JP2013163709A - Powdered sealing agent and sealing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing agent and a sealing method tightly sealable of electronic devices at low temperature.SOLUTION: The sealing agent for sealing devices is composed of powder of a copolyamide-based resin with 1 mm or less particle diameter. The copolyamide-based resin powder at least includes minute particles (for example, a copolyamide-based resin particle with average particle diameter of 20-400 μm), or may be configured by combining the minute particles with coarse particles (for example, a copolyamide-based resin particle with average particle diameter of 450-800 μm). The copolyamide-based resin may have crystallinity, the melting point or softening point of the copolyamide-based resin may be 75-160°C. The copolyamide-based resin may be a multicomponent copolymer, e.g. a binary or ternary copolymer. Further the copolyamide-based resin may include a unit derived from a long chain component having an 8-16C alkylene group (at least one component selected from a 9-17C lactam and an amino-9-17C alkane carboxylic acid).

Description

  The present invention relates to a powder sealant suitable for sealing a device (or electronic device) such as a printed circuit board on which an electronic component is mounted, and a sealing method using the powder sealant.

  In order to protect against moisture, dust, and the like, precision components (or electronic devices) such as semiconductor elements, printed boards, and solar cells are sealed with a resin. As this sealing method, there is known a method in which a precision component is placed in a mold cavity and a resin is injected to seal. In this method, a thermosetting resin having a low viscosity and a high fluidity is often used.

  However, in thermosetting resins, additives such as cross-linking agents are added, so that not only the storage period is short, but also it takes a relatively long time to cure after being injected into the mold cavity. Cannot be improved. In addition, depending on the type of resin, a curing process is required after molding, which reduces productivity.

It is also known to seal precision parts by injection molding a thermoplastic resin. However, since the thermoplastic resin is often molded at a relatively high temperature and pressure, the substrate and the electronic components mounted on the substrate are easily damaged and the reliability is impaired. In JP 2000-133665 A (Patent Document 1), a printed circuit board on which electronic components are mounted is placed in a mold cavity, and polyamide resin heated and melted at 160 to 230 ° C. is 2.5 to 25 kg / cm. A method of sealing a printed circuit board on which an electronic component is mounted by injecting into the mold cavity in a pressure range of ² is disclosed. In the example of this document, it is described that a polyamide resin / product number 817 of TRL (France) was injected into a mold at a melting temperature of 190 ° C. and a pressure of 20 kg / cm ² to seal the printed circuit board. . However, even in this method, the electronic component may be damaged because a relatively high temperature and pressure are applied to the electronic component.

  Furthermore, it is also known to seal a device using a film-like sealant. JP 2008-282906 A (Patent Document 2) relates to a method for manufacturing a solar cell module in which a solar cell is sealed with a resin between a substrate and a film, and between the substrate and the solar cell. A first sealing resin sheet that covers substantially the entire surface of the substrate, and a second sealing resin sheet that covers substantially the entire surface of the substrate between the film and the solar battery cell. A laminated body is produced, and the laminated body is stacked in a plurality of stages, and a backing plate is disposed outside the film of the uppermost laminated body, and air between the substrate and the film is discharged and heated to form a resin. It is disclosed that the sealing resin is melted and cooled to be sealed, and that the sealing resin is a kind of resin selected from the group consisting of ethylene-vinyl acetate copolymer, polyvinyl butyral, and polyurethane. That.

  Japanese Patent Application Laid-Open No. 2009-99417 (Patent Document 3) includes a barrier film for sealing an organic electronic device formed on the substrate, and a hot-melt member between the organic electronic device and the barrier film. An organic electronic device encapsulating panel is disclosed, wherein the hot melt type member contains a moisture scavenger and a wax, and the hot melt type member has a thickness of 100 μm or less. . Japanese Unexamined Patent Application Publication No. 2009-99805 (Patent Document 4) discloses a hot-melt member for an organic thin-film solar cell containing a moisture scavenger and a wax. These documents also describe that the shape of the hot-melt type member may be a thin film shape, a plate shape, an indefinite shape, or the like.

  However, since the film-like sealant has poor followability to the uneven portions of the device, it is difficult to tightly seal the details of the device. Furthermore, since the hot-melt type member contains wax as a main component, it is difficult to increase the adhesion to the device and seal it.

  Japanese Patent Laid-Open No. 2001-234125 (Patent Document 5) discloses a hindered phenolic antioxidant for 100 parts by weight of a thermoplastic resin in order to prevent discoloration even when exposed to a high-temperature flame during coating. Agent and phosphite-based antioxidant in a proportion of 0.05 to 2.0 parts by weight, with a median particle diameter of 50 to 300 μm, a bulk specific gravity of 0.30 g / ml or more, and an angle of repose of 35 degrees or less. A powder coating for thermal spray coating is disclosed. In this document, as a thermoplastic resin, polyethylene resin, polypropylene resin, nylon-11 resin, nylon-12 resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-methacrylic acid copolymer Examples include coalescent resins, modified polyethylene resins, and modified polypropylene resins, and examples using nylon (polyamide) resin (trade name “Grillamide” from EMS-CHEMIE AG) are also described.

  However, since the powder coating is melted and sprayed at a high temperature, if used for sealing an electronic component, the electronic component is likely to be damaged, and the reliability of the device may be impaired.

Japanese Unexamined Patent Publication No. 2000-133665 (Claims and Examples) JP 2008-282906 A (Claims) JP 2009-99417 A (Claims, [0024]) JP 2009-99805 A (Claims) JP 2001-234125 A (Claims, [0008], Example 6)

  Accordingly, an object of the present invention is to provide a powdery sealant capable of tightly sealing an electronic device at a low temperature and a sealing method using this sealant.

  Another object of the present invention is to provide a powdery sealant that can be tightly sealed even if there are uneven portions or narrow gaps, and a sealing method using this sealant.

  Still another object of the present invention is to provide a powdery sealant that can be deposited efficiently without being dropped even when sprayed on an electronic device, and a sealing method using this sealant.

  Another object of the present invention is to provide a powdery sealant that can be melted at a low temperature in a short time and that can prevent thermal damage of an electronic device, and a sealing method using this sealant.

  Still another object of the present invention is to provide a powdery sealant that can effectively protect an electronic device from moisture, dust, impact, and the like, and a sealing method using the sealant.

  Another object of the present invention is to provide an electronic device sealed with the powdery sealant.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that when a powdered copolyamide-based resin having a specific particle size distribution is used, (1) even when sprayed on a device or a substrate, the efficiency is improved in a predetermined part. It can be deposited well, (2) it can be melted quickly at low temperature, (3) it can shorten the sealing and molding cycle, (4) it can be easily molded even if there are irregularities on the surface, and (5) the device or The present invention has been completed by finding that (6) a thin film can be sealed or molded, and (7) a device and a substrate can be molded with high adhesion and sealing properties without being restricted by the size of the substrate.

  That is, the powdery sealant of the present invention is a sealant for sealing a device, and is composed of a copolymerized polyamide resin. This sealant contains copolymer polyamide resin particles having a particle diameter of 1 mm or less (for example, 0.5 μm to 1 mm). The copolymerized polyamide resin particles include at least (A) fine particles [for example, copolymerized polyamide resin particles having an average particle diameter of about 20 to 400 μm (for example, 40 to 350 μm)]. The copolymerized polyamide resin particles may be composed of (A) fine particles alone, but may be composed of (A) fine particles and (B) coarse particles having a large average particle diameter. The average particle size of (B) coarse particles may be about 1.2 to 20 times the average particle size of (A) fine particles. (B) The average particle diameter of the coarse particles may be about 450 to 800 μm. The proportion of (A) fine particles may be about 1 to 10 parts by weight with respect to 100 parts by weight of (B) coarse particles. The angle of repose of the entire copolymerized polyamide resin particles may be about 35 to 55 °.

The melting point or softening point of the copolymerized polyamide resin may be about 75 to 160 ° C, for example, about 90 to 160 ° C. The copolymerized polyamide resin may have crystallinity. The copolymerized polyamide-based resin may be a multi-component copolymer, for example, a binary copolymer to a quaternary copolymer (for example, a binary or ternary copolymer). Further, the copolymerized polyamide-based resin is selected from long chain components having a C _8-16 alkylene group (eg, a C _10-14 alkylene group), such as C _9-17 lactam and amino C _9-17 alkane carboxylic acid. In addition, units derived from at least one component may be included. For example, the copolyamide-based resin may contain units derived from an amide-forming component selected from polyamide 11, polyamide 12, polyamide 610, polyamide 612, and polyamide 1010. Copolyamide 6/11, copolyamide 6 / 12, copolyamide 66/11, copolyamide 66/12, copolyamide 610/11, copolyamide 612/11, copolyamide 610/12, copolyamide 612/12, copolyamide 1010/12, copolyamide 6/11 / 610, copolyamide 6/11/612, copolyamide 6/12/610, and at least one selected from copolyamide 6/12/612. The copolymerized polyamide resin is a polyamide elastomer (polyamide block copolymer) containing units derived from an amide-forming component selected from polyamide 11, polyamide 12, polyamide 610, polyamide 612 and polyamide 1010 as hard segments if necessary. Merging). Furthermore, the copolyamide-based resin may contain a unit derived from at least one component selected from laurolactam, aminoundecanoic acid and aminododecanoic acid.

  In the method of the present invention, the powdery sealant is applied (or dispersed) to at least a part of the device, and the powdery sealant is heated, melted, and cooled to coat or mold with the copolymerized polyamide resin. Device can be manufactured. Therefore, the present invention also includes a device in which at least a part is coated or molded with a film of a copolymerized polyamide resin formed by thermally fusing a powdery sealant.

  In the present specification, the “copolymerized polyamide-based resin” is not only a copolymer of a plurality of amide-forming components (copolyamide) that forms a homopolyamide, but also a plurality of amide-forming components, and The term also includes a mixture of a plurality of different types of copolymers (copolyamides).

  In the present invention, since a powdery copolyamide-based resin having a specific particle size distribution is used, it can be efficiently deposited without dropping even when dispersed on an electronic device, and can be melted at a low temperature in a short time. It can be sealed tightly and does not impair device reliability. Moreover, since the sealing agent is in the form of a granular material, even if there is an uneven part or a narrow gap, it can be tightly sealed. Therefore, the electronic device can be effectively protected from moisture, dust, impact, and the like.

FIG. 1 is a graph showing the relationship between the particle size and frequency (%) of the powder resin particles of the example. FIG. 2 is a graph showing the relationship between the particle size and cumulative frequency (integration) of the powder resin particles of the example.

  The powdery sealant (or powdery sealant) of the present invention is composed of a copolymerized polyamide resin. The powdery sealant contains copolymerized polyamide resin particles having a particle diameter of 1 mm or less (for example, 0.5 μm to 1 mm). That is, the powdery sealant may be composed of copolymerized polyamide resin particles classified by a sieve having an opening diameter of 1 mm or less (for example, 50 μm to 1 mm), and the copolymerized polyamide resin particles having a particle diameter exceeding 1 mm. May not be substantially contained.

  The copolymerized polyamide resin particles include at least fine particles (fine powder or fine particle group) having a small average particle size (or particle size). In the present invention, since it contains the fine particles, it has an appropriate powder fluidity, can be prevented from falling off even if sprayed on a device or a substrate, enhances thermal conductivity, can be rapidly melted at a low temperature, It is possible to prevent thermal damage to the device or the substrate.

The average particle diameter (particle size cumulative distribution 50% diameter: D ₅₀ ) of the copolymerized polyamide resin fine particles may be 20 to 400 μm, for example, 25 to 380 μm, preferably 30 to 370 μm, more preferably 35 to 360 μm ( For example, it may be about 35 to 300 μm), particularly about 40 to 350 μm (for example, 40 to 200 μm).

  The particle size range (particle size) of the copolymerized polyamide resin fine particles may be about 0.01 μm to 1 mm, and is usually about 0.1 to 500 μm (for example, 0.5 to 300 μm) in many cases.

  The copolymerized polyamide resin particles may be fine particles alone or in combination with fine particles and coarse particles having a large average particle size (or particle size). Coarse particles can easily fall off when sprayed on a device or substrate, and the amount of heat required for melting also increases, but by combining coarse particles and fine particles, the porosity of the powder (particle group) decreases, By increasing the number of contact points, it is possible to deposit stably and efficiently on a predetermined portion, increase the thermal conductivity between the particles, shorten the melting time, and obtain a sealing film with less surface irregularities. .

Copolymerization average particle diameter of the polyamide resin coarse particles (D ₅₀₎ may be larger than the average particle diameter of the copolymerized polyamide resin particles (D _50), the average particle diameter of the copolymerized polyamide resin particles (D ₅₀ ) For example, it may be about 1.2 to 20 times, preferably 1.5 to 18 times, more preferably about 2 to 15 times (for example, 2 to 10 times). The average particle diameter (D ₅₀ ) of the copolymerized polyamide resin coarse particles may be, for example, about 450 to 800 μm (for example, 500 to 700 μm).

  The particle size range (particle size) of the copolymerized polyamide resin coarse particles may be about 350 μm to 1 mm, and is usually about 400 to 900 μm (for example, 500 to 800 μm) in many cases.

  The ratio (weight ratio) of the fine particles can be selected from the range of, for example, about 0.1 to 10000 parts by weight, for example, 0.1 to 100 parts by weight, preferably 0.1 to 100 parts by weight of the coarse particles. It may be about 5 to 50 parts by weight, more preferably about 1 to 20 parts by weight (for example, 1 to 10 parts by weight).

  In the entire copolymerized polyamide resin particles, the particle size distribution indicating the relationship between the particle size and the frequency may have one or a plurality of peaks, or may have a shoulder portion. Fine particles (for example, fine particles having a particle size of 0.01 to 300 μm, preferably fine particles having a particle size of 0.1 to 200 μm) may occupy 0.01 to 100% of the entire copolymerized polyamide resin particles. It may occupy a part (for example, 70 to 100%, preferably 80 to 99%) or a small part (for example, 0.1 to 30%, preferably 1 to 20%). In addition, the ratio (number ratio) which microparticles occupy with respect to all the particles can be calculated based on the particle size distribution measurable by the method mentioned later, for example.

The average particle diameter (D ₅₀ ) of the entire copolymerized polyamide resin particles can be selected from a range of 1 mm or less (for example, about 1 to 800 μm, preferably about 10 to 750 μm), for example, 30 to 750 μm, preferably 35 to 700 μm. More preferably, it is about 40-650 micrometers. The total particle size distribution 30% diameter (D ₃₀ ) of the entire copolymerized polyamide resin particles is, for example, about 25 to 600 μm, preferably about _{30 to} 550 μm. Furthermore, the 70% diameter (D ₇₀ ) of the particle size cumulative distribution of the entire copolymerized polyamide resin particles is, for example, about 50 to 850 μm, preferably about 55 to 800 μm. Throughout copolymerized polyamide resin particles, the particle size cumulative distribution 70% diameter _{(D 70),} the particle size cumulative distribution 30% diameter _{(D 30) (D 70 /} D 30), for example, 1.05. It is 5 times, preferably 1.1 to 2.2 times, more preferably about 1.2 to 2 times.

  The particle size range (particle size), average particle size, and particle size distribution of the copolymerized polyamide resin particles are measured using a laser diffraction method (light scattering method), for example, a measurement device based on the Mie scattering theory [HORIBA LA920. (Made by HORIBA, Ltd.), etc.].

  The angle of repose of the entire copolymerized polyamide resin particles (or powder sealant) is particularly limited as long as it has an appropriate powder fluidity and can be stably and efficiently deposited on a predetermined part of the device or substrate. For example, it is 30 to 65 °, preferably 32 to 60 °, more preferably about 35 to 55 ° (for example, 40 to 50 °) in accordance with JIS R9301-2-2. Further, the collapse angle of the entire copolymerized polyamide resin particles (or powder sealant) may be, for example, about 10 to 30 °, preferably about 12 to 28 °, and more preferably about 15 to 25 °. The repose angle and the collapse angle can be measured using a conventional apparatus (for example, a powder tester PT-E manufactured by Hosokawa Micron Corporation). In the present invention, the difference angle (repose angle-decay angle) of the entire copolymerized polyamide resin particles can be increased, and can be stably deposited on a device or a substrate.

  The shape of the copolymerized polyamide resin particles is not particularly limited, and may be, for example, amorphous (such as a pulverized product), sphere, or ellipsoid.

  The copolymerized polyamide resin constituting the copolymerized polyamide resin particles includes a copolymerized polyamide (thermoplastic copolymerized polyamide) and a polyamide elastomer.

  The thermoplastic copolymer polyamide may be an alicyclic copolymer polyamide, but is usually an aliphatic copolymer polyamide in many cases. The copolymerized polyamide can be formed by combining a diamine component, a dicarboxylic acid component, a lactam component, and an aminocarboxylic acid component. Both the diamine component and the dicarboxylic acid component can form an amide bond of the copolymerized polyamide, and the lactam component and the aminocarboxylic acid component can each independently form an amide bond of the copolymerized polyamide. Therefore, a pair of components (both components combining a diamine component and a dicarboxylic acid component), a lactam component, and an aminocarboxylic acid component can also be referred to as amide-forming components. From such a viewpoint, the copolymerized polyamide is obtained by copolymerizing a plurality of amide-forming components selected from a pair of components (both components obtained by combining a diamine component and a dicarboxylic acid component), a lactam component, and an aminocarboxylic acid component. Can be obtained. The copolyamide is composed of at least one amide-forming component selected from a pair of components (both components obtained by combining a diamine component and a dicarboxylic acid component), a lactam component, and an aminocarboxylic acid component; It can be obtained by copolymerization with different (or the same type and different carbon number) amide-forming components. In addition, the lactam component and the aminocarboxylic acid component may be handled as equivalent components as long as they have the same carbon number and branched chain structure. Therefore, when a pair of components obtained by combining a diamine component and a dicarboxylic acid component is a first amide-forming component, and a lactam component and an aminocarboxylic acid component are second amide-forming components, for example, A copolymerized polyamide comprising an amide-forming component (a diamine component and a dicarboxylic acid component), wherein at least one of the diamine component and the dicarboxylic acid component is composed of a plurality of components having different carbon numbers; A copolymerized polyamide of an amide-forming component (diamine component and dicarboxylic acid component) and a second amide-forming component (at least one component selected from a lactam component and an aminocarboxylic acid component); a second amide-forming component (lactam) Component and at least one component selected from aminocarboxylic acid components) A copolymerized polyamide, wherein one of a lactam component and an aminocarboxylic acid component is composed of a plurality of components having different carbon numbers; a lactam component and an aminocarboxylic acid component having the same or different carbon number; It may be a copolyamide or the like.

Examples of the diamine component include aliphatic diamine or alkylene diamine components (for example, C _4-16 alkylene diamine such as tetramethylene diamine, hexamethylene diamine, trimethyl hexamethylene diamine, octamethylene diamine, and dodecane diamine). These diamine components can be used alone or in combination of two or more. A preferred diamine component contains at least an alkylene diamine (preferably a C _6-14 alkylene diamine, more preferably a C _6-12 alkylene diamine).

If necessary, as the diamine component, an alicyclic diamine component (diaminocycloalkane such as diaminocyclohexane (diamino C _5-10 cycloalkane etc.); bis (4-aminocyclohexyl) methane, bis (4-amino- Bis (aminocycloalkyl) alkanes such as 3-methylcyclohexyl) methane and 2,2-bis (4′-aminocyclohexyl) propane [bis (aminoC _5-8 cycloalkyl) C _1-3 alkane etc.]; hydrogenated Xylylenediamine etc.) and aromatic diamine components (metaxylylenediamine etc.) may be used in combination. The diamine component (for example, alicyclic diamine component) may have a substituent such as an alkyl group (C _1-4 alkyl group such as a methyl group or an ethyl group).

  The proportion of the alkylene diamine component is 50 to 100 mol%, preferably 60 to 100 mol% (eg 70 to 97 mol%), more preferably 75 to 100 mol% (eg 80 to 100 mol%) with respect to the entire diamine component. 95 mol%).

As the dicarboxylic acid component, aliphatic dicarboxylic acid or alkane dicarboxylic acid component (for example, about 4 to 36 carbon atoms such as adipic acid, pimelic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid or hydrogenated product thereof) Dicarboxylic acid or _C4-36 alkanedicarboxylic acid). These dicarboxylic acid components can be used alone or in combination of two or more. Preferred dicarboxylic acid components include C _6-36 alkane dicarboxylic acids (eg, C _6-16 alkane dicarboxylic acids, preferably C _8-14 alkane dicarboxylic acids, etc.). Furthermore, if necessary, an alicyclic dicarboxylic acid component (C _5-10 cycloalkane-dicarboxylic acid such as cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, etc.), aromatic dicarboxylic acid ( Terephthalic acid, isophthalic acid, etc.) may be used in combination. As the diamine component and dicarboxylic acid component, an alicyclic ring obtained by using the aliphatic diamine component and / or aliphatic dicarboxylic acid component exemplified above together with the alicyclic diamine component and / or alicyclic dicarboxylic acid component. The group polyamide resin is known as so-called transparent polyamide, and has high transparency.

  The proportion of the alkanedicarboxylic acid component is 50 to 100 mol%, preferably 60 to 100 mol% (eg 70 to 97 mol%), more preferably 75 to 100 mol% (eg 80 (About -95 mol%).

  In the first amide-forming component, the diamine component can be used in a range of about 0.8 to 1.2 mol, preferably about 0.9 to 1.1 mol, with respect to 1 mol of the dicarboxylic acid component.

Examples of the lactam component include C such as δ-valerolactam, ε-caprolactam, ω-heptalactam, ω-octacactam, ω-decane lactam, ω-undecanactam, ω-laurolactam (or ω-laurinlactam). such as _4-20 lactam. Examples of the aminocarboxylic acid component, for example, .omega.-aminodecanoic acid, .omega.-aminoundecanoic acid, C _6-20 aminocarboxylic acids such as .omega.-aminododecanoic acid can be exemplified. These lactam components and aminocarboxylic acid components can also be used alone or in combination of two or more.

Preferred lactam components include C _6-19 lactam, preferably C _8-17 lactam, more preferably C _10-15 lactam (such as laurolactam). Preferred aminocarboxylic acids are amino C _6-19 alkanecarboxylic acids, preferably amino C _8-17 alkanecarboxylic acids, more preferably amino C _10-15 alkanecarboxylic acids (aminoundecanoic acid, aminododecanoic acid, etc.). Contains.

  The copolymerized polyamide may be a modified polyamide such as a polyamide into which a branched chain structure is introduced using a small amount of a polycarboxylic acid component and / or a polyamine component.

  Ratio of first amide forming component (both components combining diamine component and dicarboxylic acid component), second amide forming component (at least one amide forming component selected from lactam component and aminocarboxylic acid component) (Molar ratio) can be selected from the range of the former / the latter = 100/0 to 0/100, for example, 90/10 to 0/100 (for example, 80/20 to 5/95), preferably 75/25 It may be about 10/90 (for example, 70/30 to 15/85), more preferably about 60/40 to 20/80.

Furthermore, the copolymerized polyamide preferably includes a long chain component having a long chain fatty chain (long chain alkylene group or alkenylene group) as a constituent unit (or includes a unit derived from the long chain component). Such a long chain component includes a component having a long chain fatty chain having about 8 to 36 carbon atoms or an alkylene group (preferably a C _8-16 alkylene group, more preferably a C _10-14 alkylene group). Examples of the long chain component include C _8-18 alkane dicarboxylic acid (preferably C _10-16 alkane dicarboxylic acid, more preferably C _10-14 alkane dicarboxylic acid), C _9-17 lactam (preferably laurolactam, etc.). C _11-15 lactam) and amino C _9-17 alkanecarboxylic acid (preferably amino C _11-15 alkanecarboxylic acid such as aminoundecanoic acid and aminododecanoic acid). These long chain components can be used alone or in combination of two or more. Of these long-chain components, at least one component selected from a lactam component and / or an aminoalkanecarboxylic acid component such as laurolactam, aminoundecanoic acid and aminododecanoic acid is often used. Copolyamides containing such component-derived units have high water resistance and are excellent in adhesion, wear resistance and impact resistance to electronic devices, and can effectively protect electronic devices.

  The ratio of the long chain component is 10 to 100 mol% (for example, 25 to 95 mol%), preferably 30 to 90 mol% (for example, 40 to 85 mol%) with respect to the entire monomer component forming the copolymerized polyamide. Mol%), more preferably about 50 to 80 mol% (for example, 55 to 75 mol%).

  Further, the copolyamide may be a multi-component copolymer of the amide-forming component, for example, a binary copolymer to a quaternary copolymer, but is usually a binary copolymer to a quaternary copolymer. In many cases, the polymer is a binary copolymer or a ternary copolymer.

  The copolymerized polyamide often includes, for example, an amide-forming component selected from polyamide 11, polyamide 12, polyamide 610, polyamide 612, and polyamide 1010 as a constituent unit (or a unit derived from the amide-forming component). The copolymerized polyamide may be a copolymer of a plurality of these amide-forming components, and the one or more amide-forming components and other amide-forming components (at least one selected from polyamide 6 and polyamide 66). It may be a copolymer with an amide-forming component or the like). Specifically, examples of the copolyamide include copolyamide 6/11, copolyamide 6/12, copolyamide 66/11, copolyamide 66/12, copolyamide 610/11, copolyamide 612/11, copolyamide Polyamide 610/12, copolyamide 612/12, copolyamide 10/10/12, copolyamide 6/11/610, copolyamide 6/11/612, copolyamide 6/12/610, copolyamide 6/12/612, etc. Can be mentioned. In these copolyamides, the component separated by a slash “/” indicates an amide-forming component.

  As the polyamide elastomer (polyamide block copolymer), a polyamide block copolymer composed of polyamide as a hard segment (or hard block) and a soft segment (or soft block), for example, polyamide-polyether block copolymer Examples thereof include a polymer, a polyamide-polyester block copolymer, and a polyamide-polycarbonate block copolymer.

  The polyamide constituting the hard segment may be a homopolymer or a copolymer (homopolyamide, copolyamide) of one or more amide-forming components. The homopolyamide as the hard segment may contain the above-exemplified long chain component as a constituent unit, and the preferred long chain component is the same as described above. Typical homopolyamides include polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and the like. Further, the copolyamide as the hard segment is the same as the copolyamide exemplified above. Of these polyamides, homopolyamides such as polyamide 11, polyamide 12, polyamide 1010, and polyamide 1012 are preferred.

A typical polyamide elastomer is a polyamide-polyether block copolymer. In the polyamide-polyether block copolymer, as the polyether (polyether block), for example, polyalkylene glycol (for example, poly C _2-6 alkylene glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, preferably Poly _C2-4 alkylene glycol) and the like.

  Examples of such a polyamide-polyether block copolymer include a block copolymer obtained by copolycondensation of a polyamide block having a reactive end group and a polyether block having a reactive end group. Ether amide [for example, a block copolymer of a polyamide block having a diamine end and a polyalkylene glycol block having a dicarboxyl end (or a polyoxyalkylene block), a polyamide block having a dicarboxyl end and a polyalkylene glycol having a diamine end Block (or block copolymer with polyoxyalkylene block, etc.)], polyether ester amide [polyamide block having dicarboxyl terminal and polyalkylene glycol having dihydroxy terminal] Block (or polyoxyalkylene block) block copolymers], and others. The polyamide elastomer may have an ester bond, but may not have an ester bond in order to improve acid resistance. Also, commercially available polyamide elastomers usually have few amino groups.

  In the polyamide elastomer (polyamide block copolymer), the number average molecular weight of the soft segment (polyether block, polyester block, polycarbonate block, etc.) can be selected from a range of about 100 to 10000, preferably 300 to 6000 (for example, 300 to 5000), more preferably 500 to 4000 (for example, 500 to 3000), particularly about 1000 to 2000.

  In the polyamide elastomer (polyamide block copolymer), the ratio (weight ratio) between the polyamide block (polyamide segment) and the soft segment block is, for example, the former / the latter = 75/25 to 10/90, preferably 70. / 30 to 15/85, more preferably about 60/40 to 20/80 (for example, 50/50 to 25/75).

  These copolymer polyamide resins may be used alone or in combination of two or more. Of these copolymer polyamide resins, copolymer polyamides (non-polyamide elastomers or polyamide random copolymers) are preferable from the viewpoint of sealing properties of electronic devices. In particular, amide-forming components derived from polyamide 12 are constituent units. Copolyamides included as are preferred.

  The amino group concentration of the copolymerized polyamide resin is not particularly limited, and may be, for example, about 10 to 300 mmol / kg, preferably about 15 to 280 mmol / kg, more preferably about 20 to 250 mmol / kg.

  The carboxyl group concentration of the copolymerized polyamide resin is not particularly limited, and may be, for example, about 10 to 300 mmol / kg, preferably about 15 to 280 mmol / kg, more preferably about 20 to 250 mmol / kg. A high carboxyl group concentration in the copolymerized polyamide resin is advantageous in that the thermal stability is high.

  The number average molecular weight of the copolymerized polyamide-based resin can be selected from the range of, for example, about 5000 to 200000, for example, 6000 to 100,000, preferably 7000 to 70000 (for example, 7000 to 15000), and more preferably 8000 to 40000 (for example, 8000-12000), usually about 8000-30000. The molecular weight of the copolymerized polyamide resin can be measured in terms of polymethyl methacrylate by gel permeation chromatography using HFIP (hexafluoroisopropanol) as a solvent.

  The amide bond content of the copolymerized polyamide-based resin can be selected, for example, from a range of 100 units or less per molecule of the copolymerized polyamide-based resin. From the viewpoint of device sealing properties, 30 to 90 units, preferably 40 to It may be about 80 units, more preferably about 50 to 70 units (for example, 55 to 60 units). The amide bond content can be calculated, for example, by dividing the number average molecular weight by the molecular weight of the repeating unit (1 unit).

  The copolymerized polyamide resin may be amorphous or may have crystallinity. The crystallinity of the copolymerized polyamide resin may be, for example, 20% or less, preferably 10% or less. The crystallinity can be measured by a conventional method, for example, a measurement method based on density or heat of fusion, an X-ray diffraction method, an infrared absorption method, or the like.

  The heat melting property of the amorphous copolymerized polyamide resin can be measured as a softening temperature with a differential scanning calorimeter, and the melting point of the crystalline copolymerized polyamide resin can be measured with a differential scanning calorimeter (DSC).

  The melting point or softening point of the copolymerized polyamide resin (or copolymerized polyamide or polyamide elastomer) is 75 to 160 ° C. (for example, 80 to 150 ° C.), preferably 90 to 140 ° C. (for example, 95 to 135 ° C.), Preferably, it may be about 100 to 130 ° C, and is usually about 90 to 160 ° C (for example, 100 to 150 ° C). Since the copolymerized polyamide-based resin has a low melting point or softening point, it is useful for melting and following the surface shape of the device surface, such as an uneven part (such as a corner part of a step). The melting point of the copolymerized polyamide resin means a temperature corresponding to a single peak when each component is compatible and a single peak is generated in DSC, each component is incompatible, and DSC When a plurality of peaks occur, the temperature corresponding to the peak on the high temperature side among the plurality of peaks is meant.

  The copolymerized polyamide-based resin preferably follows a surface shape such as a concavo-convex portion on the surface of the device and has high melt fluidity so as to be able to enter a gap. The melt flow rate (MFR) of the copolymerized polyamide resin is 1 to 350 g / 10 minutes, preferably 3 to 300 g / 10 minutes, more preferably about 5 to 250 g / 10 minutes at a temperature of 160 ° C. and a load of 2.16 kg. It may be.

  In addition, you may add homopolyamide (For example, the homopolyamide by the component which forms the said copolyamide etc.) to the copolyamide-type resin in the range which does not impair the characteristics, such as adhesiveness. The proportion of the homopolyamide is 30 parts by weight or less (for example, 1 to 25 parts by weight), preferably 2 to 20 parts by weight, more preferably about 3 to 15 parts by weight with respect to 100 parts by weight of the copolymerized polyamide resin. There may be.

  The copolymerized polyamide-based resin may be used in combination with other resins, for example, a thermosetting resin such as an epoxy resin, a thermoplastic resin such as an ethylene-vinyl acetate copolymer, if necessary. The ratio of the other resin is, for example, 100 parts by weight or less (for example, about 1 to 80 parts by weight), preferably 2 to 70 parts by weight, and more preferably 2 to 50 parts with respect to 100 parts by weight of the copolymerized polyamide resin. It may be 30 parts by weight or less (for example, about 3 to 20 parts by weight). That is, the proportion of the copolymerized polyamide-based resin is 50 to 100% by weight, preferably 60 to 100% by weight (for example, 70 to 99.9% by weight), based on the entire resin component of the powder sealant, Preferably, it may be about 80 to 100% by weight (for example, 90 to 99% by weight).

  The copolymerized polyamide resin particles (a powdered mixture of copolymerized polyamide resins) may be a mixture of each polyamide particle or a mixture of particles of a melt mixture of each polyamide. In the form of such a mixture, the polyamides may be compatible with each other. In addition, in the particle size distribution showing the relationship between the particle size and frequency of the copolymerized polyamide resin particles, when having a plurality of peaks (particle groups), the type of copolymerized polyamide resin corresponding to each peak (particle group) is , May be the same or different.

  The powdery sealant (or copolymerized polyamide resin particles) of the present invention may contain various additives such as fillers, stabilizers (heat stabilizers, weathering stabilizers, etc.), colorants, plasticizers, if necessary. A lubricant, a flame retardant, an antistatic agent, a heat conductive agent, and the like may be included. The additives may be used alone or in combination of two or more. Of these additives, stabilizers, heat conducting agents and the like are widely used.

  As described above, the powdery sealant of the present invention is a copolymerized polyamide resin, a mixture of a plurality of types of copolymerized polyamide resins, or a copolymerized polyamide resin and other components (homopolyamide, other resins). , Additives, etc.) and a mixture (copolymerized polyamide resin composition).

  The powdery or granular sealant may be produced by pulverization by a conventional method such as freeze pulverization and classification using a sieve or the like.

  When the copolymerized polyamide-based resin is used as a sealant in the form of a granular material having a specific particle size distribution, (1) it has a powder fluidity capable of flowing on the device surface and is dispersed on the device or the substrate. Can be deposited stably and efficiently without dropping, (2) can be melted quickly at low temperature, and (3) the sealing / molding cycle can be shortened compared to thermosetting resins. In addition, (4) film-like sealants cannot follow surface irregularities (particularly severe surface irregularities), while powdery sealants easily follow surface irregularities for coating or sealing. (5) In injection molding (especially low-pressure injection molding) or molding using hot melt resin, there is a restriction on the size of the device or the substrate due to the relationship with the mold, While only the substrate can be sealed, the powdery sealant can seal without being restricted by the size of the device. Furthermore, (6) unlike the injection molding or molding using hot melt resin, a powdery sealant can be molded by forming a thin film, and can be made light and compact. (7) High adhesion and sealing properties Can mold the device. Therefore, the electronic device can be heat-sealed to the electronic device or the like, so that the electronic device can be waterproofed and moisture-proof, and contamination caused by dust can be protected. In particular, since the powdery sealant contains a copolymerized polyamide-based resin, adhesion to the device can be improved, high impact resistance and wear resistance can be imparted to the device, and the protective effect on the device can be enhanced. .

  In the method of the present invention, the powdered sealant is applied (or dispersed) to at least a part of the device, the powdered sealant is heated and melted, and the process is cooled. A device coated or molded with a polymerized polyamide resin can be produced.

  Examples of the device include various organic or inorganic devices that need to be molded or sealed, such as semiconductor elements, electroluminescent (EL) elements, light emitting diodes, precision components such as solar cells, various electronic components, or electronic elements. An electronic component (particularly, a precision electronic component or an electronic device) such as a printed circuit board on which the component is mounted can be exemplified.

  In the application step, the powdery sealant may be applied or spread over the entire device, or may be applied or spread only on a predetermined site by masking if necessary. The powder sealant may immerse the device in the powder sealant (such as fluidized immersion) and adhere to the device. However, the powder sealant has an appropriate powder fluidity and is efficiently applied to a predetermined part of the device. Since it can deposit, it is preferable to make it adhere to a device by spraying a powdery sealing agent on the device mounted on the predetermined member. It should be noted that the spraying amount or the adhesion amount may be increased in a predetermined part of the device, for example, a rising part or a corner part. The device may also be coated with a volatile liquid to temporarily hold the powder sealant. Furthermore, if necessary, the device may be heated (for example, heated to a temperature equal to or higher than the melting point or softening point of the sealant), and the powdery sealant may be attached (or partially fused). In this case, the excess powdery sealant may be removed by methods such as vibration, rotation, and wind force.

The use amount (or adhesion amount) of the powdery sealant can be selected according to the mold or the coating amount, for example, 0.1 to 100 mg / cm ² , preferably 0.5 to 50 mg / cm ² , more preferably. About 1-30 mg / cm < ² > may be sufficient.

  In the heating step, the copolymerized polyamide resin can be welded to the device by heating and melting the powdery sealant in accordance with the heat resistance of the device. The heating temperature is, for example, about 75 to 200 ° C., preferably 80 to 180 ° C., more preferably 100 to 175 ° C. (for example, 110 to 150 ° C.), depending on the melting point and softening point of the copolymerized polyamide resin. May be. Heating can be performed in air or in an inert gas atmosphere. Heating can be performed in an oven, and if necessary, ultrasonic heating or high-frequency heating (electromagnetic induction heating) may be used. The heating and melting step may be performed under normal pressure or under pressure, and if necessary, degassing may be performed under reduced pressure.

  Furthermore, if necessary, the application step and the heating step may be repeated. In addition, after forming a copolymerized polyamide resin film on one surface (for example, the upper surface) of the device as described above, a powdery sealing agent is applied or dispersed on the other surface (for example, the bottom surface) of the device. Then, heat sealing may be performed, and both sides including the end face of the device may be molded with a copolymerized polyamide resin coating and sealed.

  In the cooling step, the fused copolymer polyamide resin may be naturally cooled, may be cooled stepwise or continuously, or may be rapidly cooled.

  By passing through such a process, the device by which at least one part was coat | covered or molded with the coating film of the copolyamide-type resin formed by heat-sealing a powdery sealing agent can be obtained. The mold part of the device is usually a part that is easily damaged, for example, an electronic element mounting part or a wiring part in many cases.

  In the present invention, since the powdery sealant can be fused at a relatively low temperature, the device is less likely to be thermally damaged and the reliability of the device can be improved. In addition, unlike injection molding or the like, high pressure does not act on the device, so that the device is not damaged by the pressure. Therefore, the device can be molded and sealed with high reliability. And since it can heat and cool within a short time, productivity of a mold or a sealing device can be improved greatly.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the evaluation method of each evaluation item in an Example is as follows.

[Particle size distribution and average particle size]
About the powder resin particle | grains of the Example and the comparative example, the particle size distribution and the average particle diameter were measured using the laser diffraction apparatus (Horiba Ltd. make, HORIBA LA920).

[Angle of repose]
According to JIS R9301-2-2, from 9 cm above a horizontal metal table (radius 4 cm), a glass funnel (maximum inner diameter of inclined funnel portion: 70 mm, inner diameter x length of foot part: 5 mm x 50 mm) ), 200 g of the powder resin particles of the example and the comparative example are dropped and deposited on the metal table, and an angle formed by the generatrix direction of the generated conical deposit and the surface direction of the metal table ( The outer angle was measured with a protractor, and the base angle (rest angle) of the conical sediment was calculated.

[Collapse angle]
The decay angle was measured using “Powder Tester PT-E” manufactured by Hosokawa Micron Corporation.

[Melting time]
A 26 mm × 76 mm glass plate (preparation) is placed on an iron plate (thickness 1 mm) to form a test body, and 0.2 g of the powder resin particles of the examples and comparative examples are dispersed in the center of each glass plate so as not to spill, It was placed in an oven at 170 ° C. and the time until the surface became flat was measured.

[Sealing]
The sealing property at a flat substrate surface and the sealing property at a convex portion having a side surface (height: 2 mm or 20 mm) rising perpendicularly from the flat substrate surface were evaluated according to the following criteria.
5: Completely covered 4: Almost completely covered, but some air intrusion is observed 3: Half is floating 2: Some are adhered to the object to be coated, but most are Floating 1: The coating film is completely floating.

[Peel test]
The adhesiveness was evaluated by a cross-cut peel test using the glass epoxy substrates sealed with the sealing agents of Examples and Comparative Examples.

[Water resistance test]
The glass epoxy substrates sealed with the sealants of Examples and Comparative Examples were immersed in water at 23 ° C. for 100 hours, and then water resistance was evaluated by a cross-cut peel test.

[LED lighting test]
After immersing the LED mounting substrate sealed with the sealing agent of the example and the comparative example in water at 23 ° C. for 100 hours and then energizing and the LED is turned on, it is evaluated as “◯”, and when it is not turned on, it is evaluated as “×”. did.

Example 1
Copolymerized polyamide (VESTAMELT X1051, manufactured by Evonik, containing C _10-14 alkylene group, melting point 130 ° C. (DSC), melt flow rate 15 g / 10 min (temperature 160 ° C. and load 2.16 kg)) was frozen and ground. Classification was performed using a wire mesh having an opening diameter of 60 μm to obtain powder resin particles having an average particle diameter of 44 μm and a particle size of 0.5 to 60 μm. The resin particles were evenly dispersed on a glass epoxy resin electronic substrate (200 mm × 200 mm) using a wire mesh (opening diameter 200 μm), and then heated in an atmosphere at a temperature of 170 ° C. and coated with a transparent resin. A substrate was obtained.

Example 2
Copolymerized polyamide (VESTAMELT X1051) was freeze-pulverized and classified using a wire mesh having an opening diameter of 80 μm to obtain powder resin particles having an average particle diameter of 49 μm and a particle size of 0.5 to 80 μm. The resin particles were evenly dispersed on a glass epoxy resin electronic substrate (200 mm × 200 mm) using a wire mesh (opening diameter 200 μm), and then heated in an atmosphere at a temperature of 170 ° C. and coated with a transparent resin. A substrate was obtained.

Example 3
Copolymerized polyamide (VESTAMELT X7079, manufactured by Evonik, containing C _10-14 alkylene group, melting point 130 ° C. (DSC), melt flow rate 3 g / 10 min (temperature 160 ° C. and load 2.16 kg)) was frozen and ground. Classification was performed using a wire mesh having an opening diameter of 120 μm to obtain powder resin particles having an average particle diameter of 78 μm and a particle size of 0.5 to 120 μm. The resin particles were evenly dispersed on a glass epoxy resin electronic substrate (200 mm × 200 mm) using a wire mesh (opening diameter 250 μm), and then heated in an atmosphere at a temperature of 170 ° C. and coated with a transparent resin. A substrate was obtained.

Example 4
Copolymerized polyamide (VESTAMELT X7079) was freeze-pulverized and classified using a wire mesh having an opening diameter of 160 μm to obtain powder resin particles having an average particle diameter of 85 μm and a particle size of 0.5 to 160 μm. The resin particles were evenly dispersed on a glass epoxy resin electronic substrate (200 mm × 200 mm) using a wire mesh (opening diameter 250 μm), and then heated in an atmosphere at a temperature of 170 ° C. and coated with a transparent resin. A substrate was obtained.

Example 5
Copolymerized polyamide (VESTAMELT X1051) was freeze-pulverized and classified using a wire mesh having an opening diameter of 300 μm to obtain powder resin particles having an average particle diameter of 183 μm and a particle size of 0.5 to 300 μm. The resin particles were dispersed evenly on a glass epoxy resin electronic substrate (200 mm × 200 mm) using a wire mesh (opening diameter: 500 μm), and then heated in an atmosphere at a temperature of 170 ° C. and coated with a transparent resin. A substrate was obtained.

Example 6
Copolymerized polyamide (VESTAMELT X1051) was freeze-pulverized and classified using a wire net having an opening diameter of 500 μm to obtain powder resin particles having an average particle diameter of 278 μm and a particle size of 0.5 to 500 μm. The resin particles were evenly dispersed on a glass epoxy resin electronic substrate (200 mm × 200 mm) using a wire mesh (opening diameter 710 μm), and then heated in an atmosphere at a temperature of 170 ° C. and coated with a transparent resin. A substrate was obtained.

Example 7
Copolymerized polyamide (VESTAMELT X1051) was freeze-pulverized and classified using a wire mesh having an opening diameter of 1000 μm to obtain powder resin particles having an average particle diameter of 308 μm and a particle size of 0.5 to 1000 μm. The resin particles were evenly dispersed on a glass epoxy resin electronic substrate (200 mm × 200 mm) using a wire mesh (opening diameter 710 μm), and then heated in an atmosphere at a temperature of 170 ° C. and coated with a transparent resin. A substrate was obtained.

Example 8
Copolymerized polyamide (VESTAMELT X1051) was frozen and pulverized and classified using a wire mesh having an opening diameter of 80 μm and 160 μm to obtain powder resin particles having an average particle diameter of 148 μm and a particle size of 80 to 160 μm. The resin particles were spread evenly on a glass epoxy resin electronic substrate (200 mm × 200 mm) using a wire mesh (opening diameter: 300 μm), and then heated in an atmosphere at a temperature of 170 ° C. and coated with a transparent resin. A substrate was obtained.

Example 9
Copolymerized polyamide (VESTAMELT X1051) was freeze-pulverized and classified using a wire mesh having an opening diameter of 80 μm and 200 μm to obtain powder resin particles having an average particle diameter of 169 μm and a particle size of 80 to 200 μm. The resin particles were spread evenly on a glass epoxy resin electronic substrate (200 mm × 200 mm) using a wire mesh (opening diameter: 300 μm), and then heated in an atmosphere at a temperature of 170 ° C. and coated with a transparent resin. A substrate was obtained.

Example 10
Copolymerized polyamide (VESTAMELT X1051) was freeze-pulverized and classified using a wire mesh having an opening diameter of 80 μm and 500 μm to obtain powder resin particles having an average particle diameter of 340 μm and a particle size of 80 to 500 μm. The resin particles were evenly dispersed on a glass epoxy resin electronic substrate (200 mm × 200 mm) using a wire mesh (opening diameter 710 μm), and then heated in an atmosphere at a temperature of 170 ° C. and coated with a transparent resin. A substrate was obtained.

Example 11
Copolymerized polyamide (VESTAMELT X1051) was freeze-pulverized and classified using a wire mesh having an opening diameter of 500 μm and 1000 μm to obtain first powder resin particles having an average particle diameter of 617 μm and a particle size of 500 to 1000 μm. Moreover, the copolymerized polyamide (VESTAMELT X1051) was frozen and pulverized and classified using a wire mesh having an opening diameter of 200 μm to obtain second powder resin particles having an average particle diameter of 160 μm and a particle size of 0.5 to 200 μm. The second resin particles are mixed at a ratio of 5 parts by weight with respect to 100 parts by weight of the first resin particles, and this mixture is used for a glass epoxy resin electronic substrate (200 mm × 200 mm) using a wire mesh (opening diameter: 710 μm). ) After spraying evenly on, it was heated in an atmosphere at a temperature of 170 ° C. to obtain a substrate coated with a transparent resin.

Comparative Example 1
Copolymerized polyamide (VESTAMELT X1051) was frozen and pulverized and classified using a wire mesh with an opening diameter of 1000 μm to obtain powder resin particles having an average particle diameter of 1300 μm or more and a particle size exceeding 1000 μm. The resin particles were evenly dispersed on a glass epoxy resin electronic substrate (200 mm × 200 mm) using a wire mesh (opening diameter 2000 μm), and then heated in an atmosphere at a temperature of 170 ° C., but the powder spilled from the substrate. And a uniformly coated substrate was not obtained.

Comparative Example 2
Copolyamide (VESTAMELT 350, manufactured by Evonik Co., Ltd., spherical pellets containing C _10-14 alkylene group and having an average particle size of about 3000 μm, melting point 105 ° C. (DSC), melt flow rate 15 g / 10 min (temperature 160 ° C. and load) 2.16 kg)) was evenly sprayed on a glass epoxy resin electronic substrate (200 mm × 200 mm) and then heated in an atmosphere at a temperature of 170 ° C., but a uniformly coated substrate was not obtained.

Comparative Example 3
Polyamide 12 (Daiamide A1709, manufactured by Daicel Evonik, average particle size 80 μm, particle size 0.5 to 160 μm, melting point 178 ° C. (DSC), melt flow rate 70 g / 10 min (temperature 190 ° C. and load 2.16 kg)) After spraying evenly on a glass epoxy resin electronic substrate (200 mm × 200 mm), the substrate was heated in an atmosphere at a temperature of 220 ° C. to obtain a substrate coated with a transparent resin.

  Table 1 shows the physical properties of the powder resin particles of Examples and Comparative Examples, FIG. 1 shows the relationship between the particle size and the frequency, and FIG. 2 shows the relationship between the particle size and the accumulated amount of passage. In addition, since the measurement limit (upper limit value) of the laser diffractometer is 2 mm, the frequency of the particle diameter exceeding 2 mm and the accumulated amount of the powder resin particles of Comparative Example 3 are omitted in FIGS. 1 and 2. .

  With respect to the sealants of Examples and Comparative Examples, sealing properties, peelability, and water resistance were evaluated. The results are shown in Table 2. In addition, in the table | surface, each numerical value in a peeling test and a water resistance test shows the number of the grid which peeled among the 100 grids in the grid peel test.

  As is clear from Table 2, compared to the comparative example, in the example, the sealing performance at the flat portion and the convex portion is high, and the adhesion and water resistance are also excellent.

  INDUSTRIAL APPLICABILITY The present invention is useful for molding or sealing an electronic element or electronic component such as a semiconductor element, an EL element, or a solar battery cell, a printed board on which various electronic components or electronic elements are mounted, or the like at a low temperature.

Claims (18)

  A sealing agent for sealing a device, comprising copolymerized polyamide-based resin particles composed of a copolymerized polyamide-based resin and having a particle diameter of 1 mm or less, wherein the copolymerized polyamide-based resin particles are at least A powdery sealant containing copolymerized polyamide resin particles (A) having an average particle size of 20 to 400 μm.   The powdery sealant according to claim 1, wherein the average particle diameter of the copolymerized polyamide resin particles (A) is 40 to 350 µm.   The copolymerized polyamide resin particles further include copolymerized polyamide resin particles (B) having an average particle diameter of 1.2 to 20 times the average particle diameter of the copolymerized polyamide resin particles (A). The powdery sealant according to claim 1 or 2.   The powdery sealing agent according to claim 3, wherein the average particle diameter of the copolymerized polyamide resin particles (B) is 450 to 800 µm.   The powdery sealant according to claim 3 or 4, wherein the proportion of the copolymerized polyamide resin particles (A) is 1 to 10 parts by weight with respect to 100 parts by weight of the copolymerized polyamide resin particles (B).   The powdery sealant according to any one of claims 1 to 5, wherein the repose angle of the entire copolymerized polyamide resin particles is 35 to 55 °.   The powdery sealant according to any one of claims 1 to 6, wherein the copolymerized polyamide resin has a melting point or softening point of 75 to 160 ° C.   The powdery sealing agent according to any one of claims 1 to 7, wherein the copolymerized polyamide resin has crystallinity.   The powdery sealant according to any one of claims 1 to 8, wherein the copolymerized polyamide-based resin has crystallinity and has a melting point of 90 to 160 ° C.   The powdery sealing agent according to any one of claims 1 to 9, wherein the copolymerized polyamide resin is a multi-component copolymer.   The powdery sealant according to any one of claims 1 to 10, wherein the copolymerized polyamide resin is a binary copolymer to a quaternary copolymer. The powdery sealant according to any one of claims 1 to 11, wherein the copolymerized polyamide-based resin contains a unit derived from a long-chain component having a _C8-16 alkylene group. The powdery sealing agent according to any one of claims 1 to 12, wherein the copolymerized polyamide-based resin includes a unit derived from at least one component selected from C _9-17 lactam and amino C _9-17 alkanecarboxylic acid. .   The powdery sealing agent according to any one of claims 1 to 13, wherein the copolymerized polyamide resin includes units derived from an amide-forming component selected from polyamide 11, polyamide 12, polyamide 610, polyamide 612, and polyamide 1010. .   Copolyamide resin is copolyamide 6/11, copolyamide 6/12, copolyamide 66/11, copolyamide 66/12, copolyamide 610/11, copolyamide 612/11, copolyamide 610/12, copolyamide At least one selected from polyamide 612/12, copolyamide 1010/12, copolyamide 6/11/610, copolyamide 6/11/612, copolyamide 6/12/610, and copolyamide 6/12/612 The powdery sealant according to any one of claims 1 to 14.   The powdery sealing agent according to any one of claims 1 to 15, wherein the copolymerized polyamide-based resin contains a unit derived from at least one component selected from laurolactam, aminoundecanoic acid and aminododecanoic acid.   The powdery sealant according to any one of claims 1 to 16 is applied to at least a part of the device, the powdery sealant is heated and melted, cooled, and coated or molded with a copolymerized polyamide resin. A method of manufacturing a device.   A device in which at least a part is coated or molded with a coating of a copolymerized polyamide resin formed by heat-sealing the powdery sealant according to any one of claims 1 to 16.

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