Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/18—Suspension polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/24—Polymer with special particle form or size
• • 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
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1339—Gaskets; Spacers; Sealing of cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/254—Polymeric or resinous material
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

• Patent Document 2 discloses a method of interposing a spacer between electronic members to be joined when a plurality of electronic members are stacked.
• the spacer particles described in Patent Documents 4 to 8 have too high compressive strength, they are too hard and may damage a member that contacts the adhesive layer.
• the spacer particles described in Patent Documents 4 to 8 have poor compressibility of the adhesive layer because the compressive strength is too high. For this reason, when the member in contact with the adhesive layer must be deformed (for example, when the member in contact with the adhesive layer is a diaphragm of a pressure sensor), the performance of the device using the adhesive layer (for example, the adhesive layer) The sensitivity of the pressure sensor using the sensor will be reduced.
• the laminated sheet having the above structure is a spacer particle for the resin composition layer of the present invention in which the spacer particles contained in the resin composition layer are softer than the conventional spacer particles and have sufficient elasticity.
• the spacer particles can be prevented from being damaged on the sheet base material.
• the spacer particle for a resin composition layer having the above-described configuration has a rate of change in compressive strength at 10% compression displacement due to a temperature change from ⁇ 20 ° C. to room temperature of 30% or less. Thereby, in the temperature range from ⁇ 20 ° C. to 50 ° C., changes in the properties of the resin composition layer due to temperature changes can be suppressed.
• the spacer particles for the resin composition layer having the above-described configuration are compressed at room temperature measured as a compressive load at the time of 10% compression displacement in the resin composition layer thickness direction in a state where 48% by mass is added to the resin composition layer. More preferably, the strength is 0.1 N or more. Thereby, while being able to control the film thickness of a resin composition layer to a more suitable film thickness, the addition amount of the spacer particle
• the coefficient of variation of the particle size of the resin composition layer spacer particles having the above-described configurations is more preferably 12% or less. Thereby, the film thickness of the resin composition layer can be controlled with higher accuracy.
• the spacer particles for the resin composition layer of the present invention are preferably made of a resin, and more preferably a cross-linked resin because of excellent solvent resistance.
• the spacer particles for the resin composition layer of the present invention are more preferably made of a cross-linked acrylic ester resin.
• the acrylate ester monofunctional monomer is an acrylate ester having one polymerizable alkenyl group (broadly-defined vinyl group) in one molecule.
• the acrylate ester monofunctional monomer it is preferable to use an oil-soluble monomer.
• the acrylate ester monofunctional monomer is preferably an acrylate ester monofunctional monomer having 1 to 12 carbon atoms as a substituent that forms an ester bond with acrylic acid.
• acrylate ester monofunctional monomer having 1 to 12 carbon atoms as a substituent that forms an ester bond with acrylic acid include methyl acrylate, ethyl acrylate, n-butyl acrylate, Examples thereof include acrylic acid esters such as isobutyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate.
• the amount of the acrylate ester monofunctional monomer is preferably in the range of 50 to 95% by mass, more preferably in the range of 80 to 90% by mass, based on the total amount of the monomer mixture. .
• grains for resin composition layers excellent in solvent resistance can be implement
• These acrylic ester monofunctional monomers may be used alone or in combination of two or more.
• the spacer particles for a resin composition layer of the present invention are obtained by polymerizing a monomer mixture containing 50 to 95% by mass of an acrylate monofunctional monomer and 5 to 50% by mass of a crosslinkable monomer. It is particularly preferable that the acrylate ester monofunctional monomer is an acrylate ester of an alcohol having 1 to 8 carbon atoms.
• a polymerization initiator In the aqueous suspension polymerization, a polymerization initiator, a dispersant, a surfactant, and the like are used in the reaction system as necessary when the monomer mixture is polymerized.
• the polymerization reaction consists of an oil phase (monomer mixture and a polymerization initiator used as necessary) and an aqueous phase (aqueous medium, a dispersant used as needed, and a surface activity used as needed). Agent) and the like, and then heated while stirring.
• the surfactant may be added to the aqueous phase after the first stage temperature increase (primary temperature increase) and before the second stage temperature increase (secondary temperature increase).
• the spacer particles for the resin composition layer of the present invention may be those in which an inorganic powder adheres to the surface of the spacer particles for the resin composition layer. Said inorganic powder is used in order to prevent adhesion of the spacer particles for resin composition layers. In addition, it is considered that the inorganic powder does not substantially affect the compressive strength of the resin composition layer spacer particles.
• the inorganic powder can be added in any of the polymerization process, the filtration process, the drying process, the pulverization process, and the classification process in the production process of the spacer particles for the resin composition layer. It is preferable to add.
• the inorganic powder is preferably added in the range of 0.1 to 5 parts by mass, and preferably in the range of 0.5 to 4 parts by mass, with respect to 100 parts by mass of the spacer particles for the resin composition layer. Is more preferable. When the addition amount of the inorganic powder is less than the above range, coalescence of the resin composition layer spacer particles is likely to occur.
• the laminated sheet of the present invention is a laminated sheet comprising a resin composition layer containing the spacer particles for the resin composition layer and a sheet base material, wherein the resin composition layer is formed on the sheet base material. It is what.
• the shape of the laminated sheet of the present invention is not particularly limited, and may be a shape having a relatively thick thickness generally called a plate, or a shape having a relatively thin thickness commonly called a film. It may be.
• a diaphragm having a thin part deformable by pressure a piezoelectric vibrating piece having a piezoelectric vibrating piece body and a pair of electrodes formed on the piezoelectric vibrating piece body, and between the piezoelectric vibrating piece and the diaphragm
• the piezoelectric vibrating piece and a resin composition layer that adheres to the diaphragm The piezoelectric vibrating piece is deformed together with the diaphragm due to the pressure applied to the diaphragm, and changes according to the degree of deformation.
• a diaphragm that can be deformed by pressure, a first electrode formed on the diaphragm, and a second electrode disposed on the first electrode via a resin composition layer
• An electrode, and a plurality of the first electrode and the second electrode are bonded to each other by the resin composition layer, and the distance between the first electrode and the second electrode is kept constant.
• the first electrode produced by the change in the distance between the first electrode and the second electrode caused by the deformation of the diaphragm, wherein the spacer particles for the resin composition layer are added to the resin composition layer
• a capacitance type pressure sensor that outputs an electric signal indicating a pressure value by converting a change in capacitance between the first electrode and the second electrode into an electric signal is known.
• the spacer particles for a resin composition layer of the present invention can also be suitably used as spacer particles for a resin composition layer used in this capacitance type pressure sensor. That is, in the capacitance type pressure sensor, when the compressive strength of the resin composition layer spacer particles changes due to a temperature change, the ease of changing the particle diameter of the resin composition layer spacer particles due to pressure changes, When the same pressure is applied to the capacitive pressure sensor, the amount of change in the distance between the first electrode and the second electrode changes with temperature. As a result, the output electric signal of the capacitive pressure sensor when the same pressure is applied to the capacitive pressure sensor, that is, the sensitivity of the capacitive pressure sensor changes.
• the temperature is at least in a temperature range from room temperature to 50 ° C., or at least in a temperature range from ⁇ 50 ° C. to 50 ° C. A change in sensitivity due to the change is suppressed, and a capacitive pressure sensor having good measurement accuracy can be realized.
• Rate of change (%) ((F rt ⁇ F 50 ) ⁇ F rt ) ⁇ 100 (In the above formula, F rt represents the compressive strength (MPa) at room temperature, and F 50 represents the compressive strength (MPa) at 50 ° C.)
• F rt represents the compressive strength (MPa) at room temperature
• F 50 represents the compressive strength (MPa) at 50 ° C.
• the measurement of the compressive strength of the resin composition layer spacer particles at ⁇ 20 ° C. at 10% compression displacement is performed by a compression test using a micro hardness tester (trade name “HM2000”) manufactured by Fisher Instruments Inc. It was. That is, first, spacer particles for a resin composition layer were placed on a stage adjusted to ⁇ 20 ° C.
• the rate of change of compressive strength at 10% compressive displacement due to temperature change from -20 ° C to room temperature is the compressive strength at 10% compressive displacement at -20 ° C and 10% compressive displacement at room temperature. From the compressive strength, the following formula was used.
• the main component of a two-component acrylic resin as a binder resin (trade name “VM-D Medium”, manufactured by Dainichi Seika Kogyo Co., Ltd., a kind of polyol compound-vinyl acetate-vinyl acetate is placed in a container for centrifugal dispersion.
• -Acrylic acid terpolymer 5.8 parts by mass and 4.2 parts by mass of methyl ethyl ketone as a solvent were added, and the main component of the acrylic resin was dissolved in methyl ethyl ketone to obtain a solution of the main component of the acrylic resin.
• a test body film including the resin composition layer spacer particles to be measured was prepared. That is, a particle dispersion liquid in which spacer particles for the resin composition layer are dispersed in an acrylic resin solution is prepared by using a transparent PET film (trade name “OHP film PP2500”, manufactured by Sumitomo 3M Limited, outer dimensions: width 210 mm ⁇ length 297 mm ⁇ thickness. 100 ⁇ m), and the particle dispersion was applied onto an acrylic transparent film by a bar coating method to form a wet film (particle dispersion) having a thickness (wet film thickness) of 100 ⁇ m on the transparent PET film. . Then, the test body film (5 cm x 5 cm) which consists of two layers of the layer (resin composition layer) of the hardened particle dispersion and transparent PET film was produced by hardening a wet film
• the rate of change (%) ((F -50 -F 50) ⁇ F -50) ⁇ 100 (In the formula, F -50 represents the compressive strength of a film state under -50 ° C. atmosphere (N), F 50 represents the compressive strength of a film state under 50 ° C.
• Example 2 First, an oil phase and an aqueous phase were prepared in the same manner as in Example 1.
• the dispersant (magnesium pyrophosphate) contained in the suspension was decomposed with hydrochloric acid. Thereafter, the suspension was dehydrated by filtration to separate the solid content, and the solid content was washed with sufficient water. By adding 2.5 parts by mass of hydrophobic colloidal silica (trade name “AEROSIL (registered trademark) R974” manufactured by Nippon Aerosil Co., Ltd.) as an inorganic powder to the solid content after washing, the resin particles are dried under reduced pressure. Got. Finally, by classifying the resin particles, the particle size of the resin particles was adjusted to obtain resin particles that are spacer particles for the resin composition layer.
• hydrophobic colloidal silica trade name “AEROSIL (registered trademark) R974” manufactured by Nippon Aerosil Co., Ltd.
• the oil phase and the aqueous phase are mixed with a homomixer (a desktop high-speed emulsifier / disperser manufactured by PRIMIX Co., Ltd., trade name “TK homomixer MARK II 2.5 type”) at a rotational speed of 2000 rpm for 10 minutes.
• a homomixer a desktop high-speed emulsifier / disperser manufactured by PRIMIX Co., Ltd., trade name “TK homomixer MARK II 2.5 type”
• the oil phase was dispersed in the aqueous phase to obtain a suspension.
• the suspension was put into a polymerization vessel equipped with a stirrer and a thermometer, and the suspension was stirred at 50 ° C. for 3 hours to carry out a suspension polymerization reaction.
• the oil phase was dispersed in the aqueous phase to obtain a dispersion.
• the dispersion is put into a polymerization vessel equipped with a stirrer and a thermometer, and the suspension is stirred for about 10 minutes with the stirrer at a stirring rotation speed of 250 rpm in a 30 ° C. atmosphere. Produced.
• the internal temperature of the polymerization vessel was raised to 50 ° C. and stirring of the suspension was continued for 3 hours, and then the internal temperature of the polymerization vessel was raised to 105 ° C., and the suspension was further heated at 105 ° C.
• the suspension polymerization reaction was completed by stirring for 1.0 hour.
• Compressive strength at the time of 10% compression displacement in a room temperature atmosphere Compressive strength at room temperature
• 10% compression in a 50 ° C. atmosphere measured for the spacer particles for the resin composition layer of Example 2 and Comparative Example 2 Compressive strength at the time of displacement (compressive strength at 50 ° C), change in compressive strength at 10% compression displacement due to temperature change from room temperature to 50 ° C (change in compressive strength), and temperature from room temperature to 50 ° C
• Table 1 summarizes the rate of change in compressive strength (rate of change in compressive strength) at 10% compression displacement due to change.
• the spacer particles for the resin composition layer of Example 1 have a compressive strength of 0.147 MPa at 10% compression displacement in an atmosphere of ⁇ 20 ° C., and 10 due to a temperature change from ⁇ 20 ° C. to room temperature.
• the rate of change in compressive strength at% compression displacement was 26.5%.
• the spacer particles for the resin composition layer of Example 3 have a compressive strength of 0.113 MPa at 10% compression displacement in a ⁇ 20 ° C. atmosphere, and at 10% compression displacement due to a temperature change from ⁇ 20 ° C. to room temperature.
• the rate of change in compressive strength was 8.8%.
• Compressive strength at 10% compression displacement (compressive strength at 50 ° C.) in a 50 ° C. atmosphere measured from the spacer particles for the resin composition layer of Example 1 and Comparative Example 1 and from room temperature to 50 ° C.
• Table 2 summarizes the rate of change in compressive strength at 10% compression displacement due to temperature change (rate of change in compressive strength from room temperature to 50 ° C.).
• the K value of the spacer particles for the resin composition layer of Example 1 and Example 2 is significantly lower than the K value of the spacer particles for the resin composition layer of Comparative Example 1 and Comparative Example 2, and Patent Literature It was significantly lower than the numerical value range of K value specified in 4 to 8 (980 to 4900 N / mm 2 ). This is because the spacer particles for the resin composition layer of Example 1 and Example 2 are the spacer particles for the resin composition layer of Comparative Example 1 and Comparative Example 2 and the spacer particles for the resin composition layer of Patent Documents 4 to 8. This is because it has a remarkably low compressive strength.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polymerisation Methods In General (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Graft Or Block Polymers (AREA)
• Liquid Crystal (AREA)

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• 2012
  • 2012-09-27 MY MYPI2014700669A patent/MY165741A/en unknown
  • 2012-09-27 JP JP2013536373A patent/JP5689975B2/ja active Active
  • 2012-09-27 CN CN201280047445.4A patent/CN103842388B/zh active Active
  • 2012-09-27 EP EP12836070.8A patent/EP2762500B1/en active Active
  • 2012-09-27 US US14/345,500 patent/US9975970B2/en active Active
  • 2012-09-27 WO PCT/JP2012/074855 patent/WO2013047643A1/ja not_active Ceased
  • 2012-09-27 KR KR1020147006713A patent/KR101607080B1/ko active Active
• 2015
  • 2015-01-29 JP JP2015015551A patent/JP6060188B2/ja active Active

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