JP2005272647A - Structural adhesive composition - Google Patents
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- JP2005272647A JP2005272647A JP2004088253A JP2004088253A JP2005272647A JP 2005272647 A JP2005272647 A JP 2005272647A JP 2004088253 A JP2004088253 A JP 2004088253A JP 2004088253 A JP2004088253 A JP 2004088253A JP 2005272647 A JP2005272647 A JP 2005272647A
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本発明は、自動車、産業用車両等の車体パネル等の構造接着に使用する構造用接着剤組成物に関するものであり、特に、車両用外装パネルともう１枚の車両用パネルを接着するために使用される構造用接着剤組成物に関するものである。 The present invention relates to a structural adhesive composition used for structural bonding of body panels of automobiles, industrial vehicles, and the like, and in particular, for bonding a vehicle exterior panel to another vehicle panel. It relates to the structural adhesive composition used.
構造用接着剤組成物としては、特許文献１、特許文献２、特許文献３に開示されているようなエポキシ樹脂系構造用接着剤が広く知られており、車両用外装パネルの接着にも、一般に、このようなエポキシ樹脂系熱硬化性構造用接着剤が使用されている。 As structural adhesive compositions, epoxy resin-based structural adhesives such as those disclosed in Patent Literature 1, Patent Literature 2, and Patent Literature 3 are widely known, and for adhesion of exterior panels for vehicles, In general, such epoxy resin-based thermosetting structural adhesives are used.
しかし、車両用外装パネルの場合には接着面積が広いため、エポキシ樹脂系構造用接着剤を熱硬化させた後、常温まで冷える間に、接着剤の硬化収縮や車両用外装パネルとエポキシ樹脂との熱膨張率の差等によって内部応力が生じ、車両用外装パネルに歪が生じるという問題点があった。 However, in the case of an exterior panel for a vehicle, the adhesive area is wide, so the epoxy resin structural adhesive is thermally cured and then cooled to room temperature. There is a problem that internal stress is generated due to the difference in thermal expansion coefficient between the two, and the exterior panel for a vehicle is distorted.
このため、車両用外装パネルの剛性を高くするか、エポキシ樹脂系構造用接着剤の使用量を少なくすることによって、歪の発生を防止していた。
しかしながら、車両用外装パネルの剛性を高くするためには、車両用外装パネルの厚さを厚くしなければならず、車両全体の重量が増すとともにコスト高になり、また、エポキシ樹脂系構造用接着剤の使用量を少なくすると接着力が低下してしまうという問題点があった。 However, in order to increase the rigidity of the vehicle exterior panel, it is necessary to increase the thickness of the vehicle exterior panel, which increases the weight of the entire vehicle and increases the cost. When the amount of the agent used is reduced, there is a problem that the adhesive strength is lowered.
そこで、本発明は、通常の厚さの車両用外装パネル等の所定の面積を有するパネルを用いて十分な量の接着剤を使用しても、接着したパネルに歪が生じることがない構造用接着剤組成物の提供を課題とするものである。 Therefore, the present invention is for a structure in which a bonded panel is not distorted even when a sufficient amount of adhesive is used using a panel having a predetermined area such as a vehicle exterior panel having a normal thickness. It is an object to provide an adhesive composition.
請求項１の発明にかかる構造用接着剤組成物は、所定の面積を有するパネル相互間の接合を行う構造用接着剤組成物において、加熱硬化前には常温で流動状態であり、加熱硬化後のガラス転移温度を約６０℃〜約１２０℃の範囲内に設定し、かつ、前記パネルの温度の降下速度を前記構造用接着剤組成物の温度の降下速度よりも遅くしたものである。 The structural adhesive composition according to the invention of claim 1 is a structural adhesive composition for joining panels having a predetermined area, and is in a fluid state at room temperature before heat-curing, and after heat-curing The glass transition temperature is set in the range of about 60 ° C. to about 120 ° C., and the rate of temperature decrease of the panel is made slower than the rate of temperature decrease of the structural adhesive composition.
請求項２の発明にかかる構造用接着剤組成物は、請求項１の構成において、前記構造用接着剤組成物の加熱硬化条件は約１５０℃〜約２１５℃の温度範囲内において約２０分〜約６０分の硬化時間であり、１８０℃から５０℃までの冷却時間が約５分〜約１０分であるものである。 The structural adhesive composition according to the invention of claim 2 is the structure of claim 1, wherein the heat curing condition of the structural adhesive composition is about 20 minutes within a temperature range of about 150 ° C. to about 215 ° C. The curing time is about 60 minutes, and the cooling time from 180 ° C. to 50 ° C. is about 5 minutes to about 10 minutes.
請求項３の発明にかかる構造用接着剤組成物は、請求項１または請求項２の構成において、前記構造用接着剤組成物の硬化物の線膨張係数は約５〜７×１０-5／℃であり、前記パネルの線膨張係数は約１〜３×１０-5／℃であるものである。 The structural adhesive composition according to the invention of claim 3 is the structure of claim 1 or claim 2, wherein the linear expansion coefficient of the cured product of the structural adhesive composition is about 5 to 7 × 10 −5 / The linear expansion coefficient of the panel is about 1 to 3 × 10 −5 / ° C.
請求項４の発明にかかる構造用接着剤組成物は、請求項１乃至請求項３のいずれか１つの構成において、前記構造用接着剤組成物の硬化物の弾性率は約５００〜４０００ＭＰａであり、前記パネルの弾性率は約６００００〜３０００００ＭＰａであるものである。 The structural adhesive composition according to a fourth aspect of the present invention is the structural adhesive composition according to any one of the first to third aspects, wherein the elastic modulus of the cured product of the structural adhesive composition is about 500 to 4000 MPa. The elastic modulus of the panel is about 60000-300000 MPa.
請求項５の発明にかかる構造用接着剤組成物は、請求項１乃至請求項４のいずれか１つの構成において、液状エポキシ樹脂または液状エポキシ樹脂と変性エポキシ樹脂の混合物と、エポキシ系希釈剤と、硬化剤と、硬化促進剤とを含有し、前記液状エポキシ樹脂は線状脂肪族エポキサイド型エポキシ樹脂または脂肪族エポキサイド型エポキシ樹脂であり、前記変性エポキシ樹脂はゴム変性エポキシ樹脂・ウレタン変性エポキシ樹脂・ダイマー酸変性エポキシ樹脂のいずれかであるものである。 The structural adhesive composition according to the invention of claim 5 is the structure according to any one of claims 1 to 4, wherein a liquid epoxy resin or a mixture of a liquid epoxy resin and a modified epoxy resin, an epoxy diluent, The liquid epoxy resin is a linear aliphatic epoxide type epoxy resin or an aliphatic epoxide type epoxy resin, and the modified epoxy resin is a rubber-modified epoxy resin or a urethane-modified epoxy resin. -It is one of dimer acid-modified epoxy resins.
請求項１の発明にかかる構造用接着剤組成物は、所定の面積を有するパネル相互間の接合を行うもので、加熱硬化前には常温で流動状態であり、加熱硬化後のガラス転移温度（Ｔｇ）を約６０℃〜約１２０℃の範囲内に設定し、かつ、パネルの温度の降下速度を構造用接着剤組成物の温度の降下速度よりも遅くしたものである。これによって、硬化した構造用接着剤組成物が冷えてくるときに、なるべく低温までガラス転移温度以上に保つことによって、硬化した構造用接着剤組成物が極力軟らかい状態に維持され、車両用外装パネル等の所定の面積を有するパネルと構造用接着剤組成物との熱膨張率の差によって生じる内部応力を分散させて、パネルに歪が生じないようにすることができる。 The structural adhesive composition according to the invention of claim 1 performs bonding between panels having a predetermined area, is in a fluid state at room temperature before heat-curing, and has a glass transition temperature ( Tg) is set in the range of about 60 ° C. to about 120 ° C., and the rate of temperature decrease of the panel is made slower than the rate of temperature decrease of the structural adhesive composition. As a result, when the cured structural adhesive composition cools, the cured structural adhesive composition is maintained in a soft state as much as possible by keeping the cured structural adhesive composition above the glass transition temperature as low as possible. It is possible to disperse the internal stress generated by the difference in thermal expansion coefficient between the panel having a predetermined area such as the above and the structural adhesive composition so that the panel is not distorted.
この作用効果が得られる加熱硬化物のガラス転移温度は最高で約１２０℃であり、これ以上ガラス転移温度が高くなると、冷却時にパネルに歪が生じてしまう。また、ガラス転移温度が約６０℃以下になると、パネルが５０℃以上になったときの接着強度（剪断強度）が低下するので好ましくない。 The glass transition temperature of the heat-cured product that can provide this effect is about 120 ° C. at the maximum. If the glass transition temperature is higher than this, the panel is distorted during cooling. On the other hand, when the glass transition temperature is about 60 ° C. or lower, the adhesive strength (shear strength) when the panel is 50 ° C. or higher is lowered.
さらに、パネルの温度の降下速度を構造用接着剤組成物の温度の降下速度よりも遅くしたことによって、パネルに加わる冷却歪を極力小さくすることができ、よりパネルに歪が生じ難くすることができる。 Furthermore, by making the temperature drop rate of the panel slower than the temperature drop rate of the structural adhesive composition, the cooling strain applied to the panel can be made as small as possible, and the panel can be made more difficult to be distorted. it can.
このようにして、通常の厚さの車両用外装パネル等の所定の面積を有するパネルを用いて十分な量の接着剤を使用しても接着したパネルに歪が生じることがない構造用接着剤組成物となる。 In this way, a structural adhesive that does not cause distortion in a bonded panel even when a sufficient amount of adhesive is used using a panel having a predetermined area such as a vehicle exterior panel having a normal thickness. It becomes a composition.
請求項２の発明にかかる構造用接着剤組成物は、加熱硬化条件が約１５０℃〜約２１５℃の温度範囲内において約２０分〜約６０分の硬化時間であり、１８０℃から５０℃までの冷却時間が約５分〜約１０分であるものである。このため、加熱硬化に長時間かかることなく工程を短縮することができ、かつ１８０℃から５０℃までの冷却時間が約５分〜約１０分であることによって、パネルの温度の降下速度を構造用接着剤組成物の温度の降下速度よりも遅くすることができ、ガラス転移温度が約６０℃〜約１２０℃の範囲内であることと相俟って、パネルに加わる冷却歪を極力小さくすることができ、よりパネルに歪が生じ難くすることができる。 The structural adhesive composition according to the invention of claim 2 has a curing time of about 20 minutes to about 60 minutes in a temperature range of about 150 ° C. to about 215 ° C., and from 180 ° C. to 50 ° C. The cooling time is about 5 minutes to about 10 minutes. For this reason, the process can be shortened without taking a long time for heat curing, and the cooling time from 180 ° C. to 50 ° C. is about 5 minutes to about 10 minutes. The cooling strain applied to the panel can be made as small as possible in combination with the glass transition temperature being in the range of about 60 ° C. to about 120 ° C. It is possible to make the panel more difficult to be distorted.
このようにして、通常の厚さの車両用外装パネル等の所定の面積を有するパネルを用いて十分な量の接着剤を使用しても接着したパネルに歪が生じることがない構造用接着剤組成物となる。 In this way, a structural adhesive that does not cause distortion in a bonded panel even when a sufficient amount of adhesive is used using a panel having a predetermined area such as a vehicle exterior panel having a normal thickness. It becomes a composition.
請求項３の発明にかかる構造用接着剤組成物は、硬化物の線膨張係数が約５〜７×１０-5／℃であり、パネルの線膨張係数が約１〜３×１０-5／℃であるものである。このように、構造用接着剤硬化物の線膨張係数がパネルの線膨張係数より余り大きくないことによって、ガラス転移温度が約６０℃〜約１２０℃の範囲内であることと相俟って、冷却時に構造用接着剤硬化物からパネルに掛かる冷却歪を極力小さくすることができ、よりパネルに歪が生じ難くすることができる。 In the structural adhesive composition according to the invention of claim 3, the cured product has a linear expansion coefficient of about 5 to 7 × 10 −5 / ° C., and the panel has a linear expansion coefficient of about 1 to 3 × 10 −5 / ° C. It is what is ° C. Thus, in combination with the glass transition temperature being in the range of about 60 ° C. to about 120 ° C. due to the fact that the linear expansion coefficient of the cured structural adhesive is not much larger than the linear expansion coefficient of the panel, The cooling strain applied to the panel from the structural adhesive cured product during cooling can be reduced as much as possible, and the panel can be made more difficult to be distorted.
このようにして、通常の厚さの車両用外装パネル等の所定の面積を有するパネルを用いて十分な量の接着剤を使用しても接着したパネルに歪が生じることがない構造用接着剤組成物となる。 In this way, a structural adhesive that does not cause distortion in a bonded panel even when a sufficient amount of adhesive is used using a panel having a predetermined area such as a vehicle exterior panel having a normal thickness. It becomes a composition.
請求項４の発明にかかる構造用接着剤組成物は、硬化物の弾性率が約５００〜４０００ＭＰａであり、パネルの弾性率は約６００００〜３０００００ＭＰａであるものである。このように、構造用接着剤硬化物の弾性率がパネルの弾性率より二桁から三桁小さいことによって、ガラス転移温度が約６０℃〜約１２０℃の範囲内であることと相俟って、冷却時に構造用接着剤硬化物からパネルに掛かる冷却歪を極力小さくすることができ、よりパネルに歪が生じ難くすることができる。 In the structural adhesive composition according to the invention of claim 4, the elastic modulus of the cured product is about 500 to 4000 MPa, and the elastic modulus of the panel is about 60000 to 300000 MPa. Thus, combined with the fact that the glass transition temperature is in the range of about 60 ° C. to about 120 ° C. because the elastic modulus of the cured structural adhesive is two to three orders of magnitude smaller than the elastic modulus of the panel. The cooling strain applied to the panel from the cured structural adhesive during cooling can be reduced as much as possible, and the panel can be made less likely to be distorted.
このようにして、通常の厚さの車両用外装パネル等の所定の面積を有するパネルを用いて十分な量の接着剤を使用しても接着したパネルに歪が生じることがない構造用接着剤組成物となる。 In this way, a structural adhesive that does not cause distortion in a bonded panel even when a sufficient amount of adhesive is used using a panel having a predetermined area such as a vehicle exterior panel having a normal thickness. It becomes a composition.
請求項５の発明にかかる構造用接着剤組成物は、液状エポキシ樹脂または液状エポキシ樹脂と変性エポキシ樹脂の混合物と、エポキシ系希釈剤と、硬化剤と、硬化促進剤とを含有し、液状エポキシ樹脂は線状脂肪族エポキサイド型エポキシ樹脂または脂肪族エポキサイド型エポキシ樹脂であり、変性エポキシ樹脂はゴム変性エポキシ樹脂・ウレタン変性エポキシ樹脂・ダイマー酸変性エポキシ樹脂のいずれかである。 The structural adhesive composition according to the invention of claim 5 comprises a liquid epoxy resin or a mixture of a liquid epoxy resin and a modified epoxy resin, an epoxy-based diluent, a curing agent, and a curing accelerator. The resin is a linear aliphatic epoxide type epoxy resin or an aliphatic epoxide type epoxy resin, and the modified epoxy resin is any one of a rubber-modified epoxy resin, a urethane-modified epoxy resin, and a dimer acid-modified epoxy resin.
液状エポキシ樹脂として線状脂肪族エポキサイド型エポキシ樹脂または脂肪族エポキサイド型エポキシ樹脂を用い、変性エポキシ樹脂としてゴム変性、ウレタン変性、ダイマー酸変性エポキシ樹脂のいずれかを主体とすることによって、加熱硬化物のガラス転移温度を低くすることができる。また、エポキシ系希釈剤として一官能基型のｎ−ブタノールグリシジルエーテル、（以下、グリシジルエーテルを「ＧＥ」とも略する。）高級アルコールＧＥ、ブチルフェニルＧＥ、メタアクリル酸グリシジルエステル等、多官能基型の１，４−ブタンジオール・ジＧＥ、１，６−ヘキサンジオール・ジＧＥ、トリメチロールプロパン・トリＧＥ、ポリエチレングリコール・ジＧＥ、ダイマー酸・ジグリシジルエステル等を加えることによっても加熱硬化物のガラス転移温度を低くすることができるとともに、加熱硬化前の流動性を適度に増して塗布し易くする。 A linear aliphatic epoxide-type epoxy resin or an aliphatic epoxide-type epoxy resin is used as the liquid epoxy resin, and the heat-cured product is mainly composed of either a rubber-modified, urethane-modified, or dimer-acid-modified epoxy resin as the modified epoxy resin. The glass transition temperature of can be lowered. In addition, a monofunctional n-butanol glycidyl ether (hereinafter, abbreviated as “GE”), a higher alcohol GE, butylphenyl GE, methacrylic acid glycidyl ester, etc. Heat-cured product by adding 1,4-butanediol / diGE, 1,6-hexanediol / diGE, trimethylolpropane / triGE, polyethylene glycol / diGE, dimer acid / diglycidyl ester, etc. The glass transition temperature of the resin can be lowered, and the fluidity before heat curing is moderately increased to facilitate application.
さらに、硬化剤、硬化促進剤はエポキシ樹脂の加熱硬化に必須である。なお、低コスト化のために充填剤（炭酸カルシウム、タルク、鉱物繊維、金属粉末等）、取扱い性向上のためにチキソ剤（カーボンブラック、シリカ、微粒炭酸カルシウム、セピオライト等）を加えても良い。 Furthermore, the curing agent and the curing accelerator are essential for the heat curing of the epoxy resin. In addition, fillers (calcium carbonate, talc, mineral fiber, metal powder, etc.) may be added for cost reduction, and thixotropic agents (carbon black, silica, fine calcium carbonate, sepiolite, etc.) may be added to improve handling. .
このような成分を含有する構造用接着剤組成物の加熱硬化物のガラス転移温度を約６０℃〜約１２０℃の範囲内とすることによって、車両用外装パネル等の所定面積を有するパネルの接着に用いてもパネルに歪が生じることがない。 Adhesion of panels having a predetermined area, such as exterior panels for vehicles, by setting the glass transition temperature of the heat-cured product of the structural adhesive composition containing such components within a range of about 60 ° C. to about 120 ° C. Even if it is used, the panel will not be distorted.
このようにして、通常の厚さの車両用外装パネル等の所定の面積を有するパネルを用いて十分な量の接着剤を使用しても接着したパネルに歪が生じることがない構造用接着剤組成物となる。 In this way, a structural adhesive that does not cause distortion in a bonded panel even when a sufficient amount of adhesive is used using a panel having a predetermined area such as a vehicle exterior panel having a normal thickness. It becomes a composition.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
まず、本実施の形態にかかる構造用接着剤組成物の組成について説明する。 First, the composition of the structural adhesive composition according to this embodiment will be described.
実施例１として、液状エポキシ樹脂としてのビスフェノールＡ型エポキシ樹脂１００重量部に対して、エポキシ系希釈剤としてグリシジルエーテル５０重量部、硬化剤としてジシアンジアミド１０重量部、硬化促進剤として３−（３，４−ジクロロフェニル）−１，１−ジメチル尿素５重量部、充填剤として炭酸カルシウム５０重量部、チキソ剤としてカーボンブラック２重量部を配合した組成物を用いた。 As Example 1, with respect to 100 parts by weight of a bisphenol A type epoxy resin as a liquid epoxy resin, 50 parts by weight of glycidyl ether as an epoxy diluent, 10 parts by weight of dicyandiamide as a curing agent, and 3- (3,3 as a curing accelerator A composition containing 5 parts by weight of 4-dichlorophenyl) -1,1-dimethylurea, 50 parts by weight of calcium carbonate as a filler, and 2 parts by weight of carbon black as a thixotropic agent was used.
また、実施例２として、液状エポキシ樹脂としてのビスフェノールＡ型エポキシ樹脂５０重量部、変性エポキシ樹脂としてのゴム変性エポキシ樹脂５０重量部、エポキシ系希釈剤としてグリシジルエーテル１０重量部、そして硬化剤、硬化促進剤、充填剤、チキソ剤としては実施例１と同じものを同量配合した組成物を用いた。 Further, as Example 2, 50 parts by weight of a bisphenol A type epoxy resin as a liquid epoxy resin, 50 parts by weight of a rubber-modified epoxy resin as a modified epoxy resin, 10 parts by weight of glycidyl ether as an epoxy diluent, and a curing agent and curing As an accelerator, a filler, and a thixotropic agent, a composition containing the same amount as in Example 1 was used.
具体的な材料としては、ビスフェノールＡ型エポキシ樹脂としては旭電化工業（株）の商品名「アデカレジンＥＰ−４１００」を、ゴム変性エポキシ樹脂としては旭電化工業（株）の商品名「アデカレジンＥＰＲ−４０２６」を、グリシジルエーテルとしては旭電化工業（株）の商品名「アデカグリシロールＥＤ−５０６」をそれぞれ使用した。 As specific materials, the product name “Adeka Resin EP-4100” of Asahi Denka Kogyo Co., Ltd. is used as the bisphenol A type epoxy resin, and the product name “Adeka Resin EPR-” of Asahi Denka Kogyo Co., Ltd. is used as the rubber-modified epoxy resin. As the glycidyl ether, “Adeka Glycilol ED-506” (trade name of Asahi Denka Kogyo Co., Ltd.) was used.
さらに、比較のために、比較例１として実施例１におけるエポキシ系希釈剤としてのグリシジルエーテルを１０重量部に減らしたものを、また比較例２として実施例１におけるエポキシ系希釈剤としてのグリシジルエーテルを１００重量部に増やしたものを、それぞれ用いた。 Further, for comparison, a glycidyl ether as an epoxy diluent in Example 1 as a comparative example 1 was reduced to 10 parts by weight as an epoxy diluent in Example 1, and a glycidyl ether as an epoxy diluent in Example 1 as a comparative example 2. Each was increased to 100 parts by weight.
構造用接着剤組成物の実施例１，２及び比較例１，２の組成を、表１にまとめて示す。 Table 1 summarizes the compositions of Examples 1 and 2 and Comparative Examples 1 and 2 of the structural adhesive composition.
これらの組成物のガラス転移温度、剪断強度、及び鋼板の接着剤として用いた場合の歪の有無について、測定・評価を行った。 These compositions were measured and evaluated for the glass transition temperature, shear strength, and the presence or absence of distortion when used as an adhesive for steel sheets.
ガラス転移温度の測定は、各構造用接着剤組成物を１８０℃×３０分の条件で熱風オーブン中で硬化させ、１０ｍｍ×３０ｍｍ×２ｍｍの試験片を作製して、（株）オリエンテック製ガラス転移温度測定装置（レオバイブロン）を使用して測定した。 The glass transition temperature was measured by curing each structural adhesive composition in a hot air oven under conditions of 180 ° C. × 30 minutes, producing a 10 mm × 30 mm × 2 mm test piece, and glass manufactured by Orientec Co., Ltd. It measured using the transition temperature measuring apparatus (leovibron).
剪断強度の測定は、ＪＩＳ Ｋ６８５０に準じて行った。各構造用接着剤組成物を１８０℃×３０分の条件で熱風オーブン中で硬化させ、２５ｍｍ×１００ｍｍ×１．６ｍｍの板を作製して、測定雰囲気温度を２０℃と５０℃の二点として測定した。 The shear strength was measured according to JIS K6850. Each structural adhesive composition is cured in a hot air oven under conditions of 180 ° C. × 30 minutes, a plate of 25 mm × 100 mm × 1.6 mm is prepared, and the measurement atmospheric temperature is set to two points of 20 ° C. and 50 ° C. It was measured.
鋼板の歪性については、２００ｍｍ×３００ｍｍ×０．８ｍｍの鋼板を使用し、鋼板の中央部分に各構造用接着剤組成物を１０ｍｍφ半円ビード×１００ｍｍの形状に塗布し、次にもう１枚の２００ｍｍ×３００ｍｍ×０．８ｍｍの鋼板で接着剤の厚さが１ｍｍとなるように潰して、１８０℃×３０分の条件で熱風オーブン中で硬化させた。冷却後、歪の目視評価をするために、鋼板に黒色塗料を塗布した。 Regarding the distortion of the steel plate, a steel plate of 200 mm × 300 mm × 0.8 mm is used, and each structural adhesive composition is applied to the central part of the steel plate in a shape of 10 mmφ semicircle bead × 100 mm, and then another sheet. A 200 mm × 300 mm × 0.8 mm steel plate was crushed to a thickness of 1 mm and cured in a hot air oven at 180 ° C. for 30 minutes. After cooling, a black paint was applied to the steel plate for visual evaluation of strain.
以上の各項目についての構造用接着剤組成物の実施例１，２及び比較例１，２についての測定・評価結果を、表２にまとめて示す。 Table 2 summarizes the measurement / evaluation results for Examples 1 and 2 and Comparative Examples 1 and 2 of the structural adhesive compositions for the above items.
表２に示されるように、実施例１の構造用接着剤組成物はガラス転移温度が１０１℃であり、剪断強度も２０℃，５０℃とも充分であり、鋼板の歪も発生しなかった。また、実施例２の構造用接着剤組成物についてはガラス転移温度が８３℃であり、剪断強度も２０℃，５０℃とも充分であり、鋼板の歪も発生しなかった。 As shown in Table 2, the structural adhesive composition of Example 1 had a glass transition temperature of 101 ° C., sufficient shear strengths of 20 ° C. and 50 ° C., and no distortion of the steel sheet. Further, the structural adhesive composition of Example 2 had a glass transition temperature of 83 ° C., sufficient shear strengths of 20 ° C. and 50 ° C., and no distortion of the steel sheet.
これに対して、比較例１の構造用接着剤組成物はガラス転移温度が１４５℃と高く、剪断強度は２０℃，５０℃とも充分であるが、鋼板に歪が発生した。また、比較例２の構造用接着剤組成物はガラス転移温度が５２℃と低く、鋼板の歪は発生しなかったが、５０℃における剪断強度が低く、構造用パネル用としては接着強度が不十分である。 In contrast, the structural adhesive composition of Comparative Example 1 had a high glass transition temperature of 145 ° C. and sufficient shear strength of 20 ° C. and 50 ° C., but distortion occurred in the steel sheet. In addition, the structural adhesive composition of Comparative Example 2 had a low glass transition temperature of 52 ° C. and no distortion of the steel sheet, but the shear strength at 50 ° C. was low, and the adhesive strength was not good for structural panels. It is enough.
このように、本実施の形態の実施例１及び実施例２にかかる構造用接着剤組成物においては、加熱硬化物のガラス転移温度が約６０℃〜約１２０℃の範囲内である。これによって、硬化した構造用接着剤組成物が冷えてくるときに、なるべく低温までガラス転移温度以上に保つことによって、硬化した構造用接着剤組成物が極力軟らかい状態に維持されているから、車両用外装パネルと構造用接着剤組成物との熱膨張率の差によって生じる内部応力が分散されて、車両用外装パネルに歪が生じないようにすることができる。 Thus, in the structural adhesive composition according to Example 1 and Example 2 of the present embodiment, the glass transition temperature of the heat-cured product is in the range of about 60 ° C to about 120 ° C. As a result, when the cured structural adhesive composition cools, the cured structural adhesive composition is maintained in a soft state as much as possible by keeping the cured structural adhesive composition at a temperature as low as possible. The internal stress generated by the difference in coefficient of thermal expansion between the exterior panel for a vehicle and the structural adhesive composition can be dispersed to prevent the vehicle exterior panel from being distorted.
本実施の形態においては、液状エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂を用いているが、他のエポキシ樹脂を用いても良い。また、本実施の形態においては、変性エポキシ樹脂としてゴム変性エポキシ樹脂を用いているが、これに限られるものでなく、ウレタン変性エポキシ樹脂、ダイマー酸変性エポキシ樹脂等を用いることもできる。 In this embodiment, bisphenol A type epoxy resin is used as the liquid epoxy resin, but other epoxy resins may be used. In this embodiment, a rubber-modified epoxy resin is used as the modified epoxy resin. However, the present invention is not limited to this, and a urethane-modified epoxy resin, a dimer acid-modified epoxy resin, or the like can also be used.
さらに、本実施の形態においては、エポキシ系希釈剤としてグリシジルエーテルを用いているが、他のエポキシ系希釈剤を用いても良い。 Furthermore, in this embodiment, glycidyl ether is used as the epoxy diluent, but other epoxy diluents may be used.
また、本実施の形態においては、充填剤（炭酸カルシウム）、チキソ剤（カーボンブラック）を用いているが、必ずしも用いなくても良く、さらにエポキシ樹脂以外の熱硬化性樹脂、熱可塑性樹脂、可塑剤等を適宜加えても良い。 In this embodiment, a filler (calcium carbonate) and a thixotropic agent (carbon black) are used. However, it is not always necessary to use them, and thermosetting resins other than epoxy resins, thermoplastic resins, plastics An agent or the like may be added as appropriate.
構造用接着剤組成物のその他の部分の組成、成分、配合量、材質、大きさ等についても、本実施の形態に限定されるものではない。 The composition, components, blending amount, material, size, etc. of other parts of the structural adhesive composition are not limited to the present embodiment.
そして、発明者らの実験によれば、本実施の形態の構造用接着剤を熱硬化させ、常温まで冷える間に、接着剤の硬化収縮や車両用外装パネルとエポキシ樹脂との熱膨張率の差等によって内部応力が生じ難いから、車両用外装パネルに歪が生じ難くなり、鋼鈑からなる車両用外装パネル等の材料が限定されることなく、所定の面積を有するパネル相互間の接合にも使用されることが判明した。
According to the experiments by the inventors, while the structural adhesive of the present embodiment is thermally cured and cooled to room temperature, the curing shrinkage of the adhesive and the coefficient of thermal expansion between the vehicle exterior panel and the epoxy resin are reduced. Because internal stress is unlikely to occur due to differences, etc., it is difficult for the exterior panel for a vehicle to be distorted, and the materials such as the exterior panel for a vehicle made of steel are not limited. Also turned out to be used.
Claims (5)
加熱硬化前には常温で流動状態であり、加熱硬化後のガラス転移温度を約６０℃〜約１２０℃の範囲内に設定し、かつ、前記パネルの温度の降下速度を前記構造用接着剤組成物の温度の降下速度よりも遅くしたことを特徴とする構造用接着剤組成物。 In the structural adhesive composition for bonding between panels having a predetermined area,
Before heating and curing, it is in a fluid state at room temperature, the glass transition temperature after heating and curing is set within a range of about 60 ° C. to about 120 ° C., and the rate of temperature decrease of the panel is set as the structural adhesive composition A structural adhesive composition characterized by being made slower than the rate of temperature drop of the object.
前記液状エポキシ樹脂は線状脂肪族エポキサイド型エポキシ樹脂または脂肪族エポキサイド型エポキシ樹脂であり、前記変性エポキシ樹脂はゴム変性エポキシ樹脂・ウレタン変性エポキシ樹脂・ダイマー酸変性エポキシ樹脂のいずれかであることを特徴とする請求項１乃至請求項４のいずれか１つに記載の構造用接着剤組成物。
Contains a liquid epoxy resin or a mixture of a liquid epoxy resin and a modified epoxy resin, an epoxy diluent, a curing agent, and a curing accelerator,
The liquid epoxy resin is a linear aliphatic epoxide type epoxy resin or an aliphatic epoxide type epoxy resin, and the modified epoxy resin is any one of a rubber-modified epoxy resin, a urethane-modified epoxy resin, and a dimer acid-modified epoxy resin. The structural adhesive composition according to any one of claims 1 to 4, characterized in that:
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| CN100451085C (en) * | 2006-03-21 | 2009-01-14 | 上海市合成树脂研究所 | Epoxy binder in monocomponent in use for insulation of electrical motor |
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| US10669419B2 (en) | 2013-06-07 | 2020-06-02 | Kaneka Corporation | Curable resin composition, structural adhesive, coating material or fiber reinforced composite material using the same, foam body using the same, laminate using the same, and cured material thereof |
| US10920073B2 (en) | 2015-12-11 | 2021-02-16 | Kaneka Corporation | Polyurethane curable composition containing polymer fine particles excellent in mechanical strength |
| CN110922926A (en) * | 2019-12-09 | 2020-03-27 | 南京金世家新材料科技有限公司 | Low-temperature cured single-component transparent epoxy glue and preparation method and application thereof |
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