WO2013015160A1 - 粒子材料の動的粘弾性測定方法 - Google Patents
粒子材料の動的粘弾性測定方法 Download PDFInfo
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- WO2013015160A1 WO2013015160A1 PCT/JP2012/068146 JP2012068146W WO2013015160A1 WO 2013015160 A1 WO2013015160 A1 WO 2013015160A1 JP 2012068146 W JP2012068146 W JP 2012068146W WO 2013015160 A1 WO2013015160 A1 WO 2013015160A1
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- dynamic viscoelasticity
- measurement
- particulate material
- adhesive layer
- sheet
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N19/00—Investigating materials by mechanical methods
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N19/00—Investigating materials by mechanical methods
- G01N19/04—Measuring adhesive force between materials, e.g. of sealing tape, of coating
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N3/32—Investigating strength properties of solid materials by application of mechanical stress by applying repeated or pulsating forces
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/2813—Producing thin layers of samples on a substrate, e.g. smearing, spinning-on
- G01N2001/2833—Collecting samples on a sticky, tacky, adhesive surface
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N2203/0001—Type of application of the stress
- G01N2203/0005—Repeated or cyclic
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N2203/0058—Kind of property studied
- G01N2203/0092—Visco-elasticity, solidification, curing, cross-linking degree, vulcanisation or strength properties of semi-solid materials
- G01N2203/0094—Visco-elasticity
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N2203/02—Details not specific for a particular testing method
- G01N2203/022—Environment of the test
- G01N2203/0222—Temperature
- G01N2203/0224—Thermal cycling
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N2203/02—Details not specific for a particular testing method
- G01N2203/026—Specifications of the specimen
- G01N2203/0298—Manufacturing or preparing specimens
Definitions
- the present invention relates to a method for measuring dynamic viscoelasticity of a particulate material.
- the glass transition temperature of the resin material is often measured by a DSC (Differential Scanning Calorimetry) method, but depending on the type of material, there are cases where a signal due to the glass transition cannot be detected. In such a case, a relatively large amount of the material to be measured must be prepared and molded into a sheet-like specimen or a fiber-like specimen.
- the loss tangent tan ⁇ is obtained by dynamic viscoelasticity measurement, and the temperature at the maximum peak is used as the measured glass transition temperature of the resin material.
- thermosetting epoxy resin 100 parts by mass of a thermosetting epoxy resin is used. It has been proposed that a composition containing 50 to 150 parts by mass of polymer resin particles is poured into a strip-shaped mold and cured to prepare a strip-shaped test piece (Patent Document 1). In addition, it is proposed that a dispersion obtained by dispersing 100 parts by mass of acrylic polymer particles in 100 parts by mass of diisononyl phthalate is cast and heated to prepare a sheet-like test piece (Patent Document 2). ).
- An object of the present invention is to solve the above-mentioned problems of the prior art, and when measuring the dynamic viscoelasticity of a particulate material, a test piece capable of measuring the dynamic viscoelasticity can be simply, quickly, and reduced.
- the purpose is to shorten the dynamic viscoelasticity measurement time including the creation time of the sheet-like test piece and to reduce the measurement cost by making it possible to produce at a cost.
- the present inventor measured the dynamic viscoelasticity of a sheet piece obtained by adhering the particulate material to be measured to the pressure-sensitive adhesive layer of the heat-resistant sheet base material on which the pressure-sensitive adhesive layer was formed. It was found that a maximum peak other than the maximum peak of loss tangent tan ⁇ derived from the layer (that is, the maximum peak of loss tangent tan ⁇ derived from the particle material) was observed, and the present invention was completed.
- the present invention is a method for measuring the dynamic viscoelasticity of a particulate material.
- a sample used for measurement of dynamic viscoelasticity a sheet-shaped test piece in which a particle material to be measured is attached to the adhesive layer of the heat-resistant sheet base material on which the adhesive layer is formed is used.
- a method for measuring viscoelasticity is provided.
- the particulate material to be measured is attached to the adhesive layer of the heat-resistant sheet substrate on which the adhesive layer is formed.
- This sheet-shaped test piece can be easily and quickly manufactured at a low cost using a very small amount of particulate material by a method such as spraying, and the adhesive layer is formed on the heat-resistant sheet substrate.
- An inexpensive commercially available masking tape can be applied as the sheet material. Therefore, the dynamic viscoelasticity measurement time including the creation time of the sheet-like test piece can be shortened and the measurement cost can be reduced.
- FIG. 1 is a cross-sectional view of a sheet-like test piece.
- FIG. 2 is a partially enlarged view of the sheet-like test piece of FIG.
- FIG. 3A is a cross-sectional view of an adhesive sheet used for producing a sheet-like test piece.
- FIG. 3B is an explanatory diagram of the dispersion of the particulate material at the time of creating the sheet-like test piece.
- FIG. 3C is an explanatory view of a squeegee at the time of creating a sheet-like test piece.
- FIG. 3D is an explanatory diagram of the state of the particulate material after the squeegee when the sheet-like test piece is created.
- FIG. 3E is an explanatory diagram of air blow at the time of producing a sheet-like test piece.
- FIG. 4A is a dynamic viscoelasticity chart of a peroxide curable silicone adhesive.
- FIG. 4B is a dynamic viscoelasticity chart of an addition curing type silicone adhesive.
- FIG. 4C is a dynamic viscoelasticity chart of a two-component acrylic adhesive.
- FIG. 5 is a dynamic viscoelasticity chart of the heat-resistant masking tape used in producing the sheet-like test piece.
- 6A is a scanning electron micrograph (magnification 2000 times) of the particulate material adhering surface of the sheet-like test piece used in Example 1.
- FIG. 1 is a scanning electron micrograph (magnification 2000 times) of the particulate material adhering surface of the sheet-like test piece used in Example 1.
- FIG. 6B is a scanning electron micrograph (magnification 5000 times) of the particle material adhesion surface of the sheet-like test piece used in Example 1.
- FIG. 7A is a dynamic viscoelasticity chart of the sheet-like test piece used in Example 1.
- 7B is a DSC chart of the sheet-like test piece used in Example 1.
- FIG. 8A is a dynamic viscoelasticity chart of the sheet-like test piece used in Example 2.
- FIG. 8B is a DSC chart of the sheet-like test piece used in Example 2.
- FIG. 9A is a particle size distribution chart in terms of volume of the particulate material C used in Example 3.
- FIG. 9B is a scanning electron micrograph (magnification 2000 times) of the particulate material adhering surface of the sheet-like test piece used in Example 3.
- FIG. 10A is a particle size distribution chart in terms of volume of the particulate material D used in Example 4.
- FIG. 10B is a scanning electron micrograph (magnification 2000 times) of the particulate material adhering surface of the sheet-like test piece used in Example 4.
- FIG. 11 is a dynamic viscoelasticity chart of the sheet-like test pieces used in Examples 3 and 4.
- FIG. 12A is a scanning electron micrograph (magnification 5000 times) of the particle material adhesion surface of the sheet-like test piece used in Reference Example 5.
- FIG. 12B is a dynamic viscoelasticity chart of a sheet-like test piece of Reference Example 5 using monodisperse acrylic polymer particles having a CV value of 6.89%.
- the particulate material to be measured is attached to the adhesive layer of the heat-resistant sheet base material on which the adhesive layer is formed as a sample to be used for measurement of dynamic viscoelasticity.
- a sheet-like test piece is used.
- the dynamic viscoelasticity of the particle material can be measured by the dynamic viscoelasticity measuring method of the present invention. That is, as shown in FIG. 1, the sheet-like test piece 10 in which the particulate material 3 adheres to one side of the adhesive layer 2 of the heat-resistant sheet substrate 1 is subjected to, for example, a sinusoidal tensile deformation (arrow in the figure). As shown in FIG. 2, the adhesive layer 2 is also deformed following the deformation of the heat-resistant sheet substrate 1. Further, since the particulate material 3 is held by the adhesive force of the deformable adhesive layer 2, each particulate material 3 is deformed as the adhesive layer 2 is deformed.
- the individual particle material 3 can be sinusoidally tensile deformed, and as a result, the dynamic viscoelasticity of the particle material can be measured. It is considered to be.
- the amount of the particulate material 3 to be attached to the adhesive layer 2 may not be attached to the entire surface of the adhesive layer 2 as long as the dynamic viscoelasticity characteristic can be detected with respect to the deformation.
- the adhesive layer 2 is attached so as to cover the entire surface.
- the particulate material lump that is not directly deformed by the pressure-sensitive adhesive layer 2 is concerned that the collapse of the lump resulting from the deformation of the pressure-sensitive adhesive layer 2 affects the dynamic viscoelastic properties of the particle material 3. Therefore, it is preferable that the particulate material 3 is adhered to the adhesive layer 2 in a single layer shape.
- a dynamic viscoelasticity measurement method applied to the present invention a known dynamic viscoelasticity measurement method (see JIS K7244) can be appropriately employed, and a commercially available dynamic viscoelasticity measurement device is also used. (For example, DMS6100, Seiko Instruments Inc.).
- the measurement deformation mode of the sine wave or synthetic wave control applicable to the dynamic viscoelasticity measuring method of the present invention there are a tensile mode, a shear shear mode, a torsional shear mode, a film shear mode, a three-point bending mode, etc., respectively. It is done. Of these, a sine wave controlled tensile mode is preferable from the viewpoint of measurement accuracy of the sheet-like test piece.
- variations of dynamic viscoelasticity measurement include frequency dependent measurement, linear viscoelasticity area measurement, temperature dependent measurement, and time dependent measurement.
- frequency-dependent measurement is to measure dynamic viscoelastic properties while increasing the frequency under a constant stress (or constant strain), in order to evaluate the cohesiveness, entanglement, leveling properties, etc. of the material. Is what you do.
- the linear viscoelasticity region measurement is to measure dynamic viscoelasticity characteristics while increasing strain (or stress) under a certain frequency, and is used for evaluating the yield behavior of a material.
- Temperature-dependent measurement measures dynamic viscoelastic properties while changing temperature continuously under constant strain (or constant stress) and constant frequency. This is done to evaluate.
- Time-dependent measurement measures dynamic viscoelasticity that changes with time under constant strain (or constant stress), and quantitatively evaluates changes in material curing behavior due to curing conditions such as curing wavelength and strength. Is.
- the temperature at which the loss tangent tan ⁇ shows the maximum peak corresponds to the glass transition temperature of the particle material to be measured.
- a preferred example of a series of operations for attaching the particulate material to the adhesive layer on the heat-resistant sheet substrate is that when the particulate material is attached to the adhesive layer, the particulate material is applied to one side of the adhesive layer, and then the particle material is applied to the adhesive layer.
- the squeegee and / or the air blow are performed, and this example will be described below with reference to the drawings.
- an adhesive sheet having an adhesive layer 2 formed on a heat-resistant sheet substrate 1 is prepared.
- the maximum peak top of the loss tangent tan ⁇ is the maximum peak of the loss tangent tan ⁇ of the particle material to be measured in the measurement temperature range of the dynamic viscoelasticity measurement. It is preferable to form each from the material which does not overlap with a top. Furthermore, it is more preferable that it is made of a material that does not show a maximum peak of loss tangent tan ⁇ in the measurement temperature range of dynamic viscoelasticity measurement. Thereby, it becomes easy to specify the loss tangent tan ⁇ of the particle material to be measured.
- an adhesive layer 2 and heat-resistant sheet substrate 1 include a peroxide as a curing agent as the adhesive layer 2 when the measurement temperature range of dynamic viscoelasticity measurement is ⁇ 50 to 250 ° C. What used the thing formed from the polyimide adhesive as the heat-resistant sheet base material 1 is used.
- FIG. 4A relates to a peroxide curable silicone adhesive
- FIG. 4B relates to an addition curable silicone adhesive
- FIG. 4C relates to a two-component acrylic adhesive.
- the peroxide-curing type silicone adhesive of FIG. 4A does not have a maximum peak in the loss tangent tan ⁇ chart in the measurement temperature range. It can be seen that the present invention can be preferably applied.
- the maximum peak of their loss tangent tan ⁇ may overlap the maximum peak of the loss tangent tan ⁇ of the particle material in the measurement temperature range of dynamic viscoelasticity measurement.
- the range of the particulate material that can be measured is expected to be very narrow.
- the thickness of the heat-resistant sheet substrate 1 is determined according to the deformation mode of dynamic viscoelasticity measurement and the physical properties of the material, but is usually 5 ⁇ m to 1 mm, preferably 10 ⁇ m to 0.1 mm.
- the thickness of the adhesive layer 2 is also determined according to the deformation mode of the dynamic viscoelasticity measurement, the physical properties of the material, the size of the particle material to be measured, and the like, but is usually 1 ⁇ m to 1 mm, preferably 1 ⁇ m to 0. 1 mm.
- the particulate material 3 is sprayed from above the adhesive layer 2.
- a sieve 4 it is preferable to use a sieve 4.
- the particle material 3 is also preferably pulverized in advance by a known method (for example, jet mill treatment).
- the particulate material 3 is squeezed with a squeegee tool 5 for printing. Thereby, the particulate material 3 is in a state as shown in FIG. 3D.
- a squeegee tool 5 As the squeegee tool 5, a rubber spatula, a metal blade, a waste cloth or the like can be used.
- particles composed of various materials can be used as long as they follow the deformation of the adhesive layer.
- thermoplastic resin particles, thermosetting resin particles, cured resin particles, polysaccharide particles, protein particles, metal or ceramic-coated resin particles, and the like can be used.
- the shape of these particle materials is preferably substantially spherical because it is desirable that the entire particle material 3 attached to the adhesive layer 2 be deformed in the same manner.
- the average particle size is preferably 0.5 to 100 ⁇ m, more preferably 1 to 1 ⁇ m. 30 ⁇ m.
- the coefficient of variation (CV value) of the particle size distribution is preferably 5 to 70%, more preferably 10 to 50%. This is because the loss tangent tan ⁇ curve of the particulate material becomes broad if it is out of this range, making it difficult to distinguish a clear glass transition temperature. The reason is considered to be because the occupied area ratio of the particulate material 3 on the adhesive layer 2 is reduced even if the CV value is too small or too large.
- Such a particulate material is a particulate material in which an aluminum chelating agent is held on porous resin particles obtained by interfacial polymerization of a polyfunctional isocyanate (Example 1 of JP-A-2009-212465).
- Measuring device DMS6100, Seiko Instruments Inc. Measurement temperature: 40-220 ° C Temperature increase rate: 5 ° C / min Measurement frequency: 10Hz Deformation mode: sinusoidal tension mode
- this masking tape is used for the particle material in which the maximum peak of the loss tangent tan ⁇ is assumed in the measurement temperature range of 40 to 220 ° C. It turns out that it is suitable for dynamic viscoelasticity measurement.
- Reference example 2 Polyurea-urethane-polydivinylbenzene porous particles were produced in accordance with Example 1 of JP-A-2009-212465 as the particulate material A to be measured for dynamic viscoelasticity.
- aqueous phase was prepared by placing in a 3 liter interfacial polymerization vessel equipped with a thermometer and mixing uniformly.
- Reference example 3 Polyurea-urethane-polydivinylbenzene porous aluminum chelate curing catalyst particles were produced according to Example 1 of Japanese Patent Application Laid-Open No. 2009-212465 as the particle material B to be measured for dynamic viscoelasticity.
- the curing catalyst particles are obtained by holding an aluminum chelating agent in the pores of the porous resin particles (particulate material A) of Reference Example 2.
- an aqueous phase was prepared in the same manner as in Reference Example 2.
- the aqueous phase was further mixed with 100 parts by mass of a 24% isopropanol solution of aluminum monoacetylacetonate bis (ethylacetoacetate) (Aluminum Chelate D, Kawaken Fine Chemical Co., Ltd.) and methylenediphenyl-4, polyfunctional isocyanate compound.
- the polymerization reaction solution is allowed to cool to room temperature, and the polymer particles are filtered off and dried naturally to obtain 80 parts by mass of spherical aluminum chelate curing catalyst particles (particle material B) having a particle size of about 3 ⁇ m. It was.
- aqueous phase was prepared by placing in a 3 liter interfacial polymerization vessel equipped with a thermometer and mixing uniformly.
- the aqueous phase was further mixed with 11 parts by mass of a 24% isopropanol solution of aluminum monoacetylacetonate bis (ethylacetoacetate) (Aluminum Chelate D, Kawaken Fine Chemicals Co., Ltd.) and methylenediphenyl-4,4′-diisocyanate ( 3 mol) of trimethylolpropane (1 mol) adduct (D-109, Mitsui Chemicals, Inc.) 11 parts by mass, an oil phase dissolved in 30 parts by mass of ethyl acetate was added, and a homogenizer (11000 rpm / 10 min.
- Example 1 On a flat table, a heat-resistant masking tape (5413, Sumitomo 3M Co., Ltd.) having a total thickness of 66 ⁇ m in which a peroxide-curing silicone adhesive layer is formed on a polyimide film substrate is placed so that the adhesive layer faces upward. Then, the particulate material A was sprayed on the exposed adhesive layer using a spatula. After spraying, a squeegee was used with a clean wiper (FF-390C, Kuraray Laflex Co., Ltd.), and then the surface was air blown. This obtained the sheet-like test piece for the dynamic viscoelasticity measurement of the particulate material A. Scanning electron micrographs of this sheet-like test piece are shown in FIG. 6A (magnification 2000 times) and FIG. 6B (magnification 5000 times). From these photographs, it can be seen that most of the particulate material A is adhered to the adhesive layer as a single layer.
- FIG. 7A A dynamic viscoelasticity test was performed on the obtained sheet-like test piece in the same manner as in Reference Example 1, and the obtained dynamic viscoelasticity chart is shown in FIG. 7A.
- a maximum peak of loss tangent tan ⁇ derived from the particulate material A was observed, and the temperature of the maximum peak was 69.2 ° C. (glass transition temperature).
- the obtained sheet-like test piece is once subjected to thermal analysis ( (Measurement amount: 5 mmg; temperature increase rate: 10 ° C./min), and then allowed to cool and perform a second thermal analysis.
- the obtained DSC chart is shown in FIG. 7B.
- FIG. 7B shows that no inflection point was observed in the second DSC chart. Therefore, it was found that the glass transition temperature of the particulate material A cannot be measured by DSC.
- Example 2 A sheet-like test piece was prepared in the same manner as in Example 1 except that the particulate material B of Reference Example 3 was used in place of the particulate material A, and dynamic viscoelasticity measurement was performed. The obtained result is shown in FIG. 8A. As can be seen from FIG. 8A, a maximum peak of loss tangent tan ⁇ derived from the particulate material B was observed, and the temperature of the maximum peak was 63.5 ° C. (glass transition temperature). Considering this result and the result of Example 1, it is found that when the aluminum chelating agent is held in the porous resin particles, the polymerization wall is plasticized and the glass transition temperature is lowered by about 5 ° C.
- the obtained sheet-like test piece is once subjected to thermal analysis ( (Measurement amount: 5 mmg; temperature increase rate: 10 ° C./min), and then allowed to cool and perform a second thermal analysis.
- the obtained DSC chart is shown in FIG. 8B.
- FIG. 8B shows that no inflection point was observed in the second DSC chart. Therefore, it was found that the glass transition temperature of the particulate material B cannot be measured by DSC.
- Examples 3 and 4 One half of the particulate material C of Reference Example 4 was pulverized using a jet mill (AO-JET MILL, Seishin Enterprise Co., Ltd.) into primary particles, and the particulate material D was used. The particle size distribution of each of the particle materials C and D was measured using a particle size distribution meter (SD-2000, Sysmex Corporation). The obtained results (volume conversion) are shown in FIG. 9A (particulate material C) and FIG. 10A (particulate material D). 9A and 10A, the particle size distribution CV value (%) of the particle material C that has not been crushed is 72.1%, and the particle size distribution CV value (%) of the particle material D that has been crushed is 31. It was 8%.
- a sheet-like test piece is prepared in the same manner as in Example 1 except that the particle material C (Example 3) or the particle material D (Example 4) is used instead of the particle material A, and dynamic viscoelasticity measurement is performed. It was. Scanning electron micrographs of these sheet-like test pieces are shown in FIG. 9B (Example 3, magnification 2000 times) and FIG. 10B (Example 4, magnification 2000 times). Moreover, the obtained dynamic viscoelasticity measurement result is shown in FIG. As can be seen from FIG. 11, a maximum peak of loss tangent tan ⁇ derived from the particle materials C and D is observed, and the temperature of the maximum peak is 64.6 ° C. for the particle material C and 65.1 for the particle material D. Although there was no significant difference between the two, the maximum peak of the loss tangent tan ⁇ of the particle material C in which a relatively large amount of large aggregates existed tended to be broad.
- Reference Example 5 A sheet similar to Example 1 except that monodisperse acrylic polymer particles (Art Pearl J-5P, Negami Kogyo Co., Ltd.) having a particle size distribution CV value (%) of 6.89% are used in place of the particulate material
- a test piece was prepared and subjected to dynamic viscoelasticity measurement.
- a scanning electron micrograph of this sheet-like test piece is shown in FIG. 12A (magnification 5000 times).
- FIG. 12B the obtained dynamic viscoelasticity measurement result is shown in FIG. 12B.
- the maximum peak of the loss tangent tan ⁇ is very broad compared to the cases of Examples 3 and 4 with a CV value of 30% or more.
- the dynamic viscoelasticity measuring method of the present invention is a sheet-like test in which a particulate material to be measured is attached to the adhesive layer of a heat-resistant sheet base material on which an adhesive layer is formed as a sample for measurement of dynamic viscoelasticity.
- This sheet-shaped test piece can be easily and quickly manufactured at a low cost using a very small amount of particulate material by a method such as spraying, and the adhesive layer is formed on the heat-resistant sheet substrate.
- An inexpensive commercially available masking tape can be applied as the sheet material. Therefore, since the dynamic viscoelasticity measurement time including the preparation time of the sheet-like test piece can be shortened and the measurement cost can be reduced, it is useful for the dynamic viscoelasticity measurement of the particulate material.
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Abstract
Description
動的粘弾性の測定に供するサンプルとして、粘着層が形成された耐熱シート基材の当該粘着層に測定対象である粒子材料を付着させたシート状試験片を使用することを特徴とする動的粘弾性測定方法を提供する。
昇温速度0.01~100℃/分の範囲内の一定温度(例えば5℃/分)、
測定周波数0.01~100Hzの範囲内の一定周波数(例えば10Hz)
正弦波制御の引張りモード。
以下の実施例並びに比較例で使用したポリイミドフィルムに過酸化物硬化型シリコーン粘着層が形成された市販の粘着シート(耐熱マスキングテープ5413、住友3M(株))について、それ自体の動的粘弾性測定を以下の条件で行った。得られた結果を図5に示す。
測定温度: 40~220℃
昇温速度: 5℃/分
測定周波数: 10Hz
変形モード: 正弦波引張りモード
動的粘弾性測定対象の粒子材料Aとして、ポリウレア-ウレタン-ポリジビニルベンゼン多孔質粒子を、特開2009-221465号公報の実施例1に従って製造した。
動的粘弾性測定対象の粒子材料Bとして、ポリウレア-ウレタン-ポリジビニルベンゼン多孔質型アルミニウムキレート硬化触媒粒子を、特開2009-221465号公報の実施例1に従って製造した。この硬化触媒粒子は、参考例2の多孔質樹脂粒子(粒子材料A)の孔にアルミニウムキレート剤を保持させたものである。
動的粘弾性測定対象の粒子材料Cとして、ポリウレア-ウレタン多孔質型アルミニウムキレート硬化触媒粒子を、特許4381255号明細書の実施例1に従って製造した。
平坦なテーブル上に、ポリイミドフィルム基材に過酸化物硬化型シリコーン粘着層が形成された総厚66μmの耐熱マスキングテープ(5413、住友3M(株))を粘着層が上向きとなるように載置し、露出した粘着層にスパチュラを用いて粒子材料Aを散布した。散布後、クリーンワイパー(FF-390C、クラレクラフレックス(株))を用いてスキージし、続いて表面をエアブローした。これにより、粒子材料Aの動的粘弾性測定用のシート状試験片を得た。このシート状試験片の走査型電子顕微鏡写真を図6A(倍率2000倍)と図6B(倍率5000倍)とに示す。これらの写真から、粒子材料Aの殆どが粘着層に単層で付着していることがわかる。
粒子材料Aに代えて参考例3の粒子材料Bを使用すること以外、実施例1と同様にシート状試験片を作成し、動的粘弾性測定を行った。得られた結果を図8Aに示す。図8Aからわかるように、粒子材料B由来の損失正接tanδの極大ピークが観察され、その極大ピークの温度は63.5℃(ガラス転移温度)であった。この結果と実施例1の結果とを考慮すると、多孔質樹脂粒子にアルミニウムキレート剤を保持させると、重合壁が可塑化されガラス転移温度が約5℃低下することがわかる。
参考例4の粒子材料Cの半分を、ジェットミル(AO-JET MILL、(株)セイシン企業)を用いて解砕処理して一次粒子化したものを粒子材料Dとした。粒子材料C及びDのそれぞれの粒度分布を粒度分布計(SD-2000、シスメックス(株))を用いて測定した。得られた結果(体積換算)を図9A(粒子材料C)と図10A(粒子材料D)に示す。図9A及び図10Aから、解砕処理していない粒子材料Cの粒度分布CV値(%)は72.1%であり、解砕処理した粒子材料Dの粒度分布CV値(%)は31.8%であった。
粒子材料Aに代えて、粒度分布CV値(%)が6.89%の単分散アクリルポリマー粒子(アートパールJ-5P、根上工業(株))を用いること以外、実施例1と同様にシート状試験片を作成し、動的粘弾性測定を行った。このシート状試験片の走査型電子顕微鏡写真を図12A(倍率5000倍)に示す。また、得られた動的粘弾性測定結果を図12Bに示す。図12Bからわかるように、損失正接tanδの極大ピークが、CV値が30%以上の実施例3及び4の場合に比べて、非常にブロードとなることがわかる。
2 粘着層
3、3′ 粒子材料
4 篩
5 スキージ具
6 エアノズル
10 シート状試験片
Claims (9)
- 粒子材料の動的粘弾性測定方法であって、
動的粘弾性の測定に供するサンプルとして、粘着層が形成された耐熱シート基材の当該粘着層に測定対象である粒子材料を付着させたシート状試験片を使用することを特徴とする動的粘弾性測定方法。 - 動的粘弾性測定が、以下の測定条件
測定温度-150~300℃の範囲内の所定温度範囲、
昇温速度0.01~100℃/分の範囲内の一定温度、
測定周波数0.01~100Hzの範囲内の一定周波数、及び
正弦波制御の引張りモード
で行われる温度依存測定である請求項1記載の動的粘弾性測定方法。 - 予め解砕処理しておいた粒子材料を粘着層に付着させる請求項1記載の動的粘弾性測定方法。
- 粒子材料を粘着層に付着させる際、粒子材料を粘着層の片面に散布した後、粒子材料の散布面を、スキージ及び/又はエアブローを行う請求項1~3のいずれかに記載の動的粘弾性測定方法。
- 動的粘弾性測定として、損失正接tanδを測定する請求項1~4のいずれかに記載の動的粘弾性測定方法。
- 粘着層及び耐熱シート基材として、動的粘弾性測定の測定温度範囲において、それらの損失正接tanδの極大ピークトップが、測定対象である粒子材料の損失正接tanδの極大ピークトップと重ならない材料からそれぞれ形成されている請求項2~5のいずれかに記載の動的粘弾性測定方法。
- 動的粘弾性測定の測定温度範囲が-50~250℃である場合に、粘着層として過酸化物を硬化剤として使用したシリコーン粘着剤から形成されたものを使用し、耐熱シート基材としてポリイミド樹脂から形成されたものを使用する請求項6記載の動的粘弾性測定方法。
- 粒子材料として、粒径分布の変動係数(CV値)が5~70%の樹脂粒子を使用する請求項1~7のいずれかに記載の動的粘弾性測定方法。
- 粒子材料が、多官能イソシアネートを界面重合させた多孔質樹脂粒子にアルミニウムキレート剤が保持された粒子材料である請求項8記載の動的粘弾性測定方法。
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Publication number | Priority date | Publication date | Assignee | Title |
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CN104897567A (zh) * | 2015-06-16 | 2015-09-09 | 安徽工业大学 | 一种定量检测涂层不粘性能装置及涂层不粘性能检测方法 |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06123696A (ja) * | 1992-10-13 | 1994-05-06 | Seiko Instr Inc | 動的粘弾性装置 |
JPH08221741A (ja) * | 1995-02-20 | 1996-08-30 | Fuji Photo Film Co Ltd | 磁気記録媒体 |
JP2007086062A (ja) * | 2005-08-26 | 2007-04-05 | Shiseido Co Ltd | 樹脂を含む材料を通じた流体の透過性の評価方法、生分解性樹脂を含む材料の処理方法、生分解性樹脂を含む材料、及び生分解性樹脂成形体 |
JP2008186761A (ja) * | 2007-01-31 | 2008-08-14 | Tokai Rubber Ind Ltd | 粒子転写膜の製造方法および粒子保持膜の製造方法ならびに異方性導電膜 |
JP2009064043A (ja) * | 2008-12-11 | 2009-03-26 | Oji Tac Hanbai Kk | 再剥離性粘着シート |
JP2010074006A (ja) * | 2008-09-19 | 2010-04-02 | Fujifilm Corp | 表面処理用マスク及びその製造方法、表面処理方法、光学デバイス、並びに、粒子含有フィルム及びその製造方法 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08231731A (ja) * | 1995-02-23 | 1996-09-10 | Nitto Denko Corp | ポリマー粒子およびそれを用いた樹脂組成物 |
US6660326B2 (en) * | 2000-08-04 | 2003-12-09 | Tomoegawa Paper Co. Ltd. | Production method for monolayer powder film and production apparatus therefor |
CN100537643C (zh) * | 2002-10-08 | 2009-09-09 | 电气化学工业株式会社 | 热收缩性薄膜 |
JP4381255B2 (ja) | 2003-09-08 | 2009-12-09 | ソニーケミカル&インフォメーションデバイス株式会社 | 潜在性硬化剤 |
WO2005070692A1 (ja) * | 2004-01-27 | 2005-08-04 | Asahi Kasei Chemicals Corporation | レーザー彫刻可能な印刷基材の製造方法 |
JP4559745B2 (ja) * | 2004-01-28 | 2010-10-13 | 大日本印刷株式会社 | 単粒子膜の形成方法およびこれを用いた電気泳動表示装置の製造方法 |
JP2005232297A (ja) * | 2004-02-19 | 2005-09-02 | Mitsubishi Rayon Co Ltd | アクリル系重合体微粒子及びプラスチゾル組成物 |
US7901857B2 (en) * | 2005-03-15 | 2011-03-08 | Fuji Xerox Co., Ltd. | Electrostatic latent image developing toner, production method thereof, electrostatic latent image developer, and image forming method |
JP4355010B2 (ja) | 2006-10-04 | 2009-10-28 | 昭栄化学工業株式会社 | 積層電子部品用導体ペースト |
JP5049584B2 (ja) * | 2006-12-25 | 2012-10-17 | 東レ・ダウコーニング株式会社 | 過酸化物硬化型シリコーン系感圧接着剤組成物および粘着テープ |
JP5458596B2 (ja) * | 2008-02-18 | 2014-04-02 | デクセリアルズ株式会社 | アルミニウムキレート系潜在性硬化剤、その製造方法及び熱硬化型エポキシ樹脂組成物 |
EP2249208B1 (en) * | 2008-02-25 | 2014-09-24 | Canon Kabushiki Kaisha | Toner |
WO2010032543A1 (ja) * | 2008-09-19 | 2010-03-25 | 富士フイルム株式会社 | 表面処理用マスク及びその製造方法、表面処理方法、並びに、粒子含有フィルム及びその製造方法 |
CN101788281B (zh) * | 2009-01-22 | 2013-06-19 | 北京航空航天大学 | 非晶合金自由体积的测定方法 |
JP2010276938A (ja) * | 2009-05-29 | 2010-12-09 | Bridgestone Corp | 表示媒体用粒子の色味評価方法 |
KR20110006452A (ko) * | 2009-07-14 | 2011-01-20 | 삼성전자주식회사 | 전자사진용 토너 및 그의 제조방법 |
-
2011
- 2011-07-25 JP JP2011162016A patent/JP5842433B2/ja active Active
-
2012
- 2012-07-18 CN CN201280036784.2A patent/CN103718021B/zh active Active
- 2012-07-18 US US14/124,492 patent/US9459197B2/en active Active
- 2012-07-18 WO PCT/JP2012/068146 patent/WO2013015160A1/ja active Application Filing
- 2012-07-18 EP EP12817168.3A patent/EP2738542A4/en not_active Withdrawn
- 2012-07-18 KR KR1020147001720A patent/KR101986391B1/ko active IP Right Grant
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06123696A (ja) * | 1992-10-13 | 1994-05-06 | Seiko Instr Inc | 動的粘弾性装置 |
JPH08221741A (ja) * | 1995-02-20 | 1996-08-30 | Fuji Photo Film Co Ltd | 磁気記録媒体 |
JP2007086062A (ja) * | 2005-08-26 | 2007-04-05 | Shiseido Co Ltd | 樹脂を含む材料を通じた流体の透過性の評価方法、生分解性樹脂を含む材料の処理方法、生分解性樹脂を含む材料、及び生分解性樹脂成形体 |
JP2008186761A (ja) * | 2007-01-31 | 2008-08-14 | Tokai Rubber Ind Ltd | 粒子転写膜の製造方法および粒子保持膜の製造方法ならびに異方性導電膜 |
JP2010074006A (ja) * | 2008-09-19 | 2010-04-02 | Fujifilm Corp | 表面処理用マスク及びその製造方法、表面処理方法、光学デバイス、並びに、粒子含有フィルム及びその製造方法 |
JP2009064043A (ja) * | 2008-12-11 | 2009-03-26 | Oji Tac Hanbai Kk | 再剥離性粘着シート |
Non-Patent Citations (1)
Title |
---|
See also references of EP2738542A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104897567A (zh) * | 2015-06-16 | 2015-09-09 | 安徽工业大学 | 一种定量检测涂层不粘性能装置及涂层不粘性能检测方法 |
CN104897567B (zh) * | 2015-06-16 | 2017-05-03 | 安徽工业大学 | 一种定量检测涂层不粘性能装置 |
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