WO2022138703A1 - 気体発生剤、粘着組成物、及び粘着シート - Google Patents
気体発生剤、粘着組成物、及び粘着シート Download PDFInfo
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- WO2022138703A1 WO2022138703A1 PCT/JP2021/047514 JP2021047514W WO2022138703A1 WO 2022138703 A1 WO2022138703 A1 WO 2022138703A1 JP 2021047514 W JP2021047514 W JP 2021047514W WO 2022138703 A1 WO2022138703 A1 WO 2022138703A1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229940042596 viscoat Drugs 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
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
- 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
- C09J7/10—Adhesives in the form of films or foils without 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/23—Azo-compounds
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- 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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
-
- 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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- 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
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
-
- 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
-
- 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
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
- C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present disclosure relates to a gas generator, a pressure-sensitive adhesive composition containing the gas-generating agent, and a pressure-sensitive adhesive sheet.
- the pressure-sensitive adhesive composition containing a pressure-sensitive adhesive component is widely used as a binder agent such as a pressure-sensitive adhesive, a sealing agent, a paint, and a coating agent, and a pressure-sensitive adhesive material such as an pressure-sensitive adhesive tape or a pressure-sensitive adhesive sheet.
- a binder agent such as a pressure-sensitive adhesive, a sealing agent, a paint, and a coating agent
- a pressure-sensitive adhesive material such as an pressure-sensitive adhesive tape or a pressure-sensitive adhesive sheet.
- the thick film wafer is adhered to an adhesive sheet. It has been proposed that the work be carried out efficiently by reinforcing it. Further, when dicing a thin film wafer ground to a predetermined thickness into individual semiconductor chips, an adhesive sheet called a dicing tape is used as a temporary fixing support. Further, in the manufacturing process of the laminated ceramic capacitor (MLCC), the adhesive sheet is temporarily used when the sheet of the dielectric paste on which the electrodes are printed is laminated and then pressed to be pressure-bonded and integrated into chips. Used as a fixed support.
- MLCC laminated ceramic capacitor
- the adhesive sheet is used as a process support for temporary fixing. Further, in the manufacturing process of the flexible printed wiring board and the flexible organic EL display, the above-mentioned is aimed at preventing the substrate from being scratched or contaminated by chemicals, and deterioration of the substrate due to chemicals or heating used in the manufacturing process.
- a protective sheet that protects the surface of the substrate may be used, and the adhesive sheet is used as the temporary protective sheet.
- Patent Document 1 discloses an adhesive tape using a photocurable adhesive which is cured by irradiation with light such as ultraviolet rays to reduce the adhesive strength. .. It is said that such an adhesive tape can be easily peeled off by irradiating it with ultraviolet rays or the like while adhering it during the processing process. However, with such an adhesive tape, the decrease in adhesive strength after irradiation with ultraviolet rays or the like is insufficient, and it is difficult to peel off the thin film wafer, the semiconductor chip, or the like without damaging them.
- Patent Document 2 discloses an adhesive tape having an adhesive layer containing a gas generating agent that generates a gas by stimulation, such as an azo compound.
- a gas generating agent that generates a gas by stimulation, such as an azo compound.
- Patent Document 3 as an adhesive composition which has high adhesiveness, can be easily peeled off, and has excellent heat resistance, a gas is generated by irradiation with light, and tetrazole having high heat resistance. Adhesive compositions using compounds have been proposed. However, even if the above-mentioned azo compound or tetrazole compound is used, there are problems that the peeling power is not sufficiently reduced and that the addition amount must be increased in order to sufficiently reduce the peeling power.
- the process is such that the adherend itself and the surface of the adherend are easily destroyed due to the thinning of the adherend itself, the integration of functions, and the miniaturization. While the inside is firmly adhered, it is required to be easily peeled off with less load on the adherend after the process is completed.
- the improvement of the adhesive strength and the improvement of the easy peeling property and the conventional adhesive material for the purpose of high adhesive and easy peeling has not yet been sufficiently easy to peel off.
- the present disclosure has been made in view of the above circumstances, and is a gas generator that generates a gas by light irradiation, which can improve the effect of imparting peelability to the surface, and when the gas generator is used, when used.
- a pressure-sensitive adhesive composition that has sufficient adhesive strength and is capable of forming an adhesive layer that is easily peeled off from an adherend when peeled off. It is an object of the present invention to provide an adhesive sheet having excellent peelability from an adherend.
- One embodiment of the present disclosure is represented by at least one of the following general formulas (1) and (2), the maximum value of the molar extinction coefficient at a wavelength of 240 to 450 nm is 7,000 or more, and gas is generated by light irradiation.
- a gas generating agent is provided.
- A independently represents a gas generating part represented by the following general formulas (A-1), (A-2) or (A-3).
- L each independently represents a direct bond or a divalent linking group.
- Q1 has 2 to 8 carbon atoms to which a fluorine atom is directly bonded, may contain an ether bond (—O—) in the carbon chain, and may have a substituent.
- Q2 has a divalent fluorinated aliphatic hydrocarbon group having 2 to 8 carbon atoms to which a fluorine atom is directly bonded and may contain an ether bond (—O—) in the carbon chain, or a divalent fluorinated aliphatic hydrocarbon group. Represents a divalent organopolysiloxane group.
- R 1 is an aromatic group having 3 to 20 carbon atoms which may have a substituent
- R 2 is independent of each other.
- a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R3 are each independently or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
- Cyan group, -COOR 5 , or -CONR 6 R 7 , R 4 may have a substituent, a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, -COOR 5 , -CONR 6 R 7 , Or the above-LQ 1 , R 5 and R 7 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R 6 is a hydrogen atom or a hydrogen atom or. Represents a hydrocarbon group having 1 to 5 carbon atoms.
- Q1 is a monovalent fluorination of any one represented by the following (Rf-1) to (Rf-5). It represents an aliphatic hydrocarbon group or a monovalent organopolysiloxane group represented by the following (Si-1), and Q2 is a divalent fluorinated aliphatic hydrocarbon represented by the following (Rf-6). It may represent a hydrogen group or a divalent organopolysiloxane group represented by the following (Si-2).
- n independently represents an integer of 2 to 8, and in the formula (Rf-4), n'is 4 to 4 to.
- n is an integer of 0 to 8
- m is an integer of 0 to 8
- n + n" ⁇ m is an integer of 2 to 8.
- J 1 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an amino group, a carboxy group, or a (meth) acryloyloxy group
- n is an integer of 1 to 8, and n "is 0 to 0.
- An integer of 7, m is an integer of 0 to 7, where n + n ” ⁇ m is an integer of 2 to 8).
- R 11 independently has a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, a hydrogen atom, a hydroxyl group, and the like.
- J2 is a monovalent hydrocarbon having 1 to 20 carbon atoms which may have a substituent. It represents a group, a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an amino group, a carboxy group, or a (meth) acryloyloxy group.
- A independently represents a number of 1 to 100.
- R 12 has a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, or 1 to 20 carbon atoms, each of which may independently have a substituent. Represents an alkoxy group of, and b represents a number from 0 to 100.
- L is directly bonded or directly bonded to each other, or -SCH 2 CH 2 COO-, -SCH 2 CH (CH 3 ) COO, respectively.
- One or more selected from the group consisting of -COS-, -SO 2 NH-, or -O- and -S- may be contained, and the hydroxyl group may be substituted with 1 to 22 carbon atoms. It may represent the hydrocarbon group of the above, or a combination thereof.
- Another embodiment of the present disclosure provides a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive component and the gas generating agent of one embodiment of the present disclosure.
- Another embodiment of the present disclosure comprises a pressure-sensitive adhesive layer and a substrate or mold release sheet on one surface of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer is a pressure-sensitive adhesive composition or a cured product thereof containing a pressure-sensitive adhesive component and the gas generating agent of one embodiment of the present disclosure, and the pressure-sensitive adhesive layer is reduced from the initial pressure-sensitive adhesive force by light irradiation.
- an adhesive sheet having the characteristics of
- the pressure-sensitive adhesive composition of the present disclosure and the pressure-sensitive adhesive composition in the pressure-sensitive adhesive sheet may contain a photocurable component and a photoinitiator.
- the pressure-sensitive adhesive composition of the present disclosure and the pressure-sensitive adhesive composition in the pressure-sensitive adhesive sheet may contain a heat-crosslinking agent.
- the pressure-sensitive adhesive sheet of the present disclosure may further include a release sheet on the surface of the pressure-sensitive adhesive layer opposite to the base material or the release sheet side.
- a gas generator that generates a gas by light irradiation, which can improve the effect of imparting peelability to the surface, and the gas generator, which has sufficient adhesive strength at the time of use.
- a pressure-sensitive adhesive composition capable of forming an adhesive layer having excellent peelability from the adherend, and the pressure-sensitive adhesive composition is used, while having sufficient adhesive strength at the time of use, it is adhered. It is possible to provide an adhesive sheet having excellent peelability from the body.
- (meth) acrylic represents each of acrylic or methacrylic
- (meth) acrylate represents each of acrylate or methacrylate.
- the "sheet” also includes a member called a "film”.
- the “film” also includes a member called a "sheet”.
- the "sheet surface (film surface)” is the plane direction of the target sheet-like member (film-like member) when the target sheet-like member (film-like member) is viewed as a whole and from a broad perspective. Refers to the matching plane.
- the "light” includes light including ultraviolet rays.
- the gas generator, the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive sheet of the present disclosure will be described in detail in order.
- the gas generator of one embodiment of the present disclosure is represented by at least one of the following general formulas (1) and (2), and has a maximum molar extinction coefficient of 7,000 or more at a wavelength of 240 to 450 nm. It is a gas generating agent that generates gas by light irradiation.
- A independently represents a gas generating part represented by the following general formulas (A-1), (A-2) or (A-3).
- L each independently represents a direct bond or a divalent linking group.
- Q1 has 2 to 8 carbon atoms to which a fluorine atom is directly bonded, may contain an ether bond (—O—) in the carbon chain, and may have a substituent.
- Q2 has a divalent fluorinated aliphatic hydrocarbon group having 2 to 8 carbon atoms to which a fluorine atom is directly bonded and may contain an ether bond (—O—) in the carbon chain, or a divalent fluorinated aliphatic hydrocarbon group. Represents a divalent organopolysiloxane group.
- R 1 is an aromatic group having 3 to 20 carbon atoms which may have a substituent
- R 2 is independent of each other.
- Cyan group, -COOR 5 , or -CONR 6 R 7 , R 4 may have a substituent, a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, -COOR 5 , -CONR 6 R 7 , Or the above-LQ 1 , R 5 and R 7 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R 6 is a hydrogen atom or a hydrogen atom or. Represents a hydrocarbon group having 1 to 5 carbon atoms.
- the gas generator of the present disclosure has the gas generating part having the specific structure and the specific fluorinated aliphatic hydrocarbon group or the specific organopolysiloxane group, and has a molar absorption coefficient at a wavelength of 240 to 450 nm.
- the gas generated from the gas generating agent is applied to the surface of the adhesive layer, that is, the interface with the adherend by irradiating light after use. It is released and the pressure causes at least a portion of the adherend to peel off.
- the adhesive layer has a reduced contact area with the adherend and can be easily peeled off.
- the gas-generating agent is uniformly dispersed in the pressure-sensitive adhesive layer.
- the gas generating agent of the present disclosure the specific fluorinated aliphatic hydrocarbon group or the specific organopolysiloxane group is introduced into the gas generating portion having the specific structure.
- the gas generating agent tends to be localized on the surface of the pressure-sensitive adhesive layer. Therefore, when irradiated with light, the gas-generating agent localized on the surface of the pressure-sensitive adhesive layer releases gas. It is generated and the gas is easily released to the surface of the adhesive layer.
- the amount of gas generated on the surface of the pressure-sensitive adhesive layer is efficiently increased, so that the adhesive layer is excellent in easy peeling property from the adherend.
- the gas generating agent of the present disclosure is easily localized on the surface of the adhesive layer, the amount of gas generated on the surface of the adhesive layer can be efficiently increased without increasing the content of the gas generating agent. , It is possible to suppress a decrease in the adhesive strength of the adhesive layer and white turbidity. As described above, it is presumed that the gas generating agent of the present disclosure can improve the effect of imparting peelability to the surface.
- the gas generating agent of the present disclosure can be decomposed by light irradiation to generate a gas. Since the gas generator of the present disclosure has a maximum molar extinction coefficient of 7,000 or more at a wavelength of 240 to 450 nm, it can efficiently absorb light containing ultraviolet rays, and can be efficiently irradiated with light containing ultraviolet rays. It can be decomposed to generate gas.
- A independently represents the gas generating portion represented by the general formula (A-1), (A-2) or (A-3).
- the tetrazole ring is decomposed by light irradiation to generate nitrogen gas.
- the gas generating portion represented by the general formula (A-3) is decomposed at the azo group portion by light irradiation to generate nitrogen gas.
- the compound satisfies the maximum value of the specific molar extinction coefficient. It may be selected as appropriate.
- the aromatic group having 3 to 20 carbon atoms include an aromatic hydrocarbon group and an aromatic heterocyclic group.
- aromatic hydrocarbon group examples include an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms is preferable, for example, a phenyl group, a biphenyl group, a naphthyl group, and an anthryl group. , Phenantril group, fluorenyl group, naphthylphenyl group, pyrenyl group and the like.
- aromatic heterocyclic group include an aromatic heterocyclic group having 3 to 20 carbon atoms containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom, and an aromatic heterocyclic group having 3 to 10 carbon atoms.
- a pyrrolyl group, a frill group, a thienyl group, a pyrazolyl group, an imidazolyl group, an oxazolyl group, an isooxazolyl group, a thiazolyl group, an isothiazolyl group, a carbazole group and the like can be mentioned.
- the substituent that the aromatic group may have include a halogen atom such as F, Cl and Br, an alkoxy group such as a nitro group, an alkyl group, an alkenyl group, an aralkyl group and a methoxy group, and a diphenylamino group.
- Examples thereof include an acyl group such as a tertiary amino group and a benzoyl group.
- the alkyl group, alkenyl group, and aralkyl group may be the same as the alkyl group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms, and the aralkyl group, which will be described later, but the alkyl group having 1 to 14 carbon atoms, It is preferably an alkenyl group having 2 to 14 carbon atoms and an aralkyl group having 7 to 14 carbon atoms.
- Examples of the substituent that changes the absorption wavelength of light toward the long wavelength side include an alkoxy group such as a methoxy group, a diarylamino group such as a diphenylamino group, and an acyl group such as a benzoyl group.
- R1 may be an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent because the absorption wavelength region can be expanded and the wavelength can be lengthened. Among them, R1 has a substituent. It is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a phenyl group, a naphthyl group, or an anthryl group which may have a substituent, and irradiate light containing ultraviolet rays. In some cases, a naphthyl group is more preferable because the sensitivity is high and the gas generation efficiency is improved.
- Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R2 include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group, and an aryl group. And so on.
- the alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or 2-.
- Examples thereof include ethylhexyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group substituted adamantyl group and the like.
- the alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, a propenyl group and the like.
- the position of the double bond of the alkenyl group is not limited, but from the viewpoint of reactivity, it is preferable that the double bond is at the end of the alkenyl group.
- the aryl group may be the same as the aromatic hydrocarbon group in R 1 , but a phenyl group, a biphenyl group, a naphthyl group and the like are preferably used.
- the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like.
- the carbon number of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.
- Examples of the substituent that the hydrocarbon group may have include halogen atoms such as F, Cl and Br, a nitro group and the like.
- the alkyl group may be used as the substituent of the aromatic ring such as the aryl group or the aralkyl group.
- the preferable carbon number does not include the carbon number of the substituent.
- R2 is a hydrocarbon group having 1 to 6 carbon atoms which may have a hydrogen atom or a substituent in terms of solubility and reactivity of an organic solvent and a nitrogen content in one molecule. It is preferable that all three atoms are hydrogen atoms.
- the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R 3 , R 4 , R 5 and R 7 may have a substituent in R 2 and has 1 to 20 carbon atoms.
- the same as 20 hydrocarbon groups can be mentioned.
- the hydrocarbon group having 1 to 5 carbon atoms in R 6 corresponds to the hydrocarbon group having 1 to 5 carbon atoms among the hydrocarbon groups having 1 to 20 carbon atoms which may have the substituent in R2 .
- Something similar to what you do. -L-Q 1 in R 4 may be the same as described later.
- the hydrocarbons R5 and R7 may have substituents having 1 to 20 carbon atoms independently from the viewpoint of the solubility of the organic solvent and the nitrogen content in one molecule. It is preferably a group, and more preferably a hydrocarbon group having 1 to 10 carbon atoms. From the viewpoint of the nitrogen content contained in one molecule, R 6 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
- R 3 is a hydrocarbon group or a hydrocarbon group which may independently have a substituent having 1 to 10 carbon atoms, in terms of the solubility of an organic solvent and the content of nitrogen contained in one molecule.
- a cyano group is preferable, a hydrocarbon group having 1 to 5 carbon atoms is more preferable, and a methyl group or an ethyl group may be used.
- the R4 is a hydrocarbon group having 1 to 10 carbon atoms or the above-mentioned ⁇ L— from the viewpoint of solubility in an organic solvent and localization to the surface of the adhesive layer.
- Q 1 is preferable, and —L—Q 1 is more preferable.
- A can represent the gas generating part represented by the general formula (A-1) in terms of heat resistance and nitrogen content in one molecule. preferable.
- the gas generating unit represented by the general formula (A-1) is exemplified below, but is not limited thereto.
- Q1 has 2 to 8 carbon atoms to which a fluorine atom is directly bonded, and contains an ether bond (—O—) in the carbon chain. It may also represent a monovalent fluorinated aliphatic hydrocarbon group or a monovalent organopolysiloxane group which may have a substituent, and Q2 is the number of carbon atoms to which the fluorine atom is directly bonded. It represents 2 to 8 and represents a divalent fluorinated aliphatic hydrocarbon group or a divalent organopolysiloxane group which may contain an ether bond (—O—) in the carbon chain.
- Examples of the fluorinated aliphatic hydrocarbon group in Q1 and Q2 include a linear or branched saturated or unsaturated fluorinated aliphatic hydrocarbon group. If the number of carbon atoms to which the fluorine atom is directly bonded is 2 to 8, the fluorinated aliphatic hydrocarbon group in Q1 and Q2 contains a carbon atom to which the fluorine atom is not directly bonded. It may be. For example, when the fluorinated aliphatic hydrocarbon group contains an alkynyl group, a carbon atom to which a fluorine atom is not directly bonded is included.
- the fluorinated aliphatic hydrocarbon groups in Q1 and Q2 do not have to be all substituted with fluorine atoms in the carbon atom to which the fluorine atom is directly bonded, and some of them have hydrogen atoms or substituents. It may be included.
- the substituent may be, for example, a reactive group used when linking with a gas generating part, and may be a hydroxyl group, an amino group, a carboxy group, or a (meth) acryloyloxy group, a vinyl ether group, a phosphoric acid group, or the like. Examples include an epoxy group.
- the fluorinated aliphatic hydrocarbon group in Q1 and Q2 preferably contains 4 or more fluorine atoms, and more preferably 6 or more, from the viewpoint of the effect of surface localization.
- the number of fluorine atoms in the fluorinated aliphatic hydrocarbon group may be 17 or less, and may be 16 or less.
- Q1 is one of the following (Rf-1) to (Rf-5) from the viewpoint of the effect of surface localization.
- Rf-6 a fluorinated aliphatic hydrocarbon group represented by the following (Rf-6).
- n independently represents an integer of 2 to 8, and in the formula (Rf-4), n'is 4 to 4 to.
- n represents an integer of 1 to 8
- n represents an integer of 1 to 8
- n represents an integer of 0 to 7
- m represents an integer of 0 to 7
- n + n" ⁇ m represents an integer of 2 to 8.
- J 1 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an amino group, a carboxy group, or a (meth) acryloyloxy group
- n is an integer of 0 to 8
- n is an integer of 0 to 4.
- M is an integer of 0 to 8, where n + n ” ⁇ m is an integer of 2 to 8).
- n independently represents an integer of 2 to 8, but from the viewpoint of the effect of surface localization, n is among them. It preferably represents an integer of 4-8.
- n' represents an integer of 4 to 10, but from the viewpoint of the effect of surface localization, n is preferably an integer of 5 to 10.
- n is an integer of 1 to 8
- m is an integer of 0 to 7
- n + n" ⁇ m is an integer of 2 to 8.
- n represents an integer of 2 to 8
- n represents an integer of 1 to 7
- m represents an integer of 1 to 7
- n + n" ⁇ m represents an integer of 3 to 8. It is preferable to represent it.
- n is an integer of 0 to 8
- n is an integer of 0 to 4
- m is an integer of 0 to 8
- n + n" xm is an integer of 2 to 8.
- n represents an integer of 2 to 8
- n represents an integer of 1 to 7
- m represents an integer of 1 to 7
- n + n" ⁇ m represents an integer of 3 to 8. It is preferable to represent it.
- J 1 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an amino group, a carboxy group, or a (meth) acryloyloxy group.
- J 1 is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom, but may be a hydroxyl group, an amino group, a carboxy group, or a (meth) acryloyloxy group.
- J 1 has such a reactive group, it may be used, for example, for binding other components in the pressure-sensitive adhesive composition to a gas generating agent.
- the structure of the general formula (1) is obtained even when the gas generating part is not introduced at both ends and the gas generating part is introduced only at one end.
- it may have a reactive group such as a hydroxyl group, an amino group, a carboxy group, or a (meth) acryloyloxy group at the terminal.
- Q 1 is preferably any one monovalent fluorinated aliphatic hydrocarbon group represented by the above (Rf-1) or (Rf-5), and the above (Rf-1) or (Rf-1) or ( It is more preferable that it is any one monovalent fluorinated aliphatic hydrocarbon group represented by Rf-5), and any one monovalent fluorinated aliphatic hydrocarbon represented by the above (Rf-1). It is more preferably a hydrocarbon group.
- the organopolysiloxane group in Q1 and Q2 has a siloxane bond- (O-Si) a- (where a is the number of repetitions) in the main chain and a hydrocarbon group in at least a part of the side chain. Refers to a group containing.
- organopolysiloxane group in Q1 and Q2 examples include a monovalent organopolysiloxane group represented by the following (Si-1) in terms of the effect of surface localization, and Q2 .
- Si-1 a monovalent organopolysiloxane group represented by the following (Si-1) in terms of the effect of surface localization
- Q2 a divalent organopolysiloxane group represented by the following (Si-2).
- R 11 independently has a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, a hydrogen atom, a hydroxyl group, and the like.
- J2 is a monovalent hydrocarbon having 1 to 20 carbon atoms which may have a substituent. It represents a group, a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an amino group, a carboxy group, or a (meth) acryloyloxy group.
- A independently represents a number of 1 to 100.
- R 12 has a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, or 1 to 20 carbon atoms, each of which may independently have a substituent. Represents an alkoxy group of, and b represents a number from 0 to 100.
- the hydrocarbon having 1 to 20 carbon atoms which may have a substituent in R 11 and R 12 the hydrocarbon having 1 to 20 carbon atoms which may have a substituent in R 2 is mentioned. It may be the same as the hydrogen group.
- the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R 11 and R 12 among them, the hydrocarbon group having 1 to 10 carbon atoms which may have a substituent may be present.
- an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group and a trill group, and an aralkyl group such as a benzyl group and a phenethyl group.
- Examples thereof include a 3-trifluoropropyl group.
- the alkoxy group having 1 to 20 carbon atoms in R 11 and R 12 is preferably an alkoxy group having 1 to 10 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group and a butoxy group.
- R 11 and R 12 from the viewpoint of solubility in an organic solvent, an alkyl group having 1 to 10 carbon atoms, an aryl group, or a group represented by the general formula (Si-3) is preferable, and the group has the same number of carbon atoms. It is more preferably 1 to 5 alkyl groups.
- the R 12 is preferably an alkyl group or an aryl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
- J 2 may have a substituent and is a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an amino group, a carboxy group, or (meth). Represents an acryloyloxy group.
- J 2 is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent, but a hydroxyl group, an amino group, and the like. It may be a carboxy group or a (meth) acryloyloxy group.
- J 2 When J 2 has such a reactive group, it may be used, for example, for binding other components in the pressure-sensitive adhesive composition to a gas generating agent.
- the compound of the general formula (2) When the compound of the general formula (2) is prepared, the structure of the general formula (1) is obtained even when the gas generating part is not introduced at both ends and the gas generating part is introduced only at one end.
- it may have a reactive group such as a hydroxyl group, an amino group, a carboxy group, or a (meth) acryloyloxy group at the terminal.
- a represents a number from 1 to 100. Since a may have a distribution, it may be an average value. Among them, a preferably represents a number of 1 to 50, more preferably represents a number of 5 to 45, and further preferably represents a number of 10 to 40 in terms of the nitrogen content in one molecule. Further, in the general formula (Si-3), b represents a number from 0 to 100. Since b can also have a distribution, it may be an average value. Among them, b preferably represents a number of 0 to 40, and more preferably represents a number of 0 to 30.
- Q1 When used in the fields related to semiconductors and displays, Q1 has 2 to 8 carbon atoms to which fluorine atoms are directly bonded, and ether bonds (ether bonds in the carbon chain) ( Q1 ) because the possibility of contamination is low. It is preferably a monovalent fluorinated aliphatic hydrocarbon group which may contain —O—) and may have a substituent, and Q2 is the number of carbon atoms to which the fluorine atom is directly bonded. Is 2 to 8, and is preferably a divalent fluorinated aliphatic hydrocarbon group which may contain an ether bond (—O—) in the carbon chain.
- L independently represents a direct bond or a divalent linking group, respectively.
- L represents a portion connecting the gas generating portion and the specific fluorinated aliphatic hydrocarbon group or the organopolysiloxane group, and the gas generating portion includes the specific portion. It is not particularly limited as long as it is a connecting portion to which a fluorinated aliphatic hydrocarbon group or an organopolysiloxane group can be bonded.
- the direct bond means that L does not have an atom, that is, the carbon atom of A in the general formulas (1) and ( 2 ) and the carbon atom or silicon atom of Q1 or Q2 are other. It means that they are bonded without interposing atoms.
- the Ls in the general formulas (1) and (2) are independently, for example, directly bonded, or -SCH 2 CH 2 COO-, -SCH 2 CH (CH 3 ) COO-, -SCH 2 CH ( OH) CH 2- , -OCH 2 CH (OH) CH 2- , -SCH (CH 3 ) O-, -OCH (CH 3 ) O-, -COO-, -CONH-, -COS-, -SO 2
- a hydrocarbon group having 1 to 22 carbon atoms which may contain one or more selected from the group consisting of NH- or -O- and -S-, and may have a hydroxyl group substituted, or a hydrocarbon group having 1 to 22 carbon atoms.
- the direction of the bond may be arbitrary. That is, when L is -SCH 2 CH 2 COO-, S is bonded to the carbon atom of A, O is bonded to the carbon atom or silicon atom of Q 1 or Q 2 , and S is the above. This includes the case where it is bonded to the carbon atom or silicon atom of Q1 or Q2 and O is bonded to the carbon atom of A.
- hydrocarbon group having 1 to 22 carbon atoms examples include a methylene group, an ethylene group, a propylene group (trimethylene group and a methylethylene group), a butylene group (tetramethylene group and a methylpropylene group), a pentamethylene group and a hexamethylene group.
- examples thereof include an alkylene group such as a group, an octamethylene group and a cyclohexylene group, an arylene group such as a phenylene group, and a combination of two or more of these groups (alkylene arylene group).
- Examples of the combination in L in the general formulas (1) and (2) include, for example.
- j, k, and l each independently represent an integer of 1 to 8, and Rf is the above general formula (where). Any one monovalent fluorinated aliphatic hydrocarbon group represented by Rf-1) to (Rf-3)), but is not limited thereto.
- the j, k, and l each independently represent an integer of 2 to 6, and more preferably an integer of 2 to 4.
- the gas generating agent of the present invention is represented by at least one of the following (1-1) and (2-1) from the viewpoint of foamability in the ultraviolet region, and has the maximum molar extinction coefficient at a wavelength of 240 to 450 nm. It is preferably a gas generating agent having a value of 7,000 or more and generating a gas by light irradiation.
- R1 , L, Q1 and Q2 independently represent the same as the general formulas (1) and (2), respectively. .
- Examples of the compound represented by the general formula (1-1) include, but are not limited to, the following compounds.
- A is the above (a-1-1) to (a-1-15)
- L is the above (L1) to (L11)
- Q1 is the above (Rf-1) to (Rf-5)
- Si any combination of -3) can be mentioned.
- Examples of the compound represented by the general formula (2-1) include, but are not limited to, the following compounds.
- the gas generating agent of the present disclosure can efficiently generate a gas by light irradiation because the maximum value of the molar extinction coefficient at a wavelength of 240 to 450 nm is 7,000 or more.
- the gas generator of the present disclosure preferably has a maximum molar extinction coefficient of 8000 or more, preferably 9000 or more, at a wavelength of 240 to 450 nm. Is more preferable.
- the molar absorption coefficient of the present specification is 230 nm by dissolving the gas generator in ethyl acetate so as to be 0.1 mM and using an ultraviolet visible spectrophotometer (for example, Shimadzu Corporation, ultraviolet visible spectrophotometer UV2700).
- an ultraviolet visible spectrophotometer for example, Shimadzu Corporation, ultraviolet visible spectrophotometer UV2700.
- ⁇ A / c ⁇ d (In the formula, ⁇ represents the molar extinction coefficient, A represents the absorbance, c represents the molar concentration, and d represents the cell thickness.)
- a solvent that does not cause a problem in the reproducibility of the molar extinction coefficient of the gas generator is appropriately selected and dissolved in 0.1 mM, and the same as above is obtained.
- the solvent that does not cause a problem in the reproducibility of the molar absorption coefficient of the gas generating agent include organic solvents that do not have an absorption spectrum in the wavelength range of 230 nm to 800 nm and do not react with the gas generating agent.
- the maximum value of the molar extinction coefficient at a wavelength of 240 to 450 nm is 7,000 or more, as long as the value of the molar extinction coefficient at any wavelength between the wavelengths of 240 to 450 nm is 7,000 or more. , The peak may not be present between the wavelengths of 240 and 450 nm.
- the molecular weight or mass average molecular weight Mw of the gas generator of the present disclosure is not particularly limited, but is preferably 200 to 2000, preferably 300 to 1000, from the viewpoint of the nitrogen atom content in one molecule. Is more preferable.
- the molecular weight of the gas generator can be determined by liquid chromatography-mass spectrometry (LC-MS).
- LC-MS liquid chromatography-mass spectrometry
- the gas generating agent contains an organopolysiloxane group, it may be specified by the mass average molecular weight, and the mass average molecular weight can be obtained as a standard polystyrene-equivalent value by gel permeation chromatography (GPC). can.
- the method for producing the gas generating agent of the present disclosure is not particularly limited, and for example, a gas generating portion having a reactive group, a reactive group that reacts with the reactive group of the gas generating portion to form a bond, and fluorination.
- the gas generator of the present disclosure can be obtained by reacting and bonding with a compound having an aliphatic hydrocarbon group or an organopolysiloxane group.
- Examples of the combination of the reactive groups include a thiol group and a (meth) acryloyloxy group, a thiol group and an epoxy group, a thiol group and a vinyl ether group, a hydroxyl group and a vinyl ether group, a hydroxyl group and an epoxy group, a hydroxyl group and an isocyanate group, and an amino group.
- a sulfonyl chloride group, a carboxy group, an epoxy group and the like but the present invention is not limited thereto.
- each combination which may be the reactive group on the gas generating part side and which may be the reactive group on the compound side having a fluorinated aliphatic hydrocarbon group or an organopolysiloxane group.
- a compound having an organopolysiloxane group By reacting a naphthoquinone diazide compound having a sulfonic acid chloride group with an organopolysiloxane compound having an amino group, a compound having an organopolysiloxane group can be synthesized with reference to. Further, with reference to Macromolecules, Volume: 37, Issue: 18, Pages: 6673-6675, Journal, 2004, by reacting a vinyl ether group having a fluorinated aliphatic hydrocarbon group with an azo compound having a carboxyl group. Compounds having a fluorinated aliphatic hydrocarbon group can be synthesized. Alternatively, as the compound having a reactive group and a fluorinated aliphatic hydrocarbon group or an organopolysiloxane group, a commercially available product may be appropriately selected and used.
- the gas generating agent of the present disclosure Since the gas generating agent of the present disclosure has the specific fluorinated aliphatic hydrocarbon group or the specific organopolysiloxane group in the gas generating portion having the specific structure, it is easy to be localized on the surface. .. Therefore, as will be described later, the gas generating agent of the present disclosure is applied to an adhesive material for the purpose of high adhesiveness and easy peeling, and is suitably used for improving the easy peeling property.
- the adhesive composition of one embodiment of the present disclosure contains a pressure-sensitive adhesive component and the gas generating agent of the present disclosure. Since the pressure-sensitive adhesive composition of one embodiment of the present disclosure contains the gas-generating agent of the present disclosure, the amount of gas generated on the surface of the pressure-sensitive adhesive layer due to the action of the gas-generating agent that easily localizes to the surface as described above. Efficiently increases, so that it has good adhesive strength when used when adhesive strength is required, but when the adhesive force that peels off the adhesive layer from the adherend becomes unnecessary, it is removed from the adherend. It is possible to form an adhesive layer having excellent peelability.
- the pressure-sensitive adhesive component is not particularly limited, and may be a non-photocurable type pressure-sensitive adhesive component or a photo-curable type pressure-sensitive adhesive component.
- a gas is generated from the gas generating agent of the present disclosure by irradiating with light, and the generated gas generates a peeling stress and is adhered.
- the area of adhesion to the body decreases and peels off.
- the pressure-sensitive adhesive component is a photocurable pressure-sensitive adhesive component, the area of adhesion to the adherend due to the generation of gas from the gas generating agent of the present disclosure by irradiating with light is reduced, and the pressure-sensitive adhesive is used. Peeling becomes easier due to the synergistic effect of reducing the adhesive strength of the pressure-sensitive adhesive component itself due to the photo-curing of the component. Therefore, the pressure-sensitive adhesive component is preferably a photocurable type.
- the photocurable pressure-sensitive adhesive component is not particularly limited, and examples thereof include those containing a photocurable component and a photoinitiator while containing a pressure-sensitive adhesive.
- the photocurable pressure-sensitive adhesive component used in the pressure-sensitive adhesive composition of one embodiment of the present disclosure is a composition containing (i) a pressure-sensitive adhesive, a photo-curable polyfunctional compound, and a photoinitiator.
- a composition containing a pressure-sensitive adhesive having two or more photocurable functional groups in one molecule and a photoinitiator may be mentioned.
- the photocurable pressure-sensitive adhesive component is a composition containing (i) a pressure-sensitive adhesive, a photo-curable polyfunctional compound, and a photoinitiator, so that the adhesive strength can be easily adjusted. Is preferable.
- the pressure-sensitive adhesive may have a photocurable functional group.
- the adhesive is not particularly limited, and for example, a rubber adhesive, an acrylic adhesive, a vinyl alkyl ether adhesive, a silicone adhesive, a polyester adhesive, a polyamide adhesive, a urethane adhesive, and styrene.
- a rubber adhesive an acrylic adhesive, a vinyl alkyl ether adhesive, a silicone adhesive, a polyester adhesive, a polyamide adhesive, a urethane adhesive, and styrene.
- Adhesives and the like can be mentioned.
- the pressure-sensitive adhesive is preferably a (meth) acrylic acid ester-based polymer, which is called an acrylic pressure-sensitive adhesive, from the viewpoint of compatibility with a photocurable component and adjustment of adhesive strength.
- the (meth) acrylic acid ester-based polymer includes a structural unit derived from a (meth) acrylic acid alkyl ester monomer having 1 or more and 20 or less carbon atoms in a linear or branched alkyl group used as an acrylic pressure-sensitive adhesive, and if necessary. It is preferable to use a (meth) acrylic acid ester-based copolymer obtained by copolymerizing with another monomer.
- the (meth) acrylic acid ester-based polymers a structural unit derived from a (meth) acrylic acid alkyl ester monomer having a linear or branched alkyl group having 1 or more and 20 or less carbon atoms and a crosslinkable group-containing monomer are derived. It is preferably a (meth) acrylic acid ester-based copolymer having a constituent unit.
- the (meth) acrylic acid ester-based copolymer can be crosslinked with a heat-crosslinking agent or the like, which will be described later, by utilizing the crosslinkable group introduced into the molecule of the (meth) acrylic acid ester polymer, and is adherent. It is possible to improve the cohesive force of the composition and obtain an adhesive layer having a good balance between easy peeling property and durability under a predetermined environment.
- Examples of the (meth) acrylic acid alkyl ester monomer having a linear or branched alkyl group having 1 or more and 20 or less carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n.
- a linear or (meth) acrylic acid alkyl ester having a branched alkyl group having 4 to 14 carbon atoms is preferable, and a linear chain having 7 to 13 carbon atoms is preferable from the viewpoint of exhibiting wettability and adhesiveness to an adherend.
- a (meth) acrylic acid alkyl ester having a branched alkyl group is more preferable.
- crosslinkable group of the crosslinkable group-containing monomer used in the (meth) acrylic acid ester-based polymer examples include a hydroxyl group, an epoxy group, an isocyanate group, a carboxy group, and an amino group. From the viewpoint of stability during polymerization and storage of the polymer, it is preferable to include a structural unit derived from a monomer containing at least one selected from the group consisting of a hydroxyl group, an epoxy group, a carboxy group, and an amino group. It is preferable to include a structural unit derived from a hydroxyl group-containing monomer from the viewpoint of high stability and excellent reactivity of the thermal cross-linking agent.
- Examples of the monomer for inducing a structural unit derived from the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and glycerin mono (meth) acrylate.
- Examples of the monomer for inducing a structural unit derived from the epoxy group-containing monomer include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.
- Examples of the monomer for inducing a structural unit derived from the isocyanate group-containing monomer include 2- (meth) acryloyloxyethyl isocyanate and alkylene oxide adducts thereof.
- Examples of the monomer for inducing a structural unit derived from an amino group-containing monomer include ethylaminoethyl (meth) acrylate and dimethylaminoethyl (meth) acrylate.
- Examples of the monomer for inducing a constituent unit derived from the carboxy group-containing monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, ⁇ -carboxy-polycaprolactone mono (meth) acrylate and the like.
- the (meth) acrylic acid ester-based polymer may further have a photocurable functional group in the side chain.
- the photocurable functional group it is preferable to have an ethylenically unsaturated bond, and a (meth) acryloyl group, a vinyl group, an allyl group and the like are preferable.
- a method for introducing a photocurable functional group into the side chain of the (meth) acrylic acid ester-based polymer a conventionally known production method may be appropriately selected and used.
- a glycidyl (meth) acrylate may be reacted with a (meth) acrylic acid ester-based polymer having a carboxy group, or a hydroxyethyl (meth) acrylate may be reacted with a (meth) acrylic acid ester-based polymer having an isocyanate group.
- a photocurable functional group can be added by reacting a (meth) acrylic acid ester-based polymer having a hydroxyl group with 2-isocyanatoethyl (meth) acrylate.
- the (meth) acrylic acid ester-based polymer may contain a structural unit derived from other monomers as long as it functions as an acrylic pressure-sensitive adhesive.
- the other monomer for example, a rigid monomer such as cyclohexyl methacrylate, benzyl methacrylate, adamantyl methacrylate and the like can be used.
- the content of the (meth) acrylic acid ester monomer is the main component constituting the (meth) acrylic acid ester-based polymer, the content thereof is usually 50% by mass or more with respect to the total monomer component (100% by mass). Is preferable. Above all, the content of the (meth) acrylic acid alkyl ester monomer may be, for example, 50% by mass or more, 60% by mass or more, or 80% by mass or more with respect to all the monomer components. , 90% by mass or more. On the other hand, the content of the (meth) acrylic acid alkyl ester monomer is, for example, 99.5% by mass or less, 99% by mass or less, and 98% by mass or less with respect to all the monomer components. You may.
- the content of the crosslinkable group-containing monomer may be appropriately selected from the viewpoint of the balance between the adhesive force and the peeling force, but is, for example, 0.5% by mass or more and 1% by mass or more with respect to all the monomer components. It may be present, and may be 2% by mass or more. On the other hand, the content of the crosslinkable group-containing monomer may be, for example, 15% by mass or less, 13% by mass or less, or 10% by mass or less with respect to all the monomer components.
- the content of other monomers in the (meth) acrylic acid ester-based polymer may be appropriately selected from the viewpoint of the balance between the adhesive force and the peeling force and the performance to be imparted, and is, for example, 0% by mass or more and 49.5% by mass. % Or less, and may be 39% by mass or less, or 18% by mass or less.
- the mass average molecular weight of the (meth) acrylic acid ester-based polymer is preferably 100,000 to 5 million, more preferably 200,000 to 4 million, and even more preferably, from the viewpoint of improving the adhesive force and the peeling force. Is 300,000 to 3 million, and even more preferably 400,000 to 1 million. If the mass average molecular weight is less than 100,000, the cohesive force may be small, and there is a possibility that adhesive residue may be generated on the surface of the adherend after peeling, or the adhesive effect may not be obtained. Further, if the mass average molecular weight exceeds 5 million, the wettability of the surface of the adherend after peeling off the adhesive layer may be insufficient.
- the mass average molecular weight of the (meth) acrylic acid ester polymer can be determined by gel permeation chromatography (GPC) as a standard polystyrene-equivalent value.
- a commercially available acrylic pressure-sensitive adhesive may be used, for example, SK Dyne 2971 (manufactured by Soken Chemical Co., Ltd.), SK Dyne 2975 (manufactured by Soken Chemical Co., Ltd.), SK Dyne 1811L. (Soken Chemical), SK Dyne 2950 (Soken Chemical), SK Dyne 2094 (Soken Chemical), Oliveine EG-654 (Toyochem) and the like can be preferably used.
- the pressure-sensitive adhesive can be used alone or in combination of two or more.
- the content of the pressure-sensitive adhesive may be, for example, 20% by mass or more, or 30% by mass or more, based on the solid content of the pressure-sensitive adhesive composition, from the viewpoint of the effect of adhesive strength. Further, the content of the pressure-sensitive adhesive may be, for example, 80% by mass or less, or 70% by mass or less, based on the solid content of the pressure-sensitive adhesive composition from the viewpoint of re-peeling of the pressure-sensitive adhesive layer.
- a solid content means all components other than a solvent.
- the photocurable polyfunctional compound is a monomer, an oligomer, or a polymer containing two or more photocurable groups in one molecule.
- a photocurable polyfunctional compound By containing a photocurable polyfunctional compound, it can be three-dimensionally crosslinked, and further, when the (meth) acrylic acid ester-based polymer has photocurability, it is a (meth) acrylic acid ester-based polymer. By reacting with the polymer, the (meth) acrylic acid ester-based polymer can be polymerized or three-dimensionally crosslinked.
- photocurable polyfunctional compound examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol di (meth).
- Bifunctional polyfunctional (meth) acrylate-based monomer isocyanuric acid ethylene oxide-modified triacrylate, trimethylolpropanetri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, Trifunctional polyfunctional (meth) acrylate-based monomers such as pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol propanetri (meth) acrylate, tris (meth) acryloxyethyl isocyanurate, and diglycerin tetra (meth) acrylate.
- a tetrafunctional type such as pentaerythritol tetra (meth) acrylate, for example, a pentafunctional polyfunctional (meth) acrylate-based monomer such as propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, In a hexafunctional polyfunctional (meth) acrylate-based monomer such as caprolactone-modified dipentaerythritol hexa (meth) acrylate, and in molecules called urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate. Oligos with hundreds to thousands of molecular weights with several (meth) acryloyl groups Mar can be preferably used.
- a pentafunctional polyfunctional (meth) acrylate-based monomer such as propionic acid-modified dipentaery
- photocurable polyfunctional compounds there are several (in the molecules called urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate from the viewpoint of the balance between adhesive force and peeling force. Meta) It is preferable to use an oligomer having an acryloyl group and having a molecular weight of several hundreds to several thousand.
- the photocurable polyfunctional compound can be used alone or in combination of two or more.
- the content of the photocurable polyfunctional compound is, for example, 10 parts by mass or more with respect to 100 parts by mass of the pressure-sensitive adhesive such as the (meth) acrylic acid ester-based polymer. It may be 20 parts by mass or more, 50 parts by mass or more, while it may be 300 parts by mass or less, 200 parts by mass or less, and 150 parts by mass or less. You may. If the content of the photocurable polyfunctional compound is too small, the addition effect may not be exhibited. On the other hand, if the content of the photocurable polyfunctional compound is too large, the properties such as storage stability, substrate adhesion, tackiness, and peelability of the pressure-sensitive adhesive composition may be significantly deteriorated.
- the total content of the pressure-sensitive adhesive and the photocurable polyfunctional compound may be, for example, 10% by mass or more with respect to the solid content of the pressure-sensitive adhesive composition from the viewpoint of the balance of the peeling force after light irradiation. It may be mass% or more.
- the total content of the pressure-sensitive adhesive and the photocurable polyfunctional compound is, for example, 70% by mass or less with respect to the solid content of the pressure-sensitive adhesive composition from the viewpoint of adhesive strength and suppression of contamination of the adherend. It may be present, and may be 60% by mass or less.
- any compound that can generate radicals when irradiated with a predetermined amount of light such as ultraviolet rays can be used.
- benzoine benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin- n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1 -On, 1-Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-) 2-propyl) ketone, benzophenone, p-pheny
- an acylphosphine oxide-based initiator a group consisting of an acylphosphine oxide-based initiator, an ⁇ -aminoalkylphenone-based initiator, an ⁇ -hydroxyketone-based initiator, and an oxime ester-based initiator in order to cure to the inside of the coating film and improve durability. At least one selected from is preferred.
- the photoinitiator can be used alone or in combination of two or more.
- the content of the photoinitiator may be, for example, 0.5% by mass or more, and 1.0% by mass or more, based on the solid content of the pressure-sensitive adhesive composition, from the viewpoint of sufficiently curing the pressure-sensitive adhesive composition. You may. Further, the content of the photoinitiator may be, for example, 10.0% by mass or less and 5.0% by mass or less with respect to the solid content of the pressure-sensitive adhesive composition from the viewpoint of the balance between the adhesive force and the peeling force. May be.
- the pressure-sensitive adhesive composition of the present disclosure preferably further contains a thermal cross-linking agent.
- the thermal cross-linking agent refers to a compound that promotes a cross-linking reaction by the action of heat.
- thermal cross-linking agent examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, aziridine-based cross-linking agents, and metal chelate-based cross-linking agents.
- isocyanate-based cross-linking agents and epoxy-based cross-linking agents are preferable because the effects of the present disclosure can be easily exhibited.
- isocyanate-based cross-linking agent examples include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, and 2,4-tolylene diisocyanate.
- lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate
- alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate
- 2,4-tolylene diisocyanate examples include 2,4-tolylene diisocyanate.
- Aromatic isocyanates such as isocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, trimethylol propane / tolylene diisocyanate trimer adduct (trade name "Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylol propane / to Examples thereof include isocyanate adducts such as xamethylene diisocyanate trimer adduct (trade name "Coronate HL” manufactured by Nippon Polyurethane Industry Co., Ltd.) and isocyanurates of hexamethylene diisocyanate (trade name "Coronate HX” manufactured by Nippon Polyurethane Industry Co., Ltd.).
- epoxy-based cross-linking agent examples include bisphenol A, epichlorohydrin-type epoxy-based resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, and trimethylol.
- the heat cross-linking agent can be used alone or in combination of two or more.
- the content of the heat-crosslinking agent may be appropriately adjusted depending on the balance between the adhesive force and the peeling force, but is, for example, 1.0% by mass or more with respect to the solid content of the adhesive composition from the viewpoint of obtaining the above effects. It may be 2.0% by mass or more. Further, the content of the heat-crosslinking agent may be, for example, 10.0% by mass or less, and 8.0% by mass or less, based on the solid content of the pressure-sensitive adhesive composition from the viewpoint of adhesiveness before energy irradiation. You may.
- the pressure-sensitive adhesive composition of the present disclosure contains the gas generating agent of the present disclosure. Since the gas generating agent of the present disclosure is easily localized on the surface of the pressure-sensitive adhesive material, the amount of gas generated on the surface of the pressure-sensitive adhesive material can be efficiently increased without increasing the content of the gas-generating agent in the pressure-sensitive adhesive composition. Since it can be increased, it is easy to suppress a decrease in the adhesive strength of the adhesive material and white turbidity.
- the content of the gas generating agent of the present disclosure may be, for example, 2% by mass or more, and 3% by mass, based on the solid content of the pressure-sensitive adhesive composition, from the viewpoint of effectively reducing the peeling force at the time of peeling. It may be the above. Further, the content of the gas generating agent of the present disclosure may be, for example, 40% by mass or less with respect to the solid content of the pressure-sensitive adhesive composition from the viewpoint of suppressing a decrease in the pressure-sensitive adhesive force and white turbidity of the pressure-sensitive adhesive material. It may be 30% by mass or less.
- the white turbidity of the adhesive material can be suppressed and the transparency is high, for example, precise appearance defects can be confirmed by a camera or the like via the adhesive layer, and the adhesive layer is also suitable for a process-removable adhesive sheet. It can be used for a wide range of purposes.
- the pressure-sensitive adhesive composition of the present disclosure may further contain a solvent.
- a solvent By containing the solvent, it is possible to improve the applicability to the base material and the like and the mixability of the compounding components.
- the solvent does not react with each component in the composition, and can be appropriately selected and used from the solvents capable of dissolving or dispersing them.
- the solvent include esters, aromatic hydrocarbons, ketones and ethers. More specifically, since it has good solubility in (meth) acrylic acid ester-based polymers and is easy to handle, methyl acetate, ethyl acetate, n-butyl acetate, i-butyl acetate, benzene, etc.
- Examples thereof include one or a combination of two or more of toluene, xylene, acetone, cyclohexane, cyclohexanone, methylethylketone, tetrahydrofuran and the like.
- the content of the solvent may be appropriately adjusted from the viewpoint of applicability to the base material and the like and the mixing property of the compounding components, but with respect to the total amount (100% by mass) of the pressure-sensitive adhesive composition including the solvent. For example, 5% by mass or more and 40% by mass or less can be mentioned.
- the pressure-sensitive adhesive composition of the present disclosure may further contain various additives, if necessary, as long as the object of the present disclosure is not impaired.
- various additives include cross-linking accelerators, antioxidants, stabilizers, viscosity modifiers, tackifier resins, organic or inorganic fillers and the like.
- the cross-linking accelerator include those of triethylamine type, cobalt naphthenate type, tin type, zinc type, titanium type and zirconium type.
- cross-linking agent is an isocyanate-based cross-linking agent
- zinc-based, titanium-based and zirconium-based accelerators such as alkoxides, acylates and complexes, and stannous chloride, tetra-n-butyltin, stannic chloride and trimethyltin hydroxide are used.
- Dimethylditin chloride, di-n-butyltin dilaurate and other tin-based accelerators are preferably used.
- examples of the antioxidant include a phenolic antioxidant and the like.
- the method for producing the pressure-sensitive adhesive composition is not particularly limited.
- the pressure-sensitive adhesive composition can be obtained by adding, dissolving or dispersing each of the above-mentioned components and various additives added as needed in any order.
- the mixing of each component can be carried out using, for example, a mixer such as a dissolver, a planetary mixer, a butterfly mixer, or a kneader.
- the use of the pressure-sensitive adhesive composition of the present disclosure is not particularly limited, but it can be suitably used for the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet described later, and can be suitably used for the use described for the pressure-sensitive adhesive sheet described later.
- the pressure-sensitive adhesive composition of the present disclosure can be used for a pressure-sensitive adhesive material that is not in the form of a sheet, and can be applied to, for example, a temporary fixing adhesive or the like.
- Adhesive Sheet The adhesive sheet of one embodiment of the present disclosure comprises an adhesive layer and a base material or a release sheet on one surface of the adhesive layer.
- the pressure-sensitive adhesive layer is a pressure-sensitive adhesive composition or a cured product thereof containing the pressure-sensitive adhesive component and the gas generating agent of the present disclosure, and the pressure-sensitive adhesive layer has a property that the pressure-sensitive adhesive force is reduced from the initial adhesive force by light irradiation. , Adhesive sheet.
- the pressure-sensitive adhesive sheet 10 of the present disclosure in FIG. 1 includes a pressure-sensitive adhesive layer 1 and a base material or a release sheet 2 arranged on one surface of the pressure-sensitive adhesive layer 1.
- the pressure-sensitive adhesive sheet 10 of the present disclosure in FIG. 2 includes a pressure-sensitive adhesive layer 1, a base material or a mold release sheet 2 arranged on one surface of the pressure-sensitive adhesive layer 1, and the base material or a mold-release sheet 2 of the pressure-sensitive adhesive layer 1. It is provided with a mold release sheet 3 arranged on a surface opposite to the side.
- the release sheet is placed on the surface of the adhesive layer opposite to the base material or the release sheet 2 side until it is attached to the adherend. You may stick them together.
- the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of the present disclosure is a pressure-sensitive adhesive composition containing the pressure-sensitive adhesive component and the gas generating agent of the present disclosure, or a cured product thereof.
- the pressure-sensitive adhesive composition containing the pressure-sensitive adhesive component and the gas generating agent of the present disclosure may be the same as the pressure-sensitive adhesive composition of the present disclosure, and thus the description thereof is omitted here.
- the pressure-sensitive adhesive composition contains a curable pressure-sensitive adhesive component
- the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of the present disclosure may be a cured product of the pressure-sensitive adhesive composition.
- the film thickness of the adhesive layer can be adjusted as appropriate according to the purpose.
- the film thickness of the adhesive layer may be, for example, 100 ⁇ m or less, and may be 90 ⁇ m or less, or 80 ⁇ m or less, from the viewpoint of removability of the adhesive layer.
- the film thickness of the adhesive layer may be, for example, 10 ⁇ m or more, and may be 20 ⁇ m or more, or 40 ⁇ m or more, from the viewpoint of developing adhesive force.
- the adhesive layer has an initial adhesive force before light irradiation, which is 0 for a glass plate (trade name: non-alkali glass OA-11, manufactured by Nippon Electric Glass) at a peeling speed of 300 mm / min and a peeling angle of 180 degrees. It may be 1 N / 25 mm or more, and may be 0.2 N / 25 mm or more. On the other hand, the peeling force at the peeling angle of 180 degrees may be 30 N / 25 mm or less, or 20 N / 25 mm or less.
- a glass plate trade name: non-alkali glass OA-11, manufactured by Nippon Electric Glass
- the peeling force at the peeling angle of 180 degrees may be 30 N / 25 mm or less, or 20 N / 25 mm or less.
- the adhesive layer has an adhesive force after light irradiation, which is a peeling force of 300 mm / min for a glass plate (trade name: non-alkali glass OA-11, manufactured by Nippon Electric Glass) at a peeling angle of 180 degrees. It may be 0N / 25mm or more, and may be 0.01N / 25mm or more. On the other hand, the peeling force at the peeling angle of 180 degrees may be 1 N / 25 mm or less, or 0.1 N / 25 mm or less.
- the light irradiation amount may be appropriately selected, and for example, the adhesive force after irradiation with ultraviolet rays (UV) at an exposure amount of 3000 mJ / cm 2 can be used as one index of the adhesive force after light irradiation.
- UV ultraviolet rays
- the total light transmittance of the adhesive layer is preferably 80% or more, and more preferably 90% or more in the state before light irradiation. Further, the adhesive layer preferably has a haze of 1.5% or less, more preferably 1.0% or less, in a state before light irradiation.
- the total light transmittance of the present disclosure can be measured according to JIS K7361-1, and can be measured by, for example, a haze meter (for example, HM150 manufactured by Murakami Color Technology Laboratory).
- the haze value can be measured by a method conforming to JIS K-7136, and can be measured by, for example, a haze meter (for example, HM150 manufactured by Murakami Color Technology Research Institute).
- the transparency of the adhesive layer is good, and the adherend can be precisely checked and inspected by a camera or the like with the adhesive sheet attached.
- LC-MS is preferably mentioned, and in addition, LC fractionation, GPC fractionation, NMR, IR, GC-MS, XPS, TOF-SIMS and a combination method thereof can be applied. can.
- the base material used for the pressure-sensitive adhesive sheet of the present disclosure may be appropriately selected and used, and is not particularly limited. Since it is preferable to reduce the adhesive force from the initial adhesive force of the adhesive layer by irradiating light from the substrate side of the adhesive sheet, it is preferable to use a transparent substrate.
- the base material used for the pressure-sensitive adhesive sheet of the present disclosure preferably has a total light transmittance of 80% or more, and more preferably 90% or more. Further, the base material used for the pressure-sensitive adhesive sheet of the present disclosure preferably has a haze of 1.5% or less, and more preferably 1.0% or less.
- the base material used for the pressure-sensitive adhesive sheet of the present disclosure is preferably one having heat resistance, and for example, in addition to polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polyimide resin, polycarbonate resin, polystyrene resin, and polyamide resin. , Polyetherimide resin, polyetherketone resin, polyphenylene sulfide resin, polyacrylate resin, polyester ether resin, polyamideimide resin, polymethylmethacrylate resin, fluororesin and the like. Polyethylene terephthalate is a particularly preferable base material in terms of economy and performance.
- the base material may have a single-layer structure or may have a multi-layer structure. Further, the base material may be surface-treated on the surface on which the adhesive layer is arranged in order to enhance the adhesion to the adhesive layer.
- the film thickness of the base material may be appropriately selected according to the use of the adhesive sheet, and is not particularly limited.
- the film thickness of the base material may be, for example, a thickness that can be supported with the required strength, and the thickness of what has been conventionally used as a base film, for example, a film thickness of about 10 to 200 ⁇ m is preferable. Used.
- the release sheet is not particularly limited as long as it can be peeled off from the adhesive layer, and can have enough strength to protect the adhesive layer.
- Examples of such a release sheet include a release film, a release paper, and the like. Further, any known release sheet can be used, and it may have a single-layer structure or a multi-layer structure.
- Examples of the release sheet having a single-layer structure include a release PET film, a fluororesin-based film, and the like. Further, as the release sheet having a multi-layer structure, for example, a laminated body having a release layer on one side or both sides of the base material layer can be mentioned.
- Examples of the base material layer include resin films such as polypropylene, polyethylene and polyethylene terephthalate, and papers such as high-quality paper, coated paper and impregnated paper.
- the material of the release layer is not particularly limited as long as it is a material having releasability, and for example, a silicone compound, an organic compound modified silicone compound, a fluorine compound, an aminoalkyd compound, a melamine compound, an acrylic compound, a polyester compound, and a length. Examples thereof include chain alkyl compounds. These compounds can be emulsion type, solvent type or solvent-free type.
- the thickness of the release sheet can be, for example, about 15 to 200 ⁇ m.
- the pressure-sensitive adhesive sheet of the present disclosure can be produced by any suitable method.
- the pressure-sensitive adhesive sheet of the present disclosure can be obtained by producing a base material or a laminate of a release sheet and a pressure-sensitive adhesive layer.
- Such a laminate is, for example, (1) A method of forming a pressure-sensitive adhesive layer by applying a solution of a pressure-sensitive adhesive composition or a heat-melted liquid onto a base material or a release sheet. (2) A method of transferring an adhesive layer applied and formed on a release sheet onto a substrate according to the above (1). (3) A method of extruding an adhesive composition onto a substrate to form and apply it. (4) A method of extruding a base material layer and an adhesive layer in two or multiple layers, It can be manufactured by any suitable method, such as. Above all, the production method of (1) above is preferably used.
- the surface of the base material used for the pressure-sensitive adhesive sheet of the present disclosure can be surface-treated if desired.
- the surface treatment at this time includes, for example, (1) discharge treatment such as corona discharge treatment and glow discharge treatment, (2) plasma treatment, (3) flame treatment, (4) ozone treatment, (5) ultraviolet treatment and electron beam. , Ionizing active ray treatment such as radiation treatment, (6) roughening treatment such as sand mat treatment and hairline treatment, (7) chemical treatment, (8) anchor layer formation and the like.
- As the anchor layer a polyurethane resin, a polyester resin, an acrylic resin, a polyester polyurethane resin, or the like is used. The thickness of this anchor layer is usually in the range of 0.01 to 1.5 ⁇ m.
- a known method can be appropriately selected and used.
- a coating method such as a method, a bar coating method, an extrusion coating method, an E-type coating method, various printing methods, and a transfer method using a mold or the like.
- the pressure-sensitive adhesive composition layer applied on the base material or the release sheet may be formed into a pressure-sensitive adhesive layer by thermally cross-linking the heat-crosslinking agent by removing (drying) the solvent as necessary and heating. can.
- the pressure-sensitive adhesive sheet of the present disclosure is provided with a pressure-sensitive adhesive composition containing the pressure-sensitive adhesive component and the gas-generating agent of the present disclosure, or a pressure-sensitive adhesive layer which is a cured product thereof. It is an adhesive sheet that can reduce the peeling force from the adherend at the time of peeling while having a force, and has excellent peelability from the adherend. Further, since the content of the gas generating agent can be reduced, the adhesive layer is less likely to become cloudy and has high transparency. Since the adhesive sheet of the present disclosure is excellent in easy peeling property from the adherend after use, for example, the adherend itself can be thinned and functioned by refining and complicating various electronic members and optical members. When the adherend itself or the surface of the protected member is easily destroyed due to the integration and miniaturization of It can also be used as a suitable pressure-sensitive adhesive sheet when the force required for peeling is increased.
- the pressure-sensitive adhesive sheet of the present disclosure can be suitably used as a process pressure-sensitive adhesive material for the purpose of high adhesiveness and easy peeling.
- Temporarily fixed support temporary fixing support when dicing a thin film wafer to a semiconductor chip, temporary fixing when cutting a crimp-integrated sheet in the manufacturing process of a laminated ceramics capacitor (MLCC) to make a chip
- MLCC laminated ceramics capacitor
- Examples thereof include a support for temporary fixing in the manufacturing process of a flexible printed wiring board, a removable adhesive protective sheet for a process that protects the surface of the substrate in the manufacturing process of a flexible printed wiring board and a flexible organic EL display, and the like. ..
- Comparative Production Example 1 Production of Comparative Compound 1 except that 1.3 g (0.0112 mol) of 5-mercapto-1-methyl-1H tetrazole (manufactured by Tokyo Kasei) was used instead of 5-mercapto-1-phenyl-1H tetrazole. In the same manner as in No. 1, 5.68 g (0.0106 mol, yield 95%) of Comparative Compound 1 represented by the following formula was obtained. 1 It was confirmed that the target product could be synthesized by 1 H-NMR (solvent: CDCl 3 ).
- the molar absorption coefficient is determined by dissolving the obtained compound in ethyl acetate so as to be 0.1 mM, and using an ultraviolet-visible spectrophotometer (UV2700, Shimadzu Corporation's ultraviolet-visible spectrophotometer UV2700) in the wavelength range of 230 nm to 800 nm. The absorption spectrum was measured, and the value obtained by calculation by the following formula was obtained using the absorbance in the obtained absorption spectrum.
- UV2700 ultraviolet-visible spectrophotometer
- ⁇ A / c ⁇ d (In the formula, ⁇ represents the molar extinction coefficient, A represents the absorbance, c represents the molar concentration, and d represents the cell thickness.) Table 3 shows the maximum value of the molar extinction coefficient at a wavelength of 240 to 450 nm and the terminal absorption wavelength on the long wavelength side where the absorbance is 0.01.
- Lumirer U34 75 ⁇ m manufactured by Toray was coated with an applicator (manufactured by Yoshimitsu Seiki) so that the film thickness after drying was 50 ⁇ m.
- an applicator manufactured by Yoshimitsu Seiki
- the adhesive layer side of the adhesive sheet from which the release PET film was peeled off by cutting to a width of 25 mm was placed on the adhesive layer side of the glass plate adherend (trade name: non-alkali glass).
- OA-11, manufactured by Nippon Electric Glass is reciprocated once with a 2 kg roller (manufactured by Tester Sangyo), and then left for 3 hours under the conditions of 23 ° C and 60% humidity, and then exposed using an ultra-high pressure mercury lamp.
- UV irradiation was performed at 3000 mJ / cm 2 , and it was observed whether bubbles were generated at the interface with the glass adherend. (Evaluation criteria for the presence or absence of gas generation) ⁇ : Gas is generated. X: No gas is generated.
- Example 1 (1) Preparation of adhesive composition (meth) Acrylic acid ester polymer (trade name: SK Dyne 1811L, manufactured by Soken Kagaku) 100 parts by mass, photocurable polyfunctional compound (trade name: urethane acrylate U-10PA, new) Nakamura Chemical Co., Ltd.) 50 parts by mass, photoinitiator (trade name: Omnirad 819, IGM Resins B.V.) 1.5 parts by mass, thermal cross-linking agent (isocyanate-based cross-linking agent, trade name: Coronate L, Nippon Polyurethane Industry) (Manufactured by) 6 parts by mass, compound 1 (gas generator) of Production Example 1 by 39.4 parts by mass, solvent (trade name: KT-11, manufactured by Showa Ink) 659.19 parts by mass, respectively, in Example 1 The pressure-sensitive adhesive composition 1 of the above was obtained.
- Acrylic acid ester polymer trade name: SK Dyne 1811L, manufactured by Soken Kagaku
- Example 1 (1) Preparation of Adhesive Composition
- the compound 1 of Production Example 1 was changed to the compound 2 of Production Example 2 or the compound 3 of Production Example 3, respectively.
- the pressure-sensitive adhesive composition 2 or 3 was obtained in the same manner as in 1).
- Example 4 (1) Preparation of Adhesive Composition In (1) of Example 1, 39.4 parts by mass of compound 1 (gas generator) of Production Example 1 and 6.6 parts by mass of compound 3 (gas generator) of Production Example 3 The pressure-sensitive adhesive composition 4 was obtained in the same manner as in (1) of Example 1 except that the parts were changed to parts.
- Comparative Example 1 (1) Preparation of Comparative Adhesive Composition
- compound 1 of Production Example 1 was changed to Comparative Compound 1 of Comparative Production Example 1 in the same manner as in Example 1 (1).
- the comparative pressure-sensitive adhesive composition 1 was obtained.
- Comparative Example 2 (1) Preparation of Comparative Adhesive Composition The same as (1) of Example 1 except that the compound 1 of Production Example 1 was changed to the comparative compound 2 of Comparative Production Example 2 in (1) of Example 1. The comparative pressure-sensitive adhesive composition 2 was obtained.
- Comparative Example 3 (1) Preparation of Comparative Adhesive Composition
- 39.4 parts by mass of compound 1 (gas generator) of Production Example 1 was used, and comparative compound 2 (gas generator) 6 of Comparative Production Example 2 was used.
- a comparative pressure-sensitive adhesive composition 3 was obtained in the same manner as in (1) of Example 1 except that the composition was changed to 6.6 parts by mass.
- Comparative Example 4 (1) Preparation of Comparative Adhesive Composition
- compound 1 of Production Example 1 was changed to comparative compound 3 (5-mercapto-1-phenyl-1H tetrazole (manufactured by Tokyo Kasei)). Obtained a comparative adhesive composition 4 in the same manner as in (1) of Example 1.
- Comparative Example 5 (1) Preparation of Comparative Adhesive Composition In (1) of Example 1, 39.4 parts by mass of compound 1 (gas generator) of Production Example 1 was added to comparative compound 3 (5-mercapto-1-phenyl-1H tetrazole). ) The comparative adhesive composition 5 was obtained in the same manner as in (1) of Example 1 except that the composition was changed to 6.6 parts by mass.
- Comparative Example 6 (1) Preparation of Comparative Adhesive Composition Same as (1) of Example 1 except that 39.4 parts by mass of compound 1 (gas generator) of Production Example 1 was not used in (1) of Example 1. A comparative adhesive composition 6 was obtained.
- UV irradiation was further performed with an exposure amount of 3000 mJ / cm 2 using an ultra-high pressure mercury lamp, and then the peeling force after UV irradiation was measured.
- the peeling force was measured by a 180 ° tensile test (moving speed 300 mm / min, peeling angle 180 degrees, moving 50 mm) using Tensilon (RTF-1150-H manufactured by A & D Co., Ltd.).
- the total light transmittance of the adhesive sheet before UV irradiation was measured by a haze meter (HM150 manufactured by Murakami Color Technology Research Institute) in accordance with JIS K7361-1. (Evaluation criteria for the condition of the adhesive layer) Transparency: The total light transmittance is 80% or more. White turbidity: Total light transmittance is less than 80%.
- Comparative Example 1 using the gas generating agent of Comparative Compound 1 although gas was not generated by light irradiation although it was localized on the surface, the decrease in peeling power after light irradiation was inferior.
- Comparative Examples 2 and 3 using the gas generating agent of Comparative Compound 2 when the content of the gas generating agent was 20% by mass in the solid content, gas was generated on the surface of the adhesive layer, but the gas generating agent. When the content of was as small as 4% by mass in the solid content, no gas generation was observed. In Comparative Examples 2 and 3, the peeling force after light irradiation was almost the same as that of Comparative Example 6 in which the gas generating agent was not used.
- Comparative Example 4 using the gas generating agent of Comparative Compound 3 used in the prior art, gas was generated on the surface of the adhesive layer, but the adhesive layer became cloudy and the peeling force after light irradiation. Was inferior. It is considered that UV curing inhibition was caused by the poor compatibility of the gas generating agent of Comparative Compound 3 and the cloudiness of the adhesive layer.
- Comparative Example 5 in which the content of the gas generating agent of Comparative Compound 3 was reduced to 4% by mass in the solid content, no gas generation was observed, and the peeling force after light irradiation was higher than that of Comparative Example 6 in which the gas generating agent was not used. It was inferior.
- Adhesive layer 2 Base material or mold release sheet 3 Release sheet 10 Adhesive sheet
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Abstract
Description
しかしながら、上記アゾ化合物やテトラゾール化合物を用いても剥離力の低下が不十分であったり、剥離力を十分に低下させるには添加量を多くしなければならないという問題があった。
しかしながら、粘着力の向上と、易剥離性の向上はトレードオフの関係にあり、従来の高接着易剥離を目的とした粘着材料は、易剥離性が未だ不十分であった。
Aはそれぞれ独立に、下記一般式(A-1)、(A-2)又は(A-3)で表される気体発生部を表し、
Lはそれぞれ独立に、直接結合又は2価の連結基を表し、
Q1は、フッ素原子が直接結合した炭素原子の数が2~8であり、炭素鎖中にエーテル結合(-O-)を含んでいてもよく、置換基を有していてもよい1価のフッ素化脂肪族炭化水素基、又は、1価のオルガノポリシロキサン基を表し、
Q2は、フッ素原子が直接結合した炭素原子の数が2~8であり、炭素鎖中にエーテル結合(-O-)を含んでいてもよい2価のフッ素化脂肪族炭化水素基、又は、2価のオルガノポリシロキサン基を表す。)
前記粘着層は、粘着剤成分と前記本開示の1実施形態の気体発生剤とを含有する粘着組成物又はその硬化物であり、当該粘着層は、光照射により初期粘着力から粘着力が低下する特性を有する、粘着シートを提供する。
「本明細書において、ある部材又はある領域等のある構成が、他の部材又は他の領域等の他の構成の「上に(又は下に)」あるとする場合、特段の限定がない限り、これは他の構成の直上(又は直下)にある場合のみでなく、他の構成の上方(又は下方)にある場合を含み、すなわち、他の構成の上方(又は下方)において間に別の構成要素が含まれている場合も含む。
また、本明細書において「シート」には、「フィルム」と呼ばれる部材も含まれる。また、「フィルム」には、「シート」と呼ばれる部材も含まれる。また、「シート面(フィルム面)」とは、対象となるシート状(フィルム状)の部材を全体的かつ大局的に見た場合において対象となるシート状部材(フィルム状部材)の平面方向と一致する面のことを指す。
なお、本開示において「光」としては、紫外線を含む光が挙げられる。
以下、本開示の気体発生剤、粘着組成物、及び粘着シートについて順に詳細に説明する。
本開示の1実施形態の気体発生剤は、下記一般式(1)及び(2)の少なくとも1種で表され、波長240~450nmにおけるモル吸光係数の最大値が7000以上であり、光照射により気体が発生する気体発生剤である。
Aはそれぞれ独立に、下記一般式(A-1)、(A-2)又は(A-3)で表される気体発生部を表し、
Lはそれぞれ独立に、直接結合又は2価の連結基を表し、
Q1は、フッ素原子が直接結合した炭素原子の数が2~8であり、炭素鎖中にエーテル結合(-O-)を含んでいてもよく、置換基を有していてもよい1価のフッ素化脂肪族炭化水素基、又は、1価のオルガノポリシロキサン基を表し、
Q2は、フッ素原子が直接結合した炭素原子の数が2~8であり、炭素鎖中にエーテル結合(-O-)を含んでいてもよい2価のフッ素化脂肪族炭化水素基、又は、2価のオルガノポリシロキサン基を表す。)
高接着易剥離を目的とした気体発生剤を含有する粘着層においては、使用後に光を照射することによって、気体発生剤から発生した気体が、粘着層の表面、すなわち被着体との界面に放出され、その圧力によって被着体の少なくとも一部が剥離する。当該気体の粘着層表面への放出により、粘着層は、被着体との接触面積が減少して、容易に剥離できるようになる。従来の気体発生剤を含有する粘着層においては、気体発生剤が粘着層中に均一に分散されることから、光を照射しても、粘着層内部に存在する気体発生剤からは、気体が粘着層の表面に放出され難く、粘着層表面付近に存在する気体発生剤から発生した気体だけでは、粘着層表面での気体発生量が不十分となるため、剥離力の低下が不十分で、易剥離性が不十分であった。粘着層表面での気体発生量を多くするために、粘着層中の気体発生剤の含有量を多くすると、粘着層の粘着力の低下が生じたり、粘着層の白濁が生じたりすることから、気体発生剤の添加による剥離力の向上に限界があった。
それに対して、本開示の気体発生剤は、前記特定の構造を有する気体発生部に、前記特定のフッ素化脂肪族炭化水素基、又は、前記特定のオルガノポリシロキサン基が導入されていることから、表面に局在化しやすい。本開示の気体発生剤を含有する粘着層においては、気体発生剤が粘着層の表面に局在化しやすいことから、光を照射すると、粘着層表面に局在化している気体発生剤が気体を発生し、当該気体は粘着層の表面に放出されやすい。本開示の気体発生剤を含有する粘着層においては、粘着層表面での気体発生量が効率的に増加するため、被着体からの易剥離性に優れる。本開示の気体発生剤は、粘着層の表面に局在化しやすいことから、気体発生剤の含有量を多くしなくても粘着層表面での気体発生量を効率的に増加することができるので、粘着層の粘着力の低下や白濁を抑制することができる。このように、本開示の気体発生剤は、剥離性を表面に与える効果を向上することができると推定される。
一般式(1)及び(2)中、Aはそれぞれ独立に、前記一般式(A-1)、(A-2)又は(A-3)で表される気体発生部を表す。
前記一般式(A-1)で表される気体発生部は、光照射により、テトラゾール環が分解して、窒素ガスを発生する。
前記一般式(A-2)で表される気体発生部は、光照射により、-(C=O)-(C=N2)-結合が、-(C=C=O)-結合と窒素ガスに分解して、窒素ガスを発生する。
前記一般式(A-3)で表される気体発生部は、光照射により、アゾ基部分で分解して、窒素ガスを発生する。
炭素数3~20の芳香族基としては、芳香族炭化水素基、及び芳香族複素環基が挙げられる。
芳香族複素環基としては、窒素原子、酸素原子、及び硫黄原子の少なくとも1つを含む炭素数3~20の芳香族複素環基が挙げられ、炭素数3~10の芳香族複素環基が好ましく、例えば、ピロリル基、フリル基、チエニル基、ピラゾリル基、イミダゾリル基、オキサゾリル基、イソオキサゾリル基、チアゾリル基、イソチアゾリル基、カルバゾール基等が挙げられる。
前記芳香族基が有していてもよい置換基としては、F、Cl、Brなどのハロゲン原子、ニトロ基、アルキル基、アルケニル基、アラルキル基、メトキシ基などのアルコキシ基、ジフェニルアミノ基などの3級アミノ基、ベンゾイル基などのアシル基等が挙げられる。アルキル基、アルケニル基、アラルキル基としては、後述する炭素数1~20のアルキル基、炭素数2~20のアルケニル基、アラルキル基と同様であって良いが、炭素数1~14のアルキル基、炭素数2~14のアルケニル基、炭素数7~14のアラルキル基であることが好ましい。前記芳香族基の置換基を適宜選択することにより、光の吸収波長を変化させたり、他の成分との相溶性を向上することができる。光の吸収波長を長波長側に変化させる置換基としては、例えば、メトキシ基などのアルコキシ基、ジフェニルアミノ基などのジアリールアミノ基、ベンゾイル基などのアシル基等が挙げられる。
前記炭素数1~20のアルキル基は、直鎖状、分岐状、環状のいずれであってもよく、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、2-エチルヘキシル基、シクロペンチル基、シクロヘキシル基、ボルニル基、イソボルニル基、ジシクロペンタニル基、アダマンチル基、低級アルキル基置換アダマンチル基などを挙げることができる。
前記炭素数2~20のアルケニル基は、直鎖状、分岐状、環状のいずれであってもよい。このようなアルケニル基としては、例えばビニル基、アリル基、プロペニル基などを挙げることができる。アルケニル基の二重結合の位置には限定はないが、反応性の点からは、アルケニル基の末端に二重結合があることが好ましい。
アリール基としては、前記R1における芳香族炭化水素基と同様であってよいが、フェニル基、ビフェニル基、ナフチル基等が好適に用いられる。
また、アラルキル基としては、ベンジル基、フェネチル基、ナフチルメチル基、ビフェニルメチル基等が挙げられる。アラルキル基の炭素数は、7~20が好ましく、更に7~14が好ましい。
前記アリール基やアラルキル基等の芳香環の置換基としては、前記アルキル基であっても良い。
なお、前記好ましい炭素数には、置換基の炭素数は含まれない。
R6における炭素数1~5の炭化水素基は、前記R2における置換基を有していてもよい炭素数1~20の炭化水素基のうち、炭素数1~5の炭化水素基に相当するものと同様のものが挙げられる。
R4における-L-Q1は、後述と同様であって良い。
R6は、1分子中に含まれる窒素含有量の点から、中でも水素原子又はメチル基であることが好ましく、さらに水素原子であることがより好ましい。
前記一般式(A-1)で表される気体発生部を以下に例示するがこれらに限定されるものではない。
Q1及びQ2における、フッ素化脂肪族炭化水素基は、フッ素原子が直接結合した炭素原子の数が2~8であれば、その一部にフッ素原子が直接結合していない炭素原子が含まれていてもよい。例えば、フッ素化脂肪族炭化水素基にアルキニル基が含まれている場合には、フッ素原子が直接結合していない炭素原子が含まれる。
前記(Rf-4)において、n’は4~10の整数を表すが、表面局在化の効果の点から、中でもnは5~10の整数を表すことが好ましい。
前記(Rf-5)において、nは1~8の整数、n”は0~7の整数、mは0~7の整数、但しn+n”×mは2~8の整数を表すが、表面局在化の効果の点から、nは2~8の整数、n”は1~7の整数、mは1~7の整数を表すことが好ましく、中でもn+n”×mは3~8の整数を表すことが好ましい。
前記(Rf-6)において、nは0~8の整数、n”は0~4の整数、mは0~8の整数、但しn+n”×mは2~8の整数を表すが、表面局在化の効果の点から、nは2~8の整数、n”は1~7の整数、mは1~7の整数を表すことが好ましく、中でもn+n”×mは3~8の整数を表すことが好ましい。
前記一般式(2)の化合物を調製する際に、両末端に気体発生部が導入されず、片末端のみに気体発生部が導入された場合にも、前記一般式(1)の構造を有し、末端に水酸基、アミノ基、カルボキシ基、又は(メタ)アクリロイルオキシ基等の反応性基を有する場合がある。
R11及びR12における炭素数1~20のアルコキシ基としては、炭素数1~10のアルコキシ基が好ましく、具体的には、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等が挙げられる。
R11及びR12としては、有機溶剤への溶解性の点から、炭素数1~10のアルキル基、アリール基、又は、前記一般式(Si-3)で表される基が好ましく、炭素数1~5のアルキル基であることがより好ましい。R12としては、炭素数1~10のアルキル基又はアリール基であることが好ましく、炭素数1~5のアルキル基であることがより好ましい。
前記一般式(2)の化合物を調製する際に、両末端に気体発生部が導入されず、片末端のみに気体発生部が導入された場合にも、前記一般式(1)の構造を有し、末端に水酸基、アミノ基、カルボキシ基、又は(メタ)アクリロイルオキシ基等の反応性基を有する場合がある。
また、前記一般式(Si-3)中、bは0~100の数を表す。bも分布を有し得るため、平均値であって良い。bは、中でも0~40の数を表すことが好ましく、0~30の数を表すことがより好ましい。
なお直接結合とは、Lが原子を有しないこと、即ち、一般式(1)及び(2)における前記Aの炭素原子と、前記Q1又はQ2の炭素原子又はケイ素原子とが、他の原子を介さずに結合していることを意味する。
(L1):-SCH2CH2COO-(CjH2j)-、
(L2):-SCH2CH2COO-(CjH2j)-O-(CkH2k)-、
(L3):-SCH2CH2COO-(CjH2j)-NHCO-(CkH2k)-、
(L4):-SCH2CH2CO-OCH2CH(OH)CH2O-(CjH2j)-、
(L5):-SCH2CH2CO-OCH2CH(OH)-(CjH2j)-、
(L6):-SCH2CH2COO-(CjH2j)-NHCO-CH{CH2O-(CkH2k)-Rf}-CH2O-(ClH2l)-、
(L7):-SCH2CH2COO-CH{CH2O-(CjH2j)-Rf}-CH2O-(CkH2k)-、
(L8):-SCH2CH2COO-(CjH2j)-N(CkH2k+1)SO2-、
(L9):-SCH2CH2CON(CjH2j+1)-(CkH2k)-、
(L10):-SCH2CH2COO-(CjH2j)-N(CkH2k+1)CO-、
(L11):-OCH(CH3)O-(CjH2j)-等(ここで、j、k、及びlはそれぞれ独立に、1~8の整数を表し、Rfは、前記一般式(Rf-1)~(Rf-3)で表されるいずれか1つの1価のフッ素化脂肪族炭化水素基)が挙げられるが、これらに限定されるものではない。
前記j、k、及びlはそれぞれ独立に、2~6の整数を表すことが好ましく、2~4の整数を表すことがより好ましい。
本開示の気体発生剤は、波長240~450nmにおけるモル吸光係数の最大値が7000以上であることにより、光照射により、効率的に気体を発生することができる。効率的に気体を発生させ、易剥離性を向上する点から、本開示の気体発生剤は、波長240~450nmにおけるモル吸光係数の最大値が、8000以上であることが好ましく、9000以上であることがより好ましい。
本明細書のモル吸光係数は、気体発生剤を0.1mMになるように酢酸エチルに溶解させ、紫外可視分光光度計(例えば、島津製作所製、紫外可視分光光度計UV2700)を用いて、230nm~800nmの波長域の吸収スペクトルを測定し、得られた吸収スペクトルにおける吸光度を用いて、下記式により計算して得られる値をいう。
ε=A/c×d
(式中εはモル吸光係数を表し、Aは吸光度、cはモル濃度を表し、dはセル厚みを表す。)
気体発生剤が酢酸エチルに0.1mM溶解しない場合には、気体発生剤のモル吸光係数の再現性に問題を生じない溶剤を適宜選定して0.1mM溶解させ、上記と同様に求める。気体発生剤のモル吸光係数の再現性に問題を生じない溶剤としては、例えば、230nm~800nmの波長域の吸収スペクトルをもたない有機溶剤であって、気体発生剤と反応しない有機溶剤が挙げられ、具体例としては、アセトニトリル、ジクロロメタン等が挙げられる。
なお、本明細書において、波長240~450nmにおけるモル吸光係数の最大値が7000以上であるとは、波長240~450nmの間のいずれかの波長におけるモル吸光係数の値が7000以上であればよく、波長240~450nmの間にピークが存在しなくてもよい。
ここで、気体発生剤の分子量は、液体クロマトグラフィー質量分析(LC-MS)により求めることができる。
また、気体発生剤がオルガノポリシロキサン基を含む場合には、質量平均分子量で特定されてよく、質量平均分子量は、ゲル・パーミエーション・クロマトグラフィー(GPC)により、標準ポリスチレン換算値として求めることができる。
前記本開示の気体発生剤の製造方法は、特に限定されず、例えば、反応性基を有する気体発生部と、当該気体発生部の反応性基と反応し結合を形成する反応性基とフッ素化脂肪族炭化水素基又はオルガノポリシロキサン基とを有する化合物とを、反応させて結合することによって、本開示の気体発生剤を得ることができる。
反応性基同士の組み合わせとしては、例えば、チオール基と(メタ)アクリロイルオキシ基、チオール基とエポキシ基、チオール基とビニルエーテル基、水酸基とビニルエーテル基、水酸基とエポキシ基、水酸基とイソシアネート基、アミノ基とスルホニルクロリド基、カルボキシ基とエポキシ基等が挙げられるが、これらに限定されるものではない。各組み合わせにおいて、どちらが気体発生部側の反応性基となり、どちらがフッ素化脂肪族炭化水素基又はオルガノポリシロキサン基を有する化合物側の反応性基となってもよい。
また、反応性基とフッ素化脂肪族炭化水素基又はオルガノポリシロキサン基とを有する化合物は、例えば、特許6137289号公報、ChemistrySelect,Volume:3,Issue:15,Pages:4129-4132,Journal,2018を参照して、スルホン酸クロリド基を有するナフトキノンジアジド化合物とアミノ基を持つオルガノポリシロキサン化合物を反応させることにより、オルガノポリシロキサン基とを有する化合物を合成することができる。また、Macromolecules,Volume:37,Issue:18,Pages:6673-6675,Journal,2004を参照して、フッ素化脂肪族炭化水素基を有するビニルエーテル基とカルボキシル基をもつアゾ系化合物を反応させることでフッ素化脂肪族炭化水素基を有する化合物を合成することができる。或いは、反応性基とフッ素化脂肪族炭化水素基又はオルガノポリシロキサン基とを有する化合物としては、市販品を適宜選択して用いても良い。
本開示の気体発生剤は、前記特定の構造を有する気体発生部に、前記特定のフッ素化脂肪族炭化水素基、又は、前記特定のオルガノポリシロキサン基を有することから、表面に局在化しやすい。そのため、本開示の気体発生剤は、後述するように、高接着易剥離を目的とした粘着材料に適用し、易剥離性を向上するために好適に用いられる。
本開示の1実施形態の粘着組成物は、粘着剤成分と、前記本開示の気体発生剤とを含有する。
本開示の1実施形態の粘着組成物は、前記本開示の気体発生剤を含有することから、前述のような表面に局在化しやすい気体発生剤の作用により、粘着層表面での気体発生量が効率的に増加するため、粘着力が必要な使用時には良好な粘着力を有しながら、被着体から粘着層を剥離するような粘着力が不要になった際には、被着体からの易剥離性に優れた粘着層を形成可能である。
粘着剤成分は特に限定されず、非光硬化型の粘着剤成分であっても、光硬化型の粘着剤成分であってもよい。
粘着剤成分が非光硬化型の粘着剤成分である場合には、光を照射することにより前記本開示の気体発生剤から気体が発生し、発生した気体により剥離応力が発生し、また被着体との接着面積が減少して剥離する。
粘着剤成分が光硬化型の粘着剤成分である場合には、光を照射することにより前記本開示の気体発生剤から気体が発生することによる被着体との接着面積が減少と、粘着剤成分が光硬化することによる粘着剤成分自体の粘着力の低下の相乗効果によって、剥離がより容易になる。そのため、粘着剤成分は光硬化型であることが好ましい。
本開示の1実施形態の粘着組成物に用いられる光硬化型の粘着剤成分は、(i)粘着剤と、光硬化性多官能化合物と、光開始剤とを含有する組成物である場合、(ii)1分子中に2個以上の光硬化性官能基を有する粘着剤と、光開始剤とを含有する組成物である場合等が挙げられる。中でも、前記光硬化型の粘着剤成分は、(i)粘着剤と、光硬化性多官能化合物と、光開始剤とを含有する組成物であることが、粘着力を容易に調整しやすい点から好ましい。なお、前記(i)の場合において、粘着剤が光硬化性官能基を有していてもよい。
粘着剤としては、特に限定されず、例えば、ゴム系粘着剤、アクリル系粘着剤、ビニルアルキルエーテル系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ポリアミド系粘着剤、ウレタン系粘着剤、スチレン・ジエンブロック共重合体系粘着剤等が挙げられる。
(メタ)アクリル酸エステル系重合体としては、アクリル系粘着剤として用いられる直鎖又は分岐アルキル基の炭素数が1以上20以下の(メタ)アクリル酸アルキルエステルモノマー由来の構成単位と必要に応じて他のモノマーとを共重合させた(メタ)アクリル酸エステル系共重合体を用いることが好ましい。
(メタ)アクリル酸エステル系重合体としては、中でも、直鎖又は分岐アルキル基の炭素数が1以上20以下の(メタ)アクリル酸アルキルエステルモノマー由来の構成単位と、架橋性基含有モノマー由来の構成単位とを有する(メタ)アクリル酸エステル系共重合体であることが好ましい。当該(メタ)アクリル酸エステル系共重合体は、(メタ)アクリル酸エステル重合体の分子内に導入された架橋性基を利用して、後述する熱架橋剤等との架橋が可能となり、粘着組成物の凝集力を向上させ、易剥離性及び所定環境下における耐久性とのバランスが良好な粘着層を得ることができる。
重合体の重合時及び保存時の安定性の点から、水酸基、エポキシ基、カルボキシ基、及びアミノ基からなる群から選択される1種以上を含有するモノマー由来の構成単位を含むことが好ましく、水酸基含有モノマー由来の構成単位を含むことが、安定性が高く、熱架橋剤の反応性に優れる点から好ましい。
エポキシ基含有モノマー由来の構成単位を誘導するモノマーとしては、例えば、グリシジル(メタ)アクリレート、3,4-エポキシシクロヘキシルメチル(メタ)アクリレート等が挙げられる。
イソシアネート基含有モノマー由来の構成単位を誘導するモノマーとしては、例えば、2-(メタ)アクリロイルオキシエチルイソシアネートやそれらのアルキレンオキサイド付加物等が挙げられる。
アミノ基含有モノマー由来の構成単位を誘導するモノマーとしては、例えば、エチルアミノエチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート等が挙げられる。
カルボキシ基含有モノマー由来の構成単位を誘導するモノマーとしては、例えば、(メタ)アクリル酸、ビニル安息香酸、マレイン酸、ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレート等が挙げられる。
光硬化性官能基としては、エチレン性不飽和結合を有することが好ましく、(メタ)アクリロイル基、ビニル基、アリル基等が好ましい。
(メタ)アクリル酸エステル系重合体の側鎖に光硬化性官能基を導入する方法としては、従来公知の製造方法を適宜選択して用いればよい。
例えば、カルボキシ基を有する(メタ)アクリル酸エステル系重合体にグリシジル(メタ)アクリレートを反応させたり、イソシアネート基を有する(メタ)アクリル酸エステル系重合体にヒドロキシエチル(メタ)アクリレートを反応させたり、水酸基を有する(メタ)アクリル酸エステル系重合体に2-イソシアナトエチル(メタ)アクリレートを反応させたりして、光硬化性官能基を付加することができる。
その他のモノマーとしては、例えば、シクロヘキシルメタクリレート、ベンジルメタクリレート、アダマンチルメタクリレート等の剛直性のあるモノマー等を用いることができる。
中でも、(メタ)アクリル酸アルキルエステルモノマーの含有量は、全モノマー成分に対して、例えば、50質量%以上であり、60質量%以上であってもよく、80質量%以上であってもよく、90質量%以上であってもよい。一方、当該(メタ)アクリル酸アルキルエステルモノマーの含有量は、全モノマー成分に対して、例えば、99.5質量%以下であり、99質量%以下であってもよく、98質量%以下であってもよい。
(メタ)アクリル酸エステル系重合体の質量平均分子量は、ゲル・パーミエーション・クロマトグラフィー(GPC)により、標準ポリスチレン換算値として求めることができる。
粘着剤の含有量は、粘着力の効果の点から、粘着組成物の固形分に対して、例えば、20質量%以上であってよく、30質量%以上であってもよい。また、前記粘着剤の含有量は、粘着層の再剥離の点から、粘着組成物の固形分に対して、例えば、80質量%以下であってよく、70質量%以下であってもよい。
なお、本明細書において固形分とは、溶剤以外のすべての成分を意味する。
光硬化性成分として、光硬化性多官能化合物を含有することが好ましい。光硬化性多官能化合物は、光硬化性基を1分子中2個以上含有するモノマー、オリゴマー、ポリマーである。
光硬化性多官能化合物を含有することにより、三次元架橋化することができ、更に、前記(メタ)アクリル酸エステル系重合体が光硬化性を有する場合には、(メタ)アクリル酸エステル系重合体と反応して、(メタ)アクリル酸エステル系重合体を高分子量化したり、三次元架橋化することができる。
光硬化性成分を含有することにより、粘着層を形成した場合の基材密着性、凝集性等を所望範囲に容易に制御することができる。
光硬化性多官能化合物を用いる場合の光硬化性多官能化合物の含有量は、前記(メタ)アクリル酸エステル系重合体等の粘着剤100質量部に対して、例えば、10質量部以上であってよく、20質量部以上であってもよく、50質量以上であってもよく、一方で、300質量部以下であってよく、200質量部以下であってもよく、150質量部以下であってもよい。
光硬化性多官能化合物の含有量が少なすぎると、添加効果が発現しない場合がある。一方、光硬化性多官能化合物の含有量が多すぎると、粘着組成物の保存安定性、基材密着性、粘着性、又は剥離性等の特性が著しく低下する場合がある。
光開始剤としては、紫外線等の光を所定量照射した場合に、ラジカル発生可能な化合物であれば使用可能であるが、例えば、ベンソイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン-n-ブチルエーテル、ベンゾインイソブチルエーテル、アセトフェノン、ジメチルアミノアセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、2,2-ジエトキシ-2-フェニルアセトフェノン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノ-プロパン-1-オン、4-(2-ヒドロキシエトキシ)フェニル-2-(ヒドロキシ-2-プロピル)ケトン、ベンゾフェノン、p-フェニルベンゾフェノン、4,4’-ジエチルアミノベンゾフェノン、ジクロロベンゾフェノン、2-メチルアントラキノン、2-エチルアントラキノン、2-ターシャリ-ブチルアントラキノン、2-アミノアントラキノン、2-メチルチオキサントン、2-エチルチオキサントン、2-クロロチオキサントン、2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン、ベンジルジメチルケタール、アセトフェノンジメチルケタール、p-ジメチルアミノ安息香酸エステル、オリゴ[2-ヒドロキシ-2-メチル-1[4-(1-メチルビニル)フェニル]プロパノン]、2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド等が挙げられる。
中でも、塗膜の内部まで硬化し耐久性が向上するため、アシルフォスフィンオキサイド系開始剤、α-アミノアルキルフェノン系開始剤、α-ヒドロキシケトン系開始剤、及びオキシムエステル系開始剤よりなる群から選択される少なくとも1種が好ましい。
光開始剤は、1種又は2種以上組み合わせて用いることができる。
本開示の粘着組成物には、更に、熱架橋剤を含有することが好ましい。熱架橋剤とは、熱の作用で架橋反応を進行させる化合物をいう。
本開示の粘着組成物に熱架橋剤を含有することにより、前記粘着剤に含まれる架橋性基と反応させて、膜形成後に粘着組成物自身の流動性をなくしたり、光照射前の粘着力乃至剥離力を調整することができる。
熱架橋剤の含有量は、粘着力と剥離力のバランスにより適宜調整されればよいが、上記効果を得る点から、粘着組成物の固形分に対して、例えば1.0質量%以上であってよく、2.0質量%以上であってもよい。また、熱架橋剤の含有量は、エネルギー照射前の粘着性の点から、粘着組成物の固形分に対して、例えば10.0質量%以下であってよく、8.0質量%以下であってもよい。
本開示の粘着組成物は、前記本開示の気体発生剤を含有する。
本開示の気体発生剤は、粘着材料の表面に局在化しやすいことから、粘着組成物中の気体発生剤の含有量を多くしなくても、粘着材料表面での気体発生量を効率的に増加することができるので、粘着材料の粘着力の低下や白濁を抑制しやすい。
粘着材料の白濁を抑制でき、透明性が高いと、例えば、粘着層を介してカメラ等による精密な外観欠陥確認等を行うこともでき、粘着層を工程用再剥離型の粘着シートにも好適に用いることができるなど、用途が広がる。
本開示の粘着組成物は、更に、溶剤を含有してもよい。溶剤を含有することにより、基材等に対する塗布性や配合成分の混合性を向上させることができる。
溶剤は、組成物中の各成分とは反応せず、これらを溶解乃至分散可能な溶剤の中から、適宜選択して用いることができる。溶剤としては、例えば、エステル類、芳香族炭化水素、ケトン類、エーテル類が挙げられる。
より具体的には、(メタ)アクリル酸エステル系重合体等に対する溶解性が良好であって、取り扱いが容易なことから、酢酸メチル、酢酸エチル、酢酸n-ブチル、酢酸i-ブチル、ベンゼン、トルエン、キシレン、アセトン、シクロヘキサン、シクロヘキサノン、メチルエチルケトン、テトラヒドロフラン等の1種又は2種以上の組み合わせが挙げられる。
本開示の粘着組成物には、本開示の目的が損なわれない範囲で、必要に応じて更に各種添加剤を含むものであってよい。
各種添加剤としては、例えば架橋促進剤、酸化防止剤、安定剤、粘度調整剤、粘着付与樹脂、有機又は無機質充填剤などが挙げられる。
架橋促進剤としては、例えば、トリエチルアミン系、ナフテン酸コバルト系、スズ系、亜鉛系、チタン系、ジルコニウム系などのものが挙げられる。架橋剤がイソシアネート系架橋剤の場合、特にアルコキシドやアシレート、錯体などの亜鉛系、チタン系及びジルコニウム系促進剤や、塩化第一スズ、テトラ-n-ブチルスズ、塩化第二スズ、トリメチルスズヒドロキシド、ジメチル2塩化スズ、ジ-n-ブチルスズジラウレートなどのスズ系促進剤を使用するのが好ましい。
また、酸化防止剤としては、フェノール系酸化防止剤などが挙げられる。
粘着組成物の製造方法は、特に限定されない。
粘着組成物は、前述した各成分、さらに必要に応じて添加される各種添加剤を任意の順序で添加し、溶解又は分散させることにより得ることができる。前記各成分の混合は、例えば、ディゾルバー、プラネタリーミキサー、バタフライミキサー等の混合機あるいは混練機を用いて行うことができる。
本開示の粘着組成物の用途は、特に限定されないが、後述する粘着シートの粘着層に好適に用いることができ、後述する粘着シートに記載した用途に好適に用いることができる。
その他にも、本開示の粘着組成物は、シート状にしない粘着材料にも用いることができ、例えば、仮止め接着剤等に適用することもできる。
本開示の1実施形態の粘着シートは、粘着層と、前記粘着層の一方の面に基材又は離型シートを備え、
前記粘着層は、粘着剤成分と前記本開示の気体発生剤とを含有する粘着組成物又はその硬化物であり、当該粘着層は、光照射により初期粘着力から粘着力が低下する特性を有する、粘着シートである。
図1における本開示の粘着シート10は、粘着層1と、前記粘着層1の一方の面に配置された基材又は離型シート2とを備える。
図2における本開示の粘着シート10は、粘着層1と、前記粘着層1の一方の面に配置された基材又は離型シート2と、前記粘着層1の前記基材又は離型シート2側とは反対側の面に配置された、離型シート3とを備える。本開示の粘着シートは、その取り扱いの容易化を図るため、被着体と貼り合わされるまでは、粘着層の前記基材又は離型シート2側とは反対側の面に、離型シートを貼り合せておいてよい。
本開示の粘着シートにおける粘着層は、粘着剤成分と前記本開示の気体発生剤とを含有する粘着組成物又はその硬化物である。
粘着剤成分と前記本開示の気体発生剤とを含有する粘着組成物は、前記本開示の粘着組成物と同様であってよいので、ここでの説明を省略する。
粘着組成物が硬化型の粘着剤成分を含む場合、本開示の粘着シートにおける粘着層は、粘着組成物の硬化物であってよい。
また、前記粘着層は、光照射後の粘着力として、ガラス板(商品名:無アルカリガラス OA‐11、日本電気硝子製)に対する剥離速度300mm/分、剥離角度180度での剥離力が、0N/25mm以上であってよく、0.01N/25mm以上であってもよい。一方で、前記剥離角度180度での剥離力は1N/25mm以下であってもよく、0.1N/25mm以下であってもよい。光照射量は適宜選択されればよいが、例えば、露光量3000mJ/cm2で紫外線(UV)照射を行った後の粘着力を光照射後の粘着力の1つの指標とすることができる。
なお、一般に、剥離速度が大きくなればなるほど、剥離力は大きくなる。
このような範囲であれば、粘着層としての透明性が良好であり、粘着シートを付着したまま、被着体について、カメラ等による精密な確認や検査等を行うことができる。
本開示の粘着シートに用いられる基材は、適宜選択して用いられれば良く、特に限定されない。粘着シートの基材側から光を照射することにより、粘着層の初期粘着力から粘着力を低下させることが好ましいことから、透明な基材を用いることが好ましい。
本開示の粘着シートに用いられる基材は、全光線透過率が80%以上であることが好ましく、更に90%以上であることが好ましい。また、本開示の粘着シートに用いられる基材は、ヘイズが1.5%以下であることが好ましく、更に1.0%以下であることが好ましい。
また、基材は、前記粘着層との密着性を高めるため、粘着層が配置される面に表面処理が施されていてもよい。
離型シートは、粘着層から剥離可能であれば特に限定されず、粘着層を保護することが可能な程度の強度を有することができる。このような離型シートとしては、例えば、離型フィルム、剥離紙等を挙げることができる。また、離型シートは、公知の何れのものも使用することができ、単層構造を有していてもよく、複層構造を有していてもよい。
また、複層構造の離型シートとしては、例えば、基材層の片面または両面に離型層を有する積層体が挙げられる。基材層としては、例えば、ポリプロピレン、ポリエチレン、ポリエチレンテレフタレート等の樹脂フィルムや、上質紙、コート紙、含浸紙等の紙が挙げられる。離型層の材料としては、離型性を有する材料であれば特に限定されず、例えば、シリコーン化合物、有機化合物変性シリコーン化合物、フッ素化合物、アミノアルキド化合物、メラミン化合物、アクリル化合物、ポリエステル化合物、長鎖アルキル化合物等が挙げられる。これらの化合物は、エマルジョン型、溶剤型または無溶剤型のいずれもが使用できる。
離型シートの厚みは、例えば15~200μm程度にすることができる。
本開示の粘着シートは、任意の適切な方法により製造することができる。
本開示の粘着シートは、基材又は離型シートと粘着層との積層体を製造することによって得ることができる。このような積層体は、例えば、
(1)粘着組成物の溶液や熱溶融液を基材又は離型シート上に塗布して粘着層を形成する方法、
(2)前記(1)に準じ、離型シート上に塗布、形成した粘着層を基材上に転写する方法、
(3)粘着組成物を基材上に押出して形成塗布する方法、
(4)基材層と粘着層を二層または多層にて押出しする方法、
などの、任意の適切な方法によって製造することができる。
中でも前記(1)の製造方法が好適に用いられる。
本開示の粘着シートは、使用後の被着体からの易剥離性に優れているので、例えば、各種電子部材や光学部材などの精密化や複雑化による、被着体自体の薄膜化、機能の集積化、微細化に伴い、被着体自身や被保護部材表面が破壊しやすい場合や、被着体において保護シートを貼付する側の面が幅広の広面積で、被着体から保護シートを剥離するのに要する力が増す場合にも、好適な粘着シートとして用いることができる。
製造した各化合物は、1H-NMR測定(装置名AVANCE 400MHz、BRUKER製)により、化学構造を確認した。
冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器にメチルエチルケトン(MEK、昭和インク製)15.61g、5-メルカプト-1-フェニル-1Hテトラゾール(東京化成製)2g(0.0112mol)、2-(パーフルオロヘキシル)エチルアクリレート(ビスコート13F 大阪有機化学製)4.69g(0.0112mol)、ジメチルフェニルホスフィン0.1g(触媒:アクリレートに対して6mol%)を添加し、窒素バブリングを10分間行った後、窒素雰囲気にし、80℃で6時間撹拌した。
6時間後、室温に戻し、MEKと純水で分液を行い、MEKを留去し真空乾燥後、下記式で表される化合物1を5.95g(0.010mol、収率89%)得た。1H-NMR(溶媒:CDCl3)により目的物が合成できていることを確認した。
NMRケミカルシフトppm(多重度、プロトン数):7.50-7.57(m、5H)、4.40-4.44(m、2H)、3.60-3.64(m、2H)、3.0-3.10(m、2H)、2.50-2.60(m、2H)
製造例1において、2-(パーフルオロヘキシル)エチルアクリレートの代わりに、2-(パーフルオロブチル)エチルアクリレート(東京化成製)3.57g(0.0112mol)を用いた以外は、製造例1と同様にして、下記式で表される化合物2を5.4g(0.0108mol、収率97%)得た。1H-NMR(溶媒:CDCl3)により目的物が合成できていることを確認した。
NMRケミカルシフトppm(多重度、プロトン数):7.50-7.57(m、5H)、4.40-4.44(m、2H)、3.60-3.64(m、2H)、3.0-3.10(m、2H)、2.50-2.60(m、2H)
(1)化合物3の化合物中間体1(5-メルカプト-1-ナフチル-1Hテトラゾール)の合成
冷却管、添加用ロート、Ar用インレット、機械的攪拌機、デジタル温度計を備えた反応器にアセトニトリル(富士フィルム和光純薬製)500g、1-ナフチルイソチオシアネート(東京化成製)25g(0.135mol)、アジ化ナトリウム(富士フィルム和光純薬製)25g(0.162mol)、塩化亜鉛(富士フィルム和光純薬製)22.1g(0.162mol)、を添加し、Arバブリングを10分間行った後、Ar雰囲気にし、80℃で2時間撹拌した。
2時間後、室温に戻し、反応液を35℃で濃縮させ、5wt%のNaOH水溶液500mLを加え、室温で30分攪拌後、吸引ろ過により不要物を除去し、クロロホルムを用いて3回洗浄し有機層を除去し、濃塩酸40mLを滴下し、0℃から10℃にて10分間攪拌後、吸引ろ過およびイオン交換水150mLを用いて洗浄・乾燥後、再びアセトニトリル500mLを加え懸濁洗浄し、濃縮後吸引ろ過および減圧乾燥後、下記式で表される化合物中間体1を13.6g(0.060mol、収率44.2%、)を得た。1H-NMR(溶媒:DMSO-d6)により目的物が合成できていることを確認した。
NMRケミカルシフトppm(多重度、プロトン数):8.23-8.25(d、1H)、8.12-8.15(d、1H)、7.59-7.80(m、4H)、7.42-7.45(d、1H)
製造例1において、5-メルカプト-1-フェニル-1Hテトラゾールの代わりに、化合物中間体1を2.55g(0.0112mol)用いた以外は、製造例1と同様にして、下記式で表される化合物3を 6.50 g(0.0101mol、収率90%)得た。1H-NMR(溶媒:CDCl3)により目的物が合成できていることを確認した。
NMRケミカルシフトppm(多重度、プロトン数):8.07-8.10(d、1H)、7.97-8.00(d、1H)、7.50-7.60(m、5H)、4.40-4.44(m、2H)、3.60-3.64(m、2H)、3.0-3.10(m、2H)、2.50-2.60(m、2H)
製造例1において、5-メルカプト-1-フェニル-1Hテトラゾールの代わりに、5-メルカプト-1-メチル-1Hテトラゾール(東京化成製)1.3g(0.0112mol)を用いた以外は、製造例1と同様にして、下記式で表される比較化合物1を5.68g(0.0106mol、収率95%)得た。1H-NMR(溶媒:CDCl3)により目的物が合成できていることを確認した。
NMRケミカルシフトppm(多重度、プロトン数):4.40-4.44(m、2H)、4.00-4.10(s、3H)、3.60-3.64(m、2H)、3.0-3.10(m、2H)、2.50-2.60(m、2H)
製造例1において、2-(パーフルオロヘキシル)エチルアクリレートの代わりに、エチルアクリレート(東京化成製)1.12g(0.0112mol)を用いた以外は、製造例1と同様にして、下記式で表される比較化合物2を2.99g(0.0108mol、収率96%)得た。1H-NMR(溶媒:CDCl3)により目的物が合成できていることを確認した。
NMRケミカルシフトppm(多重度、プロトン数):4.35-4.40(t、2H)、3.55-3.60(t、2H)、3.0-3.10(t、2H)、2.40-2.60(m、3H)
<モル吸光係数>
モル吸光係数は、得られた化合物を0.1mMになるように酢酸エチルに溶解させ、紫外可視分光光度計(島津製作所製 紫外可視分光光度計UV2700)を用いて、230nm~800nmの波長域の吸収スペクトルを測定し、得られた吸収スペクトルにおける吸光度を用いて、下記式により計算して得られる値を求めた。
ε=A/c×d
(式中εはモル吸光係数を表し、Aは吸光度、cはモル濃度を表し、dはセル厚みを表す。)
波長240~450nmにおけるモル吸光係数の最大値と、吸光度が0.01となる長波長側の末端吸収波長を表3に示す。
(メタ)アクリル酸エステル系重合体(商品名:SKダイン1811L、綜研化学製)100質量部、熱架橋剤(イソシアネート系架橋剤、商品名:コロネートL、日本ポリウレタン工業製)6質量部、化合物1~3及び比較化合物1~3の各化合物39.4質量部、溶剤(商品名:商品名:KT-11、昭和インク製)486.77質量部をそれぞれ混合し、PET基材(商品名:ルミラーU34 75μm東レ製)に乾燥後の膜厚50μmになるようアプリケーター(ヨシミツ精機製)で塗工した。80℃オーブンで3分間加熱後、粘着層を得た後、25mm幅にカットして、離型PETフィルムを剥離した粘着シートの粘着層側を、ガラス板被着体(商品名:無アルカリガラス OA-11、日本電気硝子製)に2kgローラー(テスター産業製)で1往復させ貼りつけた後、23℃、湿度約60%の条件下で3時間放置後に超高圧水銀灯を用いて、露光量3000mJ/cm2で紫外線(UV)照射を行い、ガラス被着体との界面に気泡が発生するか観察した。
(気体発生の有無の評価基準)
〇:気体が発生する。
×:気体が全く発生しない。
(1)粘着組成物の調製
(メタ)アクリル酸エステル系重合体(商品名:SKダイン1811L、綜研化学製)100質量部、光硬化性多官能化合物(商品名:ウレタンアクリレート U-10PA、新中村化学製)50質量部、光開始剤(商品名:Omnirad 819、IGM Resins B.V.製)1.5質量部、熱架橋剤(イソシアネート系架橋剤、商品名:コロネートL、日本ポリウレタン工業製)6質量部、製造例1の化合物1(気体発生剤)39.4質量部、溶剤(商品名:KT-11、昭和インク製)659.19質量部をそれぞれ混合して、実施例1の粘着組成物1を得た。
上記で得られた粘着組成物1をPET基材(商品名:ルミラーU34 75μm東レ製)に乾燥後の膜厚50μmになるようアプリケーター(ヨシミツ精機製)で塗工した。80℃オーブンで3分間加熱後、粘着層を得た。その後、粘着層に離型PETフィルム(商品名:E7006、東洋紡製)をクリーンローラーで貼合わせ、粘着シート1を製造した。
(1)粘着組成物の調製
実施例1の(1)において、製造例1の化合物1を、製造例2の化合物2又は製造例3の化合物3にそれぞれ変更した以外は、実施例1の(1)と同様にして、粘着組成物2又は3を得た。
実施例1の(2)において、粘着組成物1を粘着組成物2又は3にそれぞれ変更した以外は、実施例1の(2)と同様にして、実施例2又は3の粘着シート2又は3を得た。
(1)粘着組成物の調製
実施例1の(1)において、製造例1の化合物1(気体発生剤)39.4質量部を、製造例3の化合物3(気体発生剤)6.6質量部に変更した以外は、実施例1の(1)と同様にして、粘着組成物4を得た。
実施例1の(2)において、粘着組成物1を粘着組成物4に変更した以外は、実施例1の(2)と同様にして、実施例4の粘着シート4を得た。
(1)比較粘着組成物の調製
実施例1の(1)において、製造例1の化合物1を、比較製造例1の比較化合物1に変更した以外は、実施例1の(1)と同様にして、比較粘着組成物1を得た。
実施例1の(2)において、粘着組成物1を比較粘着組成物1に変更した以外は、実施例1の(2)と同様にして、比較例1の比較粘着シート1を得た。
(1)比較粘着組成物の調製
実施例1の(1)において、製造例1の化合物1を、比較製造例2の比較化合物2に変更した以外は、実施例1の(1)と同様にして、比較粘着組成物2を得た。
実施例1の(2)において、粘着組成物1を比較粘着組成物2に変更した以外は、実施例1の(2)と同様にして、比較例2の比較粘着シート2を得た。
(1)比較粘着組成物の調製
実施例1の(1)において、製造例1の化合物1(気体発生剤)39.4質量部を、比較製造例2の比較化合物2(気体発生剤)6.6質量部に変更した以外は、実施例1の(1)と同様にして、比較粘着組成物3を得た。
実施例1の(2)において、粘着組成物1を比較粘着組成物3に変更した以外は、実施例1の(2)と同様にして、比較例3の比較粘着シート3を得た。
(1)比較粘着組成物の調製
実施例1の(1)において、製造例1の化合物1を、比較化合物3(5-メルカプト-1-フェニル-1Hテトラゾール(東京化成製))に変更した以外は、実施例1の(1)と同様にして、比較粘着組成物4を得た。
実施例1の(2)において、粘着組成物1を比較粘着組成物4に変更した以外は、実施例1の(2)と同様にして、比較例4の比較粘着シート4を得た。
(1)比較粘着組成物の調製
実施例1の(1)において、製造例1の化合物1(気体発生剤)39.4質量部を、比較化合物3(5-メルカプト-1-フェニル-1Hテトラゾール)6.6質量部に変更した以外は、実施例1の(1)と同様にして、比較粘着組成物5を得た。
実施例1の(2)において、粘着組成物1を比較粘着組成物5に変更した以外は、実施例1の(2)と同様にして、比較例5の比較粘着シート5を得た。
(1)比較粘着組成物の調製
実施例1の(1)において、製造例1の化合物1(気体発生剤)39.4質量部を用いなかった以外は、実施例1の(1)と同様にして、比較粘着組成物6を得た。
実施例1の(2)において、粘着組成物1を比較粘着組成物6に変更した以外は、実施例1の(2)と同様にして、比較例6の比較粘着シート6を得た。
<気体発生の有無>
25mm幅にカットして、離型PETフィルムを剥離した粘着シートの粘着層側を、ガラス板被着体(商品名:無アルカリガラス OA-11、日本電気硝子製)に2kgローラー(テスター産業製)で1往復させ貼りつけた後、23℃、湿度約60%の条件下で3時間放置後に超高圧水銀灯を用いて、露光量3000mJ/cm2で紫外線(UV)照射を行い、ガラス被着体との界面に気泡が発生するか観察した。
(気体発生の有無の評価基準)
〇:気体が発生。
×:気体が全く発生しない。
25mm幅にカットして、離型PETフィルムを剥離した粘着シートの粘着層側を、ガラス板被着体(商品名:無アルカリガラス OA-11、日本電気硝子製)に2kgローラー(テスター産業製)で1往復させ貼りつけた後、23℃、湿度約60%の条件下で3時間放置後にUV照射前剥離力(初期剥離力)を測定した。その後さらに、超高圧水銀灯を用いて、露光量3000mJ/cm2で紫外線(UV)照射を行った後に、UV照射後剥離力を測定した。
剥離力の測定は、テンシロン(RTF-1150-H エー・アンド・デイ製)を用いて、180°引っ張り試験(移動速度300mm/分、剥離角度180度、50mm移動)にて行った。
UV照射前の粘着シートの全光線透過率を、JIS K7361-1に準拠して、ヘイズメーター(村上色彩技術研究所製 HM150)により測定した。
(粘着層の状態の評価基準)
透明:全光線透過率80%以上である。
白濁:全光線透過率80%未満である。
本開示の気体発生剤を添加した粘着組成物の硬化物である粘着層を備えた実施例1~4の粘着シートでは、比較例に比べても光(UV)照射後剥離力が大きく低下したものであり、易剥離性に優れ、更に白濁も生じず、透明性にも優れたものであった。
実施例4に示されるように、本開示の気体発生剤は粘着層の固形分中に4質量%と少量であっても、効率的に気体を発生し、光照射前の粘着力を高く保持しながら、光照射後剥離力が大きく低下することが明らかにされた。
一方で、比較化合物1の気体発生剤を用いた比較例1では、表面に局在化したものの光照射による気体発生がみられておらず、光照射後剥離力の低下が劣っていた。比較化合物2の気体発生剤を用いた比較例2及び3では、気体発生剤の含有量が固形分中20質量%であれば、粘着層表面に気体の発生がみられたが、気体発生剤の含有量が固形分中4質量%と少量にすると、気体発生がみられなかった。比較例2及び3では、光照射後剥離力が、気体発生剤を用いない比較例6とほぼ同様であった。
また、従来技術で用いられていた比較化合物3の気体発生剤を用いた比較例4では、粘着層表面に気体の発生がみられたが、粘着層が白濁し、且つ、光照射後剥離力の低下が劣っていた。比較化合物3の気体発生剤の相溶性が悪く粘着層が白濁することで、UV硬化阻害を引き起こしたと考えられる。比較化合物3の気体発生剤の含有量を固形分中4質量%と減らした比較例5では、気体発生がみられず、光照射後剥離力が、気体発生剤を用いない比較例6よりも劣っていた。
2 基材又は離型シート
3 離型シート
10 粘着シート
Claims (10)
- 下記一般式(1)及び(2)の少なくとも1種で表され、波長240~450nmにおけるモル吸光係数の最大値が7000以上であり、光照射により気体が発生する気体発生剤。
Aはそれぞれ独立に、下記一般式(A-1)、(A-2)又は(A-3)で表される気体発生部を表し、
Lはそれぞれ独立に、直接結合又は2価の連結基を表し、
Q1は、フッ素原子が直接結合した炭素原子の数が2~8であり、炭素鎖中にエーテル結合(-O-)を含んでいてもよく、置換基を有していてもよい1価のフッ素化脂肪族炭化水素基、又は、1価のオルガノポリシロキサン基を表し、
Q2は、フッ素原子が直接結合した炭素原子の数が2~8であり、炭素鎖中にエーテル結合(-O-)を含んでいてもよい2価のフッ素化脂肪族炭化水素基、又は、2価のオルガノポリシロキサン基を表す。)
- 前記一般式(1)及び(2)において、
Q1は、下記(Rf-1)~(Rf-5)で表されるいずれか1つの1価のフッ素化脂肪族炭化水素基、又は、下記(Si-1)で表される1価のオルガノポリシロキサン基を表し、
Q2は、下記(Rf-6)で表される2価のフッ素化脂肪族炭化水素基、又は、下記(Si-2)で表される2価のオルガノポリシロキサン基を表す、請求項1に記載の気体発生剤。
- 前記一般式(1)及び(2)において、
Lは、それぞれ独立に、直接結合、或いは、-SCH2CH2COO-、-SCH2CH(CH3)COO-、-SCH2CH(OH)CH2-、-OCH2CH(OH)CH2-、-SCH(CH3)O-、-OCH(CH3)O-、-COO-、-CONH-、-COS-、-SO2NH-、又は、-O-及び-S-からなる群から選択される1種以上が含まれていても良く、水酸基が置換されていても良い炭素数1~22の炭化水素基、或いは、これらの組み合わせを表す、請求項1又は2に記載の気体発生剤。 - 粘着剤成分と、請求項1~3のいずれか1項に記載の気体発生剤とを含有する、粘着組成物。
- 光硬化性成分と、光開始剤とを含有する、請求項4に記載の粘着組成物。
- 熱架橋剤を含有する、請求項4又は5に記載の粘着組成物。
- 粘着層と、前記粘着層の一方の面に基材又は離型シートを備え、
前記粘着層は、粘着剤成分と請求項1~3のいずれか1項に記載の気体発生剤とを含有する粘着組成物又はその硬化物であり、当該粘着層は、光照射により初期粘着力から粘着力が低下する特性を有する、粘着シート。 - 前記粘着層の前記基材又は離型シート側とは反対側の面に、更に離型シートを備える、請求項7に記載の粘着シート。
- 前記粘着組成物が、光硬化性成分と、光開始剤とを含有する、請求項7又は8に記載の粘着シート。
- 前記粘着組成物が、熱架橋剤を含有する、請求項7~9のいずれか1項に記載の粘着シート。
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CN202180087145.8A CN116615415A (zh) | 2020-12-25 | 2021-12-22 | 气体产生剂、粘合组合物及粘合片材 |
US18/269,072 US20240141213A1 (en) | 2020-12-25 | 2021-12-22 | Gas generating agent, pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
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WO2011118506A1 (ja) * | 2010-03-24 | 2011-09-29 | 積水化学工業株式会社 | 接着剤組成物、接着テープ、半導体ウエハの処理方法、及び、tsvウエハの製造方法 |
WO2013105582A1 (ja) * | 2012-01-12 | 2013-07-18 | 積水化学工業株式会社 | 粘着剤組成物、粘着テープ、及び、ウエハの処理方法 |
JP2014196284A (ja) * | 2013-03-05 | 2014-10-16 | キヤノン株式会社 | 感光性ガス発生剤、光硬化性組成物 |
WO2014175249A1 (ja) * | 2013-04-23 | 2014-10-30 | 積水化学工業株式会社 | テトラゾール化合物又はその塩、接着剤組成物及び接着テープ |
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JP2601956B2 (ja) | 1991-07-31 | 1997-04-23 | リンテック株式会社 | 再剥離型粘着性ポリマー |
JP2003231872A (ja) | 2001-08-03 | 2003-08-19 | Sekisui Chem Co Ltd | 両面粘着テープ及びそれを用いたicチップの製造方法 |
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WO2011118506A1 (ja) * | 2010-03-24 | 2011-09-29 | 積水化学工業株式会社 | 接着剤組成物、接着テープ、半導体ウエハの処理方法、及び、tsvウエハの製造方法 |
WO2013105582A1 (ja) * | 2012-01-12 | 2013-07-18 | 積水化学工業株式会社 | 粘着剤組成物、粘着テープ、及び、ウエハの処理方法 |
JP2014196284A (ja) * | 2013-03-05 | 2014-10-16 | キヤノン株式会社 | 感光性ガス発生剤、光硬化性組成物 |
WO2014175249A1 (ja) * | 2013-04-23 | 2014-10-30 | 積水化学工業株式会社 | テトラゾール化合物又はその塩、接着剤組成物及び接着テープ |
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US20240141213A1 (en) | 2024-05-02 |
CN116615415A (zh) | 2023-08-18 |
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