Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

• the present invention relates to a temperature-sensitive adhesive composition.
• a temperature-sensitive adhesive is known as an adhesive capable of reversibly controlling the adhesive force by heat (for example, see Patent Document 1).
• the conventional temperature-sensitive adhesive as described in Patent Document 1 is usually a polymer solution obtained by polymerizing monomers in an organic solvent, and this polymer solution is applied to a film-like substrate and dried. It is processed into adhesive tape.
• the adhesive tape is used in various applications, for example, an adhesive tape having a thick adhesive layer so as to follow the step of the adherend may be required.
• the conventional temperature-sensitive pressure-sensitive adhesive has a problem that when the thickness of the coating film is increased to increase the thickness of the pressure-sensitive adhesive layer, bubbles are generated in the film due to volatilization of the organic solvent when dried. . Moreover, since the conventional temperature sensitive adhesive uses the organic solvent, there also existed a problem that environmental impact was large.
• a pressure-sensitive adhesive not containing an organic solvent a liquid pressure-sensitive adhesive composition comprising an acrylic monomer, a viscosity adjusting polymer, and a photo radical initiator is known.
• this pressure-sensitive adhesive composition has a problem in that sufficient pressure-sensitive adhesive properties cannot be obtained, although a thick pressure-sensitive adhesive layer can be formed by coating and UV curing.
• An object of the present invention is to provide a temperature-sensitive adhesive composition capable of forming a thick adhesive layer having excellent adhesive properties.
• the temperature-sensitive adhesive composition of the present invention contains at least a side-chain crystalline (meth) acrylic polymer, a (meth) acrylic monomer, a polyfunctional (meth) acrylate, and a photo radical initiator, and has ultraviolet curability. And it is liquid.
• thermosensitive adhesive composition a temperature-sensitive adhesive composition according to an embodiment of the present invention (hereinafter sometimes referred to as “adhesive composition”) will be described in detail.
• the pressure-sensitive adhesive composition of the present embodiment contains at least a side chain crystalline (meth) acrylic polymer, a (meth) acrylic monomer, a polyfunctional (meth) acrylate, and a photoradical initiator, and ultraviolet (Ultra Violet: It may be referred to as “UV”.) It is UV curable by being irradiated and is liquid.
• the side chain crystalline (meth) acrylic polymer of this embodiment is a polymer obtained by polymerizing a (meth) acrylate having a linear alkyl group having at least 16 carbon atoms.
• the linear alkyl group having 16 or more carbon atoms functions as a side chain crystalline part in the side chain crystalline (meth) acrylic polymer. That is, the side chain crystalline (meth) acrylic polymer is a comb-shaped polymer having a linear alkyl group having 16 or more carbon atoms in the side chain, and the side chain is aligned in an ordered arrangement by intermolecular force or the like. To crystallize.
• the side chain crystalline (meth) acrylic polymer of this embodiment has a melting point in connection with the crystallization described above.
• the melting point is a temperature at which a specific portion of the polymer that is initially aligned in an ordered arrangement becomes disordered by an equilibrium process, and is measured by a differential thermal scanning calorimeter (DSC) at 10 ° C./min. It means the value obtained in this way.
• DSC differential thermal scanning calorimeter
• the side-chain crystalline (meth) acrylic polymer of the present embodiment has a temperature sensitivity that crystallizes at a temperature lower than the above-described melting point and undergoes phase transition at a temperature higher than the melting point to exhibit fluidity. Therefore, the pressure-sensitive adhesive composition of this embodiment containing a side-chain crystalline (meth) acrylic polymer adheres when the side-chain crystalline (meth) acrylic polymer flows at a temperature equal to or higher than the melting point after UV curing. When the side chain crystalline (meth) acrylic polymer is crystallized at a temperature lower than the melting point, the adhesive strength is lowered. If the pressure-sensitive adhesive composition is heated again to a temperature equal to or higher than the melting point, the side chain crystalline (meth) acrylic polymer exhibits fluidity, and thus the adhesive strength is recovered. Therefore, it can be used repeatedly.
• Examples of the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms constituting the side chain crystalline (meth) acrylic polymer include cetyl (meth) acrylate, stearyl (meth) acrylate, and eicosyl (meth) acrylate. And (meth) acrylates having a linear alkyl group having 16 to 22 carbon atoms, such as behenyl (meth) acrylate, and these may be used alone or in combination of two or more.
• (Meth) acrylate means acrylate or methacrylate. This is the same for other (meth) acrylates.
• the side chain crystalline (meth) acrylic polymer of the present embodiment can be further polymerized with, for example, (meth) acrylate having a C 1-6 alkyl group, a polar monomer, or the like.
• Examples of the (meth) acrylate having an alkyl group having 1 to 6 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and the like. You may use a seed
• polar monomers include ethylenically unsaturated monomers having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Examples thereof include ethylenically unsaturated monomers having a hydroxyl group such as (meth) acrylate and 2-hydroxyhexyl (meth) acrylate, and these may be used alone or in combination of two or more.
• Each of the above-mentioned monomers is, for example, 20 to 100 parts by weight of (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, and 0 to 70 parts by weight of (meth) acrylate having an alkyl group having 1 to 6 carbon atoms. It is preferable to polymerize the polar monomer at a ratio of 0 to 10 parts by weight.
• a reactive fluorine compound can be further polymerized to the side chain crystalline (meth) acrylic polymer of the present embodiment.
• the releasability due to the reactive fluorine compound is added, so that the peelability of the pressure-sensitive adhesive composition can be improved.
• the reactive fluorine compound means a fluorine compound having a reactive functional group.
• the functional group showing reactivity include a group having an ethylenically unsaturated double bond such as vinyl group, allyl group, (meth) acryl group, (meth) acryloyl group, (meth) acryloyloxy group; epoxy group (Including glycidyl group and epoxycycloalkyl group), mercapto group, carbinol group, carboxyl group, silanol group, phenol group, amino group, hydroxyl group and the like.
• reactive fluorine compound examples include compounds represented by the following general formula (I). [Wherein R 1 represents a group: CH 2 ⁇ CHCOOR 2 — or CH 2 ⁇ C (CH 3 ) COOR 2 — (wherein R 2 represents an alkylene group). ]
• alkylene group represented by R 2 for example, methylene group, ethylene group, trimethylene group, methylethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, etc. -6 straight chain or branched alkylene groups.
• Specific examples of the compound represented by the general formula (I) include compounds represented by the following formulas (Ia) and (Ib).
• Examples of commercially available reactive fluorine compounds include “Biscoat 3F”, “Biscoat 3FM”, “Biscoat 4F”, “Biscoat 8F”, “Biscoat 8FM” manufactured by Osaka Organic Chemical Industry Co., Ltd., Kyoeisha Chemical Co., Ltd. “Light Ester M-3F” manufactured by the same company.
• the reactive fluorine compound is preferably polymerized with the above-mentioned monomer at a ratio of 1 to 10 parts by weight.
• the side chain crystalline (meth) acrylic polymer of the present embodiment can be further polymerized with, for example, (meth) acrylate having an ethylene glycol group, high acrylate acrylate, vinyl monomer and the like.
• (meth) acrylate having an ethylene glycol group examples include 2-ethylhexyl-diglycol (meth) acrylate, methoxyethyl (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, ethoxy-diethylene glycol (meth) acrylate, methoxy -Triethylene glycol (meth) acrylate and the like may be mentioned, and these may be used alone or in combination of two or more.
• Examples of the high Tg acrylate include isobornyl acrylate (light acrylate IB-XA: Kyoeisha Chemical), isobornyl methacrylate (light ester IB-X: Kyoeisha Chemical), methyl methacrylate, tertiary butyl cyclohexyl methacrylate (TBCHMA: NOF), dicyclopentanyl acrylate (FA513-AS: Hitachi Chemical), dicyclopentanyl methacrylate (FA513-M: Hitachi Chemical), 1-adamantyl acrylate (ADA: Osaka Organic Chemical), 1-adamantyl methacrylate (ADMA) : Osaka Organic Chemistry) and the like.
• the vinyl monomer examples include styrene and vinyl acetate, and these may be used as a mixture.
• the ratio when each of the above-described (meth) acrylate having an ethylene glycol group, a high Tg acrylate, and a vinyl monomer is polymerized is not particularly limited.
• the melting point of the side chain crystalline (meth) acrylic polymer is preferably 5 to 80 ° C., more preferably 10 to 70 ° C.
• the melting point can be adjusted by changing the composition of the side chain crystalline (meth) acrylic polymer. Further, the melting point tends not to change substantially before and after UV irradiation. That is, the melting point after UV curing tends to be substantially the same value as the melting point before UV curing.
• the weight average molecular weight of the side chain crystalline (meth) acrylic polymer is preferably 450,000 or more, more preferably 1 million or more, further preferably 2 million or more, and 24.5 million or more. Is more preferable.
• the upper limit of the weight average molecular weight of the side chain crystalline (meth) acrylic polymer is preferably 3 million or less, but is not limited thereto.
• the weight average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) and converting the obtained measurement value to standard polystyrene. Examples of the measurement solvent for GPC include tetrahydrofuran (THF).
• the above-described monomer polymerization is preferably performed by bulk polymerization. Thereby, an adhesive composition can be made into the state which does not contain an organic solvent.
• the bulk polymerization is preferably performed while irradiating UV. Thereby, the monomer can be polymerized in a relatively short time. Therefore, the side-chain crystalline (meth) acrylic polymer of this embodiment is obtained by adding a photoradical initiator, which will be described later, to a monomer containing a (meth) acrylate having a linear alkyl group having at least 16 carbon atoms. It is preferable that the polymer is polymerized by bulk polymerization while irradiating.
• the term “monomer” is not limited to an acrylic monomer, but includes a reactive fluorine compound and the like as long as it includes a (meth) acrylate having a linear alkyl group having at least 16 carbon atoms. is there.
• the polymerization temperature in the bulk polymerization is preferably 30 to 60 ° C.
• the polymerization time is preferably 30 seconds to 5 minutes.
• the intensity of UV is preferably 1 to 100 mW / cm 2 (365 nm).
• the polymerization conditions are not limited to the polymerization conditions described above as long as the side chain crystalline (meth) acrylic polymer can be synthesized.
• Bulk polymerization may be performed in the presence of a chain transfer agent in order to control the molecular weight.
• the addition amount of the chain transfer agent is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the monomer.
• Examples of the chain transfer agent include thiol chain transfer agents such as dodecyl mercaptan, but are not limited thereto.
• the pressure-sensitive adhesive composition of the present embodiment contains a (meth) acrylic monomer.
• the pressure-sensitive adhesive composition of the present embodiment is liquid due to containing a (meth) acrylic monomer. Therefore, the pressure-sensitive adhesive composition of the present embodiment can exhibit excellent coating properties.
• the adhesive composition of this embodiment is liquid, it is not necessary to contain an organic solvent like the conventional temperature-sensitive adhesive. Therefore, according to the pressure-sensitive adhesive composition of the present embodiment, there is no problem due to the inclusion of the organic solvent described above, and it is possible to form a thick pressure-sensitive adhesive layer having excellent pressure-sensitive adhesive properties.
• the pressure-sensitive adhesive composition of this embodiment does not contain an organic solvent.
• liquid means that the viscosity at 50 ° C. of the mixture containing at least the side chain crystalline (meth) acrylic polymer and the (meth) acrylic monomer is 100 to 10,000 mPa ⁇ s. It shall be.
• the viscosity is a value before UV curing, and is a value obtained by measurement by the method described in Examples described later.
• the pressure-sensitive adhesive composition preferably has the largest total content of side chain crystalline (meth) acrylic polymer and (meth) acrylic monomer.
• an adhesive composition will contain a side chain crystalline (meth) acrylic polymer and a (meth) acryl monomer as a main component, As a result, the outstanding coating property and adhesive physical property can be exhibited.
• the pressure-sensitive adhesive composition comprises 5 to 40% by weight of the side chain crystalline (meth) acrylic polymer with respect to 100% by weight of the total of the side chain crystalline (meth) acrylic polymer and the (meth) acrylic monomer. Preferably, it is contained in a proportion of 10 to 30% by weight. In other words, the pressure-sensitive adhesive composition contains 60 to 95% by weight of the (meth) acrylic monomer with respect to 100% by weight of the total of the side chain crystalline (meth) acrylic polymer and the (meth) acrylic monomer. The content is preferably 70 to 90% by weight. According to these configurations, the pressure-sensitive adhesive composition has an appropriate viscosity, and therefore can exhibit excellent coating properties, and suppresses the (meth) acrylic monomer remaining after UV curing. As a result, excellent adhesive properties can be exhibited.
• the (meth) acrylic monomer of this embodiment is the same as the monomer constituting the side chain crystalline (meth) acrylic polymer. Thereby, the (meth) acryl monomer can exhibit excellent compatibility with the side chain crystalline (meth) acrylic polymer.
• the (meth) acrylic monomer of the present embodiment corresponds to a residual monomer when the above-described monomers constituting the side chain crystalline (meth) acrylic polymer are polymerized.
• the (meth) acrylic monomer the same monomer as exemplified in the above-mentioned side chain crystalline (meth) acrylic polymer, that is, (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, carbon number Examples thereof include (meth) acrylates having 1 to 6 alkyl groups and polar monomers.
• the ratio of the side-chain crystalline (meth) acrylic polymer is 5 to 40% by weight, preferably 10% with respect to 100% by weight of the total of the side-chain crystalline (meth) acrylic polymer and the (meth) acrylic monomer. It is preferable to polymerize the above-described monomer so that it is ⁇ 30% by weight.
• the polyfunctional (meth) acrylate is a curable compound having a property of curing when irradiated with UV, and is a (meth) acrylate having two or more double bonds capable of radical polymerization in the molecule. Since the pressure-sensitive adhesive composition of the present embodiment contains a polyfunctional (meth) acrylate as described above, the cohesive force can be improved after UV curing, and as a result, excellent heat resistance can be exhibited. .
• the pressure-sensitive adhesive composition comprises 0.1 to 30 parts by weight of a polyfunctional (meth) acrylate with respect to 100 parts by weight in total of the side chain crystalline (meth) acrylic polymer, the (meth) acrylic monomer, and the photoradical initiator. It is preferable to contain by a ratio.
• the polyfunctional (meth) acrylate is preferably bifunctional (meth) acrylate or trifunctional (meth) acrylate and has a weight average molecular weight of 200 to 1,200.
• polyfunctional (meth) acrylate examples include 1,6-hexanediol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, and ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate. These may be used, and one kind or a mixture of two or more kinds may be used.
• polyfunctional (meth) acrylates Commercially available products can be used for the polyfunctional (meth) acrylates described above.
• examples of commercially available polyfunctional (meth) acrylates include “NK Ester A-HD-N”, “NK Ester A-BPE-10”, and “NK Ester A-9300-1CL” manufactured by Shin-Nakamura Chemical Co., Ltd. , “NK ester A-9300-6CL” and the like.
• the pressure-sensitive adhesive composition of the present embodiment contains a photo radical initiator.
• the photoradical initiator is not particularly limited as long as it is a compound that can initiate radical polymerization by receiving light irradiation.
• the photoradical initiator of the present embodiment is used at the time of polymerization of the above-described monomers constituting the side chain crystalline (meth) acrylic polymer, and is also used at the time of UV curing of the pressure-sensitive adhesive composition.
• the pressure-sensitive adhesive composition contains a photoradical initiator in a proportion of 0.2 to 1.9 parts by weight with respect to 100 parts by weight of the total of the side chain crystalline (meth) acrylic polymer and the (meth) acrylic monomer. Is preferred.
• the total amount of the photo radical initiator may be added all at once during the polymerization of the monomer, or may be added separately during the polymerization of the monomer and during the UV curing of the pressure-sensitive adhesive composition.
• photo radical initiator Commercially available products can be used as the above-mentioned photo radical initiator.
• examples of commercially available photo radical initiators include “IRGACURE 184” and “IRGACURE 500” manufactured by BASF Japan.
• tackifier such as a tackifier, an anti-aging agent, and a crosslinking agent can be added to the pressure-sensitive adhesive composition of the present embodiment described above.
• the use of the pressure-sensitive adhesive composition of the present embodiment is not particularly limited.
• a pressure-sensitive adhesive tape having a thick pressure-sensitive adhesive layer is required so as to follow the level difference of the adherend. It can be suitably used as a pressure-sensitive adhesive composition in certain fields.
• the temperature-sensitive adhesive tape of this embodiment includes a base material and an adhesive layer.
• the base material of this embodiment is a film form.
• the film shape is not limited to a film shape, and is a concept including a film shape or a sheet shape as long as the effects of the present embodiment are not impaired.
• Examples of the constituent material of the base material include polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamide, polyimide, polycarbonate, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene polypropylene copolymer, and polyvinyl chloride. Synthetic resins are mentioned.
• the substrate may be either a single layer or a multilayer, and the thickness is usually about 5 to 500 ⁇ m.
• the substrate can be subjected to surface treatment such as corona discharge treatment, plasma treatment, blast treatment, chemical etching treatment, primer treatment, etc. in order to improve the adhesion to the pressure-sensitive adhesive layer.
• the pressure-sensitive adhesive layer of this embodiment is laminated on one side or both sides of the above-mentioned base material, and the temperature-sensitive pressure-sensitive adhesive composition according to the above-described embodiment is applied to the base material, and UV is applied. It consists of the hardened
• the pressure-sensitive adhesive composition is excellent in coating properties for the reasons described above, and has no problem due to containing an organic solvent. Therefore, the temperature-sensitive adhesive tape of the present embodiment has no bubbles generated due to volatilization of the organic solvent in the adhesive layer, and can increase the thickness of the adhesive layer, resulting in excellent adhesive properties. It can be demonstrated.
• the thickness of the pressure-sensitive adhesive layer can be set from a wide range of 1 to 1,000 ⁇ m, preferably 40 to 500 ⁇ m.
• the thickness of the adhesive layer can be set larger from the exemplified range.
• the thickness of the pressure-sensitive adhesive layer on one side and the thickness of the pressure-sensitive adhesive layer on the other side may be the same or different.
• the amount of UV irradiation is preferably 1,000 mJ / cm 2 or more.
• the upper limit value of the UV irradiation amount is preferably 10,000 mJ / cm 2 or less, but is not limited thereto.
• a film-like air blocking member on the surface of the coating film made of the pressure-sensitive adhesive composition.
• UV can be irradiated and hardened
• the air blocking member include those obtained by applying a release agent such as silicone or silicon to the surface of a film made of polyethylene terephthalate or the like.
• an applicator for example, an applicator, a coater and the like can be mentioned.
• the coater include a knife coater, a roll coater, a calendar coater, a comma coater, a gravure coater, and a rod coater.
• the adhesive layer of one side consists of the adhesive composition mentioned above
• the adhesive layer of another side is not specifically limited.
• the composition may be the same as or different from the composition of the pressure-sensitive adhesive layer on one side. Good.
• the pressure-sensitive adhesive layer on the other surface can be constituted by, for example, a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive.
• the pressure-sensitive adhesive is a tacky polymer, and examples thereof include natural rubber adhesives, synthetic rubber adhesives, styrene / butadiene latex-based adhesives, and acrylic adhesives.
• release film on the surface of the temperature-sensitive adhesive tape described above.
• the release film include a film made of polyethylene terephthalate or the like and a release agent such as silicone or silicon applied to the surface of the film.
• the temperature-sensitive adhesive sheet of the present embodiment is formed of a cured product obtained by processing the pressure-sensitive adhesive composition according to the above-described embodiment into a sheet shape and irradiating it with UV.
• the thickness of the temperature-sensitive adhesive sheet is preferably 1 to 1,000 ⁇ m, more preferably 40 to 500 ⁇ m.
• the upper limit of the thickness of the thermosensitive adhesive sheet is not particularly limited as long as it can be cured by UV irradiation. Since the other structure is the same as that of the temperature-sensitive adhesive tape which concerns on one Embodiment mentioned above, description is abbreviate
• the (meth) acrylic monomer is a residual monomer obtained by polymerizing the monomer constituting the side chain crystalline (meth) acrylic polymer.
• An acrylic monomer may be contained in the pressure-sensitive adhesive composition as a new monomer instead of a residual monomer.
• a new (meth) acrylic monomer may be further contained in the pressure-sensitive adhesive composition. Good.
• the pressure-sensitive adhesive composition is a temperature-sensitive pressure-sensitive adhesive tape and a temperature-sensitive pressure-sensitive adhesive sheet has been described, but instead, the pressure-sensitive adhesive composition is directly applied to an adherend. , UV may be irradiated and cured.
• the flask was immersed in a hot water bath, the mixture was heated to 40 ° C., and nitrogen was bubbled for 30 minutes while stirring at 150 rpm to remove oxygen in the mixture. Then, the monomer was bulk polymerized while irradiating the mixture with UV from a UV irradiation head at the top of the flask.
• the liquid mixture of the side chain crystalline (meth) acrylic polymer and the (meth) acrylic monomer (behenyl acrylate, methyl acrylate, acrylic acid) was obtained by the bulk polymerization described above.
• the weight average molecular weight of the side chain crystalline (meth) acrylic polymer, the content of the side chain crystalline (meth) acrylic polymer and the (meth) acrylic monomer, and the viscosity of the liquid mixture were measured in the obtained liquid mixture.
• Each measurement result and measurement method are as follows.
• Weight average molecular weight of side chain crystalline (meth) acrylic polymer 500,000 Content of side chain crystalline (meth) acrylic polymer: 20% by weight Content of (meth) acrylic monomer: 80% by weight Viscosity of liquid mixture: 200 mPa ⁇ s
• Examples 1 to 4 ⁇ Manufacture of temperature-sensitive adhesive tape>
• the liquid mixture obtained in Synthesis Example 1 was used.
• polyfunctional acrylate was added to 100 g of this liquid mixture.
• the added polyfunctional acrylate is as follows. Multifunctional acrylate: 1,6-hexanediol diacrylate “NK Ester A-HD-N” manufactured by Shin-Nakamura Chemical Co., Ltd.
• Example 1 The amount of polyfunctional acrylate added to 100 g of the liquid mixture is as follows.
• Example 2 0.5 g
• Example 3 1.0 g
• Example 4 1.0 g
• liquid mixture to which the polyfunctional acrylate was added was applied to one side of the film-like substrate with an applicator.
• the used film-like base materials are as follows. Substrate: 100 ⁇ m thick polyethylene terephthalate film “Embret SB-100” manufactured by Unitika Co., Ltd. with one side corona-treated
• the gap of the applicator is as follows.
• Example 1 10 mil
• Example 2 5 mil
• Example 3 5 mil
• Example 4 10 mil
• a film-like air blocking member was laminated on the surface of the coating film, and UV was irradiated from above the coating film.
• Air blocking member 25 ⁇ m thick polyethylene terephthalate film “PET25 ⁇ 1-J0L” manufactured by Nipper Co., Ltd.
• UV irradiation conditions are as follows. UV irradiation device: “HLR100T-2 / HB100A-1” manufactured by ASONE UV amount: 1,500 mJ / cm 2
• the temperature sensitive adhesive tape which provided the adhesive layer which has the thickness shown in Table 1 on the single side
• the thickness of the adhesive layer in Table 1 is a value obtained by measuring with a dial gauge.
• Adhesive layer state The presence or absence of air bubbles was evaluated by visually observing the pressure-sensitive adhesive layer of the temperature-sensitive pressure-sensitive adhesive tape. The evaluation criteria were set as follows. A: There were no bubbles in the pressure-sensitive adhesive layer. ⁇ : A small number of bubbles were present in the pressure-sensitive adhesive layer. X: Many air bubbles existed in the adhesive layer.
• a stainless steel plate (hereinafter referred to as “SUS plate”) at each ambient temperature of 23 ° C. after passing through 80 ° C., 80 ° C., 23 ° C., 120 ° C. and 120 ° C. 180 ° peel strength was measured according to JIS Z0237. Specifically, a temperature-sensitive adhesive tape was attached to a SUS plate under the following conditions, and then peeled 180 ° using a load cell at a speed of 300 mm / min.
• Example 5 A feeling that a pressure-sensitive adhesive layer having a thickness shown in Table 1 is provided on one side of a film-like substrate in the same manner as in Example 1 except that the liquid mixture obtained in Synthesis Example 2 was used as the coating liquid. A warm adhesive tape was obtained.
• Example 1 The obtained temperature sensitive adhesive tape, it carried out similarly to Example 1 mentioned above, and evaluated the state and 180 degree peel strength of the adhesive layer. The results are shown in Table 1.
• the adhesive tape which provides the adhesive layer which has the thickness shown in Table 1 on the single side
• the coating solution the polymer solution obtained in the comparative synthesis example was used. First, triethylamine was added at a rate of 9 g to 100 g of this polymer solution, and a crosslinking agent was further added.
• the added crosslinking agent is as follows.
• Cross-linking agent aziridine compound “Chemite PZ-33” manufactured by Nippon Shokubai Co., Ltd.
• the amount of the crosslinking agent added to 100 g of the polymer solution is as follows. Comparative Example 2: 0.5 g Comparative Example 3: 0.5 g Comparative Example 4: 0.5 g Comparative Example 5: 1.0 g
• Example 2 a polymer solution to which triethylamine and a crosslinking agent were added was applied to one side of a film-like substrate with an applicator.
• the same substrate as in Example 1 was used.
• the gap of the applicator is as follows. Comparative Example 2: 10 mil Comparative Example 3: 15 mil Comparative Example 4: 20 mil Comparative Example 5: 10 mil
• the crosslinking agent was subjected to a crosslinking reaction by heating in a hot air oven at 110 ° C. for 10 minutes to obtain an adhesive tape having an adhesive layer having a thickness shown in Table 1 on one side of the film-like substrate.
• Example 1 As can be seen from Table 1, in all of Examples 1 to 5, there are no bubbles in the pressure-sensitive adhesive layer, the thickness of the pressure-sensitive adhesive layer can be increased, and the adhesive properties are excellent.
• the pressure-sensitive adhesive layer was collected from the temperature-sensitive adhesive tape after UV curing, and the melting point of the side chain crystalline (meth) acrylic polymer was measured by DSC under the measurement conditions of 10 ° C./min. As a result, the melting points of Examples 1 to 5 were 55 ° C.
• Comparative Example 1 when an adhesive layer having a thickness larger than 10 ⁇ m was formed, dripping occurred and the coating could not be performed. In Comparative Examples 2 to 5, more bubbles were generated as the thickness of the pressure-sensitive adhesive layer was increased. In Comparative Examples 3 and 4, a tape could not be produced.

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