sensitive adhesive layer when the adhesive sheet is pressed and pasted, and the preferred range is 0.1 to SOμ, particularly preferably 0.
1-6μ, more preferably O, S to 3 tones.

Furthermore, the term "coat" as used in the present invention refers to, for example, spray coat, dip 7, bath N, roll coat, bar code, printing coat, etc., and includes printing coats such as gravure, screen, letterpress, offset, jet spray, roll coat, etc. is preferred, and a gravure printing coat is preferred for 411F.

In addition, in the present invention, "directly coating" in "directly or indirectly coating" refers to directly coating the pressure sensitive adhesive layer (1) with a fluid substance that can solidify, and "indirectly coating" refers to directly coating the pressure sensitive adhesive layer (1) with a fluid substance that can solidify. "Coating" means coating a removable support layer (4) or other support with a fluid substance that can be solidified, and then transferring it to the surface of the N contact agent layer (11) or solidifying the fluid material after solidification. It means to transfer first and then solidify.

Furthermore, in the case of "indirect coating", a removable support layer (4
) is coated with an animal substance that can be solidified, and after solidification,
There are cases in which a pressure-sensitive adhesive is applied thereon and dried, and cases in which a pressure-sensitive adhesive layer formed on another support is pressure-bonded and transferred, but the latter is particularly preferred in the present invention.

Furthermore, when producing the pressure-sensitive adhesive sheet-like structure of the present invention, the non-adhesive solid layer (2) may be formed by adhering it on the removable support layer (4). (2) may be formed by directly adhering to the surface of the pressure sensitive adhesive layer (1) or Table 1.

In addition, after the above-mentioned non-adhesive solid/*t21 is once attached and formed on another releasable support, it is transferred onto the surface of the pressure sensitive adhesive layer (11), and this transferred composite layer is applied to the final releasable support. It may be transferred onto layer (4) for convenient use.

In addition, when the adhesive solid layer (2) is once formed on another releasable support and then transferred, the temporary removability of the adhesive solid layer (2) and the other releasable support is In order to improve the optical surface of the support, it is possible to make the optical surface of the support slightly rougher or to slightly increase the temporary adhesion force between the adhesive solid layer and the support to prevent peeling between the adhesive solid layer and the support during storage. can.

The most important thing when obtaining an adhesive increase by the indirect coating of the present invention is that the adhesive solid layer formed by coating on the releasable support (4) or other support can be applied to the pressure sensitive M wound.
1t (11).When the pressure-sensitive adhesive sheets (1), (2), and (3) of the pressure-sensitive adhesive sheet-like wooden material are peeled off from the releasable support layer (4), the pressure-sensitive adhesive sheets (1), (2), and (3) are difficult to adhere to. Solid layer (2)
The skin that does not substantially transfer to the pressure-sensitive adhesive layer (1) but remains substantially on the support layer (4), such as the silicone layer of release paper whose surface is coated with silicone, which is commonly used. This is different from the adhesive solid layer (2) of the present invention.

In addition, a flat pressure-sensitive adhesive layer is a layer of N agent J-
In the present invention, the pressure-sensitive adhesive layer (11) which is in contact with the adhesive solid layer (2) is as smooth as possible. It is preferable to use this method because the hard-to-adhesive solid layer can be uniformly formed in the desired ratio.

As for the degree of flatness and smoothness, the surface roughness of the surface of the pressure-sensitive adhesive layer (1) in contact with the releasing adhesive solid No. (2) is 15μ or less, preferably 14μ or less, particularly preferably 10μ or less,
More preferably, it is in the range of aμ or less. However, roll coating marks, printing marks, scratches, omissions, etc. that occur due to insufficient flow when coating with a fluid substance are within an acceptable range.

Furthermore, the releasability, the openings and embossments of paper on the surface of the support layer, etc. are within an acceptable range. - The pressure-sensitive adhesive layer (1) not in contact with the non-viscous solid layer (2) is the base material (3).
) There is no problem with having unevenness depending on the unevenness of the surface.

Also, the "fluidity" of "fluidity" that can be solidified means that it has fluidity at the time of coating (for example, JJQ'f!A
When coating with a sheet, it can be used in the present invention as long as it has fluidity during heating. The degree of fluidity may be appropriately selected depending on the coating type, but generally the viscosity is 1 cps to 10,000 cps, sometimes preferably 2S to 10,000 cps, more preferably S cp1~5000
You can select cpa viscosity.

Various types of adhesives are known as pressure-sensitive adhesives forming the pressure-sensitive adhesive layer (1) of the present invention, and can be used in the present invention. Preferably, a type of adhesive commonly referred to as a pressure-sensitive adhesive that exhibits tackiness at room temperature is used.

Examples of such pressure sensitive adhesives include rubber adhesives, acrylic adhesives, vinyl acetate adhesives, urethane adhesives, and silicone adhesives.

Other adhesives and their suitable mixtures may also be mentioned.

Examples of the rubber-based WkN agent include natural rubber, imprene rubber, styrene-butadiene rubber, styrene-butadiene block copolymer, styrene-isoprene block copolymer, butylcom, polyisobutylene, silicone rubber, polyvinyl isobutyl ether, and chloroprene rubber. , nitrile rubber, mixtures thereof, or at least one of them as a main component.

Moreover, those having a slight crosslinked structure between molecules can also be preferably used.

Examples of acrylic adhesives and vinyl acetate adhesives include adhesives made from solvent-type adhesives containing unsaturated carboxylic acid ester copolymers as a main component, especially unsaturated carboxylic acid esters. Monomer 99.9-851
11i part and 0.1 vinyl monomer that carries the crosslinkable functional group
The glass transition temperature (Tg
) is -20℃ or less copolymer 100 weight ts1 solvent 70 ~
An adhesive layer formed from a bath agent type adhesive comprising 400 parts by weight and 0.01 to 20 parts by weight of a crosslinking agent capable of crosslinking with the above-mentioned crosslinkable functional group is preferred.

Examples of unsaturated carboxylic acid ester monomers for applying the copolymer constituting the adhesive include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)decrylate, and pentyl (methaneacrylate). Monomers of (meth)acrylic esters such as hexyl (meth)acrylate, heptyl (meth)acrylate, and octyl (meth)acrylate, monomers of vinyl esters such as vinyl acetate and vinyl propionate, etc. It will be done.

In addition, vinyl monomers having a crosslinkable functional group for obtaining the above-mentioned copolymer include vinyl monomers having a carboxyl group such as acrylic acid, methacrylic acid and itaconic acid, and hydroxymethyl ester, hydroxyethyl ester of acrylic acid, hydroxypropyl ester,
Examples include hydroxyethyl ester, hydroxypentyl ester, hydroxyhexyl ester, hydroxymethyl ester, hydroxyethyl ester, hydroxybutyl ester, hydroxypropyl ester, hydroxypentyl ester, and hydroxyhexyl ester of methacrylic acid, and vinyl monomers carrying hydroxyl groups. Also included are vinyl monomers that carry epoxy groups and amino groups.

In addition, as a solvent, ethyl acetate, toluene, acetone,
Isopropyl alcohol and the like are preferred.

As the crosslinking agent capable of crosslinking with the carboxyl ester of the vinyl monomer having a crosslinkable functional group, a metal crosslinking agent and an organic polyvalent isocyanate compound are mainly used. nate, aluminum isopropylate, aluminum secondary butyrate, titanium tetraisopropylate, titanium tetra-normal butyrate, titanium tetra-2-ethylhexylate, antimony butyrate, zirconium secondary butyrate, zirconium jetoxy tertiary butyrate, hafnium tertiary butyrate Polymerization of titanium tetrabutyrate as examples of butyrate, ethyl acetate acetate aluminum diisopropylate, triethanolamine titanium diisopropylate, ammonium salt of titanium lactate, tetraoctylene glycol titanate, polyalkyl titanate, polytitanium acylate and polymerized titanium oleate. Examples of the organic polyvalent incyanate compounds include P-phenylene diisocyanate, -41-diphenylmethane diisocyanate), &4-tolylene diisocyanate, 2.6-1
- So-called polyinocyanates such as lylene diisocyanate, xylylene diisocyanate, triisocyanate, naphthalene L5-diisocyanate; pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 4'-dicyctohexylmethane diisocyanate, etc. be.

The glass transition a degree Tg of the co-monomer is a value determined by the following measuring method.

Approximately lθ■ of a resin bath sample was weighed into a cell, and the sample was dried at 100° C. for 2 hours and used as a measurement sample. Shimadzu Ura Seisakusho DT-
80 type differential scanning calorimeter (D [ferenti (17)
Sci+nning C(17)orimeter)
Measurement is determined using a heating rate of 8 G°C/mn from -SO°C. Use nitrogen gas as the carrier gas! L O
Measurements are made using a flow rate of oc,” min.

Examples of the urethane-based post-adhesive agent include triphenylmethane-p + p', p'-triisocyanate, hexamethylene diisocyanate, diphenylmethane ichiban, 4'-diisocyanate, toluene diisocyanate, and other incyanates and active hydrogen. Compounds with atoms, for example, those consisting of polymeric compounds produced by reaction with polyesters, polyether glycols, polyacrylates, polyamides, etc. having active hydrogen atoms, mixtures thereof, or at least one strain thereof as the main component An example can be given as follows.

For the pressure-sensitive adhesive layer 8 of the present invention, adhesives such as those exemplified above can be appropriately selected and used; If you are using a soft adhesive and want the crimping machine to develop adhesive force relatively slowly, use a relatively hard adhesive.
It is better to use an agent. Furthermore, the degree of softness of the 41 adhesive can be selected appropriately depending on the workability of pasting, initial adhesion, physical properties of the hard-to-stick solid layer, coating area, thickness, printing pattern, etc., and can be selected within a wide range. It can be changed with . For example, J.I.
8 ZO! 8? The tack (ball rolling method) shown in is 1-2!
One with a tack of 5 to SO is preferably used, and more preferably one with a tack of 5 to SO is used.

Pressure-sensitive adhesive of the present invention 7m (11 preferably has an adhesive strength of 0.4 to l6 Kp/cm%%, preferably 0.5 to 11%)
1 B K9/cm, preferably S-8Kf/c
Acrylic adhesives, comb adhesives, etc. can be used, and the thickness of the adhesive layer (1) is generally preferably 10 to 10%.
100μ, particularly preferably zO to 70μ, even more preferably 85-5Qμ.

The base material layer (3) of the present invention is preferably a resin film, paper such as Japanese paper, Western paper, natural paper, or synthetic paper, synthetic cloth, cloth such as natural cloth such as hemp or silk, aluminum sheet, copper sheet, synthetic Examples include metal sheets such as metal sheets, and preferably resin films.

Preferred embodiments of the synthetic resin forming the resin film include polyvinyl chloride, polystyrene, low-density polyethylene, polypropylene, and polymethyl (meth).
Synthetic resins with good transparency, such as acrylic resin, polycarbonate, and door-shaped polyester, are suitable. Among them, vinyl chloride-based synthetic resins, methyl and (meth)acrylic resin-based synthetic resins are particularly preferred, and vinyl chloride-based synthetic resins are more preferred.

Among them, polyvinyl chloride synthetic resins are most preferred.

In addition to the vinyl chloride homopolymer, the vinyl chloride synthetic resin includes a vinyl chloride copolymer containing a copolymer component of about 30% by weight or less, and a blend of a vinyl chloride homopolymer and a vinyl chloride copolymerg! J etc. can be used.

Examples of such copolymer components include ethylene, propylene, butene, acrylic acid ester, vinylidene chloride,
Examples include monomers such as vinyl ester, vinyl ether, and vinyl acetate.

Furthermore, a vinyl chloride resin blend obtained by blending these vinyl chloride resins with a polymer other than the vinyl chloride resin at a ratio of about 801 filtration or less can also be used.

Further, a semi-rigid vinyl chloride resin molding composition disclosed in JP-A-60-4548 can also be used. That is,
The vinyl chloride resin paste composition contains the following compounds and/or (
(g)) and/or (C).

(4) For vinyl chloride paste containing a polymeric component of O to about 20 hours, preferably about 0 to about 1 hour.
00 parts by weight, φ) Number average molecular weight (Mn) is about 1600 or more, preferably about L500~e, o o o, more preferably about 1
．． 600-4000, more preferably about 000
Approximately 25 to 6 liters of liquid polyester plasticizer
( Q Number average molecular weight (M+n) is about 1,500 to about 60
．． 000.

Preferably, a low molecular weight acrylic or methacrylic resin having a molecular weight of about &lgr; about 0.8 to about 2
Also preferred are compositions comprising from about 10% by weight to about 100% by weight ISO, more preferably from about 100% by weight.

The pre-synthetic resin layer (2) may contain additives such as stabilizers, antioxidants, lubricants, plasticizers, and ultraviolet absorbers. The amount of these additives to be used can be selected as appropriate, but is approximately 0.00 parts by weight based on 100 parts by weight of the mixed resin component. 5～～1031
about 0.01 to about 2 parts by weight of an antioxidant, about 0.1 to about 10 parts by weight of a lubricant, about 1 to about 60 parts by weight of a plasticizer, about 0.1 to about 2 parts by weight of a plasticizer, For example, the amount of ultraviolet absorber used may be 6 parts by weight of OS-6.

Specific examples of these additives include calcium-zinc stabilizer (#Takako Q.CZ-1 9J), tin-based stabilizer (PI!! manufactured by Takako, 181F8J), and barium zinc stabilizer. (manufactured by Katsuta Kako ■, BZ61J), lead stearate stabilizer (manufactured by Kosei ■, pb-st): For example, monophenolic antioxidants (Yoshitomi Pharmaceutical ■)
Antioxidants such as amine-based antioxidants (Yoshitomi Pharmaceutical Co., Ltd., Yoshinox BHT), polyphenol-based antioxidants (Chipa-Geigi Co., Ltd., Irganox 1010); , person C-6) Fatty acid-based lubricant (manufactured by Yoken Fine Chemical, ?-8) Fatty acid ester-based lubricant (manufactured by Hoechst Japan, Hoechst VAXOP) Fatty alcohol-based lubricant (manufactured by Kako Soap, alcohol 85); for example, phthal Acid plasticizer (manufactured by Sanjo Kako@, DOP), epoxy storm softener (Adeka Argus ■ back, Adeka Cider 0-180P)
, Adipinkyo ester plasticizer (manufactured by Block Chemical Industry @, D
plasticizers such as polyester plasticizers (manufactured by Rohm and Haas, Paraflex ash); for example, benzotriazole-based ultraviolet absorbers (manufactured by Ciba-Geigi, Tinuvin P Tinuvin 8B6,817), hydroxybenzophenone-based ultraviolet absorbers ( Examples include ultraviolet absorbers such as Cyasorb UV-9) manufactured by American Cyanamid.

As the synthetic resin film (3) or sheet, preferably a cast film is used, and a solvent solution containing the resin component and mosquito mica is applied by a method known per se, such as a casting method or a coater method. It can be obtained by forming the film using a fi-stretching method such as film forming means, and is preferably used in the form of an unstretched film.

Examples of the solvent to be used include tetrahydrofuran, methyl ethyl ketone, methylene chloride, dimethylformamide, and alcohol.

The yield stress of the obtained synthetic resin layer (3) is preferably l
-S Kg/-1 preferably 1.2 to 45 to/-1
More preferably, L5-4 is 4/-.

The releasable support layer (4) is not particularly limited as long as it has a supporting force and is removable from the pressure-sensitive adhesive layer, and may be a conventional releasable support, such as a silicone resin coated layer. 4! R mallet release sheets, as well as polypropylene tar, polymer-coated or laminated release sheets, etc., can be mentioned, and each mallet sheet coated with the silicone resin etc. can be made of nonwoven fabric, synthetic fiber, net, paper, or plastic film. , polyethylene film or polyolefin film and paper laminates can also be used.

Particularly preferred examples include silicone resin coated release paper, polyester film, and polypropylene terpolymer coated paper. In addition, the peelable support layer (
4) can be selected and used as appropriate depending on the purpose of use and manufacturing method of the pressure-sensitive adhesive sheet-like structure, taking into consideration the smoothness, peel resistance, type of material, etc. of the peelable support layer (4). However, for example, if the base layer (3) is a soft vinyl chloride resin film, this M! As in claims 3z and 38,
If a solidizable flowable material is to be applied onto the peelable support layer (4), a peelable support (4) having a peel resistance value of about 800 to 600 grams/inch, such as generally a process paper, is used. It is preferable to use a polypropylene terpolymer coated paper called .

In addition, when it becomes a peelable support layer of a final product of a pressure-sensitive adhesive sheet-like structure, it is preferably 3 to 100 grams/inch, more preferably 4 to 50 grams/inch, particularly preferably 5 to 15 grams/inch. It is preferred to use a releasable support (4) such as a silicone resin-coated release paper.

The pressure-sensitive adhesive sheet of the present invention may be produced by any method as long as it satisfies the structure of the pressure-sensitive adhesive sheet of the present invention, but a preferred production method is a method of producing a flat pressure-sensitive adhesive layer (1). A flat pressure-sensitive adhesive layer (1) that has a base material layer (3) on one side, and is produced by indirectly coating a fluid substance that can solidify on the other side (-1) and then solidifying it. )
A non-adhesive solid layer (2) thinner than that on the inner side or surface layer of the flat pressure-sensitive adhesive layer (1), and further peeled to the outside of the flat pressure-sensitive adhesive layer (1). in a pressure-sensitive adhesive sheet-like structure having a flexible support layer (4), an FL-active physical substance that can be solidified on a peelable support layer (4);
A method for producing a pressure-sensitive adhesive sheet-like structure comprising the step of providing a non-adhesive solid layer (2), further comprising a pressure-sensitive adhesive layer (after providing the non-adhesive solid layer (2)) 1) and further laminated with a base material layer (3), a method for manufacturing a pressure-sensitive adhesive sheet-like structure, a base material layer having a pressure-sensitive adhesive layer after providing the non-adhesive solid layer (2); A method for producing a pressure-sensitive adhesive sheet-like structure in which a composite layer consisting of
Method for producing a pressure-sensitive adhesive sheet-like structure by screen printing or roll coat printing; - of a flat pressure-sensitive adhesive layer (1)
It has a base material layer (3) on one side and a flat pressure-sensitive adhesive layer (1) produced by directly coating a fluid substance that can solidify on the other side and then solidifying it. thin 1i
A IIk (17) solid layer (2) is provided on the surface or surface layer of the flat pressure-sensitive adhesive layer (1), and a releasable solid layer (2) is further provided on the outside of the flat pressure-sensitive adhesive M1 (11). A method for producing a pressure-sensitive adhesive sheet-like structure characterized by having a support layer (4), wherein the non-adhesive solid layer (2) is a hot melt a
Examples include a method for producing a pressure-sensitive adhesive sheet-like structure that is a disintegrating solid layer, an electronic II (if! type) hard-to-adhesive solid layer, and an ultraviolet-curable MS adhesive solid layer. To explain a preferred embodiment, in the present invention, first, the printed layer (2), which is a Jil adhesive solid layer (2), is printed on a releasable support layer (4) by conventional gravure printing, screen printing, or roll printing. It is formed by means such as coat printing.

The form of the printing Fill 12) may be selected as desired.For example, when pasting the adherend Jζ as a pressure-sensitive adhesive sheet, if high initial adhesion strength and free positioning are required, the form should be as small as possible. It is best to cover the entire surface of the pressure-sensitive adhesive layer (1) discontinuously depending on the printing area (for example, very fine dot printing can be applied to the entire surface of the support layer at a high degree of printing). In the second aspect of the invention, such a desired form can be easily achieved with high precision by processing a gravure printing roll, a screen plate, or the like.

The printed layer (2) is a non-viscous or low-adhesive layer (2) that is used as a layer (2) to achieve low adhesion when applied as a pressure-sensitive adhesive sheet to the object.

Cover the entire surface of the contact layer with a continuous layer of printed material, and crush the printed layer (2) with pressure when pasting a pressure-sensitive adhesive sheet to achieve contact between the adhesive layer and the adherend. However, in order to achieve higher initial adhesive strength, it is preferable to form a discontinuous printed layer in advance, that is, a printed layer that does not entirely cover the adhesive layer, as described above.

The printed support layer is used as it is as a mount for adhesive coating, and the adhesive agent is directly formed on the printed layer by a normal solution coating method, etc., and then the resin film layer is bonded to the adhesive layer. .

After the pressure-sensitive adhesive sheet is pasted, the support layer (4) is removed and the sheets are pasted together.

At that time, it is necessary that the printing layer (2) remains on the adhesive layer (11 side), so the support layer (4) of the printing layer (2) must remain on the adhesive layer (11 side).
It is preferable to keep the adhesion strength to ( ) as low as possible.

On the other hand, as a support layer having a printed layer (2) before the adhesive layer (1) is formed, the printed layer (2) is
It is necessary that the printing layer (2) is adhered to the support layer (4) so that the printing layer (2) does not fall off.

Therefore, the printing layer (2) is designed so that the adhesive force to the adhesive layer (1) is higher than the adhesive force to the support layer (4).

In addition, a preferred embodiment of the method for bonding the obtained pressure-sensitive adhesive sheet includes a flat pressure-sensitive adhesive layer (11) having a base material layer (3) on one surface and solidifying on the other surface. The adhesive solid layer (2), which is less than SOμ and thinner than the flat pressure-sensitive adhesive layer (1), is formed by directly or indirectly coating and then solidifying the obtained fluidity**. The pressure-sensitive adhesive sheet on the surface or in the surface layer of the pressure-sensitive adhesive layer (1) is pasted on the surface of the M substrate to be pasted (5), and after alignment of the pasting to the desired pasting area, the base material layer ( By pressing from the back side of 3), the adhesive force of the pressure sensitive adhesive layer (1) is exerted,
A method for attaching a pressure-sensitive adhesive sheet characterized by attaching it to a substrate to which it is attached.

An example of the pasting method is that the pressure bonding from the back surface is pressure bonding by linear pressure using a squeegee or the like.

EXAMPLES Next, the pressure-sensitive adhesive layer, pressure-sensitive adhesive sheet, pressure-sensitive adhesive sheet-like structure, and manufacturing method thereof of the present invention will be explained with reference to Examples. First, the test methods carried out in Examples and Comparative Examples are as follows.

■ The loop tack test was carried out using a Tensilon universal test rock; model UTM-4 manufactured by Toyo Baldwin Co., Ltd.

The test piece was 90×50. After cutting and peeling off the release paper,
With the adhesive side facing outside, put both ends 1bfi together and insert into the Tensilon chuck to make a loop with circumference a(lu+).

Next JI8 21-0118? Polished 8
The 08804 steel plate is raised at a speed of 800 tz/min and brought into contact with the loop. At that time, the distance from the 808 steel plate to the bottom of the chuck is designed to be 5 m'l.

When the lifting of the 8U8 steel plate is completed, the test piece comes into contact with the SU8 steel plate with the loop collapsed.

Stay still in this state for 10 seconds, then move to 8
The 1908 steel plate was lowered at a speed of 00 m/n1ln. The adhesive force between the SUS steel plate and the test piece at this time was used as a loop tack.

■ Mobility on adherend Cut the test piece into $5 x 150 ml pieces, peel off the release paper,
Place the adhesive side down on an acrylic painted board (Hurame, Japan Test Panel Industry Co., Ltd.).

The specimen was moved from side to side by hand to examine its freedom of movement.

Evaluation was performed on a three-level scale of O1× and Δ.

○...The test piece can be moved freely on the adherend.

Δ: Adhesive force is partially developed, making it difficult to move the test piece.

×・・・・・・Difficulty in moving the test piece.

■ Adhesive strength test piece was 1O-)100. After cutting and peeling off the release paper, JIS Z-0118? It was crimped onto an acrylic coated plate (made by Nippon Test Panel Kogyo Co., Ltd.) using a crimping device specified by , and then crimped S times with a squeegee.

After a predetermined period of time, 18 (1
"The peeling adhesive strength was measured.However, the pulling speed was B
00[/min].

■ Optical surface condition of base material after crimping Observe with the naked eye whether the surface is rough or clear.

O...Smooth and good.

Δ...Lack of smoothness, but no noticeable roughness or unevenness.

×......The rough surface is noticeably uneven.

implementation? 111 Peelable support made of paper laminated with polyethylene (4
) After applying a weak corona discharge to the polyethylene surface,
Gravure printing was carried out using an ink containing 70 parts by weight of crosslinkable epoxy resin and 80 parts by weight of titanium oxide pigment, and the thickness was 3 μm.
Square halftone dots with side lengths of approximately IIIJll were printed to create a release adhesive solid layer (2). The total area printed out of the total area was 60-.

On this support, an adhesive made from natural rubber was applied and dried to form a pressure sensitive adhesive layer +11, and a 60 μm thick adhesive was applied on top of this.
The nonwoven fabric was crimped. Further, the same adhesive was applied onto a nonwoven fabric and then strongly dried to thoroughly remove the solvent. The total thickness of the molded material (including the nonwoven fabric) at this time was approximately 160 μm. The printed surface of the printed support was further pressed onto this to produce a double-sided pressure-sensitive adhesive sheet. This double-sided adhesive sheet was cut to 801×son and the support was peeled off.The printed layer was transferred to the adhesive surface and the initial adhesiveness was low enough to be supported by pinching with fingers. Other than that, positioning it on the board and temporarily gluing it was easy, and the pasting operation was completed in about 3 seconds.

Furthermore, when a soft polyvinyl chloride sheet with a thickness of 160 μm was placed on top of the sheet and crimped firmly with a squeegee, the point IJ m
The PVC sheet was strongly bonded to the aluminum plate without any defects.

Comparative Example 1 In Example 1, instead of the releaseable support (4) on which the adhesive solid layer was printed, silicone treatment was performed on a laminate of paper and polyethylene. A double-sided adhesive sheet was produced in exactly the same manner except for using a paper pattern.

When I cut this into 80mm x 80mm pieces and peeled off the release paper that was the support, the double-sided adhesive sheet stuck to my fingers, and before I could position it on the aluminum plate, it wrinkled and overlapped and stuck to the aluminum plate. positioning was not possible.

-1. When I peeled off the release paper on one side little by little and attached it to the aluminum plate, I was able to position it, but the operation took about 15 seconds.

The other sheet of pattern paper II was also removed, and soft polyvinyl chloride sheets were laminated in the same manner. However, the positioning of the soft polyvinyl chloride sheet was performed at the turning part, and the laminated polyvinyl chloride sheets were wrinkled.

Example 3 As a releasable support layer (4), an acrylic resin solution was printed on polybrobylene terpolymer one-step paper by screen printing and dried to form a layer with a diameter of about 0.5 fl and a thickness of about 2 μm.
Dot printing was formed at a rate of about 116 (11) per 100. (Resin layer (2)) An acrylic adhesive solution (manufactured by Nippon Carbide Kogyo ■, trade name KP-) was applied on this printing process paper.
80fiLC) was applied and dried at 100° C. for 1 minute to form a pressure-sensitive adhesive layer (1) with a thickness of about 80 μm.

This pressure sensitive W! A white vinyl chloride film (base material/IIL+31) (Hinisu Paint 6010 manufactured by Nippon Carbide Industries, Ltd.) was laminated onto the cleaning agent layer (11) using a com roll to produce a pressure-sensitive adhesive sheet.

The resulting pressure-sensitive adhesive sheet can move freely on the layered object,
And Wj after crimping! The adhesive sheet developed adhesion quickly, and the surface condition of the sheet after crushing was also extremely smooth, which fully achieved the object of the present invention.

The results are shown in Table 1.

Comparative Example 3 As an example of distributing hollow balloons to improve the surface of the contact layer, Minnesota Mining and Manufacturer V
The control-Tac 180-10J test results are shown in Table 1.

Example 8 Acrylic adhesive Soryu i& (trade name KP-80B LC manufactured by E1 Hon Carbide Kogyo Shimbun) was applied on a transparent 75μ film of polyethylene terephthalate (substrate m (31)) and dried at 100°C for 1 minute. , a pressure sensitive adhesive layer (1) with a thickness of about 80μ was made.

A methacrylic resin liquid was sprayed onto this pressure-sensitive adhesive layer (11) using a spray machine, and dried at 100° C. for 1 minute to print dots with a thickness of about 1 μm and a diameter of about 1 strip. The printed area of the total area was approximately 40 cm.The test results are shown in Table 1.

The obtained pressure-sensitive adhesive sheet can move freely on the layered object, has very good positioning workability, and develops adhesive force quickly after pressure bonding (and the narrow surface state of the sheet after pressure bonding is also extremely low). It was a smooth adhesive sheet that fully achieved the purpose of the present invention.

EXAMPLE As the support layer (4), a methacrylic resin solution was printed on a 75 μm polyethylene terephthalate film by gravure printing and dried to a thickness of about 0. ! A hard-to-stick solid layer (2) was created that covered 90% of the total area of 1μ.

On top of this resin layer (2), an acrylic adhesive solution (product name PR-121 manufactured by Nippon Carbide Kogyo@, -100 weight parts, CK-1018 weight sa solution) was applied with a tube cloth and dried.
A pressure sensitive adhesive layer with a thickness of about 3Sμ was created.

A pressure-sensitive adhesive sheet was made by laminating a white vinyl chloride film (base layer (31) (Hinispaint 5010 manufactured by Nippon Carbide Industries @) on this pressure-sensitive adhesive layer (1) using a rubber roll. When the polyethylene terephthalate film serving as the support layer (4) of this pressure-sensitive adhesive sheet was peeled off, the resin layer (2) was transferred to the adhesive layer.) Its performance was evaluated. The results are shown in Table 1.

The resulting pressure-sensitive adhesive sheet can move freely on the adherend,
The adhesive sheet had very good positioning workability, developed adhesive strength when sufficiently pressed with a squeegee, and had an extremely good condition on the other side of the sheet after being pressed.This adhesive sheet fully achieved the object of the present invention.

Example 5.6,? and 8. Print a transparent methacrylic resin solution by gravure printing on polypropylene tarpolymer one-step paper as the support layer (4), dry it, and print dots with diameters O and S fins and a thickness of about 3μ per 100 mm. It was formed at a ratio of SO. (resin/#(
2)) Clear acrylic adhesive on this printing process paper! 1
'lI (Product name: KP-80SL manufactured by Nippon Carbide Industries)
Apply C) and dry at 100℃ for 1 minute to a thickness of about 40μ.
pressure sensitive adhesive layer (11).

A pressure-sensitive adhesive sheet was prepared by laminating the following base material layer (3) on the pressure-sensitive adhesive Jim (11) using a rubber roll.

Example 5 Base layer: Transparent vinyl chloride film (Hinispaint 5oso manufactured by Nippon Carbide Kogyo@) The paper was removed from the obtained pressure-sensitive adhesive sheet (the printed layer was transferred to the adhesive side). Performance was evaluated. The obtained sheet has very good transparency and can move freely on the adherend...Example 6 Base layer: nonwoven fabric example with a thickness of about 60μ Base material I-: thickness Approximately 16μ household aluminum foil Example 8 Base layer; thickness approximately 8! The process paper was removed from each pressure-sensitive adhesive sheet obtained in sμ white paper Example 5.6.7.8 (all the printed layers were transferred to the adhesive N agent layer side), and then pressure-sensitive adhesive was added. A silicone resin-coated release paper was bonded to the agent layer (1) (including one adhesive solid layer + 21 layers) as a support layer (4) to prepare a pressure-sensitive adhesive sheet-like structure. After 78 days, the peelable support layer was peeled off and the adhesion test was conducted. Table 1 shows the results.
It is written in

The obtained pressure-sensitive adhesive sheet can move freely on the adherend (5) and has very good positioning workability. When sufficiently pressed with a squeegee, adhesive force is developed, and the surface condition of the sheet after pressing is also good. This was a pressure-sensitive adhesive sheet that satisfactorily achieved the object of the present invention.

Example 9.10.11. lsa The polybrobylene terpolymer first-process paper of the pressure-sensitive adhesive sheet obtained in Example 2 was peeled off, and the following releasable support was bonded to produce a pressure-sensitive adhesive sheet-like structure.

Example 9 Ii1 where paper was coated with silicone resin! Pattern Example 10 Releaseable film made by laminating polyethylene film and paper Example 11 M-type fabric made of synthetic fiber coated with silicone resin Example IB Releaseable nonwoven fabric made of nonwoven fabric coated with silicone resin Releaseable after 1 month The adhesion test was conducted with the support layer peeled off, and good results equivalent to those of Example 2 were obtained in all cases.

Example 18 As a releasable support layer (4), an acrylic resin solution was printed on a polypropylene turbo polymer one-step paper by screen printing and dried to a diameter of approximately (L 618% thickness HL).
y 2 s) Dotted printing o x o.

- formed at a rate of about 26 pieces per. (Resin layer (2)) (
Sheet λ) On the other hand, acrylic adhesive [13 molten aL Nippon Carbide Industries @3m1 trade name KP-80$ILC] was applied to the white fumed vinyl film (base layer (3)) and dried at 100°C for 1 minute. , a pressure-sensitive adhesive film with a thickness of approximately 80 μm was prepared (see) B).

Both sheets were joined so that the printed layer of the sheet and the adhesive layer of Sheet B were in contact with each other and bonded together using a rubber roll to create a pressure-sensitive forging sheet-like structure. The obtained pressure-sensitive adhesive sheet obtained the same pasting test results as in Example 3. In other words, it is a pressure-sensitive adhesive sheet that can move freely on an adherend, exhibits adhesive strength quickly after pressure bonding, and has an extremely smooth optical surface state after pressure bonding, which fully satisfies the purpose of the present invention. Ta.

Example 14 White vinyl chloride film of Example 8 (base layer (3))
Except that the following vinyl chloride film was used instead of
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 8, and its physical properties were tested.

100 parts by weight of vinyl chloride resin (Zeon 1B1. Crystal manufactured by Nippon Zeon Co., Ltd., average polymerization coefficient: 1500), 40 parts by weight of polyester ligating agent (I'M-446, manufactured by Adeka Argus Chemical Co., Ltd., number average molecular weight approximately BOOO), and acrylic resin (
Butyl methacrylate: Acrylonitrile dimethacrylic acid 95:8:B, number average molecular weight approximately 9400°TgB
The property at 33°C and 5°C is solid, and the solvent contains parts by weight of toluene sO, as well as a tin-based stabilizer (TM-181F8) per 100 parts by weight of vinyl chloride resin.
B weight part Katsuta Kako Co., Ltd.) B a/Z n-based stabilizer (AP-589; L, 5
Parts by weight: Adeka Argus Chemical Co., Ltd. Ester detergent (Bu-8s; 0.1 parts by weight) Benzotriazole ultraviolet absorber, manufactured by Kawayo Fine Chemicals Co., Ltd. 2 parts by weight (
A composition containing Tinuvin P (product of Ciba Geigy Co., Ltd.) and a solvent (mineral spirit; 10 inch part Shell Kagaku Co., Ltd.) is kneaded for 30 minutes at room temperature using an Ishikawa-type!N@Iso and taken out. Add an additional 40 parts by weight of solvent i. at room temperature.

After stirring for a minute, sol liquid 8 was obtained. Apply this sol solution onto paper coated with silicone resin using a No. 46 wire parser) 1. ．． The mixture was heated and gelled at 180° C. for 5 minutes in a hot air dryer to obtain a semisol cast film having a thickness of 50 μm.

The obtained pressure-sensitive adhesive sheet obtained the same test results as in Example 8, and was able to move freely on the adherend, quickly develop adhesive strength after pressure bonding, and furthermore, the sheet was light-resistant after pressure bonding. The adhesive sheet had an extremely smooth surface and fully achieved the object of the present invention.

Example 1B White vinyl chloride film of Example 18 (base layer (3)
), except that the vinyl chloride film (semi-sol cast film) used in Example 14 was used.
The same pressure-sensitive adhesive sheet structures as in Example 18 were prepared and their physical properties were tested.

The obtained pressure-sensitive adhesive sheet-like structure obtained the same application test results as Example 18. That is, it could move freely on the adherend (5) and had very good positioning workability. It was a pressure-sensitive adhesive sheet that fully achieved the object of the present invention, exhibiting adhesive strength when sufficiently pressed with a squeegee, and having an extremely good surface condition after being pressed.

〔Effect of the invention〕 Pressure sensitive adhesive of the present invention! -1 Pressure sensitive adhesive sheet.

Pressure-sensitive adhesive sheet-like structures have excellent positioning and other workability, and can be easily and freely controlled as desired by changing the form of printing after the adhesive force is developed. This is an extremely excellent adhesive sheet that can be used to coat the adhesive and provide an excellent surface condition even after application.

Furthermore, the pressure-sensitive adhesive sheet of the present invention is very easy to manufacture and can be easily supplied by the manufacturing method of the present invention. Used as fleet marking and masking film for advertisements, information boards, etc.

[Brief explanation of the drawing]

Figure 1 is the drawing described in Section 1 of the Sakigori Ellipse, and Figure 2 is
The figure is a drawing of Example 1. (a) (b) (C) (d) (e) (f) (x) in Figure 8
is an example of a preferred embodiment. (Plan view) Fig. 4 is a sectional view of one example of the embodiment, (a) is a support/II
(41 pressure-sensitive adhesive sheet, (b) is a cross-sectional view of the support N (4) peeled off and temporarily adhered to the layered body, (C) is a cross-section of the pressure-sensitive adhesive sheet adhered to the body after pressure bonding) Figure 1, pressure-sensitive adhesive layer 2, non-adhesive solid layer 8, base material layer support layer 5, adherend 6, crimping with squeegee No. 3 TI!J Drawing width 3 Figure 3 Figure 4ff1 Procedural amendment form (Method) Date: May 2, 1986

Claims (40)

[Claims] (1) A flat pressure-sensitive adhesive layer (
The flat pressure-sensitive adhesive layer (2), which is thinner than the flat pressure-sensitive adhesive layer (1) and is produced by solidifying after directly or indirectly coating the flat pressure-sensitive adhesive layer (2) on the flat pressure-sensitive adhesive layer (1), is (1
) on at least one surface or surface layer of the pressure-sensitive adhesive layer. (2) The pressure-sensitive adhesive layer according to claim 1, wherein the hard-tack solid layer (2) is a printed layer (2). (3) The pressure-sensitive adhesive layer according to claim 2, wherein the printing layer (2) is a gravure printing layer, a screen printing layer, an offset printing layer, a jet spray printing layer, or a roll coat printing layer. (4) The pressure-sensitive adhesive layer according to claim 2, wherein the printing layer (2) is a gravure printing layer. (5) The pressure-sensitive adhesive layer according to claim 1, wherein the fluid substance that can be solidified is a resin liquid or a resin liquid containing a filler. (6) The pressure-sensitive adhesive layer according to claim 1, wherein the non-adhesive solid layer (2) is a partially formed non-adhesive solid layer (2). (7) The pressure-sensitive adhesive layer according to claim 6, wherein the area occupied by the partially formed non-adhesive solid layer (2) is 8 to 98% of the entire pressure-sensitive adhesive layer. . (8) The pressure-sensitive adhesive layer according to claim 6, wherein the area occupied by the partially formed non-adhesive solid layer (2) is 85 to 95% of the entire pressure-sensitive adhesive layer. . (9) The pressure-sensitive adhesive layer according to any one of claims 1 to 8, wherein the non-adhesive solid layer (2) has a thickness of 80 μm or less. (10) The pressure-sensitive adhesive layer according to any one of claims 1 to 8, wherein the non-adhesive solid layer (2) has a thickness of 10 μm or less. (11) The pressure-sensitive adhesive layer according to any one of claims 1 to 8, wherein the non-adhesive solid layer (2) has a thickness of 8.5 μm or less. (12) The partially formed non-adhesive solid layer (2)
7. The pressure-sensitive adhesive layer according to claim 6, wherein the area occupied by the non-adhesive solid layer is substantially 85 to 98%, and the thickness of the non-adhesive solid layer is 5 μm or less. (13) Having a base material layer (3) on one side of a flat pressure-sensitive adhesive layer (1), and solidifying after directly or indirectly coating a fluid substance that can solidify on the other side. A non-adhesive solid layer (2) thinner than the flat pressure-sensitive adhesive layer (1) produced by the above-mentioned flat pressure-sensitive adhesive layer (1) is provided on or in the surface layer of the flat pressure-sensitive adhesive layer (1). Features a pressure-sensitive adhesive sheet. (14) Consisting of a double-sided pressure-sensitive adhesive layer having a pressure-sensitive adhesive layer (6) on the other side of the flat surface of the base layer (3) having the pressure-sensitive adhesive (1). A pressure-sensitive adhesive sheet according to claim 13, characterized in that: (15) The pressure-sensitive adhesive layer (6) has the low-adhesive solid layer (
2) The pressure-sensitive adhesive sheet according to claim 14. (16) Having a base material layer (3) on one side of a flat pressure-sensitive adhesive layer (1), and solidifying after directly or indirectly coating a fluid substance that can solidify on the other side. This was caused by the A non-adhesive solid layer (2) thinner than the flat pressure-sensitive adhesive layer (1) is provided on or in the surface layer of the flat pressure-sensitive adhesive layer (1), and the flat pressure-sensitive adhesive layer (2) is thinner than the flat pressure-sensitive adhesive layer (1). Agent layer (1
) A pressure-sensitive adhesive sheet-like structure having a releasable support layer (4) on the outside thereof. (17) The pressure-sensitive adhesive sheet-like structure according to claim 16, wherein the base layer (2) is a resin film (2). (18) The pressure-sensitive adhesive sheet-like structure according to claim 16, wherein the base layer (2) is paper (2). (19) The pressure-sensitive adhesive sheet-like structure according to claim 16, wherein the base layer (2) is cloth (2). (20) The pressure-sensitive adhesive sheet-like structure according to claim 16, wherein the base layer (2) is a metal sheet (2). (21) The pressure-sensitive adhesive sheet-like structure according to claim 16, wherein the base layer (2) has a decorative layer (5). (22) The pressure-sensitive adhesive sheet-like structure according to claim 16, wherein the base layer (2) has a thickness of 20 to 500 μm. (23) The pressure-sensitive adhesive sheet-like structure according to claim 16, wherein the base layer (2) is a plate-like material. (24) The yield stress of the resin film (2) is 1 to 5 kg
/mm^2. The pressure-sensitive adhesive sheet-like structure according to claim 17. (25) The pressure-sensitive adhesive sheet-like structure according to claim 17, wherein the resin film (2) is made of a vinyl chloride resin. (26) The pressure-sensitive adhesive sheet-like structure according to claim 25, wherein the vinyl chloride resin is a paste vinyl chloride resin. (27) The flat pressure-sensitive adhesive layer (1) has an adhesive strength of 0.4 to
27. The pressure-sensitive adhesive sheet-like structure according to any one of claims 1 to 26, which is a (meth)acrylic acid ester adhesive having a pressure of 15 kg/cm. (28) The pressure-sensitive adhesive sheet-like structure according to any one of claims 1 to 27, wherein the flat pressure-sensitive adhesive layer (1) is a crosslinked pressure-sensitive adhesive layer. (29) The pressure-sensitive adhesive sheet-like structure according to claim 16, wherein the peelable support layer (4) is a nonwoven fabric, synthetic fiber, net, paper, or plastic film. (30) The pressure-sensitive adhesive sheet-like structure according to claim 10, wherein the peelable support layer (4) is a laminate of a polyethylene film or a polyolefin film and paper. (31) The pressure-sensitive adhesive sheet-like structure according to claim 16, wherein the peelable support layer (4) is treated with a release agent. (32) A flat pressure-sensitive adhesive layer (1) has a base layer (3) on one side, and the other side is indirectly coated with a fluid substance that can be solidified, and then solidified. A non-adhesive solid layer (2) thinner than the flat pressure-sensitive adhesive layer (1) produced by this process is provided on or in the surface layer of the flat pressure-sensitive adhesive layer (1), and In a pressure-sensitive adhesive sheet-like structure having a releasable support layer (4) on the outside of a pressure-sensitive adhesive layer (1), a fluid substance that can be solidified is placed on the releasable support layer (4). A method for producing a pressure-sensitive adhesive sheet-like structure, comprising the step of coating and providing a hard-to-adhesive solid layer (2). (33) A pressure-sensitive adhesive layer (1) is further formed after the non-adhesive solid layer (2) is provided, and the pressure-sensitive adhesive layer (1) is further bonded to the base material layer (3). A method for producing a pressure-sensitive adhesive sheet-like structure as described in 2. (34) The pressure-sensitive material according to claim 32, characterized in that after providing the non-adhesive solid layer (2), a composite layer consisting of a base material layer having a pressure-sensitive adhesive layer is laminated. A method for manufacturing an adhesive sheet-like structure. (35) The method for producing a pressure-sensitive adhesive sheet-like structure according to claim 32, wherein the non-adhesive solid layer is provided by printing. (36) The method for producing a pressure-sensitive adhesive sheet-like structure according to claim 32, wherein the printing is gravure printing, screen printing, or roll coat printing. (37) By having a base material layer (3) on one side of a flat pressure-sensitive adhesive layer (1), and directly coating the other side with a fluid substance that can be solidified, and then solidifying it. A non-tacky solid layer (2) thinner than the resulting flat pressure-sensitive adhesive layer (1).
) on or in the surface layer of the flat pressure-sensitive adhesive layer (1), and further comprising a peelable support layer (4) on the outside of the flat pressure-sensitive adhesive layer (1). A method for producing a pressure-sensitive adhesive sheet-like structure characterized by: (38) Claim 37, wherein the non-adhesive solid layer (2) is a hot-melt non-adhesive solid layer, an electron beam-curable non-adhesive solid layer, or an ultraviolet-curable non-adhesive solid layer. A method for producing the pressure-sensitive adhesive sheet-like structure described above. (39) Having a base material layer (3) on one side of a flat pressure-sensitive adhesive layer (1), and solidifying after directly or indirectly coating a fluid substance that can solidify on the other side. A non-adhesive solid layer (2) thinner than the flat pressure-sensitive adhesive layer (1) is formed on or in the surface layer of the flat pressure-sensitive adhesive layer (1). The pressure-sensitive adhesive layer (1) is attached by pasting the pressure-adhesive sheet on the surface of the substrate to be adhered (5), aligning the adhesion to the desired adhesion site, and then applying pressure from the back side of the base layer (3). A method for attaching a pressure-sensitive adhesive sheet, which is characterized by exhibiting adhesive strength and attaching it to a substrate to which it is attached. (40) The method for pasting a pressure-sensitive adhesive sheet according to claim 39, wherein the pressure-sensitive adhesive sheet is crimped from the back surface of the base layer (3) by substantial linear pressure.