JP2804743B2 - Pressure-sensitive adhesive sheet-like structure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a pressure-sensitive adhesive sheet-like structure.
More specifically, when attaching to the adherend, the adherend
It facilitates the positioning of the surface to the desired position,
If necessary, wrinkles, air bubbles, swelling, etc.
Correction movement is possible on the surface of the adherend to avoid generation of
Small enough initial adhesion (before crimping
Adhesive strength when lightly contacting the surface of the adhesive;
(Represented by a flap, etc.)
Quickly develops adhesive force and remarkable final adhesion value
Large, the surface condition after crimping is smooth, and production is extremely high
Pressure-sensitive welding with improved characteristics such as easy and easy
It relates to an adhesive layer. [0002] Substrates such as films, tapes and sheets
Pressure-sensitive adhesive sheet-like structure having a pressure-sensitive adhesive layer on its surface
Are known and used for building materials such as wallpaper
Temporarily hiding the part to be painted during repair painting
Is temporarily hidden to protect the aluminum sash surface during transport.
So-called masking applications such as masking and the background color of signboards,
Characters and patterns, motorcycles, cars, trains and other vehicles
Half as decorative patterns, stripes, letters, etc.
In so-called permanent marking applications,
It is attached to the surface of the adherend and is widely used. [0003] Such a pressure-sensitive adhesive layer has an initial adhesive strength.
Is too high, even skilled workers can
It is extremely difficult to apply it exactly once to the desired position.
You. For this reason, correction of the sticking position, wrinkles, bubbles,
Correction such as re-pasting for removal of
Such corrections often involve problems such as substrate deformation or breakage.
Occurs. The technical section of the pressure-sensitive adhesive layer as described above
To achieve the desired final contact of the pressure sensitive adhesive layer
Only the initial adhesive strength is reduced without substantially reducing the adhesive strength.
Several attempts have been made to
You. As one of such proposals, Japanese Patent Publication No. Sho 44
No. 3120 discloses that at least one surface has a uniform
With friable and crushable non-adhesive protrusions distributed on the surface
An adhesive adhesive layer is disclosed, and according to this proposal urea
-Formaldehyde resin hollow microballoons and glass
Distribute hollow micro-balloons on the surface of the adhesive layer for initial contact
When the adherend is pressed down, the hollow fine
The small balloon is broken and the adhesive strength of the adhesive layer is developed.
You. As another proposal, Japanese Patent Publication No. 44-17040
The publication contains at least about¹/_FourNon-adhesive brittle over the height of
At least about 15 microns high with a protective sheath
Adhesive with small projections distributed on the surface
An agent layer is disclosed, and a desired position is placed on the surface of the adherend.
And then touch it by simply pressing
It is said that it can be. [0007] However, in these proposals,
Without substantially affecting the adhesion after crimping,
It is difficult to make the initial adhesive strength small enough to satisfy
Yes, if the initial adhesive strength is small enough to satisfy,
Trouble that may have a substantial adverse effect on the adhesion after crimping
I knew it. Described in JP-B-44-3120
Crushable and crushable hollow micro balloons and Tokiko Sho44-
The non-adhesive brittle protective jacket described in 17040 is
During crimping, it is broken into relatively large pieces, etc.
Since the fragments cannot be dispersed inside the adhesive layer, the surface of the adhesive layer
Surface, which significantly prevents the increase in adhesive strength
Harmful, and these fragments degrade the surface smoothness
Therefore, a pressure-sensitive adhesive sheet having these pressure-sensitive adhesive layers
-Like structures, especially when used for the above marking applications
Was found to have the following problems. On top of that, the former smell
Partially embedded hollow microballoons on the surface of the adhesive layer
It is practically difficult to disperse while submerging and projecting the rest.
Difficult and industrially difficult to produce, in the latter case
Manufacturing has the disadvantage that it is more difficult and cumbersome. The present inventor has ameliorated the above disadvantages of the prior art.
For this reason, the enthusiastic research was repeated, and JP-A-58-13682 was disclosed.
In the above, the particle size is smaller than the thickness of the pressure-sensitive adhesive layer,
Non-hollow solid particles having an average particle size of less than 10μ and having poor adhesion
A pressure-sensitive adhesive is applied to the dispersion layer of the solid particles in which the particles are uniformly dispersed.
On at least one surface of the agent layer or on the surface layer
A pressure-sensitive adhesive layer characterized by the following was proposed. JP-A-58
The pressure-sensitive adhesive layer according to the invention described in JP-A-13682 is acceptable.
Has a low initial adhesive strength and reaches the end after crimping
Adhesive force is sufficiently high, pressure-sensitive adhesive sheet for the marking application
Good performance as a girder-shaped structure, but practical application is progressing
Requires a certain amount of time to develop the adhesive strength after crimping.
Signs are obstacles for applications using application tapes, etc.
I've come to know. For example, on the surface of an adherend such as an automobile body
Indication consisting of multiple characters, eg "TURBO"
Is performed with a pressure-sensitive adhesive sheet structure, the transparent sheet
A place to print "TURBO" etc. on the structure and press it on
In some cases, each character is separately
Cut out from the marking sheet of the object, these characters
Is applied to weak adhesive paper called application tape.
The base material layer on the surface is adhered to the
・ After arranging the tape in a predetermined arrangement,
Peel off the release paper and apply this application tape.
Crimping on the surface of the body
The method of transferring from tape to the adherend is adopted.
You. Applications using such application tapes
For example, if it takes time to develop the adhesive force after crimping,
Marking sheet to be applied is application tape
Trouble that remains on the top and is not transferred to the adherend
Was found to occur frequently. [0010] The present inventors have developed the prior art as described above.
To provide a pressure-sensitive adhesive layer that solves all of the problems
After conducting research, the present invention was completed. According to the present invention, the average particle size is 10 to 60 μm.
Non-adhesive solid particles are dispersed uniformly in the adhesive layer
At least one surface of the solid particles and at least about
Half are at least about average particle size¹/_FourAt the height corresponding to
Protruding from the surface of the adhesive layer and the solid particles are hollow
In the case of particles, the hollow particle wall is crushed by the pressing pressure
No pressure sensitive adhesive layer is provided. The pressure-sensitive adhesive layer according to the present invention comprises a pressure-sensitive adhesive
When used as a sheet-like structure and attached to an adherend,
Easy alignment of the bonding position to the desired bonding position on the adherend surface
If necessary, apply wrinkles, air bubbles, blisters, etc.
Correction movement on the surface of the adherend to avoid the occurrence of poor adhesion
Has an initial adhesive strength small enough to allow
Since the adhesive strength after crimping is fast,
No trouble occurs when transferring using tape, etc.
The ultimate adhesion is remarkably large, and the surface condition after crimping is smooth
In addition, it is extremely easy to manufacture industrially, etc.
With improved properties, the pressure-sensitive welding of the present invention
Adhesive layer for pressure-sensitive adhesive sheet-like structures, especially for marking
It is very useful for the pressure-sensitive adhesive sheet-like structure. The objects, features and advantages of the present invention are as follows:
It will be even clearer than listed. The pressure-sensitive adhesive layer according to the present invention has an average particle size of 1
0-60μ, preferably about 20-40μ, most preferably
Has a uniform dispersion of about 25 to about 40 microns of non-adhesive solid particles.
The dispersed layer is preferably about 10 to about 100 μ, more preferably
About 10 to about 60μ, most preferably about 20 to about 5
0μ, having at least one surface of an adhesive layer having a thickness of
At least about half of the solid particles, preferably at least about 7
0% is at least about 1/4 of its average particle size, preferably
At least about 1/3, most preferably at least about 2/5,
Projecting from the surface of the adhesive layer at a height corresponding to
When the solid particles are hollow particles,
SkyA pressure-sensitive adhesive layer in which the particle walls are not crushed. In a preferred embodiment of the present invention,
At least about half of the adherent solid particles are at least about 7μ, preferably
Preferably, projecting from the surface of the adhesive layer to a height of about 10μ
I have. In a preferred embodiment of the present invention,
The average particle size of the adhesive solid particles is 1.1 times the thickness of the adhesive layer.
And no more than about 50% by weight of the non-adhesive solid particles.
The upper part falls within the particle size range of ± 5μ of the average particle size and about 90 weight
% Or more has a particle size distribution falling within the weight range of ± 8μ. Book
In a further preferred embodiment of the invention, non-adhesive solid particles
Approximately 50% by weight of the particles are in the average particle size range of ± 3μ.
And about 90% by weight or more in the particle size range of average particle size ± 5μ
enter. Preferred and More Preferred Embodiments Above
Fine particles of about 10μ or less in the particle size distribution of all solid particles
It is particularly preferred that the content is 10% by weight or less. In the pressure-sensitive adhesive layer of the present invention,
Non-adhesive solid particles satisfying the particle size condition
A part uniformly dispersed on at least one surface of the pressure-sensitive adhesive layer
Has a dispersed layer. Here, “uniformly distributed” means regularly
Means that there is no need to distribute uniformly, macroscopically uniform
It is sufficient if they are dispersed. For example, means such as a powdering machine
The pressure-sensitive adhesive layer may be uniformly powdered on the surface. In a preferred embodiment of the present invention,
The coverage ratio of the adhesive solid particles covering the surface of the adhesive layer is about 3
To about 30%, preferably about 5 to about 20%, most preferably
Is about 5 to about 18%. In a more preferred embodiment of the present invention,
Average particle size of 10 to 60μ, preferably about 15 to about 50μ,
More preferably from about 20 to about 40μ, most preferably about 2
5 to about 40μ of the non-adhesive solid particles comprise at least about half
The number, preferably 70%, is at least about
¹/_Four, Preferably at least about¹/_ThreeAnd most preferably about^Two/_Five
And projecting from the surface of the adhesive layer at a height corresponding to
About 3 to about 30%, preferably about
5% to about 20%, most preferably about 5% to about 18%.
A dispersion layer is dispersed on at least one surface of the adhesive layer.
A pressure-sensitive adhesive layer is provided. The above (A) average particle size in a specific range and (B) characteristics
The non-adhesive solid particles have a certain range of protrusion height and (c)
The requirements of (a) to (c) that the coverage is within the specified range are the same.
If you are satisfied sometimes, decrease the initial adhesive strength,
All of the above factors, such as the speed of onset of adhesion and the ultimate adhesion
It is clear from the present invention that the properties are more significantly improved.
I got it. The pressure-sensitive adhesive layer of the present invention exhibits excellent properties.
Although the reason for the application is not necessarily clear, it has a moderate particle size.
Non-adhesive particles to protrude moderately from the adhesive layer surface,
Adhesive layer and the surface of the adherend are separated appropriately, so initial bonding
Non-adhesive particles with very low force and moderate particle size
Are uniformly dispersed with moderate coverage,
Non-adhesive particles are quickly buried in the adhesive layer during crimping
Rapid development of adhesion and remarkably high final adhesion
It is supposed to be. The non-adhesive solid particles used in the present invention are:
As long as the above particle size conditions are satisfied, special
It can be used without any restrictions. Examples of such solid particles include carbon dioxide.
Lucium, barium carbonate, calcium sulfate, aluminum sulfate
, Molybdenum disulfide, titanium oxide, alumina, silicon
Lica, magnesium oxide, calcium oxide, calcium hydroxide
Of calcium, ferrous oxide, ferric oxide, glass beads, etc.
Inorganic solid particles; furthermore, cured rubber, ebonite, ligni
Phenolic resin, styrene resin, vinyl chloride resin,
(Meth) acrylic resin, polypropylene resin, polyethylene
Resin, melamine resin, urea resin and other resins
Solid organic particles can be mentioned. These are used alone
The invention is not limited to this, and a plurality of types can be used in combination as appropriate. The non-adhesive solid particles used in the present invention
As a child, the hollow particle wall is not crushed by the pressing pressure.
Hollow non-adhesive that satisfies the above particle size conditions
Solid particles can also be used. Such a hollow non-adhesive solid
Examples of particles include urea resin balloons and melamine resin balloons.
Runes, phenolic resin balloons, polyvinylidene chloride
Organic balloons, such as balloons and epoxy resin balloons
Glass balloon, shirasu balloon, carbon balloon,
Inorganic valves such as alumina balloons and silica sand balloons
The hollow particle wall is not crushed by the pressure of
Examples include empty non-adhesive solid particles. here
The term "not crushed" means that even part of the hollow particle wall breaks
Meaning that the gas in the hollow particles does not leak out
It is used in. Breaking of hollow particles on the surface of the adhesive layer
It is said that the pieces cause a decrease in the ultimate adhesion.
However, after compression, the hollow particle wall was partially damaged and
Gas is trapped between the substrate layer and the adherend,
After pasting, apply a further clear lacquer coating on it
In applications where heat is applied to dry the rack,
The gas inflated expands on the surface of the marking sheet.
Troubles such as damage to the appearance
Become. On the other hand, when the pressure-sensitive adhesive layer of the present invention is formed,
Various adhesives are known as pressure-sensitive adhesives.
Available in Preferably sticky at room temperature
Use a type of adhesive that is generally called a pressure-sensitive adhesive
Is good. Examples of such pressure-sensitive adhesives include rubber
Adhesives, acrylic adhesives, vinyl acetate adhesives,
Urethane adhesive, silicone adhesive, and other adhesives
And their appropriate mixed adhesives. Examples of the rubber-based adhesive include natural adhesives.
Rubber, isoprene rubber, styrene butadiene rubber, styrene
Lenbutadiene block copolymer, styrene isoprene
Block copolymer, butyl rubber, polyisobutylene, silicone
Silicone rubber, polyvinyl isobutyl ether, chloro
Those made of plain rubber, nitrile rubber, etc.
Or a mixture of at least one of them as a main component
Can be exemplified. Some cross-linking structure between molecules
Those having the following can also be preferably used. Acrylic adhesive, vinyl acetate adhesive
For example, an unsaturated carboxylic acid eslute copolymer is used.
Adhesion formed by solvent-type adhesive as the main component
In the agent layer, especially the unsaturated carboxylic acid ester monomer 99.
Vinyl monomer having 9 to 85 parts by weight and a crosslinkable functional group
Glass transition temperature (T) derived from 0.1 to 15 parts by weight.
g) 100 parts by weight of a copolymer having a temperature of -20 ° C or less, and a solvent of 70 to
400 parts by weight and a crosslinking agent capable of crosslinking with the crosslinking functional group
Formed from solvent type adhesive consisting of 0.01 to 20 parts by weight
The formed adhesive layer is preferred. Obtaining the above-mentioned copolymer constituting the above-mentioned adhesive
As unsaturated carboxylic acid ester monomers for
Methyl (meth) acrylate, ethyl (meth) acrylate,
(Meth) butyl acrylate, (meth) pentyl acrylate,
Hexyl (meth) acrylate, heptyl (meth) acrylate
And (meth) acrylic acid acrylates such as
Stele monomer, vinyl acetate and vinyl propionate
And the like, and vinyl ester monomers. Further, a cross-linking agent for obtaining the above copolymer may be used.
Examples of the vinyl monomer having a functional group include acrylic acid,
Has a carboxyl group such as tacrylic acid and itaconic acid
Vinyl monomer and hydroxymethyl acrylate
Stele, hydroxyethyl ester, hydroxypropyl
Ester, hydroxybutyl ester, hydroxype
Ethyl esters and hydroxyhexyl esters, and
Methacrylic acid hydroxymethyl ester, hydroxy
Ciethyl ester, hydroxybutylethyl, hydroxy
Cypropyl ester, hydroxypentyl ester and
Vinyl having hydroxyl group such as hydroxyhexyl ester
Monomers and the like, and further include an epoxy group and an amino group.
And a vinyl monomer having the same. Ethyl acetate, toluene
Titanium tetrabutyle as an example of
Polymerized of titanium oxide, polymerized of titanium oleate
And the above-mentioned organic polyisocyanate compound.
As a product, P-phenylenediisocyanate, 4,4 '
-Diphenylmethane diisocyanate, 2,4-toluylene
Diisocyanate, 2,6-toluylene diisocyanate
G, xylylene diisocyanate, triisocyanate
So-called aromatics such as naphthalene 1,5-diisocyanate
Polyisocyanate; pentamethylene diisocyanate,
Hexamethylene diisocyanate, heptamethylene dii
Socyanate, 4,4'-dicyclohexylmethanediiso
And cyanate. The copolymer has a glass transition temperature Tg.
Is a value determined by the following measurement method. About 10 mg of a resin solution sample is weighed into a cell, and
A sample dried at 00 ° C. for 2 hours is used as a measurement sample. Shimadzu
DT-30 differential scanning calorimeter (manufactured by Seisakusho)
anning Calorimeter) and the rate of temperature rise from -80 ° C.
Measure and determine at 20 ° C / min. As carrier gas
Is measured using nitrogen gas at a flow rate of 20 cc / min. Examples of the urethane-based adhesive include:
Triphenylmethane-p, p ′, p ″ -triisocyanate,
Hexamethylene diisocyanate, diphenylmethane-
4,4'-diisocyanate, toluene diisocyanate
Compounds having active hydrogen atoms with isocyanates such as, for example
For example, polyesters and polyethers with active hydrogen atoms
Anti-glycol, polyacrylate, polyamide
Consisting of a polymer compound produced by
These mixtures or at least one of them as the main component
Can be exemplified. The method for producing the pressure-sensitive adhesive layer of the present invention is not particularly limited.
Although not to be preferred, preferably, the peelable support layer
Non-adhesive with average particle size of 10-60μ on at least one surface
After uniformly dispersing the conductive solid particles, at least
About half of its average particle size is at least about¹/_FourHit depth
The solid particles are pressed by pressure so as to be embedded in the support layer.
Into the support layer, and then the solid particles dispersed and pressed into the support.
Manufacturing method of pressure-sensitive adhesive layer to form adhesive layer on the surface of carrier layer
Is adopted. The releasable support used in the above preferred manufacturing method
As body layer, after laminating polyethylene on the surface
The surface of the polyethylene layer of the paper was further siliconized
Release paper, silicone-treated polypropylene film or
Is a silicone-treated polyethylene film
Wear. Non-adhesive solid particles are deposited on the surface of the support layer.
There are no special restrictions on the means of dispersing
Powders such as powdering machines, powder dispersers, powder sprayers, etc.
Can be used. Or
Also, a slurry in which the solid particles are dispersed in an appropriate dispersion medium liquid
-Means for applying, spraying, etc., and then drying,
After distributing excess solid particles, brush-like
Means to remove extra particles with appropriate scraper means
Can be used. As described above, the non-adhesive solid particles are uniformly
The support layer dispersed in, after heating, if necessary,
Use appropriate pressure means such as pressure rolls and press machines
Embedded in the support layer to a desired depth.
Apply a pressure-sensitive adhesive in the usual way by applying or laminating
By applying, the pressure-sensitive adhesive layer of the present invention can be obtained.
Can be. As described above, the pressure-sensitive adhesive layer of the present invention
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 are dispersed uniformly in the adhesive layer
On one surface of which at least about half of the solid particles are
Average particle size of at least about¹/_FourThe adhesive layer at a height corresponding to
And the solid particles are hollow particles.
Pressure does not break the hollow particle wall
Pressure-sensitive adhesive layer, (B) adhesive layer table of the non-adhesive solid particles
Contact the protruding part of the surface and close the protruding part
A releasable support layer having a complementary surface dent; and
(C) a dispersion layer of the non-adhesive solid particles of the pressure-sensitive adhesive layer
Having a base material layer laminated on the side having no
A pressure-sensitive adhesive sheet-like structure is provided.
Structures have their advantages, especially in marking sheet applications
Is to maximize. The pressure-sensitive adhesive sheet provided by the present invention
FIG. 1 shows a schematic sectional view of the structure. The base material layer has a thickness of about 10 to about 1000 μm,
Preferably about 20 to about 200μ, more preferably about 25 to
About 100μ of thermoplastic polymer film is used,
Such thermoplastic polymer films include the following polymers
Examples of body films are: polyethylene,
Polypropylene, vinyl chloride, vinyl acetate, acrylic,
Uniform with urethane, polyester and other polymers
Or blend and use
Paper such as soft paper, high quality paper, glassine paper, etc.
it can. The base material layer may be colored if necessary.
Including various additives such as agents, stabilizers, modifiers, plasticizers, etc.
Good, and various prints may be applied on the substrate layer
No. A method of laminating the above substrate layer on a pressure-sensitive adhesive layer
As the method, a method such as pressure bonding lamination can be appropriately adopted.
You. The non-adhesive solid particles in the present specification
Is measured by the following method. Micrograph of solid particles at 300 times magnification
And the maximum diameter of 50 individual particles in the photograph
The average value is taken as the average particle size. Further, the solid particles in this specification are used as an adhesive.
The height protruding above the surface of the layer is measured by the following method.
It is. The non-adhesive solid particles protrude from the surface of the adhesive layer.
In contact with the protruding portion and tightly complement the protruding portion.
Having a peelable support layer having a concave surface
About the recess of this support layer,
If not, repeat the solid particle protruding surface of the adhesive layer.
For Rica, this replica dent was measured for surface roughness.
Measure the depth of the center of the dent with a measuring instrument. Solid particles having an average value of the depths of 10 dents
The amount of child protrusion. Measuring instrument Kosaka Manufacturing Co., Ltd. Surface roughness measuring instrument Surf coder SE-30D The solid particles in this specification cover the surface of the adhesive layer
The coverage is measured by the following method. The protruding surface of the solid particles of the adhesive layer is increased by a factor of 300
Take a micrograph at the rate, and a 10 × 10 cm frame of this photo
Measure the occupied area of solid particles in the
The coverage was taken. The pressure-sensitive adhesive layer of the present invention has a sufficiently low initial adhesion as described above.
Despite its strength, it has a fast and
When the ultimate adhesion is remarkably large, it has conflicting properties.
When used for pressure-sensitive adhesive sheet-like structures,
The back substrate surface is smooth and beautiful, and has water-resistant adhesive strength and gasoline resistance.
Excellent phosphorus adhesion, and transparent paint on base material after application
Excellent when blistering does not occur even after coating and drying
Has characteristics. And the pressure-sensitive adhesive layer of the present invention is
Industrially very easy to manufacture, as evident from the description
It also has the advantage of being capable. The details of the present invention will be described below with reference to examples.
This will be described specifically. Unless otherwise specified, quantity display
All depended on weight. First, the test methods performed in Examples and Comparative Examples are as follows.
It is as follows. (1) Loop tack The test was made by Toyo Seiki Seisakusho Co., Ltd.
Was carried out using A test piece (pressure-sensitive adhesive sheet) is 20 × 150 mm
And peel off the release paper.
Align the end 25mm and insert it into the stroking chuck
Make a loop of 100mm circumference. Next, an alkyd melamine coated plate (Nippon Tesu Corporation)
To the panel at a speed of 500 mm / min.
The lid is lowered to contact the alkyd melamine coated plate.
At that time, the length of the loop contact is designed to be 30mm
I do. When the lowering of the loop is completed, the test piece is
Contact with the alkyd melamine coated board in the collapsed state
The Rukoto. In this state, the stationary state is maintained for 15 seconds.
After that, raise the loop at a speed of 300mm / min
Was. At this time, between the alkyd melamine coated plate and the test piece
Loop tack with adhesive strength. (2) Mobility on the adherend Cut the test piece (pressure-sensitive adhesive sheet) to 25 x 150 mm and peel
After peeling off the release paper, fold one end 25mm with the adhesive side inside.
Rimage, placed on horizontal alkyd melamine painted board
Lay down with the wearing surface down. However, at this time, the test piece was
The test piece is in a state where only its own weight is loaded. Next, one end (the bent side) of the test piece was
To check the freedom of movement.
The mobility of the load was used. The evaluation was performed in three steps of 〇, × and Δ. ... Freely move the test piece on the adherend
Can be scraped. Δ: Partially develops adhesive strength and tests
The movement of the piece is inconvenient. ×: It is difficult to move the test piece. A load of 50 g was evenly placed on the test piece.
And evaluate in the same way as above,
Gender. (3) Expression of adhesive strength (g / cm) Cut the test piece (pressure-sensitive adhesive sheet) to 10 x 200 mm and peel
After peeling off the release paper, use a squeegee to
Crimped on a painted panel (manufactured by Nippon Test Panel Industries, Ltd.)
did. A predetermined time (3 minutes, 10 minutes, 2 hours, 24:00
180) Peeling 180 ° after using STROGRAPH M-50
The peel strength was measured. However, the pulling speed is 200mm / min
I went in. The ultimate adhesion was 168 hours after application.
Values are shown. (4) Short-term adhesive strength expression rate After crimping to the value of the ultimate adhesion strength specified in (3)
Short-term adhesive strength with a percentage value of 10 minutes adhesive strength
The expression rate was used. (5) Water-resistant adhesive strength The test piece was cut to 20 × 150 mm and the release paper was peeled off
Later, using a squeegee, the alkyd melamine painted plate
(This test panel industry Co., Ltd.). Next, after leaving this at room temperature for 72 hours, 40
Immersed in water at ℃ for 162 hours.
After a predetermined time (1 minute, 72 hours)
Using M-50, measure 180 ° peel adhesion
Was. However, the pulling speed was 200 mm / min. (6) Swelling test After cutting the test piece to 60 x 60 mm and peeling off the release paper,
Using a squeegee to paint alkamine melamine (Nippon Tes
(Made by Topanel Kogyo Co., Ltd.). Then, after leaving this at room temperature for 30 minutes,
Resin (manufactured by NOF CORPORATION; Bellcoat No. 5100k)
100 parts by weight of rear HK and a solvent (manufactured by NOF Corporation;
Bellcoat No. 5100 Thinner No. 4) 30 parts by weight
After applying the mixed solution and leaving it at room temperature for 12 minutes, 70 ° C. × 10
Then dry at 150 ° C for 15 minutes
Perform surface coating and evaluate the surface condition after 24 hours.
Was. The evaluation was performed in three levels of 〇, × and Δ. 〇: There is almost no change in the surface state. Δ... 30 blisters having a diameter of 0.5 mm or less
It is recognized as individual. Or the end of the test piece is turned up by 1-2mm
You. × ··························································
Alternatively, the end of the test piece is turned up by 2 mm or more. (7) Gasoline resistance test After cutting the test piece to 60 x 60 mm and peeling off the release paper,
Using a squeegee to paint alkamine melamine (Nippon Tes
(Made by Topanel Kogyo Co., Ltd.). Next, after leaving this at room temperature for 72 hours,
Immerse in Sorin for 1 hour, take out and dry, evaluate the surface condition
Valued. The evaluation was performed in three grades of 〇, ×, and Δ. 〇: There is almost no change in the surface state. Δ: 30 blisters having a diameter of 0.5 mm or less
It is recognized as individual. Or the end of the test piece is turned up by 1-2mm
You. × ····························································
Or the end of the test piece is turned up from Δ. (8) Surface condition after crimping Observe the surface roughness and smoothness with the naked eye. Δ: Smooth and good Δ: poor smoothness, but outstanding
No rough surface unevenness. X: Roughness on the rough surface. (9) Average pressure-sensitive adhesive thickness, thickness variation width Create a part that does not spray non-adhesive solid particles, and
Adhesive layer thickness of 40μ (thickness accuracy ± 0.5μ or less)
20mm × 20 transferred to vinyl chloride film
Make a 0 mm sample. 10 points at almost equal intervals in the length direction of this sample
Thickness measured by dial gauge specified in JISB7509
Is measured. Adhesive with average value of 10 points of adhesive thickness
The agent average thickness was used. Next, a test piece similar to the above was placed on a slide glass.
Paste, surface roughness measuring instrument (Kosaka Seisakusho Co., Ltd .;
(Based on JIS B0651)
Using the skid as a guide, measure based on the track
A stylus with a stylus radius of a specified size
The trajectory of the stylus movement obtained in each case, that is, the "section curve"
Is measured. The skid is R40mm (measurement direction) x R2mm
Use the one made of Sapphire. From this sectional curve, JIS
  Obtain the value of Rmax (maximum height) based on B0601,
And the thickness variation width. (10) Percentage of non-adhesive solid particles remaining after crushing Test: Release paper (trade name QKC-105P, manufactured by Oji Chemical Co., Ltd.)
SG-Q), about 1 million solid particles to be tested /
100cm^TwoSpread evenly at the rate of The release paper was heated to about 100 ° C. using an infrared heater.
To a 40mm diameter, 330mm long steamer
Roll while pressing it with a weight of 20 kg.
Embed body particles in release paper. Next, an acrylic pressure-sensitive adhesive is placed on the release paper.
(PE-121 manufactured by Nippon Carbide Industry Co., Ltd.) 100
Parts by weight and a crosslinking agent (trade name of Nippon Polyurethane Industry Co., Ltd.
Lonate L) 1 part by weight of the mixed solution is applied, dried and thickened.
An adhesive layer of about 35 μm is formed. Further, on this pressure-sensitive adhesive layer, a vinyl chloride-based transparent
Mei-Film (trade name of HS, manufactured by Nippon Carbide Industry Co., Ltd.)
Paint 5080) to form a pressure-sensitive adhesive sheet.
You. Next, the release paper of the pressure-sensitive adhesive sheet was peeled off.
And lightly affix it to a glass plate. Then 1.5mm thick
, 95mm wide polypropylene plastic key
Press tightly with a pressure of about 5 kg. After that, the solid particles were observed with a microscope,
Observe the destruction state and determine the residual ratio of unbroken particles.
Confuse. In the present invention, the residual ratio is 80% or more, especially
Preferably 90% or more, more preferably 100% solids
Particles can be used very well. Embodiment 1 Polymethyl methacrylate prepared by suspension polymerization
Classified rimer beads (weight average molecular weight about 300,000)
Spherical solid particles with a mean particle size of about 30μ (non-adhesive solid
Particles) with release paper (peelable support layer) (trade name, manufactured by Oji Chemical Industries, Ltd.)
Spread evenly over the product name (QKC-105PSG-Q)
Was. Release paper was heated to about 100 ° C. using an infrared heater.
Heated to 40mm diameter, 330mm length steel under heating
Press the roll while applying a load of 20kg and rotate it.
Then, the polymer beads were embedded in release paper. Embedding amount
(Projection amount of solid particles) is about 14μ,
The surface coverage was about 8%. Next, an acrylic pressure-sensitive adhesive is placed on the release paper.
(PE-121 manufactured by Nippon Carbide Industry Co., Ltd.) 100
Parts by weight and a crosslinking agent (trade name of Nippon Polyurethane Industry Co., Ltd.
Lonate L) 1 part by weight of the mixed solution is applied, dried and thickened.
A pressure-sensitive adhesive layer of about 35 μm was formed. Adhesive layer thickness
The variation width was 10 μ. Further, a base material layer is formed on the adhesive layer.
Vinyl chloride film (manufactured by Nippon Carbide Industry Co., Ltd.)
Name HS Paint 5010)
I made a card. Table 1 shows the physical properties of the obtained pressure-sensitive adhesive sheet.
As shown, it is free to move on the adherend and after crimping
The short-term adhesive strength expression rate is fast, the final
Includes durability such as water resistance, blister resistance, gasoline resistance, etc.
Excellent surface condition after crimping
An adhesive sheet which can sufficiently achieve the object of the present invention.
Was. Comparative Examples 1 and 2 Average particle diameter 63μ (Comparative Example 1), average particle diameter 8μ (Comparative Example
Pressure-sensitive welding was performed in the same manner as in Example 1 except that 2) was used.
I made a seat. As shown in Table 1, the obtained sheets were compared with each other.
In Example 1, the surface condition of the sheet after crimping was very poor
A pressure-sensitive adhesive sheet with poor swelling and gasoline resistance
Was. In Comparative Example 2, the mobility on the adherend
The object of the present invention, which is difficult, is not satisfied. Embodiment 2 Average obtained by classification instead of polymer beads
Glass microballoon with a particle size of 28μ (crushing residual rate 10
0%) was used in the same manner as in Example 1 except that
A pressure-bonded sheet was made. As shown in Table 1, the obtained sheet
It was enough to satisfy the purpose of Ming. Embodiment 3 Average particles obtained by classification instead of polymer beads
Using glass beads with a diameter of 33μ (crushing residual rate 100%)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except for
I got it. The obtained sheet is as shown in Table 1
It was enough to satisfy the purpose of Ming. Comparative Example 3 Adjust the load of steel roll and embed polymer beads
Except that the only amount was about 6 μm, the sensitivity was the same as in Example 1.
A pressure-bonded sheet was made. The obtained sheet is difficult to move on the adherend.
The present invention does not satisfy the object of the present invention. Comparative Example 4 The average particle size of about 50μ obtained by dispersion is easily damaged,
All examples except for the use of a crushable glass balloon
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 2. The obtained sheet was crimped as shown in Table 1.
Poor surface condition afterwards, durability such as blister resistance and gasoline resistance
However, the object of the present invention was not satisfied. Examples 4 and 5 Average particle size of about 22μ (Example 4), about 39μ (Example 5)
Same as Example 1 except for using polymer beads
To produce a pressure-sensitive adhesive sheet. The obtained sheet is as shown in Table 1. Examples 4 and 5; adhesive sheets capable of sufficiently achieving the object of the present invention.
I was in a party. Embodiment 6 Adjust the load of steel roll and embed polymer beads
Except that the amount was about 8 μm,
A pressure-bonded sheet was made. The obtained sheet was prepared according to the present invention as shown in Table 1.
This was an adhesive that could fully achieve the purpose of (1). Embodiments 7 and 8 Change the amount of polymer beads sprayed to increase the solid particle surface coverage
All except for about 5% (Example 8) and about 18% (Example 9)
Thus, a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1. As shown in Table 1, the obtained sheet
It was an adhesive sheet that could sufficiently achieve the objectives of the present invention. Comparative Example 5 Fine particle calcium carbonate with an average particle size of about 0.6μ (Product name "NCC # 410" manufactured by Nitto Powder Chemical Co., Ltd.)
With a release paper (trade name “KOM-1” manufactured by Shikoku Paper Co., Ltd.)
1 "). Disperse the carbon dioxide on release paper.
Spread excess lucium and use a brush to spread it evenly over the surface
After dispersing, scrape off excess with scraper
This was achieved by: At this time, the distribution of calcium carbonate
The amount is about 1g / m^TwoIt was. Next, an acrylic pressure-sensitive adhesive is placed on the release paper.
(PE-121 manufactured by Nippon Carbide Industry Co., Ltd.) 100
Parts by weight and a crosslinking agent (trade name of Nippon Polyurethane Industry Co., Ltd.
Lonate L) 1 part by weight of the mixed solution is applied, dried and thickened.
A pressure-sensitive adhesive layer of about 35 μm was formed. Adhesive layer thickness
The variation width was 10 μ. In addition, on this adhesive layer
Vinyl chloride film (Nippon Carbide
Laminated with the trade name “HIS PAINT 5010” manufactured by Sangyo Co., Ltd.
A pressure-sensitive adhesive sheet was made. As shown in Table 1, the obtained sheets were short-term.
Adhesive sheet with very poor adhesive strength
I was in a party. [0119] [Table 1][0120] [Table 2]

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

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-58-13682 (JP, A) JP-A-59-129853 (JP, U) JP-B-44-3120 (JP, B1) (58) Field (Int.Cl. ⁶ , DB name) C09J 7/02 B32B 7/12 C09J 11/00

Claims (1)

(57) [Claims] (A) A non-adhesive solid particle having an average particle size of 10 to 40 μ is uniformly dispersed on one surface of the adhesive layer, and at least about half of the solid particles have an average particle size of pasting if and protrudes from the surface of the adhesive layer solid particles are hollow particles at least a height which corresponds to about 1/4 of the
Yotsute crimping pressure on adherend are those hollow particles walls are not crushed, and pressure-sensitive adhesive layer coverage of about 3 to about 30% with respect to the surface area of the adhesive layer of the non-adhesive solid particles, ( B) a releasable support layer having a surface dent that comes into contact with a portion of the non-adhesive solid particles protruding from the surface of the adhesive layer and closely complements the protruding portion; and (C) a pressure-sensitive adhesive layer. A pressure-sensitive adhesive sheet-like structure, comprising: a base material layer laminated on a surface having no dispersion layer of the non-adhesive solid particles. 2. The structure according to claim 1, which is a pressure-sensitive adhesive sheet-like structure for marking. 3. 3. The structure of claim 1 wherein the non-adhesive solid particles have an average particle size of about 20 to about 40 microns. 4. The structure of any of claims 1 to 3, wherein said coverage is from about 5 to about 20%. 5. At least about half of the non-adhesive solid particles are at least about 7
2. A projection projecting from the surface of the adhesive layer at a height of μ.
The structure according to any one of claims 1 to 4. 6. 6. The method of claim 1, wherein at least about 50% by weight of the non-adhesive solid particles fall within a size range of ± 5 μ of the average particle size, and at least about 90% by weight fall within a size range of ± 8 μ of the average particle size. The structure described in Crab.