JP2007254658A - Heat and pressure sensitive adhesive and heat and pressure sensitive adhesive sheet, and method of adhering the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat and pressure-sensitive adhesive and a heat and pressure sensitive adhesive sheet capable of easily extracting the air involved in between an adhesive layer and an adherend when pasting, pasting finely and effectively, and being produced with high productivity. <P>SOLUTION: The heat and pressure sensitive adhesive comprises a synthetic organic polymer (A) having a glass transition temperature of from -45°C to +20°C, and a resin (B) having a softening point of 70-180°C, and is a nonaqueous liquid wherein the constituent (B) is dispersed in a continuous layer of the constituent (A), the organic polymer (A) being preferably one member or a mixture of at least two members selected from the group consisting of olefinic resins. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a heat-sensitive pressure-sensitive adhesive, a heat-sensitive pressure-sensitive adhesive sheet, and a method for applying the heat-sensitive pressure-sensitive adhesive, and more particularly, to easily remove air trapped between an adhesive layer and an adherend layer during application. The present invention relates to a heat-sensitive pressure-sensitive adhesive, a heat-sensitive pressure-sensitive adhesive sheet, and a method for applying the same, which can be applied beautifully and efficiently, and have good productivity.

  Conventionally, an adhesive film has been widely used for advertisement, guidance, heat insulation, or decoration, but when the adhesive film is applied, air is entrained between the adhesive layer and the adherend, and air is entrained. Since the transparency of the part is lowered, there is a problem that the design property is lowered, and it takes considerable skill to stick so that air is not involved, and there is a problem that requires labor and time for work. there were.

  As an improvement method, Patent Document 1 discloses a pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive is interspersed in a dot system or a streak pattern to make the adhesive layer discontinuous so that air can be easily extracted. Has been. However, this proposal has a problem that a special coating machine is required and irregularities are generated on the film surface due to locally arranged dots and streak patterns.

  Patent Document 2 discloses a pressure-sensitive adhesive sheet obtained by applying a pressure-sensitive adhesive prepared by mixing hollow glass particles that are lightweight, hard, thin, and brittle with a liquid adhesive. This pressure-sensitive adhesive sheet is characterized in that the pressure-sensitive adhesive floats from the adherend and easily shifts due to the contained particles, so that positioning and air extraction are easy, and construction efficiency is improved.

  However, it is difficult to uniformly disperse the hollow glass particles in the pressure-sensitive adhesive, and problems such as crushing of the glass particles during stirring and mixing are unavoidable. It was not easy to get.

  Patent Document 3 discloses a pressure-sensitive adhesive sheet to which a pressure-sensitive adhesive composed of elastic microspheres and an adhesive is applied. The technology is prepared by dispersing elastic microspheres obtained by a suspension polymerization method using water as a medium as a pressure-sensitive adhesive to prepare a pressure-sensitive adhesive composition and applying it to a substrate. A pressure-sensitive adhesive sheet is formed. This pressure-sensitive adhesive sheet has insufficient pressure-sensitive adhesive adhesive strength, poor creep characteristics under high temperature and high humidity, difficulty in sticking curved surfaces, pressure, heat at the time of heat-sensitive adhesive layer formation and storage, There are many problems such as changes in physical properties due to external factors such as humidity and light.

  As described above, the conventional various proposals for the pressure-sensitive adhesive tape and the pressure-sensitive adhesive sheet have their respective problems, and the actual situation is that a pressure-sensitive adhesive sheet that simultaneously solves these problems has not yet been completed.

The present invention intends to solve these problems at the same time.
Shokai 59-37343 JP 45-17074 Japanese Patent Laid-Open No. 8-113768

  The difficulty of sticking the pressure-sensitive adhesive sheet is strong even during the sticking work, and once the pressure-sensitive adhesive sheet contacts the adherend, it is difficult to align, It is to trap the entrained air. Therefore, in order to make the sticking work efficient, it is necessary to impart a property of having a low adhesion during the sticking work and a strong adhesion after sticking.

  Based on such circumstances, the present invention can easily remove air entrained between the adhesive layer and the adherend during application, can be applied beautifully and efficiently, and has good productivity. An object is to provide a heat-sensitive pressure-sensitive adhesive, a heat-sensitive pressure-sensitive adhesive sheet, and a method for attaching the same.

  The present invention has been made as a result of intensive studies in order to solve the above problems. Specifically, the organic polymer (A) having a glass transition point of −45 to + 20 ° C. and a softening point of 70 to 180 ° C. A heat-sensitive pressure-sensitive adhesive comprising a non-aqueous liquid material containing the resin component (B) and present in a state where the resin component (B) is dispersed in a continuous layer of the organic polymer (A). It is to provide.

  In addition, the present invention provides the above heat-sensitive pressure-sensitive adhesive, wherein the organic polymer (A) is one or a mixture of two or more selected from the group of acrylic resins and olefin resins, and a resin component ( B) is rosin, coumarone / indene resin, α-pinene resin, β-pinene resin, terpene resin, terpene / phenol resin, phenol / formaldehyde resin, xylene / formaldehyde resin, petroleum hydrocarbon resin, hydrogenated hydrocarbon resin And it is providing the said thermosensitive pressure-sensitive adhesive which is 1 type, or 2 or more types of mixtures chosen from the group of turpentine resin.

  Furthermore, the present invention provides a thermosensitive pressure-sensitive adhesive sheet, wherein the thermosensitive pressure-sensitive adhesive is applied on one or both sides of a thermoplastic resin base material so as not to contain bubbles, and the above-mentioned An object of the present invention is to provide a heat and pressure-sensitive adhesive sheet, wherein the heat and pressure-sensitive adhesive is coated on one or both sides of a long substrate made of thermoplastic resin so as not to contain bubbles.

  Furthermore, the present invention provides a thermosensitive pressure-sensitive adhesive sheet characterized by sticking the above thermosensitive pressure-sensitive adhesive sheet to the surface of an adherend, performing an operation of extracting the entrained air, and then heating and bonding. It is to provide a sticking method.

  The heat-sensitive pressure-sensitive adhesive sheet of the present invention is easy to align, and can be easily stuck because it can easily remove air trapped between the adhesive layer and the adherend layer. It is also excellent in productivity.

  The adhesive of the present invention contains an organic polymer (A) having a glass transition point of −45 to + 20 ° C. and a resin component (B) having a softening point of 70 to 180 ° C., and an organic polymer (A ), A non-aqueous dispersion containing the resin component (B) in a dispersed state.

  As the organic polymer (A), an organic polymer having a glass transition point of −45 to + 20 ° C. is used. In general, an acrylic resin or an olefin resin is desirable.

  Examples of the acrylic resin include an acrylic monomer (a), a functional monomer (b) having a radical polymerizable unsaturated group and a functional group, and an acrylic monomer ( Those obtained by copolymerizing a comonomer (c) other than a) and the functional monomer (b) are preferably used.

  As the acrylic monomer (a), acrylate and methacrylate are used. Specifically, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl are used. Acrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate, lauryl acrylate, stearyl acrylate, lauryl methacrylate, stearyl methacrylate, etc. can be used, linear or branched alkyl group having 1 to 18 carbon atoms, carbon A linear or branched alkenyl group having 12 to 18 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms is preferable.

  These can be used alone or in combination of two or more. Further, the functional monomer (b) having a radical polymerizable unsaturated group and a functional group is copolymerizable with the acrylic monomer (a), and examples thereof include (meth) acrylic acid and itaconic acid. , Crotonic acid, (anhydrous) maleic acid, (anhydrous) fumaric acid, carboxyl group-containing monomers such as carboxyalkyl (meth) acrylates, acrylonitrile, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, (meth) Nitrogen-containing unsaturated compounds such as acryloylmorpholine, (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, N-methylolmethacrylamide, 2-hydroxyethyl ( (Meth) acrylate, 2-hydroxypropyl (meth) acrylate Rate, hydroxyl group-containing vinyl monomers such as 2-hydroxybutyl (meth) acrylate.

  When the content of the functional monomer (b) decreases, it becomes difficult to obtain sufficient strength, and when it increases, it becomes difficult to obtain sufficient adhesive strength. Therefore, the total amount of monomers is 25% by weight or less, preferably 0. Desirably, a range of 1 to 10% by weight, particularly preferably 0.5 to 8% by weight is desirable.

  Further, a comonomer (c) other than the acrylic monomer (a) and the functional monomer (b) is added in accordance with the acrylic monomer (a) and the functional monomer (b). be able to. As the comonomer (c), for example, vinyl monomers such as vinyl formate, vinyl acetate, vinyl persate, vinyl pivalate, acrylonitrile, methacrylonitrile, vinyl propionate, styrene, vinyl toluene, or ethyl vinyl benzene, Or the methacrylate which does not correspond to acrylic monomers (a), such as ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, can be used.

  When the content of the comonomer (c) increases, it becomes difficult to obtain a sufficient adhesive strength. Therefore, the content of the comonomer (c) is 70% by weight or less, preferably 50% by weight or less in the total amount of the monomers.

  As the organic polymer (A) that can be used in the present invention, in addition to such an acrylic resin, as described above, for example, ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin, etc. The olefin resin can be used.

  The glass transition point (hereinafter sometimes abbreviated as Tg) of the organic polymer (A) used in the present invention needs to be −45 to + 20 ° C., preferably −40 to + 10 ° C.

  When the Tg exceeds the upper limit, the adhesive strength of the resulting adhesive may be insufficient, which is not preferable. When the Tg is less than the lower limit, the tackiness of the obtained adhesive becomes too strong. It is not preferable because air trapped between the adhesive layer and the adherend layer may not be easily removed.

  The organic polymer (A) can be used as a mixture of two or more as described above. In this case, it is not necessary that the Tg of each resin to be mixed satisfy the above range. It is necessary that the Tg of the resulting mixture satisfies this range.

  The organic polymer (A) used in the present invention preferably has a weight average molecular weight (hereinafter sometimes abbreviated as Mw) of 50,000 or more, and particularly preferably 100,000 to 1,000,000. If the value of Mw is equal to or higher than this lower limit, the adhesive force and cohesive force of the resulting adhesive are preferable because of a good balance, and if it is equal to or lower than the upper limit, the adhesive used to form the adhesive sheet When coating the composition solution, a suitable coating viscosity can be obtained without significantly reducing the solid content of the composition solution, so that it can be dried and cured in a relatively short time to form an adhesive layer, Since the amount of the organic solvent to be volatilized does not increase, it is preferable in terms of cost and environmental hygiene.

  The “weight average molecular weight” of the organic polymer (A) in the present invention refers to a value measured by the GPC method, and the glass transition point (Tg) of the organic polymer (A) refers to a value measured by the DSC method. Further, as will be described later, when the organic polymer (A) is crosslinked with a crosslinking agent or the like, the Mw and Tg of the organic polymer (A) measured with the Mw and Tg of the organic polymer (A) measured before crosslinking To do.

  If necessary, a chain transfer agent, a tackifier, a stabilizer, a plasticizer, and the like may be added to the polymerizable composition as long as the physical properties are not impaired. Generally, the amount is 10 parts by weight or less with respect to 100 parts by weight of the product.

  The adhesive composition used for the heat-sensitive pressure-sensitive adhesive sheet of the present invention comprises a resin component (B) having a softening point of 70 to 180 ° C. together with the organic polymer (A).

  The resin component (B) functions as a tackifier. Examples of the resin component (B) include rosin, coumarone / indene resin, α-pinene resin, β-pinene resin, terpene resin, terpene / phenol resin, pt-Butylphenol / acetylene resin, phenol / formaldehyde resin, xylene / formaldehyde resin, petroleum hydrocarbon resin, hydrogenated hydrocarbon resin, turpentine resin, etc. can be used. Good adhesion and curved surface adhesion From the viewpoints of the above, use of rosin, α-pinene resin, and petroleum hydrocarbon resin is preferable. The softening point of the resin component (B) used in the present invention needs to be 70 to 180 ° C, preferably 75 to 160 ° C, and particularly preferably 80 to 150 ° C.

  When the softening point of the resin component (B) is less than the lower limit value, the tackiness of the adhesive is too strong, and it is difficult to easily remove the air trapped between the adhesive layer and the adherend layer during sticking. On the other hand, if it exceeds the upper limit, the temperature at which the tackiness is exhibited is too high, which is not preferable. The measurement of the softening point of the resin is a value measured according to the ring and ball method of JIS K-2531.

  The resin component (B) that can be suitably used in the present invention is required to have a weight average molecular weight (hereinafter sometimes abbreviated as Mw) of 5000 or less, particularly 2000 to 4000. If the value of Mw exceeds the upper limit value, it is not preferable because the adhesive properties such as the adhesive strength and curved surface adhesiveness of the obtained adhesive tend to decrease. On the other hand, if it is more than the lower limit, there is no inconvenience such as a decrease in cohesive strength of the obtained adhesive layer, which is preferable.

  In addition, Mw of the resin component (B) in this invention says the value measured by the method similar to an organic polymer (A). The organic polymer (A) and the resin component (B) that can be used in the present invention include, for example, solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, or radiation polymerization using ultraviolet rays, electron beams, ion polymerization, It can be produced by a conventionally known method such as addition polymerization or polycondensation.

  The ratio of the organic polymer (A) and the resin component (B) contained in the heat-sensitive pressure adhesive in the present invention is 100% by weight of the organic polymer (A) and the resin component (B). (A) 30 to 95% by weight, particularly 40 to 90% by weight, and resin component (B) 70 to 5% by weight, particularly 60 to 10% by weight are preferred. If the content ratio of the organic polymer (A) is less than or equal to the upper limit value, the adhesive strength and curved surface tackiness of the obtained adhesive will not be insufficient, and if it is greater than or equal to the lower limit value, the adhesive agglomerates. This is preferable because power is not insufficient.

  If necessary, an organic solvent is added to the heat-sensitive pressure adhesive in the present invention. As the organic solvent, ketone, ether, cellosolve, alcohol, aromatic hydrocarbon, linear hydrocarbon and the like can be used.

  As a method for preparing a heat-sensitive pressure-sensitive adhesive that can be suitably used in the present invention, for example, a non-aqueous resin dispersion containing the organic polymer (A) as a dissolved component and the resin component (B) as a dispersed component is used. Forming method: Using a core-shell type aqueous resin dispersion having the resin component (B) as the core and the organic polymer (A) as the shell, and if necessary, from the organic polymer (A) A method of forming using a blend of ordinary aqueous resin dispersions can be suitably employed, but the organic polymer (A) is a dissolved component from the viewpoint of the weather resistance and water resistance of the resulting adhesive. It is particularly preferable to use a method of forming a non-aqueous resin dispersion containing the resin component (B) as a dispersion component.

  The production of the non-aqueous resin dispersion that can be suitably used in the present invention is not particularly limited and can be performed by a known method. For example, first, the resin component (B) is dissolved in an organic solvent. Then, in the organic solvent solution containing the resin component (B), a monomer that is soluble in the organic solvent, and the resulting (co) polymer has a low solubility of the resin component (B). Can be prepared by precipitating the resin component (B) by selecting such a monomer and (co) polymerizing with an oil-soluble polymerization initiator to form the organic polymer (A). it can. Thus, the method of forming the translucent non-aqueous resin dispersion which uses the organic polymer (A) as a dissolving component and the resin component (B) as a dispersing component can be mentioned.

  The adhesive in the present invention can be formed from an appropriately crosslinked organic polymer (A) as necessary. However, in this case, it is important to consider that the adhesive does not lose the balance between preferable adhesive force and cohesive force.

  Examples of the crosslinking method include a method in which a polyfunctional crosslinking agent is added and kneaded to the adhesive composition, and then formed into a sheet shape and irradiated with ultraviolet rays or an electron beam, or a polyfunctional crosslinking agent is previously contained in the polymerizable composition. Is added to form a sheet, followed by irradiation with ultraviolet rays or an electron beam for crosslinking.

  Examples of the polyfunctional crosslinking agent include an isocyanate group-containing compound, an epoxy group (or glycidyl group) -containing compound, an aziridinyl group-containing compound, a metal complex, and a melamine compound. Specifically, p- or m- Divalent, trivalent, such as phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or dimers or trimers thereof, isocyanate and ethylene glycol or trimethylolpropane Isocyanate compounds such as adducts with polyols, polyethylene glycol diglycidyl ether, epoxy compounds such as 1,3bis- (N, N diglycidylaminomethyl) cyclohexane, aluminum-tri-2-acetylacetate, aluminum Organic metal compounds such as Um -t- propiolate is used. These may be used alone or in combination of two or more. Among these, an isocyanate compound, a polyglycidylamine compound, or an organic metal compound is preferable.

  Moreover, an inorganic filler can be added in an adhesive composition. Examples of the inorganic filler include talc, clay, mica, calcium carbonate, barium sulfate, wollastonite, zeolite, silica, calcium silicate, and the like.

  Furthermore, it is possible to mix | blend a small amount of plasticizers in an adhesive composition. The kind of plasticizer to be blended is not limited. For example, an ester of an aliphatic polyvalent carboxylic acid such as adipic acid diester, an ester of an aromatic polyvalent carboxylic acid such as dioctyl phthalate, or a trimethylolpropane benzoate. Examples thereof include solid plasticizers such as low molecular weight plasticizers such as phosphate esters, and polymer plasticizers such as polyester and process oil. The blending amount is preferably 10% by weight or less.

  Further, it is desirable to add a benzotriazole-based compound to the adhesive. Benzotriazole-based compounds are known to have an effect of preventing metal corrosion, and by incorporating this, discoloration due to metal corrosion can be more effectively prevented. An effective amount of the benzotriazole-based compound may be added, and is about 0.1 to 10% by weight. Further, an ultraviolet ray inhibitor, an antioxidant, and a light stabilizer can be added to the adhesive.

  As shown in FIG. 1, the heat-sensitive adhesive of the present invention can be applied to a substrate 2 to form an adhesive layer 1 to obtain a heat-sensitive adhesive sheet 3. The base material 2 in the present invention may have any shape and thickness, and generally includes what are called plate bodies and tapes. Examples of the material of the substrate 2 include metal, glass, paper, cloth, a thermosetting resin or a sheet of thermoplastic resin. In particular, a thermoplastic resin excellent in heat resistance is preferable, and polypropylene, polyester, and polyamide are preferable. Further, depending on the purpose, as shown in FIG. 2, the woven fabric 4 can be lined. Hand cutting properties can be improved by laminating the woven fabric.

  In order to enhance the adhesive force with the heat-sensitive pressure-sensitive adhesive on the application surface on which the adhesive layer 1 is applied, the surface is subjected to physical treatment such as sandblasting or flame treatment, corona treatment or plasma treatment, etc. It is preferable to perform chemical treatment or primer treatment. The adhesive is usually dissolved in an appropriate organic solvent and then coated on the base material 2 and then dried, or coated on a process paper that has been subjected to a release treatment on the sheet and then dried. A thing is transcribe | transferred on a support body and it is set as the thermosensitive adhesive sheet 3 by which the base material 2 and the adhesive bond layer 1 were laminated | stacked. There is no limitation on the coating means and the drying method, and a known method can be adopted, but it is important to prevent bubbles from being generated in the thermosensitive adhesive layer. Moreover, although the adhesive bond layer 1 formed on the base material 2 is not specifically limited, It is preferable that the thickness is 10 micrometers-0.5 mm. When the thickness of the adhesive layer is less than 10 μm, the rough pressure-sensitive adhesiveness and the unevenness followability of the thermosensitive pressure-sensitive adhesive sheet 3 may be insufficient. Conversely, when the thickness of the adhesive layer 1 exceeds 0.5 mm In some cases, the stickiness and adhesive strength can be high, even though they no longer improve.

  When using the heat-sensitive pressure-sensitive adhesive sheet 3 of the present invention, the heat-pressure-sensitive adhesive sheet 3 is attached to the surface of an adherend (not shown), aligned, vented, and then heated. it can. Heating can be performed using a hot plate such as hot air or an iron.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in more detail, it cannot be overemphasized that the content of this invention is not limited to these Examples. In addition, the preparation method of the adhesive agent of this invention and the test sheet of an adhesive sheet, adhesive force, bubble-removing property, and the measuring method of the unevenness | corrugation on the film surface are as follows.

(Adhesive force)
A test piece cut out in a 25 mm width strip from an adhesive sheet was heated in a drier set at 120 ° C. for 30 seconds to develop adhesiveness, and then the adhesive strength after 1 day was peeled off by 180 ° according to JIS Z0237. Was measured.

(Bubble removal)
A 100 mm × 100 mm sample from which the release film was peeled off was placed on a smooth acrylic plate and pressure-bonded toward the center with a squeegee. Thereafter, a 2 kg roller was rolled to observe how bubbles were removed.
○: Bubbles were completely removed within 5 round trips.
X: Some bubbles remained after 5 reciprocations.

(Unevenness on the film surface)
A 300 mm × 300 mm sample was attached to a smooth acrylic plate, and the unevenness of the film surface was visually observed.
○: There is little unevenness and cannot be confirmed visually.
X: Unevenness can be confirmed.

Example 1
In a flask equipped with a reflux condenser, a thermometer, a stirrer, and a sequential dropping device, α-pinene resin “Picolite A115” which is the resin component (B) [trade name: manufactured by Sojitz Chemical Co., Ltd.] 100 parts by weight , 63 parts by weight of butyl acrylate (BA), 32 parts by weight of methyl methacrylate (MMA), 5 parts by weight of acrylic acid (AA), 0.3 parts by weight of azobis-i-butyronitrile (AIBN), 200 parts by weight of ethyl acetate (EAc) Were mixed and dissolved to prepare a mixture.

  As an initial charge, 50% by weight of this mixture was placed in a flask, heated with stirring, polymerized for 40 minutes under reflux at an internal temperature of 80 to 85 ° C., and then the mixture was maintained at an internal temperature of 80 to 85 ° C. 150% by weight of was successively added dropwise over 120 minutes. After maintaining at the reflux temperature for 120 minutes, 100 parts by weight of EAc was added for dilution, and the organic polymer (A) having a solid content of about 40% by weight and a viscosity of 8,000 mPaS (B type rotational viscosity type, 30 ° C., 10 rpm). Was formed to obtain a translucent non-aqueous resin dispersion having the resin component (B) as a dispersion component.

  To 100 parts by weight of the resulting dispersion, 1 part by weight of an isocyanate compound “Coronate L55E” [trade name: manufactured by Nippon Polyurethane Co., Ltd.] as a crosslinking agent (D) was stirred and mixed, and then the thickness after drying was 25 μm. Thus, it applied to the 50-micrometer-thick polyester film, it dried at 100 degreeC for 5 minute (s), the peeling film was laminated | stacked, and the adhesive sheet was obtained. Various adhesive physical properties were measured using the obtained adhesive sheet. The copolymer composition, viscosity, solid content, Mw and Tg of the organic polymer (A) used for forming the adhesive, the type and softening point of the resin component (B), the components (A) and (B) Table 1 shows the content ratio, the kind and amount of the crosslinking agent, and Table 3 shows the measurement results of the adhesive properties.

(Examples 2 to 4, Comparative Example 1)
In Example 1, the ratio between the synthetic organic polymer (A) and the resin component (B) is changed (Examples 2 to 4), or the resin component (B) is not used (Comparative Example 1). In the same manner as in Example 1, a non-aqueous resin dispersion was prepared and evaluated. The results are shown in Tables 1 and 3.

(Examples 5-6, Comparative Examples 2-3)
In Example 1, non-aqueous resin dispersions were prepared and evaluated in the same manner as in Example 1 except that the usage ratios of BA and MMA were changed or MMA was not used. The results are shown in Tables 1 and 3.

(Examples 7 to 9, Comparative Example 4)
In Example 1, instead of using “Picolite A-115”, a styrene type resin “FTR6100” [trade name: manufactured by Mitsui Chemicals, Inc.] or a special rosin ester resin “Superester A-75” [trade name: Arakawa Chemical Industries, Ltd.], terpene phenol resin “Tamanol 803L” [trade name: Arakawa Chemical Industries, Ltd.], xylene resin “Nikanol H” [trade name: Mitsubishi Gas Chemical Co., Ltd.] were used. A non-aqueous resin dispersion was prepared and evaluated in the same manner as Example 1 except for the above. The results are shown in Tables 1 and 3.

(Example 10)
In Example 1, a non-aqueous resin dispersion was prepared and evaluated in the same manner as in Example 1 except that 25 parts by weight of trimethylolpropane benzoate (softening point: 85 ° C.) was additionally added as additive (C). went. The results are shown in Tables 2 and 3.

(Examples 11 to 12)
Instead of using “Coronate L55E” as the crosslinking agent (D) in Example 1, the polyglycidylamine compound “Tetrad C” [trade name: manufactured by Mitsubishi Gas Chemical Co., Ltd.] or the organometallic compound “Aluminum Chelate A” [ A non-aqueous resin dispersion was prepared and evaluated in the same manner as in Example 1 except that the product name: Kawaken Fine Chemical Co., Ltd. was used. The results are shown in Tables 2 and 3.

(Example 13)
Instead of using “Coronate L55E” as the crosslinking agent (D) in Example 1, except that polyunsaturated monomer: trimethylolpropane triacrylate (TMPTA) and photopolymerization initiator: Irgacure 184 (IC184) were used. A non-aqueous resin dispersion was prepared in the same manner as in Example 1, and the results are shown in Table 2. In addition, a pressure-sensitive adhesive sheet was prepared, and the pressure-sensitive adhesive sheet was prepared and evaluated by irradiating ultraviolet rays at 500 mJ / cm ² to crosslink the adhesive layer. The results are shown in Table 3.

(Example 14)
In a pressure-resistant autoclave equipped with a stirrer, 100 parts by weight of “Picolite A115” which is a resin component (B) and 200 parts by weight of EAc were mixed and dissolved at room temperature, and nitrogen and ethylene substitution was performed with stirring. Next, the system temperature was heated to 70 ° C., and 68 parts by weight of vinyl acetate (VAc), 2 parts by weight of AA, and 0.3 part by weight of AIBN were added dropwise simultaneously over 6 hours. During this time, the reaction temperature was adjusted to 70 ° C., and the ethylene (Et) pressure was always 60 kg / cm ² during the polymerization. Thereafter, after further aging at 70 ° C. for 2 hours, 100 parts by weight of EAc was added to dilute, and the organic content having a solid content of about 40% by weight and a viscosity of 7,000 mPaS (B type rotational viscosity type, 30 ° C., 10 rpm) was obtained. A molecule (A) was generated to form a dissolved component, and a translucent non-aqueous resin dispersion having the resin component (B) as a dispersion component was obtained. The monomer composition of the organic polymer (A) was Et 30% by weight, VAc 69% by weight, and AA 1% by weight. The evaluation results are shown in Tables 2 and 3.

Sectional drawing which shows the example of this invention pressure sensitive adhesive sheet Sectional drawing which shows the other example of this invention pressure sensitive adhesive sheet

Explanation of symbols

1: Heat-sensitive pressure-sensitive adhesive layer 2: Base layer
3: Pressure sensitive adhesive sheet 4: Woven fabric

Claims (6)

  An organic polymer (A) having a glass transition point of −45 to + 20 ° C. and a resin component (B) having a softening point of 70 to 180 ° C. are contained in the continuous layer of the organic polymer (A). A thermosensitive pressure-sensitive adhesive, characterized in that B) is a non-aqueous liquid that exists in a dispersed state.   The heat-sensitive pressure-sensitive adhesive according to claim 1, wherein the organic polymer (A) is one or a mixture of two or more selected from the group of acrylic resins and olefin resins.   Resin component (B) is rosin, coumarone / indene resin, α-pinene resin, β-pinene resin, terpene resin, terpene / phenol resin, phenol / formaldehyde resin, xylene / formaldehyde resin, petroleum hydrocarbon resin, hydrogenated The thermosensitive pressure-sensitive adhesive according to claim 1 or 2, which is one or a mixture of two or more selected from the group consisting of hydrocarbon resins and turpentine resins.   The heat and pressure sensitive adhesive sheet according to any one of claims 1 to 3, wherein the heat and pressure sensitive adhesive sheet is coated so as not to contain bubbles on one or both sides of a thermoplastic resin base material. .   The heat-sensitive pressure-sensitive adhesive according to any one of claims 1 to 3, wherein the heat-sensitive pressure-sensitive adhesive is coated so as not to contain bubbles on one or both sides of a long substrate made of a thermoplastic resin. Pressure adhesive sheet.   A method for applying a heat-sensitive pressure-sensitive adhesive sheet, comprising: attaching the heat-sensitive pressure-sensitive adhesive sheet according to claim 4 or 5 to an adherend surface;

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