JP4898191B2 - Adhesive composition - Google Patents
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- JP4898191B2 JP4898191B2 JP2005315841A JP2005315841A JP4898191B2 JP 4898191 B2 JP4898191 B2 JP 4898191B2 JP 2005315841 A JP2005315841 A JP 2005315841A JP 2005315841 A JP2005315841 A JP 2005315841A JP 4898191 B2 JP4898191 B2 JP 4898191B2
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- alumina powder
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- 239000000853 adhesive Substances 0.000 title claims description 52
- 230000001070 adhesive effect Effects 0.000 title claims description 52
- 239000000203 mixture Substances 0.000 title claims description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 53
- 239000000843 powder Substances 0.000 claims description 53
- 239000002245 particle Substances 0.000 claims description 42
- 230000001186 cumulative effect Effects 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 18
- 239000008119 colloidal silica Substances 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000007787 solid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RQFRTWTXFAXGQQ-UHFFFAOYSA-N [Pb].[Mo] Chemical compound [Pb].[Mo] RQFRTWTXFAXGQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- ASTDPSSQLZVNNF-UHFFFAOYSA-N diethyl-methyl-[5-(oxiran-2-ylmethoxy)pentan-2-yloxy]silane Chemical compound C(C1CO1)OCCCC(C)O[Si](CC)(CC)C ASTDPSSQLZVNNF-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- -1 γ-aminopropyl Chemical group 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
- Common Detailed Techniques For Electron Tubes Or Discharge Tubes (AREA)
Description
本発明は、接着性組成物に関する。 The present invention relates to an adhesive composition.
光源装置などに用いられる電球を構成するガラスバルブを口金、ミラー材料、磁製ベースなどと接着する方法としては、ガラスバルブと口金等との間の隙間に接着性組成物を充填し、硬化させる方法が一般的であり、接着性組成物としては、隙間への充填が容易で、硬化後には十分な接着力を示し、ガラスバルブ内のフィラメントや、これを支えるリード線からの熱を外部に伝えて放熱するための高い熱伝導性を示すことが求められている。 As a method of adhering a glass bulb constituting a light bulb used in a light source device to a base, a mirror material, a magnetic base, etc., an adhesive composition is filled in a gap between the glass bulb and the base and cured. The method is general, and as an adhesive composition, it is easy to fill in the gap and shows sufficient adhesive force after curing, and heat from the filament in the glass bulb and the lead wire that supports it is externally exposed. It is required to exhibit high thermal conductivity to convey and dissipate heat.
このような接着性組成物として、例えば特許文献１〔特開平１１−１１６８９９号公報〕には、耐火物粉末として窒化アルミニウム粉末を、無機バインダーとして燐酸アルミニウムを含む接着性組成物が開示されている。特許文献２〔特開２００１−３１６６３８号公報〕には、耐火物粉末として炭化珪素粉末を、無機バインダーとしてコロイダルシリカを含む接着性組成物が開示されている。 As such an adhesive composition, for example, Patent Document 1 (Japanese Patent Laid-Open No. 11-116899) discloses an adhesive composition containing an aluminum nitride powder as a refractory powder and an aluminum phosphate as an inorganic binder. . Patent Document 2 (Japanese Patent Laid-Open No. 2001-316638) discloses an adhesive composition containing silicon carbide powder as a refractory powder and colloidal silica as an inorganic binder.
しかし、特許文献１に記載の接着性組成物は、無機バインダーとして燐酸アルミニウムを用いているため、十分な接着力を示すよう硬化させるには、充填後、２４時間、室温で保持した後に加熱する必要があり、実用的ではない。特許文献２に記載の接着性組成物は、高価な炭化硅素粉末を使用するものであり、経済性の点で実用的ではない。
However, since the adhesive composition described in Patent Document 1 uses aluminum phosphate as an inorganic binder, in order to cure it so as to exhibit a sufficient adhesive force, it is heated after being held at room temperature for 24 hours after filling. Needed and not practical. The adhesive composition described in
このようなことから、隙間へ容易に充填でき、硬化後には十分な接着力と高い熱伝導性を示すとともに、比較的安価な原材料から製造でき、短時間で硬化し得る接着性組成物が求められている。 For this reason, there is a need for an adhesive composition that can be easily filled into the gap, exhibits sufficient adhesive strength and high thermal conductivity after curing, can be manufactured from relatively inexpensive raw materials, and can be cured in a short time. It has been.
このような状況の下で本発明者は、ガラスバルブと口金等との接着に使用し得る接着性組成物について鋭意検討した結果、本発明に至った。 Under such circumstances, the present inventors have intensively studied an adhesive composition that can be used for adhesion between a glass bulb and a die, etc., and as a result, have reached the present invention.
すなわち本発明は、累積質量百分率５０％相当粒子径(Ｄ50)が４μｍ〜９０μｍであり、該累積質量百分率５０％相当粒子径(Ｄ50)に対して累積質量百分率１０％相当粒子径(Ｄ10)が１／２０〜１／４倍、累積質量百分率９０％相当粒子径(Ｄ90)が４倍〜１０倍である球状アルミナ粉末、コロイダルシリカ、無機分散剤およびシランカップリング剤を含むことを特徴とする接着性組成物を提供するものである。
That is, in the present invention, the
本発明の接着性組成物は、比較的安価な原材料から製造でき、また短時間で硬化し得、硬化後の接着力および熱伝導性に優れているので、電球を構成するガラスバルブと、口金、ミラー材料、磁製ベースなどとを接着するための接着性組成物として有用である。 The adhesive composition of the present invention can be produced from a relatively inexpensive raw material, can be cured in a short time, and is excellent in adhesive strength and thermal conductivity after curing. It is useful as an adhesive composition for bonding a mirror material, a magnetic base, and the like.
本発明の接着性組成物に適用される球状アルミナ粉末は、外形が球状であるアルミナ粒子であって、通常は球状のα−アルミナ粉末が用いられる。球状アルミナ粉末は、十分な接着力を示す点で、最小粒子径が通常０．１μｍ以上であり、ガラスバルブと口金等との間に充填し易い点で、最大粒子径が通常２００μｍ以下であり、好ましくは１６０μｍを超える粒子の含有量が１質量％以下である。 The spherical alumina powder applied to the adhesive composition of the present invention is an alumina particle having a spherical outer shape, and usually a spherical α-alumina powder is used. Spherical alumina powder has a minimum particle size of usually 0.1 μm or more in terms of sufficient adhesive strength, and a maximum particle size of usually 200 μm or less in terms of easy filling between a glass bulb and a die. The content of particles preferably exceeding 160 μm is 1% by mass or less.
アルミナ粉末の累積質量百分率５０％相当粒子径(Ｄ50)は、十分な接着力が得られ易く、硬化後の熱伝導性に優れている点で通常４μｍ以上、好ましくは１０μｍ以上であり、ガラスバルブと口金等との間の隙間に充填しやすい点で、通常９０μｍ以下、好ましくは７０μｍ以下である。 The particle diameter (D50) corresponding to a cumulative mass percentage of 50% of the alumina powder is usually 4 μm or more, preferably 10 μm or more in terms of easy obtaining of sufficient adhesive force and excellent thermal conductivity after curing. The thickness is usually 90 μm or less, preferably 70 μm or less, in that it can be easily filled in the gap between the base and the die.
累積質量百分率１０％相当粒子径(Ｄ10)は、高い熱伝導性を示す点で、Ｄ50の１／２０倍以上、Ｄ50の１／４倍以下である。累積質量百分率９０％相当粒子径(Ｄ90)は、高い熱伝導性を示す点で、Ｄ50の４倍以上であり、隙間へ充填し易い点で、１０倍以下である。
The particle size (D10) corresponding to a cumulative mass percentage of 10% is at least 1/20 of D50 and not more than 1/4 of D50 in that it exhibits high thermal conductivity. The
球状アルミナ粉末は、質量基準の粒度分布曲線において粒子径６０μｍ〜１１０μｍの範囲に極大ピークを有するものであることが好ましい。 The spherical alumina powder preferably has a maximum peak in a particle size range of 60 μm to 110 μm in a mass-based particle size distribution curve.
本発明で規定するＤ50、Ｄ10およびＤ90を示す球状アルミナ粉末は、例えば互いに粒度分布の異なる複数の球状アルミナ粉末を混合することにより調製することができ、具体的にはＤ50が８０μｍ〜９０μｍの球状アルミナ粉末、Ｄ50が６μｍ〜１０μｍの球状アルミナ粉末およびＤ50が１μｍ〜５μｍの球状アルミナ粉末を適宜混合する方法により調製することができる。 The spherical alumina powder showing D50, D10 and D90 defined in the present invention can be prepared, for example, by mixing a plurality of spherical alumina powders having different particle size distributions. Specifically, the spherical alumina powder having D50 of 80 μm to 90 μm. An alumina powder, a spherical alumina powder having a D50 of 6 μm to 10 μm, and a spherical alumina powder having a D50 of 1 μm to 5 μm can be appropriately prepared.
コロイダルシリカは、シリカ〔ＳｉＯ2〕の微細な粒子であり、その含有量（ＳｉＯ2換算）は、アルミナ粉末１００質量部あたり、十分な接着力が得られる点で３質量部以上、好ましくは５質量部以上であり、ガラスバルブと口金等との間の隙間に必要量の接着性組成物を保持することが容易である点で、１５質量部以下、好ましくは１０質量部以下である。 Colloidal silica is a fine particle of silica [SiO 2 ], and its content (in terms of SiO 2 ) is 3 parts by mass or more, preferably 5 in terms of obtaining sufficient adhesive force per 100 parts by mass of alumina powder. The amount is 15 parts by mass or less, preferably 10 parts by mass or less, in that it is easy to hold a necessary amount of the adhesive composition in the gap between the glass bulb and the base.
無機分散剤は、接着性組成物中にアルミナ粉末およびコロイダルシリカを均一に分散させる機能を示す無機化合物であり、例えばモンモリロナイトなどが好ましく用いられ、その使用量は、上記アルミナ粉末１００質量部あたり０．１質量部〜１．５質量部、好ましくは０．３質量部〜１質量部である。 The inorganic dispersant is an inorganic compound having a function of uniformly dispersing alumina powder and colloidal silica in the adhesive composition. For example, montmorillonite is preferably used, and the amount used is 0 per 100 parts by mass of the alumina powder. .1 part by mass to 1.5 parts by mass, preferably 0.3 part by mass to 1 part by mass.
シランカップリング剤は、加水分解により分子中に２個以上のシラノール基を生ずる化合物であり、例えばγ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエチルエトキシシラン、γ-アミノプロピルトリメトキシシランなどが挙げられる。シランカップリング剤は、その一部または全部が加水分解されていてもよい。シランカップリング剤の使用量は、上記アルミナ粉末１００質量部あたり０．１質量部〜１．５質量部、好ましくは０．２質量部〜１質量部である。 Silane coupling agents are compounds that produce two or more silanol groups in the molecule by hydrolysis, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethylethoxysilane, γ-aminopropyl. Examples include trimethoxysilane. A part or all of the silane coupling agent may be hydrolyzed. The usage-amount of a silane coupling agent is 0.1 mass part-1.5 mass parts per 100 mass parts of said alumina powders, Preferably they are 0.2 mass part-1 mass part.
本発明の接着性組成物は、通常、水で希釈された状態で用いられる。水の使用量は、接着性組成物を加熱して硬化させた後の固形分に対して、隙間への充填が容易である点で通常０．２質量倍以上であり、充填した後に必要量の接着性組成物を隙間に保持しやすい点で通常０．４質量倍以下である。 The adhesive composition of the present invention is usually used in a state diluted with water. The amount of water used is usually 0.2 mass times or more in terms of easy filling into the gap with respect to the solid content after the adhesive composition is heated and cured, and the necessary amount after filling. The adhesive composition is usually 0.4 mass times or less in that it is easy to hold the adhesive composition in the gap.
本発明の接着性組成物は、例えば球状アルミナ粉末、コロイダルシリカ、無機分散剤およびシランカップリング剤を混合する方法により容易に製造することができる。コロイダルシリカは、通常、水に分散された水分散液として市販されているので、このコロイダルシリカの水分散液に、球状アルミナ粉末、無機分散剤およびシランカップリング剤を加えて混合することにより、本発明の接着性組成物を調製することができ、通常は、無機分散剤およびシランカップリング剤を加え、撹拌して均一に混合した後に、球状アルミナ粉末を加えて撹拌混合することにより調製できる。 The adhesive composition of the present invention can be easily produced by, for example, a method of mixing spherical alumina powder, colloidal silica, an inorganic dispersant, and a silane coupling agent. Colloidal silica is usually marketed as an aqueous dispersion dispersed in water. By adding a spherical alumina powder, an inorganic dispersant and a silane coupling agent to the aqueous dispersion of colloidal silica, the mixture is mixed. The adhesive composition of the present invention can be prepared. Usually, it can be prepared by adding an inorganic dispersant and a silane coupling agent, stirring and mixing uniformly, and then adding a spherical alumina powder and stirring and mixing. .
本発明の接着性組成物を用いて、ガラスバルブと、金属製の口金、金属製のミラー材料または磁製ベースとが接着された電球を製造するには、例えばガラスバルブと、口金、ミラー材料または磁製ベースとの間の隙間に、本発明の接着性組成物を充填し、加熱すればよい。加熱温度は通常１５０℃〜２００℃であり、通常は５℃／分〜３０℃／分の昇温速度で昇温する。加熱時間は通常１０分〜１時間である。加熱することにより、接着性組成物が硬化して、ガラスバルブと口金等とが、本発明の接着性組成物の加熱硬化物により接着された電球を得ることができる。 In order to manufacture a light bulb in which a glass bulb and a metal base, a metal mirror material, or a magnetic base are bonded using the adhesive composition of the present invention, for example, the glass bulb, the base, and the mirror material Alternatively, the adhesive composition of the present invention may be filled in a gap between the magnetic base and heated. The heating temperature is usually 150 ° C. to 200 ° C., and the temperature is usually raised at a rate of temperature increase of 5 ° C./min to 30 ° C./min. The heating time is usually 10 minutes to 1 hour. By heating, the adhesive composition is cured, and a light bulb in which the glass bulb and the base are bonded by the heat-cured product of the adhesive composition of the present invention can be obtained.
以下、実施例によって本発明をより詳細に説明するが、本発明は、かかる実施例によって限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
なお、各実施例で用いた粉末および得られた接着性組成物は、以下の方法で評価した。
（１）粒度分布
レーザー回折式粒度分布測定装置〔(株)島津製作所製、「ＳＡＬＤ２２００」〕を用いて粒子径０．０３μｍから１０００μｍの範囲で粒子径を測定し、粒度分布曲線を求めた。また、０．０３μｍからの累積質量が全質量の５０％となる粒子径を累積質量百分率５０％相当粒子径(Ｄ50)、１０％となる粒子径を累積質量百分率１０％相当粒子径(Ｄ10)、９０％となる粒子径を累積質量百分率９０％相当粒子径(Ｄ90)として、それぞれ求めた。
（２）粘度
粘度計〔リオン(株)製、「ビスコテスターＶＴ−０４」〕を用い、同装置に付属のＮｏ．
２号ローターを用いて２５℃にて１分後の粘度を測定した。
（３）固形分濃度
各実施例で得た接着性組成物約５０ｇ（Ｗ）を３００ｍＬビーカーに秤取り、加熱して１
０℃／分の昇温速度で１５０℃まで昇温し、同温度で１６時間保持して硬化させた後の加
熱硬化物の質量（Ｗ150）から、式（１）
固形分濃度（％）＝（Ｗ150−Ｗ）／Ｗ × １００・・・（１）
に従い求めた。
（４）接着力
内径１２ｍｍのガラス管内に、外径９ｍｍのガラス製の丸棒を入れ、管と丸棒との間に接着性組成物１．５ｇを均一に充填し、１５０℃にて１時間保持して硬化させた。その後、精密万能試験機〔(株)島津製作所製、「オートグラフＡＧＳ１０００Ｂ型」〕にて丸棒をガラス管から押し抜くに要する力（Ｎ）を測定して、接着力とした。
（５）自動充填性
ステンレス製ニードルバルブ〔岩下エンジニアリング(株)製、「ＡＶ−５０１」〕およびニードルノズル〔ＪＩＳ規格に規定の１３Ｇ型のニードル（内径１．５ｍｍ、外径２．０ｍｍ、長さ４０ｍｍ、ステンレス製、電解研磨注射針）〕を備え、コントローラー〔岩下エンジニアリング(株)製、「ＡＤ−３０００」〕により吐出時間および吐出サイクルを調整可能に構成した定量供給装置を用いて、ニードルノズルから、吐出時間１．２秒、吐出間隔７秒で繰り返し連続して２０００ショット、接着性組成物を吐出し、その間の１回あたりの吐出量（ｇ）を測定して自動充填性を評価した。吐出量の振れが小さいほど、自動充填性が良好であることを示す。
In addition, the powder used in each Example and the obtained adhesive composition were evaluated by the following methods.
(1) Particle size distribution A particle size distribution curve was determined by measuring the particle size in the range of 0.03 μm to 1000 μm using a laser diffraction particle size distribution measuring apparatus (manufactured by Shimadzu Corporation, “SALD2200”). In addition, the particle diameter at which the cumulative mass from 0.03 μm becomes 50% of the total mass is equivalent to the
(2) Using a viscosity viscometer [manufactured by Lion Co., Ltd., “Viscotester VT-04”], No.
The viscosity after 1 minute was measured at 25 ° C. using a No. 2 rotor.
(3) Solid content concentration About 50 g (W) of the adhesive composition obtained in each example was weighed into a 300 mL beaker and heated to 1
From the mass (W150) of the heat-cured product after being heated to 150 ° C. at a rate of temperature increase of 0 ° C./min and held at that temperature for 16 hours to cure, the formula (1)
Solid content concentration (%) = (W150−W) / W × 100 (1)
Sought in accordance with
(4) A glass round bar with an outer diameter of 9 mm is placed in a glass tube with an inner diameter of 12 mm, and 1.5 g of the adhesive composition is uniformly filled between the tube and the round bar. Hold for time to cure. Thereafter, the force (N) required to push out the round bar from the glass tube was measured with a precision universal testing machine [manufactured by Shimadzu Corporation, “Autograph AGS1000B type”] to obtain an adhesive force.
(5) Self-filling stainless steel needle valve (“AV-501” manufactured by Iwashita Engineering Co., Ltd.) and needle nozzle [13G type needle defined by JIS standard (inner diameter 1.5 mm, outer diameter 2.0 mm, long 40 mm, stainless steel, electrolytic polishing needle), and a needle using a quantitative supply device configured to adjust the discharge time and the discharge cycle by a controller (“AD-3000” manufactured by Iwashita Engineering Co., Ltd.) From the nozzle, 2000 shots of the adhesive composition were repeatedly and continuously discharged at a discharge time of 1.2 seconds and a discharge interval of 7 seconds. did. The smaller the fluctuation of the discharge amount, the better the automatic filling property.
実施例１
コロイダルシリカ液〔旭電化(株)製「アデライトＡＴ−４０」、ＳｉＯ2換算含有量４０質量％〕３６０ｇ（ＳｉＯ2換算１４４ｇ）に、無機分散剤〔(株)ホージュン製「ベンゲル」、モンモリロナイトの粉末、Ｅ2/3Ｓｉ8(Ａｌ10/3Ｍｇ2/3)Ｏ20・(ＯＨ)4、（Ｅはナトリウム、カリウムなどでイオン交換可能な原子を示す。）〕９．０ｇおよびシランカップリング剤〔東レダウコーニングシリコーン(株)製「ＳＨ６０４０」、γ−グリシドキシプロピルトリメトキシシラン〕３．６ｇを加え、３時間、撹拌混合した。
Example 1
To the colloidal silica liquid [Adelite AT-40 manufactured by Asahi Denka Co., Ltd., SiO 2 equivalent content: 40% by mass] 360 g (144 g SiO 2 equivalent), an inorganic dispersant [“Bengel” manufactured by Hojun Co., Ltd., montmorillonite Powder, E 2/3 Si 8 (Al 10/3 Mg 2/3 ) O 20. (OH) 4 (E represents an atom capable of ion exchange with sodium, potassium, etc.)] 9.0 g and silane cup 3.6 g of a ring agent [“SH6040” manufactured by Toray Dow Corning Silicone Co., Ltd., γ-glycidoxypropyltrimethoxysilane] was added and mixed with stirring for 3 hours.
次いで、以下の球状アルミナ粉末(Ａ)、球状アルミナ粉末(Ｂ)および球状アルミナ粉末(Ｃ)を第１表に示す量だけ加え、３０分間、撹拌混合して、接着性組成物を得た。なお、球状アルミナ粉末(Ａ)、球状アルミナ粉末(Ｂ)および球状アルミナ粉末(Ｃ)を上記と同じ量比で混合した混合物の粒度分布曲線（質量基準）を図１に示す。この混合物は、粒子径分布曲線において粒子径約９０μｍの位置に極大ピークを示す。また、この粒度分布曲線から求めた累積質量百分率５０％相当粒子径(Ｄ50)、累積質量百分率１０％相当粒子径(Ｄ10)および累積質量百分率９０％相当粒子径(Ｄ90)をそれぞれ第１表に示す。
Next, the following spherical alumina powder (A), spherical alumina powder (B) and spherical alumina powder (C) were added in the amounts shown in Table 1 and stirred and mixed for 30 minutes to obtain an adhesive composition. In addition, the particle size distribution curve (mass standard) of the mixture which mixed spherical alumina powder (A), spherical alumina powder (B), and spherical alumina powder (C) by the same amount ratio as the above is shown in FIG. This mixture shows a maximum peak at a particle size of about 90 μm in the particle size distribution curve. The
球状アルミナ粉末(Ａ)：(株)マイクロン製「ＡＷ７０−１２５」、α−アルミナ、
粒子径は５０μｍ〜１５５μｍ、Ｄ50は８７μｍ
球状アルミナ粉末(Ｂ)：(株)マイクロン製「ＡＸ１０−３２」、α−アルミナ、
粒子径は０．３μｍ〜５５μｍ、Ｄ50は８μｍ
球状アルミナ粉末(Ｃ)：(株)マイクロン製「ＡＸ３−３２」、α−アルミナ、
粒子径は０．２μｍ〜４５μｍ、Ｄ50は４μｍ
Spherical alumina powder (A): “AW70-125” manufactured by Micron Corporation, α-alumina,
Particle size is 50μm ~ 155μm, D50 is 87μm
Spherical alumina powder (B): “AX10-32” manufactured by Micron Corporation, α-alumina,
Particle size is 0.3μm to 55μm, D50 is 8μm
Spherical alumina powder (C): “AX3-32” manufactured by Micron Corporation, α-alumina,
Particle size is 0.2μm ~ 45μm, D50 is 4μm
ＪＤＲタイプ電球〔定格電圧１２Ｖ、定格電力１５０Ｗ〕に用いられ、モリブデン製リード線が封止されたガラスバルブの封止部分に、上記で得た接着性組成物により熱電対を取り付け、予め１５０℃に加熱した炉内に入れて接着性組成物を硬化させることにより、熱電対をガラスバルブに固定した。次いで、このガラスバルブを口金にセットし、口金との間の隙間に上記で得た接着性組成物を充填したのち、１５０℃で３０分間加熱して、電球を得た。このようにして得た電球５個について、それぞれ消費電力１５０Ｗ（電圧は約１２Ｖ）で点灯させ、ＪＩＳ Ｃ７５０１に準拠して上記熱電対によりリード線封止部分の温度を測定し、その平均温度を求めた。結果を第１表に示す。 A thermocouple is attached to the sealing portion of a glass bulb used for a JDR type light bulb [rated voltage 12 V, rated power 150 W] and sealed with a molybdenum lead wire by using the adhesive composition obtained above, and 150 ° C. in advance. The thermocouple was fixed to the glass bulb by placing it in a furnace heated to 1 to cure the adhesive composition. Next, this glass bulb was set in a base, and the adhesive composition obtained above was filled in a gap between the base and the base, and then heated at 150 ° C. for 30 minutes to obtain a light bulb. The five light bulbs thus obtained were each lit at a power consumption of 150 W (voltage is about 12 V), the temperature of the lead wire sealed portion was measured by the thermocouple in accordance with JIS C7501, and the average temperature was determined. Asked. The results are shown in Table 1.
実施例２
コロイダルシリカ液〔アデライトＡＴ−４０〕、無機分散剤〔ベンゲル〕、シランカップリング剤、球状アルミナ粉末(Ａ)、球状アルミナ粉末(Ｂ)および球状アルミナ粉末(Ｃ)の使用量を第１表のとおりとする以外は実施例１と同様に操作して接着性組成物を得た。結果を第１表に示す。
Example 2
The amount of colloidal silica liquid [Adelite AT-40], inorganic dispersant [Bengel], silane coupling agent, spherical alumina powder (A), spherical alumina powder (B) and spherical alumina powder (C) is shown in Table 1. An adhesive composition was obtained by operating in the same manner as in Example 1 except that it was as described above. The results are shown in Table 1.
第 １ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
例 実施例１ 実施例２
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
球状アルミナ粉末(Ａ) [ｇ] ９００ ７２０
球状アルミナ粉末(Ｂ) [ｇ] ５４０ ７２０
球状アルミナ粉末(Ｃ) [ｇ] ３６０ ３６０
Ｄ50 [μｍ] ２５．３ １６．２
Ｄ10 [μｍ] １．５１ １．２７
Ｄ90 [μｍ]１０８．３ １０３．２
極大ピークの位置 [μｍ] ９０ ９０
───────────────────────────────
コロイダルシリカ(SiO2算) [ｇ] １４４ １０２
無機分散剤 [ｇ] ９．０ ６．４
シランカップリング剤 [ｇ] ３．６ ２．６
───────────────────────────────
粘度 [cP]２００００ ２００００
固形分濃度 [％] ８９．８ ９１．５
接着力 [Ｎ] ３００ ３００
吐出量 [ｇ] ０．５±０．１ −
封止部分の温度 [℃] ２５９ ２５９
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Table 1
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example Example 1 Example 2
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Spherical alumina powder (A) [g] 900 720
Spherical alumina powder (B) [g] 540 720
Spherical alumina powder (C) [g] 360 360
D50 [μm] 25.3 16.2
D10 [μm] 1.51 1.27
D90 [μm] 108.3 103.2
Maximum peak position [μm] 90 90
───────────────────────────────
Colloidal silica (SiO 2 count) [g] 144 102
Inorganic dispersant [g] 9.0 6.4
Silane coupling agent [g] 3.6 2.6
───────────────────────────────
Viscosity [cP] 20000 20000
Solid content concentration [%] 89.8 91.5
Adhesive strength [N] 300 300
Discharge amount [g] 0.5 ± 0.1 −
Temperature of sealed portion [° C.] 259 259
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
比較例１〜比較例３
コロイダルシリカ液〔アデライトＡＴ−４０〕、無機分散剤〔ベンゲル〕、シランカップリング剤、球状アルミナ粉末(Ａ)、球状アルミナ粉末(Ｂ)および球状アルミナ粉末(Ｃ)の使用量を第２表のとおりとする以外は実施例１と同様に操作して接着性組成物を得た。結果を第２表に示す。
Comparative Examples 1 to 3
The amount of colloidal silica liquid [Adelite AT-40], inorganic dispersant [Bengel], silane coupling agent, spherical alumina powder (A), spherical alumina powder (B) and spherical alumina powder (C) is shown in Table 2. An adhesive composition was obtained by operating in the same manner as in Example 1 except that it was as described above. The results are shown in Table 2.
第 ２ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
例 比較例１ 比較例２ 比較例３
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
球状アルミナ粉末(Ａ) [ｇ]１８００ ０ ０
球状アルミナ粉末(Ｂ) [ｇ] ０ １８００ ０
球状アルミナ粉末(Ｃ) [ｇ] ０ ０ １８００
Ｄ50 [μｍ] ８６．７ ８．２ ４．１
Ｄ10 [μｍ] ６５．７ ２．９ ０．８
Ｄ90 [μｍ]１１７．９ ２４．１ １０．９
───────────────────────────────────────
コロイダルシリカ(SiO2算)[ｇ] １９４ １８０ ２１６
無機分散剤 [ｇ] １２．１ １１．３ １３．５
シランカップリング剤 [ｇ] ４．９ ４．５ ５．４
───────────────────────────────────────
粘度 [cP]２１０００ ２００００ ２００００
固形分濃度 [％] ８７．２ ８８．０ ８６．２
接着力 [Ｎ] ２００ ２５０ ２００
吐出量 [ｇ] ０．５±０．１ − −
封止部分の温度 [℃] ２８３ ２８０ ２９２
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Table 2
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example Comparative Example 1 Comparative Example 2 Comparative Example 3
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Spherical alumina powder (A) [g] 1800 0 0
Spherical alumina powder (B) [g] 0 1800 0
Spherical alumina powder (C) [g] 0 0 1800
D50 [μm] 86.7 8.2 4.1
D10 [μm] 65.7 2.9 0.8
D90 [μm] 117.9 24.1 10.9
───────────────────────────────────────
Colloidal silica (SiO 2 count) [g] 194 180 216
Inorganic dispersant [g] 12.1 11.3 13.5
Silane coupling agent [g] 4.9 4.5 5.4
───────────────────────────────────────
Viscosity [cP] 21000 20000 20000
Solid content concentration [%] 87.2 88.0 86.2
Adhesive strength [N] 200 250 200
Discharge amount [g] 0.5 ± 0.1 − −
Temperature of sealed portion [° C.] 283 280 292
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
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