WO2016158413A1 - Temperature-sensitive adhesive composition - Google Patents
Temperature-sensitive adhesive composition Download PDFInfo
- Publication number
- WO2016158413A1 WO2016158413A1 PCT/JP2016/058297 JP2016058297W WO2016158413A1 WO 2016158413 A1 WO2016158413 A1 WO 2016158413A1 JP 2016058297 W JP2016058297 W JP 2016058297W WO 2016158413 A1 WO2016158413 A1 WO 2016158413A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- sensitive adhesive
- temperature
- acrylic polymer
- chain crystalline
- Prior art date
Links
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.
Abstract
Description
以下、本発明の一実施形態に係る感温性粘着剤組成物(以下、「粘着剤組成物」と言うことがある。)について詳細に説明する。 <Temperature sensitive adhesive composition>
Hereinafter, 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.
本実施形態の側鎖結晶性(メタ)アクリルポリマーは、少なくとも炭素数16以上の直鎖状アルキル基を有する(メタ)アクリレートを重合させることによって得られるポリマーである。 [Side-chain crystalline (meth) acrylic polymer]
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.
本実施形態の粘着剤組成物は、上述のとおり、(メタ)アクリルモノマーを含有する。本実施形態の粘着剤組成物は、(メタ)アクリルモノマーを含有することに起因して、液状である。したがって、本実施形態の粘着剤組成物は、優れた塗工性を発揮することができる。また、本実施形態の粘着剤組成物は、液状であることから、従来の感温性粘着剤のように有機溶剤を含有する必要がない。それゆえ、本実施形態の粘着剤組成物によれば、上述した有機溶剤を含有することによる問題がなく、粘着物性に優れる厚みの大きい粘着剤層を形成することが可能となる。 [(Meth) acrylic monomer]
As described above, 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. Moreover, since 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.
多官能(メタ)アクリレートは、UVが照射されることによって硬化する性質を有する硬化性化合物であり、分子内にラジカル重合可能な二重結合を2個以上有する(メタ)アクリレートである。本実施形態の粘着剤組成物は、上述のとおり、多官能(メタ)アクリレートを含有することから、UV硬化後に凝集力を向上させることができ、結果として優れた耐熱性を発揮することができる。 [Multifunctional (meth) acrylate]
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. .
本実施形態の粘着剤組成物は、上述のとおり、光ラジカル開始剤を含有する。光ラジカル開始剤は、光照射を受けることによってラジカル重合を開始させることが可能となる化合物であればよく、特に限定されるものではない。本実施形態の光ラジカル開始剤は、側鎖結晶性(メタ)アクリルポリマーを構成する上述したモノマーの重合時に使用されるとともに、粘着剤組成物のUV硬化時にも使用される。 [Photo radical initiator]
As described above, 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.
次に、本発明の一実施形態に係る感温性粘着テープについて説明する。
本実施形態の感温性粘着テープは、基材および粘着剤層を備えている。 <Temperature sensitive adhesive tape>
Next, the temperature sensitive adhesive tape which concerns on one Embodiment of this invention is demonstrated.
The temperature-sensitive adhesive tape of this embodiment includes a base material and an adhesive layer.
本実施形態の基材は、フィルム状である。フィルム状とは、フィルム状のみに限定されるものではなく、本実施形態の効果を損なわない限りにおいて、フィルム状ないしシート状をも含む概念である。基材の構成材料としては、例えば、ポリエチレン、ポリエチレンテレフタレート、ポリプロピレン、ポリエステル、ポリアミド、ポリイミド、ポリカーボネート、エチレン酢酸ビニル共重合体、エチレンエチルアクリレート共重合体、エチレンポリプロピレン共重合体、ポリ塩化ビニルなどの合成樹脂が挙げられる。 (Base material)
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.
本実施形態の粘着剤層は、上述した基材の片面または両面に積層されているものであって、基材に上述した一実施形態に係る感温性粘着剤組成物を塗工し、UVを照射して硬化させた硬化物からなる。ここで、粘着剤組成物は、上述した理由から塗工性に優れ、有機溶剤を含有することによる問題がない。それゆえ、本実施形態の感温性粘着テープは、粘着剤層に有機溶剤が揮発することによって発生する気泡がなく、粘着剤層の厚みを大きくすることができ、結果として優れた粘着物性を発揮することができる。 (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 | cured material hardened by irradiating. Here, 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.
次に、本発明の一実施形態に係る感温性粘着シートについて説明する。
本実施形態の感温性粘着シートは、上述した一実施形態に係る粘着剤組成物をシート状に加工してUVを照射して硬化させた硬化物からなる。感温性粘着シートの厚さとしては、1~1,000μmが好ましく、40~500μmがより好ましい。感温性粘着シートの厚さの上限値としては、UVの照射によって硬化できる限り、特に限定されるものではない。
その他の構成は、上述した一実施形態に係る感温性粘着テープと同様であるので、説明を省略する。 <Temperature sensitive adhesive sheet>
Next, the temperature sensitive adhesive sheet which concerns on one Embodiment of this invention is demonstrated.
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 μm, more preferably 40 to 500 μm. 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 | omitted.
まず、フラスコ上部に窒素導入管、温度計、冷却管およびUV照射ヘッドを備える500mlのフラスコに、ベヘニルアクリレートを135g、メチルアクリレートを150g、アクリル酸を15g、および光ラジカル開始剤(光重合開始剤)としてBASFジャパン社製の「IRGACURE 500」を3gの割合で投入し、混合液を得た。 (Synthesis Example 1)
First, 135 g of behenyl acrylate, 150 g of methyl acrylate, 15 g of acrylic acid, and a photoradical initiator (photopolymerization initiator) are placed in a 500 ml flask equipped with a nitrogen introduction tube, a thermometer, a cooling tube and a UV irradiation head at the top of the flask. ) “IRGACURE 500” manufactured by BASF Japan Ltd. was added at a rate of 3 g to obtain a mixed solution.
重合温度:40℃
重合時間:2分
UVの強度:40mW/cm2(365nm) The conditions for bulk polymerization are as follows.
Polymerization temperature: 40 ° C
Polymerization time: 2 minutes UV intensity: 40 mW / cm 2 (365 nm)
側鎖結晶性(メタ)アクリルポリマーの含有量:18重量%
(メタ)アクリルモノマーの含有量:82重量%
液状混合物の粘度:800mPa・s Weight average molecular weight of side chain crystalline (meth) acrylic polymer: 2.5 million Content of side chain crystalline (meth) acrylic polymer: 18% by weight
Content of (meth) acrylic monomer: 82% by weight
Viscosity of liquid mixture: 800 mPa · s
GPCによって測定し、得られた測定値を標準ポリスチレン換算して得た。GPCの測定溶媒には、THFを使用した。 (Weight average molecular weight)
It measured by GPC, and the obtained measured value was obtained by standard polystyrene conversion. THF was used as a measurement solvent for GPC.
上述した重量平均分子量の測定結果において、ポリマー分とモノマー分との検出面積比から算出した。 (Content)
In the measurement result of the weight average molecular weight described above, it was calculated from the detection area ratio of the polymer component and the monomer component.
以下の測定条件で測定した。
測定装置:英弘精機社製のデジタル粘度計「DV-II+Pro」
コーンプレート:CPE-42
回転数:30rpm
測定温度:50℃ (viscosity)
The measurement was performed under the following measurement conditions.
Measuring device: Digital viscometer “DV-II + Pro” manufactured by Eihiro Seiki Co., Ltd.
Cone plate: CPE-42
Rotation speed: 30rpm
Measurement temperature: 50 ° C
連鎖移動剤としてドデシルメルカプタンを0.3gの割合で加えた以外は、上述した合成例1と同様にしてUVを照射しながらモノマーをバルク重合して、側鎖結晶性(メタ)アクリルポリマーと(メタ)アクリルモノマーとの液状混合物を得た。 (Synthesis Example 2)
Except for adding 0.3 g of dodecyl mercaptan as a chain transfer agent, the monomers were bulk polymerized while being irradiated with UV in the same manner as in Synthesis Example 1 described above, and the side chain crystalline (meth) acrylic polymer ( A liquid mixture with a (meth) acrylic monomer was obtained.
側鎖結晶性(メタ)アクリルポリマーの含有量:20重量%
(メタ)アクリルモノマーの含有量:80重量%
液状混合物の粘度:200mPa・s 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
まず、フラスコ上部に窒素導入管、温度計、冷却管を備える500mlのフラスコに、ベヘニルアクリレートを45g、メチルアクリレートを50g、アクリル酸を5g、および重合開始剤として日油社製の「パーブチルND」を0.5gの割合で投入して混合物を得た。次に、酢酸エチル:ヘプタン=7:3(重量比)の混合溶媒をフラスコに投入し、混合物の濃度が固形分換算で30重量部になるように調整し、混合液を得た。 (Comparative synthesis example)
First, 45 g of behenyl acrylate, 50 g of methyl acrylate, 5 g of acrylic acid, and “Perbutyl ND” manufactured by NOF Corporation as a polymerization initiator are placed in a 500 ml flask equipped with a nitrogen introduction tube, a thermometer and a cooling tube at the top of the flask. Was added at a rate of 0.5 g to obtain a mixture. Next, a mixed solvent of ethyl acetate: heptane = 7: 3 (weight ratio) was added to the flask, and the concentration of the mixture was adjusted to be 30 parts by weight in terms of solid content to obtain a mixed solution.
ポリマー溶液の粘度:1,000mPa・s Weight average molecular weight of polymer: 600,000 Viscosity of polymer solution: 1,000 mPa · s
<感温性粘着テープの製造>
塗工液として、合成例1で得られた液状混合物を使用した。そして、まず、この液状混合物100gに対して多官能アクリレートを添加した。 [Examples 1 to 4]
<Manufacture of temperature-sensitive adhesive tape>
As the coating liquid, the liquid mixture obtained in Synthesis Example 1 was used. First, polyfunctional acrylate was added to 100 g of this liquid mixture.
多官能アクリレート:新中村化学工業社製の1,6-ヘキサンジオールジアクリレート「NKエステルA-HD-N」 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.
実施例1:0.5g
実施例2:0.5g
実施例3:1.0g
実施例4:1.0g The amount of polyfunctional acrylate added to 100 g of the liquid mixture is as follows.
Example 1: 0.5 g
Example 2: 0.5 g
Example 3: 1.0 g
Example 4: 1.0 g
基材:片面をコロナ処理したユニチカ社製の厚さ100μmのポリエチレンテレフタレートフィルム「エンブレットSB-100」 The used film-like base materials are as follows.
Substrate: 100 μm thick polyethylene terephthalate film “Embret SB-100” manufactured by Unitika Co., Ltd. with one side corona-treated
実施例1:10mil
実施例2: 5mil
実施例3: 5mil
実施例4:10mil The gap of the applicator is as follows.
Example 1: 10 mil
Example 2: 5 mil
Example 3: 5 mil
Example 4: 10 mil
空気遮断部材:ニッパ株式会社製の表面をシリコン処理した厚さ25μmのポリエチレンテレフタレートフィルム「PET25×1-J0L」 The air blocking member used is as follows.
Air blocking member: 25 μm thick polyethylene terephthalate film “PET25 × 1-J0L” manufactured by Nipper Co., Ltd.
UV照射装置:アズワン社製の「HLR100T-2/HB100A-1」
UV量:1,500mJ/cm2 The UV irradiation conditions are as follows.
UV irradiation device: “HLR100T-2 / HB100A-1” manufactured by ASONE
UV amount: 1,500 mJ / cm 2
得られた感温性粘着テープについて、粘着剤層の状態および180°剥離強度を評価した。各評価方法を以下に示すとともに、その結果を表1に示す。 <Evaluation>
About the obtained temperature-sensitive adhesive tape, the state of the adhesive layer and the 180 ° peel strength were evaluated. Each evaluation method is shown below, and the results are shown in Table 1.
感温性粘着テープの粘着剤層を目視観察することによって、気泡混入の有無を評価した。なお、評価基準は、以下のように設定した。
○:粘着剤層中に気泡がなかった。
△:粘着剤層中に少数の気泡が存在していた。
×:粘着剤層中に多数の気泡が存在していた。 (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.
Δ: A small number of bubbles were present in the pressure-sensitive adhesive layer.
X: Many air bubbles existed in the adhesive layer.
得られた感温性粘着テープについて、80℃、80℃を経た後の23℃、120℃および120℃を経た後の23℃の各雰囲気温度におけるステンレス鋼製の板(以下、「SUS板」と言うことがある。)に対する180°剥離強度をJIS Z0237に準拠して測定した。具体的には、以下の条件で感温性粘着テープをSUS板に貼着した後、ロードセルを用いて300mm/分の速度で180°剥離した。 (180 ° peel strength)
About the obtained temperature-sensitive adhesive tape, 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.
感温性粘着テープをSUS板に貼り付けた状態で雰囲気温度を80℃にし、この雰囲気温度で20分間静置した後、180°剥離した。 [80 ° C]
With the temperature sensitive adhesive tape attached to the SUS plate, the ambient temperature was set to 80 ° C., left at this ambient temperature for 20 minutes, and then peeled 180 °.
感温性粘着テープをSUS板に貼り付けた状態で雰囲気温度を80℃にし、この雰囲気温度で20分間静置した後、雰囲気温度を23℃に下げ、この雰囲気温度で20分間静置した後、180°剥離した。 [23 ° C after 80 ° C]
After the ambient temperature is set to 80 ° C. with the temperature-sensitive adhesive tape attached to the SUS plate and left at this ambient temperature for 20 minutes, the ambient temperature is lowered to 23 ° C. and left at this ambient temperature for 20 minutes. , Peeled 180 °.
感温性粘着テープをSUS板に貼り付けた状態で雰囲気温度を120℃にし、この雰囲気温度で20分間静置した後、180°剥離した。 [120 ° C]
With the temperature-sensitive adhesive tape attached to the SUS plate, the ambient temperature was set to 120 ° C., left at this ambient temperature for 20 minutes, and then peeled 180 °.
感温性粘着テープをSUS板に貼り付けた状態で雰囲気温度を120℃にし、この雰囲気温度で20分間静置した後、雰囲気温度を23℃に下げ、この雰囲気温度で20分間静置した後、180°剥離した。 [23 ° C. after 120 ° C.]
After the ambient temperature is set to 120 ° C. with the temperature-sensitive adhesive tape attached to the SUS plate and left at this ambient temperature for 20 minutes, the ambient temperature is lowered to 23 ° C. and left at this ambient temperature for 20 minutes. , Peeled 180 °.
塗工液として、合成例2で得られた液状混合物を使用した以外は、上述した実施例1と同様にして表1に示す厚みを有する粘着剤層をフィルム状の基材の片面に備える感温性粘着テープを得た。 [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.
まず、ベヘニルアクリレートを135g、メチルアクリレートを150g、アクリル酸を15g、および光ラジカル開始剤(光重合開始剤)としてBASFジャパン社製の「IRGACURE 500」を3gの割合で混合した混合液に、多官能アクリレートを0.5gの割合で加えて塗工液を得た。なお、多官能アクリレートは、実施例1と同じものを使用した。 [Comparative Example 1]
First, 135 g of behenyl acrylate, 150 g of methyl acrylate, 15 g of acrylic acid, and 3 g of “IRGACURE 500” manufactured by BASF Japan Ltd. as a photo radical initiator (photo polymerization initiator) Functional acrylate was added at a ratio of 0.5 g to obtain a coating solution. The same polyfunctional acrylate as in Example 1 was used.
塗工液として、比較合成例で得られたポリマー溶液を使用した。そして、まず、このポリマー溶液100gに対してトリエチルアミンを9gの割合で添加し、架橋剤をさらに添加した。 [Comparative Examples 2 to 5]
As 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.
架橋剤:日本触媒社製のアジリジン化合物「ケミタイトPZ-33」 The added crosslinking agent is as follows.
Cross-linking agent: aziridine compound “Chemite PZ-33” manufactured by Nippon Shokubai Co., Ltd.
比較例2:0.5g
比較例3:0.5g
比較例4:0.5g
比較例5:1.0g 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
比較例2:10mil
比較例3:15mil
比較例4:20mil
比較例5:10mil 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
Claims (11)
- 少なくとも側鎖結晶性(メタ)アクリルポリマー、(メタ)アクリルモノマー、多官能(メタ)アクリレートおよび光ラジカル開始剤を含有するとともに、紫外線硬化性を有し、かつ液状である、感温性粘着剤組成物。 A temperature-sensitive adhesive that contains at least a side-chain crystalline (meth) acrylic polymer, a (meth) acrylic monomer, a polyfunctional (meth) acrylate, and a photoradical initiator, and is UV-curable and liquid. Composition.
- 前記側鎖結晶性(メタ)アクリルポリマーが、少なくとも炭素数16以上の直鎖状アルキル基を有する(メタ)アクリレートを含むモノマーに光ラジカル開始剤を添加して紫外線を照射しながらバルク重合したポリマーである、請求項1に記載の感温性粘着剤組成物。 Polymer in which the side chain crystalline (meth) acrylic polymer is bulk polymerized while adding a photo radical initiator to a monomer containing (meth) acrylate having a linear alkyl group having at least 16 carbon atoms and irradiating ultraviolet rays The temperature-sensitive adhesive composition according to claim 1, wherein
- 前記側鎖結晶性(メタ)アクリルポリマーの重量平均分子量が、45万以上である、請求項1または2に記載の感温性粘着剤組成物。 The temperature-sensitive adhesive composition according to claim 1 or 2, wherein the side chain crystalline (meth) acrylic polymer has a weight average molecular weight of 450,000 or more.
- 前記側鎖結晶性(メタ)アクリルポリマー、前記(メタ)アクリルモノマー、前記多官能(メタ)アクリレートおよび前記光ラジカル開始剤のうち、前記側鎖結晶性(メタ)アクリルポリマーおよび前記(メタ)アクリルモノマーの合計含有量が最も多い、請求項1~3のいずれかに記載の感温性粘着剤組成物。 Among the side chain crystalline (meth) acrylic polymer, the (meth) acrylic monomer, the polyfunctional (meth) acrylate, and the photo radical initiator, the side chain crystalline (meth) acrylic polymer and the (meth) acrylic The temperature-sensitive adhesive composition according to any one of claims 1 to 3, wherein the total monomer content is the highest.
- 前記側鎖結晶性(メタ)アクリルポリマーおよび前記(メタ)アクリルモノマーの合計100重量%に対して、前記側鎖結晶性(メタ)アクリルポリマーを5~40重量%の割合で含有する、請求項1~4のいずれかに記載の感温性粘着剤組成物。 The side chain crystalline (meth) acrylic polymer is contained in a proportion of 5 to 40% by weight with respect to a total of 100% by weight of the side chain crystalline (meth) acrylic polymer and the (meth) acrylic monomer. 5. The temperature-sensitive adhesive composition according to any one of 1 to 4.
- 有機溶剤を含有していない、請求項1~5のいずれかに記載の感温性粘着剤組成物。 The temperature-sensitive adhesive composition according to any one of claims 1 to 5, which does not contain an organic solvent.
- 紫外線硬化後において、前記側鎖結晶性(メタ)アクリルポリマーの融点以上の温度で粘着力を発現し、かつ前記融点未満の温度で粘着力が低下する、請求項1~6のいずれかに記載の感温性粘着剤組成物。 The adhesive strength is exhibited at a temperature equal to or higher than the melting point of the side-chain crystalline (meth) acrylic polymer after ultraviolet curing, and the adhesive strength is decreased at a temperature lower than the melting point. Temperature-sensitive adhesive composition.
- 前記(メタ)アクリルモノマーが、前記側鎖結晶性(メタ)アクリルポリマーを構成するモノマーと同一である、請求項1~7のいずれかに記載の感温性粘着剤組成物。 The temperature-sensitive adhesive composition according to any one of claims 1 to 7, wherein the (meth) acrylic monomer is the same as the monomer constituting the side chain crystalline (meth) acrylic polymer.
- フィルム状の基材と、
前記基材の片面または両面に積層されている粘着剤層と、を備え、
前記粘着剤層が、請求項1~8のいずれかに記載の感温性粘着剤組成物の硬化物からなる、感温性粘着テープ。 A film-like substrate;
A pressure-sensitive adhesive layer laminated on one side or both sides of the base material,
A temperature-sensitive adhesive tape, wherein the pressure-sensitive adhesive layer comprises a cured product of the temperature-sensitive adhesive composition according to any one of claims 1 to 8. - 請求項1~8のいずれかに記載の感温性粘着剤組成物の硬化物からなる、感温性粘着シート。 A temperature-sensitive adhesive sheet comprising a cured product of the temperature-sensitive adhesive composition according to any one of claims 1 to 8.
- 少なくとも側鎖結晶性(メタ)アクリルポリマー、(メタ)アクリルモノマー、多官能(メタ)アクリレートおよび光ラジカル開始剤を含有するとともに、紫外線硬化性を有し、かつ液状である、感温性粘着剤組成物の製造方法であって、
少なくとも炭素数16以上の直鎖状アルキル基を有する(メタ)アクリレートを含むモノマーに光ラジカル開始剤を添加して紫外線を照射しながらバルク重合することによって前記側鎖結晶性(メタ)アクリルポリマーを得る、感温性粘着剤組成物の製造方法。 A temperature-sensitive adhesive that contains at least a side-chain crystalline (meth) acrylic polymer, a (meth) acrylic monomer, a polyfunctional (meth) acrylate, and a photoradical initiator, and is UV-curable and liquid. A method for producing a composition comprising:
The side chain crystalline (meth) acrylic polymer is obtained by bulk polymerization while adding a photo radical initiator to a monomer containing a (meth) acrylate having a linear alkyl group having at least 16 carbon atoms and irradiating with ultraviolet rays. A method for producing a temperature-sensitive adhesive composition.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017509533A JP6898226B2 (en) | 2015-04-01 | 2016-03-16 | Temperature sensitive adhesive composition |
CN201680012265.0A CN107406737B (en) | 2015-04-01 | 2016-03-16 | Temperature sensitive adhesive composition |
KR1020177021134A KR102452985B1 (en) | 2015-04-01 | 2016-03-16 | Temperature-sensitive adhesive composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015075115 | 2015-04-01 | ||
JP2015-075115 | 2015-04-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016158413A1 true WO2016158413A1 (en) | 2016-10-06 |
Family
ID=57007084
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/058297 WO2016158413A1 (en) | 2015-04-01 | 2016-03-16 | Temperature-sensitive adhesive composition |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6898226B2 (en) |
KR (1) | KR102452985B1 (en) |
CN (1) | CN107406737B (en) |
TW (1) | TWI589658B (en) |
WO (1) | WO2016158413A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018024795A (en) * | 2016-08-12 | 2018-02-15 | ニッタ株式会社 | Temperature-sensitive adhesive tape and temperature-sensitive adhesive sheet |
KR20180118517A (en) * | 2017-04-21 | 2018-10-31 | 니타 가부시키가이샤 | Temperature sensitive adhesive |
KR20190046192A (en) * | 2017-10-25 | 2019-05-07 | (주)켐베이스 | Temperature sensitive adhesive composition |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007254590A (en) * | 2006-03-23 | 2007-10-04 | Nippon Steel Chem Co Ltd | Die bond dicing film |
JP2009179781A (en) * | 2008-02-01 | 2009-08-13 | Nippon Shokubai Co Ltd | Ionizing radiation curable adhesive composition for removal, and use thereof |
JP2009256607A (en) * | 2008-03-17 | 2009-11-05 | Nitto Denko Corp | Acrylic adhesive, acrylic adhesive layer, and acrylic adhesive tape or sheet |
JP2011099042A (en) * | 2009-11-06 | 2011-05-19 | Nitta Corp | Temperature-sensitive adhesive |
JP2012087218A (en) * | 2010-10-20 | 2012-05-10 | Nitta Corp | Thermosensitive pressure-sensitive adhesive |
JP2016094569A (en) * | 2014-11-17 | 2016-05-26 | 日東電工株式会社 | Optical double-sided adhesive sheet |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09153471A (en) * | 1995-11-30 | 1997-06-10 | Mitsui Toatsu Chem Inc | Adhesive film for dicing semiconductor wafer and use thereof |
JP3485412B2 (en) | 1996-03-15 | 2004-01-13 | ニッタ株式会社 | Temporary adhesive tape for laminated ceramic capacitor laminating process and method for producing laminated ceramic capacitor |
US5888650A (en) * | 1996-06-03 | 1999-03-30 | Minnesota Mining And Manufacturing Company | Temperature-responsive adhesive article |
JP4579363B2 (en) * | 1999-10-28 | 2010-11-10 | 古河電気工業株式会社 | Adhesive tape for semiconductor processing |
JP5165282B2 (en) * | 2007-06-12 | 2013-03-21 | 日東電工株式会社 | Identification adhesive sheet and method for producing the same |
KR101639700B1 (en) * | 2009-02-16 | 2016-07-14 | 니타 가부시키가이샤 | Heat-sensitive adhesive and heat-sensitive adhesive tape |
WO2011001550A1 (en) * | 2009-07-02 | 2011-01-06 | ニッタ株式会社 | Functional film-attached adhesive tape, and method for transferring functional film |
JP2012052038A (en) * | 2010-09-01 | 2012-03-15 | Nitto Denko Corp | Temporary fixing sheet for manufacturing process of electronic part |
KR101740536B1 (en) * | 2011-01-12 | 2017-05-26 | 동우 화인켐 주식회사 | Adhesive composition for optical use |
JP5908337B2 (en) * | 2011-06-13 | 2016-04-26 | 日東電工株式会社 | Cooling release adhesive sheet |
WO2013161812A1 (en) * | 2012-04-27 | 2013-10-31 | 荒川化学工業株式会社 | Ultraviolet light curing adhesive composition and adhesive layer |
JP2014172999A (en) * | 2013-03-08 | 2014-09-22 | Nitto Denko Corp | Pressure sensitive adhesive sheet |
JP6147105B2 (en) * | 2013-06-10 | 2017-06-14 | ニッタ株式会社 | Temperature-sensitive adhesive sheet, temperature-sensitive adhesive tape, and pressure-sensitive adhesive sheet forming method |
-
2016
- 2016-03-16 WO PCT/JP2016/058297 patent/WO2016158413A1/en active Application Filing
- 2016-03-16 CN CN201680012265.0A patent/CN107406737B/en active Active
- 2016-03-16 KR KR1020177021134A patent/KR102452985B1/en active IP Right Grant
- 2016-03-16 JP JP2017509533A patent/JP6898226B2/en active Active
- 2016-03-25 TW TW105109398A patent/TWI589658B/en active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007254590A (en) * | 2006-03-23 | 2007-10-04 | Nippon Steel Chem Co Ltd | Die bond dicing film |
JP2009179781A (en) * | 2008-02-01 | 2009-08-13 | Nippon Shokubai Co Ltd | Ionizing radiation curable adhesive composition for removal, and use thereof |
JP2009256607A (en) * | 2008-03-17 | 2009-11-05 | Nitto Denko Corp | Acrylic adhesive, acrylic adhesive layer, and acrylic adhesive tape or sheet |
JP2011099042A (en) * | 2009-11-06 | 2011-05-19 | Nitta Corp | Temperature-sensitive adhesive |
JP2012087218A (en) * | 2010-10-20 | 2012-05-10 | Nitta Corp | Thermosensitive pressure-sensitive adhesive |
JP2016094569A (en) * | 2014-11-17 | 2016-05-26 | 日東電工株式会社 | Optical double-sided adhesive sheet |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018024795A (en) * | 2016-08-12 | 2018-02-15 | ニッタ株式会社 | Temperature-sensitive adhesive tape and temperature-sensitive adhesive sheet |
KR20180118517A (en) * | 2017-04-21 | 2018-10-31 | 니타 가부시키가이샤 | Temperature sensitive adhesive |
JP2018178057A (en) * | 2017-04-21 | 2018-11-15 | ニッタ株式会社 | Temperature-sensitive adhesive |
KR102431157B1 (en) | 2017-04-21 | 2022-08-10 | 니타 가부시키가이샤 | Temperature sensitive adhesive |
KR20190046192A (en) * | 2017-10-25 | 2019-05-07 | (주)켐베이스 | Temperature sensitive adhesive composition |
KR102031621B1 (en) * | 2017-10-25 | 2019-10-14 | (주)켐베이스 | Temperature sensitive adhesive composition |
Also Published As
Publication number | Publication date |
---|---|
TWI589658B (en) | 2017-07-01 |
CN107406737B (en) | 2020-03-17 |
KR102452985B1 (en) | 2022-10-11 |
CN107406737A (en) | 2017-11-28 |
KR20170134972A (en) | 2017-12-07 |
JP6898226B2 (en) | 2021-07-07 |
JPWO2016158413A1 (en) | 2018-01-25 |
TW201704420A (en) | 2017-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2016153504A (en) | Acrylic adhesive tape and method for producing the same | |
TWI646169B (en) | Thermosensitivity adhesive agent, thermosensitivity adhesive sheet, and thermosensitivity adhesive tape | |
JP6546910B2 (en) | Temperature sensitive adhesive | |
JP5639438B2 (en) | Temperature sensitive adhesive | |
JP7460451B2 (en) | temperature sensitive adhesive | |
JP7225530B2 (en) | Solvent-free resin composition | |
JP6898226B2 (en) | Temperature sensitive adhesive composition | |
KR102655512B1 (en) | Temperature-sensitive adhesive, temperature-sensitive adhesive sheet and temperature-sensitive adhesive tape | |
JP6898227B2 (en) | Temperature-sensitive adhesive tape and temperature-sensitive adhesive sheet | |
KR20170113269A (en) | Temperature-sensitive adhesive | |
JP6697395B2 (en) | UV curable acrylic polymer and UV curable acrylic hot melt adhesive containing the same | |
JP6479540B2 (en) | Temperature sensitive adhesive | |
JP6440407B2 (en) | TSV wafer manufacturing method | |
JP6792509B2 (en) | Temperature sensitive adhesive | |
JP6813988B2 (en) | Temperature-sensitive adhesive tape and temperature-sensitive adhesive sheet | |
KR20170113401A (en) | Temperature-sensitive adhesive | |
JP2004010835A (en) | Ultraviolet-curable acrylic pressure sensitive adhesive, process for producing it and pressure sensitive adhesive sheet | |
JP2001354932A (en) | Ultraviolet-curable pressure-sensitive adhesive and pressure-sensitive adhesive sheet | |
JP6393510B2 (en) | Temperature-sensitive adhesive composition | |
JP2023108686A (en) | Adhesive, hot melt adhesive, and label | |
JP2002275441A (en) | Adhesive paper |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16772296 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017509533 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20177021134 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 16772296 Country of ref document: EP Kind code of ref document: A1 |