WO2016047610A1 - 積層体 - Google Patents
積層体 Download PDFInfo
- Publication number
- WO2016047610A1 WO2016047610A1 PCT/JP2015/076728 JP2015076728W WO2016047610A1 WO 2016047610 A1 WO2016047610 A1 WO 2016047610A1 JP 2015076728 W JP2015076728 W JP 2015076728W WO 2016047610 A1 WO2016047610 A1 WO 2016047610A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- foam layer
- adhesive foam
- adhesive
- laminate according
- foam
- Prior art date
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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
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- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/006—Presence of (meth)acrylic polymer in the substrate
-
- 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
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/50—Protective arrangements
- G02F2201/503—Arrangements improving the resistance to shock
Definitions
- the present invention relates to a laminate comprising an adhesive foam excellent in impact absorption even if the thickness is small, and the generation of wrinkles and the like is suppressed during handling.
- an image display member fixed to an image display device such as a liquid crystal display, an electroluminescence display, a plasma display, a display member attached to a so-called “mobile phone”, “smart phone”, “portable information terminal”, camera,
- a foam material is used when an optical member such as a lens is fixed to a predetermined part (for example, a housing).
- Examples of such a foam material include a low-foam, fine-cell urethane-based foam having a closed cell structure and a product obtained by compression molding a highly foamed urethane, and a polyethylene-based foam having a closed cell and an expansion ratio of about 30 times. It was used.
- a gasket made of a polyurethane foam having an apparent density of 0.3 to 0.5 g / cm 3 , or an electrical / electric structure made of a foam structure having an average cell diameter of 1 to 500 ⁇ m.
- a sealing material for electronic devices is used.
- shock absorbing sheets used to prevent damage to display members, etc. As electronic devices such as PCs (personal computers), tablet PCs, PDAs (personal personal digital assistants), and mobile phones become more sophisticated. These members (for example, a heat conductive layer) are stacked and incorporated. Due to the further thinning of electronic devices in recent years, it has become desirable to further reduce the thickness of members such as the shock absorbing sheet used therein, and the adhesiveness at the time of lamination of the shock absorbing sheet and other members is increased. There is a demand for thinning of the adhesive layer or no adhesive layer.
- the shock absorbing sheet is composed of an adhesive foam, and a release liner or the like is laminated on both sides of the sheet and wound into a roll shape to be distributed in the market
- the adhesive foam is wrinkled or broken at the time of production, distribution or use.
- an object of the present invention is a laminate including an adhesive foam that exhibits excellent shock absorption even when the thickness is very small, and the adhesive foam is produced during the production or distribution of the laminate.
- An object of the present invention is to provide a laminate that does not cause wrinkles or breakage in the adhesive foam during use of the body.
- the present inventors have found that in a laminate in which a support is laminated on both sides of an adhesive foam layer, the adhesive foam layer has a specific average cell diameter.
- the laminate is manufactured and distributed, and the adhesive foam layer is used.
- the present invention has been completed by finding that the adhesive foam can suppress the occurrence of wrinkles and creases and that the adhesive foam exhibits excellent shock absorption.
- the present invention is a laminate having a support on both sides of an adhesive foam layer composed of a foam having an average cell diameter of 10 to 200 ⁇ m, the bending elastic modulus (23 ° C.) of at least one support. ) Is 300 to 4000 MPa, tensile strength (23 ° C., tensile speed 200 mm / min) is 100 MPa or less, and tensile elongation (23 ° C., tensile speed 200 mm / min) is 80% or more. To do.
- the thickness of the adhesive foam layer is preferably 30 to 1000 ⁇ m, and the apparent density of the foam constituting the adhesive foam layer is preferably 0.2 to 0.7 g / cm 3 .
- the foam constituting the adhesive foam layer has a loss tangent (tan ⁇ ), which is a ratio of storage elastic modulus and loss elastic modulus at an angular frequency of 1 rad / s in dynamic viscoelasticity measurement, of ⁇ 30 ° C. or more and 30 ° C. It is preferable to have a peak top in the following range.
- the 180 ° peel adhesive strength (23 ° C., tensile speed 300 mm / min) to the SUS304BA plate on at least one surface of the adhesive foam layer is 0.05 N / 25 mm or more (particularly 0.1 N / 25 mm or more). ) Is preferable.
- the foam constituting the adhesive foam layer is formed of at least one resin material selected from the group consisting of acrylic polymer, rubber, urethane polymer, and ethylene-vinyl acetate copolymer. Is preferred.
- the adhesive foam layer may be formed through Step A for mechanically foaming the emulsion resin composition. Moreover, the said adhesive foam layer may be formed through the process B which further coats the emulsion resin composition foamed mechanically on the base material, and dries.
- the step B includes a preliminary drying step B1 of drying the bubble-containing emulsion resin composition applied on the substrate at 50 ° C. or higher and lower than 125 ° C., and then a main drying step of further drying at 125 ° C. or higher and 200 ° C. or lower. B2 may be included.
- the bending elastic modulus (23 ° C.) of the at least one support is preferably 350 to 3000 MPa, more preferably 400 to 2500 MPa.
- the thickness of the adhesive foam layer is preferably 40 to 500 ⁇ m, more preferably 50 to 300 ⁇ m.
- the apparent density of the foam constituting the adhesive foam layer is preferably 0.21 to 0.6 g / cm 3 , more preferably 0.22 to 0.5 g / cm 3 .
- the present invention also provides a wound body in which the laminate is wound into a roll.
- the laminate of the present invention is a laminate having supports on both sides of an adhesive foam layer having an average cell diameter of 10 to 200 ⁇ m, and the bending elastic modulus, tensile strength, and tensile elongation of at least one of the supports. Since the degree is within a specific range, it is possible to suppress the occurrence of wrinkles and creases in the adhesive foam during the production and distribution of the laminate, the use of the adhesive foam layer, etc., and the adhesive foam Exhibits excellent shock absorption.
- FIG. 1 It is a schematic block diagram of a pendulum type impact tester (impact test device). It is a figure which shows schematic structure of the holding member of a pendulum type impact tester (impact test apparatus).
- the laminate of the present invention is a laminate having supports on both sides of an adhesive foam layer composed of a foam having an average cell diameter of 10 to 200 ⁇ m, and has a flexural modulus (23 of at least one support).
- ° C. is 300 to 4000 MPa
- tensile strength 23 ° C., tensile speed 200 mm / min
- tensile elongation 23 ° C., tensile speed 200 mm / min
- the laminate of the present invention has an adhesive foam layer.
- the pressure-sensitive adhesive foam layer is used as a foam sheet (in particular, a shock absorbing foam sheet).
- the adhesive foam layer has tack at room temperature (23 ° C.). Therefore, adhesion and fixation with an adherend or another member can be easily performed.
- an adhesive foam layer may be comprised only from the foam, the adhesive layer (adhesion layer) may be provided in the at least one surface of the foam.
- the average cell diameter of the foam constituting the adhesive foam layer is 10 to 200 ⁇ m, and the lower limit thereof is preferably 15 ⁇ m, more preferably 20 ⁇ m, and the upper limit is preferably 150 ⁇ m, more preferably 130 ⁇ m, still more preferably. Is 100 ⁇ m. When the average cell diameter is 10 ⁇ m or more, excellent impact absorbability is exhibited. Moreover, since the average cell diameter is 200 ⁇ m or less, the compression recovery property is also excellent.
- the maximum cell diameter of the foam is, for example, 40 to 800 ⁇ m, the lower limit is preferably 60 ⁇ m, more preferably 80 ⁇ m, and the upper limit is preferably 400 ⁇ m, more preferably 220 ⁇ m.
- the minimum cell diameter of the foam is, for example, 5 to 70 ⁇ m, and the lower limit is preferably 8 ⁇ m, more preferably 10 ⁇ m, and the upper limit is preferably 60 ⁇ m, more preferably 50 ⁇ m.
- the thickness of the adhesive foam layer (foam) is not particularly limited, but is, for example, 30 to 1000 ⁇ m.
- the lower limit is more preferably 40 ⁇ m, still more preferably 50 ⁇ m, and the upper limit is more preferably 500 ⁇ m, still more preferably 300 ⁇ m, and particularly preferably 200 ⁇ m.
- the thickness of the pressure-sensitive adhesive foam layer is 30 ⁇ m or more, it is possible to contain bubbles uniformly and to exhibit more excellent impact absorbability.
- by setting the thickness of the adhesive foam layer to 1000 ⁇ m or less, it is possible to easily follow a minute clearance. In the present invention, even if the thickness of the adhesive foam layer is as thin as 30 to 1000 ⁇ m, the shock absorption is excellent.
- the ratio of the average cell diameter ( ⁇ m) to the thickness of the adhesive foam layer ( ⁇ m) is in the range of 0.1 to 0.9. Is preferred.
- the lower limit of the ratio of the average cell diameter ( ⁇ m) to the thickness of the adhesive foam layer ( ⁇ m) is preferably 0.2, more preferably 0.3, and the upper limit is preferably 0.85. Preferably it is 0.8.
- the apparent density of the foam constituting the adhesive foam layer is not particularly limited, but is preferably 0.2 to 0.7 g / cm 3 .
- the lower limit is more preferably 0.21 g / cm 3 , further preferably 0.22 g / cm 3
- the upper limit is more preferably 0.6 g / cm 3 , still more preferably 0.5 g / cm 3 , and particularly preferably 0.4 g / cm 3 .
- the apparent density of the foam is 0.2 g / cm 3 or more, higher strength can be maintained, and when it is 0.7 g / cm 3 or less, higher impact absorbability is exhibited. Further, when the apparent density of the foam is in the range of 0.2 to 0.4 g / cm 3 , higher impact absorbability is exhibited.
- the impact absorption can be adjusted by selecting the average cell diameter, apparent density, etc., but when the thickness of the adhesive foam layer is very small (for example, when the thickness is 30 to 500 ⁇ m, it may not be possible to sufficiently absorb the impact only by adjusting these characteristics. This is because, when the thickness of the adhesive foam layer is very thin, the bubbles in the adhesive foam layer are immediately crushed by impact, and the impact buffering function by the bubbles disappears.
- the peak top of the loss tangent (tan ⁇ ) which is the ratio of the storage elastic modulus to the loss elastic modulus at an angular frequency of 1 rad / s in the dynamic viscoelasticity measurement of the foam constituting the adhesive foam layer. Is preferably in the range of ⁇ 30 ° C. or higher and 30 ° C. or lower. By doing in this way, even after bubbles are crushed, the constituent material of the foam exerts more functions of buffering the impact.
- the lower limit of the temperature range where the loss tangent peak top is present is more preferably ⁇ 25 ° C., further preferably ⁇ 20 ° C., particularly preferably ⁇ 10 ° C., and the upper limit is more preferably 20 ° C., further preferably 10 ° C.
- the peak temperature is ⁇ 30 ° C. or higher, more excellent compression recovery is exhibited.
- the peak temperature is 30 ° C. or lower, higher flexibility is exhibited, and more excellent shock absorption is exhibited.
- the peak top strength (maximum value) of loss tangent (tan ⁇ ) in the range of ⁇ 30 ° C. or higher and 30 ° C. or lower is preferably higher from the viewpoint of shock absorption, for example, 0.2 or higher, preferably 0.3 or higher.
- the upper limit value of the peak top intensity (maximum value) is, for example, 2.0.
- the peak temperature of the loss tangent (tan ⁇ ) often contributes to the impact absorption of the foam.
- the peak top of the loss tangent (tan ⁇ ) which is the ratio of the storage elastic modulus and loss elastic modulus at an angular frequency of 1 rad / s in the dynamic viscoelasticity measurement of the foam, is in the range of ⁇ 30 ° C.
- the reason why the shock absorption of the foam is high is not necessarily clear, but it is presumed that the loss tangent (tan ⁇ ) peak exists at the frequency matching the shock. That is, the range where the loss tangent (tan ⁇ ) is ⁇ 30 ° C. or higher and 30 ° C.
- the storage elastic modulus is a repulsive force against the impact energy applied to the foam, and when the storage elastic modulus is high, the impact is repelled as it is.
- the loss elastic modulus is a physical property that changes impact energy applied to the foam to heat, and the higher the loss elastic modulus, the more the impact energy is changed to heat, so the impact is absorbed and the strain is reduced.
- the foam has a higher shock absorption rate as the foam has a larger loss tangent (tan ⁇ ), which is a ratio of the storage elastic modulus and the loss elastic modulus, which changes the impact to heat and has a smaller repulsive force. .
- the foam constituting the adhesive foam layer is not particularly limited in its composition and cell structure as long as it has the above-mentioned characteristics.
- the cell structure may be any of an open cell structure, a closed cell structure, and a semi-continuous semi-closed cell structure. From the viewpoint of impact absorption, an open cell structure and a semi-open semi-closed cell structure are preferable.
- the adhesive foam layer in the present invention has an excellent impact absorbability even though it is thin because the average cell diameter of the foam is 10 to 200 ⁇ m.
- the impact absorption rate (%) defined by the following formula is expressed as an adhesive foam. Dividing by the layer thickness ( ⁇ m), the shock absorption rate R per unit thickness is obtained.
- R of the adhesive foam layer in this invention will be 0.08 or more, for example.
- the upper limit value of R is, for example, about 0.5 (usually about 0.3).
- Impact absorption rate (%) ⁇ (F 0 ⁇ F 1 ) / F 0 ⁇ ⁇ 100 (In the above formula, F 0 is the impact force when the impactor collides only with the support plate, and F 1 is the impactor on the support plate of the structure composed of the support plate and the adhesive foam layer). (Impact force when the two are collided)
- the impact absorption rate varies depending on the thickness of the adhesive foam layer and the like, but is usually 5 to 70%, and the lower limit is preferably 7%, more preferably 9%, and particularly preferably 10%.
- the upper limit is preferably 60% (usually about 30%).
- the impact test apparatus 1 (pendulum tester 1) includes a holding member 3 as a holding means for holding the test piece 2 (adhesive foam layer 2) with an arbitrary holding force, An impact load member 4 that applies an impact stress to the test piece 2 and a pressure sensor 5 as an impact force detection means that detects an impact force of the impact load member 4 against the test piece 2 are configured.
- the holding member 3 that holds the test piece 2 with an arbitrary holding force includes a fixing jig 11 and a holding jig 12 that is slidable so as to sandwich and hold the test piece 2 facing the fixing jig 11. It is configured.
- the pressing jig 12 is provided with a pressing pressure adjusting means 16.
- the impact load member 4 for applying an impact force to the test piece 2 held by the holding member 3 is supported so that one end 22 is pivotally supported with respect to the column 20 and an impactor 24 is provided on the other end side. It is composed of a rod 23 (shaft 23) and an arm 21 that lifts and holds the impactor 24 at a predetermined angle.
- a steel ball is used as the impactor 24, it is possible to lift the impactor 24 integrally by a predetermined angle by providing an electromagnet 25 at one end of the arm.
- the pressure sensor 5 that detects the impact force acting on the test piece 2 by the impact load member 4 is provided on the opposite side of the surface of the fixing jig 11 that contacts the test piece.
- the impactor 24 is a steel ball (iron ball).
- the angle at which the impactor 24 is lifted by the arm 21 is 47 °.
- the weight of the steel ball (iron ball) is 96 g.
- the test piece 2 (adhesive foam layer 2) has a high elasticity such as a resin plate (such as an acrylic plate or a polycarbonate plate) or a metal plate between the fixing jig 11 and the holding jig 12. It is clamped via a support plate 28 made of a flexible plate material.
- a resin plate such as an acrylic plate or a polycarbonate plate
- a metal plate between the fixing jig 11 and the holding jig 12. It is clamped via a support plate 28 made of a flexible plate material.
- the impact absorbability is an impact force F 0 measured by causing the impactor 24 to collide with the support plate 28 after tightly fixing the fixing jig 11 and the support plate 28 using the impact test apparatus described above.
- the impact force F 1 measured by causing the impactor 24 to collide with the support plate 28 after inserting the test piece 2 between the fixing jig 11 and the support plate 28 and fixing the test piece 2 tightly is calculated.
- the Note that the impact test apparatus is the same apparatus as that of Example 1 of JP-A-2006-47277.
- the foam which comprises the said adhesive foam layer can be comprised with the resin composition containing a resin material (polymer).
- the loss which is a ratio of the storage elastic modulus and the loss elastic modulus at an angular frequency of 1 rad / s in the dynamic viscoelasticity measurement of the resin composition in an unfoamed state [resin composition when not foamed (solid matter)]
- the peak top of the tangent (tan ⁇ ) is preferably in the range of ⁇ 30 ° C. to 30 ° C.
- the lower limit of the temperature range where the loss tangent peak top is present is more preferably ⁇ 25 ° C., further preferably ⁇ 20 ° C., particularly preferably ⁇ 10 ° C., and the upper limit is more preferably 20 ° C., further preferably 10 ° C.
- the peak top strength of (tan ⁇ ) (corresponding to the value obtained by dividing the apparent density (g / cm 3 ) of the foam) is preferably higher from the viewpoint of impact absorption.
- the peak top strength of the loss tangent (tan ⁇ ) in the range of ⁇ 30 ° C. to 30 ° C. of the resin composition (solid material) is preferably 0.9 (g / cm 3 ) ⁇ 1 or more,
- the upper limit is, for example, about 3 (g / cm 3 ) ⁇ 1 .
- the resin material (polymer) constituting the foam of the adhesive foam layer is not particularly limited, and a known or well-known resin material constituting the foam can be used.
- the resin material include acrylic polymers, rubbers, urethane polymers, and ethylene-vinyl acetate copolymers. Among these, acrylic polymers, rubbers, and urethane polymers are preferable from the viewpoint of impact absorption.
- One type of resin material (polymer) constituting the foam may be used alone, or two or more types may be used.
- the Tg of the resin material (polymer) can be used as an index or a guide.
- the resin material (polymer) has a Tg of ⁇ 50 ° C. or more and less than 50 ° C. (lower limit is preferably ⁇ 40 ° C., more preferably ⁇ 30 ° C., upper limit is preferably 40 ° C., more preferably 30 ° C.) It can be selected from resin materials (polymers) in the range.
- the ratio of the storage elastic modulus and loss elastic modulus at an angular frequency of 1 rad / s in dynamic viscoelasticity measurement is obtained by adjusting the amount ratio of the former monomer and the latter monomer.
- a foam having a loss tangent (tan ⁇ ) peak top of ⁇ 30 ° C. or higher and 30 ° C. or lower can be obtained relatively easily.
- glass transition temperature (Tg) when forming a homopolymer means “glass transition temperature (Tg of homopolymer of the monomer)”.
- Tg of homopolymer glass transition temperature (Tg of homopolymer of the monomer).
- the Tg of a homopolymer of a monomer not described in the above document refers to, for example, a value obtained by the following measurement method (see JP 2007-51271 A).
- this homopolymer solution is cast-coated on a separator and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm.
- This test sample was punched into a disk shape having a diameter of 7.9 mm, sandwiched between parallel plates, and subjected to a shear strain at a frequency of 1 Hz using a viscoelasticity tester (ARES, manufactured by Rheometrics). Viscoelasticity is measured in a shear mode at a heating rate of 150 ° C. and 5 ° C./min, and the peak top temperature of tan ⁇ is defined as Tg of the homopolymer.
- the Tg of the resin material (polymer) can also be measured by this method.
- the Tg is, for example, ⁇ 10 ° C. to 250 ° C., preferably 10 to 230 ° C., more preferably 50 to 200 ° C.
- Examples of the homopolymer having a Tg of ⁇ 10 ° C. or more include, for example, (meth) acrylonitrile; amide group-containing monomers such as (meth) acrylamide and N-hydroxyethyl (meth) acrylamide; (meth) acrylic acid; methacrylic acid (Meth) acrylic acid alkyl esters having homopolymers such as methyl and ethyl methacrylate having a Tg of ⁇ 10 ° C. or higher; (meth) acrylic acid isobornyl; heterocycle-containing vinyl monomers such as N-vinyl-2-pyrrolidone; Examples thereof include hydroxyl group-containing monomers such as ethyl methacrylate. These can be used individually by 1 type or in combination of 2 or more types. Among these, (meth) acrylonitrile (especially acrylonitrile) is particularly preferable in terms of impact absorption.
- amide group-containing monomers such as (meth) acrylamide and N-
- the Tg is, for example, ⁇ 70 ° C. or more and less than ⁇ 10 ° C., preferably ⁇ 70 ° C. to ⁇ 12 ° C., more preferably ⁇ 65 ° C. to ⁇ 15 ° C. .
- Examples of the homopolymer having a Tg of less than ⁇ 10 ° C. include, for example, (meth) acrylic acid alkyl esters having a homopolymer Tg of less than ⁇ 10 ° C., such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. Is mentioned. These can be used individually by 1 type or in combination of 2 or more types. Among these, acrylic acid C 2-8 alkyl ester is particularly preferable.
- the content of the monomer having a Tg of -10 ° C. or more of the homopolymer is, for example, 2 to 30% by weight with respect to all the monomer components forming the acrylic polymer (total amount of monomer components), and the lower limit is preferably 3% by weight. %, More preferably 4% by weight, and the upper limit is preferably 25% by weight, more preferably 20% by weight.
- the content of the monomer having a Tg of the homopolymer of less than ⁇ 10 ° C. with respect to all the monomer components forming the acrylic polymer (total amount of monomer components) is, for example, 70 to 98% by weight, and the lower limit is preferably The upper limit is preferably 97% by weight, more preferably 96% by weight.
- the viscosity of the composition decreases when the emulsion resin composition is foamed by applying mechanical shearing or the like. Many bubbles are likely to be taken into the emulsion, and when the emulsion resin composition containing the bubbles is applied onto a substrate and dried in a stationary state, the composition tends to aggregate and the viscosity is increased. The foam rises and the bubbles are retained in the composition and hardly diffused to the outside, so that a foam having excellent foaming characteristics can be obtained.
- nitrogen atom-containing copolymerizable monomer examples include cyano group-containing monomers such as (meth) acrylonitrile; lactam ring-containing monomers such as N-vinyl-2-pyrrolidone; (meth) acrylamide, N And amide group-containing monomers such as hydroxyethyl (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and diacetoneacrylamide.
- cyano group-containing monomers such as acrylonitrile and lactam ring-containing monomers such as N-vinyl-2-pyrrolidone are preferable.
- a nitrogen atom containing monomer can be used individually by 1 type or in combination of 2 or more types.
- the content of the structural unit derived from the nitrogen atom-containing monomer is preferably 2 to 2 with respect to all the structural units constituting the acrylic polymer.
- the lower limit is more preferably 3% by weight, still more preferably 4% by weight, and the upper limit is more preferably 25% by weight, still more preferably 20% by weight.
- an acrylic acid C 2-18 alkyl ester (particularly acrylic acid C 2 -8 alkyl ester) is preferred.
- Acrylic acid C 2-18 alkyl ester can be used alone or in combination of two or more.
- the content of structural units derived from acrylic acid C 2-18 alkyl esters (particularly acrylic acid C 2-8 alkyl esters) is based on the total structural units constituting the acrylic polymer.
- the lower limit is more preferably 75% by weight, still more preferably 80% by weight, and the upper limit is more preferably 97% by weight, still more preferably 96% by weight. .
- the rubber may be natural rubber or synthetic rubber.
- examples of the rubber include nitrile rubber (NBR), methyl methacrylate-butadiene rubber (MBR), styrene-butadiene rubber (SBR), acrylic rubber (ACM, ANM), urethane rubber (AU), and silicone rubber.
- NBR nitrile rubber
- MRR methyl methacrylate-butadiene rubber
- SBR styrene-butadiene rubber
- ACM acrylic rubber
- AU urethane rubber
- silicone rubber silicone rubber.
- urethane polymer examples include polycarbonate polyurethane, polyester polyurethane, and polyether polyurethane.
- ethylene-vinyl acetate copolymer a known or well-known ethylene-vinyl acetate copolymer can be used.
- the foam constituting the foam sheet contains a surfactant, a crosslinking agent, a thickener, a rust inhibitor, a silicone compound, and other additives as necessary. Also good.
- an optional surfactant may be included for the purpose of reducing the bubble diameter and stabilizing the foam.
- the surfactant is not particularly limited, and any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like may be used. From the viewpoint of the stability of the foam, an anionic surfactant is preferable, and a fatty acid ammonium surfactant such as ammonium stearate is more preferable.
- Surfactant may be used individually by 1 type and may be used in combination of 2 or more type. Different surfactants may be used in combination, for example, an anionic surfactant and a nonionic surfactant, or an anionic surfactant and an amphoteric surfactant may be used in combination.
- the addition amount [solid content (nonvolatile content)] of the surfactant is, for example, 0 to 10 parts by weight with respect to 100 parts by weight of the resin material (polymer) [solid content (nonvolatile content)], and the lower limit is preferably 0.5 part by weight, the upper limit is preferably 8 parts by weight.
- an arbitrary cross-linking agent may be included.
- the crosslinking agent is not particularly limited, and any of oil-soluble and water-soluble may be used.
- examples of the crosslinking agent include epoxy, oxazoline, isocyanate, carbodiimide, melamine, and metal oxide. Among these, an oxazoline-based crosslinking agent is preferable.
- the addition amount [solid content (nonvolatile content)] of the crosslinking agent is, for example, 0 to 10 parts by weight with respect to 100 parts by weight of the resin material (polymer) [solid content (nonvolatile content)], and the lower limit is preferably 0. 0.01 parts by weight, more preferably 0.1 parts by weight, and the upper limit is preferably 9 parts by weight, more preferably 8 parts by weight.
- an optional thickener may be included.
- the thickener is not particularly limited, and examples thereof include acrylic acid type, urethane type, and polyvinyl alcohol type. Of these, polyacrylic acid thickeners and urethane thickeners are preferred.
- the addition amount of the thickener is, for example, 0 to 10 parts by weight with respect to 100 parts by weight of the resin material (polymer) [solid content (nonvolatile content)], and the lower limit is preferably 0.1 parts by weight, the upper limit is preferably 5 parts by weight.
- an arbitrary rust inhibitor may be included to prevent corrosion of the metal member adjacent to the adhesive foam layer.
- an azole ring-containing compound is preferable. When an azole ring-containing compound is used, it is possible to achieve both high levels of corrosion prevention for metals and adhesion to adherends.
- the azole ring-containing compound may be a compound having a 5-membered ring containing one or more nitrogen atoms in the ring.
- compounds having a ring, a thiazole ring, or an isothiazole ring may be condensed with an aromatic ring such as a benzene ring to form a condensed ring.
- Examples of the compound having such a condensed ring include a compound having a benzimidazole ring, a benzopyrazole ring, a benzotriazole ring, a benzoxazole ring, a benzoisoxazole ring, a benzothiazole ring, or a benzoisothiazole ring.
- the azole ring and the condensed ring each may have a substituent.
- substituents include alkyl groups having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms) such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; methoxy group, ethoxy group, isopropyloxy
- a compound in which an azole ring forms a condensed ring with an aromatic ring such as a benzene ring is preferable.
- a benzotriazole compound (a compound having a benzotriazole ring), a benzothiazole compound ( A compound having a benzothiaazole ring) is particularly preferred.
- benzotriazole compounds include 1,2,3-benzotriazole, methylbenzotriazole, carboxybenzotriazole, carboxymethylbenzotriazole, and 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole.
- 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole, 2,2 ′-[[(methyl-1H-benzotriazol-1-yl) methyl] imino] bisethanol, or these A sodium salt etc. are mentioned.
- benzothiazole compound examples include 2-mercaptobenzothiazole, 3- (2- (benzothiazolyl) thio) propionic acid, or a sodium salt thereof.
- the azole ring-containing compound may be used alone or in combination of two or more.
- the addition amount [solid content (nonvolatile content)] of the rust inhibitor (for example, the azole ring-containing compound) [solid content (nonvolatile content)] is within a range that does not impair the adhesion to the adherend and the original properties of the foam.
- 0.2 to 5 parts by weight is preferable with respect to 100 parts by weight of the resin material (polymer) [solid content (nonvolatile content)].
- the lower limit is more preferably 0.3 parts by weight, still more preferably 0.4 parts by weight, and the upper limit is more preferably 3 parts by weight, still more preferably 2 parts by weight.
- a silicone compound may be added to improve the thickness recoverability and recovery speed of the pressure-sensitive adhesive foam layer after being compressed.
- a silicone-modified polymer for example, a silicone-modified acrylic polymer, a silicone-modified urethane polymer, etc.
- a silicone-modified urethane polymer may be used as at least a part of the resin material (polymer). These can be used alone or in combination of two or more.
- the silicone compound is preferably a silicone compound having a siloxane bond of 2000 or less.
- examples of the silicone compound include silicone oil, modified silicone oil, and silicone resin.
- silicone oil straight silicone oil
- examples of silicone oil include dimethyl silicone oil and methylphenyl silicone oil.
- modified silicone oil examples include polyether-modified silicone oil (polyether-modified dimethyl silicone oil, etc.), alkyl-modified silicone oil (alkyl-modified dimethyl silicone oil, etc.), aralkyl-modified silicone oil (aralkyl-modified dimethyl silicone oil, etc.), higher fatty acids
- modified silicone oil examples include ester-modified silicone oil (higher fatty acid ester-modified dimethyl silicone oil and the like), fluoroalkyl-modified silicone oil (fluoroalkyl-modified dimethyl silicone oil and the like), and the like.
- polyether-modified silicone is preferred.
- examples of commercially available polyether-modified silicone oils include “PEG11 methyl ether dimethicone”, “PEG / PPG-20 / 22 butyl ether dimethicone”, “PEG-9 methyl ether dimethicone”, “PEG-32 methyl ether dimethicone”, “ Linear type such as “PEG-9 dimethicone”, “PEG-3 dimethicone”, “PEG-10 dimethicone”; branched such as “PEG-9 polydimethylsiloxyethyl dimethicone”, “lauryl PEG-9 polydimethylsiloxyethyl dimethicone” Examples include the type (manufactured by Shin-Etsu Silicone).
- the silicone resin includes straight silicone resin and modified silicone resin.
- the straight silicone resin include methyl silicone resin and methylphenyl silicone resin.
- the modified silicone resin include alkyd-modified silicone resin, epoxy-modified silicone resin, acrylic-modified silicone resin, and polyester-modified silicone resin.
- the total content of the silicone compound and the silicone chain part present in the silicone-modified polymer in the adhesive foam layer (foam) is 100 parts by weight of the resin material (polymer) in the adhesive foam layer. On the other hand, it is, for example, 0.01 to 5 parts by weight in terms of non-volatile content (in terms of solid content).
- the lower limit of the total content is preferably 0.05 parts by weight, more preferably 0.1 parts by weight, and the upper limit is preferably 4 parts by weight, more preferably 3 parts by weight.
- the total content of the silicone compound and the silicone chain portion present in the silicone-modified polymer in the adhesive foam layer (foam) is, in terms of non-volatile content (solid content), for example, 0. 01 to 5% by weight.
- the lower limit of the total content is preferably 0.05% by weight, more preferably 0.1% by weight, and the upper limit is preferably 4% by weight, more preferably 3% by weight.
- the adhesive foam layer may contain any appropriate other component within a range not impairing the impact absorbability.
- Such other components may contain only 1 type and may contain 2 or more types.
- the other components include polymer components other than those described above, softeners, antioxidants, anti-aging agents, gelling agents, curing agents, plasticizers, fillers, reinforcing agents, foaming agents (such as baking soda), micro Capsules (thermally expandable microspheres, etc.), flame retardants, light stabilizers, UV absorbers, colorants (pigments, dyes, etc.), pH adjusters, solvents (organic solvents), thermal polymerization initiators, photopolymerization initiators, etc. Is mentioned.
- the addition amount [solid content (nonvolatile content)] of these components may be in a range that does not impair the adhesion to the adherend and the original properties of the foam.
- resin material (polymer) solid content (nonvolatile content)
- a range of 0.2 to 60 parts by weight per 100 parts by weight is preferable.
- the amount of foaming agent (such as baking soda) added [solid content (nonvolatile content)] is more preferably 0.5 to 20 parts by weight relative to 100 parts by weight of the resin material (polymer) [solid content (nonvolatile content)]. It is.
- the addition amount [solid content (nonvolatile content)] of microcapsules (thermally expandable microspheres, etc.) is more preferably 0.2 parts per 100 parts by weight of resin material (polymer) [solid content (nonvolatile content)]. ⁇ 10 parts by weight.
- the addition amount [solid content (nonvolatile content)] of the filler is more preferably 0.3 to 50 parts by weight with respect to 100 parts by weight of the resin material (polymer) [solid content (nonvolatile content)].
- the filler examples include silica, clay (mica, talc, smectite, etc.), alumina, aluminum hydroxide, alkaline earth metal hydroxide (magnesium hydroxide, etc.), and alkaline earth metal carbonate (carbonic acid). Calcium, etc.), titania, zinc oxide, tin oxide, zeolite, graphite, carbon black, carbon nanotube, inorganic fiber (carbon fiber, glass fiber, potassium titanate fiber, etc.), organic fiber, metal powder (silver, copper, etc.), Examples thereof include wax (polyethylene wax, polypropylene wax, etc.).
- piezoelectric particles titanium oxide, barium titanate, etc.
- conductive particles conductive carbon black, conductive titanium oxide, tin oxide, etc.
- thermally conductive particles boron nitride, etc.
- organic filler Silicone powder, polyethylene powder, polypropylene powder, etc.
- silica is used as the filler, the amount added is particularly preferably in the range of 0.5 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin [solid content (nonvolatile content)].
- the addition amount is particularly preferably in the range of 0.3 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin [solid content (nonvolatile content)].
- the addition amount thereof is particularly preferably in the range of 5 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin [solid content (nonvolatile content)].
- the addition amount thereof is particularly preferably in the range of 5 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin [solid content (nonvolatile content)].
- the adhesive foam layer in the present invention can be produced by subjecting a resin composition containing a resin material (polymer) constituting the foam to foam molding.
- foaming method bubble forming method
- methods usually used for foam molding such as physical methods and chemical methods, can be employed.
- the physical method is to disperse a gas component such as air or nitrogen in a polymer solution and form bubbles by mechanical mixing.
- the chemical method is a method of obtaining a foam by forming cells with a gas generated by thermal decomposition of a foaming agent added to a polymer base. From the viewpoint of environmental problems, a physical method is preferable. Bubbles formed by physical methods are often open cells.
- the resin composition containing the resin material (polymer) to be subjected to foam molding a resin solution in which the resin material is dissolved in a solvent may be used. From the viewpoint of cellularity, it is preferable to use an emulsion containing the resin material. . As an emulsion, you may blend and use 2 or more types of emulsion.
- the solid content concentration of the emulsion is preferably higher from the viewpoint of film formability.
- the solid content concentration of the emulsion is preferably 30% by weight or more, more preferably 40% by weight or more, and further preferably 50% by weight or more.
- a method of producing an adhesive foam layer (foam) through a step of foaming the emulsion resin composition mechanically is preferred.
- the foaming device is not particularly limited, and examples thereof include a high-speed shearing method, a vibration method, and a pressurized gas discharge method. Among these, the high-speed shearing method is preferable from the viewpoint of finer bubble diameter and production of a large capacity.
- Bubbles when foamed by mechanical stirring are gas (gas) taken into the emulsion.
- the gas is not particularly limited as long as it is inert to the emulsion, and examples thereof include air, nitrogen, carbon dioxide and the like. Among these, air is preferable from the viewpoint of economy.
- the adhesive foam layer (foam) in the present invention can be obtained through a step (Step B) in which the emulsion resin composition foamed by the above method is applied onto a substrate and dried.
- a step (Step B) in which the emulsion resin composition foamed by the above method is applied onto a substrate and dried.
- the peeled plastic film peeling-treated polyethylene terephthalate film etc.
- the plastic film polyethylene terephthalate film etc.
- Step B a general method can be adopted as a coating method and a drying method.
- Step B includes a preliminary drying step B1 for drying the bubble-containing emulsion resin composition applied on the substrate at 50 ° C. or higher and lower than 125 ° C., and then a main drying step B2 for further drying at 125 ° C. or higher and 200 ° C. or lower. Preferably it is.
- the preliminary drying step B1 and the main drying step B2 it is possible to prevent the bubbles from being coalesced and the bubbles to burst due to a rapid temperature rise.
- the bubbles are united or ruptured due to a rapid rise in temperature, so that it is significant to provide the preliminary drying step B1.
- the temperature in the preliminary drying step B1 is preferably 50 ° C. or higher and 100 ° C. or lower.
- the time of the preliminary drying step B1 is, for example, 0.5 minutes to 30 minutes, preferably 1 minute to 15 minutes. Moreover, the temperature in this drying process B2 becomes like this.
- the main drying step B2 is, for example, 0.5 minutes to 30 minutes, preferably 1 minute to 15 minutes.
- the average cell diameter, maximum cell diameter, and minimum cell diameter of the foam constituting the adhesive foam layer can be adjusted by adjusting the type and amount of the surfactant, and by adjusting the stirring speed and stirring time during mechanical stirring. By doing so, a foam having an average cell diameter in the range of 10 to 150 ⁇ m can be obtained.
- the apparent density of the foam constituting the adhesive foam layer can be controlled by adjusting the amount of gas (gas) component taken into the emulsion resin composition during mechanical stirring.
- the adhesive foam layer in the present invention may have an adhesive layer (adhesive layer) on one or both sides of the sheet-like foam as described above. It does not specifically limit as an adhesive which comprises an adhesive layer, For example, any of an acrylic adhesive, a rubber adhesive, a silicone adhesive, etc. may be sufficient. In addition, when the foam which comprises the adhesive foam layer of this invention has tackiness, it is not necessary to provide an adhesive layer.
- the thickness of the pressure-sensitive adhesive layer is, for example, 1 to 100 ⁇ m, and the lower limit is preferably 4 ⁇ m, more preferably 5 ⁇ m, and the upper limit is preferably 50 ⁇ m, more preferably 30 ⁇ m.
- the 180 ° peel adhesive strength (measuring condition: 23 ° C., tensile speed 300 mm / min) to the SUS304BA plate on at least one surface of the adhesive foam layer is preferably 0.05 N / 25 mm or more.
- the lower limit of the 180 ° peel adhesive strength is preferably 0.07 N / 25 mm, more preferably 0.10 N / 25 mm, and the upper limit is preferably 2.00 N / 25 mm, more preferably 1.00 N / 25 mm. .
- the adherend when the 180 ° peel adhesive strength is in the above range, when the adhesive foam layer is used as an adhesive foam sheet, the adherend may be used without newly providing an adhesive layer on the foam sheet.
- a laminate with another member for example, a heat conductive layer
- the thickness of the laminate of the foamed sheet and the other member can be reduced, which can contribute to further thinning of electrical / electronic devices and the like to be attached. Furthermore, the manufacturing efficiency of the laminate can be improved and the cost can be reduced.
- the 180 ° peel peel force for the SUS304BA plate on at least one surface of the adhesive foam layer is, for example, the type of monomer constituting the resin material (polymer) constituting the foam of the adhesive foam layer and its composition It can be adjusted by selecting the ratio.
- the Tg of the homopolymer is less than ⁇ 10 ° C. (for example, ⁇ 70 ° C. or more and less than ⁇ 10 ° C., preferably ⁇ 70 ° C. to ⁇ 12 ° C., more preferably ⁇ 65 ° C.
- the resin material polymer such as acrylic polymer
- the resin material polymer such as acrylic polymer
- 70 to 98% by weight the lower limit is preferably 75% by weight, the upper limit is preferably 97% by weight
- the 180 ° peel release force is set as described above by appropriately selecting the type and amount of other monomers. Can be in the range.
- the laminate of the present invention has supports on both sides of the adhesive foam layer. Even if the support is a “release liner” (separator) that is peeled and removed when the adhesive foam layer is used as an adhesive foam sheet, the adhesive foam layer is used as an adhesive foam sheet. It may be a “base material” used in a form integrated with the adhesive foam layer without being removed. However, at least one of the supports on both sides of the adhesive foam layer is a release liner. More preferably, the supports on both sides of the adhesive foam layer are release liners.
- the “release liner” is not particularly limited, and a known or commonly used release paper can be used.
- a support having a release layer such as a plastic film, paper, cloth, non-woven fabric, felt, or net that has been surface-treated with a release agent such as silicone, long-chain alkyl, fluorine, or molybdenum sulfide; polytetrafluoroethylene , Low-adhesive support made of a fluoropolymer such as polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, chlorofluoroethylene / vinylidene fluoride copolymer;
- a low-adhesive support made of a nonpolar polymer such as a series resin (for example, polyethylene, polypropylene, etc.) can be used.
- the “base material” is not particularly limited, and base materials of various materials can be used.
- fiber base materials such as cloth, nonwoven fabric, felt and net; paper systems such as various papers
- Base materials Plastic base materials such as films and sheets made of various resins; Rubber base materials such as rubber sheets; Foams such as foam sheets; Use of appropriate thin leaves such as metal foil and laminates thereof it can.
- the material or material of the plastic base material include polyester (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc.), polyolefin (polyethylene, polypropylene, ethylene-propylene copolymer, etc.), polyvinyl, and the like.
- the base material may have a single layer form or may have a multiple layer form. When a base material has a form of a multilayer, each layer may be the same base material and may combine a different base material.
- the thickness of the support is not particularly limited, but is preferably about 8 to 100 ⁇ m, the lower limit is more preferably 10 ⁇ m, particularly preferably 20 ⁇ m, and the upper limit is more preferably 80 ⁇ m, particularly preferably 70 ⁇ m. is there. If the thickness of the support is less than the above range, the strength of the laminate is too low, which may impair practicality. On the other hand, if the thickness of the support exceeds the above range, it is bulky, inferior in handleability and economy, and particularly when the support is the above-mentioned “base material”, the electric / electronic component comprising this can be thinned. It tends to be difficult.
- the bending elastic modulus (23 ° C.) of at least one of the supports on either side of the adhesive foam layer (which may be a “release liner” or a “substrate”) is 300. It is important that the tensile strength (23 ° C., tensile speed 200 mm / min) is 100 MPa or less and the tensile elongation (23 ° C., tensile speed 200 mm / min) is 80% or more.
- the tensile strength and tensile elongation of at least one direction (for example, MD direction) of the support in the MD direction and the TD direction may be in the above ranges, respectively.
- the lower limit of the flexural modulus is preferably 350 MPa, more preferably 400 MPa, and the upper limit is preferably 3000 MPa, more preferably 2500 MPa. Further, the lower limit of the tensile strength is, for example, 5 MPa, preferably 10 MPa, and the upper limit thereof is preferably 80 MPa, more preferably 60 MPa.
- the lower limit of the tensile elongation is preferably 100%, more preferably 120%, and the upper limit is, for example, 400%, preferably 250%.
- the adhesive foam is produced during production and distribution of the laminate.
- the layer is used as an impact absorbing sheet, the adhesive foam layer is less likely to be wrinkled or broken.
- the adhesive foam layer does not wrinkle or break, and the appearance and appearance stability are improved. It will be excellent.
- the flexural modulus of the support on both sides of the adhesive foam layer is less than 300 MPa, the function as the support is lowered, and the flexural modulus of the support on both sides of the adhesive foam layer is both 4000 MPa.
- trackability with respect to winding falls and it becomes easy to produce a wrinkle and a crease in an adhesive foam layer.
- the tensile strength of the support on both sides of the adhesive foam layer exceeds 100 MPa, or when the tensile elongation of the support on both sides of the adhesive foam layer is less than 80%, When the body is used as a wound body, the followability with respect to winding is reduced, and the adhesive foam layer is likely to be wrinkled or broken.
- the adhesive foam layer which may be a “release liner” or a “substrate”
- the product of the thickness ( ⁇ m) of the adhesive foam layer is preferably 9000 to 1000000 (MPa ⁇ ⁇ m), and the lower limit thereof is more preferably 10,000 (MPa ⁇ ⁇ m), and particularly preferably 12000 (MPa ⁇ ⁇ m).
- the upper limit is more preferably 300,000 (MPa ⁇ ⁇ m), and particularly preferably 150,000 (MPa ⁇ ⁇ m).
- the flexural modulus may be outside the range of 300 to 4000 MPa, but in order to maintain the function as a support, 300 MPa or more. Is preferred.
- the tensile strength of one of the supports on both sides of the adhesive foam layer may not be 100 MPa or less, but is preferably in the range of 50 to 300 MPa.
- the tensile elongation of one of the supports on both sides of the adhesive foam layer may not be 80% or more, but is preferably in the range of 50 to 300%.
- the flexural modulus, tensile strength, and tensile elongation of the support can be within the above ranges.
- a particularly preferable material for bringing the flexural modulus, tensile strength, and tensile elongation of the support within the above ranges include polyolefins such as polyethylene and unstretched polypropylene; and nonwoven fabrics.
- the release force of the release liner (peeling force against the adhesive foam layer) (23 ° C., tensile speed 300 mm) / Min, 180 ° peel peel force) is preferably 0.01 to 1 N / 50 mm, more preferably 0.02 to 0.5 N / 50 mm, and still more preferably 0.04 to 0.1 N / 50 mm.
- the release force of the release liner is in the above range, the release liner can be prevented from floating from the adhesive foam layer when the laminate is wound, and when the adhesive foam layer is used, The release liner can be easily peeled and removed.
- the laminate of the present invention may be distributed on the market as a wound body (rolled material) wound in a roll shape. Even when the laminate of the present invention is used as a wound body, it can be smoothly wound, and the support does not float from the adhesive foam layer, and wrinkles or breakage does not occur in the adhesive foam layer.
- the adhesive foam layer in the laminate of the present invention is excellent in impact absorption even if the thickness is small. Therefore, for example, in an electrical / electronic device, various members or parts (for example, optical members) are used for attaching (attaching) a predetermined part (for example, a housing) to a member for electrical / electronic devices, In particular, it is useful as an impact absorbing sheet.
- an image display member mounted on an image display device such as a liquid crystal display, an electroluminescence display, or a plasma display (particularly, a small image display).
- display members such as touch panels attached to mobile communication devices such as so-called “mobile phones”, “smartphones” and “portable information terminals”, cameras and lenses (particularly small cameras and lenses), etc. Can be mentioned.
- the electric / electronic device is, for example, an electric / electronic device provided with a display member, and the above-mentioned adhesive foam layer (or an adhesive foam layer having a substrate on one side) is the electric or electronic device.
- An electrical / electronic device having a structure sandwiched between a housing of the device and the display member is included.
- Examples of the electric / electronic devices include mobile communication devices such as so-called “mobile phones”, “smartphones”, and “portable information terminals”.
- % representing the content means% by weight.
- all the compounding parts are values in terms of solid content (non-volatile content).
- Example 1 100 parts by weight of acrylic emulsion solution (solid content 55%, ethyl acrylate-butyl acrylate-acrylonitrile copolymer (weight ratio 45: 48: 7)), fatty acid ammonium surfactant (aqueous dispersion of ammonium stearate, 3 parts by weight of solid content (33%), 0.35 parts by weight of oxazoline-based crosslinking agent (“Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd., 39% solid content), polyacrylic acid thickener (ethyl acrylate-acrylic acid) 0.8 part by weight of a copolymer (acrylic acid 20% by weight, solid content 28.7%) was stirred and mixed with a disper (“Robomix” Primix) to make foam.
- a disper Robot
- This foamed composition was applied onto a release-treated PET (polyethylene terephthalate) film (trade name “MRF # 38”, manufactured by Mitsubishi Plastics, thickness: 38 ⁇ m) (release liner I), and 4. 5 minutes, dried at 140 ° C. for 4.5 minutes, open cell with thickness 130 ⁇ m, apparent density 0.27 g / cm 3 , bubble rate 73.0%, maximum cell diameter 109 ⁇ m, minimum cell diameter 10 ⁇ m, average cell diameter 47 ⁇ m An adhesive foam layer with a structure was prepared.
- a polyethylene release liner A (trade name “PE-50-SU-C1 (Tomei)”, manufactured by Fujiko Co., Ltd., thickness: 50 ⁇ m, flexural modulus: 1000 MPa, tensile strength : 20 MPa, tensile elongation: 180%) (release liner II) was laminated to obtain a laminate having a layer configuration of release liner I / adhesive foam layer / release liner II.
- the tan ⁇ peak top temperature of the foam of the adhesive foam layer is ⁇ 3 ° C.
- the strength (maximum value) is 0.37
- the shock absorption rate is 16.4%
- the shock absorption per unit thickness was 0.13 (% / ⁇ m).
- Example 2 In Example 1, instead of the polyethylene release liner A, the polyethylene release liner B (trade name “80RL-02 Milky White”, manufactured by Oji Ftec Co., Ltd., thickness: 80 ⁇ m, flexural modulus: 900 MPa, A laminate having a layer configuration of release liner I / adhesive foam layer / release liner II is obtained in the same manner as in Example 1 except that tensile strength: 19.6 MPa and tensile elongation: 250% are used. It was.
- the polyethylene release liner B trade name “80RL-02 Milky White”, manufactured by Oji Ftec Co., Ltd., thickness: 80 ⁇ m, flexural modulus: 900 MPa
- a laminate having a layer configuration of release liner I / adhesive foam layer / release liner II is obtained in the same manner as in Example 1 except that tensile strength: 19.6 MPa and tensile elongation: 250% are used. It was.
- Example 3 In Example 1, as the release liner II, instead of the polyethylene release liner A, an unstretched polypropylene release liner A (trade name “CPP-40-SU-C1”, manufactured by Fujiko Co., Ltd., thickness: 40 ⁇ m, flexural elasticity A laminate having a layer configuration of release liner I / adhesive foam layer / release liner II in the same manner as in Example 1 except that rate: 2000 MPa, tensile strength: 40 MPa, and tensile elongation: 200%. Got.
- CPP-40-SU-C1 unstretched polypropylene release liner A
- flexural elasticity A laminate having a layer configuration of release liner I / adhesive foam layer / release liner II in the same manner as in Example 1 except that rate: 2000 MPa, tensile strength: 40 MPa, and tensile elongation: 200%.
- Example 4 In Example 1, instead of the polyethylene release liner A, the nonwoven fabric A (trade name “EH-5030”, manufactured by Asahi Kasei Fibers Co., Ltd., thickness: 30 ⁇ m, flexural modulus: 500 MPa, tensile strength: 15 MPa is used as the release liner II. , Tensile elongation: 130%) was used in the same manner as in Example 1 to obtain a laminate having a layer configuration of release liner I / adhesive foam layer / release liner II.
- the nonwoven fabric A trade name “EH-5030”, manufactured by Asahi Kasei Fibers Co., Ltd., thickness: 30 ⁇ m, flexural modulus: 500 MPa, tensile strength: 15 MPa is used as the release liner II. , Tensile elongation: 130%) was used in the same manner as in Example 1 to obtain a laminate having a layer configuration of release liner I / adhesive foam layer / release liner II.
- Example 5 In Example 1, instead of the polyethylene release liner A, the nonwoven fabric B (trade name “EH-5025”, manufactured by Asahi Kasei Fibers Co., Ltd., thickness: 25 ⁇ m, flexural modulus: 800 MPa, tensile strength: 15 MPa is used as the release liner II. , Tensile elongation: 130%) was used in the same manner as in Example 1 to obtain a laminate having a layer configuration of release liner I / adhesive foam layer / release liner II.
- the nonwoven fabric B trade name “EH-5025”, manufactured by Asahi Kasei Fibers Co., Ltd., thickness: 25 ⁇ m, flexural modulus: 800 MPa, tensile strength: 15 MPa is used as the release liner II. , Tensile elongation: 130%) was used in the same manner as in Example 1 to obtain a laminate having a layer configuration of release liner I / adhesive foam layer / release liner II.
- Example 1 As the release liner II, instead of the polyethylene release liner A, a release-treated PET (polyethylene terephthalate) film (thickness: 25 ⁇ m, trade name “MRF # 25”, manufactured by Mitsubishi Plastics, Inc., flexural elasticity)
- Example 2 In Example 1, as the release liner II, instead of the polyethylene release liner A, a PET (polyethylene terephthalate) film (thickness: 38 ⁇ m, trade name “MRF # 38”, manufactured by Mitsubishi Plastics, Inc., flexural elasticity) A laminate having a layer configuration of release liner I / adhesive foam layer / release liner II in the same manner as in Example 1 except that the ratio was 9100 MPa, the tensile strength was 270 MPa, and the tensile elongation was 130%. Got.
- a PET polyethylene terephthalate film
- An average cell diameter ( ⁇ m) was obtained by capturing an enlarged image of the foam cross section with a low vacuum scanning electron microscope (“S-3400N scanning electron microscope” manufactured by Hitachi High-Tech Science Systems) and analyzing the image. The number of bubbles analyzed is about 10 to 20. Similarly, the minimum cell diameter ( ⁇ m) and the maximum cell diameter ( ⁇ m) of the foam were determined.
- the adhesive foam layer (foam) is punched with a 100 mm ⁇ 100 mm punching blade mold, and the dimensions of the punched sample are measured. Further, the thickness is measured with a 1/100 dial gauge having a measurement terminal diameter ( ⁇ ) of 20 mm. The volume of the foam was calculated from these values. Next, the weight of the foam is measured with an upper pan balance having a minimum scale of 0.01 g or more. From these values, the apparent density (g / cm 3 ) of the foam was calculated.
- Impact absorption rate (%) ⁇ (F 0 ⁇ F 1 ) / F 0 ⁇ ⁇ 100 (In the above equation, F 0 is the impact force when the impactor collides only with the support plate, and F 1 is when the impactor collides with the support plate of the structure consisting of the support plate and the test piece A. Impact force)
- Each foam sheet (adhesive foam layer) (25 mm ⁇ 150 mm) obtained in the examples and comparative examples is lined with a PET # 25 film and attached to a SUS304BA plate, making one round trip at a speed of 2 mm roller 5 mm / sec. Crimp. After standing at 23 ° C. for 20-40 minutes, the force (N / 25 mm) when peeled at 180 ° at a speed of 300 mm / min was measured with a tensile tester (JIS Z 1528).
- a release liner [80 mm ⁇ 10 mm ⁇ h (thickness) 4 mm] of the same material as each release liner II used in the examples and comparative examples was used as a test piece.
- the test piece was supported with a fulcrum interval of 64 mm, and a bending load was applied by applying a pressure wedge to the center thereof (three-point bending test; conforming to JIS K7171). More specifically, pressure was applied at 2 mm / min with a load cell. The load when the test piece was 0.25% distorted was measured, and the flexural modulus (MPa) was calculated by the following equation.
- E L 3 W / 4bh 3 Y
- E flexural modulus (MPa)
- L distance between fulcrums (64 mm)
- b width of test piece (10 mm)
- h thickness of test piece (4 mm)
- W when distorted by 0.25%
- Each release liner II used in the examples and comparative examples is made to have a size of 10 mm ⁇ 150 mm (MD direction: 150 mm), and a parallel marked line with a 50 mm separation is provided at the center. This was pulled with a tensile tester at a speed of 300 mm / min, and the force at break was measured. This force was divided by the volume in the thickness direction to calculate the strength per unit area (MPa) (according to JIS K7127).
- the adhesive foam layer in the laminate of the present invention is excellent in impact absorption even if the thickness is small. Therefore, for example, in an electrical / electronic device, various members or parts (for example, optical members) are used for attaching (attaching) a predetermined part (for example, a housing) to a member for electrical / electronic devices, In particular, it is useful as an impact absorbing sheet.
- an optical member that can be mounted (mounted) using the laminate of the present invention for example, an image display member mounted on an image display device such as a liquid crystal display, an electroluminescence display, or a plasma display (particularly, a small image display).
- the electric / electronic device is, for example, an electric / electronic device provided with a display member, and the above-mentioned adhesive foam layer (or an adhesive foam layer having a substrate on one side) is the electric or electronic device.
- An electrical / electronic device having a structure sandwiched between a housing of the device and the display member is included. Examples of the electric / electronic devices include mobile communication devices such as so-called “mobile phones”, “smartphones”, and “portable information terminals”.
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Abstract
Description
本発明の積層体は粘着性発泡体層を有している。粘着性発泡体層は、発泡シート(特に衝撃吸収用発泡シート)として使用に供される。粘着性発泡体層は、室温(23℃)においてタックを有している。そのため、被着体或いは他の部材との接着、固定を簡易に行うことができる。なお、粘着性発泡体層は発泡体のみから構成されていてもよいが、発泡体の少なくとも一方の面に粘着剤層(粘着層)が設けられていてもよい。
衝撃吸収率(%)={(F0-F1)/F0}×100
(上記式において、F0は支持板のみに衝撃子を衝突させた時の衝撃力のことであり、F1は支持板と粘着性発泡体層とからなる構造体の支持板上に衝撃子を衝突させた時の衝撃力のことである)
本発明の積層体は、前記粘着性発泡体層の両側に支持体を有する。支持体は、前記粘着性発泡体層を粘着性発泡シートとして使用する際に剥離除去される「剥離ライナー」(セパレータ)であっても、前記粘着性発泡体層を粘着性発泡シートとして使用する際に除去することなく該粘着性発泡体層と一体となった形態で用いられる「基材」であってもよい。しかし、前記粘着性発泡体層の両側の支持体のうち少なくとも一方は剥離ライナーである。前記粘着性発泡体層の両側の支持体がともに剥離ライナーであることがより好ましい。
アクリルエマルション溶液(固形分量55%、アクリル酸エチル-アクリル酸ブチル-アクリロニトリル共重合体(重量比45:48:7))100重量部、脂肪酸アンモニウム系界面活性剤(ステアリン酸アンモニウムの水分散液、固形分量33%)3重量部、オキサゾリン系架橋剤(「エポクロスWS-500」日本触媒社製、固形分量39%)0.35重量部、ポリアクリル酸系増粘剤(アクリル酸エチル-アクリル酸共重合体(アクリル酸20重量%)、固形分量28.7%)0.8重量部をディスパー(「ロボミックス」プライミクス社製)で撹拌混合して起泡化した。この発泡組成物を、剥離処理をしたPET(ポリエチレンテレフタレート)フィルム(商品名「MRF♯38」、三菱樹脂社製、厚さ:38μm)(剥離ライナーI)上に塗布し、70℃で4.5分、140℃で4.5分乾燥させ、厚さ130μm、見掛け密度0.27g/cm3、気泡率73.0%、最大セル径109μm、最小セル径10μm、平均セル径47μmの連続気泡構造の粘着性発泡体層を作製した。次いで、この粘着性発泡体層の表面に、ポリエチレン製剥離ライナーA(商品名「PE-50-SU-C1(トウメイ)」、フジコー社製、厚さ:50μm、曲げ弾性率:1000MPa、引張強度:20MPa、引張伸度:180%)(剥離ライナーII)を積層し、剥離ライナーI/粘着性発泡体層/剥離ライナーIIの層構成を有する積層体を得た。なお、前記粘着性発泡体層の発泡体のtanδのピークトップの温度は-3℃、その強度(最大値)は0.37、衝撃吸収率は16.4%、単位厚さ当たりの衝撃吸収率は0.13(%/μm)であった。
実施例1において、剥離ライナーIIとして、ポリエチレン製剥離ライナーAの代わりに、ポリエチレン製剥離ライナーB(商品名「80RL-02 乳白」、王子エフテック社製、厚さ:80μm、曲げ弾性率:900MPa、引張強度:19.6MPa、引張伸度:250%)を用いたこと以外は実施例1と同様にして、剥離ライナーI/粘着性発泡体層/剥離ライナーIIの層構成を有する積層体を得た。
実施例1において、剥離ライナーIIとして、ポリエチレン製剥離ライナーAの代わりに、無延伸ポリプロピレン製剥離ライナーA(商品名「CPP-40-SU-C1」、フジコー社製、厚さ:40μm、曲げ弾性率:2000MPa、引張強度:40MPa、引張伸度:200%)を用いたこと以外は実施例1と同様にして、剥離ライナーI/粘着性発泡体層/剥離ライナーIIの層構成を有する積層体を得た。
実施例1において、剥離ライナーIIとして、ポリエチレン製剥離ライナーAの代わりに、不織布A(商品名「EH-5030」、旭化成せんい社製、厚さ:30μm、曲げ弾性率:500MPa、引張強度:15MPa、引張伸度:130%)を用いたこと以外は実施例1と同様にして、剥離ライナーI/粘着性発泡体層/剥離ライナーIIの層構成を有する積層体を得た。
実施例1において、剥離ライナーIIとして、ポリエチレン製剥離ライナーAの代わりに、不織布B(商品名「EH-5025」、旭化成せんい社製、厚さ:25μm、曲げ弾性率:800MPa、引張強度:15MPa、引張伸度:130%)を用いたこと以外は実施例1と同様にして、剥離ライナーI/粘着性発泡体層/剥離ライナーIIの層構成を有する積層体を得た。
実施例1において、剥離ライナーIIとして、ポリエチレン製剥離ライナーAの代わりに、剥離処理をしたPET(ポリエチレンテレフタレート)フィルム(厚さ:25μm、商品名「MRF♯25」、三菱樹脂社製、曲げ弾性率:9000MPa、引張強度:270MPa、引張伸度:130%)を用いたこと以外は実施例1と同様にして、剥離ライナーI/粘着性発泡体層/剥離ライナーIIの層構成を有する積層体を得た。
実施例1において、剥離ライナーIIとして、ポリエチレン製剥離ライナーAの代わりに、剥離処理をしたPET(ポリエチレンテレフタレート)フィルム(厚さ:38μm、商品名「MRF♯38」、三菱樹脂社製、曲げ弾性率:9100MPa、引張強度:270MPa、引張伸度:130%)を用いたこと以外は実施例1と同様にして、剥離ライナーI/粘着性発泡体層/剥離ライナーIIの層構成を有する積層体を得た。
実施例及び比較例で得られた積層体について、物性の測定及び評価を以下の方法により行った。結果を表1に示す。
低真空走査電子顕微鏡(「S-3400N型走査電子顕微鏡」日立ハイテクサイエンスシステムズ社製)により、発泡体断面の拡大画像を取り込み、画像解析することにより平均セル径(μm)を求めた。なお解析した気泡数は10~20個程度である。同様にして、発泡体の最小セル径(μm)及び最大セル径(μm)を求めた。
100mm×100mmの打抜き刃型にて粘着性発泡体層(発泡体)を打抜き、打抜いた試料の寸法を測定する。また、測定端子の直径(φ)20mmである1/100ダイヤルゲージにて厚さを測定する。これらの値から発泡体の体積を算出した。
次に、発泡体の重量を最小目盛り0.01g以上の上皿天秤にて測定する。これらの値より発泡体の見掛け密度(g/cm3)を算出した。
粘弾性測定装置(「ARES2KFRTN1-FCO」TA Instruments Japan社製)のフィルム引張り測定モードにて、角振動数1rad/sで温度分散性試験を行った。その際の貯蔵弾性率E'と損失弾性率E''の比率である損失正接(tanδ)のピークトップの温度(℃)と強度(最大値)を測定した。
実施例及び比較例で得られた粘着性発泡体層(発泡体)(サンプルサイズ:20mm×20mm)(試験片A)について、前記の振り子型衝撃試験機(衝撃試験装置)(図1及び図2参照)を用い、23℃、衝撃子の重さ96g、振り上げ角度47°の条件で衝撃吸収性試験を行った。下記式により衝撃吸収率を求めた。
衝撃吸収率(%)={(F0-F1)/F0}×100
(上記式において、F0は支持板のみに衝撃子を衝突させた時の衝撃力、F1は支持板と試験片Aとからなる構造体の支持板上に衝撃子を衝突させた時の衝撃力である)
実施例及び比較例で得られた各発泡シート(粘着性発泡体層)(25mm×150mm)にそれぞれPET#25フィルムを裏打ちし、SUS304BA板に張り付け、2kgローラー5mm/秒の速さで1往復圧着する。23℃に20~40分放置後、引張試験機で300mm/分の速さで180°で引き剥がした際の力(N/25mm)を測定した(JIS Z 1528)。
実施例及び比較例で用いた各剥離ライナーIIと同材料の剥離ライナー[80mm×10mm×h(厚さ)4mm]を試験片とした。この試験片を64mmの支点間隔をもって支え、その中央に加圧くさびを当てて曲げ荷重を加えた(三点曲げ試験;JIS K7171に準ずる)。より具体的には、ロードセルで2mm/minで加圧した。試験片が0.25%歪んだ際の荷重を測定し、以下の式により曲げ弾性率(MPa)を算出した。
E=L3W/4bh3Y
[E:曲げ弾性率(MPa)、L:支点間距離(64mm)、b:試験片の幅(10mm)、h:試験片の厚さ(4mm)、W:0.25%歪んだ際の荷重(N)、Y:荷重Wでの歪み(4mm×0.0025=0.01mm)]
実施例及び比較例で用いた各剥離ライナーIIを10mm×150mm(MD方向:150mm)の大きさにし、中央部に50mm離し平行な標線をつける。これを引張試験機で300mm/minの速度で引張り、破断した際の力を測定した。この力を厚さ方向の体積で割り単位面積当たりの強度(MPa)を算出した(JIS K7127に準ずる)。
上記試験において50mm離した平行な標線が破断する直前にどれだけ伸びたかを確認し、下記式により引張伸度(%)を算出した(JIS K 7127に準ずる)。
{破断直前の長さ(mm)-基準長さ(50mm)}/基準長さ(50mm)×100
実施例及び比較例で得られた各積層体(50mm×150mm)の剥離ライナーI側を補助板に固定し、23℃に20~40分放置後、引張試験機で、剥離ライナーIIを300mm/分の速さで180°で引き剥がした際の力(N/50mm)を測定した。
実施例及び比較例で得られた各積層体をそれぞれ、直径85mmの巻き芯に10m以上ロール状に巻回して巻回体(ロール状物)を作製した。23℃で1日間保存後、粘着性発泡体層にシワや折れがないかを目視にて確認した。そして、以下の基準で評価した。
<巻きシワ>
○:シワの発生無し
×:シワの発生有り
<折れ>
○:折れの発生無し
×:折れの発生有り
2 試験片(発泡シート)
3 保持部材
4 衝撃負荷部材
5 圧力センサー
11 固定治具
12 押さえ治具
16 圧力調整手段
20 支柱
21 アーム
22 支持棒(シャフト)の一端
23 支持棒(シャフト)
24 衝撃子
25 電磁石
28 支持板
a 振り上げ角度
Claims (15)
- 平均セル径が10~200μmの発泡体で構成された粘着性発泡体層の両側に支持体を有する積層体であって、少なくとも一方の支持体の曲げ弾性率(23℃)が300~4000MPa、引張強度(23℃、引張速度200mm/min)が100MPa以下、引張伸度(23℃、引張速度200mm/min)が80%以上であることを特徴とする積層体。
- 前記粘着性発泡体層の厚さが30~1000μm、該粘着性発泡体層を構成する発泡体の見掛け密度が0.2~0.7g/cm3である請求項1記載の積層体。
- 前記粘着性発泡体層を構成する発泡体が、動的粘弾性測定における角振動数1rad/sでの貯蔵弾性率と損失弾性率の比率である損失正接(tanδ)が-30℃以上30℃以下の範囲にピークトップを有する請求項1又は2記載の積層体。
- 前記粘着性発泡体層の少なくとも一方の面のSUS304BA板に対する180°ピール接着力(23℃、引張速度300mm/min)が0.05N/25mm以上である請求項1~3の何れか1項に記載の積層体。
- 前記粘着性発泡体層を構成する発泡体が、アクリル系ポリマー、ゴム、ウレタン系ポリマー、及びエチレン-酢酸ビニル共重合体からなる群より選択された少なくとも1種の樹脂材料で形成されている請求項1~4の何れか1項に記載の積層体。
- 前記粘着性発泡体層は、エマルション樹脂組成物を機械的に発泡させる工程Aを経て形成される請求項1~5の何れか1項に記載の積層体。
- 前記粘着性発泡体層は、さらに、機械的に発泡させたエマルション樹脂組成物を基材上に塗工して乾燥する工程Bを経て形成される請求項6に記載の積層体。
- 前記工程Bが、基材上に塗布した気泡含有エマルション樹脂組成物を50℃以上125℃未満で乾燥する予備乾燥工程B1と、その後さらに125℃以上200℃以下で乾燥する本乾燥工程B2を含んでいる請求項7記載の積層体。
- 前記少なくとも一方の支持体の曲げ弾性率(23℃)が、350~3000MPaである請求項1~8の何れか1項の記載の積層体。
- 前記少なくとも一方の支持体の曲げ弾性率(23℃)が、400~2500MPaである請求項9に記載の積層体。
- 前記粘着性発泡体層の厚さが40~500μmである請求項2~10の何れか1項に記載の積層体。
- 前記粘着性発泡体層の厚さが50~300μmである請求項11に記載の積層体。
- 前記粘着性発泡体層を構成する発泡体の見掛け密度が0.21~0.6g/cm3である請求項2~12の何れか1項に記載の積層体。
- 前記粘着性発泡体層を構成する発泡体の見掛け密度が0.22~0.5g/cm3である請求項13に記載の積層体。
- 請求項1~14の何れか1項に記載の積層体がロール状に巻回された巻回体。
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CN115044317B (zh) * | 2022-06-29 | 2024-05-28 | 湖北祥源高新科技有限公司 | 一种双面自粘结聚氨酯泡棉的制备方法和产品 |
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CN115181501B (zh) * | 2022-09-14 | 2022-11-22 | 杭州福斯特应用材料股份有限公司 | 一种封装胶膜及光伏组件 |
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KR102434784B1 (ko) | 2022-08-22 |
CN105745263A (zh) | 2016-07-06 |
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JPWO2016047610A1 (ja) | 2017-07-06 |
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JPWO2016047611A1 (ja) | 2017-07-06 |
WO2016047612A1 (ja) | 2016-03-31 |
US20160303822A1 (en) | 2016-10-20 |
KR102441216B1 (ko) | 2022-09-06 |
KR102454590B1 (ko) | 2022-10-13 |
WO2016047611A1 (ja) | 2016-03-31 |
CN111690165A (zh) | 2020-09-22 |
JPWO2016047612A1 (ja) | 2017-04-27 |
CN105745263B (zh) | 2020-08-28 |
JP2021008636A (ja) | 2021-01-28 |
KR20170063530A (ko) | 2017-06-08 |
JP6082498B2 (ja) | 2017-02-15 |
JP6785156B2 (ja) | 2020-11-18 |
CN106660305B (zh) | 2019-06-18 |
CN105745262B (zh) | 2020-01-07 |
KR20170058882A (ko) | 2017-05-29 |
CN111690165B (zh) | 2023-02-28 |
CN105745262A (zh) | 2016-07-06 |
CN106660305A (zh) | 2017-05-10 |
KR20170059914A (ko) | 2017-05-31 |
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