JP2006312278A - Joining method of hydroxyapatite and silicone resin and composite - Google Patents
Joining method of hydroxyapatite and silicone resin and composite Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
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Abstract
Description
本発明はヒドロキシアパタイトとシリコン樹脂との接合方法、及びその複合体に関する。 The present invention relates to a method for bonding hydroxyapatite and silicon resin, and a composite thereof.
生体治療における外科的手法は最先端科学技術を駆逐した取り組みが行われ、健康回復・維持には従来にない新たな治療技術の展開をもたらしつつある。
切り傷などの創傷、骨折などは通常の治療手当が確立され、現在の治療法によってほとんど生体機能の低下を招くことなく治癒するに至る。その一方、人体の特殊部位の骨損傷や機能低下に対する外科的治療など、必要に応じて生体親和性のよい材料やその他の材料を複合して生体内に適用し、骨等による生体機能の回復を図る必要がでてくる。
Surgical methods in biomedical treatments are being advanced through cutting-edge science and technology, and new therapeutic technologies are being developed that are unprecedented in restoring and maintaining health.
Normal treatment allowance is established for wounds such as cuts, fractures, etc., and they are cured by current therapies with almost no deterioration of biological functions. On the other hand, recovery of biological functions by bones, etc., when necessary, combined with materials with good biocompatibility and other materials, such as surgical treatment for bone damage and functional deterioration of special parts of the human body It is necessary to plan.
上記生体親和性のよい材料として、ヒドロキシアパタイトがある。更に、この材料を同じく生体に用いることができる材料としてのシリコン樹脂と接合して用いる場合が生じる。そしてこの場合には、十分な接合強度（例えば生体内の骨の代替的使用の場合は１５０Ｎ／ｃｍ２以上）の確保、生体内での耐久性・信頼性が要求される。また接合は凹凸接合等、平面間接合以外の場合においても良好に行われることが要求される場合がある。 Hydroxyapatite is an example of the material having good biocompatibility. Further, there is a case where this material is used by being bonded to a silicon resin as a material that can be used for a living body. In this case, sufficient bonding strength (for example, 150 N / cm 2 or more in the case of alternative use of bone in the living body) and durability and reliability in the living body are required. Further, there are cases where the bonding is required to be performed well in cases other than the bonding between planes, such as uneven bonding.
従来、ヒドロキシアパタイトを用いた表面処理として、ヒドロキシアパタイト焼結体の表面に、例えばシランカップリング剤を用いて官能基を修飾したものを高分子基材と化学結合させた複合体の製造方法（特許文献１）や、ヒドロキシアパタイトの表面にシランカップリング剤をリンカーとして有機物を結合してなる有機物修飾ヒドロキシアパタイト多孔体（特許文献２）、有機高分子基材をシランカップリング処理した後、カルシウムイオンとリン酸イオンとを作用させることで前記基材表面に水酸アパタイトをコーティングする方法（特許文献３）等が開示されている。
ところが上記特許文献１、２においては、ヒドロキシアパタイトが結合すべき相手がシリコン樹脂である場合についての解決手段が示されておらず、また特許文献３は有機高分子の表面に水酸アパタイト膜を析出させるものであって、何れもヒドロキシアパタイトとシリコン樹脂との接合を開示するものではない。 However, Patent Documents 1 and 2 do not disclose a solution for the case where the partner to which hydroxyapatite is bonded is a silicon resin, and Patent Document 3 discloses a hydroxyapatite film on the surface of an organic polymer. None of them are intended to disclose the bonding between hydroxyapatite and silicon resin.
そこで本発明は上記従来の問題を解消し、生体親和性のよいヒドロキシアパタイトとシリコン樹脂とを強固に安定して接合することができるヒドロキシアパタイトとシリコン樹脂との接合方法と、その接合によって得られる複合体の提供を課題とする。 Accordingly, the present invention solves the above-mentioned conventional problems, and is obtained by a bonding method of hydroxyapatite and silicon resin capable of firmly and stably bonding hydroxyapatite and silicon resin having good biocompatibility, and the bonding thereof. The issue is to provide a complex.
上記課題を解決するため、本発明のヒドロキシアパタイトとシリコン樹脂との接合方法は、ヒドロキシアパタイト基材の接合表面をシランカップリング処理してＮＨ２基を修飾し、一方、シリコン樹脂基材の接合表面にアクリル酸処理してＣＯＯＨ基を修飾した後、両接合表面を合わせて、加圧状態下及び加温状態下において接合することを第１の特徴としている。
また本発明のヒドロキシアパタイトとシリコン樹脂との接合方法は、上記第１の特徴に加えて、接合時において１３０〜２５０℃で所定時間保持することを第２の特徴としている。
また本発明のヒドロキシアパタイトとシリコン樹脂との接合方法は、上記第２の特徴に加えて、接合時において室温から１〜１０℃／ｍｉｎの昇温速度で加熱してゆくことを第３の特徴としている。
また本発明のヒドロキシアパタイトとシリコン樹脂との接合方法は、上記第１〜第３の何れかの特徴に加えて、０．５〜１０ｋｇ／ｃｍ２の加圧下で接合を行うことを第４の特徴としている。
また本発明のヒドロキシアパタイトとシリコン樹脂との接合方法は、上記第１〜第４の何れかの特徴に加えて、ヒドロキシアパタイト基材の接合表面及びシリコン樹脂基材の接合表面を予め１００〜４００番のサンドペーパで研磨して接合表面を清浄化した後、相対湿度を３０％以下で接合を行うことを第５の特徴としている。
また本発明のヒドロキシアパタイト−シリコン樹脂複合体は、上記第１〜第５の何れかの特徴に記載の接合方法で接合されてなることを第６の特徴としている。
In order to solve the above problems, the method for bonding hydroxyapatite and silicon resin according to the present invention modifies NH 2 groups by silane coupling treatment of the bonding surface of the hydroxyapatite substrate, while bonding of the silicon resin substrate. The first feature is that after the surface is modified with acrylic acid to modify the COOH group, the bonding surfaces are joined together and bonded under a pressurized condition and a heated condition.
In addition to the first feature, the method for joining hydroxyapatite and silicon resin of the present invention has a second feature of holding at 130 to 250 ° C. for a predetermined time during joining.
In addition to the second feature described above, the method for joining hydroxyapatite and silicon resin of the present invention is a third feature in that heating is performed at a heating rate of 1 to 10 ° C./min from room temperature during joining. It is said.
Moreover, the joining method of the hydroxyapatite of this invention and a silicon resin WHEREIN: In addition to any one of the said 1st-3rd characteristics, joining is performed under the pressurization of 0.5-10 kg / cm < 2 >. It is a feature.
Moreover, in addition to any one of the first to fourth characteristics, the method for bonding hydroxyapatite and silicon resin of the present invention is performed by previously setting the bonding surface of the hydroxyapatite substrate and the bonding surface of the silicon resin substrate to 100 to 400. The fifth feature is that the bonding surface is cleaned by polishing with sandpaper and then bonded at a relative humidity of 30% or less.
Moreover, the hydroxyapatite-silicone resin composite of the present invention is characterized by being bonded by the bonding method described in any one of the first to fifth characteristics.
請求項１に記載の発明によれば、前処理としてヒドロキシアパタイト基材の接合表面にＮＨ２基が修飾され、またシリコン樹脂基材の接合表面にＣＯＯＨ基が修飾される。前処理後に、ヒドロキシアパタイト基材とシリコン樹脂基材とを両者の接合表面を合わせて、加温状態で、加圧することで接合される。
前記接合は、ヒドロキシアパタイト基材のＮＨ２基とシリコン樹脂基材のＣＯＯＨ基とが縮合反応を起こすことによってアミド結合（−ＣＯ−ＮＨ−）を構成することで、強固に接合する。その際、加温状態下に加圧することで、接合力を増すことができる。
よって請求項１に記載の発明によれば、従来において困難であったヒドロキシアパタイト基材とシリコン樹脂基材との強固な接合を可能とすることができる。
According to the first aspect of the present invention, the NH 2 group is modified on the bonding surface of the hydroxyapatite substrate and the COOH group is modified on the bonding surface of the silicon resin substrate as pretreatment. After the pretreatment, the hydroxyapatite base material and the silicon resin base material are joined together by applying pressure in a heated state with the joining surfaces of the two being matched.
In the joining, the NH 2 group of the hydroxyapatite base material and the COOH group of the silicon resin base material form an amide bond (—CO—NH—) by causing a condensation reaction, thereby firmly joining. In that case, a joining force can be increased by pressurizing under a heating state.
Therefore, according to the first aspect of the present invention, it is possible to firmly join the hydroxyapatite base material and the silicon resin base material, which has been difficult in the past.
請求項２に記載の発明によれば、上記請求項１に記載の構成による効果に加えて、接合時において１３０〜２５０℃で所定時間保持することにより、接合強度を一層大きくすることができる。 According to invention of Claim 2, in addition to the effect by the structure of said Claim 1, joining strength can be made still larger by hold | maintaining at 130-250 degreeC for predetermined time at the time of joining.
また請求項３に記載の発明によれば、上記請求項２に記載の構成による効果に加えて、接合の際に、保持温度１３０〜２５０℃になるまでの昇温速度を１〜１０℃／ｍｉｎとすることで、シランカップリング処理剤やアクリル酸の揮発を緩慢にすることができる。これによってそれら接着剤層の緻密性を確保することができ、接合強度を一層向上させることができる。 According to the invention described in claim 3, in addition to the effect of the configuration described in claim 2, the temperature increase rate until the holding temperature becomes 130 to 250 ° C. is increased to 1 to 10 ° C. / By setting it as min, volatilization of the silane coupling agent or acrylic acid can be slowed down. As a result, the denseness of these adhesive layers can be ensured, and the bonding strength can be further improved.
また請求項４に記載の発明によれば、上記請求項１〜３の何れかに記載の構成による効果に加えて、０．５〜１０ｋｇ／ｃｍ２の加圧下で接合することで、強固な結合を確実なものとすることができる。 According to the invention described in claim 4, in addition to the effects of the structure described in any one of claims 1 to 3, the bonding is performed under a pressure of 0.5 to 10 kg / cm 2 , thereby Bonding can be ensured.
また請求項５に記載の発明によれば、上記請求項１〜４の何れかに記載の構成による効果に加えて、ヒドロキシアパタイト基材の接合表面及びシリコン樹脂基材の接合表面を予め１００〜４００番のサンドペーパで研磨して接合表面を清浄化等することで、接合環境を整えることができる。加えて接合時における相対湿度を３０％以下とすることで、水分露点を低くし、接合条件を一層良好にして強固な接合を可能とすることができる。 According to the invention described in claim 5, in addition to the effect of the structure according to any one of claims 1 to 4, the bonding surface of the hydroxyapatite substrate and the bonding surface of the silicon resin substrate are previously set to 100 to 100. The bonding environment can be adjusted by polishing with a No. 400 sandpaper to clean the bonding surface. In addition, by setting the relative humidity at the time of bonding to 30% or less, the moisture dew point can be lowered, the bonding conditions can be further improved, and strong bonding can be achieved.
また請求項６に記載の発明によれば、請求項１〜５の何れかの接合方法で接合されてなるヒドロキシアパタイト−シリコン樹脂複合体であることにより、ヒドロキシアパタイト基材とシリコン樹脂基材とが強固に接合された複合体を提供することができ、骨機能修復等の骨関連の材料として好ましく用いることができる。 Moreover, according to invention of Claim 6, it is a hydroxyapatite base material and a silicon resin base material by being a hydroxyapatite-silicone resin composite joined by the joining method in any one of Claims 1-5. Can be provided, and can be preferably used as a bone-related material for bone function repair and the like.
本発明の実施形態を以下に説明する。
本発明の方法及び複合体に用いられるヒドロキシアパタイトは、化学式として次の式で表すことができる。
Ｃａ１０（ＰＯ４）６（ＯＨ）２
ヒドロキシアパタイト基材としては、Ｃａ２＋、ＰＯ４ ３−、ＯＨ−以外にＮａ＋、Ｋ＋、Ｍｇ２＋、Ｆ−、Ｃｌ−、ＣＯ３−、等の陽・陰イオンを含有していてもよい。
Embodiments of the present invention will be described below.
The hydroxyapatite used in the method and composite of the present invention can be represented by the following formula as a chemical formula.
Ca 10 (PO 4 ) 6 (OH) 2
The hydroxyapatite base material may contain cations and anions such as Na + , K + , Mg 2+ , F − , Cl − and CO 3− in addition to Ca 2+ , PO 4 3− and OH −. Good.
一方、シリコン樹脂は、メチルシリコン樹脂、フッ化シリコン樹脂、フェニルシリコン樹脂、ビニルメチルシリコン樹脂等の有機シリコン樹脂を用いることができる。 On the other hand, as the silicon resin, an organic silicon resin such as a methyl silicon resin, a silicon fluoride resin, a phenyl silicon resin, or a vinyl methyl silicon resin can be used.
本発明の接合方法における実施形態では、次の処理工程において工夫した。
（１）接合基材相互の接合面の前処理
（２）接合時の環境条件の設定
In embodiment in the joining method of this invention, it devised in the next process process.
(1) Pretreatment of bonding surfaces between bonding substrates (2) Setting of environmental conditions during bonding
接合基材相互の接合表面の前処理として、
ヒドロキシアパタイト基材の接合表面にＮＨ２基を付加し、反応性を高める。具体的には、ヒドロキシアパタイト基材の接合表面を１００番〜４００番のサンドペーパで研磨し、シランカップリング薬剤、例えばＨ２ＮＣ３Ｈ６Ｓｉ（ＯＣ２Ｈ５）３を塗布して、接合表面にＮＨ２基を付加する。
一方、シリコン樹脂については、その接合表面の鋭敏化・アンカー効果の増大を図るため、表面を１００番〜４００番のサンドペーパで研磨し、アクリル酸（ＣＨ２（ＣＨＣＯＯＨ））を塗布し、接合表面にＣＯＯＨ基を付加する。
As a pretreatment of the bonding surface between bonding substrates,
NH 2 group is added to the bonding surface of the hydroxyapatite base material to increase the reactivity. Specifically, the bonding surface of the hydroxyapatite base material is polished with No. 100 to No. 400 sand paper, and a silane coupling agent such as H 2 NC 3 H 6 Si (OC 2 H 5 ) 3 is applied and bonded. Add NH 2 groups to the surface.
On the other hand, for silicon resin, the surface is polished with No. 100 to No. 400 sand paper and acrylic acid (CH 2 (CHCOOH)) is applied to increase the sensitivity of the bonding surface and increase the anchoring effect. A COOH group is added to the.
接合基材相互の接合面の接合時の環境設定として、
ＮＨ２基を修飾したヒドロキシアパタイト基材及びＣＯＯＨ基を修飾したシリコン樹脂基材は、表面汚染、不純物の混入を防止するため、少なくともクリーンレベル１０００以上の清浄な場所で接合作業を行う。
また相対湿度３０％以下の場所で接合作業を行う。相対湿度を３０％以下とすることで、接合表面の湿気を減じ、均一で安定した接合強度をもたらす。
As an environment setting at the time of joining of joining surfaces of joining base materials,
The hydroxyapatite base material modified with NH 2 group and the silicon resin base material modified with COOH group are joined in a clean place at least at a clean level of 1000 or more in order to prevent surface contamination and impurities.
Also, joining work is performed in a place where the relative humidity is 30% or less. By setting the relative humidity to 30% or less, the moisture on the bonding surface is reduced, and uniform and stable bonding strength is provided.
接合作業は、前記ヒドロキシアパタイト基材とシリコン樹脂基材の接合表面を相互に合わせ、真空又は減圧下にて接合部分に介在する空気等の気体を一定時間脱ガスした後、０．５〜１０ｋｇ／ｃｍ２の圧力を加えながら行う。０．５ｋｇ／ｃｍ２未満では接合強度が上がらない。また１０ｋｇ／ｃｍ２を超える圧力を加えても、接合強度のそれ以上の上昇は望めない一方、基材の破損を招く可能性がある。
前記脱ガスを行うのは、接合作業において接合面に介在するガスが良好な接合を妨げるのを防止するためである。特に本発明の場合には加温を行うので、気泡が発達するのを防止する必要がある。脱ガスは両基材を合わせて加圧した状態で行ってもよい。脱ガス作業を行うことで、強固で安定した接合を達成することができる。
The bonding operation is performed by matching the bonding surfaces of the hydroxyapatite substrate and the silicon resin substrate with each other, and degassing a gas such as air intervening in the bonded portion under a vacuum or reduced pressure, and then 0.5 to 10 kg. / Cm 2 while applying pressure. If it is less than 0.5 kg / cm 2 , the bonding strength does not increase. Further, even if a pressure exceeding 10 kg / cm 2 is applied, no further increase in bonding strength can be expected, but the substrate may be damaged.
The degassing is performed in order to prevent the gas present on the bonding surface from interfering with good bonding in the bonding operation. Particularly in the case of the present invention, since heating is performed, it is necessary to prevent bubbles from developing. Degassing may be performed in a state where both base materials are pressurized together. By performing the degassing operation, a strong and stable joining can be achieved.
接合作業は加温しながら行う。
加温は室温から１〜１０℃／ｍｉｎの加熱速度とし、１３０〜２５０℃まで上昇させ、その温度で１０分〜４時間保持する。
前記昇温速度を１〜１０℃／ｍｉｎの緩慢な速度とすることで、シランカップリング処理剤やアクリル酸（修飾ＮＨ２基や修飾ＣＯＯＨ基）の揮発、その他の分解等を緩慢にすることができる。これによって、それら接着剤層の緻密性等を確保することができ、接合強度を一層向上させることができる。１０℃／ｍｉｎ以上の昇温速度では、昇温速度が速すぎて接合強度が上がらず、安定しない。１／ｍｉｎ未満では昇温に時間がかかりすぎる。昇温速度は、好ましくは４〜７℃／ｍｉｎがよい。
前記保持温度を１３０〜２５０℃とし、０．５〜４時間保持することで、接合強度を少なくとも１５０Ｎ／ｃｍ２以上にすることができる。
保持温度が１３０℃未満になると、接合強度を１５０Ｎ／ｃｍ２以上に安定して確保することが難しくなる。また２５０℃を超える場合も接合強度が低下し、またエネルギ−ロスが大きい。保持温度は、強度的には１６０〜２２０℃が好ましい。
保持時間が１０分未満では、十分な強度と安定性が得られない懸念がある。また保持時間が４時間を越えても、それ以上の強度は期待できず、エネルギーと時間の無駄になる。保持時間は、好ましくは３０分〜４時間とする。
Joining is performed while heating.
The heating is performed at a heating rate of 1 to 10 ° C./min from room temperature, is increased to 130 to 250 ° C., and is maintained at that temperature for 10 minutes to 4 hours.
By slowing the rate of temperature increase from 1 to 10 ° C./min, volatilization of silane coupling agent and acrylic acid (modified NH 2 group and modified COOH group), other decomposition, etc. are slowed down. Can do. As a result, the denseness of the adhesive layer can be ensured, and the bonding strength can be further improved. At a temperature increase rate of 10 ° C./min or more, the temperature increase rate is too high and the bonding strength does not increase and is not stable. If it is less than 1 / min, it takes too much time to raise the temperature. The temperature rising rate is preferably 4 to 7 ° C./min.
By maintaining the holding temperature at 130 to 250 ° C. and holding for 0.5 to 4 hours, the bonding strength can be at least 150 N / cm 2 or more.
When the holding temperature is less than 130 ° C., it is difficult to stably secure the bonding strength at 150 N / cm 2 or more. When the temperature exceeds 250 ° C., the bonding strength is reduced and the energy loss is large. The holding temperature is preferably 160 to 220 ° C. in terms of strength.
If the holding time is less than 10 minutes, there is a concern that sufficient strength and stability cannot be obtained. Even if the holding time exceeds 4 hours, no further strength can be expected, and energy and time are wasted. The holding time is preferably 30 minutes to 4 hours.
前記接合作業中においては、接合表面が相互にずれたりしないように、両基材を適切に固定しておくことが必要である。
接合作業が終了すると、両基材に対する加圧及び加温状態が解かれる。以上の作業によってヒドロキシアパタイトとシリコン樹脂との接合が完了し、ヒドロキシアパタイトとシリコン樹脂とが接合された複合体が完成される。
During the joining operation, it is necessary to fix both base materials appropriately so that the joining surfaces do not deviate from each other.
When the joining operation is completed, the pressurization and heating states for both base materials are released. By the above operation, the joining of hydroxyapatite and silicon resin is completed, and a composite body in which hydroxyapatite and silicon resin are joined is completed.
（実施例１）
本発明方法の実施試験１〜３と比較試験１〜３について、何れも同一のサンドペーパ処理をした後、本発明方法の実施試験１〜３については、本発明の方法による接合表面の前処置をした後、約１ＫＰａ程度の減圧デシケータ内に約３０分保持して脱ガスし、略１．６ｋｇ／ｃｍ２の加圧下、略５℃／ｍｉｎの昇温速度、略１８０℃の保持温度、略２時間の保持時間で、湿度３０％未満でヒドロキシアパタイト基材とシリコン基材との接合を行った。
一方、比較試験１〜３については、シアノアクリレート接着剤を用いて常温下、実施試験と同様の加圧下及び保持時間、湿度下においてヒドロキシアパタイト基材とシリコン基材との接合を行った。
接合完了後の接合強度と、１０００時間の水浸漬後の接合強度を測定した。
結果を表１に示す。
なお各実験試験１〜３及び比較試験１〜３においては、複数の試片について実施し、その平均値として接合強度を算出している。
Example 1
After performing the same sandpaper treatment for the execution tests 1 to 3 and the comparative tests 1 to 3 of the method of the present invention, the pretreatment of the bonding surface by the method of the present invention is performed for the execution tests 1 to 3 of the method of the present invention. After that, the gas is degassed by holding it in a vacuum desiccator of about 1 KPa for about 30 minutes, under a pressure of about 1.6 kg / cm 2, at a heating rate of about 5 ° C./min, a holding temperature of about 180 ° C., The hydroxyapatite base material and the silicon base material were joined at a humidity of less than 30% with a holding time of 2 hours.
On the other hand, in Comparative Tests 1 to 3, the hydroxyapatite base material and the silicon base material were joined using a cyanoacrylate adhesive at room temperature, under the same pressure, holding time, and humidity as in the test.
The bonding strength after the completion of bonding and the bonding strength after 1000 hours of water immersion were measured.
The results are shown in Table 1.
In each of the experimental tests 1 to 3 and the comparative tests 1 to 3, the test was performed on a plurality of specimens, and the bonding strength was calculated as the average value.
表１から明らかなように、本発明の方法による場合はヒドロキシアパタイト基材とシリコン樹脂基材との接合強度が１９０Ｎ／ｃｍ２程度あり、また１０００時間水浸漬後の強度も１７０Ｎ／ｃｍ２程度の水準にあり、何れも目安の１５０Ｎ／ｃｍ２を超える良好な接合強度を保っている。これに対して従来の方法による場合は、何れも強度が目安の１５０Ｎ／ｃｍ２を大きく下回る結果であった。 As is evident from Table 1, there are two approximately 190 N / cm bond strength between the hydroxyapatite substrate and the silicone resin substrate is the case of the method of the present invention, also 1000 hours water strength after immersion also 170N / cm 2 or so Both have good bonding strength exceeding the standard 150 N / cm 2 . On the other hand, in the case of using the conventional method, the strength was much lower than the standard 150 N / cm 2 .
（実施例２）
生体医療において使用されるヒドロキシアパタイト基材とシリコン樹脂基材との接合の場合は、接合面が必ずしも平面接合とならず、凹面や凸面等、非平面での接合が想定される。そこでヒドロキシアパタイト基材とシリコン樹脂基材とを相互に凹凸接合させて、その場合の接合強度を検証した。接合条件は実施例１の場合と同じである。比較例として本発明方法による平面接合の場合、及び従来のシアノアクリレート接着剤を用いた凹凸接合の場合を示す。なお各試験においては複数の試片について行ったが、ばらつきの範囲で測定結果を示す。
結果を表２に示す。
(Example 2)
In the case of bonding between a hydroxyapatite substrate and a silicon resin substrate used in biomedical treatment, the bonding surface is not necessarily flat bonding, and bonding on a non-planar surface such as a concave surface or a convex surface is assumed. Therefore, the hydroxyapatite base material and the silicon resin base material were joined to each other with unevenness, and the joint strength in that case was verified. The joining conditions are the same as those in Example 1. As a comparative example, a case of planar bonding by the method of the present invention and a case of uneven bonding using a conventional cyanoacrylate adhesive are shown. Each test was performed on a plurality of specimens, and the measurement results are shown in the range of variation.
The results are shown in Table 2.
表２からわかるように、従来の接合方法では接合強度が小さいのは元より、変動幅が大きく、信頼性に欠ける。本発明方法の場合は、凹凸接合の場合においても目安である１５０Ｎ／ｃｍ２以上を確保し、またばらつきもそれほど大きくはなく、安定していることがわかる。 As can be seen from Table 2, in the conventional joining method, the joining strength is small, the fluctuation range is large, and the reliability is lacking. In the case of the method of the present invention, it is found that 150 N / cm 2 or more which is a guideline is secured even in the case of uneven bonding, and the variation is not so large and stable.
（実施例３）
本発明の方法における接合時の加圧条件と接合強度について実験を行った。前処理は実施例１の場合と同じである。接合条件として、常温からの昇温速度を５℃／ｍｉｎ、保持温度を１８２℃、保持時間を２時間とした。加圧条件として、加圧なし、０．５ｋｇ／ｃｍ２、１．６ｋｇ／ｃｍ２、３．１ｋｇ／ｃｍ２の各場合を採用した。
結果を表３に示す。
(Example 3)
Experiments were performed on the pressurizing conditions and bonding strength during bonding in the method of the present invention. The pretreatment is the same as in the first embodiment. As bonding conditions, the temperature rising rate from room temperature was 5 ° C./min, the holding temperature was 182 ° C., and the holding time was 2 hours. As pressurization conditions, no pressurization, 0.5 kg / cm 2 , 1.6 kg / cm 2 , and 3.1 kg / cm 2 were employed.
The results are shown in Table 3.
表３から明らかなように、加圧をしない場合は強度が低く、接合面のズレ等を招く。
一方、０．５ｋｇ／ｃｍ２以上の加圧においては、目安である１５０Ｎ／ｃｍ２以上の強度を確保している。また加圧を３．１ｋｇ／ｃｍ２以上にしても、それほど接合強度が増加しないような傾向を示している。
As is apparent from Table 3, when pressure is not applied, the strength is low, resulting in misalignment of the joint surface.
On the other hand, in pressurization of 0.5 kg / cm 2 or more, a strength of 150 N / cm 2 or more, which is a standard, is secured. In addition, even when the pressure is set to 3.1 kg / cm 2 or more, the bonding strength does not increase so much.
（実施例４）
本発明の方法における接合時の加温条件と接合強度について実験を行った。前処理は実施例１の場合と同じである。加温条件として、即１８０℃に投入して保持、昇温速度を５℃／ｍｉｎで保持温度を１３０℃、昇温速度を５℃／ｍｉｎで保持温度を１６３℃、昇温速度を５℃／ｍｉｎで保持温度を１８０℃、昇温速度を５℃／ｍｉｎで保持温度を２２５℃、昇温速度を５℃／ｍｉｎで保持温度を２５１℃とした。
結果を表４に示す。
Example 4
Experiments were conducted on the heating conditions and bonding strength during bonding in the method of the present invention. The pretreatment is the same as in the first embodiment. As heating conditions, immediately put it at 180 ° C. and hold it, hold it at a heating rate of 5 ° C./min, hold it at 130 ° C., set the heating rate at 5 ° C./min, hold it at 163 ° C., and set the heating rate at 5 ° The holding temperature was 180 ° C./min, the heating rate was 5 ° C./min, the holding temperature was 225 ° C., the heating rate was 5 ° C./min, and the holding temperature was 251 ° C.
The results are shown in Table 4.
表４から明らかなように、即１８０℃に投入して保持するものでは、昇温速度を抑制した（５℃／ｍｉｎの昇温速度）ものに比べて接合強度が低下する。また５℃／ｍｉｎの昇温速度においては、保持温度が１８０℃付近で接合強度のピークとなる。 As can be seen from Table 4, when the material is immediately put at 180 ° C. and held, the bonding strength is lower than that when the temperature rising rate is suppressed (temperature rising rate of 5 ° C./min). Further, at a rate of temperature increase of 5 ° C./min, the bonding strength peaks when the holding temperature is around 180 ° C.
（実施例５）
本発明の方法における接合時の加温保持時間条件と接合強度について実験を行った。前処理は実施例１の場合と同じである。加温保持時間条件として、０．３４時間、０．７７時間、１．６５時間、２．８０時間、４．０１時間とした。
結果を表５に示す。
(Example 5)
Experiments were conducted on the heating holding time condition and the bonding strength during bonding in the method of the present invention. The pretreatment is the same as in the first embodiment. The heating holding time conditions were 0.34 hours, 0.77 hours, 1.65 hours, 2.80 hours, 4.01 hours.
The results are shown in Table 5.
表５から明らかなように、加圧を略１．６ｋｇ／ｃｍ２、昇温速度５℃／ｍｉｎ、保持温度を１８０℃とした場合に、保持時間を０．３４時間（約２０分）もすれば、１６８Ｎ／ｃｍ２となり、目安である１５０Ｎ／ｃｍ２以上を確保している。 As is apparent from Table 5, when the pressurization is approximately 1.6 kg / cm 2 , the heating rate is 5 ° C./min, and the holding temperature is 180 ° C., the holding time is 0.34 hours (about 20 minutes). if so as to ensure 168n / cm 2, and the a 150 N / cm 2 or more is a measure.
本発明の実用化により、今後の生体骨治療において、人工骨、人工骨機能の付与を可能とし、医学会の課題とされる治療技術に大きな貢献を図ることができる。 By practical application of the present invention, artificial bone and artificial bone functions can be imparted in the treatment of living bones in the future, and a great contribution can be made to the treatment technology that is the subject of the medical society.
Claims (6)
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| WO2015030079A1 (en) * | 2013-08-27 | 2015-03-05 | 国立大学法人大阪大学 | Joined body joined by chemical bonding at material interface, and joining method for joined body |
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| WO2015030079A1 (en) * | 2013-08-27 | 2015-03-05 | 国立大学法人大阪大学 | Joined body joined by chemical bonding at material interface, and joining method for joined body |
| JPWO2015030079A1 (en) * | 2013-08-27 | 2017-03-02 | 国立大学法人大阪大学 | Bonded body bonded by chemical bonding at material interface and bonding method thereof |
| US10174172B2 (en) | 2013-08-27 | 2019-01-08 | Osaka University | Joined body joined by chemical bonding at material interface, and joining method for joined body |
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