WO2024095322A1 - Adhesive composition, adhesive sheet formed of said adhesive composition, and article using said adhesive sheet - Google Patents
Adhesive composition, adhesive sheet formed of said adhesive composition, and article using said adhesive sheet Download PDFInfo
- Publication number
- WO2024095322A1 WO2024095322A1 PCT/JP2022/040745 JP2022040745W WO2024095322A1 WO 2024095322 A1 WO2024095322 A1 WO 2024095322A1 JP 2022040745 W JP2022040745 W JP 2022040745W WO 2024095322 A1 WO2024095322 A1 WO 2024095322A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- mass
- acrylate
- adhesive
- adhesive layer
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 80
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 73
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 239000012790 adhesive layer Substances 0.000 claims abstract description 40
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- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000010419 fine particle Substances 0.000 claims abstract description 25
- 239000006188 syrup Substances 0.000 claims abstract description 17
- 235000020357 syrup Nutrition 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 239000002861 polymer material Substances 0.000 claims abstract description 10
- 239000000470 constituent Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 9
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- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 42
- 239000010410 layer Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 15
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
Definitions
- the present invention relates to an adhesive composition containing hollow microparticles, an adhesive sheet formed from the adhesive composition, and an article in which the adhesive sheet is used.
- foam adhesive tapes that use foamed resin materials as a base material
- foam adhesive tapes have excellent stress relaxation properties, so they also have excellent adhesion to components with steps or unevenness, and can be used for a wider range of adherends than double-sided tapes that use nonwoven fabric or resin film as a base material.
- foam adhesive tape the resin that makes up the foam softens at high temperatures, which raises concerns that the air bubbles inside the tape may collapse and the stress relaxation properties described above may be lost.
- foam adhesive tape usually requires a separate adhesive layer to be laminated, and the adhesive strength of the adhesive layer generally decreases at high temperatures. In other words, there are limitations to its use in automotive parts that are expected to be used in high-temperature environments.
- Patent Document 1 discloses an adhesive sheet having an adhesive layer formed from an ultraviolet-curable adhesive composition containing hollow microspheres and having excellent shear strength and adhesive strength (adhesive strength) in a high-temperature environment.
- This document states that it is preferable to use hollow inorganic microspheres as hollow microspheres (hollow microspheres) from the viewpoint of efficiency and weight of polymerization using ultraviolet reaction, and further that it is possible to improve high-temperature adhesive strength without impairing other properties such as shear strength and holding power by using hollow glass balloons.
- Patent Document 2 discloses an adhesive sheet including an adhesive layer containing an acrylic polymer and hollow fine particles and containing no air bubbles. It is said that this adhesive sheet can more preferably use hollow inorganic fine particles among hollow fine particles from the viewpoint of the efficiency of polymerization using ultraviolet reaction, weight, etc.
- the pressure-sensitive adhesive sheet of Patent Document 2 is said to have both adhesiveness and reworkability, but no particular consideration is given to adhesive strength or flexibility at high temperatures. According to the findings of the present inventors, the glass balloon content (9 to 12 parts) disclosed in the examples and reference examples of Patent Document 2 is effective in improving reworkability, but the flexibility of the pressure-sensitive adhesive sheet is poor, and it is expected that the adhesive strength will decrease at high temperatures.
- JP 2008-88408 A Patent No. 5408640
- JP 2013-221073 A Patent No. 5950669
- the object of the present invention is to provide an adhesive composition capable of forming an adhesive layer that has excellent flexibility and excellent adhesive strength even at high temperatures, an adhesive sheet formed from the adhesive composition, and an article using the adhesive sheet.
- an adhesive sheet having an adhesive layer made of the above-mentioned adhesive composition, and an article using the adhesive sheet.
- the (meth)acrylic syrup (a) used in the adhesive composition of the present invention contains a copolymer having the above-mentioned two types of functional group-containing (meth)acrylate as an essential component, and therefore is easy to form a crosslinked structure regardless of the type of crosslinking agent (e). Therefore, the adhesive layer formed from the adhesive composition of the present invention can maintain high adhesive strength even at high temperatures.
- the adhesive layer is highly polarized by these functional groups, and therefore can obtain excellent adhesive strength, particularly to metals.
- the tackifier resin (b) is an essential component, the initial adhesive strength to members having irregularities or steps can be increased.
- the compressive strength and tensile strength of the adhesive layer after formation are within a specified range, making it possible to achieve a balance between the ability to conform to uneven surfaces, the ability to attach to curved surfaces, and adhesive strength at high temperatures.
- 1 is a schematic cross-sectional view of a pressure-sensitive adhesive sheet according to one embodiment of the present invention.
- 1 is a schematic cross-sectional view of a pressure-sensitive adhesive sheet according to one embodiment of the present invention.
- 1 is a schematic cross-sectional view of a pressure-sensitive adhesive sheet according to one embodiment of the present invention.
- 1 is a schematic cross-sectional view of a pressure-sensitive adhesive sheet according to one embodiment of the present invention.
- 1 is a schematic cross-sectional view of a pressure-sensitive adhesive sheet according to one embodiment of the present invention.
- the pressure-sensitive adhesive composition according to the present invention comprises: (a) 100 parts by mass of a syrup obtained by mixing a (meth)acrylic copolymer having as its constituent components an alkyl (meth)acrylate and a (meth)acrylate having a carboxyl group, an alkyl (meth)acrylate monomer, a (meth)acrylate monomer having a carboxyl group, and a (meth)acrylate monomer having a hydroxyl group; (b) 0.5 to 10 parts by mass of a tackifier resin; (c) 0.1 to 3.0 parts by mass of hollow fine particles; (d) 0.1 to 5 parts by mass of a photopolymerization initiator; (e) 0.01 to 5 parts by mass of a crosslinking agent; A pressure-sensitive adhesive composition comprising: the hollow fine particles (c) are resin-based hollow fine particles having a shell portion made of an organic poly
- the syrup of component (a) is a mixture of a (meth)acrylic copolymer (a1) having as its constituent components monomer units derived from an alkyl (meth)acrylate and a (meth)acrylate having a carboxyl group, an alkyl (meth)acrylate monomer (a2), a (meth)acrylate monomer having a carboxyl group (a3), and a (meth)acrylate monomer having a hydroxyl group (a4).
- the copolymer (a1) contains, as constituent components, monomer units derived from an alkyl (meth)acrylate and a (meth)acrylate having a carboxyl group.
- alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, hexyl (meth)acrylate, isohexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate,
- a unit derived from a monomer having a relatively long alkyl chain may be used alone or in combination of two or more.
- the proportion of the monomer units derived from alkyl (meth)acrylate relative to 100% by mass of all monomer units constituting the copolymer (a1) is preferably from 80 to 99% by mass, and more preferably from 85 to 95% by mass.
- Examples of (meth)acrylates having a carboxyl group include (meth)acrylic acid, ⁇ -carboxyethyl (meth)acrylate, itaconic acid, crotonic acid, maleic acid, and fumaric acid.
- (meth)acrylic acid is preferred from the viewpoint of higher strength of the acrylic resin composition.
- the proportion of monomer units derived from a (meth)acrylate having a carboxyl group relative to 100% by mass of all monomer units constituting the copolymer (a1) is preferably from 1 to 20% by mass, and more preferably from 5 to 15% by mass.
- the copolymer (a1) may contain (meth)acrylic monomer units other than those mentioned above, provided that the effects of the present invention are not impaired.
- examples of such units include nitrogen-containing acrylic monomer units such as (meth)acrylamide, which will be described later, and units derived from a (meth)acrylate monomer (a4) having a hydroxyl group.
- the copolymer (a1) is obtained by copolymerizing the above-mentioned monomer components, and the polymerization method is not particularly limited.
- various polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization can be performed using means such as photopolymerization or thermal polymerization.
- polymerization by radiation such as gamma rays and electron beam polymerization can also be used.
- Photopolymerization can be performed, for example, by irradiating the monomer composition with UV rays in the presence of a photopolymerization initiator.
- Thermal polymerization can be performed, for example, by heating the monomer composition to 50 to 200°C in the presence of a thermal polymerization initiator. It is also preferable to adjust the molecular weight by using a chain transfer agent such as a thiol compound in combination during polymerization. In addition, although unreacted monomers may remain, they can be used as a constituent component of the syrup (a) as is, so there is no need to isolate the copolymer. When the copolymer (a1) reaches 5 to 50% by mass, the polymerization is stopped to make a partial copolymer, which can be handled as a viscous liquid.
- the copolymer (a1) means one having a weight average molecular weight (Mw) of 100,000 or more. The Mw of the copolymer (a1) is preferably from 100,000 to 2,000,000, and more preferably from 500,000 to 1,500,000.
- alkyl (meth)acrylate monomer (a2) the alkyl (meth)acrylates listed as monomer components constituting the copolymer (a1) can be used.
- the (meth)acrylate monomer (a3) having a carboxyl group the (meth)acrylates listed as monomer components constituting the copolymer (a1) can be used. These may be used alone or in combination of two or more.
- Examples of the (meth)acrylate monomer (a4) having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, and monoesters of (meth)acrylic acid with polyethylene glycol or polypropylene glycol. These may be used alone or in combination of two or more.
- nitrogen-containing acrylic monomers may be included as other monomers.
- nitrogen-containing acrylic monomers include (meth)acrylamide, N-alkyl-substituted (meth)acrylamides such as N-isopropyl (meth)acrylamide, N,N-dialkyl-substituted (meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N,N-diethyl (meth)acrylamide, acryloylmorpholine, vinylpyridine, N-vinylpyrrolidone, aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate.
- (meth)acrylamide, N-alkyl-substituted (meth)acrylamide, N,N-dialkyl-substituted (meth)acrylamide, and acryloylmorpholine are preferred from the viewpoints of versatility and industrial commercialization. These may be used alone or in combination of two or more.
- the amounts of the components in the syrup are preferably 5-50% by mass of copolymer (a1) and a total of 50-95% by mass of other monomer components (a2)-(a4), and more preferably 8-40% by mass of copolymer (a1) and a total of 60-92% by mass of other monomer components (a2)-(a4), taking the total as 100% by mass.
- the ratio of the other monomer components (a2)-(a4) is preferably (a2)>(a3)>(a4).
- Tackifying Resin As the tackifying resin, various tackifying resins such as hydrogenated petroleum resins, rosin-based resins, terpene-based resins, hydrocarbon-based resins, and phenol-based resins can be used. These can be used alone or in combination of two or more.
- the tackifier resin (b) is blended in an amount of 0.5 to 10 parts by mass per 100 parts by mass of syrup (a), preferably 1 to 10 parts by mass per 100 parts by mass of syrup (a), and more preferably 2 to 8 parts by mass per 100 parts by mass of syrup (a).
- the hollow fine particles constituting the pressure-sensitive adhesive composition according to the present invention are resin-based hollow fine particles having a shell made of an organic polymer material.
- the organic polymer material constituting the shell is preferably, for example, a resin containing acrylonitrile as a constituent unit.
- the average particle diameter of the hollow fine particles is preferably 1 to 150 ⁇ m, more preferably 10 to 130 ⁇ m.
- the average particle diameter referred to here is the median diameter (D50) based on volume. In addition, in the case of commercially available products, the selection may be made based on the catalog value.
- the thickness of the shell is preferably 0.1 to 20 ⁇ m, and more preferably 2 to 15 ⁇ m.
- the hollow microparticles preferably contain hydrocarbons in their hollows and function as thermally expandable balloons.
- the organic polymer material (thermoplastic resin) that constitutes the shell first begins to soften, the encapsulated hydrocarbons begin to gasify, the internal pressure rises, and the balloon expands. However, once the temperature exceeds a certain level, the gas permeates and escapes from the shell, and the balloon begins to shrink.
- the content of the hollow fine particles in the acrylic resin composition is 0.1 to 3.0 parts by mass, and preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the syrup (a).
- the hollow fine particles may be appropriately subjected to a surface treatment such as a coupling treatment or a stearic acid treatment.
- Photopolymerization initiator As the photopolymerization initiator, a photoradical polymerization initiator can be used, and examples thereof include known polymerization initiators such as alkylphenones, acylphosine oxides, oxyphenyl acetates, etc. The alkylphenones are further classified into benzyl ketals, ⁇ -hydroxyalkylphenones, ⁇ -hydroxyacetophenones, ⁇ -aminoalkylphenones, etc.
- the photopolymerization initiator (d) is blended in an amount of 0.1 to 5 parts by mass, preferably 0.2 to 2 parts by mass, and more preferably 0.3 to 1 part by mass, per 100 parts by mass of the syrup (a).
- the pressure-sensitive adhesive composition according to the present invention preferably contains a crosslinking agent from the viewpoint of forming a crosslinked structure.
- a crosslinking agent from the viewpoint of reactivity with the acrylic syrup (a), at least one crosslinking agent selected from the group consisting of polyfunctional (meth)acrylic monomers, polyfunctional (meth)acrylic oligomers, bifunctional or higher glycidyl group-containing compounds, and bifunctional or higher isocyanate group-containing compounds is preferable.
- polyfunctional (meth)acrylic monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.
- polyfunctional (meth)acrylic oligomers include urethane (meth)acrylates and epoxy (meth)acrylates that are oligomerized by reacting a compound having multiple isocyanate groups or glycidyl groups with (meth)acrylic acid or a hydroxyl group-containing (meth)acrylate.
- difunctional or higher glycidyl group-containing compounds examples include 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-m-xylylenediamine, N,N,N',N'-tetraglycidylaminophenylmethane, triglycidyl isocyanurate, m-N,N-diglycidylaminophenyl glycidyl ether, N,N-diglycidyl toluidine, N,N-diglycidyl aniline, pentaerythritol polyglycidyl ether, and 1,6-hexanediol diglycidyl ether.
- bifunctional or higher isocyanate group-containing compounds include isocyanate monomers such as tolylene diisocyanate (TDI), chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate, as well as isocyanate compounds, isocyanurates, and biuret-type compounds in which these isocyanate monomers are added to trimethylolpropane, and further urethane prepolymer-type isocyanates in which these are added to polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, and polyisoprene polyols. These crosslinking agents can be used alone or in combination of two or more.
- TDI tolylene diisocyanate
- chlorophenylene diisocyanate
- the amount of crosslinking agent in the acrylic resin composition is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 1 part by mass, and even more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of the polymer (total monomers before polymerization).
- the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention after crosslinking has a 25% compressive strength of 0.06 to 0.11 MPa and a tensile strength at 23° C. of 0.35 to 0.65 MPa.
- the 25% compressive strength is a value measured by the method described in the Examples below, and if the compressive strength is less than 0.06 MPa, it becomes difficult for the sheet to maintain its shape, and if it exceeds 0.11 MPa, the ability to conform to steps and curved surfaces decreases.
- the compressive strength is more preferably 0.06 to 0.10 MPa.
- the tensile strength of the pressure-sensitive adhesive layer at 23°C is a value measured by the method described in the Examples below, and if the tensile strength is less than 0.35 MPa, the cohesive strength of the pressure-sensitive adhesive layer is weak, resulting in a decrease in holding power, while if it exceeds 0.65 MPa, the cohesive strength is too strong, resulting in a decrease in peel strength.
- the tensile strength is more preferably 0.38 to 0.56 MPa.
- the peel strength of the pressure-sensitive adhesive layer is not particularly limited as long as it has a peel strength appropriate for the purpose, but it is preferable that the peel strength of the pressure-sensitive adhesive layer after crosslinking formed from the pressure-sensitive adhesive composition of the present invention has little change between room temperature (23°C) and high temperature (90°C).
- the adhesive composition of the present invention may contain various additives known in the field of the present invention, provided that they do not affect the above-mentioned compressive strength and tensile strength.
- additives include flame retardants, pigments, antioxidants, lubricants, etc., and may contain one or a combination of two or more of these.
- the adhesive composition according to the present invention can be used as an adhesive layer formed by forming the adhesive composition into a sheet and crosslinking it.
- the adhesive layer may be formed into a sheet on its own, or may be used as a tape-like material in which an adhesive layer is formed on a substrate. In particular, it is preferably used as a double-sided adhesive sheet for bonding articles together, as described below.
- Such sheet-like and tape-like materials are collectively referred to as adhesive sheets in this specification.
- FIGS. 1 to 5 are schematic cross-sectional views illustrating the layer structure of the adhesive sheet of the present invention.
- FIG. 1 shows a sheet composed solely of an adhesive layer using the adhesive composition of the present invention, with hollow fine particles 2 dispersed in the crosslinked adhesive layer 1.
- the top and bottom surfaces of the sheet are adhesive surfaces, constituting a double-sided adhesive sheet.
- a release film is provided on the adhesive surface, and when adhering an article, the release film is peeled off and the adhesive surface is attached to the surface to which the article is to be adhered.
- Fig. 2 shows an adhesive sheet in which an adhesive layer 1 is disposed on one side of a substrate 3, and a design can be applied by printing or the like to the non-adhesive side of the substrate 3. Therefore, a receiving layer (not shown) suitable for printing or the like can be provided on the non-adhesive side of the substrate 3.
- Fig. 3 shows an adhesive sheet in which an adhesive layer 1 is disposed on both sides of the substrate 3.
- the substrate may be any substrate used in the field and has excellent adhesive strength with the pressure-sensitive adhesive layer of the present invention. For example, known films, nonwoven fabrics, foams, cloths, papers, and combinations thereof may be used.
- the thickness of the substrate is not particularly limited, but can be selected, for example, from the range of 1 ⁇ m or more and 200 ⁇ m or less.
- the surface of the substrate on which the pressure-sensitive adhesive layer is to be formed may be subjected to an easy-adhesion treatment, if necessary.
- easy-adhesion treatments include primer treatment, corona treatment, etching treatment, plasma treatment, sandblasting treatment, etc. One or a combination of two or more of these may be selected.
- the substrate may be subjected to a surface treatment such as antistatic treatment as required.
- the antistatic treatment include treatment with an antistatic agent such as a cationic surfactant, an anionic surfactant, or a nonionic surfactant.
- the substrate may be subjected to a coloring treatment by printing, kneading, or the like as required.
- Figure 4 shows an adhesive sheet having one adhesive surface which is an adhesive layer 1 containing hollow microparticles 2 according to the present invention, and the other surface which is a laminate of an adhesive layer 4 which does not contain hollow microparticles 2.
- Figure 5 shows an adhesive sheet which is a laminate in which a substrate 3 is inserted between adhesive layer 1 and adhesive layer 4.
- An adhesive layer 4 which does not contain hollow microparticles 2 may have inferior step conformability compared to an adhesive layer 1 containing hollow microparticles 2, but as long as the surface to be bonded by adhesive layer 4 is flat, there is no problem even if the step conformability is inferior.
- adhesive layer 4 a conventionally known adhesive layer or an adhesive layer obtained by removing hollow microparticles from adhesive layer 1 can be used.
- the method for producing the adhesive layer is not particularly limited, and any conventionally known method can be used.
- Articles using the adhesive sheet of the present invention include those used in fields such as automobile parts and machine parts, and can be used to bond and adhere articles that are exposed to temperatures of, for example, 50°C or higher during the manufacturing and use processes.
- parts means “parts by mass.”
- HEA hydroxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.
- AM-90G methoxypolyethylene glycol acrylate (product name: NK Ester AM-90G), manufactured by Shin-Nakamura Chemical Co., Ltd.
- IBOA isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.
- ACMO acryloylmorpholine, manufactured by KJ Chemicals Co., Ltd.
- P-125 Hydrogenated petroleum resin (softening point 125 ⁇ 5°C, product name: Alcon P-125), manufactured by Arakawa Chemical Industries Co., Ltd.
- P-140 Hydrogenated petroleum resin (softening point 140 ⁇ 5°C, product name: Alcon P-140), manufactured by Arakawa Chemical Industries Co., Ltd.
- P-90 Hydrogenated petroleum resin (softening point 90 ⁇ 5°C, product name: Alcon P-90), manufactured by Arakawa Chemical Industries Co., Ltd.
- G125 Terpene phenol resin (softening point 125 ⁇ 5°C, product name: YS Polystar G125), manufactured by Yasuhara Chemical Co., Ltd.
- KE-100 Hydrogenated rosin ester (softening point 100 ⁇ 5°C, product name: Pine Crystal KE-100), manufactured by Arakawa Chemical Industries Co., Ltd.
- F-80DE acrylonitrile copolymer hollow microparticles (average particle size 90 to 130 ⁇ m), manufactured by Matsumoto Yushi Seiyaku Co., Ltd.
- F-80SDE acrylonitrile copolymer hollow microparticles (average particle size 20 to 40 ⁇ m), manufactured by Matsumoto Yushi Seiyaku Co., Ltd.
- 30P70T inorganic hollow microparticles, manufactured by Potters Ballotini Co., Ltd.
- HAP photopolymerization initiator (d))
- HAP ⁇ -hydroxyacetophenone (product name: Omnirad 1173), manufactured by IGM Resins
- the pressure-sensitive adhesive sheets prepared above were subjected to the following evaluations. The results are shown in Tables 3-1 to 3-4.
- (Tensile test of adhesive sheet) In accordance with JIS Z 0237, a pressure-sensitive adhesive sheet having a thickness of 800 ⁇ m, a width of 25 mm, and a length of 100 mm was pulled and the maximum tensile strength was measured using a tensile tester (Strograph V-1C, manufactured by Toyo Seiki Co., Ltd.) under conditions of 23° C., 50% RH, a gripping distance of 30 mm, and a test speed of 300 mm/min. The maximum tensile strength was also measured under the same conditions, with the temperature changed to 90° C.
- the adherends were prepared as follows: a SUS 304 steel plate with a thickness of 1.5 mm, 50 mm and length of 125 mm and a BA surface (cold rolled and then bright heat treated) washed with acetone, and a polypropylene (PP) plate with a thickness of 2.0 mm, 50 mm and length of 125 mm washed with isopropyl alcohol.
- the prepared adhesive sheet was cut to 10 mm x 130 mm, one side of the release film on both sides of the adhesive sheet was peeled off, and a polyester film 50 ⁇ m thick, 15 mm wide, and 300 mm long was attached to it.
- the release film on the other side was peeled off, and the sheet was lightly attached to the adherend, and then a 5 kg roller was used to reciprocate and press the sheet against the test piece at a speed of about 300 mm per minute.
- the sheet was left at room temperature for 24 hours, and then the end of the pressure-sensitive adhesive sheet was folded back at 180 degrees and continuously peeled off at a speed of 50 ⁇ 5 mm per minute in an atmosphere of 23°C and 50% RH, and the average test force (unit: N/10 mm) was read.
- the results were displayed as SUS (23°C) and PP (23°C).
- test pieces that had been laminated and pressed together were left at room temperature for 24 hours, and then the ends of the pressure-sensitive adhesive sheet were folded back at 180 degrees and left in a hot air circulating thermostatic chamber at 90 ⁇ 3°C for 1 hour, after which the sheets were continuously peeled off at a speed of 50 ⁇ 5 mm per minute in an atmosphere of 90°C, and the average test force was read.
- the results were displayed as SUS (90°C) and PP (90°C).
- the rate of change in peel strength was calculated by dividing the difference in peel strength between 23° C. and 90° C. by the peel strength at 23° C., and the results are shown in Tables 3-1 to 3-4.
- the adherend was a polished SUS plate that had been polished back and forth 30 times with #280 abrasive paper and then washed with acetone.
- the release liner was peeled off from one side of an adhesive sheet cut to a size of 25 mm x 25 mm and attached to the end of the polished SUS plate.
- the sheet was then pressed back and forth from above the test piece using a 5 kg roller at a speed of approximately 300 mm per minute, after which the release liner on the opposite side was peeled off and aluminum foil of a thickness of 130 ⁇ 20 ⁇ m was similarly attached.
- the sample was left for 24 hours, and then a weight of 1 ⁇ 0.01 kg was hung on the aluminum foil side.
- the sample was left for 1 hour in a hot air circulating thermostatic chamber at 90 ⁇ 3° C., and the presence or absence of falling was confirmed (A: no, B: yes).
- the adhesive composition of the present invention is capable of forming an adhesive layer that has excellent flexibility and excellent adhesive strength even at high temperatures, and is capable of maintaining the desired adhesive strength even in the manufacture of articles that have irregularities and are subjected to high-temperature processing.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
Abstract
This adhesive composition comprises 100 parts by mass of (a) syrup obtained by mixing a (meth)acrylic copolymer containing alkyl (meth)acrylate and a carboxyl group-containing (meth)acrylate as constituent components, an alkyl (meth)acrylate monomer, a carboxyl group-containing (meth)acrylate monomer, and a hydroxyl group-containing (meth)acrylate monomer, 0.5-10 parts by mass of (b) a tackifying resin, 0.1-3.0 parts by mass of (c) hollow fine particles, 0.1-5 parts by mass of (d) a photopolymerization initiator, and 0.01-5 parts by mass of (e) a crosslinking agent, wherein: the hollow fine particles (c) are resin-based hollow fine particles having a shell part composed of an organic polymer material; the 25% compressive strength of a crosslinked adhesive layer formed of the adhesive composition is 0.06-0.11 MPa; and the tensile strength of the adhesive layer at 23ºC is 0.35-0.65 MPa. The adhesive composition can form an adhesive layer having excellent flexibility and having excellent adhesive strength even at a high temperature.
Description
本発明は、中空微粒子を含有する粘着剤組成物及び該粘着剤組成物から形成された粘着シート、並びに該粘着シートが用いられた物品に関する。
The present invention relates to an adhesive composition containing hollow microparticles, an adhesive sheet formed from the adhesive composition, and an article in which the adhesive sheet is used.
自動車部品や機械部品等の分野において、樹脂素材を発泡させた発泡体を基材とした粘着テープ（以下、発泡体粘着テープという）が用いられてきた。発泡体粘着テープは応力緩和性に優れることから、段差や凹凸を有する部材への接着性にも優れており、不織布や樹脂フィルムを基材とした両面テープと比較して、より幅広い用途の被着体に用いることができる。
In the fields of automobile parts and machine parts, adhesive tapes that use foamed resin materials as a base material (hereafter referred to as foam adhesive tapes) have been used. Foam adhesive tapes have excellent stress relaxation properties, so they also have excellent adhesion to components with steps or unevenness, and can be used for a wider range of adherends than double-sided tapes that use nonwoven fabric or resin film as a base material.
しかし、発泡体粘着テープは、高温においては発泡体の構成材料である樹脂が軟化することから、内部に存在する気泡が潰れ、上記した応力緩和性が失われる懸念があった。また、発泡体粘着テープは別途粘着剤層を通常積層する必要があり、粘着剤層の粘着力は高温において低下するのが一般的である。すなわち、高温環境下における使用が想定される自動車部品に用いるには限界があった。
However, with foam adhesive tape, the resin that makes up the foam softens at high temperatures, which raises concerns that the air bubbles inside the tape may collapse and the stress relaxation properties described above may be lost. In addition, foam adhesive tape usually requires a separate adhesive layer to be laminated, and the adhesive strength of the adhesive layer generally decreases at high temperatures. In other words, there are limitations to its use in automotive parts that are expected to be used in high-temperature environments.
特許文献１には、中空微小球状体を含有した紫外線硬化型粘着剤組成物から形成され、高温環境下におけるせん断強さ及び接着強度（粘着力）に優れた粘着剤層を有する粘着シートが開示されている。この文献では、中空微小球体（中空微粒子）として、紫外線反応を用いる重合の効率や重みなどの観点から、中空の無機系微粒子球状体を用いることが好ましく、さらに中空ガラスバルーンを用いることでせん断力、保持力などの他の特性を損なうことなく、高温接着力を向上させることが可能となるとされている。
しかし、このような無機系の中空微粒子を用いると、保持力や高温接着力を向上させることができるとしても、粒子自体が硬質であることから、粘着剤層の柔軟性が損なわれるおそれがあった。また、高温における粘着力が十分でない場合もある。Patent Document 1 discloses an adhesive sheet having an adhesive layer formed from an ultraviolet-curable adhesive composition containing hollow microspheres and having excellent shear strength and adhesive strength (adhesive strength) in a high-temperature environment. This document states that it is preferable to use hollow inorganic microspheres as hollow microspheres (hollow microspheres) from the viewpoint of efficiency and weight of polymerization using ultraviolet reaction, and further that it is possible to improve high-temperature adhesive strength without impairing other properties such as shear strength and holding power by using hollow glass balloons.
However, even if the use of such inorganic hollow fine particles can improve the holding power and high-temperature adhesive strength, the particles themselves are hard, so there is a risk that the flexibility of the adhesive layer will be impaired, and there are also cases where the adhesive strength at high temperatures is insufficient.
しかし、このような無機系の中空微粒子を用いると、保持力や高温接着力を向上させることができるとしても、粒子自体が硬質であることから、粘着剤層の柔軟性が損なわれるおそれがあった。また、高温における粘着力が十分でない場合もある。
However, even if the use of such inorganic hollow fine particles can improve the holding power and high-temperature adhesive strength, the particles themselves are hard, so there is a risk that the flexibility of the adhesive layer will be impaired, and there are also cases where the adhesive strength at high temperatures is insufficient.
特許文献２には、アクリル系ポリマーと中空微粒子とを含有し、気泡を含有しない粘着剤層を備えた粘着シートが開示されている。この粘着シートは、中空微粒子の中でも、紫外線反応を用いる重合の効率や重み等の観点から、中空の無機系微粒子をより好ましく用いることができるとされている。
特許文献２の粘着シートは接着性とリワーク性とを兼ね合わせたものとされているが、高温下における粘着力や柔軟性については特に考慮されていない。本発明者らの知見によると、特許文献２の実施例及び参考例等に開示されているガラスバルーンの含有量（９～１２部）ではリワーク性の向上には効果があるものの、粘着シートの柔軟性が劣り、高温において粘着力が低下するものと予想される。Patent Document 2 discloses an adhesive sheet including an adhesive layer containing an acrylic polymer and hollow fine particles and containing no air bubbles. It is said that this adhesive sheet can more preferably use hollow inorganic fine particles among hollow fine particles from the viewpoint of the efficiency of polymerization using ultraviolet reaction, weight, etc.
The pressure-sensitive adhesive sheet ofPatent Document 2 is said to have both adhesiveness and reworkability, but no particular consideration is given to adhesive strength or flexibility at high temperatures. According to the findings of the present inventors, the glass balloon content (9 to 12 parts) disclosed in the examples and reference examples of Patent Document 2 is effective in improving reworkability, but the flexibility of the pressure-sensitive adhesive sheet is poor, and it is expected that the adhesive strength will decrease at high temperatures.
特許文献２の粘着シートは接着性とリワーク性とを兼ね合わせたものとされているが、高温下における粘着力や柔軟性については特に考慮されていない。本発明者らの知見によると、特許文献２の実施例及び参考例等に開示されているガラスバルーンの含有量（９～１２部）ではリワーク性の向上には効果があるものの、粘着シートの柔軟性が劣り、高温において粘着力が低下するものと予想される。
The pressure-sensitive adhesive sheet of
本発明の課題は、柔軟性に優れ、かつ高温下においても優れた粘着力を有する粘着剤層を形成可能な粘着剤組成物、該粘着剤組成物から形成された粘着シート、並びに、該粘着シートが用いられた物品を提供することにある。
The object of the present invention is to provide an adhesive composition capable of forming an adhesive layer that has excellent flexibility and excellent adhesive strength even at high temperatures, an adhesive sheet formed from the adhesive composition, and an article using the adhesive sheet.
本発明者らは上記課題を達成すべく鋭意検討した結果、下記の粘着剤組成物から形成された粘着シートが、上記課題を解決するために非常に有効であることを見出し、本発明を完成するに至った。
すなわち、本発明の一態様に係る粘着剤組成物は、
（ａ）アルキル（メタ）アクリレート及びカルボキシル基を有する（メタ）アクリレートを構成成分とする（メタ）アクリル系共重合体、並びに、アルキル（メタ）アクリレートモノマー、カルボキシル基を有する（メタ）アクリレートモノマー及び水酸基を有する（メタ）アクリレートモノマーを混合したシロップ１００質量部と、
（ｂ）粘着付与樹脂を０．５～１０質量部と、
（ｃ）中空微粒子を０．１～３．０質量部と、
（ｄ）光重合開始剤を０．１～５質量部と、
（ｅ）架橋剤を０．０１～５質量部と、
を含有する粘着剤組成物であって、
前記中空微粒子（ｃ）が、有機高分子材料から構成される殻部を有する樹脂系中空微粒子であり、
前記粘着剤組成物から形成された架橋後の粘着剤層の２５％圧縮強度が０．０６～０．１１ＭＰａであり、
前記粘着剤層の２３℃での引張り強さが０．３５～０．６５ＭＰａであることを特徴とする。 As a result of intensive research into achieving the above-mentioned object, the inventors have found that an adhesive sheet formed from the adhesive composition described below is extremely effective in solving the above-mentioned object, and have thus completed the present invention.
That is, the pressure-sensitive adhesive composition according to one embodiment of the present invention comprises:
(a) 100 parts by mass of a syrup obtained by mixing a (meth)acrylic copolymer having an alkyl (meth)acrylate and a (meth)acrylate having a carboxyl group as constituent components, an alkyl (meth)acrylate monomer, a (meth)acrylate monomer having a carboxyl group, and a (meth)acrylate monomer having a hydroxyl group;
(b) 0.5 to 10 parts by mass of a tackifier resin;
(c) 0.1 to 3.0 parts by mass of hollow fine particles;
(d) 0.1 to 5 parts by mass of a photopolymerization initiator;
(e) 0.01 to 5 parts by mass of a crosslinking agent;
A pressure-sensitive adhesive composition comprising:
the hollow fine particles (c) are resin-based hollow fine particles having a shell portion made of an organic polymer material,
the 25% compressive strength of the pressure-sensitive adhesive layer after crosslinking formed from the pressure-sensitive adhesive composition is 0.06 to 0.11 MPa;
The pressure-sensitive adhesive layer has a tensile strength of 0.35 to 0.65 MPa at 23°C.
すなわち、本発明の一態様に係る粘着剤組成物は、
（ａ）アルキル（メタ）アクリレート及びカルボキシル基を有する（メタ）アクリレートを構成成分とする（メタ）アクリル系共重合体、並びに、アルキル（メタ）アクリレートモノマー、カルボキシル基を有する（メタ）アクリレートモノマー及び水酸基を有する（メタ）アクリレートモノマーを混合したシロップ１００質量部と、
（ｂ）粘着付与樹脂を０．５～１０質量部と、
（ｃ）中空微粒子を０．１～３．０質量部と、
（ｄ）光重合開始剤を０．１～５質量部と、
（ｅ）架橋剤を０．０１～５質量部と、
を含有する粘着剤組成物であって、
前記中空微粒子（ｃ）が、有機高分子材料から構成される殻部を有する樹脂系中空微粒子であり、
前記粘着剤組成物から形成された架橋後の粘着剤層の２５％圧縮強度が０．０６～０．１１ＭＰａであり、
前記粘着剤層の２３℃での引張り強さが０．３５～０．６５ＭＰａであることを特徴とする。 As a result of intensive research into achieving the above-mentioned object, the inventors have found that an adhesive sheet formed from the adhesive composition described below is extremely effective in solving the above-mentioned object, and have thus completed the present invention.
That is, the pressure-sensitive adhesive composition according to one embodiment of the present invention comprises:
(a) 100 parts by mass of a syrup obtained by mixing a (meth)acrylic copolymer having an alkyl (meth)acrylate and a (meth)acrylate having a carboxyl group as constituent components, an alkyl (meth)acrylate monomer, a (meth)acrylate monomer having a carboxyl group, and a (meth)acrylate monomer having a hydroxyl group;
(b) 0.5 to 10 parts by mass of a tackifier resin;
(c) 0.1 to 3.0 parts by mass of hollow fine particles;
(d) 0.1 to 5 parts by mass of a photopolymerization initiator;
(e) 0.01 to 5 parts by mass of a crosslinking agent;
A pressure-sensitive adhesive composition comprising:
the hollow fine particles (c) are resin-based hollow fine particles having a shell portion made of an organic polymer material,
the 25% compressive strength of the pressure-sensitive adhesive layer after crosslinking formed from the pressure-sensitive adhesive composition is 0.06 to 0.11 MPa;
The pressure-sensitive adhesive layer has a tensile strength of 0.35 to 0.65 MPa at 23°C.
また、本発明の一態様によれば、上記粘着剤組成物からなる粘着剤層を備える粘着シート、該粘着シートが用いられた物品を提供するものである。
In addition, according to one aspect of the present invention, there is provided an adhesive sheet having an adhesive layer made of the above-mentioned adhesive composition, and an article using the adhesive sheet.
本発明の粘着剤組成物に用いる（メタ）アクリル系のシロップ（ａ）は、上記した２種類の官能基を有する（メタ）アクリレートを必須の構成成分とする共重合体を含むため、架橋剤（ｅ）の種類によらずに架橋構造を形成しやすい。このため、本発明の粘着剤組成物から形成された粘着剤層は、高温においても高い粘着力を維持することができる。該粘着剤層はこれら官能基により高極性となるため、特に金属等に対する優れた粘着力を得ることができる。
また、粘着付与樹脂（ｂ）を必須成分とするため、凹凸や段差を有する部材等への初期粘着力を高めることができる。
さらには、無機系ではなく有機高分子材料を殻材とした樹脂系中空微粒子を比較的少量用いるため、形成後の粘着剤層の圧縮強度及び引張り強さが所定の範囲となり、段差追従性や曲面貼り付け性及び高温下における粘着力の両立を図ることができる。 The (meth)acrylic syrup (a) used in the adhesive composition of the present invention contains a copolymer having the above-mentioned two types of functional group-containing (meth)acrylate as an essential component, and therefore is easy to form a crosslinked structure regardless of the type of crosslinking agent (e). Therefore, the adhesive layer formed from the adhesive composition of the present invention can maintain high adhesive strength even at high temperatures. The adhesive layer is highly polarized by these functional groups, and therefore can obtain excellent adhesive strength, particularly to metals.
In addition, since the tackifier resin (b) is an essential component, the initial adhesive strength to members having irregularities or steps can be increased.
Furthermore, since a relatively small amount of resin-based hollow microparticles whose shell material is an organic polymer material rather than an inorganic one are used, the compressive strength and tensile strength of the adhesive layer after formation are within a specified range, making it possible to achieve a balance between the ability to conform to uneven surfaces, the ability to attach to curved surfaces, and adhesive strength at high temperatures.
また、粘着付与樹脂（ｂ）を必須成分とするため、凹凸や段差を有する部材等への初期粘着力を高めることができる。
さらには、無機系ではなく有機高分子材料を殻材とした樹脂系中空微粒子を比較的少量用いるため、形成後の粘着剤層の圧縮強度及び引張り強さが所定の範囲となり、段差追従性や曲面貼り付け性及び高温下における粘着力の両立を図ることができる。 The (meth)acrylic syrup (a) used in the adhesive composition of the present invention contains a copolymer having the above-mentioned two types of functional group-containing (meth)acrylate as an essential component, and therefore is easy to form a crosslinked structure regardless of the type of crosslinking agent (e). Therefore, the adhesive layer formed from the adhesive composition of the present invention can maintain high adhesive strength even at high temperatures. The adhesive layer is highly polarized by these functional groups, and therefore can obtain excellent adhesive strength, particularly to metals.
In addition, since the tackifier resin (b) is an essential component, the initial adhesive strength to members having irregularities or steps can be increased.
Furthermore, since a relatively small amount of resin-based hollow microparticles whose shell material is an organic polymer material rather than an inorganic one are used, the compressive strength and tensile strength of the adhesive layer after formation are within a specified range, making it possible to achieve a balance between the ability to conform to uneven surfaces, the ability to attach to curved surfaces, and adhesive strength at high temperatures.
以下、本発明の実施形態について説明するが、本発明はこれらの実施形態のみに限定されるものではない。
本発明に係る粘着剤組成物は
（ａ）アルキル（メタ）アクリレート及びカルボキシル基を有する（メタ）アクリレートを構成成分とする（メタ）アクリル系共重合体、並びに、アルキル（メタ）アクリレートモノマー、カルボキシル基を有する（メタ）アクリレートモノマー及び水酸基を有する（メタ）アクリレートモノマーを混合したシロップ１００質量部と、
（ｂ）粘着付与樹脂を０．５～１０質量部と、
（ｃ）中空微粒子を０．１～３．０質量部と、
（ｄ）光重合開始剤を０．１～５質量部と、
（ｅ）架橋剤を０．０１～５質量部と、
を含有する粘着剤組成物であって、
前記中空微粒子（ｃ）が、有機高分子材料から構成される殻部を有する樹脂系中空微粒子であり、
前記粘着剤組成物から形成された架橋後の粘着剤層の２５％圧縮強度が０．０６～０．１１ＭＰａであり、
前記粘着剤層の２３℃での引張り強さが０．３５～０．６５ＭＰａであることを特徴とする。 Hereinafter, embodiments of the present invention will be described, however, the present invention is not limited to these embodiments.
The pressure-sensitive adhesive composition according to the present invention comprises: (a) 100 parts by mass of a syrup obtained by mixing a (meth)acrylic copolymer having as its constituent components an alkyl (meth)acrylate and a (meth)acrylate having a carboxyl group, an alkyl (meth)acrylate monomer, a (meth)acrylate monomer having a carboxyl group, and a (meth)acrylate monomer having a hydroxyl group;
(b) 0.5 to 10 parts by mass of a tackifier resin;
(c) 0.1 to 3.0 parts by mass of hollow fine particles;
(d) 0.1 to 5 parts by mass of a photopolymerization initiator;
(e) 0.01 to 5 parts by mass of a crosslinking agent;
A pressure-sensitive adhesive composition comprising:
the hollow fine particles (c) are resin-based hollow fine particles having a shell portion made of an organic polymer material,
the 25% compressive strength of the pressure-sensitive adhesive layer after crosslinking formed from the pressure-sensitive adhesive composition is 0.06 to 0.11 MPa;
The pressure-sensitive adhesive layer has a tensile strength of 0.35 to 0.65 MPa at 23°C.
本発明に係る粘着剤組成物は
（ａ）アルキル（メタ）アクリレート及びカルボキシル基を有する（メタ）アクリレートを構成成分とする（メタ）アクリル系共重合体、並びに、アルキル（メタ）アクリレートモノマー、カルボキシル基を有する（メタ）アクリレートモノマー及び水酸基を有する（メタ）アクリレートモノマーを混合したシロップ１００質量部と、
（ｂ）粘着付与樹脂を０．５～１０質量部と、
（ｃ）中空微粒子を０．１～３．０質量部と、
（ｄ）光重合開始剤を０．１～５質量部と、
（ｅ）架橋剤を０．０１～５質量部と、
を含有する粘着剤組成物であって、
前記中空微粒子（ｃ）が、有機高分子材料から構成される殻部を有する樹脂系中空微粒子であり、
前記粘着剤組成物から形成された架橋後の粘着剤層の２５％圧縮強度が０．０６～０．１１ＭＰａであり、
前記粘着剤層の２３℃での引張り強さが０．３５～０．６５ＭＰａであることを特徴とする。 Hereinafter, embodiments of the present invention will be described, however, the present invention is not limited to these embodiments.
The pressure-sensitive adhesive composition according to the present invention comprises: (a) 100 parts by mass of a syrup obtained by mixing a (meth)acrylic copolymer having as its constituent components an alkyl (meth)acrylate and a (meth)acrylate having a carboxyl group, an alkyl (meth)acrylate monomer, a (meth)acrylate monomer having a carboxyl group, and a (meth)acrylate monomer having a hydroxyl group;
(b) 0.5 to 10 parts by mass of a tackifier resin;
(c) 0.1 to 3.0 parts by mass of hollow fine particles;
(d) 0.1 to 5 parts by mass of a photopolymerization initiator;
(e) 0.01 to 5 parts by mass of a crosslinking agent;
A pressure-sensitive adhesive composition comprising:
the hollow fine particles (c) are resin-based hollow fine particles having a shell portion made of an organic polymer material,
the 25% compressive strength of the pressure-sensitive adhesive layer after crosslinking formed from the pressure-sensitive adhesive composition is 0.06 to 0.11 MPa;
The pressure-sensitive adhesive layer has a tensile strength of 0.35 to 0.65 MPa at 23°C.
（ａ）シロップ
（ａ）成分のシロップは、アルキル（メタ）アクリレート及びカルボキシル基を有する（メタ）アクリレートに由来するモノマー単位を構成成分とする（メタ）アクリル系共重合体（ａ１）と、アルキル（メタ）アクリレートモノマー（ａ２）、カルボキシル基を有する（メタ）アクリレートモノマー（ａ３）、水酸基を有する（メタ）アクリレートモノマー（ａ４）を混合したものである。 (a) Syrup The syrup of component (a) is a mixture of a (meth)acrylic copolymer (a1) having as its constituent components monomer units derived from an alkyl (meth)acrylate and a (meth)acrylate having a carboxyl group, an alkyl (meth)acrylate monomer (a2), a (meth)acrylate monomer having a carboxyl group (a3), and a (meth)acrylate monomer having a hydroxyl group (a4).
（ａ）成分のシロップは、アルキル（メタ）アクリレート及びカルボキシル基を有する（メタ）アクリレートに由来するモノマー単位を構成成分とする（メタ）アクリル系共重合体（ａ１）と、アルキル（メタ）アクリレートモノマー（ａ２）、カルボキシル基を有する（メタ）アクリレートモノマー（ａ３）、水酸基を有する（メタ）アクリレートモノマー（ａ４）を混合したものである。 (a) Syrup The syrup of component (a) is a mixture of a (meth)acrylic copolymer (a1) having as its constituent components monomer units derived from an alkyl (meth)acrylate and a (meth)acrylate having a carboxyl group, an alkyl (meth)acrylate monomer (a2), a (meth)acrylate monomer having a carboxyl group (a3), and a (meth)acrylate monomer having a hydroxyl group (a4).
（メタ）アクリル系共重合体（ａ１）
共重合体（ａ１）はアルキル（メタ）アクリレートとカルボキシル基を有する（メタ）アクリレートに由来するモノマー単位を構成成分として含む。
アルキル（メタ）アクリレートの具体例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ターシャリーブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸イソヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸イソドデシル、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレートなどが挙げられる。中でも比較的アルキル鎖の長いモノマーに由来する単位を導入することが好ましい。これらは一種を用いてもよく、二種以上を併用してもよい。
共重合体（ａ１）を構成する全モノマー単位１００質量％に対する、アルキル（メタ）アクリレート由来のモノマー単位の割合は、８０～９９質量％であることが好ましく、８５～９５質量％がより好ましい。 (Meth)acrylic copolymer (a1)
The copolymer (a1) contains, as constituent components, monomer units derived from an alkyl (meth)acrylate and a (meth)acrylate having a carboxyl group.
Specific examples of alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, hexyl (meth)acrylate, isohexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isododecyl (meth)acrylate, isobornyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these, it is preferable to introduce a unit derived from a monomer having a relatively long alkyl chain. These may be used alone or in combination of two or more.
The proportion of the monomer units derived from alkyl (meth)acrylate relative to 100% by mass of all monomer units constituting the copolymer (a1) is preferably from 80 to 99% by mass, and more preferably from 85 to 95% by mass.
共重合体（ａ１）はアルキル（メタ）アクリレートとカルボキシル基を有する（メタ）アクリレートに由来するモノマー単位を構成成分として含む。
アルキル（メタ）アクリレートの具体例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ターシャリーブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸イソヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸イソドデシル、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレートなどが挙げられる。中でも比較的アルキル鎖の長いモノマーに由来する単位を導入することが好ましい。これらは一種を用いてもよく、二種以上を併用してもよい。
共重合体（ａ１）を構成する全モノマー単位１００質量％に対する、アルキル（メタ）アクリレート由来のモノマー単位の割合は、８０～９９質量％であることが好ましく、８５～９５質量％がより好ましい。 (Meth)acrylic copolymer (a1)
The copolymer (a1) contains, as constituent components, monomer units derived from an alkyl (meth)acrylate and a (meth)acrylate having a carboxyl group.
Specific examples of alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, hexyl (meth)acrylate, isohexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isododecyl (meth)acrylate, isobornyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these, it is preferable to introduce a unit derived from a monomer having a relatively long alkyl chain. These may be used alone or in combination of two or more.
The proportion of the monomer units derived from alkyl (meth)acrylate relative to 100% by mass of all monomer units constituting the copolymer (a1) is preferably from 80 to 99% by mass, and more preferably from 85 to 95% by mass.
カルボキシル基を有する（メタ）アクリレートとしては、（メタ）アクリル酸、（メタ）アクリル酸β－カルボキシエチル、イタコン酸、クロトン酸、マレイン酸、フマル酸などが挙げられる。これらの中でも、アクリル樹脂組成物の強度がより高い観点から（メタ）アクリル酸が好ましい。これらは一種を用いてもよく、二種以上を併用してもよい。
共重合体（ａ１）を構成する全モノマー単位１００質量％に対する、カルボキシル基を有する（メタ）アクリレート由来のモノマー単位の割合は、１～２０質量％が好ましく、５～１５質量％であることがより好ましい。 Examples of (meth)acrylates having a carboxyl group include (meth)acrylic acid, β-carboxyethyl (meth)acrylate, itaconic acid, crotonic acid, maleic acid, and fumaric acid. Among these, (meth)acrylic acid is preferred from the viewpoint of higher strength of the acrylic resin composition. These may be used alone or in combination of two or more.
The proportion of monomer units derived from a (meth)acrylate having a carboxyl group relative to 100% by mass of all monomer units constituting the copolymer (a1) is preferably from 1 to 20% by mass, and more preferably from 5 to 15% by mass.
共重合体（ａ１）を構成する全モノマー単位１００質量％に対する、カルボキシル基を有する（メタ）アクリレート由来のモノマー単位の割合は、１～２０質量％が好ましく、５～１５質量％であることがより好ましい。 Examples of (meth)acrylates having a carboxyl group include (meth)acrylic acid, β-carboxyethyl (meth)acrylate, itaconic acid, crotonic acid, maleic acid, and fumaric acid. Among these, (meth)acrylic acid is preferred from the viewpoint of higher strength of the acrylic resin composition. These may be used alone or in combination of two or more.
The proportion of monomer units derived from a (meth)acrylate having a carboxyl group relative to 100% by mass of all monomer units constituting the copolymer (a1) is preferably from 1 to 20% by mass, and more preferably from 5 to 15% by mass.
共重合体（ａ１）は、本発明の効果を損なわない範囲で、上記以外の（メタ）アクリル系モノマー単位を含んでいてもよく、例えば、後述する（メタ）アクリルアミド等の窒素含有アクリル系モノマー単位、水酸基を有する（メタ）アクリレートモノマー（ａ４）に由来する単位などが挙げられる。
The copolymer (a1) may contain (meth)acrylic monomer units other than those mentioned above, provided that the effects of the present invention are not impaired. Examples of such units include nitrogen-containing acrylic monomer units such as (meth)acrylamide, which will be described later, and units derived from a (meth)acrylate monomer (a4) having a hydroxyl group.
共重合体（ａ１）は、上記のモノマー成分を共重合して得られるもので、その重合方法は特に限定されず、例えば溶液重合、塊状重合、懸濁重合、乳化重合などの各種の重合方法において、光重合又は熱重合などの手段を用いて行うことができる。さらにはガンマ線のような放射線による重合や、電子線重合も用いることができる。光重合は、例えば光重合開始剤の存在下において、モノマー組成物にＵＶ線を照射して行うことができる。熱重合は、例えば熱重合開始剤の存在下において、モノマー組成物を５０～２００℃に加熱して行うことができる。重合に際してチオール化合物などの連鎖移動剤を併用して、分子量を調整することも好ましい。また、未反応モノマーが残存する場合があるが、そのままシロップ（ａ）の構成成分として使用することができるため、特に共重合体を単離する必要はない。共重合体（ａ１）が５～５０質量％に達したところで重合を停止し部分共重合体とすることで、粘性液体として取り扱うことができる。
本明細書において、共重合体（ａ１）は、重量平均分子量（Ｍｗ）が１０万以上のものを意味する。共重合体（ａ１）のＭｗとしては、１０万～２００万であることが好ましく、５０万～１５０万であることがより好ましい。 The copolymer (a1) is obtained by copolymerizing the above-mentioned monomer components, and the polymerization method is not particularly limited. For example, various polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization can be performed using means such as photopolymerization or thermal polymerization. Furthermore, polymerization by radiation such as gamma rays and electron beam polymerization can also be used. Photopolymerization can be performed, for example, by irradiating the monomer composition with UV rays in the presence of a photopolymerization initiator. Thermal polymerization can be performed, for example, by heating the monomer composition to 50 to 200°C in the presence of a thermal polymerization initiator. It is also preferable to adjust the molecular weight by using a chain transfer agent such as a thiol compound in combination during polymerization. In addition, although unreacted monomers may remain, they can be used as a constituent component of the syrup (a) as is, so there is no need to isolate the copolymer. When the copolymer (a1) reaches 5 to 50% by mass, the polymerization is stopped to make a partial copolymer, which can be handled as a viscous liquid.
In this specification, the copolymer (a1) means one having a weight average molecular weight (Mw) of 100,000 or more. The Mw of the copolymer (a1) is preferably from 100,000 to 2,000,000, and more preferably from 500,000 to 1,500,000.
本明細書において、共重合体（ａ１）は、重量平均分子量（Ｍｗ）が１０万以上のものを意味する。共重合体（ａ１）のＭｗとしては、１０万～２００万であることが好ましく、５０万～１５０万であることがより好ましい。 The copolymer (a1) is obtained by copolymerizing the above-mentioned monomer components, and the polymerization method is not particularly limited. For example, various polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization can be performed using means such as photopolymerization or thermal polymerization. Furthermore, polymerization by radiation such as gamma rays and electron beam polymerization can also be used. Photopolymerization can be performed, for example, by irradiating the monomer composition with UV rays in the presence of a photopolymerization initiator. Thermal polymerization can be performed, for example, by heating the monomer composition to 50 to 200°C in the presence of a thermal polymerization initiator. It is also preferable to adjust the molecular weight by using a chain transfer agent such as a thiol compound in combination during polymerization. In addition, although unreacted monomers may remain, they can be used as a constituent component of the syrup (a) as is, so there is no need to isolate the copolymer. When the copolymer (a1) reaches 5 to 50% by mass, the polymerization is stopped to make a partial copolymer, which can be handled as a viscous liquid.
In this specification, the copolymer (a1) means one having a weight average molecular weight (Mw) of 100,000 or more. The Mw of the copolymer (a1) is preferably from 100,000 to 2,000,000, and more preferably from 500,000 to 1,500,000.
アルキル（メタ）アクリレートモノマー（ａ２）としては、共重合体（ａ１）を構成するモノマー成分として挙げたアルキル（メタ）アクリレートが使用できる。同様に、カルボキシル基を有する（メタ）アクリレートモノマー（ａ３）は、共重合体（ａ１）を構成するモノマー成分として挙げたカルボキシル基を有する（メタ）アクリレートが使用できる。これらはそれぞれ一種を用いてもよく、二種以上を併用してもよい。
As the alkyl (meth)acrylate monomer (a2), the alkyl (meth)acrylates listed as monomer components constituting the copolymer (a1) can be used. Similarly, as the (meth)acrylate monomer (a3) having a carboxyl group, the (meth)acrylates listed as monomer components constituting the copolymer (a1) can be used. These may be used alone or in combination of two or more.
水酸基を有する（メタ）アクリレートモノマー（ａ４）としては、例えば（メタ）アクリル酸－２－ヒドロキシエチル、（メタ）アクリル酸－２－ヒドロキシプロピル、（メタ）アクリル酸－２－ヒドロキシブチル、（メタ）アクリル酸－４－ヒドロキシブチル、（メタ）アクリル酸－２－ヒドロキシヘキシル、（メタ）アクリル酸とポリエチレングリコール又はポリプロピレングリコールとのモノエステルなどが挙げられる。これらは一種を用いてもよく、二種以上を併用してもよい。
Examples of the (meth)acrylate monomer (a4) having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, and monoesters of (meth)acrylic acid with polyethylene glycol or polypropylene glycol. These may be used alone or in combination of two or more.
さらに、その他のモノマーとして、窒素含有アクリル系モノマーを含むこともできる。窒素含有アクリル系モノマーの具体例としては、（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミドなどのＮ－アルキル置換（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミドなどのＮ，Ｎ－ジアルキル置換（メタ）アクリルアミド、アクリロイルモルフォリン、ビニルピリジン、Ｎ－ビニルピロリドン、（メタ）アクリル酸アミノエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジメチルアミノプロピルなどが挙げられる。これらの中でも、汎用性や工業製品化の観点から、（メタ）アクリルアミド、Ｎ－アルキル置換（メタ）アクリルアミド、Ｎ，Ｎ－ジアルキル置換（メタ）アクリルアミド、アクリロイルモルフォリンが好ましい。これらは一種を用いてもよく、二種以上を併用してもよい。
Furthermore, nitrogen-containing acrylic monomers may be included as other monomers. Specific examples of nitrogen-containing acrylic monomers include (meth)acrylamide, N-alkyl-substituted (meth)acrylamides such as N-isopropyl (meth)acrylamide, N,N-dialkyl-substituted (meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N,N-diethyl (meth)acrylamide, acryloylmorpholine, vinylpyridine, N-vinylpyrrolidone, aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate. Among these, (meth)acrylamide, N-alkyl-substituted (meth)acrylamide, N,N-dialkyl-substituted (meth)acrylamide, and acryloylmorpholine are preferred from the viewpoints of versatility and industrial commercialization. These may be used alone or in combination of two or more.
シロップ中の成分量としては、全体を１００質量％として、共重合体（ａ１）を５～５０質量％、その他のモノマー成分（ａ２）～（ａ４）を合計で５０～９５質量％含むことが好ましく、共重合体（ａ１）を８～４０質量％、その他のモノマー成分（ａ２）～（ａ４）を合計で６０～９２質量％含むことがより好ましい。その他のモノマー成分（ａ２）～（ａ４）の割合としては、（ａ２）＞（ａ３）＞（ａ４）となるように配合することが好ましい。
The amounts of the components in the syrup are preferably 5-50% by mass of copolymer (a1) and a total of 50-95% by mass of other monomer components (a2)-(a4), and more preferably 8-40% by mass of copolymer (a1) and a total of 60-92% by mass of other monomer components (a2)-(a4), taking the total as 100% by mass. The ratio of the other monomer components (a2)-(a4) is preferably (a2)>(a3)>(a4).
（ｂ）粘着付与樹脂
粘着付与樹脂としては、水添石油樹脂、ロジン系樹脂や、テルペン系樹脂、炭化水素系樹脂、フェノール系樹脂等の各種粘着付与樹脂を用いることができ、これらの一種を単独でもしくは二種以上を組み合わせて使用することができる。 (b) Tackifying Resin As the tackifying resin, various tackifying resins such as hydrogenated petroleum resins, rosin-based resins, terpene-based resins, hydrocarbon-based resins, and phenol-based resins can be used. These can be used alone or in combination of two or more.
粘着付与樹脂としては、水添石油樹脂、ロジン系樹脂や、テルペン系樹脂、炭化水素系樹脂、フェノール系樹脂等の各種粘着付与樹脂を用いることができ、これらの一種を単独でもしくは二種以上を組み合わせて使用することができる。 (b) Tackifying Resin As the tackifying resin, various tackifying resins such as hydrogenated petroleum resins, rosin-based resins, terpene-based resins, hydrocarbon-based resins, and phenol-based resins can be used. These can be used alone or in combination of two or more.
粘着付与樹脂（ｂ）はシロップ（ａ）１００質量部に対して、０．５～１０質量部配合され、好ましくはシロップ（ａ）１００質量部に対して１～１０質量部、より好ましくはシロップ（ａ）１００質量部に対して２～８質量部で配合される。
The tackifier resin (b) is blended in an amount of 0.5 to 10 parts by mass per 100 parts by mass of syrup (a), preferably 1 to 10 parts by mass per 100 parts by mass of syrup (a), and more preferably 2 to 8 parts by mass per 100 parts by mass of syrup (a).
（ｃ）中空微粒子
本発明に係る粘着剤組成物を構成する中空微粒子としては、有機高分子材料から構成される殻部を有する樹脂系中空微粒子である。殻部を構成する有機高分子材料としては、例えば、アクリルニトリルを構成単位として含む樹脂であることが好ましい。中空微粒子の平均粒子径としては、１～１５０μｍが好ましく、１０～１３０μｍがより好ましい。ここでいう平均粒子径は体積基準のメディアン径（Ｄ５０）である。また市販品の場合は、カタログ値を元に選択してもよい。
殻部の膜厚は０．１～２０μｍ、好ましくは２～１５μｍであることが好ましい。中空微粒子の中空部には炭化水素が内包され、熱膨張性バルーンとして機能するものが好ましく使用される。熱膨張性バルーンは加熱するとまず殻部を構成する有機高分子材料（熱可塑性樹脂）の軟化が始まり、内包される炭化水素がガス化を始め内圧が上がり、バルーンが膨張する。ただし、ある温度以上になるが殻部からガスが透過逸散し、収縮に転じる。 (c) Hollow fine particles The hollow fine particles constituting the pressure-sensitive adhesive composition according to the present invention are resin-based hollow fine particles having a shell made of an organic polymer material. The organic polymer material constituting the shell is preferably, for example, a resin containing acrylonitrile as a constituent unit. The average particle diameter of the hollow fine particles is preferably 1 to 150 μm, more preferably 10 to 130 μm. The average particle diameter referred to here is the median diameter (D50) based on volume. In addition, in the case of commercially available products, the selection may be made based on the catalog value.
The thickness of the shell is preferably 0.1 to 20 μm, and more preferably 2 to 15 μm. The hollow microparticles preferably contain hydrocarbons in their hollows and function as thermally expandable balloons. When a thermally expandable balloon is heated, the organic polymer material (thermoplastic resin) that constitutes the shell first begins to soften, the encapsulated hydrocarbons begin to gasify, the internal pressure rises, and the balloon expands. However, once the temperature exceeds a certain level, the gas permeates and escapes from the shell, and the balloon begins to shrink.
本発明に係る粘着剤組成物を構成する中空微粒子としては、有機高分子材料から構成される殻部を有する樹脂系中空微粒子である。殻部を構成する有機高分子材料としては、例えば、アクリルニトリルを構成単位として含む樹脂であることが好ましい。中空微粒子の平均粒子径としては、１～１５０μｍが好ましく、１０～１３０μｍがより好ましい。ここでいう平均粒子径は体積基準のメディアン径（Ｄ５０）である。また市販品の場合は、カタログ値を元に選択してもよい。
殻部の膜厚は０．１～２０μｍ、好ましくは２～１５μｍであることが好ましい。中空微粒子の中空部には炭化水素が内包され、熱膨張性バルーンとして機能するものが好ましく使用される。熱膨張性バルーンは加熱するとまず殻部を構成する有機高分子材料（熱可塑性樹脂）の軟化が始まり、内包される炭化水素がガス化を始め内圧が上がり、バルーンが膨張する。ただし、ある温度以上になるが殻部からガスが透過逸散し、収縮に転じる。 (c) Hollow fine particles The hollow fine particles constituting the pressure-sensitive adhesive composition according to the present invention are resin-based hollow fine particles having a shell made of an organic polymer material. The organic polymer material constituting the shell is preferably, for example, a resin containing acrylonitrile as a constituent unit. The average particle diameter of the hollow fine particles is preferably 1 to 150 μm, more preferably 10 to 130 μm. The average particle diameter referred to here is the median diameter (D50) based on volume. In addition, in the case of commercially available products, the selection may be made based on the catalog value.
The thickness of the shell is preferably 0.1 to 20 μm, and more preferably 2 to 15 μm. The hollow microparticles preferably contain hydrocarbons in their hollows and function as thermally expandable balloons. When a thermally expandable balloon is heated, the organic polymer material (thermoplastic resin) that constitutes the shell first begins to soften, the encapsulated hydrocarbons begin to gasify, the internal pressure rises, and the balloon expands. However, once the temperature exceeds a certain level, the gas permeates and escapes from the shell, and the balloon begins to shrink.
アクリル樹脂組成物中の中空微粒子の含有量は、前記シロップ（ａ）１００質量部に対して０．１～３．０質量部であり、０．５～２質量部であることが好ましい。
また、粘着剤組成物中での散性を向上させるために、中空微粒子に対してカップリング処理、ステアリン酸処理等の表面処理を適宜行ってもよい。 The content of the hollow fine particles in the acrylic resin composition is 0.1 to 3.0 parts by mass, and preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the syrup (a).
In order to improve dispersibility in the pressure-sensitive adhesive composition, the hollow fine particles may be appropriately subjected to a surface treatment such as a coupling treatment or a stearic acid treatment.
また、粘着剤組成物中での散性を向上させるために、中空微粒子に対してカップリング処理、ステアリン酸処理等の表面処理を適宜行ってもよい。 The content of the hollow fine particles in the acrylic resin composition is 0.1 to 3.0 parts by mass, and preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the syrup (a).
In order to improve dispersibility in the pressure-sensitive adhesive composition, the hollow fine particles may be appropriately subjected to a surface treatment such as a coupling treatment or a stearic acid treatment.
（ｄ）光重合開始剤
光重合開始剤としては、光ラジカル重合開始剤が使用でき、アルキルフェノン系、アシルフォスシンオキサイド系、オキシフェニル酢酸エステル系等の公知の重合開始剤等が挙げられる。アルキルフェノン系は、さらに、ベンジルケタール、α－ヒドロキシアルキルフェノン、α－ヒドロキシアセトフェノン、α－アミノアルキルフェノン等に細分化される。
光重合開始剤（ｄ）はシロップ（ａ）１００質量部に対して、０．１～５質量部配合され、好ましくはシロップ（ａ）１００質量部に対して０．２～２質量部、より好ましくは、０．３～１質量部配合される。 (d) Photopolymerization initiator As the photopolymerization initiator, a photoradical polymerization initiator can be used, and examples thereof include known polymerization initiators such as alkylphenones, acylphosine oxides, oxyphenyl acetates, etc. The alkylphenones are further classified into benzyl ketals, α-hydroxyalkylphenones, α-hydroxyacetophenones, α-aminoalkylphenones, etc.
The photopolymerization initiator (d) is blended in an amount of 0.1 to 5 parts by mass, preferably 0.2 to 2 parts by mass, and more preferably 0.3 to 1 part by mass, per 100 parts by mass of the syrup (a).
光重合開始剤としては、光ラジカル重合開始剤が使用でき、アルキルフェノン系、アシルフォスシンオキサイド系、オキシフェニル酢酸エステル系等の公知の重合開始剤等が挙げられる。アルキルフェノン系は、さらに、ベンジルケタール、α－ヒドロキシアルキルフェノン、α－ヒドロキシアセトフェノン、α－アミノアルキルフェノン等に細分化される。
光重合開始剤（ｄ）はシロップ（ａ）１００質量部に対して、０．１～５質量部配合され、好ましくはシロップ（ａ）１００質量部に対して０．２～２質量部、より好ましくは、０．３～１質量部配合される。 (d) Photopolymerization initiator As the photopolymerization initiator, a photoradical polymerization initiator can be used, and examples thereof include known polymerization initiators such as alkylphenones, acylphosine oxides, oxyphenyl acetates, etc. The alkylphenones are further classified into benzyl ketals, α-hydroxyalkylphenones, α-hydroxyacetophenones, α-aminoalkylphenones, etc.
The photopolymerization initiator (d) is blended in an amount of 0.1 to 5 parts by mass, preferably 0.2 to 2 parts by mass, and more preferably 0.3 to 1 part by mass, per 100 parts by mass of the syrup (a).
（ｅ）架橋剤
本発明に係る粘着剤組成物は、架橋剤を含むことが、架橋構造を形成できる観点から好ましい。架橋剤としては、アクリル系のシロップ（ａ）との反応性の観点から、多官能性（メタ）アクリルモノマー、多官能性（メタ）アクリルオリゴマー、２官能以上のグリシジル基含有化合物、及び２官能以上のイソシアネート基含有化合物からなる群から選択される少なくとも一種の架橋剤が好ましい。 (e) Crosslinking Agent The pressure-sensitive adhesive composition according to the present invention preferably contains a crosslinking agent from the viewpoint of forming a crosslinked structure. As the crosslinking agent, from the viewpoint of reactivity with the acrylic syrup (a), at least one crosslinking agent selected from the group consisting of polyfunctional (meth)acrylic monomers, polyfunctional (meth)acrylic oligomers, bifunctional or higher glycidyl group-containing compounds, and bifunctional or higher isocyanate group-containing compounds is preferable.
本発明に係る粘着剤組成物は、架橋剤を含むことが、架橋構造を形成できる観点から好ましい。架橋剤としては、アクリル系のシロップ（ａ）との反応性の観点から、多官能性（メタ）アクリルモノマー、多官能性（メタ）アクリルオリゴマー、２官能以上のグリシジル基含有化合物、及び２官能以上のイソシアネート基含有化合物からなる群から選択される少なくとも一種の架橋剤が好ましい。 (e) Crosslinking Agent The pressure-sensitive adhesive composition according to the present invention preferably contains a crosslinking agent from the viewpoint of forming a crosslinked structure. As the crosslinking agent, from the viewpoint of reactivity with the acrylic syrup (a), at least one crosslinking agent selected from the group consisting of polyfunctional (meth)acrylic monomers, polyfunctional (meth)acrylic oligomers, bifunctional or higher glycidyl group-containing compounds, and bifunctional or higher isocyanate group-containing compounds is preferable.
多官能性（メタ）アクリルモノマーの具体例としては、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、１，２－エチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１,９－ノナンジオールジ（メタ）アクリレート、１，１２－ドデカンジオールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート等が挙げられる。
Specific examples of polyfunctional (meth)acrylic monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.
多官能性（メタ）アクリルオリゴマーの具体例としては、イソシアネート基やグリシジル基を複数有する化合物に（メタ）アクリル酸や水酸基含有（メタ）アクリレートを反応させてオリゴマー化したウレタン（メタ）アクリレートやエポキシ（メタ）アクリレート等が挙げられる。
Specific examples of polyfunctional (meth)acrylic oligomers include urethane (meth)acrylates and epoxy (meth)acrylates that are oligomerized by reacting a compound having multiple isocyanate groups or glycidyl groups with (meth)acrylic acid or a hydroxyl group-containing (meth)acrylate.
２官能以上のグリシジル基含有化合物としては、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジルアミノフェニルメタン、トリグリシジルイソシアヌレート、ｍ－Ｎ，Ｎ－ジグリシジルアミノフェニルグリシジルエーテル、Ｎ，Ｎ－ジグリシジルトルイジン、Ｎ，Ｎ－ジグリシジルアニリン、ペンタエリスリトールポリグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテルなどが挙げられる。
Examples of difunctional or higher glycidyl group-containing compounds include 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-m-xylylenediamine, N,N,N',N'-tetraglycidylaminophenylmethane, triglycidyl isocyanurate, m-N,N-diglycidylaminophenyl glycidyl ether, N,N-diglycidyl toluidine, N,N-diglycidyl aniline, pentaerythritol polyglycidyl ether, and 1,6-hexanediol diglycidyl ether.
２官能以上のイソシアネート基含有化合物としては、トリレンジイソシアネート（ＴＤＩ）、クロルフェニレンジイソシアネート、ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、水添されたジフェニルメタンジイソシアネートなどのイソシアネートモノマー及びこれらイソシアネートモノマーをトリメチロールプロパンなどに付加したイソシアネート化合物やイソシアヌレート化物、ビュレット型化合物、さらにはポリエーテルポリオールやポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオールなどに付加させたウレタンプレポリマー型のイソシアネート等が挙げられる。これらの架橋剤は一種を単独で、又は二種以上を組み合わせて使用できる。
Examples of bifunctional or higher isocyanate group-containing compounds include isocyanate monomers such as tolylene diisocyanate (TDI), chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate, as well as isocyanate compounds, isocyanurates, and biuret-type compounds in which these isocyanate monomers are added to trimethylolpropane, and further urethane prepolymer-type isocyanates in which these are added to polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, and polyisoprene polyols. These crosslinking agents can be used alone or in combination of two or more.
アクリル樹脂組成物中の架橋剤の量は、前記ポリマー（重合前の全モノマー）１００質量部に対して０．０１～１０質量部であることが好ましく、０．０３～１質量部であることがより好ましく、０．０５～０．５質量部であることがさらに好ましい。
The amount of crosslinking agent in the acrylic resin composition is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 1 part by mass, and even more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of the polymer (total monomers before polymerization).
本発明に係る粘着剤組成物から形成された架橋後の粘着剤層の２５％圧縮強度が０．０６～０．１１ＭＰａであり、前記粘着剤層の２３℃の引張り強さが０．３５～０．６５ＭＰａであることを特徴とする。
２５％圧縮強度は、後述する実施例に記載された方法で測定された値であり、圧縮強度が０．０６ＭＰａ未満ではシートとしての形状維持が困難となり、０．１１ＭＰａを越えると段差や曲面に対する追従性が低下する。圧縮強度は０．０６～０．１０ＭＰａであることがより好ましい。
また、粘着剤層の２３℃の引張り強さは、後述する実施例に記載された方法で測定された値であり、引張り強さが０．３５ＭＰａ未満では、粘着剤層の凝集力が弱いため保持力が低下し、０．６５ＭＰａを越えると凝集力が強すぎるため、剥離強さが低下する。引張り強さは、０．３８～０．５６ＭＰａであることがより好ましい。
粘着剤層の剥離強さとしては、目的に応じた剥離強さを有していれば特に制限されるものではないが、本発明に係る粘着剤組成物から形成された架橋後の粘着剤層の剥離強さとしては、常温（２３℃）と高温（９０℃）での剥離強さの変化が少ないことが好ましい。 The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention after crosslinking has a 25% compressive strength of 0.06 to 0.11 MPa and a tensile strength at 23° C. of 0.35 to 0.65 MPa.
The 25% compressive strength is a value measured by the method described in the Examples below, and if the compressive strength is less than 0.06 MPa, it becomes difficult for the sheet to maintain its shape, and if it exceeds 0.11 MPa, the ability to conform to steps and curved surfaces decreases. The compressive strength is more preferably 0.06 to 0.10 MPa.
The tensile strength of the pressure-sensitive adhesive layer at 23°C is a value measured by the method described in the Examples below, and if the tensile strength is less than 0.35 MPa, the cohesive strength of the pressure-sensitive adhesive layer is weak, resulting in a decrease in holding power, while if it exceeds 0.65 MPa, the cohesive strength is too strong, resulting in a decrease in peel strength. The tensile strength is more preferably 0.38 to 0.56 MPa.
The peel strength of the pressure-sensitive adhesive layer is not particularly limited as long as it has a peel strength appropriate for the purpose, but it is preferable that the peel strength of the pressure-sensitive adhesive layer after crosslinking formed from the pressure-sensitive adhesive composition of the present invention has little change between room temperature (23°C) and high temperature (90°C).
２５％圧縮強度は、後述する実施例に記載された方法で測定された値であり、圧縮強度が０．０６ＭＰａ未満ではシートとしての形状維持が困難となり、０．１１ＭＰａを越えると段差や曲面に対する追従性が低下する。圧縮強度は０．０６～０．１０ＭＰａであることがより好ましい。
また、粘着剤層の２３℃の引張り強さは、後述する実施例に記載された方法で測定された値であり、引張り強さが０．３５ＭＰａ未満では、粘着剤層の凝集力が弱いため保持力が低下し、０．６５ＭＰａを越えると凝集力が強すぎるため、剥離強さが低下する。引張り強さは、０．３８～０．５６ＭＰａであることがより好ましい。
粘着剤層の剥離強さとしては、目的に応じた剥離強さを有していれば特に制限されるものではないが、本発明に係る粘着剤組成物から形成された架橋後の粘着剤層の剥離強さとしては、常温（２３℃）と高温（９０℃）での剥離強さの変化が少ないことが好ましい。 The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention after crosslinking has a 25% compressive strength of 0.06 to 0.11 MPa and a tensile strength at 23° C. of 0.35 to 0.65 MPa.
The 25% compressive strength is a value measured by the method described in the Examples below, and if the compressive strength is less than 0.06 MPa, it becomes difficult for the sheet to maintain its shape, and if it exceeds 0.11 MPa, the ability to conform to steps and curved surfaces decreases. The compressive strength is more preferably 0.06 to 0.10 MPa.
The tensile strength of the pressure-sensitive adhesive layer at 23°C is a value measured by the method described in the Examples below, and if the tensile strength is less than 0.35 MPa, the cohesive strength of the pressure-sensitive adhesive layer is weak, resulting in a decrease in holding power, while if it exceeds 0.65 MPa, the cohesive strength is too strong, resulting in a decrease in peel strength. The tensile strength is more preferably 0.38 to 0.56 MPa.
The peel strength of the pressure-sensitive adhesive layer is not particularly limited as long as it has a peel strength appropriate for the purpose, but it is preferable that the peel strength of the pressure-sensitive adhesive layer after crosslinking formed from the pressure-sensitive adhesive composition of the present invention has little change between room temperature (23°C) and high temperature (90°C).
本発明の粘着剤組成物には、上記の圧縮強度及び引張り強さに影響しない範囲で、本発明の分野において公知の各種添加剤を含むことができる。係る添加剤としては、難燃剤、顔料、老化防止剤、滑剤等が挙げられ、これらの一種もしくは二種以上を組み合わせて含むことができる。
The adhesive composition of the present invention may contain various additives known in the field of the present invention, provided that they do not affect the above-mentioned compressive strength and tensile strength. Such additives include flame retardants, pigments, antioxidants, lubricants, etc., and may contain one or a combination of two or more of these.
本発明に係る粘着剤組成物は、該粘着剤組成物をシート状に成形して架橋した粘着剤層として用いることができる。粘着剤層は単独でシート状に成形しても、基材上に粘着層を形成したテープ状物として用いてもよい。特に後述する物品同士を接着する両面粘着シートとしての使用が好ましい。このようなシート状物及びテープ状物を合わせて、本明細書では粘着シートと称する。
The adhesive composition according to the present invention can be used as an adhesive layer formed by forming the adhesive composition into a sheet and crosslinking it. The adhesive layer may be formed into a sheet on its own, or may be used as a tape-like material in which an adhesive layer is formed on a substrate. In particular, it is preferably used as a double-sided adhesive sheet for bonding articles together, as described below. Such sheet-like and tape-like materials are collectively referred to as adhesive sheets in this specification.
図１～図５は、本発明の粘着シートの層構成を説明する概略断面図である。図１は、本発明に係る粘着剤組成物を用いた粘着剤層単独で構成されるシートであり、架橋した粘着剤層１中には、中空微粒子２が分散して含まれる。当該シートの紙面の上下の面は、粘着面であり、両面粘着シートを構成する。使用までの取扱性の点では、粘着面には離型フィルムが設けられており、物品の接着の際に離型フィルムを剥がして粘着面を物品の接着する面に貼り付ける。
FIGS. 1 to 5 are schematic cross-sectional views illustrating the layer structure of the adhesive sheet of the present invention. FIG. 1 shows a sheet composed solely of an adhesive layer using the adhesive composition of the present invention, with hollow fine particles 2 dispersed in the crosslinked adhesive layer 1. The top and bottom surfaces of the sheet are adhesive surfaces, constituting a double-sided adhesive sheet. In terms of ease of handling before use, a release film is provided on the adhesive surface, and when adhering an article, the release film is peeled off and the adhesive surface is attached to the surface to which the article is to be adhered.
図２は、基材３の一方の面に粘着剤層１を配置した粘着シートであり、基材３の非粘着面には印刷等による意匠を施すことができる。そのため、基材３の非粘着面側には、印刷に適した受容層（不図示）などを設けることもできる。図３は、基材３の両面に粘着剤層１を配した粘着シートを示す。
基材としては、当該分野で使用される基材であって、本発明に係る粘着剤層との接着強度に優れる材料であればいずれの材料でも使用可能である。例えば、公知のフィルム、不織布、発泡体、布、紙、及びこれらの組合せを用いることができる。
基材の厚さは特に制限されないが、例えば、１μｍ以上２００μｍ以下の範囲から選択することができる。
基材の粘着剤層を設ける面には、必要に応じて易接着処理を施してもよい。易接着処理としては、例えば、プライマー処理、コロナ処理、エッチング処理、プラズマ処理、サンドブラスト処理などが挙げられる。これらから１種の、あるいは２種以上の組合せを選択することができる。
基材には必要に応じて帯電防止等の表面処理がなされていてもよい。帯電防止処理としては、陽イオン性界面活性剤、陰イオン性界面活性剤、非イオン性界面活性剤等の帯電防止剤による処理が例として挙げられる。また、基材には必要に応じて印刷や練りこみ等により、着色処理がなされていてもよい。 Fig. 2 shows an adhesive sheet in which anadhesive layer 1 is disposed on one side of a substrate 3, and a design can be applied by printing or the like to the non-adhesive side of the substrate 3. Therefore, a receiving layer (not shown) suitable for printing or the like can be provided on the non-adhesive side of the substrate 3. Fig. 3 shows an adhesive sheet in which an adhesive layer 1 is disposed on both sides of the substrate 3.
The substrate may be any substrate used in the field and has excellent adhesive strength with the pressure-sensitive adhesive layer of the present invention. For example, known films, nonwoven fabrics, foams, cloths, papers, and combinations thereof may be used.
The thickness of the substrate is not particularly limited, but can be selected, for example, from the range of 1 μm or more and 200 μm or less.
The surface of the substrate on which the pressure-sensitive adhesive layer is to be formed may be subjected to an easy-adhesion treatment, if necessary. Examples of easy-adhesion treatments include primer treatment, corona treatment, etching treatment, plasma treatment, sandblasting treatment, etc. One or a combination of two or more of these may be selected.
The substrate may be subjected to a surface treatment such as antistatic treatment as required. Examples of the antistatic treatment include treatment with an antistatic agent such as a cationic surfactant, an anionic surfactant, or a nonionic surfactant. In addition, the substrate may be subjected to a coloring treatment by printing, kneading, or the like as required.
基材としては、当該分野で使用される基材であって、本発明に係る粘着剤層との接着強度に優れる材料であればいずれの材料でも使用可能である。例えば、公知のフィルム、不織布、発泡体、布、紙、及びこれらの組合せを用いることができる。
基材の厚さは特に制限されないが、例えば、１μｍ以上２００μｍ以下の範囲から選択することができる。
基材の粘着剤層を設ける面には、必要に応じて易接着処理を施してもよい。易接着処理としては、例えば、プライマー処理、コロナ処理、エッチング処理、プラズマ処理、サンドブラスト処理などが挙げられる。これらから１種の、あるいは２種以上の組合せを選択することができる。
基材には必要に応じて帯電防止等の表面処理がなされていてもよい。帯電防止処理としては、陽イオン性界面活性剤、陰イオン性界面活性剤、非イオン性界面活性剤等の帯電防止剤による処理が例として挙げられる。また、基材には必要に応じて印刷や練りこみ等により、着色処理がなされていてもよい。 Fig. 2 shows an adhesive sheet in which an
The substrate may be any substrate used in the field and has excellent adhesive strength with the pressure-sensitive adhesive layer of the present invention. For example, known films, nonwoven fabrics, foams, cloths, papers, and combinations thereof may be used.
The thickness of the substrate is not particularly limited, but can be selected, for example, from the range of 1 μm or more and 200 μm or less.
The surface of the substrate on which the pressure-sensitive adhesive layer is to be formed may be subjected to an easy-adhesion treatment, if necessary. Examples of easy-adhesion treatments include primer treatment, corona treatment, etching treatment, plasma treatment, sandblasting treatment, etc. One or a combination of two or more of these may be selected.
The substrate may be subjected to a surface treatment such as antistatic treatment as required. Examples of the antistatic treatment include treatment with an antistatic agent such as a cationic surfactant, an anionic surfactant, or a nonionic surfactant. In addition, the substrate may be subjected to a coloring treatment by printing, kneading, or the like as required.
図４は、一方の粘着面が本発明に係る中空微粒子２を内包する粘着剤層１であり、他方の面が中空微粒子２を含まない粘着剤層４の積層体である粘着シートを示す。図５は、粘着剤層１と粘着剤層４の間に基材３を挿入した積層体である粘着シートを示す。中空微粒子２を含まない粘着剤層４は、中空微粒子２を内包する粘着剤層１と比較して段差追従性が劣る場合があるが、粘着剤層４で接着する面が平坦であれば特に段差追従性が劣っていても問題がない。粘着剤層４としては、従来公知の粘着剤層や粘着剤層１から中空微粒子を除いた粘着剤層を用いることができる。
Figure 4 shows an adhesive sheet having one adhesive surface which is an adhesive layer 1 containing hollow microparticles 2 according to the present invention, and the other surface which is a laminate of an adhesive layer 4 which does not contain hollow microparticles 2. Figure 5 shows an adhesive sheet which is a laminate in which a substrate 3 is inserted between adhesive layer 1 and adhesive layer 4. An adhesive layer 4 which does not contain hollow microparticles 2 may have inferior step conformability compared to an adhesive layer 1 containing hollow microparticles 2, but as long as the surface to be bonded by adhesive layer 4 is flat, there is no problem even if the step conformability is inferior. As adhesive layer 4, a conventionally known adhesive layer or an adhesive layer obtained by removing hollow microparticles from adhesive layer 1 can be used.
粘着剤層の製造方法は、特に限定されず、従来公知の方法を用いることができる。
The method for producing the adhesive layer is not particularly limited, and any conventionally known method can be used.
本発明に係る粘着シートを用いた物品としては、自動車部品や機械部品等の分野に使用される物品であり、その製造過程や使用過程において、例えば５０℃以上の温度に曝される物品の接合、接着に使用することができる。
Articles using the adhesive sheet of the present invention include those used in fields such as automobile parts and machine parts, and can be used to bond and adhere articles that are exposed to temperatures of, for example, 50°C or higher during the manufacturing and use processes.
以下、実施例により本発明を更に詳細に説明する。以下の記載において「部」は「質量部」を意味する。
The present invention will be explained in more detail below with reference to examples. In the following description, "parts" means "parts by mass."
部分共重合体Ａの調製
撹拌機、還流冷却器、温度計、窒素ガス導入口を備えたフラスコに表１に示す組成を投入し、窒素雰囲気下で紫外線照射装置（パナソニック社製：Ａｉｃｕｒｅ ＵＰ５０（商品名））を用い、照射強度８００～１，２００ｍＷ／ｃｍ２（アイテックシステム社製：光量計ＵＶＭ－１００を用い測定）の紫外線を８～１２分間照射して光重合させることにより、アクリル酸－２－エチルヘキシルとアクリル酸との共重合体Ａ１を約１５質量％含有する部分共重合体Ａを製造した。共重合体Ａ１の重量平均分子量は約１００万であった。 Preparation of partial copolymer A The composition shown in Table 1 was placed in a flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen gas inlet, and photopolymerized by irradiating with ultraviolet light at an irradiation intensity of 800 to 1,200 mW/cm 2 (measured with an actinometer UVM-100 manufactured by ITEC Systems Co., Ltd.) for 8 to 12 minutes using an ultraviolet irradiation device (manufactured by Panasonic: Aicure UP50 (product name)) under a nitrogen atmosphere to produce partial copolymer A containing about 15 mass % of copolymer A1 of 2-ethylhexyl acrylate and acrylic acid. The weight average molecular weight of copolymer A1 was about 1,000,000.
撹拌機、還流冷却器、温度計、窒素ガス導入口を備えたフラスコに表１に示す組成を投入し、窒素雰囲気下で紫外線照射装置（パナソニック社製：Ａｉｃｕｒｅ ＵＰ５０（商品名））を用い、照射強度８００～１，２００ｍＷ／ｃｍ２（アイテックシステム社製：光量計ＵＶＭ－１００を用い測定）の紫外線を８～１２分間照射して光重合させることにより、アクリル酸－２－エチルヘキシルとアクリル酸との共重合体Ａ１を約１５質量％含有する部分共重合体Ａを製造した。共重合体Ａ１の重量平均分子量は約１００万であった。 Preparation of partial copolymer A The composition shown in Table 1 was placed in a flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen gas inlet, and photopolymerized by irradiating with ultraviolet light at an irradiation intensity of 800 to 1,200 mW/cm 2 (measured with an actinometer UVM-100 manufactured by ITEC Systems Co., Ltd.) for 8 to 12 minutes using an ultraviolet irradiation device (manufactured by Panasonic: Aicure UP50 (product name)) under a nitrogen atmosphere to produce partial copolymer A containing about 15 mass % of copolymer A1 of 2-ethylhexyl acrylate and acrylic acid. The weight average molecular weight of copolymer A1 was about 1,000,000.
[粘着シート作製方法]
この部分共重合体Ａを用いて、表２－１～２－４に示す組成でシロップを調製し、さらにその他の材料を加え均一に混合して、粘着剤組成物を得た。なお、表中の数値は部数を示す。
２枚のシリコーン離型処理された厚み５０μｍのＰＥＴフィルム(藤森工業社製、商品名「フィルムバイナＫＦ＃５０」）の離型処理面の間に粘着剤組成物を塗布し、照射強度３．０～５．０ｍＷ／ｃｍ２の蛍光ランプ（東芝社製：ＦＬ２０Ｓ Ｗ）を両面から２分間照射し、粘着シートを得た。粘着シートの厚さは８００μｍになるように調整した。 [How to make adhesive sheets]
Using this partial copolymer A, syrups were prepared according to the compositions shown in Tables 2-1 to 2-4, and other materials were added and mixed uniformly to obtain pressure-sensitive adhesive compositions. The values in the tables indicate the number of parts.
The adhesive composition was applied between the release-treated surfaces of two silicone release-treated PET films (manufactured by Fujimori Kogyo Co., Ltd., product name "Film Vina KF #50") with a thickness of 50 μm, and the film was irradiated from both sides with a fluorescent lamp (manufactured by Toshiba Corporation: FL20S W) with an irradiation intensity of 3.0 to 5.0 mW/cm2 for 2 minutes to obtain an adhesive sheet. The thickness of the adhesive sheet was adjusted to 800 μm.
この部分共重合体Ａを用いて、表２－１～２－４に示す組成でシロップを調製し、さらにその他の材料を加え均一に混合して、粘着剤組成物を得た。なお、表中の数値は部数を示す。
２枚のシリコーン離型処理された厚み５０μｍのＰＥＴフィルム(藤森工業社製、商品名「フィルムバイナＫＦ＃５０」）の離型処理面の間に粘着剤組成物を塗布し、照射強度３．０～５．０ｍＷ／ｃｍ２の蛍光ランプ（東芝社製：ＦＬ２０Ｓ Ｗ）を両面から２分間照射し、粘着シートを得た。粘着シートの厚さは８００μｍになるように調整した。 [How to make adhesive sheets]
Using this partial copolymer A, syrups were prepared according to the compositions shown in Tables 2-1 to 2-4, and other materials were added and mixed uniformly to obtain pressure-sensitive adhesive compositions. The values in the tables indicate the number of parts.
The adhesive composition was applied between the release-treated surfaces of two silicone release-treated PET films (manufactured by Fujimori Kogyo Co., Ltd., product name "Film Vina KF #50") with a thickness of 50 μm, and the film was irradiated from both sides with a fluorescent lamp (manufactured by Toshiba Corporation: FL20S W) with an irradiation intensity of 3.0 to 5.0 mW/cm2 for 2 minutes to obtain an adhesive sheet. The thickness of the adhesive sheet was adjusted to 800 μm.
表２－１～２－４中、材料名の詳細は以下の通りである。
（材料詳細）
（シロップ（ａ））
部分共重合体Ａ：共重合体Ａ１の約１５質量％及び約８５質量％の未反応モノマー
２－ＥＨＡ：アクリル酸－２－エチルヘキシル、三菱ケミカル社製
ＮＯＡＡ：ｎ－オクチルアクリレート、大阪有機化学工業社製
β－ＣＥＡ：β－カルボキシエチルアクリレート、ダイセル・オルネクス社製
４ＨＢＡ：４－ヒドロキシブチルアクリレート、大阪有機化学工業社製
ＨＥＡ：ヒドロキシエチルアクリレート、大阪有機化学工業社製
ＡＭ－９０Ｇ：メトキシポリエチレングリコールアクリレート（商品名：ＮＫエステルＡＭ－９０Ｇ）、新中村化学社製
ＩＢＯＡ：イソボルニルアクリレート、大阪有機化学工業社製
ＡＣＭＯ：アクリロイルモルフォリン、ＫＪケミカルズ社製 In Tables 2-1 to 2-4, the details of the material names are as follows:
(Material details)
(Syrup (a))
Partial copolymer A: about 15% by mass and about 85% by mass of unreacted monomers in copolymer A1 2-EHA: 2-ethylhexyl acrylate, manufactured by Mitsubishi Chemical Corporation NOAA: n-octyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. β-CEA: β-carboxyethyl acrylate, manufactured by Daicel Allnex Corporation 4HBA: 4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. HEA: hydroxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. AM-90G: methoxypolyethylene glycol acrylate (product name: NK Ester AM-90G), manufactured by Shin-Nakamura Chemical Co., Ltd. IBOA: isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. ACMO: acryloylmorpholine, manufactured by KJ Chemicals Co., Ltd.
（材料詳細）
（シロップ（ａ））
部分共重合体Ａ：共重合体Ａ１の約１５質量％及び約８５質量％の未反応モノマー
２－ＥＨＡ：アクリル酸－２－エチルヘキシル、三菱ケミカル社製
ＮＯＡＡ：ｎ－オクチルアクリレート、大阪有機化学工業社製
β－ＣＥＡ：β－カルボキシエチルアクリレート、ダイセル・オルネクス社製
４ＨＢＡ：４－ヒドロキシブチルアクリレート、大阪有機化学工業社製
ＨＥＡ：ヒドロキシエチルアクリレート、大阪有機化学工業社製
ＡＭ－９０Ｇ：メトキシポリエチレングリコールアクリレート（商品名：ＮＫエステルＡＭ－９０Ｇ）、新中村化学社製
ＩＢＯＡ：イソボルニルアクリレート、大阪有機化学工業社製
ＡＣＭＯ：アクリロイルモルフォリン、ＫＪケミカルズ社製 In Tables 2-1 to 2-4, the details of the material names are as follows:
(Material details)
(Syrup (a))
Partial copolymer A: about 15% by mass and about 85% by mass of unreacted monomers in copolymer A1 2-EHA: 2-ethylhexyl acrylate, manufactured by Mitsubishi Chemical Corporation NOAA: n-octyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. β-CEA: β-carboxyethyl acrylate, manufactured by Daicel Allnex Corporation 4HBA: 4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. HEA: hydroxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. AM-90G: methoxypolyethylene glycol acrylate (product name: NK Ester AM-90G), manufactured by Shin-Nakamura Chemical Co., Ltd. IBOA: isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. ACMO: acryloylmorpholine, manufactured by KJ Chemicals Co., Ltd.
（粘着付与樹脂（ｂ））
Ｐ－１２５：水添石油樹脂（軟化点１２５±５℃、商品名：アルコンＰ－１２５）、荒川化学工業社製
Ｐ－１４０：水添石油樹脂（軟化点１４０±５℃、商品名：アルコンＰ－１４０）、荒川化学工業社製
Ｐ－９０：水添石油樹脂（軟化点９０±５℃、商品名：アルコンＰ－９０）、荒川化学工業社製
Ｇ１２５：テルペンフェノール樹脂（軟化点１２５±５℃、商品名：ＹＳポリスターＧ１２５）、ヤスハラケミカル社製
ＫＥ－１００：水添ロジンエステル（軟化点１００±５℃、商品名：パインクリスタルＫＥ－１００）、荒川化学工業社製 (Tackifier resin (b))
P-125: Hydrogenated petroleum resin (softening point 125±5°C, product name: Alcon P-125), manufactured by Arakawa Chemical Industries Co., Ltd. P-140: Hydrogenated petroleum resin (softening point 140±5°C, product name: Alcon P-140), manufactured by Arakawa Chemical Industries Co., Ltd. P-90: Hydrogenated petroleum resin (softening point 90±5°C, product name: Alcon P-90), manufactured by Arakawa Chemical Industries Co., Ltd. G125: Terpene phenol resin (softening point 125±5°C, product name: YS Polystar G125), manufactured by Yasuhara Chemical Co., Ltd. KE-100: Hydrogenated rosin ester (softening point 100±5°C, product name: Pine Crystal KE-100), manufactured by Arakawa Chemical Industries Co., Ltd.
Ｐ－１２５：水添石油樹脂（軟化点１２５±５℃、商品名：アルコンＰ－１２５）、荒川化学工業社製
Ｐ－１４０：水添石油樹脂（軟化点１４０±５℃、商品名：アルコンＰ－１４０）、荒川化学工業社製
Ｐ－９０：水添石油樹脂（軟化点９０±５℃、商品名：アルコンＰ－９０）、荒川化学工業社製
Ｇ１２５：テルペンフェノール樹脂（軟化点１２５±５℃、商品名：ＹＳポリスターＧ１２５）、ヤスハラケミカル社製
ＫＥ－１００：水添ロジンエステル（軟化点１００±５℃、商品名：パインクリスタルＫＥ－１００）、荒川化学工業社製 (Tackifier resin (b))
P-125: Hydrogenated petroleum resin (softening point 125±5°C, product name: Alcon P-125), manufactured by Arakawa Chemical Industries Co., Ltd. P-140: Hydrogenated petroleum resin (softening point 140±5°C, product name: Alcon P-140), manufactured by Arakawa Chemical Industries Co., Ltd. P-90: Hydrogenated petroleum resin (softening point 90±5°C, product name: Alcon P-90), manufactured by Arakawa Chemical Industries Co., Ltd. G125: Terpene phenol resin (softening point 125±5°C, product name: YS Polystar G125), manufactured by Yasuhara Chemical Co., Ltd. KE-100: Hydrogenated rosin ester (softening point 100±5°C, product name: Pine Crystal KE-100), manufactured by Arakawa Chemical Industries Co., Ltd.
（中空微粒子（ｃ））
Ｆ－８０ＤＥ：アクリロニトリル共重合体中空微粒子（平均粒子径９０～１３０μｍ）、松本油脂製薬社製
Ｆ－８０ＳＤＥ：アクリロニトリル共重合体中空微粒子（平均粒子径２０～４０μｍ）、松本油脂製薬社製
３０Ｐ７０Ｔ：無機系中空微粒子、ポッターズ・バロティーニ社製
（光重合開始剤（ｄ））
ＨＡＰ：α－ヒドロキシアセトフェノン（商品名：Ｏｍｎｉｒａｄ１１７３）、ＩＧＭ Ｒｅｓｉｎｓ社製 (Hollow Fine Particles (c))
F-80DE: acrylonitrile copolymer hollow microparticles (average particle size 90 to 130 μm), manufactured by Matsumoto Yushi Seiyaku Co., Ltd. F-80SDE: acrylonitrile copolymer hollow microparticles (average particle size 20 to 40 μm), manufactured by Matsumoto Yushi Seiyaku Co., Ltd. 30P70T: inorganic hollow microparticles, manufactured by Potters Ballotini Co., Ltd. (photopolymerization initiator (d))
HAP: α-hydroxyacetophenone (product name: Omnirad 1173), manufactured by IGM Resins
Ｆ－８０ＤＥ：アクリロニトリル共重合体中空微粒子（平均粒子径９０～１３０μｍ）、松本油脂製薬社製
Ｆ－８０ＳＤＥ：アクリロニトリル共重合体中空微粒子（平均粒子径２０～４０μｍ）、松本油脂製薬社製
３０Ｐ７０Ｔ：無機系中空微粒子、ポッターズ・バロティーニ社製
（光重合開始剤（ｄ））
ＨＡＰ：α－ヒドロキシアセトフェノン（商品名：Ｏｍｎｉｒａｄ１１７３）、ＩＧＭ Ｒｅｓｉｎｓ社製 (Hollow Fine Particles (c))
F-80DE: acrylonitrile copolymer hollow microparticles (average particle size 90 to 130 μm), manufactured by Matsumoto Yushi Seiyaku Co., Ltd. F-80SDE: acrylonitrile copolymer hollow microparticles (average particle size 20 to 40 μm), manufactured by Matsumoto Yushi Seiyaku Co., Ltd. 30P70T: inorganic hollow microparticles, manufactured by Potters Ballotini Co., Ltd. (photopolymerization initiator (d))
HAP: α-hydroxyacetophenone (product name: Omnirad 1173), manufactured by IGM Resins
（架橋剤（ｅ））
Ｔｅｔｒａｄ Ｘ：Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン、三菱ガス化学社製
ＨＤＤＡ：１，６－ヘキサンジオールジアクリレート、大阪有機化学工業社製
Ａ－１０００：ポリエチレングリコールジアクリレート（商品名：ＮＫエステルＡ－１０００）、新中村化学工業社製
Ａ－ＤＰＨ：ジペンタエリスリトールヘキサアクリレート（商品名：ＮＫエステルＡ－ＤＰＨ、新中村化学工業社製
ＭＲ－２００：ポリメリックＭＤＩ（商品名：ミリオネートＭＲ－２００）、東ソー社製 (Crosslinking Agent (e))
Tetrad X: N,N,N',N'-tetraglycidyl-m-xylylenediamine, manufactured by Mitsubishi Gas Chemical Co., Ltd. HDDA: 1,6-hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. A-1000: polyethylene glycol diacrylate (product name: NK Ester A-1000), manufactured by Shin-Nakamura Chemical Co., Ltd. A-DPH: dipentaerythritol hexaacrylate (product name: NK Ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd. MR-200: Polymeric MDI (product name: Millionate MR-200), manufactured by Tosoh Corporation
Ｔｅｔｒａｄ Ｘ：Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン、三菱ガス化学社製
ＨＤＤＡ：１，６－ヘキサンジオールジアクリレート、大阪有機化学工業社製
Ａ－１０００：ポリエチレングリコールジアクリレート（商品名：ＮＫエステルＡ－１０００）、新中村化学工業社製
Ａ－ＤＰＨ：ジペンタエリスリトールヘキサアクリレート（商品名：ＮＫエステルＡ－ＤＰＨ、新中村化学工業社製
ＭＲ－２００：ポリメリックＭＤＩ（商品名：ミリオネートＭＲ－２００）、東ソー社製 (Crosslinking Agent (e))
Tetrad X: N,N,N',N'-tetraglycidyl-m-xylylenediamine, manufactured by Mitsubishi Gas Chemical Co., Ltd. HDDA: 1,6-hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. A-1000: polyethylene glycol diacrylate (product name: NK Ester A-1000), manufactured by Shin-Nakamura Chemical Co., Ltd. A-DPH: dipentaerythritol hexaacrylate (product name: NK Ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd. MR-200: Polymeric MDI (product name: Millionate MR-200), manufactured by Tosoh Corporation
物性評価
上記で作製した粘着シートに対して、以下の評価を実施した。結果を表３－１～３－４に示す。
（粘着シートの引張り試験）
ＪＩＳ Ｚ ０２３７に準拠して、厚み８００μｍ、幅２５ｍｍ、長さ１００ｍｍの粘着シートを、引張り試験機（東洋精機社製：ストログラフＶ－１Ｃ）を用いて２３℃，５０％ＲＨ、掴み具間距離３０ｍｍ、試験速度３００ｍｍ／ｍｉｎの条件で引張り、最大引張り強さを測定した。また、温度を９０℃に変更して同様の条件で最大引張り強さを測定した。 The pressure-sensitive adhesive sheets prepared above were subjected to the following evaluations. The results are shown in Tables 3-1 to 3-4.
(Tensile test of adhesive sheet)
In accordance with JIS Z 0237, a pressure-sensitive adhesive sheet having a thickness of 800 μm, a width of 25 mm, and a length of 100 mm was pulled and the maximum tensile strength was measured using a tensile tester (Strograph V-1C, manufactured by Toyo Seiki Co., Ltd.) under conditions of 23° C., 50% RH, a gripping distance of 30 mm, and a test speed of 300 mm/min. The maximum tensile strength was also measured under the same conditions, with the temperature changed to 90° C.
上記で作製した粘着シートに対して、以下の評価を実施した。結果を表３－１～３－４に示す。
（粘着シートの引張り試験）
ＪＩＳ Ｚ ０２３７に準拠して、厚み８００μｍ、幅２５ｍｍ、長さ１００ｍｍの粘着シートを、引張り試験機（東洋精機社製：ストログラフＶ－１Ｃ）を用いて２３℃，５０％ＲＨ、掴み具間距離３０ｍｍ、試験速度３００ｍｍ／ｍｉｎの条件で引張り、最大引張り強さを測定した。また、温度を９０℃に変更して同様の条件で最大引張り強さを測定した。 The pressure-sensitive adhesive sheets prepared above were subjected to the following evaluations. The results are shown in Tables 3-1 to 3-4.
(Tensile test of adhesive sheet)
In accordance with JIS Z 0237, a pressure-sensitive adhesive sheet having a thickness of 800 μm, a width of 25 mm, and a length of 100 mm was pulled and the maximum tensile strength was measured using a tensile tester (Strograph V-1C, manufactured by Toyo Seiki Co., Ltd.) under conditions of 23° C., 50% RH, a gripping distance of 30 mm, and a test speed of 300 mm/min. The maximum tensile strength was also measured under the same conditions, with the temperature changed to 90° C.
（粘着シートの圧縮強さ）
３０ｍｍ角の粘着シートを積層し、厚さ１２ｍｍの積層体を形成した。この積層体を圧縮試験機（島津製作所社製：ＡＧ－５０ｋＮＸ Ｐｌｕｓ）を用いて２３℃，５０％ＲＨ、試験速度１０ｍｍ／ｍｉｎの条件で圧縮し、２５％変形時における圧縮強さを測定した。 (Compressive strength of adhesive sheet)
A 30 mm square pressure sensitive adhesive sheet was laminated to form a laminate with a thickness of 12 mm. This laminate was compressed using a compression tester (Shimadzu Corporation: AG-50kNX Plus) under conditions of 23°C, 50% RH, and a test speed of 10 mm/min, and the compressive strength at 25% deformation was measured.
３０ｍｍ角の粘着シートを積層し、厚さ１２ｍｍの積層体を形成した。この積層体を圧縮試験機（島津製作所社製：ＡＧ－５０ｋＮＸ Ｐｌｕｓ）を用いて２３℃，５０％ＲＨ、試験速度１０ｍｍ／ｍｉｎの条件で圧縮し、２５％変形時における圧縮強さを測定した。 (Compressive strength of adhesive sheet)
A 30 mm square pressure sensitive adhesive sheet was laminated to form a laminate with a thickness of 12 mm. This laminate was compressed using a compression tester (Shimadzu Corporation: AG-50kNX Plus) under conditions of 23°C, 50% RH, and a test speed of 10 mm/min, and the compressive strength at 25% deformation was measured.
（剥離強さ）
被着体に厚さ１．５ｍｍ、５０ｍｍ、長さ１２５ｍｍのＳＵＳ ３０４の表面ＢＡ（冷間圧延後、光輝熱処理を施したもの）の鋼板をアセトンで洗浄したものと、厚さ２．０ｍｍ、５０ｍｍ、長さ１２５ｍｍのポリプロピレン（ＰＰ）板をイソプロピルアルコールで洗浄したものを用意した。
作製した粘着シートを１０ｍｍ×１３０ｍｍに切断し、粘着シート両面にある剥離フィルムの片面を剥がし、５０μｍ厚、１５ｍｍ幅、長さ３００ｍｍのポリエステルフィルムを貼り合わせた。次に、その反対面側の剥離フィルムを剥がし、被着体に軽く貼り付けた後、５ｋｇローラーを用いて試験片の上から毎分約３００ｍｍの速さで往復圧着した。
圧着後、室温に２４時間放置した後、粘着シートの端部を１８０度に折り返し、２３℃、５０％ＲＨ雰囲気下、毎分５０±５ｍｍの速さで連続して引き剥がし、試験力（単位：Ｎ／１０ｍｍ）の平均を読み取った。結果はＳＵＳ(２３℃)及びＰＰ（２３℃）として表示した。
同様に貼り合わせ圧着した試験片を、室温に２４時間放置した後、粘着シートの端部を１８０度に折り返し、９０±３℃の熱風循環式恒温装置内に１時間放置後、９０℃雰囲気下、毎分５０±５ｍｍの速さで連続して引き剥がし、試験力の平均を読み取った。結果はＳＵＳ(９０℃)及びＰＰ（９０℃）として表示した。
また、剥離強さの変化率として、２３℃と９０℃での剥離強さの差を２３℃の剥離強さで除した値を表３－１～３－４に示した。 (Peel Strength)
The adherends were prepared as follows: a SUS 304 steel plate with a thickness of 1.5 mm, 50 mm and length of 125 mm and a BA surface (cold rolled and then bright heat treated) washed with acetone, and a polypropylene (PP) plate with a thickness of 2.0 mm, 50 mm and length of 125 mm washed with isopropyl alcohol.
The prepared adhesive sheet was cut to 10 mm x 130 mm, one side of the release film on both sides of the adhesive sheet was peeled off, and a polyester film 50 μm thick, 15 mm wide, and 300 mm long was attached to it. Next, the release film on the other side was peeled off, and the sheet was lightly attached to the adherend, and then a 5 kg roller was used to reciprocate and press the sheet against the test piece at a speed of about 300 mm per minute.
After the pressure-bonding, the sheet was left at room temperature for 24 hours, and then the end of the pressure-sensitive adhesive sheet was folded back at 180 degrees and continuously peeled off at a speed of 50±5 mm per minute in an atmosphere of 23°C and 50% RH, and the average test force (unit: N/10 mm) was read. The results were displayed as SUS (23°C) and PP (23°C).
Similarly, the test pieces that had been laminated and pressed together were left at room temperature for 24 hours, and then the ends of the pressure-sensitive adhesive sheet were folded back at 180 degrees and left in a hot air circulating thermostatic chamber at 90±3°C for 1 hour, after which the sheets were continuously peeled off at a speed of 50±5 mm per minute in an atmosphere of 90°C, and the average test force was read. The results were displayed as SUS (90°C) and PP (90°C).
Furthermore, the rate of change in peel strength was calculated by dividing the difference in peel strength between 23° C. and 90° C. by the peel strength at 23° C., and the results are shown in Tables 3-1 to 3-4.
被着体に厚さ１．５ｍｍ、５０ｍｍ、長さ１２５ｍｍのＳＵＳ ３０４の表面ＢＡ（冷間圧延後、光輝熱処理を施したもの）の鋼板をアセトンで洗浄したものと、厚さ２．０ｍｍ、５０ｍｍ、長さ１２５ｍｍのポリプロピレン（ＰＰ）板をイソプロピルアルコールで洗浄したものを用意した。
作製した粘着シートを１０ｍｍ×１３０ｍｍに切断し、粘着シート両面にある剥離フィルムの片面を剥がし、５０μｍ厚、１５ｍｍ幅、長さ３００ｍｍのポリエステルフィルムを貼り合わせた。次に、その反対面側の剥離フィルムを剥がし、被着体に軽く貼り付けた後、５ｋｇローラーを用いて試験片の上から毎分約３００ｍｍの速さで往復圧着した。
圧着後、室温に２４時間放置した後、粘着シートの端部を１８０度に折り返し、２３℃、５０％ＲＨ雰囲気下、毎分５０±５ｍｍの速さで連続して引き剥がし、試験力（単位：Ｎ／１０ｍｍ）の平均を読み取った。結果はＳＵＳ(２３℃)及びＰＰ（２３℃）として表示した。
同様に貼り合わせ圧着した試験片を、室温に２４時間放置した後、粘着シートの端部を１８０度に折り返し、９０±３℃の熱風循環式恒温装置内に１時間放置後、９０℃雰囲気下、毎分５０±５ｍｍの速さで連続して引き剥がし、試験力の平均を読み取った。結果はＳＵＳ(９０℃)及びＰＰ（９０℃）として表示した。
また、剥離強さの変化率として、２３℃と９０℃での剥離強さの差を２３℃の剥離強さで除した値を表３－１～３－４に示した。 (Peel Strength)
The adherends were prepared as follows: a SUS 304 steel plate with a thickness of 1.5 mm, 50 mm and length of 125 mm and a BA surface (cold rolled and then bright heat treated) washed with acetone, and a polypropylene (PP) plate with a thickness of 2.0 mm, 50 mm and length of 125 mm washed with isopropyl alcohol.
The prepared adhesive sheet was cut to 10 mm x 130 mm, one side of the release film on both sides of the adhesive sheet was peeled off, and a polyester film 50 μm thick, 15 mm wide, and 300 mm long was attached to it. Next, the release film on the other side was peeled off, and the sheet was lightly attached to the adherend, and then a 5 kg roller was used to reciprocate and press the sheet against the test piece at a speed of about 300 mm per minute.
After the pressure-bonding, the sheet was left at room temperature for 24 hours, and then the end of the pressure-sensitive adhesive sheet was folded back at 180 degrees and continuously peeled off at a speed of 50±5 mm per minute in an atmosphere of 23°C and 50% RH, and the average test force (unit: N/10 mm) was read. The results were displayed as SUS (23°C) and PP (23°C).
Similarly, the test pieces that had been laminated and pressed together were left at room temperature for 24 hours, and then the ends of the pressure-sensitive adhesive sheet were folded back at 180 degrees and left in a hot air circulating thermostatic chamber at 90±3°C for 1 hour, after which the sheets were continuously peeled off at a speed of 50±5 mm per minute in an atmosphere of 90°C, and the average test force was read. The results were displayed as SUS (90°C) and PP (90°C).
Furthermore, the rate of change in peel strength was calculated by dividing the difference in peel strength between 23° C. and 90° C. by the peel strength at 23° C., and the results are shown in Tables 3-1 to 3-4.
（保持力試験）
被着体には、＃２８０研磨紙で３０往復研磨した後、アセトンで洗浄した研磨ＳＵＳ板を使用し、研磨ＳＵＳ板の端部に２５ｍｍ×２５ｍｍサイズに切断した粘着シートの一方の面の剥離ライナーを剥離し、その面を研磨ＳＵＳ板の端部に貼り付けた後、５ｋｇローラーを用いて試験片の上から毎分約３００ｍｍの速さで往復圧着した後、反対面の剥離ライナーを剥ぎ取り、厚さ１３０±２０μｍ、アルミニウム箔を同様に貼り合せた。
貼り合わせ圧着後、２４時間放置した後、アルミニウム箔側に質量１±０．０１ｋｇの重りを掛け、９０±３℃の熱風循環式恒温装置内に１時間放置し、落下の有無（Ａ：無し、Ｂ：有り）を確認した。 (Retention strength test)
The adherend was a polished SUS plate that had been polished back and forth 30 times with #280 abrasive paper and then washed with acetone. The release liner was peeled off from one side of an adhesive sheet cut to a size of 25 mm x 25 mm and attached to the end of the polished SUS plate. The sheet was then pressed back and forth from above the test piece using a 5 kg roller at a speed of approximately 300 mm per minute, after which the release liner on the opposite side was peeled off and aluminum foil of a thickness of 130±20 μm was similarly attached.
After lamination and compression bonding, the sample was left for 24 hours, and then a weight of 1±0.01 kg was hung on the aluminum foil side. The sample was left for 1 hour in a hot air circulating thermostatic chamber at 90±3° C., and the presence or absence of falling was confirmed (A: no, B: yes).
被着体には、＃２８０研磨紙で３０往復研磨した後、アセトンで洗浄した研磨ＳＵＳ板を使用し、研磨ＳＵＳ板の端部に２５ｍｍ×２５ｍｍサイズに切断した粘着シートの一方の面の剥離ライナーを剥離し、その面を研磨ＳＵＳ板の端部に貼り付けた後、５ｋｇローラーを用いて試験片の上から毎分約３００ｍｍの速さで往復圧着した後、反対面の剥離ライナーを剥ぎ取り、厚さ１３０±２０μｍ、アルミニウム箔を同様に貼り合せた。
貼り合わせ圧着後、２４時間放置した後、アルミニウム箔側に質量１±０．０１ｋｇの重りを掛け、９０±３℃の熱風循環式恒温装置内に１時間放置し、落下の有無（Ａ：無し、Ｂ：有り）を確認した。 (Retention strength test)
The adherend was a polished SUS plate that had been polished back and forth 30 times with #280 abrasive paper and then washed with acetone. The release liner was peeled off from one side of an adhesive sheet cut to a size of 25 mm x 25 mm and attached to the end of the polished SUS plate. The sheet was then pressed back and forth from above the test piece using a 5 kg roller at a speed of approximately 300 mm per minute, after which the release liner on the opposite side was peeled off and aluminum foil of a thickness of 130±20 μm was similarly attached.
After lamination and compression bonding, the sample was left for 24 hours, and then a weight of 1±0.01 kg was hung on the aluminum foil side. The sample was left for 1 hour in a hot air circulating thermostatic chamber at 90±3° C., and the presence or absence of falling was confirmed (A: no, B: yes).
本発明に係る粘着剤組成物は、柔軟性に優れ、かつ高温下においても優れた粘着力を有する粘着剤層を形成可能であり、凹凸があり、高温処理が施される物品の製造においても所望の粘着力を保持することができる。
The adhesive composition of the present invention is capable of forming an adhesive layer that has excellent flexibility and excellent adhesive strength even at high temperatures, and is capable of maintaining the desired adhesive strength even in the manufacture of articles that have irregularities and are subjected to high-temperature processing.
１ 粘着剤層
２ 中空微粒子
３ 基材
４ 他の粘着剤層 1 Pressure-sensitive adhesive layer 2 Hollow fine particles 3 Substrate 4 Other pressure-sensitive adhesive layers
２ 中空微粒子
３ 基材
４ 他の粘着剤層 1 Pressure-
Claims (8)
- （ａ）アルキル（メタ）アクリレート及びカルボキシル基を有する（メタ）アクリレートを構成成分とする（メタ）アクリル系共重合体、並びに、アルキル（メタ）アクリレートモノマー、カルボキシル基を有する（メタ）アクリレートモノマー及び水酸基を有する（メタ）アクリレートモノマーを混合したシロップ１００質量部と、
（ｂ）粘着付与樹脂を０．５～１０質量部と、
（ｃ）中空微粒子を０．１～３．０質量部と、
（ｄ）光重合開始剤を０．１～５質量部と、
（ｅ）架橋剤を０．０１～５質量部と、
を含有する粘着剤組成物であって、
前記中空微粒子（ｃ）が、有機高分子材料から構成される殻部を有する樹脂系中空微粒子であり、
前記粘着剤組成物から形成された架橋後の粘着剤層の２５％圧縮強度が０．０６～０．１１ＭＰａであり、
前記粘着剤層の２３℃での引張り強さが０．３５～０．６５ＭＰａであることを特徴とする、
粘着剤組成物。 (a) 100 parts by mass of a syrup obtained by mixing a (meth)acrylic copolymer having as its constituent components an alkyl (meth)acrylate and a (meth)acrylate having a carboxyl group, an alkyl (meth)acrylate monomer, a (meth)acrylate monomer having a carboxyl group, and a (meth)acrylate monomer having a hydroxyl group;
(b) 0.5 to 10 parts by mass of a tackifier resin;
(c) 0.1 to 3.0 parts by mass of hollow fine particles;
(d) 0.1 to 5 parts by mass of a photopolymerization initiator;
(e) 0.01 to 5 parts by mass of a crosslinking agent;
A pressure-sensitive adhesive composition comprising:
the hollow fine particles (c) are resin-based hollow fine particles having a shell portion made of an organic polymer material,
the 25% compressive strength of the pressure-sensitive adhesive layer after crosslinking formed from the pressure-sensitive adhesive composition is 0.06 to 0.11 MPa;
The pressure-sensitive adhesive layer has a tensile strength of 0.35 to 0.65 MPa at 23°C.
Adhesive composition. - 前記有機高分子材料がアクリロニトリルを構成単位として含む高分子材料の少なくとも１種である、請求項１に記載の粘着剤組成物。 The adhesive composition according to claim 1, wherein the organic polymer material is at least one type of polymer material containing acrylonitrile as a constituent unit.
- 前記樹脂系中空微粒子の体積平均粒子径Ｄ５０が１～１５０μｍの範囲である、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the volume average particle diameter D50 of the resin-based hollow microparticles is in the range of 1 to 150 μm.
- 請求項１乃至３のいずれか１項に記載の粘着剤組成物から形成された粘着剤層を備える、粘着シート。 An adhesive sheet having an adhesive layer formed from the adhesive composition according to any one of claims 1 to 3.
- 前記粘着剤層の単層で構成される、請求項４に記載の粘着シート。 The adhesive sheet according to claim 4, which is composed of a single layer of the adhesive layer.
- 前記粘着剤層が、該粘着剤層を支持する基材の少なくとも一方の面に設けられている、請求項４に記載の粘着シート。 The adhesive sheet according to claim 4, wherein the adhesive layer is provided on at least one surface of a substrate that supports the adhesive layer.
- 前記粘着剤層の少なくなくとも一部の表面に、基材及び／又は他の粘着剤層を有する、請求項４に記載の粘着シート。 The adhesive sheet according to claim 4, having a substrate and/or another adhesive layer on at least a portion of the surface of the adhesive layer.
- 少なくとも一部に、１乃至３のいずれか１項に記載の粘着剤組成物から形成された粘着剤層が貼着された物品。 An article having attached to at least a portion thereof an adhesive layer formed from the adhesive composition described in any one of 1 to 3.
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| CN115216229A (en) * | 2021-04-19 | 2022-10-21 | 三星Sdi株式会社 | (meth) acrylic adhesive film, optical member comprising same, and optical display device |
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| JP2014051644A (en) * | 2012-08-07 | 2014-03-20 | Nitto Denko Corp | Double-sided adhesive sheet and portable electronic apparatus |
| JP2015117292A (en) * | 2013-12-18 | 2015-06-25 | 日東電工株式会社 | Adhesive composition and adhesive tape |
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