JPH08325536A - Pressure-sensitive adhesive sheetlike structure - Google Patents

Abstract

PURPOSE: To obtain a pressure-sensitive adhesive sheetlike structure having low initial bond strength, rapidly developing bond strength after bonding under pressure, having a large value of final attained bond strength and a smooth surface state after bonding under pressure. CONSTITUTION: This pressure-sensitive adhesive sheetlike structure comprises (A) a pressure-sensitive adhesive having a dispersed layer, in which nonadherent solid particles 2 having 10-60μm average particle diameter are uniformly dispersed, on at least in one surface of an adhesive layer 1, at least about the half of the number of the solid particles 2 project from the surface the adhesive layer 1 to height corresponding to at least about 174 the average particle diameter, in case the solid particles 2 are hollow particles, the walls of hollow particles are not crushed by pressure in bonding under pressure and the covering ratio of the nonadherent solid particles 2 to the surface area of the adhesive layer 1 of about 3 to about 30%, (B) a releasable substrate layer 3 which is brought into contact with parts of the nonadherent solid particles 2 projecting from the surface of the adhesive layer 1 and has recessed parts on the surface, tightly compensating the projecting parts and (C) a substrate layer 4 laminated to a face not having the dispersed layer of the nonadherent solid particles 2.

Description

Detailed Description of the Invention

[0001] The present invention relates to a pressure-sensitive adhesive sheet-like structure, and more specifically, when it is adhered to an adherend, it facilitates the alignment of the surface of the adherend to a desired attachment position, If necessary, a small initial adhesive force (before the crimping operation) sufficient to allow corrective movement on the surface of the adherend to avoid the occurrence of sticking defects such as wrinkles, bubbles, and bulges. Shows the adhesive force when lightly contacting the surface of the adherend; represented by the roof tack, etc., which will be described later, and the expression of the adhesive force after crimping is rapid and the value of the final reached adhesive force is remarkable. The present invention relates to a pressure-sensitive adhesive layer which is large and has a smooth surface state after pressure bonding and can exhibit various properties such as being extremely easy to manufacture.

A pressure-sensitive adhesive sheet-like structure having a pressure-sensitive adhesive layer on the surface of a substrate such as a film, a tape, a sheet, etc. is known, and in addition to building materials such as wallpaper, repair coating for vehicles, for example. The so-called masking application and the background color of the signboard, such as temporarily hiding the coated part at the time, or temporarily hiding the surface of the aluminum sash to protect it during transportation.
In so-called marking applications that are used semipermanently as letters and patterns, decorative patterns such as motorcycles, automobiles, trains and vehicles, containers, etc., stripes and letters, etc.
It is widely used by being attached to the surface of an adherend.

If such a pressure-sensitive adhesive layer has an excessively high initial adhesive strength, it is extremely difficult for even a skilled worker to accurately and accurately apply the pressure-sensitive adhesive layer once to a desired position on the adherend. is there. For this reason, it is necessary to correct the sticking position and to correct wrinkles, bubbles, re-sticking for removing blisters, etc., but such correction often causes troubles such as deformation or breakage of the base material. .

In order to solve the technical problems in the pressure-sensitive adhesive layer as described above, it is attempted to reduce only the initial adhesive force of the pressure-sensitive adhesive layer without substantially decreasing the desired final adhesive force thereof. Several attempts have been proposed and are known.

As one of such proposals, Japanese Patent Publication No. 44
No. 3120 discloses a tacky adhesive layer having non-adhesive protrusions which are easily distributed and crushable and which are uniformly distributed on at least one surface, and according to this proposal, a hollow urea-formaldehyde resin is disclosed. The initial adhesive strength is reduced by distributing micro balloons or hollow micro balloons made of glass on the surface of the adhesive layer, and when the adherend is pressure-bonded, the hollow micro balloons are damaged and the adhesive strength of the adhesive layer is increased. Expressed.

As another proposal, Japanese Examined Patent Publication No. 44-17040
No. In Japanese, at least about _^1/4 over the height nonadhesive is distributed over the surface of the small projection having a fragile protective jacket covered with at least a height of about 15 microns with a tacky adhesive An agent layer is disclosed, and it is said that the agent layer can be brought into contact with a desired position by sliding the surface of the adherend to a desired position and then simply pressing.

However, in these proposals,
Without substantially affecting the adhesive strength after crimping,
It is difficult to make the initial adhesive strength small enough, and if the initial adhesive strength is made small enough,
It has been found that there is a problem that the adhesive strength after pressure bonding is substantially adversely affected. A hollow microballoon which is easy to break and can be crushed, as described in Japanese Patent Publication No. 44-3120, and Japanese Patent Publication No. 44-
The non-adhesive, brittle protective jacket described in Japanese Patent No. 17040,
During crimping, it is broken into relatively large pieces, and such pieces cannot be dispersed inside the adhesive layer and remain on the surface of the adhesive layer, which significantly increases the adhesive strength of the crimping property. Pressure-sensitive adhesive sheet-like structures having these pressure-sensitive adhesive layers are subject to many problems, especially when used in the above-mentioned marking applications, because they are hindered and these debris impair the surface smoothness. It turned out to have points. Furthermore, in the former, it is practically difficult and industrially difficult to disperse the hollow micro-balloons in a state where the hollow micro-balloons are partially buried in the surface portion of the adhesive layer and the rest is projected, and in the latter case, However, its production has the disadvantage of being more difficult and complicated.

The present inventor has conducted extensive studies in order to improve the above-mentioned drawbacks of the prior art, and in JP-A-58-13682, the average particle size of the pressure-sensitive adhesive layer is less than the thickness of the pressure-sensitive adhesive layer. Non-hollow solid particles having a diameter of less than 10 μm and having poor adhesion have a dispersion layer of the solid particles uniformly dispersed on at least one surface or surface layer of the pressure-sensitive adhesive layer. A pressure sensitive adhesive layer was proposed. The above-mentioned JP-A-58
The pressure-sensitive adhesive layer according to the invention described in JP-A-13682 has a fairly low initial adhesive force and a sufficiently high final adhesive force after pressure bonding, which is a good result as the pressure-sensitive adhesive sheet-like structure for the marking application. However, it has been found that, as the practical use progresses, the feature that requires a little time for the adhesive force to develop after the pressure bonding becomes an obstacle in the use of the application tape.

For example, when a pressure-sensitive adhesive sheet structure such as "TURBO", which is composed of a plurality of characters, is displayed on the surface of an adherend such as an automobile body, the transparent sheet structure has " In some cases, an indication such as "TURBO" is printed and pressure-bonded, but in many cases, each character is cut out separately from the marking sheet of the sheet structure, and these characters are weakly called an application tape. After sticking the surface base material layer on the adhesive layer of sticky paper and arranging it in the specified arrangement of the application tape, peel off the release paper of the marking sheet and attach this application tape to the adherend. A method is employed in which a desired display is transferred from an application tape to an adherend by pressure bonding to the surface. In applications using such application tapes, if it takes time to develop the adhesive force after pressure bonding, the marking sheet to be transferred remains on the application tape and is transferred to the adherend. It turns out that there are many troubles that they are not worn.

The present inventors have conducted research to provide a pressure-sensitive adhesive layer that solves all the problems of the prior art as described above, and completed the present invention.

According to the present invention, the average particle size is 10 to 60 μm.
Non-adhesive solid particles have a least one surface of the uniformly dispersed dispersion layer an adhesive layer, at least about half of the solid particles high corresponds to about _^1/4 at least in an average particle size of Moreover, when the solid particles are hollow particles and protrude from the surface of the adhesive layer, the hollow particle walls are not crushed by the pressure bonding pressure, and thus the pressure-sensitive adhesive layer is provided.

The pressure-sensitive adhesive layer according to the present invention is used as a pressure-sensitive adhesive sheet-like structure, and when it is adhered to an adherend,
On the surface of the adherend to facilitate the alignment of the adhesion position of the surface of the adherend to the desired sticking position and to avoid the occurrence of sticking failure such as wrinkles, bubbles and blisters, if necessary. It has an initial adhesive force that is small enough to allow the corrective movement of the
There were many improvements such as no trouble occurred when transferring by using tape, the final reaching adhesive strength was remarkably large, the surface condition after pressure bonding was smooth, and industrially extremely easy to manufacture. Since it has various characteristics, the pressure-sensitive adhesive layer of the present invention is extremely useful for a pressure-sensitive adhesive sheet-like structure, particularly for marking.

The objects, features and advantages of the present invention will be more apparent from the following description.

The pressure-sensitive adhesive layer according to the present invention has an average particle size of 1
A dispersion layer in which 0 to 60μ, preferably about 20 to 40μ, most preferably about 25 to about 40μ of non-adhesive solid particles is uniformly dispersed, preferably about 10 to about 100μ, more preferably about 10 to about 10. 60μ, most preferably about 20 to about 5
Having at least one surface of a 0 μ thick adhesive layer,
At least about half of the solid particles, preferably at least about 7
0%, about _^1/4 at least in their average particle size, preferably at least about _^1/3, and most preferably at least about _^2/5, protrudes from the surface of the adhesive layer to a height which corresponds to and the When the solid particles are hollow particles, the pressure-sensitive adhesive layer is such that the intermediate particle wall is not crushed by the pressing pressure.

In a preferred embodiment of the present invention, at least about half of the non-adhesive solid particles project above the surface of the adhesive layer to a height of at least about 7μ, preferably about 10μ.

In a preferred embodiment of the present invention, the average particle size of the non-adhesive solid particles is not more than 1.1 times the thickness of the adhesive layer, and the non-adhesive solid particles have a weight of about 50 weight. % Or more has a particle size distribution of ± 5μ of the average particle size and about 90% or more by weight of ± 8μ. In a more preferred embodiment of the present invention, about 50% by weight or more of the non-adhesive solid particles are in the size range of average particle size ± 3μ and about 90% by weight or more are in the size range of average particle size ± 5μ. In the particle size distributions of the preferred and more preferred embodiments described above, it is particularly preferred that the fines of less than about 10μ are up to 10% by weight of the total solid particles.

In the pressure-sensitive adhesive layer of the present invention, a non-adhesive solid particle satisfying the above-mentioned particle size conditions is uniformly dispersed on at least one surface of the pressure-sensitive adhesive layer. Have. Here, "uniformly dispersed" means that it is not necessary to be regularly and uniformly distributed, and macroscopically evenly dispersed may be used. For example, the surface of the pressure-sensitive adhesive layer may be uniformly powdered by a means such as a powdering machine.

In a preferred embodiment of the present invention, the non-adhesive solid particles cover the surface of the adhesive layer at a coverage of about 3.
To about 30%, preferably about 5 to about 20%, most preferably about 5 to about 18%.

In a more preferred embodiment of the present invention,
Average particle size 10 to 60μ, preferably about 15 to about 50μ,
More preferably about 20 to about 40μ, most preferably about 2.
5 to about 40μ of non-adhesive solid particles, at least about half, preferably 70% of which at least about its average particle size.
_^1/4, preferably at least about _^1/3, and most preferably from about ^_2/5
Which is higher than the surface of the adhesive layer and has a coverage of the surface of the adhesive layer of about 3 to about 30%, preferably about 5 to about 20%, most preferably about 5 to about 18%. A pressure sensitive adhesive layer having a dispersion layer dispersed in at least one surface of the adhesive layer is provided.

It is said that the non-adhesive solid particles have the above-mentioned (a) specific range of average particle diameter and (b) specific range of protrusion height and (c) have the above-mentioned specific range of coverage. When the requirements of (c) to (c) are satisfied at the same time, all the above-mentioned properties such as a decrease in initial adhesive strength, a speed of development of adhesive strength after crimping, and a final reached adhesive strength are more significantly improved. It has been made clear by the present invention.

The reason why the pressure-sensitive adhesive layer of the present invention exerts various excellent properties is not necessarily clear, but non-adhesive particles having an appropriate particle size are appropriately protruded from the surface of the adhesive layer,
Since the adhesive layer and the surface of the adherend are appropriately separated, the initial adhesive force is extremely low, and non-adhesive particles having an appropriate particle size are evenly dispersed with an appropriate coverage. It is presumed that the non-adhesive particles are rapidly embedded in the adhesive layer at the time of press-bonding, the adhesive force is rapidly expressed, and the final reached adhesive force is significantly increased.

The non-adhesive solid particles used in the present invention are:
As long as the above-mentioned particle size conditions are satisfied, it can be used without any special limitation on its type.

Examples of such solid particles include calcium carbonate, barium carbonate, calcium sulfate, aluminum sulfate, molybdenum disulfide, titanium oxide, alumina, silica, magnesium oxide, calcium oxide, calcium hydroxide, ferrous oxide. , Inorganic particles of ferric oxide, glass beads, etc .; further cured rubber, ebonite, lignin / phenol resin, styrene resin, vinyl chloride resin,
Examples thereof include organic solid particles such as (meth) acrylic resin, polypropylene resin, polyethylene resin, melamine resin, urea resin and other resins. These are not limited to single use, but may be appropriately used in combination of plural types.

As the non-adhesive solid particles used in the present invention, hollow non-adhesive solid particles satisfying the above-mentioned particle size conditions can also be used as long as the hollow particle walls are not crushed by the pressure bonding pressure. Examples of such hollow non-adhesive solid particles include organic balloons such as urea resin balloons, melamine resin balloons, phenol resin balloons, polyvinylidene chloride balloons and epoxy resin balloons; glass balloons, shirasu balloons, carbon balloons,
Hollow non-adhesive solid particles whose hollow particle walls are not crushed by the pressure of an inorganic balloon such as an alumina balloon or silica sand balloon may be mentioned. Here, the term “not crushed” is used in a sense that even a part of the wall of the hollow particle is broken and the gas in the hollow particle does not leak to the outside. As described above, the fragments of the hollow particles on the surface of the adhesive layer cause the final reaching adhesive force to be reduced, but after the pressure bonding, the hollow particle wall is partially damaged and the gas inside adheres to the base material layer. If trapped between the bodies,
In applications where clear Rucker coating is further applied after sticking, the above trapped gas expands during heating for Rucker drying, causing swelling on the marking sheet surface and impairing the appearance, etc. It will also cause troubles.

On the other hand, various pressure-sensitive adhesives for forming the pressure-sensitive adhesive layer of the present invention are known and can be used in the present invention. It is preferable to use an adhesive of the type generally referred to as a pressure-sensitive adhesive that exhibits tackiness at room temperature. Examples of such pressure-sensitive adhesives include rubber-based adhesives, acrylic-based adhesives, vinyl acetate-based adhesives, urethane-based adhesives, silicone-based adhesives, other adhesives, and appropriate mixtures thereof. An adhesive may be used.

Examples of the rubber adhesive include natural rubber, isoprene rubber, styrene butadiene rubber, styrene butadiene block copolymer, styrene isoprene block copolymer, butyl rubber, polyisobutylene, silicone rubber, polyvinyl isobutyl ether, chloroprene. Examples thereof include those made of rubber, nitrile rubber, etc., and mixtures thereof or those containing at least one of them as the main component. Also, those having a slight cross-linking structure between molecules can be preferably used.

The acrylic adhesive or vinyl acetate adhesive is, for example, an adhesive layer formed by a solvent-type adhesive containing an unsaturated carboxylic acid ester copolymer as a main component, and particularly an unsaturated carboxylic acid. Ester monomer 99.
Glass transition temperature (T) derived from 9 to 85 parts by weight and 0.1 to 15 parts by weight of a vinyl monomer having a crosslinkable functional group.
g) is -20 ° C or lower, 100 parts by weight of a copolymer, 70-
An adhesive layer formed of a solvent type adhesive consisting of 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 preferable.

As the unsaturated carboxylic acid ester monomer for obtaining the above-mentioned copolymer constituting the above-mentioned adhesive,
Methyl (meth) acrylate, ethyl (meth) acrylate,
(Meth) butyl acrylate, (meth) pentyl acrylate,
Examples thereof include hexyl (meth) acrylate, heptyl (meth) acrylate, and acrylate (meth) acrylate monomers, and vinyl ester monomers such as vinyl acetate and vinyl propionate.

As the vinyl monomer having a crosslinkable functional group for obtaining the above-mentioned copolymer, vinyl monomers having a carboxyl group such as acrylic acid, methacrylic acid and itaconic acid, and hydroxymethyl ester of acrylic acid, hydroxy Hydroxyl esters such as ethyl ester, hydroxypropyl ester, hydroxybutyl ester, hydroxypentyl ester and hydroxyhexyl ester, and hydroxymethyl ester of methacrylic acid, hydroxyethyl ester, hydroxybutylethyl, hydroxypropyl ester, hydroxypentyl ester and hydroxyhexyl ester. Examples thereof include vinyl monomers having, and further include vinyl monomers having an epoxy group and an amino group.

Examples of the solvent include ethyl acetate, toluene, and a polymer of titanium tetraptylate, a polymer of titanium oleate, and the like, such as titanium acylate, and the above organic polyvalent isocyanate compounds. As P-phenylene diisocyanate, 4,4 '
-So-called aromatic polyisocyanates such as diphenyl methane diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, xylylene diisocyanate, triisocyanate and naphthalene 1,5-diisocyanate; pentamethylene diisocyanate,
Hexamethylene diisocyanate, heptamethylene diisocyanate, 4,4'-dicyclohexyl methane diisocyanate and the like.

The glass transition temperature Tg of the copolymer
Is a value determined by the following measuring method.

About 10 mg of the resin solution sample was weighed in a cell and
The sample dried at 00 ° C. for 2 hours is used as a measurement sample. Shimadzu DT-30 type differential scanning calorimeter (Differential Sc
Using an anning calorimeter), the temperature is determined from -80 ° C at a heating rate of 20 ° C / min. As a carrier gas, nitrogen gas is used at a flow rate of 20 cc / min for measurement.

As an example of the urethane adhesive,
Triphenylmethane-p, p ', p "-triisocyanate,
Hexamethylene diisocyanate, diphenylmethane-
Consists of a polymer compound produced by the reaction of an isocyanate such as 4,4'-diisocyanate or toluene diisocyanate with a compound having an active hydrogen atom, for example, a polyester having an active hydrogen atom, a polyether glycol, a polyacrylate or a polyamide The thing and the thing which makes those mixture or those at least 1 type of them a main component can be illustrated.

The method for producing the pressure-sensitive adhesive layer of the present invention is not particularly limited, but it is preferable that the peelable support layer has a non-average diameter of 10 to 60 μm on at least one surface thereof. after uniformly dispersing the adhesive solid particles, the solid particles by the pressure to fill to the support layer to a depth at least about half of the solid particles strike the approximately _^1/4 at least in their average particle size Is applied to the support layer, and then a method for producing a pressure-sensitive adhesive layer is used in which an adhesive layer is formed on the surface of the support layer in which solid particles are dispersed and press-fitted.

The peelable support layer used in the above-mentioned preferred method is a release paper obtained by further treating the surface of a polyethylene layer of a high-quality paper laminated with polyethylene with silicone, a polypropylene film treated with silicone, or a polyethylene treated with silicone. Examples thereof include films.

There are no particular restrictions on the means for uniformly dispersing the non-adhesive solid particles on the surface of the support layer. For example, powders such as a dusting machine, a powder spraying machine and a powder spraying machine can be used. It is possible to use a means that can give a distributed effect. Alternatively, a means for applying a slurry in which the solid particles are dispersed in an appropriate dispersion medium liquid by a means such as coating or spraying, and then drying.
After distributing an excessive amount of the solid particles, a brush-like means or other means for removing the excessive particles by an appropriate scraper means can be used.

The support layer in which the non-adhesive solid particles are uniformly dispersed as described above is then heated, if necessary, and then
The solid particles are embedded in the support layer to a desired depth by using an appropriate pressure means such as a pressure roll and a press machine, and a pressure sensitive adhesive is applied or laminated thereon by a conventional method. The pressure-sensitive adhesive layer of the present invention can be obtained by applying the above means.

The pressure-sensitive adhesive layer of the present invention, as described above,
It can be suitably used for a pressure-sensitive adhesive sheet-like structure.
Thus, according to the present invention, (A) the average particle size is 10 to 60 μm.
Non-adhesive solid particles uniformly dispersed dispersed layer having on one surface of the adhesive layer, at least about half of the solid particles to a height which corresponds to about _^1/4 at least in an average particle size of A pressure-sensitive adhesive layer which protrudes from the surface of the adhesive layer and in which when the solid particles are hollow particles, the hollow particle walls are not crushed by the pressure bonding pressure, (B) The adhesive agent for the non-adhesive solid particles A releasable support layer having a surface depression which is in contact with and closely complements the protruding part of the layer surface;
(C) A pressure-sensitive adhesive sheet-like structure comprising a substrate layer laminated on the surface of the pressure-sensitive adhesive layer on the side not having the dispersion layer of the non-adhesive solid particles. The pressure-sensitive adhesive sheet-like structure maximizes its advantages especially in the application of marking sheets.

A schematic sectional view of the pressure-sensitive adhesive sheet-like structure provided by the present invention is shown in FIG.

The substrate layer has a thickness of about 10 to about 1000 μ,
Preferably about 20 to about 200μ, more preferably about 25 to
About 100μ of thermoplastic polymer film is used,
Examples of such a thermoplastic polymer film include the following polymer films: polyethylene,
Polypropylene, vinyl chloride, vinyl acetate, acrylic,
It may be used alone or as a blend with urethane, polyester and other polymers, and in some cases, papers such as kraft paper, high quality paper, glassine paper and the like can be mentioned.

The base layer may contain various additives such as colorants, stabilizers, modifiers, plasticizers, etc., if necessary, and various printing may be performed on the base layer. You can rub it.

As a method for laminating the base material layer on the pressure-sensitive adhesive layer, a method such as pressure laminating can be appropriately adopted.

The average particle size of the non-adhesive solid particles in this specification is measured by the following method.

Solid particles are taken in a micrograph at a magnification of 300 times, and the maximum diameter of 50 individual particles is actually measured in the photograph, and the average value is taken as the average particle diameter.

The height at which the solid particles in the present specification project from the surface of the adhesive layer is measured by the following method.

This support is provided for the one having a peelable support layer having a surface recess which is in contact with a portion of the non-adhesive solid particles projecting on the surface of the adhesive layer and which closely complements the projecting portion. Regarding the dent of the body layer, for those that do not have a support layer, the solid particle protruding surface of the adhesive layer is taken as a replica, and the depth of the center of the dent is measured with a surface roughness measuring instrument for the dent of this replica. To do.

The average value of the depths of 10 points of the depressions was used as the amount of solid particles protruding.

Measuring instrument manufactured by Kosaka Seisakusho Co., Ltd. Surface roughness measuring instrument Surfcoder SE-30D In the present specification, the coverage with which the solid particles cover the surface of the adhesive layer is measured by the following method.

The protruding surface of the solid particles of the adhesive layer was taken in a micrograph at a magnification of 300 times, and the area occupied by the solid particles was measured in the frame of 10 × 10 cm in this picture. And While the pressure-sensitive adhesive layer of the present invention has a sufficiently low initial adhesive force as described above, it also has contradictory properties when the adhesive force after pressure bonding is rapidly developed and the final reached adhesive force is remarkably large. When used in a pressure-sensitive adhesive sheet-like structure, the surface of the base material after attachment is smooth and beautiful, and the water and gasoline resistance is excellent. Furthermore, a transparent paint or the like is applied onto the base material after attachment. It has excellent properties when it does not swell even after drying. The pressure-sensitive adhesive layer of the present invention also has an advantage that it can be industrially extremely easily manufactured as is clear from the above description.

The details of the present invention will be described in more detail with reference to the following examples. Unless otherwise specified, all quantities are indicated by weight.

First, the test methods carried out in Examples and Comparative Examples are as follows.

(1) The loop tack test was performed using Toyo Seiki Seisakusho Strograph M-50 type.

20 × 150 mm test piece (pressure-sensitive adhesive sheet)
After cutting into strips and peeling off the release paper, the adhesive surface is placed outside and 25mm at both ends are put together to form a loop with a circumference of 100mm which is inserted into the chuck of the strograph.

Next, the loop is lowered on the alkyd melamine coated plate (manufactured by Japan Test Panel Industry Co., Ltd.) at a speed of 500 mm / min to bring it into contact with the alkyd melamine coated plate.
At that time, the contact length of the loop is designed to be 30 mm.

When the lowering of the loop is completed, the test piece comes into contact with the alkyd melamine coated plate with the loop collapsed.

In this state, the stationary state was maintained for 15 seconds, and then the loop was raised at a speed of 300 mm / min. At this time, the adhesive strength between the alkyd melamine coated plate and the test piece was used as a loop tack.

(2) Mobility on adherend: A test piece (pressure-sensitive adhesive sheet) was cut into 25 × 150 mm, the release paper was peeled off, and one end 25 mm was folded with the adhesive surface inside and folded. Place it on a level alkyd melamine coated plate with the adhesive side down. However, at this time, the test piece is not crimped and only the own weight is applied to the test piece.

Next, one end (folded side) of the test piece was manually held and moved to the left and right to examine the freedom of movement, and this was taken as the non-load mobility.

The evaluation was carried out by a three-level evaluation of ◯, × and Δ.

〇 ・ ・ The test piece can be freely moved on the adherend.

Δ ... Adhesive force is partially developed, and the test piece cannot move freely.

× ・ ・ ・ ・ It is difficult to move the test piece.

A load of 50 g was evenly placed on the test piece and evaluated in the same manner as above, and this was taken as the mobility under load.

(3) Development of adhesive strength (g / cm) A test piece (pressure-sensitive adhesive sheet) was cut into 10 × 200 mm, the release paper was peeled off, and then an alkyd melamine coated plate (Japan It was pressure-bonded on top of Test Panel Industry Co., Ltd.).

After a predetermined time (3 minutes, 10 minutes, 2 hours, 24 hours), 180 ° peeling adhesion was measured using Strograph M-50. However, the pulling speed is 200 mm / min
I went to.

The final adhesive strength was expressed as a value of 168 hours after application.

(4) Short-term adhesive force expression rate The short-term adhesive force expression rate was defined as the percent value of the adhesive force value 10 minutes after pressure bonding with respect to the final reached adhesive force value defined in (3).

(5) Water-resistant adhesive strength The test piece was cut into 20 × 150 mm, the release paper was peeled off, and then a squeegee was used to press-bond it onto an alkyd melamine coated plate (Japan Test Panel Industry Co., Ltd.).

Next, after leaving this at room temperature for 72 hours,
It was immersed in water at ℃ for 162 hours, taken out and allowed to air-dry at 23 ℃, and after a predetermined time (1 minute, 72 hours), 180 ° peeling adhesive strength was measured using Strograph M-50. However, the pulling speed was 200 mm / min. (6) Anti-blister test The test piece was cut into 60 × 60 mm, and after peeling off the release paper,
A squeegee was used to press-bond onto an alkyd melamine coated plate (manufactured by Japan Test Panel Industry Co., Ltd.).

Next, after leaving this for 30 minutes at room temperature, 100 parts by weight of clear resin (manufactured by NOF Corporation; Bellcoat No. 5100 Clear HK) and solvent (manufactured by NOF Corporation;
Bellcoat No. 5100 thinner No. 4) 30 parts by weight of the mixed solution was applied and left at room temperature for 12 minutes, then at 70 ° C x 10
Then, it was dried at 150 ° C. for 15 minutes, a surface coating having a thickness of 30 μ was carried out, and after 24 hours, the surface condition was evaluated.

The evaluation was carried out by the three-level evaluation of ◯, × and Δ.

∙: Almost no change in surface condition.

Δ ... 30 blisters with a diameter of 0.5 mm or less
Permitted as much as individual. Or, the edge of the test piece is turned up by 1-2 mm.

X ... Larger or larger blisters than Δ.
Or, the edge of the test piece is turned up by 2 mm or more.

(7) Gasoline resistance test A test piece was cut into a piece of 60 × 60 mm, and the release paper was peeled off.
A squeegee was used to press-bond onto an alkyd melamine coated plate (manufactured by Japan Test Panel Industry Co., Ltd.).

Next, this was left at room temperature for 72 hours, immersed in unleaded gasoline for 1 hour, taken out and dried, and then the surface condition was evaluated.

The evaluation was carried out by a three-level evaluation of ◯, × and Δ.

◯ ... Almost no change in surface condition.

Δ ... 30 blisters with a diameter of 0.5 mm or less
Permitted as much as individual. Or, the edge of the test piece is turned up by 1-2 mm.

X ... The blistering is larger or larger than Δ.
Or the edge of the test piece is turned up from Δ.

(8) Surface condition after crimping The surface is roughly and smoothly observed with the naked eye.

◯ ... Smooth and good.

Δ: The smoothness is poor, but there is no outstanding rough surface irregularity.

X ...- The rough surface is rough.

(9) Average thickness of pressure-sensitive adhesive, width of thickness variation A portion where non-adhesive solid particles are not dispersed is prepared, and the adhesive layer in this portion is a vinyl chloride film having a thickness of 40 μ (thickness accuracy within ± 0.5 μ). 20mm x 20 transferred to
Make a 0 mm sample. In the length direction of this sample, the thickness is measured with a dial gauge defined by 10-point JIS B7509 at substantially equal intervals. The average pressure-sensitive adhesive thickness of 10 points was used as the average pressure-sensitive adhesive thickness.

Next, a test piece similar to the above was attached to a slide glass, and a surface roughness measuring device (manufactured by Kosaka Seisakusho Co., Ltd .; Surfcorder SE-30D) was used to measure "a skid for guidance using JIS B0651". A trace of the stylus movement obtained by tracing the surface of the object to be measured with a stylus having a stylus radius of a specified size, that is, a "cross section curve"
To measure. As the skid, a sapphire of R40 mm (measurement direction) × R2 mm is used. From this section curve, JIS
Get the value of Rmax (maximum height) based on B0601
The thickness variation range is defined by.

(10) Crushing residual rate test of non-adhesive solid particles; Release paper (trade name QKC-105P manufactured by Oji Kako Co., Ltd.)
SG-Q), about 1 million solid particles to be tested /
Disperse evenly at a rate of 100 cm ² .

Release paper is heated to about 100 ° C. using an infrared heater.
Then, while heating, a steel roll having a diameter of 330 mm and a length of 330 mm is pressed while rotating with a weight of 20 kg to embed solid particles in the release paper.

Next, an acrylic adhesive was applied on the release paper.
(Nippon Carbide Industry Co., Ltd., trade name PE-121) 100
A mixed solution of 1 part by weight and 1 part by weight of a crosslinking agent (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) is applied and dried to form an adhesive layer having a thickness of about 35 μm.

Further, a vinyl chloride transparent film (HIS Paint 5080 manufactured by Nippon Carbide Industry Co., Ltd.) is laminated on the pressure-sensitive adhesive layer to form a pressure-sensitive adhesive sheet.

Next, the release paper of the pressure-sensitive adhesive sheet is peeled off and lightly attached to the glass plate. After that, a polypropylene plastic squeegee with a thickness of 1.5 mm and a width of 95 mm is used to strongly press-bond with a pressure of about 5 kg.

After that, the solid particles are observed with a microscope and the state of destruction thereof is observed to determine the remaining rate of the undestructed particles.

In the present invention, solid particles having a residual rate of 80% or more, particularly preferably 90% or more, more preferably 100% can be very suitably used.

Example 1 Spherical solid particles (non-adhesive solid particles) having an average particle diameter of about 30 μ obtained by classifying polymer beads of polymethylmethacrylate (weight average molecular weight of about 300,000) produced by suspension polymerization. Was uniformly sprayed on a release paper (releasable support layer) (trade name QKC-105PSG-Q manufactured by Oji Kako Co., Ltd.).

Release paper is heated to about 100 ° C. using an infrared heater.
Then, a steel roll having a diameter of 330 mm and a length of 330 mm under heating was applied with a load of 20 kg and pressed while rotating, and the polymer beads were embedded in the release paper. Embedded amount
(Solid particle protrusion amount) was about 14 μm, and the surface coverage with polymer beads was about 8%.

Next, an acrylic adhesive was applied on the release paper.
(Nippon Carbide Industry Co., Ltd., trade name PE-121) 100
A mixed solution of 1 part by weight of a cross-linking agent (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) was applied and dried to form a pressure-sensitive adhesive layer having a thickness of about 35 μm. The thickness fluctuation range of the adhesive layer was 10 μm.

Further, a vinyl chloride film (HIS Paint 5010, trade name, manufactured by Nippon Carbide Industry Co., Ltd.) was laminated on the adhesive layer as a substrate layer to prepare a pressure-sensitive adhesive sheet.

As shown in Table 1, the physical properties of the pressure-sensitive adhesive sheet thus obtained are such that the pressure-sensitive adhesive sheet can be freely moved on the adherend, the short-term adhesive force development rate after pressure bonding is fast, and the final reached adhesive force is high. The adhesive sheet was excellent in durability such as water resistance, blistering resistance, and gasoline resistance, and had a very good surface condition of the sheet after pressure bonding, and was an adhesive sheet capable of sufficiently achieving the object of the present invention.

Comparative Examples 1 and 2 A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that an average particle size of 63 μ (Comparative Example 1) and an average particle size of 8 μ (Comparative Example 2) were used.

As shown in Table 1, the obtained sheet was a pressure-sensitive adhesive sheet in Comparative Example 1 in which the surface condition of the sheet after pressure bonding was very poor and the blister resistance and gasoline resistance were poor.

In Comparative Example 2, the object of the present invention, which is difficult to move on the adherend, was not satisfied.

Example 2 Instead of polymer beads, glass microballoons having an average particle diameter of 28 μ obtained by classification (crushing residual ratio 10
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that 0%) was used.

As shown in Table 1, the obtained sheet satisfied the object of the present invention.

Example 3 A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that glass beads having an average particle size of 33 μ obtained by classification (crushing residual rate 100%) were used in place of the polymer beads. Ivy.

As shown in Table 1, the obtained sheet satisfied the object of the present invention.

Comparative Example 3 A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the load of the steel roll was adjusted so that the embedded amount of the polymer beads was about 6 μ.

The obtained sheet did not satisfy the object of the present invention, which is difficult to move on the adherend.

Comparative Example 4 The average particle size of about 50 μm obtained by dispersion is easy to break,
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 2 except that a glass balloon which was easily crushed was used.

As shown in Table 1, the obtained sheet did not satisfy the object of the present invention, which had a poor surface condition after pressure bonding and had poor durability such as blistering resistance and gasoline resistance.

Examples 4 and 5 A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that polymer beads having an average particle size of about 22 μ (Example 4) and about 39 μ (Example 5) were used. .

The obtained sheets were, as shown in Table 1, Examples 4 and 5; adhesive sheets capable of sufficiently achieving the objects of the present invention.

Example 6 A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the load of the steel roll was adjusted and the embedding amount of the polymer beads was set to about 8 μ.

As shown in Table 1, the obtained sheet was an adhesive sheet capable of sufficiently achieving the object of the present invention.

Examples 7 and 8 All were the same as Example 1 except that the amount of polymer beads sprayed was changed so that the solid particle surface coverage was about 5% (Example 8) and about 18% (Example 9). To produce a pressure sensitive adhesive sheet.

As shown in Table 1, the obtained sheet was an adhesive sheet capable of sufficiently achieving the object of the present invention.

Comparative Example 5 Fine-grained calcium carbonate having an average particle diameter of about 0.6 μ (trade name “NCC # 410”, manufactured by Nitto Koka Kogyo Co., Ltd.)
Release paper (made by Shikoku Paper Co., Ltd. under the trade name "KOM-1
1 "). Dispersion was achieved by excessively sprinkling calcium carbonate on a release paper, uniformly dispersing the calcium carbonate on the surface using a brush, and then scraping off the excess with a scraper. At this time, the distribution amount of calcium carbonate was about 1 g / m ² .

Next, an acrylic adhesive was applied on the release paper.
(Nippon Carbide Industry Co., Ltd., trade name PE-121) 100
A mixed solution of 1 part by weight of a cross-linking agent (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) was applied and dried to form a pressure-sensitive adhesive layer having a thickness of about 35 μm. The thickness fluctuation range of the adhesive layer was 10 μm. Further, a vinyl chloride film (HIS Paint 5010, trade name, manufactured by Nippon Carbide Industry Co., Ltd.) was bonded as a substrate layer on the adhesive layer to prepare a pressure-sensitive adhesive sheet.

As shown in Table 1, the obtained sheet was an adhesive sheet not having the object of the present invention, which has a very low short-term adhesive force expression rate.

[0119]

[Table 1]

[0120]

[Table 2]

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a pressure-sensitive adhesive sheet-like structure using the pressure-sensitive adhesive layer of the present invention.

Claims (6)

[Claims] 1. (A) A non-adhesive solid particle having an average particle size of 10 to 60 μ is uniformly dispersed on one surface of the adhesive layer, and at least about half of the solid particle is but not crushing by connexion hollow particle wall crimping pressure when the average particle size of at least about _^1/4 protrudes from the surface of the adhesive layer to the height and and solid particles impinging on the hollow particles And a pressure-sensitive adhesive layer having a coverage of the non-adhesive solid particles with respect to the surface area of the adhesive layer of about 3 to about 30%, (B) a portion of the non-adhesive solid particles protruding from the adhesive layer surface. Of the pressure-sensitive adhesive layer, which is in contact with and tightly fills the protruding portion, with a surface depression, and (C) the side of the pressure-sensitive adhesive layer which does not have the dispersion layer of the non-adhesive solid particles. A pressure-sensitive adhesive sheet-like structure having a base material layer laminated on a surface thereof. 2. The structure according to claim 1, which is a pressure-sensitive adhesive sheet-like structure for marking. 3. The non-adhesive solid particles have an average particle size of about 20-.
The structure of claim 1 or 2 having a size of about 40μ. 4. The structure according to claim 1, wherein the coverage is about 5% to about 20%. 5. The structure according to claim 1, wherein at least about half of the non-adhesive solid particles are projected from the surface of the adhesive layer to a height of at least about 7 μ. 6. About 50% by weight or more of the non-adhesive solid particles fall within a particle size range of ± 5 μ of the average particle size and about 90% by weight.
The above is within a particle size range of ± 8μ of the average particle size.
The structure according to any one of 5 above.