JPH0329834B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a pressure-sensitive adhesive sheet that utilizes the characteristics of solvent-suspended adhesive granules. More specifically, we will introduce a solvent-suspended adhesive granule for making a pressure-sensitive adhesive sheet that is extremely unlikely to transfer (adhesive residue) to the adherend when the pressure-sensitive adhesive sheet is attached and then peeled off. This relates to pressure-sensitive adhesive sheets made using human bodies. [Prior Art] In recent years, adhesive granules are lined up and adhered to the surface of a sheet-like substrate, such as paper, and the side of the paper where the adhesive granules are lined up is pasted to another adhered surface, and then peeled off. There are office supplies on the market that can be repeatedly attached and then peeled off again. This utilizes the characteristics of sticky particles with a particle diameter of several microns to several hundred microns. That is, since the granular adhesive resin is lined up on the surface of the paper like the suction cups of an octopus, when another surface comes into contact with that surface, adhesion occurs at countless points and both surfaces are bonded together. Then, when both sides are peeled off, the adhesive particles are peeled off from the point-adhesive area, and the adhesive particles are exposed as they are, and can be reattached to the adherend. Such paper that can be repeatedly attached and peeled off can be obtained by applying a dispersion of adhesive granules to paper. In this case, it is preferable that adhesive particles having an average particle diameter of several microns to several hundred microns are tightly arranged on the surface of the paper. Further, it is preferable that the shape of the adhesive granules is as perfectly spherical as possible. If the paper is crushed like a rugby ball, it becomes close to surface bonding, and the adhesive force becomes strong, causing paper layer delamination (paper tearing). Further, it is preferable that the particle size distribution is as narrow as possible. This is because only large particles selectively participate in adhesion, resulting in weak adhesion and impractical use. By the way, this type of adhesive granules that have been known in the past are manufactured by suspension polymerizing acrylic monomers in water using an oil-soluble polymerization initiator. Suspensions pose no problems when applied to non-water-absorbing substrates, but when applied directly to paper, the paper curls due to moisture, significantly reducing its commercial value. The solvent water was mixed with toluene, ethyl acetate, 1,
Substitute with a solvent such as 1,1-trichloroethane,
It is applied to paper as a solvent-based dispersion. Furthermore, by using a solvent-based material, there is an advantage that the drying speed is faster than that of a water-based material, and mechanical stability is extremely good. [Problems to be Solved by the Invention] However, with conventionally used resins, even if a poor solvent with low affinity is selected, the resin swells to a greater or lesser extent and the sticky granules fuse together. Since it shows a tendency to form a film, surface adhesion occurs with other adhered surfaces, and when peeled off, paper layer peeling occurs, resulting in poor re-adhesion. The present inventors have considered internally crosslinking the adhesive resin for the purpose of making it difficult to swell in solvents and imparting appropriate adhesive performance. Certain internal crosslinking monomers, tetraallyloxyethane, triallyl cyanurate, and triallyl isocyanurate, are highly reactive and uniformly internally crosslink the acrylic polymer, making it possible to use water as a suspension medium as a solvent. To obtain an aqueous suspension of perfectly spherical adhesive granules with uniform grains that hardly swell or dissolve even when substituted with solvent, and to provide a solvent-suspended adhesive granule and a pressure-sensitive adhesive sheet using the same. He invented the patent application No. 59-271305 (Japanese Unexamined Patent Publication No. 1982-
148278) and Japanese Patent Application No. 1983-271306 (Japanese Patent Application No. 148278)
-148279). This invention is an invention that exhibits extremely excellent adhesiveness. As a result of further research into this invention, the present inventors succeeded in further increasing the bond between the adhesive granules and the base sheet. Specifically, in order to firmly bond the adhesive granules to the base sheet, we investigated the use of various binders such as solvent-based resins, water-soluble resins, and water-dispersed resins, and found that a binder made of a polymer containing styrene was used. By filling the spaces between the adhesive particles arranged on the base sheet and bonding the adhesive particles to each other, the adhesive particles and the base sheet are bonded together. He succeeded in making it bigger. [Means for Solving the Problems] That is, the present invention provides 2 to 10 parts by weight of (a) methyl acrylate and/or styrene and/or methacrylate of an alcohol having 1 to 5 carbon atoms, disposed on the surface of a sheet-like substrate. , (b) 98 to 90 parts by weight of acrylate of alcohol having 2 to 12 carbon atoms and/or methacrylate of alcohol having 6 to 12 carbon atoms, (c) 0.1 to 2.0 parts by weight of maleic anhydride, (d) tetraallyloxyethane , triallyl cyanurate,
By copolymerizing 0.05 to 1.0 parts by weight of one or more selected from triallylisocyanurate, internally crosslinked adhesive granules with a particle size of 5 to 200 microns are filled between the adhesive granules. A styrene-containing polymer having a styrene content of 5 to 70% by weight, which binds the adhesive granules to the base sheet, and has a particle size of 0.02 to 3 microns, and which binds the adhesive granules to the base sheet. It is a pressure-sensitive adhesive sheet consisting of ~20% by weight of binder. [Operations and Examples] Glass transition temperature (Tg) of the homopolymer of methyl acrylate shown in section (a) used in the present invention
is 8℃. In addition, methacrylates of alcohols having 1 to 5 carbon atoms include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and pentyl methacrylate.
Each homopolymer Tg is 105
℃, 66℃, 35℃, 21℃, 10℃. Furthermore, the Tg of styrene homopolymer is 100°C. That is, all of the monomers shown in item (a) have a homopolymer Tg of 0°C or higher and around 100°C. In addition, the acrylates of alcohols having 2 to 12 carbon atoms and/or the methacrylates of alcohols having 6 to 12 carbon atoms shown in item (b) are ethyl acrylate (Tg=-22℃), butyl acrylate (Tg
= -52℃), 2-ethylhexyl acrylate (Tg = -70℃), hexyl methacrylate (Tg =
-5°C), all of the monomers shown in item (b) have a homopolymer Tg of less than 0°C, minus several tens of degrees. 2 to 10 parts by weight of the monomer in section (a) and 98 to 98 parts by weight of the monomer in section (b)
The reason for using 90 parts by weight is to essentially impart adhesive properties to the resulting resin. Adhesive resin cannot be obtained outside this range. The maleic anhydride in item (c) is used in an amount of 0.1 to 2.0 parts by weight in order to carry out the polymerization reaction smoothly and obtain a stable suspension. Tetraallyloxyethane in paragraph (d) is It is shown by the structural formula, and triallyl cyanurate is It is shown by the structural formula, and triallylisocyanurate is It is shown by the structural formula: Compared to ordinary internal crosslinking agents, it has 3 polymerizable functional groups.
It is thought that the reactivity is extremely high, and that the internal crosslinking occurs uniformly. These may be used alone or in combination. The appropriate amount to use is 0.05 to 1.0 parts by weight.
If it is less than 0.05 part by weight, the internal crosslinking effect will be small, resulting in insufficient solvent resistance, and if it is more than 1.0 part by weight, crosslinking will proceed too much and adhesive performance will deteriorate, which is not preferable. In the present invention, other monomers may be used in amounts that do not impair adhesive performance, such as N-methylolacrylamide, acrylonitrile, ethylene, vinyl chloride,
Vinyl acetate, Beoba (trade name of vinyl ester manufactured by Ciel Chemical Co., Ltd.), etc. can be used in combination in an amount of 10 parts by weight or less. As a method for manufacturing the adhesive granules used in the present invention, a known suspension polymerization method is used. Examples include a polymerization method by bulk charging, a monomer dropwise polymerization method, and an emulsified monomer dropwise polymerization method. As a polymerization initiator, benzoyl peroxide, azobisisobutyronitrile, tert-butyl peroxybenzoate, cumene hydroperoxide,
Diisopropyl peroxydicarbonate, di-
n-propyl peroxydicarbonate, di(2
-ethoxyethyl) peroxydicarbonate,
tert-butyl peroxyneodecanoate, tert
-butyl peroxypivalate, di(3,5,5
-trimethylhexanoyl) peroxide, dilauroyl peroxide, dipropionyl peroxide, diacetyl peroxide, and the like. Suspension stabilizers include polyvinyl alcohol,
Water-soluble polymers such as hydroxyethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, carboxymethylcellulose, and carboxy-modified polyacrylamide are used. Further, an anionic surfactant and a nonionic surfactant can be used in combination. In particular, in order to stably produce an aqueous suspension, it is preferable to use a large amount of anionic surfactant. In this way, an aqueous suspension of sticky particles is obtained, the particle size of which is suitably in the range of 5 microns to 200 microns. Next, the binder used in the present invention has a particle size of
0.02-3 microns, styrene content 5-70% by weight
is a styrene-containing copolymer. This is a binder for bonding internally crosslinked adhesive particles with a particle diameter of 5 to 200 microns to a substrate, but in order to manufacture this binder, α, β
Olefin monomers, such as (meth) methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, etc.
One or more selected from acrylate, vinyl acetate, vinyl ester such as Beoba (a product of Ciel Chemical Co., Ltd.), ethylene, vinyl chloride, acrylonitrile, butadiene, etc.; N-
30 to 95% by weight of a mixed monomer appropriately blended with functional or crosslinkable monomers such as methylol acrylamide, hydroxyalkyl acrylate, glycidyl methacrylate, divinylbenzene, triallylisocyanurate, and tetraallyloxyethane, and styrene. When polymerization is carried out using a known polymerization method using 5 to 70% by weight, it is obtained in an emulsified state in water. Known polymerization methods include, for example, a polymerization method by bulk charging, a monomer dropwise polymerization method, an emulsified monomer dropwise polymerization method, and a multistage polymerization method. As the polymerization initiator, the aforementioned oil-soluble initiators can also be used, but usually potassium persulfate,
Water-soluble initiators such as ammonium persulfate and hydrogen peroxide, and combinations of peroxides and reducing agents, such as redox initiators consisting of ammonium persulfate and sodium sulfite, are used. Examples of emulsifiers include anionic surfactants such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene nonyl phenyl ether sulfate, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene. Nonionic surfactants such as block copolymers of polyoxypropylene and polyoxypropylene, and water-soluble polymeric protective colloids such as polyvinyl alcohol and hydroxyethyl cellulose are used as appropriate. The particle size of the emulsion polymer obtained by the above method is
It is about 3 microns to about 0.02 microns, and in the present invention, those within this range are used,
Among them, those with a fine particle size of about 0.1 micron to about 0.02 micron have an extremely excellent binder effect. In order to obtain a polymer emulsion having such a fine particle size, a method disclosed in Japanese Patent Application Laid-Open No. 72795/1983 is used. That is, the mixed monomers or mixed monomer emulsion described above are simultaneously added to an aqueous liquid containing an anionic emulsifier together with a polymerization initiator to carry out emulsion polymerization,
This can be obtained by controlling the final solid content of the polymer emulsion so that it does not exceed 45% by weight. It can also be obtained by preparing a polymer emulsion into which an unsaturated carboxylic acid has been introduced, and neutralizing part or all of the acid groups with an alkali. If the styrene content in the styrene-containing copolymer that is the binder is less than 5% by weight, it will be solubilized in alcohol, resulting in a large flow-off loss in the next step of pouring it into methanol and condensing it. Also,
If it exceeds 70% by weight, the resin becomes too hard and the adhesive strength decreases, resulting in poor bonding effect between the adhesive granules and the base sheet. The solvent-suspended adhesive granule dispersion used for producing the pressure-sensitive adhesive sheet of the present invention is a suspension of internally crosslinked adhesive granules with a particle size of 5 to 200 microns obtained as described above, and styrene. Content rate 5-70% by weight,
Add an emulsion of a styrene-containing polymer with a particle size of 0.02 to 3 microns to 100 parts by weight of adhesive granules at a solid content of 20 parts by weight.
Mix and disperse uniformly in a proportion of ~2 parts by weight. The aqueous dispersion obtained is allowed to stand, centrifuged, or poured into methanol to agglomerate it, taken out, and dispersed in an organic solvent such as toluene, ethyl acetate, or 1,1,1-trichloroethane. The amount of styrene-containing polymer used is 2
If the amount is less than 20 parts by weight, no binding effect will be obtained, and if it is used in excess of 20 parts by weight, the adhesive particles will be coated, resulting in loss of tackiness. In addition, in order to produce a pressure-sensitive adhesive sheet that can be used repeatedly, it is necessary to coat the surface of a sheet-like substrate such as paper, cloth, nonwoven fabric, or film with a barcoder, roll coater, spray, screen printing, etc.
Approximately 2 g/m ² to 30 g/m ² of solid content may be applied. Further, if necessary, by disposing adhesive granules on a substrate coated with an anchor coating agent, a pressure-sensitive adhesive sheet with less adhesive residue can be obtained. The anchor coating agents used to form the anchor layer include polyurethane, melamine,
Aqueous solutions, aqueous dispersions, Apply in the form of a solvent solution and cure by heating, or use adhesive polymers such as vinyl acetate-acrylic acid ester copolymer, acrylic copolymer, natural rubber type, synthetic rubber type, etc. in the same condition as above. It is applied and dried to form a film. The anchor coating agent is used to improve the anchoring properties between the sheet-like substrate and the binder, or between the sheet-like substrate and the adhesive particles. Therefore, when the sheet-like substrate is difficult to adhere to, such as a plastic sheet, it is particularly effectively used to improve the adhesion of the surface. Applying the solvent-suspended adhesive granule dispersion of the present invention to a sheet-like substrate and arranging the adhesive granules on the surface of the substrate,
A pressure-sensitive adhesive sheet in which the adhesive particles are filled and bonded together by the binder contained therein, and the adhesive particles are bonded to the substrate has a property that the adhesive particles are not easily swollen by solvents and have a moderate It has excellent rigidity and well-balanced adhesive performance, so
When it is pasted on an adherend and peeled off, there is no so-called paper tearing phenomenon in which the adherend is torn off, and
Since the adhesive granules are firmly bonded to the base sheet, there is no so-called adhesive residue phenomenon in which the adhesive granules migrate toward the adherend, and furthermore, it is possible to repeat adhesion and peeling an extremely large number of times. It has excellent effects. This is because (1) the copolymer that forms the sticky granules is internally crosslinked using a specific monomer and a specific crosslinking agent, so it has little swelling property against solvents and has a well-balanced structure. (2) It contains a styrene-containing polymer as a binder, which has a smaller particle size than adhesive granules.
This firmly binds the adhesive granules onto the substrate, and the styrene-containing polymer obtained by this emulsion polymerization has excellent surface chemical affinity with the adhesive granules also obtained in an aqueous system. (3) In addition, the styrene-containing polymer produced by this emulsion polymerization has the following properties:
Since it is a high molecular weight material, it has a high cohesive force as a binder and contributes to the effect of firmly bonding the adhesive particles to the base sheet. Even if it is a molecular polymer, the styrenic polymer itself has a high affinity for general solvents, so when it is dispersed in a solvent, it exists in a semi-dissolved or swollen uniformly distributed state, and after drying, it remains uniformly distributed. (5) In order to make a solvent-suspended adhesive granule dispersion, it is necessary to mix the aqueous dispersion as described above. It is coagulated and dehydrated with alcohol, but this styrene-containing polymer has excellent alcohol resistance, so it is coagulated and dehydrated without dissolving, and can be concentrated with a higher yield than acrylic polymers, which also contributes to the effect of increasing bonding strength. This is thought to be due to the effects of Next, the present invention will be explained with reference to production examples, examples, and comparative examples. Production example 1 (Ingredients) (Parts by weight) Methyl methacrylate 15 2-ethylhexyl acrylate 405 Triallylisocyanurate 1.0 Maleic anhydride 4.0 Sodium polyacrylate 16 (degree of polymerization 3000-7000) Water 600 Azoisobutyronitrile 2.0 Dodecylbenzene Sodium Sulfonate A polymerization reaction was carried out using at least 20 components to obtain an aqueous suspension of sticky granules at least 80% of which had a particle size of 80 to 100 microns. Production example 2 (Ingredients) (Parts by weight) Styrene 12 Butyl acrylate 190 2-ethylhexyl acrylate 200 Tetraallyloxyethane 1.0 Maleic anhydride 5 Hydroxyethylcellulose 20 Water 600 Benzoyl peroxide 2.0 Sodium dodecylbenzenesulfonate 20 Using the above ingredients The polymerization reaction was carried out to obtain an aqueous suspension of sticky granules at least 80% of which had a particle size of 15 to 50 microns. Production example 3 (Ingredients) (Parts by weight) Methyl methacrylate 32 Isononyl acrylate 400 Triallyl cyanurate 3.7 Maleic anhydride 1.5 Hydroxyethyl cellulose 15 Water 600 Benzoyl peroxide 2.0 Sodium dodecylbenzenesulfonate 15 Dialkyl sulfosuccinic acid 7 70% sodium aqueous solution A polymerization reaction was carried out using the above components to obtain an aqueous suspension of sticky particles in which at least 80% had a particle size of 45 to 70 microns. Production example 4 (Components) (Parts by weight) Methyl methacrylate 32 Isononyl acrylate 400 Tetraallyloxyethane 2 Maleic anhydride 1.5 Polyvinyl alcohol 15 Water 600 Benzoyl peroxide 2.0 Sodium dodecylbenzenesulfonate 20 Polymerization reaction using the above components An aqueous suspension of sticky granules of at least 80% particle size from 35 to 60 microns was obtained. Production Example 5 (Styrene-containing polymer emulsion) (Ingredients) (Parts by weight) Styrene 200 2-ethylhexyl acrylate 134 Acrylic acid 10 Polyoxyethylene nonylphenyl 5 Ether sulfate (30%) Polyoxyethylene nonylphenyl 5 Ether (EO.10-12 mol%) Water 670 Ammonium persulfate 2 Perform a polymerization reaction using the above ingredients to reduce the pH to 8.
-9 to obtain an emulsion with an average particle size of 0.9 microns. Production Example 6 (Styrene-containing polymer emulsion) (Ingredients) (Parts by weight) Styrene 200 Butyl acrylate 134 Acrylamide 4.5 Methacrylic acid 12 Sec-Alkanesulfonic acid 18 Sodium (C ₁₂ - _{C 16} ) Polyoxyethylene nonyl phenyl 7 Ether (EO.10-12 mol%) Water 670 Potassium persulfate 2 Perform a polymerization reaction using the above ingredients to reduce the pH to 8.
-9 to obtain an emulsion with an average particle size of 0.036 microns. Production Example 7 (Styrene-containing polymer emulsion) (Ingredients) (Parts by weight) Styrene 23.2 Ethyl acrylate 207.0 2-hydroxyethyl acrylate 14 Acrylonitrile 14 Methacrylic acid 21 Trichlorobromomethane 2.8 Water 301.5 Sodium lauryl sulfate 3.3 Ammonium persulfate 1.5 Above components An emulsion was obtained by carrying out a polymerization reaction. To this emulsion were added 245 parts by weight of water and 114 parts by weight of 5.6% aqueous ammonia and aged for 1 hour to obtain an emulsion with an average particle size of 0.069 microns. Production Example 8 (Styrene-rich polymer emulsion) (Ingredients) (Parts by weight) Styrene 268 Butyl acrylate 66 Acrylamide 4.5 Methacrylic acid 12 Sec-alkanesulfonic acid 18 Sodium (C ₁₂ - C ₁₆ ) Polyoxyethylene nonyl phenyl 7 Ether (EO.10-12 mol%) Water 670 Potassium persulfate 2 Perform a polymerization reaction using the above ingredients to bring the pH to 8
An emulsion with an average particle diameter of 0.04 microns and a styrene content of 76.4% was obtained. Production Example 9 (Acrylic polymer emulsion) (Ingredients) (Parts by weight) Methyl methacrylate 200 2-ethylhexyl acrylate 134 Acrylic acid 10 Polyoxyethylene nonylphenyl 5 Ether sulfate (30%) Polyoxyethylene nonylphenyl 5 Ether (EO.10-12 mol%) Water 670 Ammonium persulfate 2 Perform a polymerization reaction using the above ingredients to reduce the pH to 8.
-9 to obtain an emulsion with an average particle size of 0.83 microns. Production example 10 (Acrylic polymer emulsion) (Ingredients) (Parts by weight) Methyl methacrylate 200 Butyl acrylate 134 Acrylamide 4.5 Methacrylic acid 12 Sec-alkanesulfonic acid 18 Sodium (C ₁₂ - C ₁₆ ) Polyoxyethylene nonyl phenyl 7 Ether (EO.10-12 mol%) Water 670 Potassium persulfate 2 Perform a polymerization reaction using the above ingredients to reduce the pH to 8.
-9 to obtain an emulsion with an average particle size of 0.04 microns. Examples 1 to 8, Comparative Examples 1 to 6 The adhesive granule dispersions obtained in Production Examples 1 to 4, the binders obtained in Production Examples 5 to 7, and the comparative binders obtained in Production Examples 8 to 10 were Mix in the ratio shown in the table, put this into methanol to coagulate, wash, take out the lumpy resin, add it to the solvent toluene, mix and stir to redisperse, and make a solvent suspension type with a concentration of about 25%. A sticky granule dispersion was prepared. Next, coat it on high-quality paper (55K) using a tabletop coater so that the dry weight is 7 to 9 g/ ^m2 , and heat it at 40℃.
A pressure-sensitive adhesive sheet was obtained by drying with hot air for 1 minute. Example 9 Approximately 1.5 g/m ² of Coponyl 4081 (50% methanol solution of acrylic/vinyl acetate copolymer resin manufactured by Nippon Gosei Kagyo Co., Ltd.) was applied as an anchor coating agent to high-quality paper (55K). A dry substrate was prepared, and the solvent-suspended adhesive granule dispersion with a concentration of about 25% used in Example 1 was applied to this substrate using a tabletop coater to give a dry weight of 7 to 9 g/g. Apply so that it becomes m ² ,
A pressure-sensitive adhesive sheet was obtained by drying with hot air at 40°C for 1 minute. Comparative Test The pressure-sensitive adhesive sheets obtained in Examples 1 to 9 and Comparative Examples 1 to 6 were tested for adhesive residue, degree of swelling, number of repeated adhesion, paper removal, adhesive strength, and tack. The test results were as shown in Table 1. (Test method) Adhesive residue test Pressure-sensitive adhesive sheet test piece (glue surface width 20 mm, length
100mm) and 2Kg specified by JIS Z 0237.
After 2 hours of pressure bonding with a rubber roller, it was peeled off at a peeling speed of 30 m/min, and the transferability of the adhesive particles to the mirror coated paper surface was measured by weight (n = 3) and expressed as the transfer rate (weight %). . Degree of swelling of particles (rate of change) Approximately 30 g/ ^m2 of the above solvent-based suspension was applied to a polyester film with a thickness of 38 microns, and the rate of change in particle diameter was determined immediately after application and after 30 minutes at room temperature. And so. Rate of change = Particle diameter immediately after application/Particle diameter after 30 minutes However, the particle diameter was measured using a microscopic photograph. Number of repeated adhesion/peeling The adhesion/peeling was repeated on the printed newspaper surface, and the number of times until it stopped adhering was determined. We also checked for print peeling (paper tearing phenomenon). Adhesive Physical Properties Adhesive force (g/25 mm) and tack (ball No.) were measured according to JIS Z 0237.

[Table] From the results in Table 1, the solvent-suspended adhesive granules obtained by the present invention have a swelling degree (rate of change) of 1.8 to 2.3, which is extremely normal. In a solvent solution, sticky granules usually swell to about twice their diameter and about 8 times their volume, and when the solvent evaporates while maintaining their spherical shape when applied to a substrate, they contract and become approximately 8 times as large in diameter. It becomes 1/2. In other words, the rate of change is 2. However,
When applied to a substrate, if it loses its shape or flows, its diameter, when viewed from above, will be larger than 1/2 of the original diameter, and sometimes even larger than the original diameter. If this happens, there will be no point adhesion and this will cause paper tearing. Moreover, the number of times of repeated peeling is also reduced. In the present application, since the sticky granules are made using a special internal crosslinking agent, the degree of swelling (rate of change) in the comparative example is 1.7 to 2.2, which is extremely normal. Therefore, no paper-picking phenomenon was observed in either case. The pressure-sensitive adhesive sheet obtained according to the present invention had very little adhesive residue and exhibited a large number of repeated peelings of 40 times or more. Also, the adhesive strength is 87~110g/25
It showed an appropriate value of mm, and the tack (ball No.) also showed an appropriate value of 5 to 6. On the other hand, in Comparative Example 1, an emulsion with a high styrene content was added as a binder, and in Comparative Example 4, a large amount of a styrene-containing emulsion was added, so adhesive residue, swelling degree, and paper peeling were good, but adhesive The force decreased, and both the tack and the number of repeated peelings showed low values. In Comparative Examples 2 and 3, acrylic emulsion was used as a binder, so when it was poured into methanol to coagulate and wash, it was dissolved in methanol and washed away.As in Comparative Example 5, when a small amount of styrene-containing emulsion was used. Also, similar to Comparative Example 6 in which no binder was used, extremely large adhesive residue was observed.

Claims (1)

[Scope of Claims] 1. (a) 2 to 10 parts by weight of methyl acrylate and/or methacrylate of styrene and/or alcohol having 1 to 5 carbon atoms disposed on the surface of the sheet-like substrate (b) 2 to 12 carbon atoms Acrylate of alcohol and/or methacrylate of alcohol having 6 to 12 carbon atoms 98 to 90 parts by weight (c) Maleic anhydride 0.1 to 2.0 parts by weight (d) From tetraallyloxyethane, triallyl cyanurate, triallyl isocyanurate Internally crosslinked particles with a diameter of 5 to 200 obtained by copolymerizing 0.05 to 1.0 parts by weight of one or more selected types
A styrene-containing polymer having a styrene content of 5 to 70% by weight, which fills and bonds between micron adhesive particles and binds the adhesive particles to a base sheet, and has a particle size of 5 to 70% by weight. A pressure-sensitive adhesive sheet having a particle size of 0.02 to 3 microns and comprising a binder in an amount of 2 to 20% by weight based on the adhesive granules. 2. An anchor layer provided on the surface of a sheet-like substrate, and (a) methyl acrylate and/or carbon number 1 provided on the anchor layer.
-5 alcohol methacrylate and/or styrene 2-10 parts by weight (b) C2-12 alcohol acrylate and/or C6-12 alcohol methacrylate 98-90 parts by weight (c) Maleic anhydride 0.1 to 2.0 parts by weight (d) Internally crosslinked particles with a diameter of 5 to 5, obtained by copolymerizing 0.05 to 1.0 parts by weight of one or more selected from tetraallyloxyethane, triallyl cyanurate, and triallyl isocyanurate. A styrene-containing polymer having a styrene content of 5 to 70% by weight, which fills and binds between the adhesive particles of 20 microns and binds the adhesive particles to the base sheet, and which has a particle size of 5 to 70% by weight. 0.02
~3 microns, and 2~3 microns for the adhesive particles.
A pressure-sensitive adhesive sheet consisting of a binder in an amount of 20% by weight.