WO2022265077A1 - 粘着フィルム、積層体、液晶ディスプレイ及び合わせガラス - Google Patents
粘着フィルム、積層体、液晶ディスプレイ及び合わせガラス Download PDFInfo
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- WO2022265077A1 WO2022265077A1 PCT/JP2022/024194 JP2022024194W WO2022265077A1 WO 2022265077 A1 WO2022265077 A1 WO 2022265077A1 JP 2022024194 W JP2022024194 W JP 2022024194W WO 2022265077 A1 WO2022265077 A1 WO 2022265077A1
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- Prior art keywords
- adhesive film
- resin
- group
- polyvinyl acetal
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- C—CHEMISTRY; METALLURGY
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- 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
- C09J2431/00—Presence of polyvinyl acetate
Definitions
- the present invention relates to an adhesive film, a laminate including the adhesive film, and a liquid crystal display and laminated glass including the laminate.
- Adhesive films are widely used to superimpose and fix surface protection panels, polarizing plates, films with touch sensors, glass with touch sensors, etc. in various displays such as liquid crystal displays, organic EL displays, and displays with touch panels.
- (meth)acrylic resins have been widely used as adhesive films from the viewpoints of transparency, adhesiveness, and the like.
- polyvinyl acetal resins has also been investigated.
- various members may be attached to the surface protection panel, laminated glass member, light control film, etc., and there is a step on the adhesive surface with the adhesive film.
- Sometimes for example, in an in-vehicle display, there is a so-called black ceramic step on the glass side constituting the surface protection panel. Therefore, in the bonding process using the adhesive film, the conformability of the adhesive film to unevenness is important.
- the plasticizer may bleed from the adhesive film during storage of the adhesive film, leading to contamination of the working environment. Furthermore, it is desirable to be able to recycle the adhesive film in order to reduce the burden on the environment.
- an object of the present invention is to provide a pressure-sensitive adhesive film excellent in step followability, bleeding property, and recyclability, a laminate comprising the pressure-sensitive adhesive film, and a liquid crystal display and laminated glass including the laminate.
- the present invention provides the following [1] to [32].
- thermoplastic resin has a weight average molecular weight (Mw) of 600,000 or less.
- Mw weight average molecular weight
- thermoplastic resin has a weight average molecular weight (Mw) of 600,000 or less.
- Mw weight average molecular weight
- the pressure-sensitive adhesive film according to [1] or [2] above which has a thickness of 100 ⁇ m or more and 2000 ⁇ m or less.
- thermoplastic resin is a polyvinyl acetal resin.
- the polyalkylene oxide structure is linked to the main chain via a single bond, or an ether bond, an ester bond, an amide bond, or a hydrocarbon group which may have at least one of these bonds.
- the adhesive film contains, as a plasticizer, an ester of a glycol and a monobasic organic acid, an ester compound of a dibasic organic acid having 4 to 12 carbon atoms and an alcohol having 4 to 10 carbon atoms, and a polyalkylene
- a laminate comprising the adhesive film according to any one of [1] to [23] above and a pair of substrates, wherein the adhesive film is disposed between the pair of substrates.
- a liquid crystal display comprising the laminate according to any one of [24] to [28] above.
- a laminated glass comprising the laminate according to any one of [24] to [28] above.
- a pressure-sensitive adhesive film excellent in step followability, bleeding property, and recyclability a laminate comprising the pressure-sensitive adhesive film, and a liquid crystal display and laminated glass including the laminate.
- FIG. 5 is a cross-sectional view showing a laminate according to a second embodiment; It is a sectional view showing a layered product concerning a 3rd embodiment. It is a sectional view showing a layered product concerning a 4th embodiment.
- the pressure-sensitive adhesive film of the present invention contains a thermoplastic resin, has a shear storage modulus at 85° C. of 0.06 ⁇ 10 6 Pa or more and 1.00 ⁇ 10 6 Pa or less, and does not contain a plasticizer, or contains a thermoplastic resin. It contains less than 20 parts by mass of the plasticizer per 100 parts by mass, and has a gel fraction of 15% or less.
- the pressure-sensitive adhesive film of the present invention having the above configuration can improve step followability, bleeding property, and recyclability.
- the pressure-sensitive adhesive film of the present invention has a shear storage elastic modulus at 85°C of 0.06 x 10 6 Pa or more and 1.00 x 10 6 Pa or less. If the shear storage elastic modulus is less than 0.06 ⁇ 10 6 Pa, foaming may occur during application, resulting in poor application properties. When the shear storage modulus is more than 1.00 ⁇ 10 6 Pa, the conformability of the pressure-sensitive adhesive film to steps becomes poor, air bubbles remain in the step portions, and the visibility and adhesion may deteriorate. From the viewpoint of adhesion of the adhesive film, the shear storage elastic modulus at 85° C. is preferably 0.08 ⁇ 10 6 Pa or more, more preferably 0.09 ⁇ 10 6 Pa or more.
- the shear storage modulus of the adhesive film at 85°C is preferably 0.70 x 106 Pa or less, more preferably 0.50 x 106 Pa or less, and even more preferably 0.30 x 106 Pa or less.
- the shear storage modulus can be measured by performing viscoelasticity measurement in shear mode using a dynamic viscoelasticity measuring device at a frequency of 1 Hz, and detecting the storage modulus (G') at 85°C.
- the adhesive film of the present invention has a gel fraction of 15% or less. If the gel fraction is more than 15%, the recyclability of the adhesive film will deteriorate. That is, if the gel fraction is greater than 15%, when the used adhesive film is recycled and used again as an adhesive film, the gel content becomes an optical defect in the adhesive film, resulting in many optical defects. In some cases, the recycled adhesive film cannot be used for applications such as displays and laminated glass. From the viewpoint of recyclability, the gel fraction is preferably 10% or less, more preferably 5% or less, still more preferably 3% or less, even more preferably 1% or less, and particularly preferably 0%. In addition, a gel fraction can be measured as follows.
- the maximum peak temperature of tan ⁇ of the adhesive film is preferably 10° C. or higher and 52° C. or lower.
- the maximum peak temperature of tan ⁇ is 52° C. or less, the resin film becomes sufficiently flexible, and the conformability to irregularities can be improved. In addition, it becomes easy to improve the adhesiveness to various resin materials and inorganic glass.
- the maximum peak temperature of tan ⁇ of the resin composition is more preferably 48° C. or less, still more preferably 44° C. or less, and even more preferably 42° C. or less.
- the maximum peak temperature of tan ⁇ is 10° C.
- the maximum peak temperature of tan ⁇ of the resin composition is preferably 12° C. or higher, more preferably 20° C. or higher.
- the maximum peak temperature of tan ⁇ of the resin film is detected by performing viscoelasticity measurement using a dynamic viscoelasticity measuring device and reading the peak temperature at which the loss tangent tan ⁇ obtained from the viscoelasticity measurement result is the maximum value. can.
- the shear storage modulus, gel fraction, and maximum peak temperature of tan ⁇ described above can be adjusted by appropriately selecting the type of resin, the molecular weight of the resin, the presence or absence of a plasticizer, and its content.
- the adhesive film contains a thermoplastic resin as described above. From the viewpoint of lowering the gel fraction, the thermoplastic resin preferably does not have a crosslinked structure, or if it does have a little crosslinked structure.
- thermoplastic resins used for adhesive films include (meth)acrylic resins, polyvinyl acetal resins, polyvinyl alcohol resins (PVA), polyurethane resins (PU), ethylene-vinyl acetate copolymer resins (EVA ), saponified ethylene-vinyl acetate copolymer (EVOH), ethylene-methacrylic acid copolymer resin, ionomer resin, isobutylene resin, styrene-isoprene copolymer resin, styrene-butadiene copolymer resin, and the like.
- Adhesive film WHEREIN A thermoplastic resin may be used individually by 1 type, and may use 2 or more types together. Among the above thermoplastic resins, polyvinyl acetal resins are preferable. By using a polyvinyl acetal-based resin, it becomes easy to improve the step followability. In addition, it becomes easier to lower the gel fraction and improve the adhesiveness. The polyvinyl acetal-based resin used for the thermoplastic resin will be described in detail below.
- the weight average molecular weight (Mw) of the thermoplastic resin is preferably 600,000 or less. By adjusting the weight average molecular weight within the above range, the flexibility of the pressure-sensitive adhesive film can be improved, and the step conformability of the pressure-sensitive adhesive film can be further improved. From this point of view, the weight average molecular weight (Mw) of the thermoplastic resin is more preferably 500,000 or less, even more preferably 400,000 or less. In addition, from the viewpoint of mechanical strength, etc., the weight average molecular weight (Mw) of the thermoplastic resin is preferably 50,000 or more, more preferably 100,000 or more, still more preferably 120,000 or more, and even more preferably 150,000 or more. preferable. The weight average molecular weight (Mw) is measured by gel permeation chromatography.
- the thermoplastic resin is preferably a polyvinyl acetal resin.
- the polyvinyl acetal resin may be a modified polyvinyl acetal resin or an unmodified polyvinyl acetal resin.
- the modified polyvinyl acetal resin may have a structure (modifying group) other than an acetal group, a hydroxyl group, and an acetyl group, and preferably has a modifying group in a side chain, as will be described later.
- a polyvinyl acetal-based resin is obtained by acetalizing polyvinyl alcohol with an aldehyde, and optionally reacting it with a modifier or re-acetylating it.
- modified polyvinyl alcohol may be used as the raw material polyvinyl alcohol.
- the structure other than the above acetal group, hydroxyl group, and acetyl group is preferably a polyalkylene oxide structure.
- the polyalkylene oxide structure is as represented by the following formula (1).
- a 1 O is an oxyalkylene group having 2 to 6 carbon atoms, m is the average number of repetitions, and is 4 to 200.
- R 1 is an alkyl group having 1 to 8 carbon atoms or It is a hydrogen atom.
- the oxyalkylene group may be of one type alone, or two or more types may be mixed.* indicates the bonding position with another group.
- the oxyalkylene group for A 1 O is an oxyalkylene group having 2 to 6 carbon atoms, preferably an oxyalkylene group having 2 to 4 carbon atoms, and more preferably an oxyalkylene group having 2 or 3 carbon atoms.
- the alkylene group in the oxyalkylene group may be linear or may have a branched structure.
- the oxyalkylene group includes, for example, an oxyethylene group, an oxypropylene group, or an oxybutylene group, preferably an oxyethylene group or an oxypropylene group.
- One type of oxyalkylene group may be used alone, but two or more types may be used in combination. When two or more types are used in combination, each oxyalkylene group may be added at random or may be added in blocks, but is more preferably added at random.
- the oxyalkylene group in the polyalkylene oxide structure preferably contains at least one of an oxyethylene group and an oxypropylene group, and preferably contains both an oxyethylene group and an oxypropylene group.
- both an oxyethylene group and an oxypropylene group may form a block structure, but more preferably a random structure.
- the ratio (PO/EO) of the oxypropylene group to the oxyethylene group is, for example, 1/9 or more and 9/1 or less, preferably 2 /8 or more and 8/2 or less, more preferably 3/7 or more and 7/3 or less.
- m represents the average number of repeating oxyalkylene groups, and is 4-200, preferably 5-100, more preferably 10-80, and still more preferably 15-50.
- the alkyl group for R 1 may be linear or may have a branched structure.
- alkyl groups for R 1 include branched butyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl and t-butyl groups, n-pentyl group, branched pentyl group, n branched heptyl groups such as -hexyl group, branched hexyl group, n-heptyl group, isoheptyl group and 3-heptyl group; branched octyl groups such as n-octyl group, isooctyl group and 2-ethylhexyl group; R 1 is preferably an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, more preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.
- the above polyalkylene oxide structure may be linked to the main chain via a single bond, but is preferably linked to the main chain via a linking group other than a single bond.
- Linking groups other than single bonds include ether bond (-O-), ester bond (-COO-), amide bond (-CONR-: R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom ), or a hydrocarbon group which may have at least one of these bonds.
- R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom
- a hydrocarbon group which may have at least one of these bonds is more preferable.
- the number of carbon atoms in the hydrocarbon group is not particularly limited, but may be, for example, about 1-10, preferably 1-4.
- the polyalkylene oxide structure is bonded to the main chain via either an ether bond or —CH 2 O—.
- the polyalkylene oxide structure is attached to the main chain through any of these to facilitate its manufacture.
- an oxygen atom is preferably bonded to the polyalkylene oxide structure.
- a polyvinyl acetal-based resin typically has an acetal group, a hydroxyl group, and an acetyl group.
- the polyvinyl acetal-based resin does not have to contain hydroxyl groups by being modified with functional groups or undergoing a re-acetylation reaction.
- the acetal group, hydroxyl group, and acetyl group are groups bonded directly to the main chain or via an oxygen atom, as shown in formulas (3-1) to (3-3) described later.
- a hydroxyl group, etc., possessed by the polyalkylene oxide structure is not included.
- the polyvinyl acetal-based resin is preferably modified to have a polyalkylene oxide structure represented by the above formula (1) as described above.
- the polyvinyl acetal resin having a polyalkylene oxide structure is sometimes described as a modified polyvinyl acetal resin (A) in order to distinguish it from other polyvinyl acetal resins.
- the modified polyvinyl acetal resin (A) preferably has a modification amount of 0.1 mol % or more and 10 mol % or less with the polyalkylene oxide structure (that is, the functional group represented by formula (1)).
- the amount of modification is within the above range, the shear storage elastic modulus at 85° C. is increased, and the conformability to irregularities can be further improved. Moreover, it becomes easy to make adhesiveness favorable.
- the amount of modification by the polyalkylene oxide structure is preferably 0.2 mol% or more, more preferably 0.3 mol% or more, further preferably 0.4 mol% or more, and 0.5 mol% or more. is particularly preferred, and 8 mol % or less is preferred, 6 mol % or less is more preferred, and 4 mol % or less is even more preferred.
- the amount of modification by the functional group represents the ratio of the functional group to all the vinyl monomer units that constitute the polyvinyl acetal-based resin.
- the amount of modification can be calculated from the spectrum obtained by subjecting the polyvinyl acetal-based resin to proton NMR measurement.
- the degree of acetalization, the amount of hydroxyl groups, and the degree of acetylation, which will be described later, can be calculated from the spectrum obtained by performing proton NMR measurement.
- the polyvinyl acetal-based resin does not have to have the polyalkylene oxide structure described above.
- a polyvinyl acetal resin may be a modified polyvinyl acetal resin having a modifying group other than the functional group represented by formula (1), or may be an unmodified polyvinyl acetal resin. Even if it is an unmodified polyvinyl acetal resin, by reducing the amount of hydroxyl groups by a re-acetylation reaction or the like as described later, the maximum peak temperature of tan ⁇ can be lowered, and the conformability to irregularities can be easily improved.
- Examples of modifying groups other than the functional groups represented by formula (1) include alkyl groups.
- the alkyl group may be linear or may have a branched structure.
- the alkyl group has, for example, 2 to 30 carbon atoms, preferably 3 to 24 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 7 to 18 carbon atoms, and even more preferably 11 to 18 carbon atoms.
- the alkyl group may be directly bonded to the main chain, preferably a structural unit derived from a vinyl group constituting the main chain, but preferably an ether bond (-O-) or an ester bond (*-COO-**).
- urethane bond (*-NHCOO-**), more preferably through an ester bond or a urethane bond.
- ester bond and urethane bond “*" and “**” are the bonding position to the alkyl group or the main chain, and in each bond, "*” is the bonding position to the alkyl group, and “**” is the main It is preferably the binding position for the strand.
- R is preferably a hydrogen atom.
- the polyvinyl acetal-based resin has a vinyl group-derived structural unit as a main chain, and the functional group represented by formula (1) is bonded to the vinyl group-derived structural unit that constitutes the main chain. good. Therefore, the polyvinyl acetal-based resin preferably has a structural unit represented by the following formula (2). It is more preferable to have
- R 2 is a single bond or a hydrocarbon group which may have at least one of an ester bond and an ether bond. or.
- a 1 O, R 1 , and m in the formulas (2), (2-1), and (2-2) are as described above, so description thereof will be omitted.
- the carbon number of R 2 in formula (2) is, for example, 1-10, preferably 1-4.
- the hydrocarbon group of R 2 may have an ester bond or an ether bond as described above, but preferably does not have an ester bond or an ether bond.
- Polyvinyl acetal-based resins typically have an acetal group, a hydroxyl group, and an acetyl group. ) and structural units represented by formula (3-3). Therefore, the modified polyvinyl acetal resin is composed of structural units represented by the following formulas (3-1), (3-2) and (3-3) and structural units represented by the above formula (2). It is preferable to have However, when the polyvinyl acetal-based resin is, for example, an unmodified polyvinyl acetal resin, it may not have a hydroxyl group as described above, and may not have a structural unit represented by formula (3-2). That is, the unmodified polyvinyl acetal resin has structural units represented by the following formulas (3-1) and (3-3), and optionally further a structural unit represented by the following formula (3-2). may have.
- R represents a hydrogen atom or a hydrocarbon group having 1 to 19 carbon atoms.
- Polyvinyl acetal resin is obtained by acetalizing polyvinyl alcohol or modified polyvinyl alcohol obtained by modifying polyvinyl alcohol with aldehyde as described above, and then modifying it as necessary. 80-99.8 mole % polyvinyl alcohol is commonly used.
- the number of carbon atoms in the acetal group contained in the polyvinyl acetal-based resin is not particularly limited. ⁇ 6 is more preferred, and 2, 3 or 4 is even more preferred. Accordingly, the number of carbon atoms in R represented by formula (3-1) is preferably 1 to 9, more preferably 1 to 5, even more preferably 1 to 3.
- the acetal group is particularly preferably a butyral group, and therefore, the polyvinyl acetal-based resin is preferably a polyvinyl butyral-based resin.
- the degree of acetalization (that is, the amount of acetal) of the polyvinyl acetal-based resin is, for example, 40% or more, preferably 60 mol% or more.
- the degree of acetalization is more preferably 65 mol% or more, still more preferably 70 mol% or more, preferably 90 mol% or less, more preferably 88 mol% or less, and still more preferably 85 mol%. It is below. By setting the degree of acetalization within these ranges, it becomes easier to contain a certain amount of the functional group represented by formula (1) while maintaining an appropriate amount of hydroxyl groups. Further, when the degree of acetalization is 60% or more, the shear storage modulus at 85° C. is easily within the above range, and the conformability to irregularities is easily improved.
- the degree of acetalization means the degree of acetoacetalization when the acetal group of the polyvinyl acetal-based resin is an acetoacetal group, and the degree of butyralization when the acetal group is a butyral group. . Further, the degree of acetalization represents the ratio of acetalized vinyl alcohol units to all vinyl monomer units constituting the polyvinyl acetal-based resin.
- the hydroxyl group content of the polyvinyl acetal-based resin is preferably 35 mol % or less, more preferably 33 mol % or less, still more preferably 30 mol % or less.
- amount of hydroxyl groups is set to the above upper limit or less, the maximum peak temperature of tan ⁇ can be easily adjusted to a suitable value, and the conformability to irregularities can be further improved.
- the hydroxyl group content of the polyvinyl acetal resin is preferably 0 mol% or more, but in the case of the modified polyvinyl acetal resin (A), from the viewpoint of preventing the adhesive film from becoming too flexible, a certain amount is preferably 5 mol % or more, preferably 9 mol % or more, more preferably 10 mol % or more, still more preferably 12 mol % or more.
- the polyvinyl acetal resin is, for example, an unmodified polyvinyl acetal resin
- the amount of hydroxyl groups in the unmodified polyvinyl acetal resin is preferably 15 mol% or less, more preferably 10 mol% or less, even more preferably 5 mol% or less, even more preferably 3 mol% or less, and most preferably 0 mol%.
- the amount of hydroxyl groups represents the ratio of hydroxyl groups to all vinyl monomer units constituting the polyvinyl acetal-based resin.
- the degree of acetylation (acetyl group content) of the polyvinyl acetal resin is, for example, 0.01 mol % or more and 50 mol % or less. In order to keep the amount of modification by the functional group above a certain value, the degree of acetylation should also be below a certain value. Therefore, the degree of acetylation of the modified polyvinyl acetal resin (A) is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 12 mol% or less, and even more preferably 5 mol% or less. The degree of acetylation of the modified polyvinyl acetal resin (A) is, for example, 0.01 mol % or more as described above, preferably 0.1 mol % or more, and more preferably 0.3 mol % or more.
- the degree of acetylation should preferably be a certain value or more from the viewpoint of reducing the amount of hydroxyl groups, lowering the maximum peak temperature of tan ⁇ , and improving step conformability. is 15 mol % or more, more preferably 25 mol % or more, and still more preferably 30 mol % or more.
- the degree of acetylation of the unmodified polyvinyl acetal resin is, for example, 50 mol % or less, preferably 45 mol % or less, and more preferably 42 mol % or less.
- the degree of acetylation represents the ratio of acetyl groups to all vinyl monomer units constituting the polyvinyl acetal-based resin.
- Aldehydes used in producing polyvinyl acetal resins are not particularly limited, and are, for example, aldehydes having 1 to 20 carbon atoms, but generally aldehydes having 2 to 10 carbon atoms are preferably used.
- the aldehyde having 2 to 10 carbon atoms is not particularly limited, and examples thereof include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, and n-octylaldehyde.
- aldehydes having 2 to 6 carbon atoms such as acetaldehyde, n-butyraldehyde, n-hexylaldehyde and n-valeraldehyde are preferable, aldehydes having 2, 3 and 4 carbon atoms are more preferable, and n-butyraldehyde is further preferable. preferable.
- aldehydes may be used alone or in combination of two or more.
- the polyvinyl acetal-based resins used in the present invention may be used singly or in combination of two or more.
- the pressure-sensitive adhesive film of the present invention may have a thermoplastic resin other than the polyvinyl acetal-based resin as long as the effects of the present invention are exhibited.
- the main component is a polyvinyl acetal-based resin.
- Thermoplastic resins other than polyvinyl acetal resins are as described above.
- the content of the polyvinyl acetal-based resin is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, based on the total amount of the thermoplastic resin contained in the adhesive film. Most preferably it is 100% by mass. Therefore, the thermoplastic resin contained in the pressure-sensitive adhesive film of the present invention may consist only of a polyvinyl acetal-based resin.
- the adhesive film of the present invention may contain a plasticizer.
- a plasticizer By containing a plasticizer, the pressure-sensitive adhesive film becomes flexible, and the maximum peak temperature of tan ⁇ of the pressure-sensitive adhesive film can be lowered to further improve the conformability to irregularities.
- the pressure-sensitive adhesive film of the present invention does not contain a plasticizer or contains a small amount of the plasticizer. Bleeding property can be improved by containing only a small amount of plasticizer or not containing it.
- even if the adhesive film of the present invention contains a small amount of plasticizer or does not contain a plasticizer by using the above-mentioned predetermined thermoplastic resin, it is possible to further improve the conformability to irregularities.
- the content of the plasticizer in the adhesive film is less than 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin contained in the adhesive film. If the plasticizer is 20 parts by mass or more, the bleeding property of the adhesive film may deteriorate. From the viewpoint of the bleeding property of the adhesive film, the content of the plasticizer is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less. is. The lower limit of the plasticizer content is 0 parts by mass.
- the modified polyvinyl acetal resin (A) the resin composition of the present invention may or may not contain a plasticizer. becomes easier to improve.
- the resin composition preferably contains a plasticizer from the viewpoint of improving the adhesiveness of the resin film.
- plasticizers examples include organic ester plasticizers, organic phosphorus plasticizers such as organic phosphate ester plasticizers and organic phosphite ester plasticizers, polyalkylene glycol plasticizers, polyoxyalkylene ether plasticizers, and the like. organic ether-based plasticizers, alcohol-based plasticizers, and the like. A plasticizer may be used individually by 1 type, and may use 2 or more types together. Among them, organic ester plasticizers are preferred. Preferred organic ester plasticizers include monobasic organic acid esters and polybasic organic acid esters.
- Monobasic organic acid esters include esters of glycols with monobasic organic acids.
- Glycols include polyalkylene glycols in which each alkylene unit has 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms, and the number of repeating alkylene units is 2 to 10, preferably 2 to 4.
- the glycol may also be a monoalkylene glycol having 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms (that is, 1 repeating unit).
- Specific examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and butylene glycol.
- Examples of monobasic organic acids include organic acids having 3 to 10 carbon atoms, and specific examples include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, and 2-ethylhexylic acid. , n-nonylic acid and decylic acid.
- Specific monobasic organic acids include triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylhexanoate, di Propylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicapryate, triethylene glycol di-n-heptanoate, tetraethylene glycol Di-n-heptanoate, triethylene glycol di-2-ethylbutyrate,
- polybasic organic acid esters examples include ester compounds of dibasic organic acids having 4 to 12 carbon atoms such as adipic acid, sebacic acid and azelaic acid and alcohols having 4 to 10 carbon atoms. .
- the alcohol having 4 to 10 carbon atoms may be linear, branched, or cyclic. Specific examples include dibutyl sebacate, dioctyl azelate, dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate, diisononyl adipate, heptyl nonyl adipate, dibutyl carbitol adipate, and mixed adipates.
- oil-modified alkyd sebacic acid may be used.
- Mixed adipates include adipates prepared from two or more alcohols selected from alkyl alcohols having 4 to 9 carbon atoms and cyclic alcohols having 4 to 9 carbon atoms.
- the organic phosphorus plasticizer include phosphoric acid esters such as tributoxyethyl phosphate, isodecylphenyl phosphate and triisopropyl phosphate.
- the organic ester plasticizer is not limited to the complete ester of each ester described above, and may be a partial ester.
- it may be a partial ester between a glycol and a monobasic organic acid, or a partial ester between a dibasic organic acid and an alcohol.
- Specific examples include triethylene glycol-mono-2-ethylhexanoate.
- it may be a trihydric or higher alcohol such as glycerin and a partial ester of a monobasic organic acid.
- Monobasic organic acids include monobasic organic acids having 3 to 24 carbon atoms, preferably 6 to 18 carbon atoms.
- partial esters of trihydric or higher alcohols and monobasic organic acids include mono- or diesters of glycerin and stearic acid and mono- or diesters of glycerin and 2-ethylhexyl acid.
- organic ester plasticizers triethylene glycol-di-2-ethylhexanoate (3GO) is particularly preferably used.
- Polyalkylene glycol-based plasticizers include polyethylene glycol, polypropylene glycol, poly(ethylene oxide/propylene oxide) block copolymer, poly(ethylene oxide/propylene oxide) random copolymer, polytetramethylene glycol and the like. Among them, polypropylene glycol is preferred.
- a polyoxyalkylene ether-based plasticizer is an ether compound of a monohydric or polyhydric alcohol and polyoxyalkylene.
- Specific polyoxyalkylene ether plasticizers include, for example, polyoxyethylene hexyl ether, polyoxyethylene heptyl ether, polyoxyethylene octyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene nonyl ether, polyoxyethylene Ethylene decyl ether, polyoxyethylene allyl ether, polyoxypropylene allyl ether, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene diglyceryl ether, polyoxypropylene diglyceryl ether, polyoxyalkylene pentaerythritol ether, etc.
- the polyoxyalkylene ether plasticizer is preferably an ether compound of polyhydric alcohol and polyoxyalkylene, more preferably an ether compound of glycerin or diglycerin and polyoxyalkylene, still more preferably glycerin or diglycerin. and polyoxypropylene.
- Alcohol-based plasticizers include various polyhydric alcohols such as butanediol, hexanediol, trimethylolpropane, and pentaerythritol. Among these, trimethylolpropane is preferred.
- the adhesive film may appropriately contain known additives used in combination with the thermoplastic resin, in addition to the plasticizer. That is, the adhesive film may be made of a thermoplastic resin such as a polyvinyl acetal-based resin. good too. Additives other than the plasticizer specifically include ultraviolet absorbers, infrared absorbers, antioxidants, light stabilizers, adhesion modifiers, pigments, dyes, fluorescent brighteners, crystal nucleating agents, and the like. . Moreover, the resin composition of the present invention may be diluted with a solvent and used in the form of a diluent.
- the adhesive film does not contain a low-molecular-weight compound, or if it does contain a small amount.
- a low-molecular-weight compound refers to a compound having a molecular weight of less than 1,000, and includes the above-described plasticizers and reactive diluents that are cured by light irradiation.
- reactive diluents include (meth)acrylic reactive diluents such as (meth)acrylic monomers and (meth)acrylic oligomers, epoxy reactive diluents such as epoxy monomers and epoxy oligomers, and alkoxysilanes. Silicone-based reactive diluents such as monomers and alkoxysilane oligomers may be used. From the viewpoint of bleeding property, the content of the low-molecular-weight compound in the adhesive film is, for example, less than 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin contained in the adhesive film.
- the content of the low-molecular-weight compound is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less, from the viewpoint of bleeding.
- the reactive diluent described above may crosslink to form a crosslinked structure after photocuring, it is preferable to reduce the content of the low-molecular-weight compound from this point as well.
- the lower limit of the content of the low molecular weight compound is 0 parts by mass.
- the polyvinyl acetal resin used in the adhesive film of the present invention is obtained by acetalizing polyvinyl alcohol (also referred to as "raw material polyvinyl alcohol") with aldehyde, and then reacting with a modifier as necessary, or re-acetylating. It is obtained by As raw material polyvinyl alcohol, unmodified polyvinyl alcohol may be used, but in the case of obtaining a modified polyvinyl acetal resin, modified polyvinyl alcohol may be used as raw material polyvinyl alcohol. For example, when producing a modified polyvinyl acetal resin (A) having a polyalkylene oxide structure, it is preferable to use the following production method (1).
- polyoxyalkylene-modified polyvinyl alcohol is produced as raw material polyvinyl alcohol. Specifically, it is obtained by polymerizing a vinyl ester and a monomer containing a vinyl monomer having a polyoxyalkylene group to obtain a polymer, and then saponifying the polymer. Alkali or acid is generally used for saponification, and alkali is preferably used.
- the polyoxyalkylene-modified polyvinyl alcohol only one type may be used, or two or more types may be used in combination.
- the polyoxyalkylene-modified polyvinyl alcohol obtained above is acetalized with an aldehyde to obtain a modified polyvinyl acetal resin (A).
- the method of acetalization is preferably carried out by a known method.
- Vinyl esters used in production method (1) include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl isoformate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, and lauric acid.
- Vinyl, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate, and the like can be used. Among these, vinyl acetate is preferred.
- vinyl monomers having a polyoxyalkylene group used in production method (1) include compounds represented by the following formula (4).
- a polyoxyalkylene vinyl ether represented by the following formula (4-1) and a polyoxyalkylene allyl ether represented by the following formula (4-2) are preferable.
- vinyl monomers having a polyoxyalkylene group include polyoxyethylene monovinyl ether, polyoxyethylene polyoxypropylene monovinyl ether, polyoxypropylene monovinyl ether, polyoxyethylene monoallyl ether, polyoxyethylene polyoxypropylene mono Allyl ether, polyoxypropylene monoallyl ether, polyoxyethylene alkyl vinyl ether, polyoxyethylene polyoxypropylene alkyl vinyl ether, polyoxypropylene alkyl vinyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene alkyl allyl ether, polyoxyethylene polyoxypropylene alkyl allyl ether, polyoxy and propylene alkyl allyl ether.
- an unmodified polyvinyl acetal resin it is preferable to manufacture it by the following manufacturing methods (2).
- Manufacturing method (2) raw polyvinyl alcohol is acetalized with aldehyde to obtain a polyvinyl acetal-based resin (hereinafter also referred to as raw polyvinyl acetal-based resin).
- raw polyvinyl acetal-based resin a polyvinyl acetal-based resin
- undenatured polyvinyl alcohol obtained by saponifying polyvinyl ester is used as raw material polyvinyl alcohol.
- the raw material polyvinyl acetal resin is preferably subjected to a re-acetylation treatment to obtain an unmodified polyvinyl acetal resin.
- the re-acetylation treatment may be performed by a conventionally known method using acetic anhydride in the presence of a base such as pyridine.
- the re-acetylation treatment may be carried out by heating at, for example, 50° C. or higher and 100° C. or lower, preferably 70° C. or higher and 90° C. or lower.
- a modified polyvinyl acetal resin having an alkyl group as a modifying group in a side chain is preferably produced by the following production method.
- a raw material polyvinyl alcohol is acetalized with an aldehyde to obtain a polyvinyl acetal-based resin (hereinafter also referred to as a raw material polyvinyl acetal-based resin).
- the raw material polyvinyl alcohol used here is obtained by saponifying a polyvinyl ester, and is preferably unmodified polyvinyl alcohol.
- the raw material polyvinyl acetal resin is reacted with a modifying agent having an alkyl group to introduce an alkyl group into the raw material polyvinyl acetal resin.
- the modifying agent is preferably a compound having a reactive group that forms a urethane bond or an ester bond by reacting with the hydroxyl group of the raw material polyvinyl acetal resin.
- alkyl isocyanates having an alkyl group having 2 to 30 carbon atoms such as n-octadecyl isocyanate.
- carboxylic acids having 3 to 31 carbon atoms, or carboxylic acid derivatives such as anhydrides, carboxylic acid esters and carboxylic acid halides of the above carboxylic acids are also included.
- Preferred carboxylic acid derivatives are carboxylic acid chlorides such as 2-ethylhexanoyl chloride, lauroyl chloride, myristyl chloride, palmitoyl chloride and stearoyl chloride.
- the pressure-sensitive adhesive film of the present invention is not only a single pressure-sensitive adhesive film, but also a layered or film-like form obtained by laminating or coating on another member. Sheets, which are relatively thick, are also called adhesive films.
- the thickness of the adhesive film is preferably 100 ⁇ m or more and 2000 ⁇ m or less, more preferably 100 ⁇ m or more and 1500 ⁇ m or less, from the viewpoint of the strength and step conformability of the adhesive film.
- the thickness of the adhesive film is more preferably 200 ⁇ m or more, still more preferably 300 ⁇ m or more, from the viewpoint of the strength of the adhesive film.
- the thickness of the adhesive film is more preferably 500 ⁇ m or less.
- the adhesive film of the present invention may consist of a single layer.
- the layers constituting the single-layer film preferably have the same composition as described for the adhesive film. That is, the layer constituting the single-layer film preferably contains a thermoplastic resin and does not contain a plasticizer, or contains a plasticizer in the above-described content. Furthermore, additives may be appropriately added as described above.
- the adhesive film of the present invention may be a multilayer film having two or more layers.
- the composition of the entire film may be as described for the adhesive film, but each layer (hereinafter also referred to as "first layer") may have the composition as described for the adhesive film.
- each first layer preferably contains a thermoplastic resin and does not contain a plasticizer, or contains a plasticizer in the amount described above, as described for the adhesive film.
- additives may be appropriately added as described above.
- the details of the thermoplastic resin, plasticizer, and additives in each first layer of the multilayer film and the details of the content of each component are as described for the adhesive film above.
- the thermoplastic resin used as the reference for the content is the thermoplastic resin contained in each first layer.
- each first layer may have the same composition or different compositions.
- the multilayer film may be a laminate of the above-described first layer and a layer other than the first layer (hereinafter also referred to as "second layer"). Specifically, for example, a three-layer structure of first layer/second layer/first layer may be used.
- each layer preferably has the same composition as described for the adhesive film.
- the adhesive film of the present invention can be produced by forming a resin composition containing a thermoplastic resin such as a polyvinyl acetal resin into a film by a known method.
- the resin composition contains at least a thermoplastic resin such as a polyvinyl acetal-based resin produced as described above, and may be prepared by adding a plasticizer, an additive, and the like, if necessary.
- the resin composition may be used by diluting it with a solvent as appropriate.
- a single-layer pressure-sensitive adhesive film is formed by coating a resin composition on a support such as a release sheet, or by pouring it into a mold, heating and drying as necessary, and forming a film. It may be molded into a thin film, or may be molded into a film by extrusion molding, press molding, or the like. Further, as described above, when the polyvinyl acetal-based resin is reacted with the modifier to obtain the polyvinyl acetal-based resin, the molding may be performed as follows.
- composition containing a raw material polyvinyl acetal resin, a modifier, and other optional additives such as a plasticizer is coated on a support such as a release sheet, or a mold and then heated to react the modifying agent with the raw material polyvinyl acetal-based resin to form a film.
- the adhesive film is a multilayer film
- each layer may be suitably laminated, and the multi-layer structure may be formed by co-extrusion or the like.
- the pressure-sensitive adhesive film of the present invention is not particularly limited and can be used for various applications, but is preferably used for various display applications, laminated glass applications, and the like.
- the display is not particularly limited, it is preferably for vehicle use.
- the display includes a liquid crystal display, an organic EL display, and the like, and among them, a liquid crystal display is preferable.
- Laminated glass is used in vehicles such as automobiles, trains, ships, airplanes, and other vehicles, buildings, condominiums, detached houses, halls, and gymnasiums, as well as machine tools for cutting and polishing, excavators, and cranes. It is used for window glass of construction machines and the like, and is preferably used for vehicles such as automobiles.
- the pressure-sensitive adhesive film of the present invention has good step followability and bleeding property, it is suitable for use in various displays such as in-vehicle displays and vehicle window glass.
- the laminated glass and display to which the pressure-sensitive adhesive film of the present invention is applied preferably include a laminate described below.
- the pressure-sensitive adhesive film of the present invention is not particularly limited, it is preferably used together with a substrate such as an organic material substrate or an inorganic material substrate, and used as part of a laminate.
- the laminate of the present invention preferably includes at least one of the adhesive film, an inorganic material substrate, and an organic material substrate.
- the adhesive film is preferably arranged so as to adhere to at least one of the inorganic material substrate and the organic material substrate, and more preferably arranged in a position to adhere to the organic material substrate. Since the adhesive film has high adhesive strength to various resin materials, it can be attached to the base material with high adhesive strength by arranging it at a position where it adheres to the organic material base material.
- a step is provided on the surface of at least one substrate to which the adhesive film is adhered.
- the pressure-sensitive adhesive film has good step followability, so that it is possible to prevent deterioration of visibility and adhesion.
- the height of the steps is not particularly limited, but is, for example, 10 to 500 ⁇ m, preferably 10 to 300 ⁇ m.
- the thickness of the adhesive film is preferably at least 1.5 times the height of the step, more preferably at least 2.0 times.
- organic material substrates include organic resin plates and resin films.
- the organic resin plate is also called an organic glass plate.
- organic resin plates include, but are not limited to, polycarbonate plates, (meth)acrylic plates such as polymethylmethacrylate plates, acrylonitrile-styrene copolymer plates, acrylonitrile-butadiene-styrene copolymer plates, polyester plates such as polyethylene terephthalate plates, Various organic glass plates such as fluorine resin plate, polyvinyl chloride plate, chlorinated polyvinyl chloride plate, polypropylene plate, polystyrene plate, polysulfone plate, epoxy resin plate, phenol resin plate, unsaturated polyester resin plate, polyimide resin plate, etc. mentioned.
- the organic resin plate may be appropriately subjected to surface treatment or the like.
- a polycarbonate plate is preferable from the viewpoint of excellent transparency and impact resistance
- a (meth)acrylic plate is preferable from the viewpoint of high transparency, excellent weather resistance, and mechanical strength. is more preferred.
- the thickness of the organic resin plate is not particularly limited, it is preferably 0.1 mm or more, more preferably 0.4 mm or more, and preferably 5.0 mm or less, further preferably 3.0 mm or less.
- the resin film is not particularly limited, but includes polyester resin films such as (meth)acrylic resin films, polycarbonate films, polyethylene terephthalate (PET) films and polyethylene naphthalate (PEN) films, polyolefin resin films such as polyethylene films and polypropylene films, A cyclic polyolefin (COP) film, a triacetyl cellulose (TAC) film, a polyether sulfone (PES) resin film, a polyimide resin film, and the like are included.
- a surface layer such as a hard coat layer made of (meth)acrylic resin may be provided on the surface of the resin film.
- the thickness of the resin film is not particularly limited, it is preferably 30 ⁇ m or more, more preferably 50 ⁇ m or more, and preferably 500 ⁇ m or less, more preferably 450 ⁇ m or less. It should be noted that while the organic resin plate is relatively thick, has low flexibility, and cannot be generally bent, it is generally referred to as a resin film, which is relatively thin and generally bendable. are not clearly distinguished.
- An inorganic glass plate can be mentioned as an inorganic material base material.
- the inorganic glass plate is not particularly limited, but examples thereof include float plate glass, tempered glass, colored glass, polished plate glass, figured glass, wired plate glass, lined plate glass, ultraviolet absorbing plate glass, infrared reflecting plate glass, and infrared absorbing plate glass. , various glass plates such as green glass.
- the inorganic glass may be subjected to surface treatment or the like.
- the thickness of the inorganic glass is not particularly limited, it is preferably 0.1 mm or more, more preferably 1.0 mm or more, and preferably 5.0 mm or less, further preferably 3.0 mm or less.
- the organic material base material or the inorganic material base material may be appropriately attached with an electrode, a sensor, or the like.
- the electrode is composed of a conductive layer laminated on each base material.
- a touch sensor is mentioned as a sensor.
- a touch sensor is a sensor that detects a touch input when a finger, touch pen, or other object approaches or touches a base material, and is composed of a conductive layer laminated on the base material.
- a touch sensor causes an electrical change such as capacitance, current, or voltage to occur in the conductive layer. Detect touch input.
- the conductive layer is not particularly limited, and conventionally known transparent electrode materials can be used without particular limitation. Examples include indium tin oxide (ITO) conductive films, tin oxide conductive films, and zinc oxide conductive films. , polymer conductive films, and the like.
- the inorganic material substrate is preferably selected from the group consisting of an inorganic glass plate and an inorganic glass plate to which at least one of an electrode and a sensor is attached.
- the organic material substrate is selected from the group consisting of polycarbonate plates, (meth)acrylic plates, PET films, COP films, polycarbonate films, and films having at least one of electrodes or sensors attached to these films. At least one is preferred.
- the organic material substrate (especially, film) on which a conductive layer such as an electrode or sensor is laminated may have the above-described hard coat layer formed on the surface opposite to the surface on which the conductive layer is provided.
- the surface provided with the conductive layer usually serves as an adhesive surface with the adhesive film, but the adhesive film of the present invention can also have high adhesive strength to the surface provided with the hard coat layer. .
- the organic material base material or the inorganic material base material may be appropriately provided with a printed portion.
- the printed portion is formed to decorate various substrates and to protect the resin used for fixing the peripheral portion of the substrate from ultraviolet rays.
- the black printed portion is also called black ceramic, and is preferably made of black ceramic.
- a black ceramic is a printed portion that is generally formed to ensure a light-shielding property.
- Black cera can be formed, for example, by printing a black cera printing ink on the surface of a substrate and baking the black cera printing ink.
- An organic material base material or an inorganic material base material may have a step due to a conductive layer and a printed portion on its surface. have.
- the printed part is preferably attached to a glass such as an inorganic glass plate or an organic glass plate.
- the laminate is not particularly limited, but includes a pair of substrates selected from inorganic material substrates and organic material substrates, and an adhesive film disposed between the pair of substrates, and has three or more layers. It preferably has a multilayer structure. In such a multilayer structure, for example, the adhesive film may be adhered to both of the pair of substrates, thereby joining the pair of substrates via the adhesive film. In this case, the adhesive film is preferably the adhesive film of the present invention described above.
- the laminate may have a structure in which another intermediate member is arranged between the pair of base materials.
- an adhesive film is provided between each base material and the intermediate member.
- the adhesive film is preferably adhered to each base material and the intermediate member, so that the base material and the intermediate member are bonded via the adhesive film.
- the adhesive film between the substrate and the intermediate member may be a resin film, and at least one of them may be the pressure-sensitive adhesive film of the present invention.
- An adhesive film is preferred.
- the intermediate member preferably has at least one of the inorganic material substrate and the organic material substrate described above, and at least one of the inorganic material substrate and the organic material substrate is arranged at a position where the pressure-sensitive adhesive film of the present invention adheres. good.
- the laminate described above may constitute a display, laminated glass, etc., but is not limited to these.
- the intermediate member may be a touch panel, a light control element, or the like, but is not limited to these.
- the inorganic material base material and the organic material base material may constitute a part of a touch panel, a light control element, a display element constituting a display, and the like.
- the laminate of the present invention can be produced, for example, by preparing an adhesive film and crimping each member through the prepared adhesive film. For example, it can be produced by laminating a base material, an adhesive film, and a base material in this order and pressing them together. Moreover, when an intermediate member is provided, it can be produced by stacking the base material, the adhesive film, the intermediate member, the adhesive film, and the base material in this order and pressing them together.
- FIG. 1 shows a laminate according to a first embodiment.
- 30 A of laminated bodies are applied to a display with a touch panel.
- the display with a touch panel is preferably an in-vehicle display.
- a laminate 30A according to the present embodiment includes a display element 31, a surface protection panel 32, and a touch panel 33 arranged between the display element 31 and the surface protection panel 32. , and between the surface protection panel 32 and the touch panel 33, adhesive films 34A and 34B are arranged, respectively.
- the surface protection panel 32 is preferably an organic resin plate or an inorganic glass plate, and preferably an inorganic glass plate.
- the display element 31 may be an organic EL display element or a liquid crystal display element.
- a polarizing plate (polarizing film) is preferably provided on the outermost surface of the display element 31 .
- the outermost surface on the front side is the outermost surface on the surface protection panel side, and the opposite side is also called the back side.
- a polarizing plate (polarizing film) generally has a structure in which protective films are provided on both sides of a polarizer such as a polyvinyl alcohol resin film.
- the protective film is composed of the resin film described above, preferably a PET film, a COP film, or a TAC film.
- an organic material substrate is generally arranged on the outermost surface on the surface side of the display element 31 .
- a protective film is provided on the outermost surface of the surface side.
- the outermost surface on the surface side of the element 31 is composed of the organic material base material.
- the touch panel 33 may be composed of any one of inorganic glass, organic resin plate, or resin film with a touch sensor attached, but inorganic glass or resin film with a touch sensor is preferable. Further, in the touch panel 33, two or more of the inorganic glass, the organic resin plate, or the resin film may be laminated to form a multilayer structure. Also in this case, the touch sensor may be attached to any one of the inorganic glass, the organic resin plate, and the resin film in the touch panel 33 . Further, the touch panel 33 may have a protective film made of a resin film on either the outermost surface on the front side or the outermost surface on the back side. Therefore, in the touch panel 33, the bonding surface with the bonding films 34A and 34B is any one of inorganic glass, organic glass, and resin film.
- the surface protection panel 32 is preferably an organic resin plate or an inorganic glass plate, but preferably an inorganic glass plate. Moreover, it is preferable that a part of the back surface of the surface protection panel 32 is provided with a printed portion.
- the printed part is, for example, black ceramic, and is provided, for example, in a frame shape on the outer edge of the surface protection panel 32, forming a step between the part where the printed part is provided and the part where it is not provided.
- the back surface of the surface protection panel 32 serves as an adhesive surface with the adhesive film 34B.
- the adhesive films 34A and 34B are adhered to the display element 31, the touch panel 33, the touch panel 33 and the surface protection panel 32 to join them together.
- Either one of the adhesive films 34A and 34B may be the adhesive film of the present invention, but both are preferably the adhesive film of the present invention.
- the pressure-sensitive adhesive film of the present invention has high adhesive strength not only to inorganic material substrates but also to various resin materials (that is, organic material substrates). Therefore, in the display element 33, the surface protection panel 32, and the touch panel 33, the adhesive surfaces of the adhesive films 34A and 34B may be composed of an organic material base material. , the display element 31 and the touch panel 33, and the surface protection panel 32 and the touch panel 33 can be joined.
- the adhesive film 34 has a high step conformability, even if it is adhered to a substrate having a step (such as the surface protection panel 32), it is possible to prevent deterioration of visibility and adhesion. Furthermore, since it has a high bleeding property, contamination of the display element 31 can be prevented.
- FIG. 2 shows a laminate according to a second embodiment.
- the laminate according to the second embodiment is also applied to a display, but the touch panel 33 is omitted in the laminate 30B. , with an adhesive film 34 disposed therebetween.
- the adhesive film 34 is made of the adhesive film of the present invention.
- the adhesive film 34 (adhesive film) is adhered to the display element 31 and the surface protection panel 32 to join them. Therefore, as in the first embodiment, the display element 31 and the surface protection panel 32 They are joined with high adhesive strength.
- the pressure-sensitive adhesive film of the present invention has high conformability to unevenness, even if it is adhered to a base material having unevenness (surface protection panel 32) as described above, it is possible to prevent deterioration of visibility and adhesion. . Furthermore, since it has a high bleeding property, contamination of the display element 31 can be prevented.
- the surface protection panel 32 may be an OGS (one glass solution) panel, and the surface protection panel 32 may be provided with a sensor such as a touch sensor. Therefore, the surface protection panel 32 may be made of inorganic glass or the like with a sensor attached.
- OGS one glass solution
- FIG. 3 shows a laminate according to a third embodiment.
- a laminated body 30C according to the third embodiment is applied to a laminated glass with a light control function.
- a laminate 30C according to the present embodiment includes a pair of laminated glass members (base materials) 41 and 42 and a light control element 43 disposed between the pair of laminated glass members 41 and 42.
- Adhesive films 34A and 34B are arranged between 41 and the light control element 43 and between the other laminated glass member 42 and the light control element 43, respectively.
- the laminated glass members 41 and 42 may be inorganic glass plates or organic resin plates, and the details thereof are as described above. Further, in the laminated glass members 41 and 42, as in the first and second embodiments, at least one of the surfaces to be adhered to the adhesive films 34A and 34B is provided with a printed portion such as black ceramic, and a stepped portion It is preferred to have
- the light control element 43 is preferably a light control film including two resin films and a light control layer arranged between the two resin films. Therefore, the adhesive surfaces of the light control element 43 and the adhesive films 34A and 34B are made of a resin material.
- resin films included in the light modulating element 43 include polyester resin films such as PET films and PEN films, (meth)acrylic resin films, TAC films, PES resin films, and polyimide resin films. Among these, polyester resin films are preferred, and PET films are more preferred, from the viewpoint of handleability and the like.
- a conductive layer forming an electrode is provided on each of the two resin films on the light control layer side.
- the light control layer changes the visible light transmittance by switching between the application and non-application of a voltage between the conductive layers of the two resin films.
- the light control layer is preferably composed of a liquid crystal layer such as polymer dispersed liquid crystal (PDLC).
- the light control film may be an SPD (Suspended Particle Device) film, an electrochromic film, an electrophoretic film device, or the like.
- the light-modulating layer may be an SPD layer comprising a resin matrix and a light-modulating suspension dispersed in the resin matrix, or it may be an electrochromic material layer.
- it may be an electrophoretic layer including electrophoretic particles and a dispersing agent for dispersing the electrophoretic particles.
- the adhesive films 34A and 34B are respectively adhered to the laminated glass member 41 and the light control element 43, and the laminated glass member 42 and the light control element 43 to join them.
- the adhesive films 34A and 34B are resin films, and one of them is preferably the adhesive film of the present invention, but both are preferably the adhesive film of the present invention.
- the pressure-sensitive adhesive film of the present invention has high adhesive strength not only to inorganic material substrates but also to various resin materials. be able to.
- the pressure-sensitive adhesive film of the present invention has high conformability to unevenness, even when the adhesive film is adhered to the laminated glass members 41 and 42 having unevenness, deterioration in visibility and adhesion can be prevented.
- it since it has a high bleeding property, it is possible to prevent contamination of the polarizing element 43 and the like due to bleeding out.
- FIG. 4 shows a laminate according to a fourth embodiment.
- a laminate 30D according to the present embodiment is applied to laminated glass.
- a laminate 30D according to the present embodiment includes a pair of laminated glass members 41 and 42 and an adhesive film 34 disposed between the pair of laminated glass members 41 and 42, and the adhesive film 34 is the above-described book. It is preferable to consist of the adhesive film of the invention.
- a pair of laminated glass members 41 and 42 are as described in the third embodiment. Since the adhesive film 34 (adhesive film) is adhered to both of the laminated glass members 41 and 42 to join them together, the laminated glass members 41 and 42 can be joined with high adhesive strength.
- the pair of laminated glass members 41 and 42 are as described in the third embodiment, and at least one of them preferably has a printed portion and a stepped portion.
- the adhesive film 34 adhered to both of the laminated glass members 41 and 42 to join them together. It is possible to prevent deterioration of the properties. In addition, since it has a high bleeding property, contamination of peripheral members can be prevented.
- the adhesive film is a single-layer adhesive film
- a multi-layer film may be used as the adhesive film.
- the structure of the multilayer film is as described above.
- the present invention will be described in more detail by way of examples, the present invention is not limited by these examples.
- the measuring method of each physical-property value in this invention, and the evaluation method are as follows.
- Weight average molecular weight (Mw) was calculated using a molecular weight calibration curve prepared from monodisperse polystyrene standard samples. Shodex GPC KF-806L (manufactured by Showa Denko) was used as a column, and tetrahydrofuran was used as an eluent.
- ⁇ Shear storage modulus and maximum peak temperature of tan ⁇ > The pressure-sensitive adhesive films obtained in Examples and Comparative Examples were cut into a length of 10 mm and a width of 5 mm, and a dynamic viscoelasticity measuring device (manufactured by IT Instrument Control Co., Ltd., trade name "DVA-200") was used to measure the following: The viscoelasticity was measured under the measurement conditions of , and the shear storage modulus (G') at 85°C was detected. Also, the peak temperature of the loss tangent tan ⁇ obtained from the results of the viscoelasticity measurement was read.
- a dynamic viscoelasticity measuring device manufactured by IT Instrument Control Co., Ltd., trade name "DVA-200
- a white plate glass manufactured by Matsunami Glass Industry Co., Ltd., S9112 having a size of 76 mm ⁇ 52 mm ⁇ thickness of 1.0 to 1.2 mm was prepared.
- the adhesive film was cut into a size of 76 mm ⁇ 52 mm, and the cut adhesive film was attached to the stepped surface of the white plate glass.
- an ITO-coated polyethylene terephthalate film (ITO-PET, manufactured by Sekisui Nanocoat Technology Co., Ltd.) was cut into a size of 76 mm ⁇ 52 mm and attached on the adhesive film to prepare a laminate. At this time, the surface opposite to the surface coated with ITO was made to be the adhesive surface with the adhesive film. In addition, when the frame, the adhesive film, and the polyethylene terephthalate film were attached, air bubbles were prevented as much as possible. Then, using a vacuum laminator, the laminate is crimped for 10 minutes under conditions of 90 ° C. and 1 atm, and then treated using an autoclave under conditions of 90 ° C. and 0.5 MPa for 30 minutes, followed by heating.
- ITO-PET ITO-coated polyethylene terephthalate film
- each adhesive film was irradiated with 4000 mJ/cm 2 of light having a wavelength of 365 nm using an ultra-high pressure mercury lamp.
- a kneader trade name “Laboplastomill”, manufactured by Toyo Seiki Seisakusho Co., Ltd.
- the adhesive film after being irradiated with light was melt-kneaded at 160° C. and 50 rpm for 10 minutes.
- the kneaded material obtained by kneading the adhesive film was recovered.
- the obtained kneaded product was press-molded under the conditions of 160° C.
- Allyl ether monomer (1) shown in Table 1 was prepared. Allyl ether monomer (1) is a compound represented by formula (4-2), A 1 O contains a mixture of oxyethylene group (EO) and oxypropylene group (PO), and these have a random structure. The molar ratio, the average repeating number of EO and PO, and the terminal group (R 1 ) are as shown in Table 1.
- the obtained polyvinyl acetal-based resin (PVB1) was press-molded at a temperature of 160° C. and a pressure of 20 MPa to obtain an adhesive film having a thickness of 200 ⁇ m.
- the maximum peak temperature of tan ⁇ , shear storage modulus (G′), and gel fraction were measured for the obtained adhesive film, and step followability, recyclability, and bleeding property were evaluated.
- Example 2-4 The same procedure as in Example 1 was carried out, except that the thickness of the adhesive film was adjusted as shown in Table 1.
- Example 5 The allyl ether monomer used was changed to allyl ether monomer (2), and 723 parts by mass of vinyl acetate, 257 parts by mass of allyl ether monomer (2), and 20 parts by mass of methanol, 2,2-azobisisobutyro PVB2 was obtained in the same manner as in Example 1 except that the nitrile was changed to 1 part by mass and the polymerization temperature was changed to 62°C. Then, using PVB2, an adhesive film was produced in the same manner as in Example 1, except that the thickness of the adhesive film was adjusted as shown in Table 1. The physical properties of the resulting adhesive film were measured or evaluated in the same manner as in Example 1.
- the allyl ether monomer (2) is a compound represented by formula (4-2), A 1 O is an oxypropylene group (PO), and the average number of repetitions and the terminal group (R 1 ) are 1.
- Example 6 552 parts by mass of vinyl acetate, 162 parts by mass of allyl ether monomer (1), 286 parts by mass of methanol, and 1.4 parts by mass of 2,2-azobisisobutyronitrile were carried out in the same manner as in Example 1. Then, PVB3 was obtained, and an adhesive film was produced in the same manner as in Example 1 except that the thickness of the adhesive film was adjusted as shown in Table 1 using PVB3. The physical properties of the resulting adhesive film were measured or evaluated in the same manner as in Example 1.
- Example 7 572 parts by mass of vinyl acetate, 143 parts by mass of allyl ether monomer (1), 286 parts by mass of methanol, and 0.7 parts by mass of 2,2-azobisisobutyronitrile were carried out in the same manner as in Example 1. Then, PVB4 was obtained, and an adhesive film was produced in the same manner as in Example 1 except that the thickness of the adhesive film was adjusted as shown in Table 1 using PVB4. The obtained adhesive film was evaluated in the same manner as in Example 1.
- Example 8 The allyl ether monomer used was changed to allyl ether monomer (3), and 751 parts by mass of vinyl acetate, 230 parts by mass of allyl ether monomer (3), and 20 parts by mass of methanol, 2,2-azobisisobutyro PVB5 was obtained in the same manner as in Example 1, except that the nitrile was changed to 1 part by mass. Then, using PVB5, an adhesive film was produced in the same manner as in Example 1, except that the thickness of the adhesive film was adjusted as shown in Table 1. The obtained adhesive film was evaluated in the same manner as in Example 1.
- the allyl ether monomer (3) is a compound represented by the formula (4-2), in which A 1 O is a mixture of an oxyethylene group (PO) and an oxypropylene group (PO), the average number of repetitions, and Terminal groups (R 1 ) are as shown in Table 1.
- Example 9 The allyl ether monomer used was changed to allyl ether monomer (4), and 834 parts by mass of vinyl acetate, 147 parts by mass of allyl ether monomer (4), 20 parts by mass of methanol, 2,2-azobisisobutyro PVB6 was obtained in the same manner as in Example 1, except that the nitrile was changed to 0.5 parts by mass and the polymerization temperature was changed to 52°C. 100 parts by mass of PVB6 was mixed with 15 parts by mass of a plasticizer (3GO) to obtain a resin composition.
- a pressure-sensitive adhesive film was obtained by press molding in the same manner as in Example 1 except for the adjustment. The obtained adhesive film was evaluated in the same manner as in Example 1.
- the allyl ether monomer (4) is a compound represented by formula (4-2), A 1 O is an oxyethylene group (EO), and the average repeating number and terminal group (R 1 ) are 1.
- the polyvinyl acetal-based resin to be used is PVB7, which is unmodified polyvinyl butyral, and 100 parts by mass of PVB7 is mixed with 40 parts by mass of a plasticizer (3GO) to obtain a resin composition, Using the obtained resin composition, press molding was performed in the same manner as in Example 1 to obtain an adhesive film. The obtained adhesive film was evaluated in the same manner as in Example 1.
- the polyvinyl acetal-based resin to be used is PVB8, which is unmodified polyvinyl butyral, and 100 parts by mass of PVB8 is mixed with 25 parts by mass of a plasticizer (3GO) to obtain a resin composition, Using the obtained resin composition, press molding was performed in the same manner as in Example 1 to obtain an adhesive film. The obtained adhesive film was evaluated in the same manner as in Example 1.
- Example 3 The polyvinyl acetal-based resin used was PVB9, which is unmodified polyvinyl butyral, and press molding was performed in the same manner as in Example 1 without mixing a plasticizer to obtain an adhesive film. The obtained adhesive film was evaluated in the same manner as in Example 1.
- PVB7 which is unmodified polyvinyl butyral, was used as the polyvinyl acetal resin.
- a plasticizer 3GO
- 10 parts by weight of a reactive diluent trimethylolpropane triacrylate: TMPA
- BP benzophenone
- the adhesive film was irradiated with light having a wavelength of 365 nm at 4000 mJ/cm using an ultra - high pressure mercury lamp. was measured. Moreover, recyclability was evaluated.
- a laminate was produced using the adhesive film produced in Comparative Example 4 as described in the evaluation method above, and an ultra-high pressure mercury lamp was used for the laminate, and light with a wavelength of 365 nm was applied. was irradiated at 4000 mJ/cm 2 . After that, the step followability was evaluated.
- the adhesive film was irradiated with 4000 mJ/cm 2 of light with a wavelength of 365 nm using an ultra-high pressure mercury lamp, and after light irradiation, the gel fraction, shear storage modulus (G'), and the maximum peak temperature of tan ⁇ were measured. It was measured.
- a laminate was produced using the adhesive film produced in Comparative Example 5 as described in the evaluation method above, and an ultra-high pressure mercury lamp was used for the laminate, and light with a wavelength of 365 nm was applied to the laminate. was irradiated at 4000 mJ/cm 2 . After that, the step followability was evaluated.
- Comparative Example 7 It was carried out in the same manner as in Comparative Example 6, except that the (meth)acrylic polymer (Ac1) was changed to the (meth)acrylic polymer (Ac2).
- PVB1 to PVB9 used in Examples and Comparative Examples are shown in Table 2 below.
- the (meth)acrylic polymers used in Comparative Examples are shown in Table 3 below.
- Table 4 shows the working conditions, physical properties and evaluation results of each example and comparative example. *1 Shows parts by mass for 100 parts by mass of thermoplastic resin. *2 Shows parts by mass for 100 parts by mass of reactive diluent.
- the pressure-sensitive adhesive film of each of the above examples has a shear storage modulus at 85° C. of 0.06 ⁇ 10 6 Pa or more and 1.00 ⁇ 10 6 Pa or less, and does not contain a plasticizer or has a plasticizer content of Since the content was less than 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin and the gel fraction was 15% or less, the conformability to irregularities, recyclability, and bleeding properties were all excellent.
- the content of the plasticizer was greater than 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin, so the bleeding property was poor.
- the gel fraction was greater than 15%, so the recyclability was poor.
- the shear storage elastic modulus at 85° C. was too low, and the step followability was also lowered.
Abstract
Description
すなわち、本発明は、以下の[1]~[32]を提供する。
[1]熱可塑性樹脂を含み、
85℃におけるせん断貯蔵弾性率が0.06×106Pa以上1.00×106Pa以下であり、
可塑剤を含まない、又は前記熱可塑性樹脂100質量部に対して可塑剤を20質量部未満で含み、
ゲル分率が15%以下である、粘着フィルム。
[2]前記熱可塑性樹脂の重量平均分子量(Mw)が600,000以下である、上記[1]に記載の粘着フィルム。
[3]厚みが100μm以上2000μm以下である、上記[1]又は[2]に記載の粘着フィルム。
[4]tanδの極大ピーク温度が10℃以上52℃以下である、上記[1]~[3]のいずれかに記載の粘着フィルム。
[5]前記熱可塑性樹脂がポリビニルアセタール系樹脂である、上記[1]~[4]のいずれかに記載の粘着フィルム。
[6]前記ポリビニルアセタール系樹脂が、以下の式(1)で示すポリアルキレンオキサイド構造を有する上記[5]に記載の粘着フィルム。
(式(1)において、A1Oは炭素数2~6のオキシアルキレン基であり、mは平均繰り返し数であり、4~200である。R1は炭素数が1~8のアルキル基又は水素原子である。なお、オキシアルキレン基は1種単独でもよいし、2種類以上が混在していてもよい。*は他の基との結合位置である。)
[7]前記ポリビニルアセタール系樹脂が、ポリアルキレンオキサイド構造を有する、上記[5]に記載の粘着フィルム。
[8]前記ポリアルキレンオキサイド構造におけるオキシアルキレン基は、オキシエチレン基及びオキシプロピレン基の少なくともいずれかを含む、上記[6]又は[7]に記載の粘着フィルム。
[9]前記ポリアルキレンオキサイド構造におけるオキシアルキレン基は、オキシエチレン基及びオキシプロピレン基の両方を含有する、上記[6]~[8]のいずれかに記載の粘着フィルム。
[10]アセタール化度が60モル%以上である、上記[6]~[9]のいずれかに記載の粘着フィルム。
[11]前記ポリアルキレンオキサイド構造が、単結合、またはエーテル結合、エステル結合、アミド結合、及びこれら結合のうち少なくともいずれかを有してもよい炭化水素基のいずれかを介して主鎖に連結される、上記[6]~[10]のいずれかに記載の粘着フィルム。
[12]前記ポリアルキレンオキサイド構造による変性量が、0.1モル%以上10モル%以下である、上記[6]~[11]のいずれかに記載の粘着フィルム。
[13]前記ポリビニルアセタール系樹脂のアセタール化度が60モル%以上90モル%以下である、上記[5]~[12]のいずれかに記載の粘着フィルム。
[14]前記ポリビニルアセタール系樹脂の水酸基量が、5モル%以上35モル%以下である、上記[5]~[13]のいずれかに記載の粘着フィルム。
[15]前記ポリビニルアセタール系樹脂のアセチル化度が、0.01モル%以上50モル%以下である、上記[5]~[14]のいずれかに記載の粘着フィルム。
[16]前記ポリビニルアセタール系樹脂が、ポリビニルブチラール系樹脂である、上記[5]~[15]のいずれかに記載の粘着フィルム。
[17]前記ポリビニルアセタール系樹脂の重量平均分子量(Mw)が、50,000以上600,000以下である、上記[5]~[16]のいずれかに記載の粘着フィルム。
[18]前記ポリビニルアセタール系樹脂の含有量は、粘着フィルムに含有される熱可塑性樹脂全量基準で、50質量%以上100質量%以下である、上記[5]~[17]のいずれかに記載の粘着フィルム。
[19]分子量1000未満の低分子量化合物を含有しないか、または、前記熱可塑性樹脂100質量部に対して、20質量部未満で含有する、上記[1]~[18]のいずれかに記載の粘着フィルム。
[20]前記可塑剤が、有機エステル可塑剤、有機リン系可塑剤、有機エーテル系可塑剤、及びアルコール系可塑剤からなる群から選択される少なくとも1種である、上記[1]~[19]のいずれかに記載の粘着フィルム。
[21]前記粘着フィルムが、可塑剤として、グリコールと一塩基性有機酸とのエステル、及び炭素数4~12の二塩基性有機酸と炭素数4~10のアルコールとのエステル化合物、ポリアルキレングリコール系可塑剤、及びポリオキシアルキレンエーテル系可塑剤からなる群から選択される少なくとも1種を含む、上記[1]~[20]のいずれかに記載の粘着フィルム。
[22]一対の基材を接合するために使用される上記[1]~[21]のいずれかに記載の粘着フィルム。
[23]第1の有機材料基材と、第2の有機材料基材もしくは無機材料基材とを接合するときに使用され、前記第1の有機材料基材及び前記第2の有機材料基材が、偏光フィルム、ポリエチレンテレフタレートフィルム、ポリカーボネート板、及び(メタ)アクリル板からなる群から選択される少なくとも1種の有機材料基材である、上記[22]に記載の粘着フィルム。
[24]上記[1]~[23]のいずれかに記載の粘着フィルムと、一対の基材を備え、前記粘着フィルムが一対の基材の間に配置される、積層体。
[25]前記基材が、タッチパネル、調光素子、及び表示素子の少なくとも一部を構成する、上記[24]に記載の積層体。
[26]前記一対の基材の間に配置される中間部材と、各基材と前記中間部材の間に配置される接着用フィルムを備え、前記接着用フィルムの少なくともいずれかが、前記粘着フィルムである、上記[25]又は[26]に記載の積層体。
[27]前記中間部材の前記粘着フィルムが接着する位置に無機材料基材、及び有機材料基材の少なくともいずれかが配置される、上記[26]に記載の積層体。
[28]前記中間部材が、タッチパネル及び調光素子のいずれかである、上記[26]又は[27]に記載の積層体。
[29]上記[24]~[28]のいずれかに記載の積層体を含む液晶ディスプレイ。
[30]上記[24]~[28]のいずれかに記載の積層体を含む合わせガラス。
[31]上記[1]~[23]のいずれかに記載の粘着フィルムのディスプレイにおける使用。
[32]上記[1]~[23]のいずれかに記載の粘着フィルムの合わせガラスにおける使用。
本発明の粘着フィルムは、熱可塑性樹脂を含み、85℃におけるせん断貯蔵弾性率が0.06×106Pa以上1.00×106Pa以下であり、可塑剤を含まない、又は熱可塑性樹脂100質量部に対して可塑剤を20質量部未満で含み、ゲル分率が15%以下となるものである。
本発明の粘着フィルムは、以上の構成を有することで、段差追従性、ブリード性及びリサイクル性を良好にできる。
[せん断貯蔵弾性率]
本発明の粘着フィルムは、85℃におけるせん断貯蔵弾性率が0.06×106Pa以上1.00×106Pa以下である。せん断貯蔵弾性率が0.06×106Pa未満であると、貼り付け時に発泡することが有り、貼り付け性が低下することが有る。せん断貯蔵弾性率が1.00×106Pa超であると、粘着フィルムの段差追従性が悪くなり、段差部分に気泡が残存し、視認性や貼り付け性が低下することがある。
粘着フィルムの貼り付け性の観点から、上記した85℃におけるせん断貯蔵弾性率は0.08×106Pa以上が好ましく、0.09×106Pa以上がより好ましくい。
なお、せん断貯蔵弾性率は、周波数1Hz、動的粘弾性測定装置を用いてせん断モードで粘弾性測定を行い、85℃における貯蔵弾性率(G’)を検出することで測定することができる。
本発明の粘着フィルムはゲル分率が15%以下である。ゲル分率が15%よりも大きいと、粘着フィルムのリサイクル性が悪くなる。すなわち、ゲル分率が15%よりも大きいと、使用済みの粘着フィルムをリサイクルして、再び粘着フィルムとして使用した場合、ゲル分が粘着フィルム中の光学欠点となることで光学欠点が多くなるので、リサイクルした粘着フィルムがディスプレイや合わせガラス等の用途に使用できない場合がある。リサイクル性の観点から、ゲル分率は、好ましくは10%以下であり、より好ましくは5%以下であり、さらに好ましくは3%以下であり、よりさらに好ましくは1%以下であり、特に好ましくは0%である。
なお、ゲル分率は、以下のようにして測定することができる。40gのTHF(テトラヒドロフラン)に粘着フィルムを約0.1g溶解し、未溶解成分を取出した後、未溶解成分を乾燥した。そして、以下の式から、ゲル分率を算出した。
ゲル分率(%)=(未溶解物の乾燥後重量)/(溶解前の粘着フィルムの重量)×100
本発明において、粘着フィルムのtanδの極大ピーク温度は、10℃以上52℃以下であることが好ましい。tanδの極大ピーク温度を52℃以下とすると、樹脂フィルムが十分に柔軟となり、段差追従性を良好にできる。また、各種樹脂材料や、無機ガラスに対する接着性を良好にしやすくなる。段差追従性の観点から、樹脂組成物のtanδの極大ピーク温度は、48℃以下がより好ましく、44℃以下がさらに好ましく、42℃以下がよりさらに好ましい。
また、tanδの極大ピーク温度が10℃以上であると、粘着性が必要以上に高くなって取扱い性が低下することを防止できる。樹脂組成物のtanδの極大ピーク温度は、好ましくは12℃以上、より好ましくは20℃以上である。
なお、樹脂フィルムのtanδの極大ピーク温度は、動的粘弾性測定装置を用いて粘弾性測定を行い、粘弾性測定の結果から得られる損失正接tanδが最大値となるピーク温度を読み取ることで検出できる。
粘着フィルムは、上記のとおり熱可塑性樹脂を含有する。熱可塑性樹脂は、ゲル分率を低くする観点から、架橋構造を有しないか、有していても少ないとよい。粘着フィルムに使用される熱可塑性樹脂としては、例えば(メタ)アクリル系樹脂、ポリビニルアセタール系樹脂、ポリビニルアルコール系樹脂(PVA)、ポリウレタン系樹脂(PU)、エチレン-酢酸ビニル共重合体樹脂(EVA)、エチレン-酢酸ビニル共重合体けん化物(EVOH)、エチレン-メタクリル酸共重合体樹脂、アイオノマー樹脂、イソブチレン樹脂、スチレン-イソプレン共重合体樹脂、スチレン-ブタジエン共重合体樹脂などが挙げられる。
粘着フィルムにおいて、熱可塑性樹脂は1種単独で用いてもよく、2種以上を併用してもよい。
熱可塑性樹脂は、上記の中では、ポリビニルアセタール系樹脂が好ましい。ポリビニルアセタール系樹脂を使用することで、段差追従性を良好にしやすくなる。また、ゲル分率を低くし、かつ接着性も良好にしやすくなる。以下、熱可塑性樹脂に使用されるポリビニルアセタール系樹脂について詳細に説明する。
なお、重量平均分子量(Mw)は、ゲル浸透クロマトグラフィーにより測定されるものである。
上記の通り熱可塑性樹脂は、ポリビニルアセタール系樹脂であることが好ましい。ポリビニルアセタール系樹脂は、変性ポリビニルアセタール樹脂であってもよいし、未変性ポリビニルアセタール樹脂であってもよい。変性ポリビニルアセタール樹脂は、後述する通り、アセタール基、水酸基、及びアセチル基以外の構造(変性基)を有すればよく、好ましくは変性基を側鎖に有する。
ポリビニルアセタール系樹脂は、ポリビニルアルコールをアルデヒドでアセタール化し、さらに必要に応じて変性剤と反応させたり、再酢化処理したりすることで得られるものである。また、変性ポリビニルアセタール樹脂を得るには、原料となるポリビニルアルコールとして変性ポリビニルアルコールを使用してもよい。
(式(1)において、A1Oは炭素数2~6のオキシアルキレン基であり、mは平均繰り返し数であり、4~200である。R1は炭素数が1~8のアルキル基又は水素原子である。なお、オキシアルキレン基は1種単独でもよいし、2種類以上が混在していてもよい。*は他の基との結合位置である。)
オキシアルキレン基におけるアルキレン基は、直鎖であってもよいし、分岐構造を有してもよい。オキシアルキレン基としては、例えばオキシエチレン基、オキシプロピレン基、又はオキシブチレン基が挙げられ、好ましくはオキシエチレン基、オキシプロピレン基である。オキシアルキレン基は1種単独で使用してよいが、2種以上を併用してもよい。2種以上を併用する場合、各オキシアルキレン基は、ランダムに付加してもよいし、ブロックで付加してもよいが、ランダムに付加されることがより好ましい。
また、R1におけるアルキル基は、直鎖であってもよいし、分岐構造を有していてもよい。
R1におけるアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、s-ブチル、t-ブチル基どの分岐ブチル基、n-ペンチル基、分岐ペンチル基、n-ヘキシル基、分岐ヘキシル基、n-ヘプチル基、イソヘプチル基、3-ヘプチル基などの分岐ヘプチル基、n-オクチル基、イソオクチル基、2-エチルヘキシル基などの分岐オクチル基などが挙げられる。
R1は、好ましくは炭素数1~6のアルキル基又は水素原子であり、より好ましは炭素数1~4のアルキル基又は水素原子である。
単結合以外の連結基としては、エーテル結合(-O-)、エステル結合(-COO-)、アミド結合(-CONR-:Rは水素原子又は炭素数1~4のアルキル基、好ましくは水素原子)、又はこれら結合のうち少なくともいずれかを有してもよい炭化水素基が挙げられる。これらの中では、エーテル結合(-O-)、エステル結合(-COO-)、又はこれら結合のうち少なくともいずれかを有してもよい炭化水素基がより好ましい。該炭化水素基の炭素数は、特に限定されないが、例えば1~10程度であればよく、好ましくは1~4である。また、これらの中では、上記ポリアルキレンオキサイド構造は、エーテル結合又は-CH2O-のいずれかを介して、主鎖に結合されることがより好ましい。ポリアルキレンオキサイド構造は、これらのいずれかを介して主鎖に結合することで、その製造が容易になる。なお、-CH2O-においては、酸素原子が上記ポリアルキレンオキサイド構造に結合するとよい。
また、ポリビニルアセタール系樹脂は、変性することで、上記の通り、上記式(1)で示されるポリアルキレンオキサイド構造を有することが好ましい。なお、以下では、ポリアルキレンオキサイド構造を有するポリビニルアセタール系樹脂は、他のポリビニルアセタール系樹脂と区別して説明するために、変性ポリビニルアセタール樹脂(A)として説明することがある。
このような観点から、ポリアルキレンオキサイド構造による変性量は、0.2モル%以上が好ましく、0.3モル%以上がより好ましく、0.4モル%以上がさらに好ましく、0.5モル%以上が特に好ましく、また、8モル%以下が好ましく、6モル%以下がより好ましく、4モル%以下がさらに好ましい。
なお、エステル結合、ウレタン結合において、「*」及び「**」は、アルキル基又は主鎖に対する結合位置であり、各結合において「*」がアルキル基に対する結合位置で、「**」が主鎖に対する結合位置であることが好ましい。また、ウレタン結合において、Rは水素原子であることが好ましい。
ただし、ポリビニルアセタール系樹脂は、例えば未変性ポリビニルアセタール樹脂などである場合、上記のとおり水酸基を有さなくてもよく、式(3-2)で示される構成単位を有さなくてもよい。すなわち、未変性ポリビニルアセタール樹脂は、以下の式(3-1)及び式(3-3)で示される構成単位を有し、さらに任意で以下の式(3-2)で示される構成単位を有してもよい。
アセタール基としては、具体的にはブチラール基が特に好ましく、したがって、ポリビニルアセタール系樹脂としては、ポリビニルブチラール系樹脂が好ましい。ポリビニルアセタール系樹脂のアセタール化度(すなわち、アセタール量)は、例えば、40%以上であり、好ましくは60モル%以上である。また、アセタール化度は、65モル%以上がより好ましく、70モル%以上がさらに好ましく、また、好ましくは90モル%以下であり、より好ましくは88モル%以下であり、さらに好ましくは85モル%以下である。アセタール化度をこれら範囲内とすることで、水酸基の量を適度な量としつつ、式(1)で示される官能基を一定量含有させやすくなる。また、アセタール化度を60%以上とすると、85℃のせん断貯蔵弾性率を上記範囲内にしやすく、段差追従性を良好にしやすくなる。
なお、アセタール化度とは、ポリビニルアセタール系樹脂のアセタール基がアセトアセタール基である場合には、アセトアセタール化度を意味し、アセタール基がブチラール基である場合には、ブチラール化度を意味する。
また、アセタール化度は、ポリビニルアセタール系樹脂を構成する全ビニル単量体単位に対する、アセタール化されたビニルアルコール単位の割合を表す。
また、ポリビニルアセタール系樹脂の水酸基量は、0モル%以上であるとよいが、変性ポリビニルアセタール樹脂(A)である場合には、粘着フィルムが柔軟になりすぎることを防止する観点から、一定量の水酸基量を含有するとよく、例えば5モル%以上、好ましくは9モル%以上、より好ましくは10モル%以上、さらに好ましくは12モル%以上である。
なお、水酸基量は、ポリビニルアセタール系樹脂を構成する全ビニル単量体単位に対する、水酸基の割合を表す。
また、変性ポリビニルアセタール樹脂(A)のアセチル化度は、上記のとおり例えば0.01モル%以上であるが、好ましくは0.1モル%以上、より好ましくは0.3モル%以上である。
なお、アセチル化度は、ポリビニルアセタール系樹脂を構成する全ビニル単量体単位に対する、アセチル基の割合を表す。
本発明で使用するポリビニルアセタール系樹脂は、1種単独で使用してもよいし、2種以上を併用してもよい。
具体的には、ポリビニルアセタール系樹脂の含有量は、粘着フィルムに含有される熱可塑性樹脂全量基準で、例えば50質量%以上であり、好ましくは70質量%以上、より好ましくは90質量%以上、最も好ましくは100質量%である。したがって、本発明の粘着フィルムに含まれる熱可塑性樹脂は、ポリビニルアセタール系樹脂のみからなるものでもよい。
本発明の粘着フィルムは、可塑剤を含有してもよい。粘着フィルムは、可塑剤を含有することにより柔軟となり、粘着フィルムのtanδの極大ピーク温度を低くして、段差追従性をさらに良好にすることができる。ただし、本発明の粘着フィルムは、可塑剤を含有しないか、含有していても少量である。可塑剤を少量のみ含有し又は含有させないことで、ブリード性を良好にすることができる。
また、本発明の粘着フィルムは、可塑剤が少量であり又は含有しなくても、上記した所定の熱可塑性樹脂を使用することで、段差追従性をさらに良好にできる。
粘着フィルムのブリード性の観点から、可塑剤の上記含有量は、好ましくは15質量部以下であり、より好ましくは10質量部以下、さらに好ましくは5質量部以下、よりさらに好ましくは1質量部以下である。可塑剤の含有量の下限は、0質量部である。
本発明の樹脂組成物は、変性ポリビニルアセタール樹脂(A)を使用する場合には、可塑剤を含有しなくてもよいし、含有してもよいが、可塑剤を含有することで段差追従性を良好にしやすくなる。一方で、樹脂組成物は、未変性ポリビニルアセタール樹脂を使用する場合には、樹脂フィルムの接着性を向上させる観点から、可塑剤を含有したほうがよい。
可塑剤は1種単独で使用してもよいし、2種以上を併用してもよい。上記したなかでも、有機エステル可塑剤が好ましい。好ましい有機エステル可塑剤としては、一塩基性有機酸エステル及び多塩基性有機酸エステル等が挙げられる。
グリコールとしては、具体的には、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコール、ブチレングリコールなどが挙げられる。
一塩基性有機酸としては、炭素数3~10の有機酸が挙げられ、具体的には、酪酸、イソ酪酸、カプロン酸、2-エチル酪酸、ヘプチル酸、n-オクチル酸、2-エチルヘキシル酸、n-ノニル酸及びデシル酸などが挙げられる。
具体的には、セバシン酸ジブチル、アゼライン酸ジオクチル、アジピン酸ジヘキシル、アジピン酸ジオクチル、アジピン酸ヘキシルシクロヘキシル、アジピン酸ジイソノニル、アジピン酸ヘプチルノニル、ジブチルカルビトールアジペート、混合型アジピン酸エステルなどが挙げられる。また、油変性セバシン酸アルキドなどでもよい。混合型アジピン酸エステルとしては、炭素数4~9のアルキルアルコール及び炭素数4~9の環状アルコールから選択される2種以上のアルコールから作製されたアジピン酸エステルが挙げられる。
上記有機リン系可塑剤としては、トリブトキシエチルホスフェート、イソデシルフェニルホスフェート及びトリイソプロピルホスフェート等のリン酸エステルなどが挙げられる。
さらに、グリセリンなどの3価以上のアルコールと、一塩基性有機酸の部分エステルなどであってよい。一塩基性有機酸としては、炭素数3~24、好ましくは炭素数6~18の一塩基性有機酸が挙げられる。3価以上のアルコールと、一塩基性有機酸の部分エステルの具体例としては、グリセリンとステアリン酸のモノ又はジエステル、グリセリンと2-エチルヘキシル酸とのモノ又はジエステルなどが挙げられる。
有機エステル可塑剤としては、上記したなかでも、トリエチレングリコール-ジ-2-エチルヘキサノエート(3GO)が特に好適に用いられる。
具体的なポリオキシアルキレンエーテル系可塑剤としては、例えば、ポリオキシエチレンヘキシルエーテル、ポリオキシエチレンヘプチルエーテル、ポリオキシエチレンオクチルエーテル、ポリオキシエチレン-2-エチルヘキシルエーテル、ポリオキシエチレンノニルエーテル、ポリオキシエチレンデシルエーテル、ポリオキシエチレンアリルエーテル、ポリオキシプロピレンアリルエーテル、ポリオキシエチレングリセリルエーテル、ポリオキシプロピレングリセリルエーテル、ポリオキシエチレンジグリセリルエーテル、ポリオキシプロピレンジグリセリルエーテル、ポリオキシアルキレンペンタエリスリトールエーテルなどが挙げられる。
ポリオキシアルキレンエーテル系可塑剤は、好ましくは多価アルコールとポリオキシアルキレンとのエーテル化合物であり、より好ましくはグリセリン又はジグリセリンとポリオキシアルキレンとのエーテル化合物であり、更に好ましくはグリセリン又はジグリセリンとポリオキシプロピレンとのエーテル化合物である。
アルコール系可塑剤としては、ブタンジオール、ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトールなどの各種の多価アルコールが挙げられる。これらの中では、トリメチロールプロパンが好ましい。
可塑剤以外の添加剤は、具体的には、紫外線吸収剤、赤外線吸収剤、酸化防止剤、光安定剤、接着力調整剤、顔料、染料、蛍光増白剤、結晶核剤等が挙げられる。また、本発明の樹脂組成物は、溶媒により希釈されて希釈液の形態で使用されてもよい。
なお、低分子量化合物は、分子量1000未満の化合物をいい、上記した可塑剤や、光照射による硬化する反応性希釈剤などが挙げられる。反応性希釈剤としては、例えば、(メタ)アクリルモノマーや(メタ)アクリルオリゴマー等の(メタ)アクリル系反応性希釈剤や、エポキシモノマー、エポキシオリゴマー等のエポキシ系反応性希釈剤や、アルコキシシランモノマー、アルコキシシランオリゴマー等のシリコーン系反応性希釈剤等が挙げられる。 粘着フィルムにおける低分子量化合物の含有量は、ブリード性の観点から、粘着フィルムに含まれる熱可塑性樹脂100質量部に対して、例えば20質量部未満である。低分子量化合物の含有量は、ブリード性の観点から、好ましくは15質量部以下であり、より好ましくは10質量部以下、さらに好ましくは5質量部以下、よりさらに好ましくは1質量部以下である。また、上記した反応性希釈剤は、光硬化後に架橋して架橋構造を形成することがあるので、その点からも低分子量化合物の含有量は少なくすることが好ましい。低分子量化合物の含有量の下限は、0質量部である。
本発明の粘着フィルムで使用されるポリビニルアセタール系樹脂は、ポリビニルアルコール(「原料ポリビニルアルコール」ともいう)をアルデヒドでアセタール化し、その後、必要に応じて変性剤と反応させ、または再酢化処理をすることで得られるものである。原料ポリビニルアルコールとしては、未変性ポリビニルアルコールでもよいが、変性ポリビニルアセタール樹脂を得る場合には、原料ポリビニルアルコールとして変性ポリビニルアルコールを使用してもよい。
例えば、ポリアルキレンオキサイド構造を有する変性ポリビニルアセタール樹脂(A)を製造する際には、以下の製造方法(1)により製造することが好ましい。
本製造方法(1)では、まず、原料ポリビニルアルコールとしてポリオキシアルキレン変性ポリビニルアルコールを製造する。具体的には、ビニルエステルと、ポリオキシアルキレン基を有するビニルモノマーを含むモノマーを重合してポリマーを得た後、ポリマーをけん化することにより得られる。ケン化には、一般に、アルカリ又は酸が用いられるが、アルカリを用いることが好ましい。ポリオキシアルキレン変性ポリビニルアルコールとしては、1種のみが用いられてもよく、2種以上が併用されてもよい。
次いで、上記で得られたポリオキシアルキレン変性ポリビニルアルコールに対して、アルデヒドでアセタール化して、変性ポリビニルアセタール樹脂(A)を得るとよい。アセタール化の方法は、公知の方法で行うとよい。
(製造方法(2))
本製造方法(2)では、原料ポリビニルアルコールをアルデヒドでアセタール化して、ポリビニルアセタール系樹脂(以下、原料ポリビニルアセタール系樹脂ともいう)を得る。ここで、原料ポリビニルアルコールとしては、ポリビニルエステルをケン化して得られた未変性ポリビニルアルコールを使用する。次いで、原料ポリビニルアセタール系樹脂に対して、再酢化処理して、未変性ポリビニルアセタール樹脂を得るとよい。再酢化処理としては、従来公知の方法で行えばよいが、無水酢酸を用いてピリジンなどの塩基存在下で行えばよい。また、再酢化処理は、例えば50℃以上100℃以下、好ましくは70℃以上90℃以下程度に加熱して行うとよい。ポリビニルアセタール系樹脂は、再酢化処理されることで、水酸基量が少なくなり、tanδの極大ピーク温度を低くしやすくなり、段差追従性がさらに良好となる。
まず、原料ポリビニルアルコールをアルデヒドでアセタール化して、ポリビニルアセタール系樹脂(以下、原料ポリビニルアセタール系樹脂ともいう)を得る。ここで使用される原料ポリビニルアルコールは、ポリビニルエステルをケン化して得られたものであり、未変性ポリビニルアルコールであることが好ましい。
次に、上記原料ポリビニルアセタール系樹脂に対して、アルキル基を有する変性剤を反応させて、原料ポリビニルアセタール系樹脂にアルキル基を導入する。変性剤としては、原料ポリビニルアセタール系樹脂が有する水酸基に反応して、ウレタン結合やエステル結合を形成する反応性基を有する化合物であるとよい。具体的には、n-オクタデシルイソシアネートなどのアルキル基の炭素数が2~30であるアルキルイソシアネートが挙げられる。また、炭素数3~31のカルボン酸、又は上記カルボン酸の無水物、カルボン酸エステル、カルボン酸ハライドなどのカルボン酸誘導体が挙げられる。カルボン酸誘導体としては、2-エチルヘキサノイルクロリド、ラウロイルクロリド、ミリスチルクロリド、パルミトイルクロリド、ステアロイルクロリドなどのカルボン酸クロリドが好ましい。
また、多層フィルムは、上記した第1の層と、第1の層以外の層(以下、「第2の層」ともいう)との積層体であってもよい。具体的には、例えば第1の層/第2の層/第1の層の3層構造などが挙げられる。
なお、本発明の粘着フィルムが2層以上の多層フィルムである場合、各層がそれぞれ上記粘着フィルムで述べたとおりの組成であることが好ましい。
本発明の粘着フィルムは、ポリビニルアセタール系樹脂などの熱可塑性樹脂を含む樹脂組成物を公知の方法でフィルム状に成形することで製造することができる。樹脂組成物は、上記の通り製造されたポリビニルアセタール系樹脂などの熱可塑性樹脂を少なくとも含み、必要に応じて、可塑剤、添加剤などを添加して調製するとよい。また、樹脂組成物は、適宜溶媒に希釈して使用してもよい。
また、上記の通り、原料ポリビニルアセタール系樹脂を変性剤と反応させて、ポリビニルアセタール系樹脂を得る場合には、以下のように成形してもよい。すなわち、原料ポリビニルアセタール系樹脂と、変性剤と、その他の必要に応じて配合される可塑剤などの添加剤を含む組成物を、剥離シートなどの支持体上に塗布して、あるいは、型枠に流し込んで、その後、加熱することで変性剤を原料ポリビニルアセタール系樹脂に反応させつつフィルム状に成形してもよい。
合わせガラスは、自動車、電車などの車両、船舶、飛行機などの各種乗り物、あるいは、ビル、マンション、一戸建て、ホール、体育館などの各種建築物、あるいは切削、研磨などの工作機械、ショベルやクレーンなどの建設機械等の窓ガラスに使用されるが、中でも自動車などの車両用途が好ましい。本発明の粘着フィルムは、段差追従性及びブリード性が良好であるので、車載用ディスプレイなどの各種ディスプレイや車両用窓ガラスに使用することが適している。
なお、本発明の粘着フィルムが適用される合わせガラス及びディスプレイは、後述する積層体を備えるとよい。
本発明の粘着フィルムは、特に限定されないが、有機材料基材、無機材料基材などの基材とともに使用され、積層体の一部として使用されることが好ましい。本発明の積層体は、具体的には、上記粘着フィルムと、無機材料基材、及び有機材料基材の少なくともいずれかを備えるとよい。また、粘着フィルムは、無機材料基材、及び有機材料基材の少なくともいずれに接着するように配置されることが好ましく、より好ましくは有機材料基材に接着する位置に配置される。粘着フィルムは、各種樹脂材料に対する接着力が高いため、有機材料基材に接着する位置に配置されることで、高い接着力で基材に接着させることができる。
また、粘着フィルムが接着される少なくとも1つの基材の表面には、段差が設けられることが好ましい。
本発明では、基材表面に段差が設けられても、粘着フィルムは、段差追従性が良好であるので、視認性や貼り付け性が低下することを防止できる。
なお、段差を有する基材の詳細は、後述するが、段差の高さとしては、特に制限されないが、例えば10~500μm、好ましくは10~300μmである。
上記した中では、透明性、耐衝撃性に優れる点から、ポリカーボネート板が好ましく、透明性が高く、耐候性、機械強度に優れる点から、(メタ)アクリル板が好ましく、これらの中ではポリカーボネート板がより好ましい。
有機樹脂板の厚さは、特に限定されないが、好ましくは0.1mm以上、さらに好ましくは0.4mm以上であり、また、好ましくは5.0mm以下、さらに好ましくは3.0mm以下である。
樹脂フィルムの厚さは、特に限定されないが、好ましくは30μm以上、さらに好ましくは50μm以上であり、また、好ましくは500μm以下、さらに好ましくは450μm以下である。
なお、厚みが比較的大きく、柔軟性が低くて、一般的に折り曲げできないようなものを有機樹脂板という一方、厚みが比較的小さく、一般的に折り曲げ可能なものを概ね樹脂フィルムというが、これらは明確に区別されるものでない。
センサーとしては、タッチセンサーが挙げられる。タッチセンサーとは、指、タッチペン、その他の物体が基材に近づき、又は接触するタッチ入力を検知するセンサーであり、上記基材に積層される導電層により構成される。タッチセンサーは、指、タッチペン、その他の物体が、基材に近づき、又は接触することで、静電容量、電流、電圧などの電気的な変化が導電層に生じ、その電気的な変化により、タッチ入力を検知する。
導電層は、特に限定されず、従来公知の透明性を有する電極材料であれば特に限定なく用いることができ、例えば、インジウム錫酸化物(ITO)導電膜、酸化錫導電膜、酸化亜鉛導電膜、高分子導電膜などが挙げられる。
また、電極、センサーなどの導電層が積層された有機材料基材(特に、フィルム)は、導電層が設けられた面とは反対側の面に上記したハードコート層が形成されてもよい。導電層が設けられた面は、通常、粘着フィルムとの接着面となるが、本発明の粘着フィルムは、ハードコート層が設けられた面に対しても高い接着力を有することが可能である。
有機材料基材、又は無機材料基材は、その表面に導電層、印刷部が付されることで、段差を有することがあるが、典型的には印刷部が付されることで、段差を有する。
印刷部は、無機ガラス板、有機ガラス板などのガラスに付されることが好ましい。
このような多層構造において、接着用フィルムは、例えば、一対の基材の両方に接着され、それにより、一対の基材が接着用フィルムを介して接合されるとよい。この場合、接着用フィルムは、上記した本発明の粘着フィルムであるとよい。
中間部材は、上記した無機材料基材、及び有機材料基材の少なくともいずれを有するとよく、本発明の粘着フィルムが接着する位置に無機材料基材、及び有機材料基材の少なくともいずれが配置されるとよい。
また、表示素子31としては、有機EL表示素子、液晶表示素子が挙げられる。表示素子31は、その表面側の最外面に偏光板(偏光フィルム)が設けられることが好ましい。なお、表面側の最外面とは、表面保護パネル側の最外面であり、その反対側を裏面側ともいう。
偏光板(偏光フィルム)は、一般的にポリビニルアルコール樹脂フィルムなどの偏光子の両面に保護フィルムが設けられた構成を有する。保護フィルムは、上記した樹脂フィルムから構成され、好ましくは、PETフィルム、COPフィルム、又はTACフィルムのいずれかである。したがって、表示素子31の表面側の最外面には、一般的に有機材料基材が配置されることになる。
また、表示素子31は、その表面側の面に偏光板(偏光フィルム)が設けられない場合でも、表面側の最外面には保護フィルムが設けられるとよく、したがって、そのような場合でも、表示素子31の表面側の最表面は有機材料基材により構成されることになる。
また、タッチパネル33において、無機ガラス、有機樹脂板、又は樹脂フィルムは、これらのうちから2以上が積層されて多層構造体であってもよい。その場合も、タッチパネル33において、無機ガラス、有機樹脂板、又は樹脂フィルムのいずれかにタッチセンサーが付されるとよい。
また、タッチパネル33は、表面側の最表面、裏面側の最表面のいずれかに樹脂フィルムからなる保護フィルムが配置されてもよい。したがって、タッチパネル33は、接着用フィルム34A、34Bとの接着面が、無機ガラス、有機ガラス、及び樹脂フィルムのいずれかとなる。
本発明の粘着フィルムは、無機材料基材のみならず、各種樹脂材料(すなわち、有機材料基材)に対しても、高い接着力を有する。したがって、表示素子33、表面保護パネル32、及びタッチパネル33は、接着用フィルム34A、34Bとの接着面が、有機材料基材により構成されることがあるが、そのような場合でも、高い接着力で、表示素子31とタッチパネル33、及び表面保護パネル32とタッチパネル33とを接合させることができる。
また、接着用フィルム34は、段差追従性が高いので、段差のある基材(表面保護パネル32など)に接着されても、視認性や貼り付け性が低下することが防止できる。さらに、ブリード性も高いので、表示素子31の汚染なども防止できる。
表示素子31と、表面保護パネル32の詳細は、第1の実施形態で述べたとおりである。
本実施形態では接着用フィルム34が本発明の粘着フィルムからなる。接着用フィルム34(粘着フィルム)は、表示素子31及び表面保護パネル32に接着されて、これらを接合し、したがって、第1の実施形態と同様に、表示素子31と表面保護パネル32とは、高い接着力で接合されることになる。
また、本発明の粘着フィルムは、段差追従性が高いので、上記のように段差のある基材(表面保護パネル32)に接着されても、視認性や貼り付け性が低下することが防止できる。さらに、ブリード性も高いので、表示素子31の汚染なども防止できる。
合わせガラス部材41、42は、無機ガラス板、有機樹脂板のいずれでもよく、これらの詳細は上記で説明したとおりである。
また、合わせガラス部材41、42は、第1及び第2の実施形態と同様に、接着用フィルム34A,34Bとの接着面の少なくともいずれかに、黒セラなどの印刷部が設けられ、段差部を有することが好ましい。
調光素子43が備える樹脂フィルムとしては、PETフィルム、PENフィルムなどのポリエステル樹脂フィルム、(メタ)アクリル樹脂フィルム、TACフィルム、PES樹脂フィルム、ポリイミド樹脂フィルムなどが挙げられる。これらの中では、取扱い性などの観点から、ポリエステル樹脂フィルムが好ましく、中でもPETフィルムがより好ましい。
また、2枚の樹脂フィルムそれぞれには調光層側の面に電極を構成する導電層が設けられる。
本発明の粘着フィルムは、無機材料基材のみならず、各種樹脂材料に対しても、高い接着力を有するので、高い接着力で、合わせガラス部材41、42と、偏光素子43とを接合させることができる。
また、本発明の粘着フィルムは、段差追従性が高いので、段差のある合わせガラス部材41、42に接着されても、視認性や貼り付け性が低下することが防止できる。さらに、ブリード性も高いので、ブリードアウトにより、偏光素子43などが汚染されることも防止できる。
一対の合わせガラス部材41、42は、第3の実施形態において説明したとおりである。接着用フィルム34(粘着フィルム)は、合わせガラス部材41、42の両方に接着されて、これらを接合するので、合わせガラス部材41、42を高い接着力で接合することができる。
一対の合わせガラス部材41、42は、第3の実施形態において説明したとおりであり、少なくとも一方に印刷部が設けられ、段差部を有することが好ましい。接着用フィルム34(粘着フィルム)は、合わせガラス部材41、42の両方に接着されて、これらを接合するので、合わせガラス部材41、42に上記の通り段差があっても、視認性や貼り付け性が低下することが防止できる。また、ブリード性も高いので、周辺部材の汚染なども防止できる。
粘着フィルムをテトラヒドロフランに0.05重量%の濃度に溶解させ、シリンジフィルター(メルク社製、Millex-LH 0.45μm)を用いてろ過した後、ゲル浸透クロマトグラフィー(Waters社製、e2690)を用いて、分子量を測定した。重量平均分子量(Mw)は、単分散ポリスチレン標準試料により作成した分子量校正曲線を使用して算出した。また、カラムはShodex GPC KF-806L(昭和電工社製)を用い、溶離液としてテトラヒドロフランを用いた。
実施例、比較例で得られた粘着フィルムを、長さ10mm、幅5mmで切り出し、動的粘弾性測定装置(アイティー計測制御株式会社製、商品名「DVA-200」)を用いて、以下の測定条件で粘弾性を測定し、85℃におけるせん断貯蔵弾性率(G’)を検出した。
また、粘弾性測定の結果から得られる損失正接tanδのピーク温度を読みとった。-50~150℃の温度領域において上記ピーク温度のうち、tanδが最大値となるピーク温度をtanδの最大ピーク温度とした。
(測定条件)
変形様式:せん断モード、測定温度:-50℃~200℃、昇温速度:5℃/分、測定周波数:1Hz、歪:1%
ポリビニルアセタール系樹脂をクロロホルム-dに溶解し、1H-NMR(核磁気共鳴スペクトル)を用いて測定し、各ユニットのモル比を分析することで求めた。
明細書記載の方法に従って、各実施例、比較例の粘着フィルムを用いて、ゲル分率を測定した。
76mm×52mm×厚み1.0~1.2mmの大きさの白板ガラス(松浪硝子工業株式会社製、S9112)を用意した。
56mm×32mmの大きさの開口を有する76mm×52mm×厚み75μmの大きさの片面に粘着剤層を備えた枠体を作製した。この枠体を白板ガラスに貼り付けて、白板ガラスに段差を形成した。
粘着フィルムを76mm×52mmの大きさに切断して、切り出した粘着フィルムを、白板ガラスの段差を形成した面に貼り付けた。
さらに、ITOがコーティングされたポリエチレンテレフタレートフィルム(ITO-PET、積水ナノコートテクノロジー株式会社製)を76mm×52mmの大きさに切断し、粘着フィルムの上に貼り付け、積層体を作製した。この際、ITOがコーティングされた面とは、反対側の面が、粘着フィルムとの接着面となるようにした。
なお、枠体、粘着フィルム及びポリエチレンテレフタレートフィルムをそれぞれ貼り付ける際、できる限り気泡が入らないようにした。
そして、真空ラミネータを使用して、90℃及び1atmの条件で積層体を10分間圧着してから、オートクレーブを使用して、90℃、0.5MPaの条件で30分間処理し、その後、加熱を止めて、オートクレーブの温度が30℃以下になってからオートクレーブを解圧して、オートクレーブから積層体を取り出し、評価用サンプルを作製した。
デジタルマイクロスコープ(株式会社キーエンス製)を使用して、評価用サンプルの段差の界面を観察し、下記基準に基づいて評価した。
(評価基準)
AA:段差の界面での気泡残存を確認できなかった。
B:段差の界面での気泡残存を確認できた。
使用済みの各構成体から粘着フィルムを回収することを想定し、各粘着フィルムに、超高圧水銀灯を用いて、365nmの波長の光を4000mJ/cm2照射した。
混練機(商品名「ラボプラストミル」、株式会社東洋精機製作所製)を用いて、光を照射した後の粘着フィルムを、160℃、50rpmの条件で、10分間、溶融混錬を行った。そして、粘着フィルムを混練して得られた混練物を回収した。
得られた混練物を160℃、20MPaの条件でプレス成型して、30cm×30cm×200μmのシート状成形体を作製した。
デジタルマイクロスコープ(株式会社キーエンス製)を使用して、5枚のシート状成形体の外観を観察し、シート状成形体中の光学欠点の数を数え、下記基準に基づいて評価した。
(評価基準)
A:5枚のシート状成形体中の光学欠点の数の合計が5個未満であった。
B:5枚のシート状成形体中の光学欠点の数の合計が5個以上であった。
赤色の油性マジックを用いて、縦方向及び横方向にそれぞれ2本ずつ線を粘着フィルムに引き、4本の線で粘着フィルムにマーキングした。
マーキングした粘着フィルムの主面が、鉛直方向と平行な平面内に位置するように、マーキングした粘着フィルムを配置して、10℃の条件で2ヶ月間放置した。
マーキングした粘着フィルムを2ヶ月放置した後、2ヶ月放置したマーキングした粘着フィルムについて、ブリードアウトした可塑剤によるマーキングの滲み及び垂れが生じているか否かを目視で確認し、下記基準に基づいて評価した。
(評価基準)
AA:4本の線のいずれにも滲み及び垂れが見られず、可塑剤のブリードアウトが生じていなかった。
A:4本の線のうち、1本の線については、滲みもしくは垂れが見られた。しかし、他の3本の線については、滲み及び垂れが見られなかった。
B:4本の線のうち、2本以上の線について、滲みもしくは垂れが見られた。
[エチレンオキサイド変性ポリビニルアルコールの合成]
表1に記載のアリルエーテルモノマー(1)を用意した。アリルエーテルモノマー(1)は、式(4-2)に示す化合物であり、A1Oには、オキシエチレン基(EO)と、オキシプロピレン基(PO)が混在し、かつこれらはランダム構造であり、そのモル比、EOとPOの平均繰り返し数、及び末端基(R1)は、表1に示すとおりである。
攪拌機、温度計、滴下ロートおよび還流冷却器を付したフラスコ中に、酢酸ビニル515質量部、アリルエーテルモノマー(1)151質量部、及びメタノール333質量部を添加し、系内の窒素置換を行った後、温度を60℃まで昇温した。この系に2,2-アゾビスイソブチロニトリル1.3質量部を添加し、重合を開始した。重合開始から5時間で重合を停止した。オーブンで加熱を行い、未反応のモノマーとメタノールを除去した後、共重合体の40質量%メタノール溶液を調製した。
得られた共重合体のメタノール溶液100質量部を40℃で攪拌しながら、3質量%のNaOHメタノール溶液7.4質量部を添加して、よく混合した後に放置した。2時間後、固化したポリマーを粉砕機で粉砕し、メタノールで洗浄後、乾燥してポリマー粉末(エチレンオキサイド変性ポリビニルアルコール)を得た。
得られたポリマー粉末280gを純水2100gに加え、90℃の温度で約2時間攪拌し溶解させた。この溶液を40℃に冷却し、濃度35質量%の塩酸160質量部とn-ブチルアルデヒド130質量部を添加し、液温を20℃まで下げ、温度を保持してアセタール化反応を行い、反応生成物を析出させた。その後、液温を40℃として3時間保持して反応を完了させ、常法により中和、水洗及び乾燥を経て、ポリビニルアセタール系樹脂(PVB1)の白色粉末を得た。
得られたポリビニルアセタール系樹脂(PVB1)を、温度160℃、圧力20MPaでプレス成形して厚み200μmの粘着フィルムを得た。得られた粘着フィルムに対して、tanδの極大ピーク温度、せん断貯蔵弾性率(G’)、及びゲル分率を測定し、段差追従性、リサイクル性、及びブリード性を評価した。
粘着フィルムの厚みを表1に示すとおりに調整する以外は、実施例1と同様に実施した。
使用するアリルエーテルモノマーを、アリルエーテルモノマー(2)に変更して、かつ酢酸ビニル723質量部、アリルエーテルモノマー(2)257質量部、及びメタノール20質量部、2,2-アゾビスイソブチロニトリルを1質量部、重合温度を62℃に変更した以外は実施例1と同様に実施して、PVB2を得た。そして、PVB2を用いて、粘着フィルムの厚みを表1に示すとおりに調整する以外は実施例1と同様に粘着フィルムを作製した。得られた粘着フィルムに対して、実施例1と同様に物性を測定し、または評価を行った。
なお、アリルエーテルモノマー(2)は、式(4-2)に示す化合物であり、A1Oがオキシプロピレン基(PO)であり、その平均繰り返し数、及び末端基(R1)は、表1に示すとおりである。
酢酸ビニル552質量部、アリルエーテルモノマー(1)162質量部、及びメタノール286質量部、2,2-アゾビスイソブチロニトリルを1.4質量部に変更した以外は実施例1と同様に実施して、PVB3を得て、PVB3を用いて、粘着フィルムの厚みを表1に示すとおりに調整する以外は実施例1と同様に粘着フィルムを作製した。得られた粘着フィルムに対して、実施例1と同様に物性を測定し、または評価を行った。
酢酸ビニル572質量部、アリルエーテルモノマー(1)143質量部、及びメタノール286質量部、2,2-アゾビスイソブチロニトリルを0.7質量部に変更した以外は実施例1と同様に実施して、PVB4を得て、PVB4を用いて、粘着フィルムの厚みを表1に示すとおりに調整する以外は実施例1と同様に粘着フィルムを作製した。得られた粘着フィルムに対して、実施例1と同様に評価した。
使用するアリルエーテルモノマーを、アリルエーテルモノマー(3)に変更して、かつ酢酸ビニル751質量部、アリルエーテルモノマー(3)230質量部、及びメタノール20質量部、2,2-アゾビスイソブチロニトリルを1質量部に変更した以外は実施例1と同様に実施して、PVB5を得た。そして、PVB5を用いて、粘着フィルムの厚みを表1に示すとおりに調整する以外は実施例1と同様に粘着フィルムを作製した。得られた粘着フィルムに対して、実施例1と同様に評価した。
なお、アリルエーテルモノマー(3)は、式(4-2)に示す化合物であり、A1Oがオキシエチレン基(PO)と、オキシプロピレン基(PO)が混在し、その平均繰り返し数、及び末端基(R1)は、は表1に示すとおりである。
使用するアリルエーテルモノマーを、アリルエーテルモノマー(4)に変更して、かつ酢酸ビニル834質量部、アリルエーテルモノマー(4)147質量部、及びメタノール20質量部、2,2-アゾビスイソブチロニトリルを0.5質量部、重合温度を52℃に変更した以外は実施例1と同様に実施して、PVB6を得た。100質量部のPVB6に対して、15質量部の可塑剤(3GO)を混合して樹脂組成物を得て、得られた樹脂組成物を用いて、粘着フィルムの厚みを表1に示すとおりに調整する以外は実施例1と同様の方法でプレス成形して、粘着フィルムを得た。得られた粘着フィルムに対して、実施例1と同様に評価した。
なお、アリルエーテルモノマー(4)は、式(4-2)に示す化合物であり、A1Oがオキシエチレン基(EO)であり、その平均繰り返し数、及び末端基(R1)は、表1に示すとおりである。
使用するポリビニルアセタール系樹脂を、未変性ポリビニルブチラールであるPVB7を使用し、かつ100質量部のPVB7に対して、40質量部の可塑剤(3GO)を混合して、樹脂組成物を得て、得られた樹脂組成物を用いて実施例1と同様の方法でプレス成形して、粘着フィルムを得た。得られた粘着フィルムに対して、実施例1と同様に評価した。
使用するポリビニルアセタール系樹脂を、未変性ポリビニルブチラールであるPVB8を使用し、かつ100質量部のPVB8に対して、25質量部の可塑剤(3GO)を混合して、樹脂組成物を得て、得られた樹脂組成物を用いて実施例1と同様の方法でプレス成形して、粘着フィルムを得た。得られた粘着フィルムに対して、実施例1と同様に評価した。
使用するポリビニルアセタール系樹脂を、未変性ポリビニルブチラールであるPVB9を使用し、かつ可塑剤の混合をせずに実施例1と同様の方法でプレス成形して、粘着フィルムを得た。得られた粘着フィルムに対して、実施例1と同様に評価した。
使用するポリビニルアセタール系樹脂を、未変性ポリビニルブチラールであるPVB7を使用した。100質量部のPVB7に対して、30質量部の可塑剤(3GO)、10質量部の反応性希釈剤(トリメチロールプロパントリアクリレート:TMPA)、及び光重合開始剤としてのベンゾフェノン(BP)0.1質量部を混合して、樹脂組成物を得て、得られた樹脂組成物を用いて実施例1と同様の方法でプレス成形して、粘着フィルムを得た。得られた粘着フィルムに対して、ブリード性の評価を行った。また、粘着フィルムに対して、超高圧水銀灯を用いて、365nmの波長の光を4000mJ/cm2照射し、光照射後に、ゲル分率、せん断貯蔵弾性率(G’)、tanδの最大ピーク温度を測定した。また、リサイクル性の評価を行った。
段差追従性については、比較例4で作製した粘着フィルムを用いて上記評価方法で述べたとおりに積層体を製造して、その積層体に対して超高圧水銀灯を用いて、365nmの波長の光を4000mJ/cm2照射した。その後、段差追従性を評価した。
原料として使用するポリビニルブチラールを、PVB1の代わりに、未変性ポリビニルブチラールであるPVB8を使用した。100質量部のPVB8に対して、10質量部の可塑剤(3GO)、20質量部の反応性希釈剤(TMPA)、及び光重合開始剤としてのベンゾフェノン0.2質量部を混合して、樹脂組成物を得て、得られた樹脂組成物を用いて実施例1と同様の方法でプレス成形して、粘着フィルムを得た。得られた粘着フィルムに対して、ブリード性の評価を行った。また、粘着フィルムに対して、超高圧水銀灯を用いて、365nmの波長の光を4000mJ/cm2照射し、光照射後にゲル分率、せん断貯蔵弾性率(G’)、tanδの最大ピーク温度を測定した。
段差追従性については、比較例5で作製した粘着フィルムを用いて上記評価方法で述べたとおりに積層体を製造して、その積層体に対して超高圧水銀灯を用いて、365nmの波長の光を4000mJ/cm2照射した。その後、段差追従性を評価した。
表3に示すモノマー比でモノマーを重合して得た(メタ)アクリル系重合体(Ac1)100質量部を固形分量45質量%になるように酢酸エチルで希釈して、固形分基準で、イソシアネート系架橋剤(日本ポリウレタン社製「コロネートL-45」、固形分量45質量%)を1質量部添加して、樹脂組成物を得た。得られた樹脂組成物を、離型PETフィルムの離型処理面に乾燥後の厚さが150μmになるように塗工して、80℃で15分間乾燥して、粘着フィルムを得た。得られた粘着フィルムに対して、23℃で5日間養生した後、実施例1と同様に評価した。
(メタ)アクリル系重合体(Ac1)を(メタ)アクリル系重合体(Ac2)に変更した点を除いて比較例6と同様に実施した。
それに対して、比較例1~3では、可塑剤の含有量が熱可塑性樹脂100質量部に対して20質量部よりも大きかったため、ブリード性が悪かった。また、比較例3~6では、ゲル分率が15%よりも大きかったため、リサイクル性が悪かった。さらん、比較例5、6では、85℃におけるせん断貯蔵弾性率が低すぎて、段差追従性も低下した。
31 表示素子
32 表面保護パネル
34、34A、34B 接着用フィルム(粘着フィルム)
32 第2の層
41、42 合わせガラス部材
43 偏光素子
Claims (14)
- 熱可塑性樹脂を含み、
85℃におけるせん断貯蔵弾性率が0.06×106Pa以上1.00×106Pa以下であり、
可塑剤を含まない、又は前記熱可塑性樹脂100質量部に対して可塑剤を20質量部未満で含み、
ゲル分率が15%以下である、粘着フィルム。 - 前記熱可塑性樹脂の重量平均分子量(Mw)が600,000以下である、請求項1に記載の粘着フィルム。
- 厚みが100μm以上2000μm以下である、請求項1又は2に記載の粘着フィルム。
- tanδの極大ピーク温度が10℃以上52℃以下である、請求項1~3のいずれか1項に記載の粘着フィルム。
- 前記熱可塑性樹脂がポリビニルアセタール系樹脂である、請求項1~4のいずれか1項に記載の粘着フィルム。
- 前記ポリアルキレンオキサイド構造におけるオキシアルキレン基は、オキシエチレン基及びオキシプロピレン基の少なくともいずれかを含む、請求項6に記載の粘着フィルム。
- 前記ポリアルキレンオキサイド構造におけるオキシアルキレン基は、オキシエチレン基及びオキシプロピレン基の両方を含有する、請求項6又は7に記載の粘着フィルム。
- アセタール化度が60モル%以上である、請求項6~8のいずれか1項に記載の粘着フィルム。
- 一対の基材を接合するために使用される請求項1~9のいずれか1項に記載の粘着フィルム。
- 第1の有機材料基材と、第2の有機材料基材もしくは無機材料基材とを接合するときに使用され、前記第1の有機材料基材及び前記第2の有機材料基材が、偏光フィルム、ポリエチレンテレフタレートフィルム、ポリカーボネート板、及び(メタ)アクリル板からなる群から選択される少なくとも1種の有機材料基材である、請求項10に記載の粘着フィルム。
- 請求項1~11のいずれか1項に記載の粘着フィルムと、一対の基材を備え、前記粘着フィルムが一対の基材の間に配置される、積層体。
- 請求項12に記載の積層体を含む液晶ディスプレイ。
- 請求項12に記載の積層体を含む合わせガラス。
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WO2017061545A1 (ja) * | 2015-10-07 | 2017-04-13 | 積水化学工業株式会社 | ポリビニルアセタール樹脂組成物、接着シート、タッチパネル用層間充填材料及び積層体 |
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JP2020131566A (ja) * | 2019-02-20 | 2020-08-31 | 住友化学株式会社 | 積層体、粘着剤層および粘着シート |
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JP2004115591A (ja) * | 2002-09-24 | 2004-04-15 | Mitsui Chemicals Inc | 粘着フィルム及びその使用方法 |
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