WO2020138237A1 - 貫通孔を含む構造体を有する積層体 - Google Patents
貫通孔を含む構造体を有する積層体 Download PDFInfo
- Publication number
- WO2020138237A1 WO2020138237A1 PCT/JP2019/051016 JP2019051016W WO2020138237A1 WO 2020138237 A1 WO2020138237 A1 WO 2020138237A1 JP 2019051016 W JP2019051016 W JP 2019051016W WO 2020138237 A1 WO2020138237 A1 WO 2020138237A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- laminate
- base
- triblock copolymer
- base material
- acrylic
- Prior art date
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- 239000000463 material Substances 0.000 claims abstract description 115
- 229920000642 polymer Polymers 0.000 claims abstract description 110
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Definitions
- the present invention relates to a laminate having a structure including an acrylic triblock copolymer base and a through hole.
- a structure having a through hole has been produced by subjecting a solid body such as a plate-like body to post-processing such as needle hole processing and performing punching processing to a fibrous material.
- post-processing such as needle hole processing and performing punching processing to a fibrous material.
- the production of these structures is problematic in that it takes time and effort.
- a laminate has been proposed in which a thermoplastic elastomer layer having one or more through-holes is molded and molded on one surface or both surfaces of a substrate sheet (for example, , Patent Document 1).
- the adhesiveness is one of the performances expected due to its softness.
- An object of the present invention is to have both visco-adhesiveness and re-peelability compatible with each other, capable of suppressing adhesive residue, and also excellent in laminating property. To provide a laminate having the same.
- the above object is [1] A laminate having a base material and a structure including a base portion and a through hole provided on at least one surface of the base material,
- the base of the structure has two polymer blocks (A1) and (A2) composed of a methacrylic acid ester unit and a general formula CH 2 ⁇ CH—COOR 1 (1) (wherein R 1 has 4 to 4 carbon atoms).
- one polymer block (B) containing an acrylic acid ester unit represented by (12 represents an organic group) has a (A1)-(B)-(A2) block structure, and has a weight average molecular weight of 50.
- Laminate [2] A laminate having a base material and a structure provided on at least one surface of the base material and including a base portion and a through hole, The base of the structure has two polymer blocks (A1) and (A2) composed of a methacrylic acid ester unit and a general formula CH 2 ⁇ CH—COOR 1 (1) (wherein R 1 has 4 to 4 carbon atoms).
- (meth)acrylic acid ester is a general term for "methacrylic acid ester” and “acrylic acid ester”
- (meth)acrylic means “methacrylic” and "acrylic”. It is a generic term.
- the laminate of the present invention has a structure containing a base containing the acrylic triblock copolymer (I) and a through hole. Since the structure includes the above-mentioned base and the through hole, not only is it excellent in breathability, but also excellent in removability after alignment, such as in positioning. Further, it becomes possible to suppress the adhesive residue. Furthermore, when the structure contained in the laminate and the adherend are stuck together, wrinkles and bubbles are unlikely to enter, and the sticking property is also excellent. It is a preferred embodiment that the above-mentioned structure is formed of a base portion and a through hole made of an acrylic triblock copolymer (I) which are continuous in a mesh shape.
- the mesh-like shape include a mesh shape, a honeycomb shape, a scale shape, and a tile shape.
- the shape of the structure may be a dot shape in which through holes are discretely provided, a stripe shape, or the like.
- the portion (base portion) of the above structure other than the through holes contains the acrylic triblock copolymer (I).
- the acrylic triblock copolymer (I) comprises two polymer blocks (A1) and (A2) each composed of a methacrylic acid ester unit and a general formula CH 2 ⁇ CH—COOR 1 (1) (wherein R 1 Represents an organic group having 4 to 12 carbon atoms) and one polymer block (B) containing an acrylate unit, and has a (A1)-(B)-(A2) block structure, The weight average molecular weight is 50,000 to 250,000, and the total content of the polymer blocks (A1) and (A2) is 35% by mass or less. Since the acrylic triblock copolymer (I) forms the base of the structure, it is possible to obtain a laminate having a structure that is excellent not only in tackiness and adhesion but also in removability.
- the acrylic triblock copolymer (I) has a polymer block composed of two methacrylic acid ester units, namely a polymer block composed of methacrylic acid ester units (A1) and (A2).
- Examples of the methacrylic acid ester serving as the constitutional units of the polymer blocks (A1) and (A2) include, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, methacrylic acid.
- a methacrylic acid ester having no functional group is preferable, and methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, Isobornyl methacrylate and phenyl methacrylate are more preferable, the phase separation between the polymer blocks (A1) and (A2) and the polymer block (B) becomes clearer, and the acrylic triblock copolymer (I) is contained.
- Methyl methacrylate is more preferable in that the cohesive force of the structure including the base portion and the through holes is increased.
- the polymer blocks (A1) and (A2) may be composed of one kind of these methacrylic acid esters or may be composed of two or more kinds thereof.
- the acrylic triblock copolymer (I) has two polymer blocks (A1) and (A2) as polymer blocks composed of methacrylic acid ester units. These polymer blocks (A1) and The methacrylic acid ester constituting (A2) may be the same or different.
- the proportion of methacrylic acid ester units contained in the polymer blocks (A1) and (A2) is preferably 60% by mass or more in each of the polymer blocks (A1) and (A2), and 80 Mass% or more is more preferable, 90 mass% or more is still more preferable, and 95 mass% or more is still more preferable.
- the ratio of the methacrylic acid ester units in the polymer blocks (A1) and (A2) may be 100% by mass.
- the stereoregularity of the methacrylic acid ester units contained in each of the polymer blocks (A1) and (A2) consisting of methacrylic acid ester units may be the same or different.
- the total content of the polymer blocks (A1) and (A2) is 35 mass% or less, preferably 30 mass% or less, and 25 mass% or less. Is more preferable.
- the total content of the polymer blocks (A1) and (A2) is preferably 4% by mass or more, more preferably 8% by mass or more.
- the cohesive force of the structure containing the base containing the acrylic triblock copolymer (I) and the through holes tends to be high.
- the tack and adhesive strength are further improved.
- the heat-resistant adhesiveness and holding power of the structure tend to be more excellent.
- the content of each of the polymer blocks (A1) and (A2) contained in the acrylic triblock copolymer (I) may be the same or different.
- the glass transition temperature (Tg) of each of the polymer blocks (A1) and (A2) is preferably 60 to 140° C., more preferably 70 to 130° C., and further preferably 80 to 130° C. preferable. When the glass transition temperature is in this range, the polymer blocks (A1) and (A2) act as physical pseudo-crosslinking points and develop a cohesive force at a normal use temperature of the laminate of the present invention. A laminate having excellent adhesive properties, durability, heat resistance, etc. can be obtained.
- the glass transition temperature in this specification is the extrapolation start temperature of the curve obtained by the DSC measurement.
- the Tg of each of the polymer blocks (A1) and (A2) may be the same or different. Even when the Tg of each of the polymer blocks (A1) and (A2) is different, it is a preferred embodiment that the Tg of both polymer blocks is within the above range.
- the acrylic triblock copolymer (I) is represented by the general formula CH 2 ⁇ CH—COOR 1 (1) (wherein R 1 represents an organic group having 4 to 12 carbon atoms), and the acrylic ester unit ( Hereinafter, it has one polymer block (B) containing the acrylic ester (1) unit).
- R 1 represents an organic group having 4 to 12 carbon atoms
- the acrylic ester unit hereinafter, it has one polymer block (B) containing the acrylic ester (1) unit.
- acrylate ester (1) examples include n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, and acrylic.
- 2-ethylhexyl acid ester 2-ethylhexyl acid ester, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isobornyl acrylate, lauryl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, and other non-functional acrylate esters;
- acrylic acid esters having a functional group such as 2-ethoxyethyl acrylate, 2-(diethylamino)ethyl acrylate, tetrahydrofurfuryl acrylate, and 2-phenoxyethyl acrylate.
- the phase separation between the polymer blocks (A1) and (A2) and the polymer block (B) becomes clearer, the cohesive force of the obtained structure is enhanced, and the obtained laminate has a wide temperature range.
- From n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and isooctyl acrylate because they have a suitable removable adhesiveness and can suppress the adhesive residue at the time of repeeling, etc. At least one selected is more preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are further preferable.
- the polymer block (B) may be composed of one kind of these acrylic acid esters, or may be composed of two or more kinds thereof.
- the proportion of acrylic acid ester units contained in the polymer block (B) is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and further preferably 95% by mass or more. Further, the proportion of acrylic acid ester units in the polymer block (B) may be 100% by mass.
- the polymer block (B) When the polymer block (B) is copolymerized with a plurality of monomers, it may be composed of a random copolymer, or may be composed of a block copolymer or a graft copolymer.
- the glass transition temperature of the polymer block (B) is more preferably ⁇ 100 to 30° C., more preferably ⁇ 80 to 10° C., and further preferably ⁇ 75 to 0° C. When the glass transition temperature is within this range, it is possible to obtain a laminate having a structure that is flexible and has high adhesiveness at a use temperature.
- the above polymer blocks (A1) and (A2) and the polymer block (B) may contain monomer units of each other within a range that does not impair the effects of the present invention.
- it may have a tapered structure at the boundary between the polymer block (A1) or (A2) and the polymer block (B).
- the polymer block (A1) or (A2) and the polymer block (B) may not contain monomer units of each other.
- the polymer blocks (A1) and (A2) and the polymer block (B) may contain other monomers, if necessary.
- examples of such other monomers include vinyl monomers having a carboxyl group such as (meth)acrylic acid, crotonic acid, maleic acid, maleic anhydride, and fumaric acid; (meth)acrylamide, (meth)acrylonitrile, Vinyl-based monomers having functional groups such as vinyl acetate, vinyl chloride, vinylidene chloride; aromatic vinyl-based monomers such as styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene; butadiene, isoprene, etc.
- conjugated diene monomer examples include olefinic monomers such as ethylene, propylene, isobutene, and octene; and lactone monomers such as ⁇ -caprolactone and valerolactone.
- the content thereof is preferably 20% by mass or less, more preferably 10% by mass, based on the total mass of the monomers constituting each polymer block. % Or less, more preferably 5% by mass or less.
- the acrylic triblock copolymer (I) has a polymer block (A1) of (A1); a polymer block (A2) of (A2); and a polymer block (B) of (B); It has a (A1)-(B)-(A2) block structure in which a polymer block (A1), a polymer block (B) and a polymer block (A2) are bonded in this order.
- the acrylic triblock copolymer (I) has this structure, it becomes a structure excellent in adhesive force, holding force and cohesive force.
- the acrylic triblock copolymer (I) has a weight average molecular weight (Mw) of 50,000 to 250,000. From the viewpoint of cohesive force and handleability during production, it is preferably 55,000 to 230,000, more preferably 60,000 to 220,000, and more preferably 65,000 to 200,000. Is more preferable. If the Mw of the acrylic triblock copolymer (I) is less than 50,000, the cohesive force may be poor. If the Mw exceeds 250,000, the handleability during production may be poor.
- the molecular weight distribution (Mw/Mn) of the acrylic triblock copolymer (I) is preferably 1.0 to 1.5, more preferably 1.0 to 1.4.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) in this specification are the weight average molecular weight and number average molecular weight of standard polystyrene conversion calculated
- the method for producing the acrylic triblock copolymer (I) used in the present invention is not particularly limited as long as a polymer satisfying the conditions of the present invention regarding the chemical structure is obtained, and it is in accordance with a known method.
- a method can be adopted.
- a method of obtaining a block copolymer having a narrow molecular weight distribution a method of living polymerization of a monomer which is a structural unit is employed.
- living polymerization methods include a method of living polymerization using an organic rare earth metal complex as a polymerization initiator (see Japanese Patent Application Laid-Open No. 06-93060), and an alkali metal or alkaline earth compound using an organic alkali metal compound as a polymerization initiator.
- Living anionic polymerization in the presence of a mineral acid salt such as a metal salt see Japanese Patent Publication No. 05-507737
- living anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound Refer to Japanese Patent Laid-Open No. 11-335432
- atom transfer radical polymerization method ATRP (Macromolecular Chemistry and Physics, 2000, 201, p. 1108 to 1114).
- a method of living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound makes the resulting block copolymer highly transparent, and has little residual monomer and odor. Is suppressed, and when used as the base of the structure, generation of bubbles after bonding can be suppressed, which is preferable.
- the molecular structure of the methacrylic acid ester polymer block becomes highly syndiotactic, which has the effect of increasing the heat resistance of the base of the structure. Living polymerization is possible under relatively mild temperature conditions and it is industrially produced. In this case, the environmental load (mainly the electric power applied to the refrigerator for controlling the polymerization temperature) is small, which is also preferable.
- organoaluminum compound examples include the following general formula (2) AlR 2 R 3 R 4 (2) (In the formula (2), R 2 , R 3 and R 4 each independently represent an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent which may have a substituent. Represents an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group or an N,N-disubstituted amino group. Or R 2 is any of the groups described above, and R 3 and R 4 together form an arylenedioxy group which may have a substituent. Aluminum compounds may be mentioned.
- isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy) is used in view of high living property of polymerization and easy handling.
- Aluminum, isobutylbis(2,6-di-tert-butylphenoxy)aluminum, isobutyl[2,2′-methylenebis(4-methyl-6-tert-butylphenoxy)]aluminum and the like are preferable.
- organic alkali metal compound examples include alkyllithium and alkyldilithium such as n-butyllithium, sec-butyllithium, isobutyllithium, tert-butyllithium, n-pentyllithium and tetramethylenedilithium; phenyllithium, p -Aryllithium and aryldilithium such as tolyllithium and lithiumnaphthalene; aralkyllithium and aralkyldilithium such as benzyllithium, diphenylmethyllithium, dilithium produced by the reaction of diisopropenylbenzene and butyllithium; lithium such as lithium dimethylamide Amides; lithium alkoxides such as methoxylithium and ethoxylithium, and the like.
- alkyllithium and alkyldilithium such as n-butyllithium, sec-butyllithium, isobutyllithium, ter
- alkyllithium is preferable because of its high polymerization initiation efficiency, and among them, tert-butyllithium and sec-butyllithium are more preferable, and sec-butyllithium is further preferable.
- the above living anionic polymerization is usually carried out in the presence of a solvent inert to the polymerization reaction.
- a solvent inert examples include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride; ethers such as tetrahydrofuran and diethyl ether.
- aromatic hydrocarbons such as benzene, toluene and xylene
- halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride
- ethers such as tetrahydrofuran and diethyl ether.
- Toluene is preferably used.
- the block copolymer is obtained by, for example, a step of forming a desired polymer block (polymer block (A2), polymer block (B), etc.) at a desired living polymer terminal obtained by polymerizing a monomer. It can be produced by repeating the desired number of times and then stopping the polymerization reaction.
- the acrylic triblock copolymer (I) can be produced by reacting with an alcohol or the like to stop the polymerization reaction. According to the method as described above, a triblock copolymer composed of the polymer block (A1)-polymer block (B)-polymer block (A2) can be produced.
- the polymerization temperature is preferably 0 to 100° C. when forming the polymer blocks (A1) and (A2) and ⁇ 50 to 50° C. when forming the polymer block (B).
- the polymer blocks (A1) and (A2) and the polymer block (B) can be polymerized in the range of 1 second to 20 hours.
- the above-mentioned acrylic triblock copolymer (I) is contained in the base component of the structure of the present invention.
- the content of the acrylic triblock copolymer (I) contained in the base component is not particularly limited, but the acrylic triblock copolymer (I) is It is preferable to contain 80 mass% or more, more preferably 85 mass% or more, further preferably 90 mass% or more, and even 100 mass% with respect to the total amount of the components.
- the base contains 80% by mass or more of the acrylic triblock copolymer (I), the characteristics of the base are more easily exhibited.
- the base of the above structure does not contain a tackifying resin.
- the laminated body of the first aspect is excellent in that it is possible to reliably suppress adhesive residue.
- a tackifying resin may be contained as a component that becomes the base of the structure, but the mass ratio of tackifying resin/acrylic triblock copolymer (I) is It is 20/100 or less.
- the layered product of the second aspect is excellent in that it is possible to easily achieve both cohesiveness and suppression of adhesive residue.
- the mass ratio of tackifying resin/acrylic triblock copolymer (I) is preferably 15/100 or less from the viewpoint of reliably suppressing adhesive residue.
- any tackifying resin that has been conventionally used in an adhesive can be used and is not particularly limited.
- a rosin-based resin rosin , Rosin derivative, hydrogenated rosin derivative, etc.
- terpene resin terpene phenol resin
- (hydrogenated) petroleum resin styrene resin
- xylene resin hydrogenated aromatic copolymer
- phenol resin coumarone-indene resin Resin etc.
- the rosin-based resin is an amber, amorphous natural resin obtained from pine, whose main component is a mixture of abietic acid and its isomers.
- the rosin-based resin also includes those modified by esterification, polymerization, hydrogenation, etc. by utilizing the reactivity of the abietic acid or its isomer.
- unmodified rosin eg, tall rosin, gum rosin, wood rosin, etc.
- polymerized rosin e.g., polymerized rosin, disproportionated rosin
- hydrogenated rosin maleic acid modified rosin, fumaric acid modified rosin, and esters thereof (eg, glycerin ester, pentane Erythritol ester, methyl ester, ethyl ester, butyl ester, ethylene glycol ester, etc.) and those further modified by hydrogenation (hereinafter, also referred to as hydrogenation) are mentioned, and particularly from the viewpoint of heat resistance and coloring resistance.
- hydrogenated rosin ester are preferably used.
- the terpene resin is an oligomer obtained by polymerizing a raw material containing a terpene monomer.
- the terpene-based resin also includes an oligomer obtained by modifying the thus obtained oligomer by hydrogenation or the like.
- the terpene generally means a polymer of isoprene (C 5 H 8 ) and is classified into monoterpene (C 10 H 16 ), sesquiterpene (C 15 H 24 ), diterpene (C 20 H 32 ), and the like.
- the terpene-based monomer is a monomer having these as a basic skeleton, and examples thereof include ⁇ -pinene, ⁇ -pinene, dipentene, limonene, myrcene, aloocimene, ocimene, ⁇ -ferrandrain, ⁇ -terpinene, and ⁇ .
- a raw material containing a terpene-based monomer another monomer copolymerizable with the terpene-based monomer, for example, a coumarone-based monomer such as benzofuran (C 8 H 6 O); styrene, ⁇ - Vinyl aromatic compounds such as methylstyrene, vinyltoluene, divinyltoluene, 2-phenyl-2-butene; phenol, cresol, xylenol, propylphenol, norylphenol, hydroquinone, resorcin, methoxyphenol, bromophenol, bisphenol A, bisphenol F And the like may contain phenolic monomers and the like.
- a coumarone-based monomer such as benzofuran (C 8 H 6 O)
- styrene ⁇ - Vinyl aromatic compounds such as methylstyrene, vinyltoluene, divinyltoluene, 2-phenyl-2-butene
- Examples of the oligomer obtained by polymerizing a raw material containing another monomer copolymerizable with the terpene-based monomer include a terpene-phenolic resin.
- the terpene-based resin also includes a product obtained by modifying the thus obtained oligomer by hydrogenation or the like.
- the (hydrogenated) petroleum-based resin means a raw material comprising a C 5 fraction, a C 9 fraction, a C 5 fraction purified component, a C 9 fraction purified component, or a mixture of these fractions or purified components. It is an oligomer obtained by polymerization. Further, the above-mentioned (hydrogenated) petroleum-based resin also includes those obtained by modifying the oligomer thus obtained by hydrogenation or the like.
- the C 5 fraction usually contains cyclopentadiene, dicyclopentadiene, isoprene, 1,3-pentadiene, 2-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene and Cyclopentene and the like are contained, and the C 9 fraction usually contains styrene, allylbenzene, ⁇ -methylstyrene, vinyltoluene, ⁇ -methylstyrene, indene and the like. Further, the C 9 fraction may contain a small amount of C 8 fraction and C 10 fraction.
- the (hydrogenated) petroleum-based resin is a C 5 fraction or a purified component thereof as a raw material, a C 5 resin, a C 9 fraction or a purified component thereof as a raw material, a C 9 resin, a C 5 fraction or a purified component thereof. It is roughly classified into C 5 -C 9 copolymer resins, which are made from a mixture of C and C 9 fractions or purified components thereof as a raw material. Among these, hydrogenated petroleum-based resins are preferably used from the viewpoint of heat resistance and coloring resistance.
- aromatic hydrocarbon resins such as styrene resins, xylene resins, hydrogenated aromatic copolymers and phenol resins are, for example, styrene, ⁇ -methylstyrene, vinyltoluene, ⁇ -methylstyrene, divinyltoluene.
- styrene resin is preferably used from the viewpoint of compatibility, heat resistance, and color resistance.
- tackifying resins may be contained alone or in combination of two or more. When two or more of these tackifying resins are contained, it is desirable in terms of excellent balance of adhesive strength and tack. Further, the softening point of the tackifying resin is preferably 50 to 160° C. from the viewpoint of exhibiting high adhesive strength.
- the component serving as the base of the structure of the present invention is another polymer, a softening agent, a plasticizer, a heat stabilizer, a light stabilizer, an antistatic agent, a flame retardant, a foaming agent as long as the effect of the present invention is not impaired.
- Additives other than the tackifying resin such as a colorant, a dyeing agent, a refractive index adjusting agent, a filler, a curing agent, a lubricant, an anti-sticking agent, an anti-termite agent, and a rodent-proofing agent may be contained.
- a colorant such as a colorant, a dyeing agent, a refractive index adjusting agent, a filler, a curing agent, a lubricant, an anti-sticking agent, an anti-termite agent, and a rodent-proofing agent.
- One of these other polymers and additives may be contained, or two or more thereof may be contained.
- the other polymers include acrylic resins such as polymethylmethacrylate and (meth)acrylic acid ester polymers or copolymers; polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polybutene-1, poly Olefin resins such as -4-methylpentene-1, polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, Styrene resin such as MBS resin; styrene-methyl methacrylate copolymer; styrene-methyl methacrylate-maleic anhydride copolymer; polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polylactic acid; nylon 6, nylon 66, Polyamides such as polyamide elastomers; polycarbonate; polyvinyl chloride;
- polymethyl methacrylate, (meth)acrylic acid ester polymer or copolymer , Ethylene-vinyl acetate copolymer, AS resin, styrene-methyl methacrylate-maleic anhydride copolymer, polylactic acid, polyvinylidene fluoride are preferred, polymethyl methacrylate, (meth)acrylic acid ester copolymer, styrene -Methyl methacrylate-maleic anhydride copolymer is more preferred.
- Examples of the (meth)acrylic acid ester polymer or copolymer include polymethyl acrylate, n-butyl polyacrylate, 2-ethylhexyl polyacrylate, random copolymer of methyl methacrylate and methyl acrylate, Examples thereof include random copolymers of methyl methacrylate and n-butyl acrylate.
- each component is known in the kneader ruder, extruder, mixing roll, Banbury mixer, etc. It can be produced by mixing at a temperature in the range of 100 to 250° C. using the mixing or kneading apparatus of Further, it may be produced by dissolving each component in an organic solvent and mixing them, and then distilling off the organic solvent. Above all, it is preferable that each component is melt-kneaded by a twin-screw extruder at a temperature in the range of 150 to 240° C., and then extruded and cut into pellets or the like.
- the method for producing the above structure is not particularly limited as long as a structure including a base portion containing the acrylic triblock copolymer (I) and a through hole can be produced.
- the following method may be mentioned.
- a compound containing the acrylic triblock copolymer (I) is melt-extruded to produce long fibers, an aggregate of short fibers is produced from the long fibers, and the aggregate of these short fibers is used as an adhesive or A method of forming a structure by pressure bonding with heat.
- the structure of the present invention can be formed by the pattern printing method because the structure including the base and the through-hole having the desired shape can be easily produced by forming the shape of the recess corresponding to the desired shape. Is a preferable embodiment.
- the laminated body of the present invention has a base material and the above-mentioned structure provided on at least one surface of the base material and including a base portion and a through hole.
- a two-layer laminate comprising the above-mentioned structure/base material including a base portion and a through hole; the above-mentioned structure body including a base portion and a through hole/a base material/the above-mentioned structure body including a through-hole
- a three-layer laminate comprising: a structure/base material including a base and a through hole/a four-layer laminate including the structure/base material including a base and a through hole; a structure including a base and a through hole /Substrate/The above-mentioned structure including the base and the through hole/Layer of 5 layers comprising the above-mentioned structure including the base and the through-hole; From the above-mentioned structure/the base including the base/base and the through-hole And the like
- the laminate of the present invention when the above-mentioned structure including the base and the through hole forms the outermost layer, for example, polyethylene, polypropylene film, release-treated PET film, release paper, etc. are provided on the outer side thereof. You may provide the peeling layer of.
- Examples of the base material used for the laminate include paper, a resin sheet or film, and a woven or non-woven fabric made of a fibrous material.
- examples of the thermoplastic polymer material that becomes the resin sheet or film or the fibrous material include vinyl chloride resins such as polyester, polyamide, acrylic resin, polyurethane, polyethylene, polypropylene, and polyvinyl chloride.
- these thermoplastic polymer materials may be melt-spun.
- these thermoplastic polymer materials may be produced by melt extrusion molding.
- fibrous materials examples include natural fibers such as cotton, hemp, silk, and wool; inorganic fibers such as glass fibers and carbon fibers; and the like. Woven fabrics made from these fibrous materials can be produced, and examples of the woven fabrics include woven fabrics and knitted fabrics. Further, a nonwoven fabric can be produced from these fibrous materials by a mechanical method, a chemical method, or a combination of these methods.
- the laminate of the present invention is obtained by laminating the structure including the base and the through hole obtained as described above on the base material.
- the method of laminating is not particularly limited as long as the laminated body of the present invention can be obtained.
- the following method may be mentioned.
- the method of (3) above which is a method for producing a laminated body through a pattern printing method, is a preferable aspect because a laminated body on which a structure having a desired shape is formed is easy to produce.
- the laminate of the present invention can be used for various purposes. Specifically, for example, surface protection, masking, packaging/packaging, office work, labels, decoration/display, bookbinding, dicing tape, medical/sanitary, laminated glass, glass shatterproof , Electrical insulation, holding and fixing of electronic devices, semiconductor manufacturing, optical display film, adhesive optical film, electromagnetic wave shielding, adhesive tape, film and sheet for encapsulation of electrical and electronic parts, medical Materials for use, filter materials, food packaging materials, housing materials, kitchen materials, hat materials, and the like.
- a surface protection application it can be used for various materials such as metal, plastic, rubber, wood, etc.
- automobile surface, optical member surface protection can be used.
- the automobile member include a coating outer plate, a wheel, a mirror, a window, a light, a light cover and the like.
- various image display devices such as a liquid crystal display, an organic EL display, a plasma display, a field emission display; a polarizing film, a polarizing plate, a retardation plate, a light guide plate, a diffusion plate, an optical disk constituent film such as a DVD; ⁇ Precise fine-coated face plate for optical applications.
- Masking applications include masking during the manufacture of printed circuit boards and flexible printed circuit boards; masking during plating and soldering of electronic devices; manufacturing of vehicles such as automobiles, painting of vehicles and buildings, printing, and civil engineering work Etc.
- the packaging uses include heavy-weight packaging, export packaging, cardboard box sealing, and can sealing.
- Examples of office use include general office work, sealing, book repair, drafting, and memo use.
- Examples of the label use include price, product display, tag, POP, sticker, stripe, name plate, decoration, and advertisement.
- Labels include paper, processed paper (aluminum deposition processing, aluminum lamination processing, varnish processing, resin processing, etc.), paper such as synthetic paper; cellophane, plastic materials, cloth, wood and metal
- Examples of the label include a film or the like as a base material layer.
- Examples of the base material layer include high-quality paper, art paper, cast paper, thermal paper, foil paper, polyethylene terephthalate film, polyvinyl chloride film, OPP film, polylactic acid film, synthetic paper, synthetic paper thermal, and overlay film. Are listed.
- Examples of the adherend of the above label include plastic products such as plastic bottles and foamed plastic cases; paper and cardboard products such as cardboard boxes; glass products such as glass bottles; metal products; ceramics and other inorganic material products.
- Decorative applications include display of danger labels, line tapes, wiring markings, phosphorescent tapes, and reflection sheets.
- a polarizing film for example, a polarizing film, a polarizing plate, a retardation film, a viewing angle expansion film, a brightness enhancement film, an antireflection film, an antiglare film, a color filter, a light guide plate, a diffusion film, a prism sheet, an electromagnetic wave shielding film.
- a polarizing film for example, a polarizing film, a polarizing plate, a retardation film, a viewing angle expansion film, a brightness enhancement film, an antireflection film, an antiglare film, a color filter, a light guide plate, a diffusion film, a prism sheet, an electromagnetic wave shielding film.
- Near-infrared absorbing film functional composite optical film, ITO laminating film, impact resistance imparting film, visibility improving film, etc.
- Such an adhesive optical film also includes a protective film used for surface protection of the optical film.
- the adhesive optical film is suitably used for various image display devices such as liquid crystal display devices, PDPs, organic
- Examples of applications for holding and fixing electronic devices include carrier tape, packaging, fixing of cathode ray tubes, splicing, rib reinforcement, and the like.
- Examples of semiconductor manufacturing include protection of silicone wafers.
- analgesic and anti-inflammatory agents plasters, paps), cold patches, antipruritic patches, keratin softeners and other percutaneous absorption applications; first-aid bandages (containing bactericides), surgical dressings/surgical tapes, bandages, Various tape applications such as hemostatic bond, tape for human excrement disposal equipment (artificial anus fixing tape), suture tape, antibacterial tape, fixed taping, self-adhesive bandage, oral mucous membrane adhesive tape, sports tape, hair removal tape, etc. Beauty applications such as face packs, moisturizing sheets, exfoliating packs and the like; Bonding of sanitary materials such as diapers and pet sheets; Cooling sheets, heating warmers, dustproof, waterproof, pest trapping, etc.
- Examples of applications for encapsulating materials for electronic and electrical parts include encapsulants for liquid crystal displays, organic EL displays, organic EL lighting, solar cells, etc.
- Examples of laminated glass applications include automobile windshields, automobile side glasses, automobile sunroofs, automobile rear glass, and head-up display glass.
- Medical materials include diaper materials, sanitary napkin materials, surgical clothes, lab coats, patient clothes, medical examination clothes materials, covering cloths, gowns, drape materials, supporter materials, sterilization bag materials, baby pads, breasts.
- the filter materials include dehumidifying filters, dust collecting filters, air filters, HEPA filters, liquid cartridge filters, automobile engine air cleaners, virus/bacteria removing filters, and dry cleaning filters.
- tray liners As food packaging materials, tray liners, towels, wipes, paper towels, dehumidifying materials, antibacterial sheets, mesh caps, etc. can be mentioned.
- Housing materials include desk mats, table mats, table cloths, table decorations, transparent films, place mats, window pasting films, window decoration sheets, window laces, bath curtains, cafe curtains, curtain liners, cushion floors, floor cloths, Floor sheet, joint mat, anti-slip sheet, anti-slip sheet between floor material and leveling material, anti-slip sheet between floor material and mortar, wall decorative sheet, decorative sheet, sitting chair, kotatsu top, panel door, Pet mats, claw scratch protection sheets, pet slopes, rug covers, moisture-permeable waterproof sheets, awnings, awnings, balcony decoration members, house wraps, soil covering materials such as roofing, and the like.
- Kitchen materials include cupboard sheets, refrigerator sheets, mesh cloth, kitchen sheets, etc.
- hats cold clothing
- underwear shirts, briefs, belly rolls, steteco, patches, shorts, girdles, petticoats, leggings, socks, tights, etc.
- sweat clothing used for sports clothing, casual clothing, etc. Examples include sheets.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polymers, block copolymers, and random copolymers were determined by GPC in terms of polystyrene-equivalent molecular weight, and from these values, the molecular weight distribution ( Mw/Mn) was calculated.
- the measuring device and conditions used in GPC are as follows.
- the content of each polymer block in the block copolymer was determined by 1 H-NMR measurement.
- the measuring apparatus and conditions used for 1 H-NMR measurement are as follows. [Apparatus and conditions for 1 H-NMR measurement] ⁇ Apparatus: Nuclear magnetic resonance device "JNM-LA400" manufactured by JEOL Ltd.
- Deuterated solvent In the deuterated chloroform 1 H-NMR spectrum, the signals near 3.6 ppm and 4.0 ppm are the ester group (—O—C H 3 ) of the methyl methacrylate unit and the acrylate ester unit, respectively.
- the laminated body consisting of is cut into a width of 10 mm and a length of 100 mm, laminated on a wooden board stored under humidity control of 40° C. and 90% RH, and then humidified air of 40° C. and 90% RH is supplied from the lower side of the wooden board. After that, the wearability was evaluated in two stages, and the breathability 2 was judged.
- both surfaces of the laminate are structural bodies, so one surface of the structural body is covered with a PET film, and then the other surface of the structural body is attached to a wooden board. After that, the air permeability 2 was judged by the same method as described above. 1. Floating occurs in part. 2. It does not come off and does not come off.
- the obtained laminated body was cut into a width of 10 mm and a length of 100 mm, the surface of the cut-out laminated body having the structure was attached to a glass plate, and reciprocated twice with a 2 kg roller to perform pressure bonding to prepare an evaluation sample. .. After allowing the evaluation sample to stand at room temperature or 70° C. for 24 hours, the laminate was peeled off and the glass surface was visually confirmed. The case where no adhesive residue was found and the adherend (glass plate) was not confirmed to be contaminated was evaluated as “none”, and the adhesive residue was observed and the adherend was confirmed to be contaminated. Yes”.
- the ratio of the through holes in the structure including the base and the through holes was calculated as the porosity. When the porosity was 50% or more, it was judged that the weight reduction was achieved, and was evaluated as “ ⁇ ”. When it was less than 50%, the weight was not reduced, and it was evaluated as “ ⁇ ”.
- test pieces each having a width of 10 mm and a length of 100 mm were cut out from the obtained laminate, the surface of one adhesive layer (structure) was covered with a PET film, and then the other adhesive layers (structure) were joined together. After they were attached so that they overlap, the removability was evaluated by the same method as described above.
- styrene-based triblock copolymer (A-1)) a polystyrene-polyisoprene-polystyrene triblock copolymer (hereinafter, referred to as styrene-based triblock copolymer (A-1)).
- the weight average molecular weight of the obtained styrene-based triblock copolymer (A-1) was 95,000, and the styrene content measured by 1 H-NMR was 18% by mass.
- styrene-based triblock copolymer (A-1) To a reaction mixture containing the styrene-based triblock copolymer (A-1), 90 g of nickel octylate (64% by mass, cyclohexane solution) and 460 g of triisopropylaluminum (20% by mass, cyclohexane solution) were separately prepared. The above hydrogenation catalyst was added, and the hydrogenation reaction was carried out in a hydrogen atmosphere at 80° C. and 1 MPa to obtain a hydrogenated product of the above-mentioned polystyrene-polyisoprene-polystyrene triblock copolymer (hereinafter referred to as styrene-based triblock copolymer). A polymer (I′-1) was obtained.
- the weight average molecular weight of the obtained styrene-based triblock copolymer (I′-1) was 102000, and the styrene content and the hydrogenation rate measured by 1 H-NMR were 17% by mass and 99%, respectively. ..
- Block structures weight average molecular weights (Mw), molecular weight distributions (Mw/Mn), and polymer blocks (of the acrylic triblock copolymers (I-1) to (I-4) obtained in Production Examples 1 to 4 above.
- PMMA is a polymer block composed of 100% by mass of methyl methacrylate unit
- PnBA is a block composed of 100% by mass of n-butyl acrylate unit
- PnBA/P2EHA is a block of butyl acrylate unit and 2-ethylhexyl acrylate. A block consisting of only units.
- tackifying resin ⁇ Product name "Foral 85E” Eastman, hydrogenated rosin ester ⁇ Product name "Foral 105E” Eastman, hydrogenated rosin ester ⁇ Product name "Ysertack 311" Euro Yser, rosin ester Made, rosin ester, trade name "Pensel D125", Arakawa Chemical Industry Co., Ltd., polymerized rosin ester, trade name "YS resin SX100", Yasuhara Chemical Co., aromatic hydrocarbon resin, trade name "Kristalex F100, Eastman, Aromatic hydrocarbon resin, trade name "Arkon P-100", manufactured by Arakawa Chemical Co., Ltd., polymerized alicyclic petroleum resin (plasticizer) ⁇ Product name "Diana Process PW-380" manufactured by Idemitsu Kosan Co., Ltd.; paraffin-based process oil)
- Example 1 [Production of Laminate (II-1) Having Structure Having Base and Through Hole and Base Material] On one surface of a 100 ⁇ m thick polyvinyl chloride (PVC) base film (manufactured by As One Co., Ltd.), a mesh shape 1 (made of the acrylic triblock copolymer (I-1) obtained in Production Example 1 ( Size of through-hole: 800 ⁇ m in length and width, thickness of base: 300 ⁇ m, thickness of 100 ⁇ m) A structure including a base and a through-hole is laminated by a known pattern printing method in which a pattern layer having irregularities is transferred in a molten state. A laminate having (Basis weight: 58 g/m 2 ) and the substrate was produced.
- PVC polyvinyl chloride
- Examples 2 to 4 [Production of a laminate (II-2 to 4) having a structure including a base portion and a through hole and a base material]
- a laminate having a structure including the base and the through holes and a base material was produced. ..
- Example 5 Provide of Laminate (II-5) Having Structure Having Base and Through Holes and Base Material.
- the base material was changed to the base material film made of polyurethane (PU) shown in Table 2 (manufactured by Seadam Co., Ltd., Higres DUS202, thickness 100 ⁇ m), the base portion and the through holes were formed.
- a laminated body having a structure including and a base material was produced.
- Examples 6 to 8 [Production of Laminates (II-6 to 8) Having a Structure Having a Base and Through Holes and a Base Material] Example 1 except that the acrylic triblock copolymer (I-1) was changed to the acrylic triblock copolymers (I-2) to (I-4) obtained in Production Examples 2 to 4. A laminate having a structure including a base portion and a through hole and a base material was produced by a method similar to.
- Examples 9 to 16 [Production of a laminate (II-9 to 16) having a structure including a base and a through hole and a base material]
- the acrylic triblock copolymer (I-1) was changed to the formulations obtained in Formulation Examples 1 to 8 shown in Tables 3 and 4, the base portion and the through holes were prepared.
- a laminated body having a structure including and a base material was produced.
- Example 17 [Production of Laminate (II-17) Having Structure Having Base and Through Holes and Base Material] A structure including a base portion and a through hole was obtained by the same method as in Example 1 except that the base material was changed to the polyester-based non-woven fabric shown in Table 5 (manufactured by Hirose Paper Co., Ltd., 15TH-36, thickness 95 ⁇ m). A laminate having a non-woven fabric substrate was produced.
- Example 18 Provide of Laminate (II-18) Having Structure Having Base and Through Hole and Base Material.
- the acrylic triblock copolymer (I-1) was changed to the acrylic triblock copolymer (I-2) obtained in Production Example 2, the base and A laminate having a structure including through holes and a non-woven fabric substrate was produced.
- Example 19 to 23 [Production of a laminate (II-19 to 23) having a structure including a base and a through hole and a base material]
- the acrylic triblock copolymer (I-1) was changed to the formulations obtained in Formulation Examples 1 to 3, 5, and 7 shown in Tables 3 and 4.
- a laminate having a structure including a base and a through hole and a non-woven fabric substrate was produced.
- Example 24 [Production of Laminate (II-24) Having Structure Having Base and Through Holes and Base Material] A mesh made of the acrylic triblock copolymer (I-1) obtained in Production Example 1 on both sides of a polyvinyl chloride (PVC) base film (made by As One Co., Ltd.) having a thickness shown in Table 7. A pattern layer having irregularities of shape 4 (size of through hole: vertical and horizontal: 800 ⁇ m, thickness of base: 300 ⁇ m, thickness of 100 ⁇ m) is laminated by a known pattern printing method in which it is transferred in a molten state, and is laminated on both sides of the base material. A laminate having a structure (structures 1 and 2) including a base portion and a through hole (basis weight: 58 g/m 2 ) was produced.
- PVC polyvinyl chloride
- Examples 25 and 26>> [Production of a laminate (II-25, 26) having a structure including a base and a through hole and a base material] A laminate having a base film and a structure including a through hole on both sides of the base material in the same manner as in Example 24 except that the base material film made of polyvinyl chloride (PVC) shown in Table 7 and the mesh shape were changed. The body was made.
- PVC polyvinyl chloride
- ⁇ Comparative Example 9>> [Manufacturing of laminated body (III-9) having structure without through hole and substrate] As shown in Table 7, a 100 ⁇ m thick PVC substrate film having a thickness of 100 ⁇ m made of the acrylic triblock copolymer (I-1) obtained in Production Example 1 (area weight: 110 g/m 2 ) of the flat layer was laminated by a known printing method in which the flat layer was transferred in a molten state to prepare a laminated body having a structure having no through holes on both surfaces of the base material.
- the porosity of the structure including the base portion and the through hole was 50% or more in all cases, and it was judged that the structure was lightened, and was designated as “ ⁇ ”. Further, when the removability between the adhesive layers (structures) was evaluated, the adhesive layer did not float at all from the base material and was “A”. In the evaluation of the laminating property 1, wrinkles and bubbles were less likely to enter when laminated to a glass plate, and the laminating could be performed neatly, and the evaluation was “A”.
- the evaluation result of the air permeability 3 is , "3"
- no stuffiness was felt, and it had a dry feeling.
- the adhesive residue on the adherend after standing for 24 hours at room temperature and 70° C. was evaluated, but no adhesive residue was observed and the evaluation was “absent”.
- the porosity of the structure including the base portion and the through hole was 50% or more in all cases, and it was judged that the structure was lightened, and was designated as “ ⁇ ”.
- the adhesive layer did not float at all from the base material and was “A”.
- wrinkles and bubbles were less likely to enter when laminated to a glass plate, and the laminating could be performed neatly, and the evaluation was “A”.
- the porosity of the structure including the base portion and the through hole was 50% or more in all cases, and it was judged that the structure was lightened, and was designated as “ ⁇ ”. Further, when the removability between the adhesive layers (structures) was evaluated, the adhesive layer did not float at all from the base material and was “A”. In the evaluation of the bondability 2, when a multi-layered product of a mortar board/a laminate/a vinyl floor sheet was produced, wrinkles and bubbles were less likely to enter, and it was possible to bond them neatly, and the evaluation was “A”.
- the adhesion was “B” because the adhesive layers slightly floated from the substrate because they adhered on the entire flat surface.
- the evaluation of the bondability 1, wrinkles and air bubbles were formed when it was bonded to a glass plate, and it was difficult to improve even after bonding, and the evaluation was “B”.
- the evaluation result of the air permeability 2 is obtained. Is “1”, and although there is a void, it is a structure including a base portion and a through hole having low air permeability, so that the influence of humidified air is large, and some floating occurs between the structure and the wooden board.
- the adhesive residue on the adherend after standing for 24 hours at room temperature and 70° C. was evaluated. However, the adhesive residue and the plasticizer were contained in large amounts, and some adhesive residue was observed. Was evaluated.
- the evaluation result of the air permeability 3 is “1” for the laminate having the structure not including the through holes and the nonwoven fabric base material, and the void portion is Because there was no swelling, the structure and the body were stuffy, and wrinkles were likely to occur.
- the structure did not have a through hole, which did not lead to weight reduction, it was evaluated as “ ⁇ ”.
- the removability of the adhesive layers (structures) was evaluated.
- the adhesion was “B” because the adhesive layers slightly floated from the substrate because they adhered on the entire flat surface. In the evaluation of the bondability 1, wrinkles and air bubbles were formed when it was bonded to a glass plate, and it was difficult to improve even after bonding, and the evaluation was “B”.
- the evaluation result of the air permeability 3 is: It was "2", and although there were voids, wrinkles were felt, although wrinkles did not occur between the structure and the body due to the structure including a base portion and a through hole having low air permeability.
- the adhesive residue on the adherend after standing for 24 hours at room temperature and 70° C. was evaluated. However, the adhesive residue and the plasticizer were contained in large amounts, and some adhesive residue was observed. Was evaluated.
- the adhesive layer slightly floated from the base material and was “B”.
- the evaluation of the laminating property 1 wrinkles and bubbles were less likely to enter when laminated to a glass plate, and the laminating could be performed neatly, and the evaluation was “A”.
- the base of the present invention containing the acrylic triblock copolymer (I) and containing no tackifying resin, or the acrylic triblock copolymer (I) and the tackifying resin at a predetermined mass ratio. It can be seen that the laminated body having the base containing and the structure including the through hole and the base material has both visco-adhesiveness and removability, is suppressed in adhesive residue, and exhibits excellent laminating property. ..
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
この手間がかかる問題を解消する一手段として、基材シートの片側表面または両側表面に、1層以上の貫通孔を有する熱可塑性エラストマー層がモールド印刷成型された積層体が提案されている(例えば、特許文献1参照)。
また板状体等の構造体がエラストマーから作製される場合、その軟質性から、粘接着性能が期待される性能の1つである。エラストマーをその材料として用いた場合、位置合わせをする必要性等から、被着体に対しての粘接着性だけでなく、被着体と構造体、または構造体同士の再剥離性が求められる場合があり、またこの再剥離等の際に糊残りしないことや、構造体が基材から剥がれにくい等の性能が求められる場合がある。
本発明の目的は、粘接着性と再剥離性が両立可能であり、糊残りの抑制が可能であり、貼合性にも優れた、基部および貫通孔を含む構造体と基材とを有する積層体を提供することである。
[1]基材と、その基材の少なくとも一方の表面に設けられた基部および貫通孔を含む構造体とを有する積層体であり、
該構造体の基部が、メタクリル酸エステル単位からなる2つの重合体ブロック(A1)および(A2)と、一般式CH2=CH-COOR1(1)(式中、R1は炭素数4~12の有機基を表す)で示されるアクリル酸エステル単位を含む1つの重合体ブロック(B)とからなり、(A1)-(B)-(A2)ブロック構造を有し、重量平均分子量が50,000~250,000であり、重合体ブロック(A1)および(A2)の合計含有量が35質量%以下であるアクリル系トリブロック共重合体(I)を含有しかつ粘着付与樹脂を含有しない、積層体、
[2]基材と、その基材の少なくとも一方の表面に設けられた基部および貫通孔を含む構造体とを有する積層体であり、
該構造体の基部が、メタクリル酸エステル単位からなる2つの重合体ブロック(A1)および(A2)と、一般式CH2=CH-COOR1(1)(式中、R1は炭素数4~12の有機基を表す)で示されるアクリル酸エステル単位を含む1つの重合体ブロック(B)とからなり、(A1)-(B)-(A2)ブロック構造を有し、重量平均分子量が50,000~250,000であり、重合体ブロック(A1)および(A2)の合計含有量が35質量%以下であるアクリル系トリブロック共重合体(I)および粘着付与樹脂を含有し、粘着付与樹脂/アクリル系トリブロック共重合体(I)の質量比が20/100以下である、積層体、
等により達成される。
上記構造体は、網目状に連続したアクリル系トリブロック共重合体(I)からなる基部および貫通孔から形成されていることが好ましい態様である。このような構造を有することで、通気性により優れるだけでなく、粘接着性と再剥離性との両立により優れる。また、糊残りの抑制や貼合性にもより優れる。
上記網目状となる形状としては、例えば、メッシュ形状、ハニカム形状、ウロコ形状、タイル形状等が挙げられる。また、上記構造体の形状としては、貫通孔が離散的に設けられたドット形状、縞形状等であってもよい。
アクリル系トリブロック共重合体(I)が構造体の基部を形成していることにより、粘接着性に優れるだけでなく、再剥離性にも優れる構造体を有する積層体が得られる。
アクリル系トリブロック共重合体(I)は、メタクリル酸エステル単位からなる重合体ブロック(A1)および(A2)の2つのメタクリル酸エステル単位からなる重合体ブロックを有する。
アクリル系トリブロック共重合体(I)は、一般式CH2=CH-COOR1(1)(式中、R1は炭素数4~12の有機基を表す)で示されるアクリル酸エステル単位(以下、アクリル酸エステル(1)単位ともいう。)を含む、1つの重合体ブロック(B)を1つ有する。重合体ブロック(B)にアクリル酸エステル(1)単位が含まれることにより、再剥離性が良好で、再剥離等の際の糊残りが抑制しやすい積層体が得られる。
AlR2R3R4 (2)
(式(2)中、R2、R3およびR4はそれぞれ独立して置換基を有してもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有してもよいアリール基、置換基を有していてもよいアラルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基またはN,N-二置換アミノ基を表すか、あるいはR2が上記したいずれかの基であり、R3およびR4が一緒になって置換基を有していてもよいアリーレンジオキシ基を形成している。)で表される有機アルミニウム化合物が挙げられる。
(1)アクリル系トリブロック共重合体(I)を含む配合物を溶融押出して長繊維を作製し、この長繊維から短繊維の集合物を作製し、これら短繊維の集合物を接着剤または熱により圧着して構造体を作製する方法。
(2)アクリル系トリブロック共重合体(I)を含む配合物の溶融物から、メルトブロー法により、構造体を作製する方法。
(3)凹凸を備えたパターン層を有する基盤上にアクリル系トリブロック共重合体(I)を含む配合物の溶融物を塗布する、若しくは基盤上で配合物を溶融させた後に基部および貫通孔を含む物を基板上から剥離することにより、構造体を作製する方法(パターン印刷法)。
上記積層体としては、例えば、基部および貫通孔を含む上記構造体/基材からなる2層の積層体;基部および貫通孔を含む上記構造体/基材/基部および貫通孔を含む上記構造体からなる3層の積層体;基部および貫通孔を含む上記構造体/基材/基部および貫通孔を含む上記構造体/基材からなる4層の積層体;基部および貫通孔を含む上記構造体/基材/基部および貫通孔を含む上記構造体/基材/基部および貫通孔を含む上記構造体からなる5層の積層体;基材/基部および貫通孔を含む上記構造体/基材からなる3層の積層体;等が挙げられる。
また、本発明の積層体において、基部および貫通孔を含む上記構造体が最外層を形成する場合は、その外側に、例えば、ポリエチレン、ポリプロピレンフィルム、離型処理されたPETフィルム、離型紙、等の剥離層を設けてもよい。
その他の繊維質材料としては、例えば、綿、麻、絹、羊毛等の天然繊維;ガラスファイバー、炭素繊維等の無機繊維;等が挙げられる。これら繊維質材料から作製された織布が作製できるが、織布としては、織物、編物等が挙げられる。また、これら繊維質材料から、機械的方法、化学的方法、あるいはこれら方法を組み合わせることにより不織布を作製できる。
(1)基部および貫通孔を含む構造体を、接着剤または熱により基材に圧着して積層体を製造する方法。
(2)上記メルトブロー法により、基材上に直接基部となる材料をメルトブローすることにより、積層体を製造する方法。
(3)凹凸を備えたパターン層を有する基盤上にアクリル系トリブロック共重合体(I)を含む配合物の溶融物を塗布した後、若しくは基盤上で配合物を溶融させた後に基部および貫通孔を含む物を基板上から剥離した後、溶融状態で基材に転写することにより積層体を製造する方法。
[GPC測定の装置および条件]
・装置:東ソー株式会社製GPC装置「HLC-8020」
・分離カラム:東ソー株式会社製「TSKgel GMHXL」、「G4000HXL」および「G5000HXL」を直列に連結
・溶離剤:テトラヒドロフラン
・溶離剤流量:1.0ml/分
・カラム温度:40℃
・検出方法:示差屈折率(RI)
[1H-NMR測定の装置および条件]
・装置:日本電子株式会社製核磁気共鳴装置「JNM-LA400」
・重溶媒:重水素化クロロホルム
1H-NMRスペクトルにおいて、3.6ppmおよび4.0ppm付近のシグナルは、それぞれ、メタクリル酸メチル単位のエステル基(-O-CH 3)およびアクリル酸エステル単位のエステル基(-O-CH 2-CH2-CH2-CH3または-O-CH 2-CH(-CH2-CH3)-CH2-CH2-CH2-CH3)に帰属され、その積分値の比によって各重合体ブロックの含有量を求めた。重合体ブロック(B)の重合に用いた混合単量体の1H-NMRスペクトルにおいて、4.0ppmおよび4.1ppm付近のシグナルは、それぞれ、アクリル酸n-ブチルのエステル基(-O-CH 2-CH2-CH2-CH3)およびアクリル酸2-エチルヘキシルのエステル基(-O-CH 2-CH(-CH2-CH3)-CH2-CH2-CH2-CH3)に帰属され、その積分値の比によって各単量体のモル比による含有量を求め、これを、単量体単位の分子量を基に質量比に換算し、重合体ブロック(B)を構成する単量体の質量比とした。
厚さ95μmのポリエステル系不織布(廣瀬製紙株式会社製、15TH-36)からなる基材の片面に、製造例1~4のアクリル系トリブロック共重合体、および配合例1~10の配合物の厚さ100μmの平面層を溶融状態で転写する公知の印刷法により積層し、貫通孔を含まない構造体を有する積層体を作製し、40℃、90%RHの雰囲気下で、JISZ0208(B法)に準拠して測定することで、アクリル系トリブロック共重合体自身、配合物自身の通気性を評価した。
実施例1~16、24~26、比較例1、3~4、9で得られた基部および貫通孔を含む構造体(または貫通孔を含まない構造体)と貫通孔を有さない基材からなる積層体を幅10mm、長さ100mmに切り出し、40℃、90%RHの調湿下に保管した木板上に貼り合わせた後、木板下側から40℃、90%RHの加湿空気を供給した後の装着性を2段階で感性評価を行い、通気性2を判断した。なお、実施例24~26、比較例9では、積層体の両面が構造体のため、一方の構造体の表面を、PETフィルムでカバーした後、他方の面の構造体を木板上に貼り合わせた後、上述と同様の手法で通気性2を判断した。
1.一部で浮きが発生する。
2.浮きが発生することなく、剥がれない。
実施例17~23、比較例5、7~8で得られた基部および貫通孔を含む構造体と不織布基材とを有する積層体を身体に装着し、かいた汗による蒸れ性を3段階で感性評価を行った。
1.蒸れが大きく、皺が発生しやすい
2.蒸れは感じられるが、皺の発生までは起きない。
3.蒸れが感じられず、さらさら感を有する。
得られた積層体を幅10mm、長さ100mmに切り出し、この切り出した積層体の構造体を有する側の面をガラス板に貼り合わせ、2kgローラで2往復させて圧着し評価用サンプルを作製した。評価用サンプルを室温、または70℃で24時間静置した後に積層体をはがし、ガラス表面を目視確認した。糊残り等は見られず、被着体(ガラス板)の汚染が確認されなかった場合を「無」と評価し、糊残り等は見られ、被着体の汚染が確認された場合を「有」と評価した。
基部および貫通孔を含む構造体における、貫通孔が占める割合を空隙率として算出した。空隙率が50%以上の場合は軽量化で来ていると判断し、「○」と評価した。50%未満の場合は、軽量化できておらず、「△」と評価した。
実施例1~23、比較例1~8では、得られた積層体から幅10mm、長さ100mmの試験片を2枚切り出し、これら試験片を粘着層(構造体)同士が重なるように貼り合わせ、2kgローラで2往復させてこれら試験片を圧着させた。その後、手でこれら試験片を引き剥がした際の粘着層の状態を確認した。基材からの浮きが全く発生しなかった場合を「A」、少しでも浮きが確認された場合を「B」と評価した。
実施例24~26、比較例9では、積層体の両面が粘着層(構造体)であるため、以下のようにして再剥離性の評価を行った。すなわち、得られた積層体から幅10mm、長さ100mmの試験片を2枚切り出し、一方の粘着層(構造体)の表面を、PETフィルムでカバーした後、他方の粘着層(構造体)同士が重なるように貼り合わせた後、上述と同様の手法で再剥離性を評価した。
実施例1~23、比較例1~8で得られた積層体から幅200mm、長さ300mmの試験片を切り出し、試験片の基部および貫通孔を含む構造体を有する側の面をガラス板に貼り合わせた時の貼合性を評価した。しわや気泡が入りにくく、きれいに貼合せできる場合を「A」、皺や気泡が入り、貼合せ後も改善されない場合を「B」と評価した。
実施例24~26、比較例9で得られた積層体から幅1000mm、長さ1000mmの試験片を切り出し、この試験片の片面の構造体(構造体1)にモルタル板(幅1000mm、長さ1000mm、厚さ10mm)を貼り合わせ、さらにその試験片の反対側の構造体(構造体2)にビニル床シート(幅1000mm、長さ1000mm、厚さ10mm)を貼り合わせることで、モルタル板/積層体/ビニル床シートの複層物を作製し、その際の貼合性を評価した。しわや気泡が入りにくく、きれいに貼合せできる場合を「A」、しわや気泡が入り、貼合せ後も改善されない場合を「B」と評価した。
モルタル板(幅1000mm、長さ1000mm、厚さ10mm)の代わりに、レベリング材(商品名「床レベラーG」宇部興産建材株式会社製)で表面処理されたコンクリート板(幅1000mm、長さ1000mm、厚さ10mm)を用い、コンクリート板の表面処理された面と試験片の片面とを貼り合わせる以外は貼合性2の試験と同様にして、レベリング材で表面処理されたコンクリート板/積層体/ビニル床シートの複層物を作製し、その際の貼合性を評価した。しわや気泡が入りにくく、きれいに貼合せできる場合を「A」、しわや気泡が入り、貼合せ後も改善されない場合を「B」と評価した。
貼合性2、および貼合性3の評価の際に作製したモルタル板/積層体/ビニル床シートの複層物、およびレベリング材で表面処理されたコンクリート板/積層体/ビニル床シートの複層物に対して、ビニル床シート側から、単輪旋回キャスターを用いて、体重90kgに相当する荷重をかけ、ランダムな方向にキャスターを2000回動かした後、複層物からビニル床シートおよびモルタル板またはレベリング材で表面処理されたコンクリート板をはがし、モルタル板、コンクリート板、ビニル床シート表面を目視確認した。糊残り等は見られず、被着体(モルタル板、レベリング材で表面処理されたコンクリート板、ビニル床シート)への汚染が確認されなかった場合を「無」と評価し、汚染等が見られた場合を「有」と評価した。
(1)3Lの三口フラスコに三方コックを付け内部を窒素で置換した後、室温で撹拌しながら、トルエン1302gと1,2-ジメトキシエタン65.1gを加え、続いて、イソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウム60.3mmolを含有するトルエン溶液120.0gを加え、さらにsec-ブチルリチウム7.50mmolを含有するsec-ブチルリチウムのシクロヘキサン溶液4.34gを加えた。
(2)続いて、これにメタクリル酸メチル53.9gを撹拌下室温で加えさらに60分間撹拌を続けた。反応液は当初、黄色に着色していたが、60分間撹拌後には無色となった。
(3)その後、重合液の内部温度を-30℃に冷却し、撹拌下アクリル酸n-ブチル360gを2時間かけて滴下し、滴下終了後-30℃でさらに5分間撹拌を続けた。
(4)その後、これにメタクリル酸メチル53.9gを加え、一晩室温で撹拌した。
(5)メタノ-ル20gを添加して重合反応を停止した後、得られた反応液を撹拌下15kgのメタノール中に注ぎ、白色沈殿物を析出させた。得られた白色沈殿物を回収し、乾燥させることにより、アクリル系トリブロック共重合体(I-1)440gを得た。得られたアクリル系トリブロック共重合体(I-1)の重量平均分子量(Mw)および数平均分子量(Mn)を上述の方法でGPC測定により求め、これら値から(Mw/Mn)を算出した。また、上述した1H-NMR測定により、アクリル系トリブロック共重合体(I-1)中のメタクリル酸メチル単位からなる重合体ブロックの合計含有量を求めた。アクリル系トリブロック共重合体(I-1)の性状を表1に示す。
(1)3Lの三口フラスコに三方コックを付け内部を窒素で置換した後、室温で撹拌しながら、トルエン1409gと1,2-ジメトキシエタン32.7gを加え、続いて、イソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウム24.5mmolを含有するトルエン溶液48.6gを加え、さらにsec-ブチルリチウム4.35mmolを含有するsec-ブチルリチウムのシクロヘキサン溶液2.55gを加えた。
(2)続いて、これにメタクリル酸メチル43.5gを撹拌下室温で加えさらに60分間撹拌を続けた。反応液は当初、黄色に着色していたが、60分間撹拌後には無色となった。
(3)その後、重合液の内部温度を-30℃に冷却し、撹拌下アクリル酸n-ブチル360gを2時間かけて滴下し、滴下終了後-30℃でさらに5分間撹拌を続けた。
(4)その後、これにメタクリル酸メチル61.5gを加え、一晩室温で撹拌した。
(5)メタノ-ル15gを添加して重合反応を停止した後、得られた反応液を撹拌下15kgのメタノール中に注ぎ、白色沈殿物を析出させた。得られた白色沈殿物を回収し、乾燥させることにより、アクリル系トリブロック共重合体(I-2)450gを得た。得られたアクリル系トリブロック共重合体(I-2)の重量平均分子量(Mw)および数平均分子量(Mn)を上述の方法でGPC測定により求め、これら値から(Mw/Mn)を算出した。また、上述した1H-NMR測定により、アクリル系トリブロック共重合体(I-2)中のメタクリル酸メチル単位からなる重合体ブロックの合計含有量を求めた。アクリル系トリブロック共重合体(I-2)の性状を表1に示す。
(1)3Lの三口フラスコに三方コックを付け内部を窒素で置換した後、室温で撹拌しながら、トルエン1409gと1,2-ジメトキシエタン32.7gを加え、続いて、イソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウム24.5mmolを含有するトルエン溶液48.6gを加え、さらにsec-ブチルリチウム3.15mmolを含有するsec-ブチルリチウムのシクロヘキサン溶液1.85gを加えた。
(2)続いて、これにメタクリル酸メチル32.6gを撹拌下室温で加えさらに60分間撹拌を続けた。反応液は当初、黄色に着色していたが、60分間撹拌後には無色となった。
(3)その後、重合液の内部温度を-30℃に冷却し、撹拌下アクリル酸n-ブチル410gを2時間かけて滴下し、滴下終了後-30℃でさらに5分間撹拌を続けた。
(4)その後、これにメタクリル酸メチル45.3gを加え、一晩室温にて撹拌した。
(5)メタノ-ル15gを添加して重合反応を停止した後、得られた反応液を撹拌下15kgのメタノール中に注ぎ、白色沈殿物を析出させた。その後、白色沈殿物を回収し、乾燥させることにより、アクリル系トリブロック共重合体(I-3)445gを得た。得られたアクリル系トリブロック共重合体(I-3)の重量平均分子量(Mw)および数平均分子量(Mn)を上述の方法でGPC測定により求め、これら値から(Mw/Mn)を算出した。また、上述した1H-NMR測定により、アクリル系トリブロック共重合体(I-3)中のメタクリル酸メチル単位からなる重合体ブロックの合計含有量を求めた。アクリル系トリブロック共重合体(I-3)の性状を表1に示す。
(1)3Lの三口フラスコに三方コックを付け内部を窒素で置換した後、室温で撹拌しながら、トルエン1038gと1,2-ジメトキシエタン43.5gを加え、続いて、イソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウム18.8mmolを含有するトルエン溶液37.4gを加え、さらにsec-ブチルリチウム4.95mmolを含有するsec-ブチルリチウムのシクロヘキサン溶液2.90gを加えた。
(2)続いて、これにメタクリル酸メチル25.4gを撹拌下室温で加えさらに60分間撹拌を続けた。反応液は当初、黄色に着色していたが、60分間撹拌後には無色となった。
(3)その後、重合液の内部温度を-30℃に冷却し、撹拌下アクリル酸n-ブチル/アクリル酸2-エチルヘキシルの混合物(質量比50/50)215gを2時間かけて滴下し、滴下終了後-30℃でさらに5分間撹拌を続けた。
(4)その後、これにメタクリル酸メチル29.4gを加え、一晩室温にて撹拌した。
(5)メタノ-ル15gを添加して重合反応を停止した後、得られた反応液を撹拌下15kgのメタノール中に注ぎ、白色沈殿物を析出させた。その後、白色沈殿物を回収し、乾燥させることにより、アクリル系トリブロック共重合体(I-4)250gを得た。得られたアクリル系トリブロック共重合体(I-4)の重量平均分子量(Mw)および数平均分子量(Mn)を上述の方法でGPC測定により求め、これら値から(Mw/Mn)を算出した。また、上述した1H-NMR測定により、アクリル系トリブロック共重合体(I-4)中のメタクリル酸メチル単位からなる重合体ブロックの合計含有量、アクリル酸n-ブチル/アクリル酸2-エチルヘキシルの質量比を求めた。アクリル系トリブロック共重合体(I-4)の性状を表1に示す。
撹拌装置付き耐圧容器中に、シクロヘキサン23kg、sec-ブチルリチウム(11質量%、シクロヘキサン溶液)99mlを加え、この溶液にスチレン467gを30分かけて加えて50℃で30分間重合した。続いてイソプレン6380gを60分かけて加えて50℃で90分間重合した。その後、さらにスチレン467gを30分かけて加えて50℃で30分間重合し、ポリスチレン-ポリイソプレン-ポリスチレントリブロック共重合体(以下、これをスチレン系トリブロック共重合体(A-1)と称する)を含む反応混合液を得た。得られたスチレン系トリブロック共重合体(A-1)の重量平均分子量は95000であり、1H-NMRによって測定したスチレン含有量は18質量%であった。
かかるスチレン系トリブロック共重合体(A-1)を含む反応混合液に、オクチル酸ニッケル(64質量%、シクロヘキサン溶液)90gにトリイソプロピルアルミニウム(20質量%、シクロヘキサン溶液)460gを加えて別途調製した水素添加触媒を添加し、80℃、1MPaの水素雰囲気下で水素添加反応を行い、上記したポリスチレン-ポリイソプレン-ポリスチレントリブロック共重合体の水素添加物(以下、これをスチレン系トリブロック共重合体(I'-1)と称する)を得た。得られたスチレン系トリブロック共重合体(I'-1)の重量平均分子量は102000であり、1H-NMRによって測定したスチレン含有量および水素添加率はそれぞれ17質量%、99%であった。
窒素置換した四口フラスコに、アクリル酸n-ブチル96質量部と、アクリル酸4質量部とを、酢酸エチルおよびトルエンの50:50溶媒30質量部中で共重合し、重量平均分子量(Mw)550,000のアクリル系ランダム共重合体(B)溶液を得た。これに酢酸エチルを加えて、アクリル系ランダム共重合体(B)を30重量%含む溶液を得た。
(粘着付与樹脂)
・商品名「Foral 85E」Eastman製、水添ロジンエステル
・商品名「Foral 105E」Eastman製、水添ロジンエステル
・商品名「Ysertack 311」Euro Yser製、ロジンエステル
・商品名「Ysertack 313」Euro Yser製、ロジンエステル
・商品名「Pensel D125」荒川化学工業株式会社製、重合ロジンエステル
・商品名「YS resin SX100」ヤスハラケミカル株式会社製、芳香族炭化水素系樹脂
・商品名「Kristalex F100」Eastman製、芳香族炭化水素系樹脂
・商品名「Arkon P-100」荒川化学工業株式会社製、重合脂環族系石油樹脂(可塑剤)
・商品名「ダイアナプロセスPW-380」出光興産株式会社製;パラフィン系プロセスオイル)
170℃に設定したニーダーに、表3、4または6に記載の配合比に基づき製造例1~4で得られたアクリル系トリブロック共重合体(I-1~4)を投入して均一に溶融させた。その後、そのニーダーの温度を155℃に設定し、粘着付与樹脂を表3または4に記載の配合比に基づき添加し、均一になるまで溶融混練させて配合物を得た。
170℃に設定したニーダーに、表4に記載の所定量の製造例5で得られたスチレン系トリブロック共重合体(I-5)を投入して均一に溶融させた。その後、そのニーダーの温度を160℃に設定し、粘着付与樹脂、可塑剤を表4に記載の配合比に基づき添加し、均一になるまで溶融混練させて配合物を得た。
厚さ100μmのポリ塩化ビニル(PVC)製の基材フィルム(アズワン株式会社製)の片面に、製造例1で得られたアクリル系トリブロック共重合体(I-1)からなるメッシュ形状1(貫通孔の大きさ:縦横800μm、基部の太さ:300μm、厚さ100μm)の凹凸を備えたパターン層を溶融状態で転写する公知のパターン印刷法により積層し、基部および貫通孔を含む構造体(目付量:58g/m2)と基材とを有する積層体を作製した。
貫通孔の形状を、表2に記載のメッシュ形状2~4に変更した以外は、実施例1と同様の手法により、基部および貫通孔を含む構造体と基材とを有する積層体を作製した。
基材を、表2に記載のポリウレタン(PU)製の基材フィルム(シーダム株式会社製、ハイグレスDUS202、厚さ100μm)に変更した以外は、実施例1と同様の手法により、基部および貫通孔を含む構造体と基材とを有する積層体を作製した。
アクリル系トリブロック共重合体(I-1)を、製造例2~4で得られたアクリル系トリブロック共重合体(I-2)~(I-4)に変更した以外は、実施例1と同様の手法により、基部および貫通孔を含む構造体と基材とを有する積層体を作製した。
アクリル系トリブロック共重合体(I-1)を、表3、4に記載の配合例1~8で得られる配合物に変更した以外は、実施例1と同様の手法により、基部および貫通孔を含む構造体と基材とを有する積層体を作製した。
基材を表5に記載のポリエステル系不織布(廣瀬製紙株式会社製、15TH-36、厚さ95μm)に変更した以外は、実施例1と同様の手法により、基部および貫通孔を含む構造体と不織布基材とを有する積層体を作製した。
アクリル系トリブロック共重合体(I-1)を、製造例2で得られたアクリル系トリブロック共重合体(I-2)に変更した以外は、実施例17と同様の手法により、基部および貫通孔を含む構造体と不織布基材とを有する積層体を作製した。
アクリル系トリブロック共重合体(I-1)を、表3、4に記載の配合例1~3、5、7で得られる配合物に変更した以外は、実施例17と同様の手法により、基部および貫通孔を含む構造体と不織布基材とを有する積層体を作製した。
表7に記載の厚みのポリ塩化ビニル(PVC)製の基材フィルム(アズワン株式会社製)の両面に、製造例1で得られたアクリル系トリブロック共重合体(I-1)からなるメッシュ形状4(貫通孔の大きさ:縦横800μm、基部の太さ:300μm、厚さ100μm)の凹凸を備えたパターン層を溶融状態で転写する公知のパターン印刷法により積層し、基材の両面に基部および貫通孔を含む構造体(構造体1および2)(目付量:58g/m2)を有する積層体を作製した。
表7に記載のポリ塩化ビニル(PVC)製の基材フィルム、メッシュ形状を変更した以外は、実施例24と同様の手法により、基材の両面に基部および貫通孔を含む構造体を有する積層体を作製した。
厚さ100μmのPVC製の基材フィルムの片面に、製造例1で得られたアクリル系トリブロック共重合体(I-1)からなる厚さ100μm(目付量:110g/m2)の平面層を溶融状態で転写する公知の印刷法により積層し、貫通孔を含まない構造体と基材とを有する積層体を作製した。
メッシュ形状1(貫通孔の大きさ:縦横800μm、基部の太さ:300μm)の凹凸を備えたパターン層を有する基盤上に製造例6で得られたアクリル系ランダム共重合体(B)の溶液をバーコーターを用いて溶液塗布した後、100℃、3分間、熱風乾燥機を用いて乾燥した。得られた構造体を厚さ100μmのPVC製の基材フィルムに公知のパターン印刷法により転写を試みたが転写させることができなかった。
アクリル系トリブロック共重合体(I-1)を、表4に記載の配合例10で得られる配合物に変更した以外は、実施例1と同様の手法により、基部および貫通孔を含む構造体と基材とを有する積層体を作製した。
アクリル系トリブロック共重合体(I-1)を、表4に記載の配合例9で得られた配合物に変更した以外は、実施例1と同様の手法により、基部および貫通孔を含む構造体と基材とを有する積層体を作製した。
基材を表6に記載のポリエステル系不織布(廣瀬製紙株式会社製、15TH-36、厚さ95μm)に変更した以外は、比較例1と同様の手法により、貫通孔含まない構造体と不織布基材とを有する積層体を作製した。
基材を表6に記載のポリエステル系不織布(廣瀬製紙株式会社製、15TH-36、厚さ95μm)に変更した以外は、比較例2と同様の手法を試みたが、比較例2と同様に、転写させることができなかった。
アクリル系トリブロック共重合体(I-1)を、表4に記載の配合例10で得られる配合物に変更した以外は、実施例17と同様の手法により、基部および貫通孔を含む構造体と不織布基材とを有する積層体を作製した。
基材を表6に記載のポリエステル系不織布(廣瀬製紙株式会社製、15TH-36、厚さ95μm)に、配合物を表6に記載の配合例11で得られる配合物に変更した以外は、比較例4と同様の手法により、基部および貫通孔を含む構造体と不織布基材とを有する積層体を作製した。
表7に記載のように、厚さ100μmのPVC製の基材フィルムの両面に、製造例1で得られたアクリル系トリブロック共重合体(I-1)からなる厚さ100μm(目付量:110g/m2)の平面層を溶融状態で転写する公知の印刷法により積層し、基材の両面に貫通孔を含まない構造体を有する積層体を作製した。
Claims (2)
- 基材と、その基材の少なくとも一方の表面に設けられた基部および貫通孔を含む構造体とを有する積層体であり、
該構造体の基部が、メタクリル酸エステル単位からなる2つの重合体ブロック(A1)および(A2)と、一般式CH2=CH-COOR1(1)(式中、R1は炭素数4~12の有機基を表す)で示されるアクリル酸エステル単位を含む1つの重合体ブロック(B)とからなり、(A1)-(B)-(A2)ブロック構造を有し、重量平均分子量が50,000~250,000であり、重合体ブロック(A1)および(A2)の合計含有量が35質量%以下であるアクリル系トリブロック共重合体(I)を含有し、かつ粘着付与樹脂を含有しない、積層体。 - 基材と、その基材の少なくとも一方の表面に設けられた基部および貫通孔を含む構造体とを有する積層体であり、
該構造体の基部が、メタクリル酸エステル単位からなる2つの重合体ブロック(A1)および(A2)と、一般式CH2=CH-COOR1(1)(式中、R1は炭素数4~12の有機基を表す)で示されるアクリル酸エステル単位を含む1つの重合体ブロック(B)とからなり、(A1)-(B)-(A2)ブロック構造を有し、重量平均分子量が50,000~250,000であり、重合体ブロック(A1)および(A2)の合計含有量が35質量%以下であるアクリル系トリブロック共重合体(I)および粘着付与樹脂を含有し、粘着付与樹脂/アクリル系トリブロック共重合体(I)の質量比が20/100以下である、積層体。
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JP (1) | JPWO2020138237A1 (ja) |
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EP3904480A1 (en) | 2021-11-03 |
CN113227288A (zh) | 2021-08-06 |
KR20210108953A (ko) | 2021-09-03 |
US20220055361A1 (en) | 2022-02-24 |
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EP3904480A4 (en) | 2022-08-24 |
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