JP6404558B2 - Manufacturing method of cured resin - Google Patents
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- JP6404558B2 JP6404558B2 JP2013217195A JP2013217195A JP6404558B2 JP 6404558 B2 JP6404558 B2 JP 6404558B2 JP 2013217195 A JP2013217195 A JP 2013217195A JP 2013217195 A JP2013217195 A JP 2013217195A JP 6404558 B2 JP6404558 B2 JP 6404558B2
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Description
本発明は、樹脂硬化物の製造方法及び硬化性樹脂組成物に関する。 The present invention relates to a method for producing a cured resin and a curable resin composition.
アクリル樹脂等の硬化性樹脂を重合させて硬化させる方法として、紫外線硬化法、赤外線硬化法、レーザ硬化法、電子線硬化法等が使用されている。 As a method for polymerizing and curing a curable resin such as an acrylic resin, an ultraviolet curing method, an infrared curing method, a laser curing method, an electron beam curing method, or the like is used.
例えば、下記特許文献１には、（Ａ）（メタ）アクリル系モノマー、（Ｂ）光重合開始剤、（Ｃ）ポリエステル樹脂を含有することを特徴とする紫外線硬化性透明樹脂組成物をフレキシブル基板表面に塗布し、紫外線を照射することで硬化塗膜を形成することが開示されている。
For example,
また、下記特許文献２には、ａ）ジアリルフタレートプレポリマー ２０〜８０重量部 ｂ）ラジカル重合性単量体 ８０〜２０重量部から実質的になる混合物に電離性放射線を照射し、さらに３〜５０μｍの波長の遠赤外線を照射することを特徴とする硬化フィルムの製造方法が開示されている。 Further, in Patent Document 2 below, a) diallyl phthalate prepolymer 20 to 80 parts by weight b) radical polymerizable monomer 80 to 20 parts by weight is irradiated with ionizing radiation, and further 3 to 3 A method for producing a cured film is disclosed which irradiates a far infrared ray having a wavelength of 50 μm.
また、下記特許文献３には、（Ａ）バインダーポリマー、（Ｂ）エチレン性不飽和結合を有する光重合性化合物及び（Ｃ）光重合開始剤を含有する感光性樹脂組成物を回路形成用基板上に積層し、その所定部分をレーザ光により直接描画露光して露光部を光硬化させることが開示されている。ここで、バインダーポリマーとしては、例えば、アクリル系樹脂、スチレン系樹脂、エポキシ系樹脂、アミド系樹脂、アミドエポキシ系樹脂、アルキド系樹脂及びフェノール系樹脂が挙げられている。 Patent Document 3 listed below discloses a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. It is disclosed to laminate on top and directly draw and expose a predetermined portion with a laser beam to photocur the exposed portion. Here, examples of the binder polymer include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins.
また、下記特許文献４には、ポリメチルペンテンと架橋処理剤とを含み、該架橋処理剤が、飽和もしくは不飽和の環構造を有し、少なくとも１つの環を形成する原子のうち少なくとも１つの原子が、アリル基、メタリル基、連結基を介したアリル基、及び連結基を介したメタリル基のいずれかのアリル系置換基と結合してなり、分子量が１０００以下である電子線硬化性樹脂組成物よりなる成形体に電子線を照射することにより、優れた耐熱性を有する硬化物が得られることが開示されている。 Patent Document 4 below includes polymethylpentene and a crosslinking agent, and the crosslinking agent has a saturated or unsaturated ring structure, and at least one of atoms forming at least one ring. An electron beam curable resin having an atom bonded to an allyl group, an allyl group, a methallyl group, an allyl group via a linking group, and a methallyl group via the linking group and having a molecular weight of 1000 or less. It is disclosed that a cured product having excellent heat resistance can be obtained by irradiating an electron beam to a molded body made of the composition.
しかし、紫外線硬化法では、紫外線硬化性樹脂組成物に含まれる光重合開始剤が、保存中に光や熱により分解されてラジカルが発生し、樹脂が硬化するという問題があった。また、紫外線が照射された部分のみが硬化されるものなので、樹脂層の内部まで硬化させることが困難であるという問題もあった。 However, the ultraviolet curing method has a problem that the photopolymerization initiator contained in the ultraviolet curable resin composition is decomposed by light or heat during storage to generate radicals, and the resin is cured. Moreover, since only the part irradiated with ultraviolet rays is cured, there is also a problem that it is difficult to cure the resin layer.
また、赤外線硬化法では、紫外線硬化法と同様にラジカル発生剤による保存中の樹脂の硬化の他、赤外線により樹脂組成物を塗布した基板も加熱され、基板材料によっては基板の熱劣化が生じるという問題があった。 In addition, in the infrared curing method, in addition to the curing of the resin being stored by the radical generator as in the ultraviolet curing method, the substrate coated with the resin composition by the infrared rays is also heated, and depending on the substrate material, the substrate may be thermally deteriorated. There was a problem.
また、レーザ硬化法では、紫外線硬化法と同様に光重合開始剤による保存中の樹脂の硬化の他、レーザが照射された部分のみが硬化されるものなので、樹脂層の内部まで硬化させることが困難であるという問題があった。 In addition, in the laser curing method, in addition to the curing of the resin during storage by the photopolymerization initiator as in the ultraviolet curing method, only the portion irradiated with the laser is cured, so that it can be cured to the inside of the resin layer. There was a problem that it was difficult.
また、電子線硬化法では、人工的に電子を加速し、ビームとして利用し、電子ビームの持つエネルギーを利用して、架橋反応、グラフト重合反応をおこなわせている。加速電圧によって、照射される製品中に浸透する深さが変化するので、例えば厚膜を硬化しようとした場合には、大きな加速電圧が必要となり、コスト的にもエックス線の漏洩対策等の安全面でも非常に問題が多くなってくる。 In the electron beam curing method, electrons are artificially accelerated and used as a beam, and the crosslinking reaction and graft polymerization reaction are performed using the energy of the electron beam. The depth of penetration into the irradiated product changes depending on the acceleration voltage. For example, when trying to cure a thick film, a large acceleration voltage is required. But it becomes very problematic.
本発明の目的は、保存中の樹脂の硬化を抑制でき、容易に樹脂層内部まで硬化することができる樹脂硬化物の製造方法及び樹脂組成物を提供することにある。 The objective of this invention is providing the manufacturing method and resin composition of a resin cured material which can suppress hardening of resin in storage and can harden | cure easily to the inside of a resin layer.
上記目的を達成するために、本発明の一実施形態は、樹脂硬化物の製造方法であって、金属、金属酸化物、カーボンのいずれかの粒子を３０質量％以上９０質量％以下含有し、かつ、光重合開始剤を含有しない樹脂組成物にパルス光を照射することを特徴とする。 In order to achieve the above object, one embodiment of the present invention is a method for producing a cured resin, comprising 30% by mass or more and 90% by mass or less of any particle of a metal, a metal oxide, or carbon, And it is characterized by irradiating the resin composition which does not contain a photoinitiator with pulsed light.
上記粒子の樹脂組成物中の含有量が５０質量％以上８５質量％以下であるのが好適である。 The content of the particles in the resin composition is preferably 50% by mass or more and 85% by mass or less.
また、上記金属または金属酸化物を構成する金属は銀、銅、ニッケル、コバルト、クロム、鉄のいずれかであるのが好適である。また、上記樹脂組成物はエポキシアクリレート樹脂を含有するのが好適である。上記パルス光の１パルスの照射期間は１０００マイクロ秒から１０ミリ秒であるのが好適である。 The metal constituting the metal or metal oxide is preferably silver, copper, nickel, cobalt, chromium, or iron. The resin composition preferably contains an epoxy acrylate resin. The irradiation period of one pulse of the pulsed light is preferably 1000 microseconds to 10 milliseconds.
また、本発明の他の実施形態は、硬化性樹脂組成物であって、金属、金属酸化物またはカーボンの粒子を３０質量％以上９０質量％以下含有し、かつ、光重合開始剤を含有しないことを特徴とする。 In addition, another embodiment of the present invention is a curable resin composition, which contains 30% by mass or more and 90% by mass or less of metal, metal oxide, or carbon particles, and does not contain a photopolymerization initiator. It is characterized by that.
上記金属または金属酸化物を構成する金属は銀、銅、ニッケル、コバルト、クロム、鉄のいずれかであるのが好適である。また、上記硬化性樹脂組成物はエポキシアクリレート樹脂を含有するのが好適である。 The metal constituting the metal or metal oxide is preferably silver, copper, nickel, cobalt, chromium, or iron. The curable resin composition preferably contains an epoxy acrylate resin.
本発明によれば、樹脂組成物中に光重合開始剤を含まないので、保存中の樹脂の硬化を抑制できるとともに、光を吸収して発熱する粒子が樹脂組成物中に略均一に分散されているため、パルス光を照射することにより容易に樹脂層内部まで硬化することができる樹脂硬化物の製造方法及び硬化性樹脂組成物を実現できる。 According to the present invention, since the photopolymerization initiator is not included in the resin composition, curing of the resin during storage can be suppressed, and particles that absorb light and generate heat are dispersed substantially uniformly in the resin composition. Therefore, the manufacturing method and curable resin composition of the resin cured material which can be hardened | cured to the inside of a resin layer easily by irradiating pulsed light are realizable.
以下、本発明を実施するための形態（以下、実施形態という）を説明する。 Hereinafter, modes for carrying out the present invention (hereinafter referred to as embodiments) will be described.
本実施形態にかかる樹脂硬化物の製造方法は、光を吸収して発熱する粒子を含有し、かつ、光重合開始剤を含有しない樹脂組成物にパルス光を照射することを特徴とする。樹脂組成物にパルス光を照射することにより樹脂組成物中に含有する光を吸収して発熱する粒子がパルス光を吸収し、光エネルギーを熱エネルギーに変換し、発生する熱により樹脂が熱重合して硬化する。この場合、上記樹脂組成物は、ポリエチレンテレフタレート等の適宜な基板上に所望のパターンで印刷され、このパターンにパルス光が照射される。なお、パターンの印刷には、スクリーン印刷、グラビア印刷、凸版印刷、凹版印刷、スプレーコート、バーコート、ロールコート、ダイコート、インクジェットコート、ディップコート、ドロップコート等を使用することができる。 The method for producing a cured resin according to this embodiment is characterized by irradiating a resin composition containing particles that absorb light to generate heat and does not contain a photopolymerization initiator with pulsed light. By irradiating the resin composition with pulsed light, particles that generate heat by absorbing the light contained in the resin composition absorb the pulsed light, convert the light energy into heat energy, and the resin is thermally polymerized by the generated heat. And harden. In this case, the resin composition is printed in a desired pattern on an appropriate substrate such as polyethylene terephthalate, and this pattern is irradiated with pulsed light. For pattern printing, screen printing, gravure printing, relief printing, intaglio printing, spray coating, bar coating, roll coating, die coating, inkjet coating, dip coating, drop coating, and the like can be used.
ここで、上記光を吸収して発熱する粒子の材料は、金属、金属酸化物、カーボンのように光を吸収して発熱するものであり、この金属または金属酸化物を構成する金属は銀、銅、ニッケル、コバルト、クロム、鉄等であるのが好適である。また、カーボンとしては、グラファイト、グラフェン、カーボンナノチューブ、カーボンナノホーン、カーボンナノバッド、ガラス状炭素、無定形炭素、カーボンナノフォーム、活性炭、カーボンブラック、黒鉛、木炭、炭素繊維等が挙げられる。以上に述べた光を吸収して発熱する粒子の樹脂組成物中の含有量は３０質量％以上９０質量％以下、より好ましくは５０質量％以上８５質量％以下である。３０質量％よりも少ないと発熱により全体を十分硬化することが出来ず、９０質量％を超えると得られる硬化物の強度が弱くなってしまう。なお、上記光を吸収して発熱する粒子の形状は限定されないが、球状、扁平形状、繊維状等が挙げられる。また、大きさは一概には規定できないが、一般には粒径が大きいほうが伝熱的に有利であり、粒径としては大きいほうが良い。ただし、あまりに大きいと沈降しやすくなる。粒子径については形状についても考慮する必要があり、一概に規定することは出来ないが、球状であればレーザー回折・散乱法の粒子径測定装置で測定した個数基準の平均粒子径Ｄ５０（メジアン径）が２０μｍ以下であることが好ましく、より好ましくは１０μｍ以下、さらに好ましくは５μｍ以下である。２０μｍよりも大きいと粒子が沈降しやすく、均一な配合物が得られにくい。また、１０μｍより小さいと粒子間の充填効率が更に良くなり、５μｍより小さいと粒子間での熱伝導が更に良くなる。ただし、あまりにも粒子径が小さいとコストが高くなるうえに混合時の粘度も高くなるので好ましくなく、少なくとも１ｎｍ以上、好ましくは１０ｎｍ以上の粒子径であることが望ましい。 Here, the material of the particles that absorbs light and generates heat is a material that absorbs light and generates heat, such as metal, metal oxide, and carbon, and the metal constituting the metal or metal oxide is silver, Copper, nickel, cobalt, chromium, iron and the like are preferable. Examples of carbon include graphite, graphene, carbon nanotube, carbon nanohorn, carbon nanobud, glassy carbon, amorphous carbon, carbon nanofoam, activated carbon, carbon black, graphite, charcoal, and carbon fiber. The content in the resin composition of the particles that absorb light and generate heat is 30% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 85% by mass or less. If it is less than 30% by mass, the whole cannot be sufficiently cured by heat generation, and if it exceeds 90% by mass, the strength of the resulting cured product is weakened. The shape of the particle that absorbs light and generates heat is not limited, and examples thereof include a spherical shape, a flat shape, and a fibrous shape. In addition, the size cannot be generally defined, but in general, a larger particle size is advantageous in terms of heat transfer, and a larger particle size is better. However, if it is too large, it tends to settle. Must also consider the shape for the particle size, but can not be unconditionally prescribed, the average particle diameter D 50 (median number basis measured by the particle diameter measuring device if spherical laser diffraction scattering method (Diameter) is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. If it is larger than 20 μm, the particles tend to settle, and it is difficult to obtain a uniform blend. If the particle size is smaller than 10 μm, the packing efficiency between the particles is further improved. However, if the particle size is too small, the cost is increased and the viscosity at the time of mixing is also increased, which is not preferable. The particle size is preferably at least 1 nm or more, preferably 10 nm or more.
なお、光を吸収して発熱する粒子の粒子径は小さいほうが樹脂組成物（インク）の粘度が高くなり印刷し難くなる傾向はあるものの印刷等で微細なパターニング形成を行うためには有利であるため、１０ｎｍ未満のナノ粒子を使うことも出来る。 In addition, although the particle diameter of the particles that absorb light and generate heat is small, the viscosity of the resin composition (ink) tends to be high and printing tends to be difficult, but it is advantageous for fine patterning formation in printing or the like. Therefore, nanoparticles less than 10 nm can be used.
ここでいう平均粒子径とは、個数基準の平均粒子径Ｄ５０（メジアン径）を意味する。 The average particle diameter here means a number-based average particle diameter D 50 (median diameter).
また、上記樹脂組成物は熱により硬化する樹脂成分を含むものであれば特に制限はなく、アクリル樹脂、エポキシアクリレート樹脂、不飽和ポリエステル樹脂、ウレタンアクリレート樹脂、アリル樹脂、ＤＡＰ樹脂、エポキシ樹脂、ウレタン樹脂、シリコーン樹脂等が挙げられるが、重合反応速度の点でアクリル樹脂を含有するのが好適である。本明細書において「アクリル樹脂」とは、アクリロイル基およびメタクリロイル基の少なくとも一方を分子中に含有するポリマー、オリゴマーのいずれかを含むものを意味する。また、本樹脂系には光重合開始剤を含まず、熱重合開始剤も必ずしも含む必要はない。 The resin composition is not particularly limited as long as it contains a resin component that is cured by heat, and is an acrylic resin, epoxy acrylate resin, unsaturated polyester resin, urethane acrylate resin, allyl resin, DAP resin, epoxy resin, urethane. Examples thereof include resins and silicone resins, but it is preferable to contain an acrylic resin in view of the polymerization reaction rate. In the present specification, the “acrylic resin” means a polymer or oligomer containing at least one of acryloyl group and methacryloyl group in the molecule. Further, the resin system does not contain a photopolymerization initiator and does not necessarily contain a thermal polymerization initiator.
アクリル樹脂は金属粒子との密着性がエポキシ樹脂やウレタン樹脂には劣る。そのため重合反応速度の点では不利であるがエポキシ樹脂やウレタン樹脂を使用したほうが金属粒子との密着性の点では好ましい。その場合には光照射強度を強くしたり、回数を多く照射することが必要となるが、それらを減らす目的で、エポキシ樹脂の場合にはイミダゾール化合物やホスフィン化合物、ウレタン樹脂の場合にはスズ化合物のような触媒を添加し、照射強度を弱くしたり回数を減らすことも出来る。また、これらの欠点を解消する目的でエポキシ樹脂中のエポキシ基と（メタ）アクリル酸を反応させた所謂エポキシアクリレート樹脂を使用することができる。エポキシアクリレート樹脂は硬化速度も速く、エポキシ樹脂に近い密着性を持っているので、非常に好ましい樹脂である。「（メタ）アクリル酸」とはアクリル酸および／またはメタクリル酸を意味する。 Acrylic resin is inferior to epoxy resin and urethane resin in adhesion to metal particles. Therefore, although it is disadvantageous in terms of the polymerization reaction rate, it is preferable to use an epoxy resin or a urethane resin in terms of adhesion to metal particles. In that case, it is necessary to increase the light irradiation intensity or to irradiate many times, but in order to reduce them, imidazole compounds and phosphine compounds in the case of epoxy resins, tin compounds in the case of urethane resins It is possible to weaken the irradiation intensity or reduce the number of times by adding a catalyst such as Moreover, what is called an epoxy acrylate resin which made the epoxy group in an epoxy resin react with (meth) acrylic acid can be used in order to eliminate these faults. Epoxy acrylate resin is a very preferable resin because it has a high curing speed and has close adhesion to epoxy resin. “(Meth) acrylic acid” means acrylic acid and / or methacrylic acid.
本実施形態にかかる樹脂硬化物の製造方法においては、樹脂組成物が光重合開始剤、例えば光ラジカル重合開始剤、光カチオン重合開始剤等を含有せず、フィラーとして上記光を吸収して発熱する粒子を含有する。このフィラーがパルス光を吸収し、光エネルギーを熱エネルギーに変換し（黒体発熱）、発生する熱により樹脂を熱重合して硬化させる。 In the method for producing a cured resin according to the present embodiment, the resin composition does not contain a photopolymerization initiator, for example, a radical photopolymerization initiator, a cationic photopolymerization initiator, etc., and absorbs the light as a filler to generate heat. Containing particles. This filler absorbs pulsed light, converts light energy into heat energy (black body heat generation), and the resin is thermally polymerized and cured by the generated heat.
本明細書中において「パルス光」とは、光照射期間（照射時間）が短時間の光であり、光照射を複数回繰り返す場合は図１に示すように、第一の光照射期間（ｏｎ）と第二の光照射期間（ｏｎ）との間に光が照射されない期間（照射間隔（ｏｆｆ））を有する光照射を意味する。図１ではパルス光の光強度が一定であるように示しているが、１回の光照射期間（ｏｎ）内で光強度が変化してもよい。上記パルス光は、キセノンフラッシュランプ等のフラッシュランプを備える光源から照射される。このような光源を使用して、上記基板に印刷された樹脂組成物にパルス光を照射する。ｎ回繰り返し照射する場合は、図１における１サイクル（ｏｎ＋ｏｆｆ）をｎ回反復する。なお、繰り返し照射する場合には、次パルス光照射を行う際に、基板を室温付近まで冷却できるようにするため基板側から冷却することが好ましい。 In this specification, “pulse light” means light having a short light irradiation period (irradiation time). When light irradiation is repeated a plurality of times, as shown in FIG. 1, the first light irradiation period (on ) And the second light irradiation period (on) means light irradiation having a period (irradiation interval (off)) in which light is not irradiated. Although FIG. 1 shows that the light intensity of the pulsed light is constant, the light intensity may change within one light irradiation period (on). The pulsed light is emitted from a light source including a flash lamp such as a xenon flash lamp. Using such a light source, the resin composition printed on the substrate is irradiated with pulsed light. When irradiation is repeated n times, one cycle (on + off) in FIG. 1 is repeated n times. In the case of repeated irradiation, it is preferable to cool from the substrate side so that the substrate can be cooled to near room temperature when the next pulse light irradiation is performed.
パルス光の１回の照射時間（ｏｎ）は、光強度にもよるが、２０マイクロ秒から５秒の範囲が好ましい。２０マイクロ秒よりも短いと樹脂の重合が進まず、樹脂を硬化させる効果が低くなる。また、５秒よりも長いと光劣化、熱劣化により樹脂や基板へ悪影響を及ぼすことがある。より好ましくは５００マイクロ秒から１秒、さらに好ましくは１０００マイクロ秒から１０ミリ秒である。上記理由により、本実施形態では連続光ではなくパルス光を用いる。パルス光の照射は単発で実施しても効果はあるが、上記の通り繰り返し実施することもできる。繰返し実施する場合照射間隔（ｏｆｆ）は２０マイクロ秒から５秒、より好ましくは２ミリ秒から２秒の範囲とすることが好ましい。２０マイクロ秒よりも短いと、連続光と近くになってしまい一回の照射後に放冷される間も無く照射されるので、樹脂や基板が加熱され温度がかなり高くなってしまう。５秒よりも長いとプロセス時間が長くなるので好ましくない。 The irradiation time (on) of the pulsed light once depends on the light intensity, but is preferably in the range of 20 microseconds to 5 seconds. When the time is shorter than 20 microseconds, the polymerization of the resin does not proceed and the effect of curing the resin becomes low. If it is longer than 5 seconds, the resin and the substrate may be adversely affected by light deterioration and heat deterioration. More preferably, it is 500 microseconds to 1 second, and still more preferably 1000 microseconds to 10 milliseconds. For this reason, pulse light is used instead of continuous light in this embodiment. Irradiation with pulsed light is effective even if performed in a single shot, but can also be performed repeatedly as described above. In the case of repeated execution, the irradiation interval (off) is preferably in the range of 20 microseconds to 5 seconds, more preferably 2 milliseconds to 2 seconds. If it is shorter than 20 microseconds, it becomes close to continuous light and is irradiated without being allowed to cool after one irradiation, so that the resin and the substrate are heated and the temperature becomes considerably high. If it is longer than 5 seconds, the process time becomes longer, which is not preferable.
本実施形態にかかる樹脂硬化物の製造方法では、パルス光として可視光を使用することにより、紫外線等が透過できない材料の内部まで容易に短時間で硬化させることができる。また、透明基板越しにパルス光を透過させつつ、基板へのパルス光入射面と反対側の面に形成された樹脂組成物の層を硬化させることもできる。 In the method for producing a cured resin according to the present embodiment, by using visible light as pulsed light, the inside of a material that cannot transmit ultraviolet light or the like can be easily cured in a short time. Moreover, the layer of the resin composition formed on the surface opposite to the pulse light incident surface on the substrate can be cured while transmitting the pulse light through the transparent substrate.
また、本システムの硬化をより適切に行うために、熱重合開始剤を加えることも出来る。このような開始剤として炭素−炭素二重結合により硬化する樹脂の場合には、過酸化物やアゾ系の開始剤、エポキシ樹脂の場合にはイミダゾール系の開始剤、ウレタン樹脂、シリコーン樹脂の場合にはスズ系の開始剤が挙げられる。 In addition, a thermal polymerization initiator can be added in order to cure the system more appropriately. In the case of a resin curable by a carbon-carbon double bond as such an initiator, in the case of a peroxide or an azo initiator, in the case of an epoxy resin, an imidazole initiator, a urethane resin, or a silicone resin Includes a tin-based initiator.
以下、本発明の実施例を具体的に説明する。なお、以下の実施例は、本発明の理解を容易にするためのものであり、本発明はこれらの実施例に制限されるものではない。
なお、実施例中の粒子径は、メーカー分析値もしくは日機装株式会社製 マイクロトラック粒度分布測定装置 ＭＴ３０００ＩＩシリーズ ＵＳＶＲ（レーザー回折・散乱法）を用いて測定した。
Examples of the present invention will be specifically described below. In addition, the following examples are for facilitating understanding of the present invention, and the present invention is not limited to these examples.
In addition, the particle diameter in an Example was measured using the manufacturer analysis value or the Nikkiso Co., Ltd microtrac particle size distribution measuring apparatus MT3000II series USVR (laser diffraction and scattering method).
実施例１．
１００ｍｌのナス型フラスコに、１，４‐シクロヘキサンジメタノールジグリシジルエーテル（ＣＤＭＤＧ）６．４０ｇ（０．０５当量）、アクリル酸３．６０ｇ（０．０５ｍｏｌ）、重合禁止剤２，６−ジ−ｔ−ブチル−４−メトキシフェノール０．１０９ｇ（０．５ｍｍｏｌ）及びトリフェニルホスフィン０．０３ｇ（０．１ｍｍｏｌ）を仕込み、空気気流下で、１３０℃で１０時間加熱し、粘稠なエポキシアクリレートを得た。
Example 1.
In a 100 ml eggplant-shaped flask, 6.40 g (0.05 equivalent) of 1,4-cyclohexanedimethanol diglycidyl ether (CDMDG), 3.60 g (0.05 mol) of acrylic acid, polymerization inhibitor 2,6-di- Charge 0.109 g (0.5 mmol) of t-butyl-4-methoxyphenol and 0.03 g (0.1 mmol) of triphenylphosphine, and heat at 130 ° C. for 10 hours under an air stream. Obtained.
次に、上記ＣＤＭＤＧのエポキシアクリレートに光を吸収して発熱するフィラーとして銀粉ＡｇＣ−１４（福田金属箔粉工業製、扁平粉、レーザ回折・散乱法で測定した平均粒子径３．６μｍ）を、エポキシアクリレート：銀粉＝２０質量％：８０質量％となるように加え、遊星型真空攪拌装置(ARV-310、（株）シンキー製)にて最大攪拌速度２０００ｒｐｍでよく混合して、インクサンプルを調製した。このサンプルを、基板として東レ（株）社製両面易接着ポリエステルフィルム：ルミラー（登録商標）１２５Ｕ９８（厚み１２５μｍ）上に、２０ｍｍ×２０ｍｍのベタ状に１５μｍ厚になるようにスクリーン印刷し、試験片とした。 Next, silver powder AgC-14 (manufactured by Fukuda Metal Foil Powder Industry, flat powder, average particle diameter measured by laser diffraction / scattering method) as a filler that generates heat by absorbing light into the epoxy acrylate of CDMDG, Epoxy acrylate: Silver powder = 20% by mass: Add to 80% by mass, and mix well with a planetary vacuum stirrer (ARV-310, manufactured by Sinky Corporation) at a maximum stirring speed of 2000 rpm to prepare an ink sample. did. This sample was screen-printed on a double-sided easily-adhesive polyester film manufactured by Toray Industries, Inc .: Lumirror (registered trademark) 125U98 (thickness 125 μm) as a substrate to a thickness of 20 μm × 20 mm to a thickness of 15 μm, and a test piece It was.
なお、膜厚は直進式ミクロンマイクロメーターＯＭＶ 株式会社ミツトヨ製を用いて測定した。 The film thickness was measured using a linear micron micrometer OMV manufactured by Mitutoyo Corporation.
ＮｏｖａＣｅｎｔｒｉｘ社製のキセノン照射装置Ｐｕｌｓｅ Ｆｏｒｇｅ３３００を使用し、１Ｈｚでパルス光を２回照射した。なお、パルス光の照射条件は、光源の駆動電圧３００Ｖ、照射時間（１回のパルス幅）３３００μｓｅｃ、照射間隔９９６．７ｍｓｅｃであった。この結果、手で触っても、べたつきが無くＣＤＭＤＧのアクリレートが硬化しタックフリーであることを確認した。また、セルロース連続長繊維不織布であるベンコット（登録商標 旭化成センイ(株)製）に、アセトンを湿らし、拭き取れないことも確認した。 Using a xenon irradiation device Pulse Forge 3300 manufactured by NovaCentrix, pulsed light was irradiated twice at 1 Hz. The irradiation conditions of the pulsed light were a light source driving voltage of 300 V, an irradiation time (one pulse width) of 3300 μsec, and an irradiation interval of 996.7 msec. As a result, it was confirmed that CDMDG acrylate was cured and tack free even when touched by hand. In addition, acetone was moistened with Bencot (registered trademark, manufactured by Asahi Kasei Sen Co., Ltd.), which is a continuous cellulose non-woven fabric, and it was confirmed that it could not be wiped off.
比較例１．
実施例１と同様にして合成したＣＤＭＤＧのエポキシアクリレートにフィラーを加えず、ＣＤＭＤＧのエポキシアクリレートのみを実施例１と同様にベタ状にスクリーン印刷し、試験片とした。なお、液状樹脂にフィラーを入れずに印刷したので、膜厚は測定できなかった。
Comparative Example 1
No filler was added to the CDMDG epoxy acrylate synthesized in the same manner as in Example 1, and only CDMDG epoxy acrylate was screen-printed in the same manner as in Example 1 to obtain a test piece. Since the liquid resin was printed without a filler, the film thickness could not be measured.
実施例１と同様にしてパルス光を１Ｈｚで２回照射した結果、べたつきがひどくＣＤＭＤＧのエポキシアクリレートは硬化が不十分であった。 As a result of irradiating the pulsed light twice at 1 Hz in the same manner as in Example 1, the stickiness was so bad that the epoxy acrylate of CDMDG was insufficiently cured.
比較例２．
ＣＤＭＤＧのエポキシアクリレートの割合を７５質量％（銀粉を２５質量％）にして、実施例１と同様にベタ状にスクリーン印刷し、試験片とした。なお、フィラー量が少なすぎたために、ベタつきがひどく膜厚は測定できなかった。
Comparative Example 2
The ratio of the epoxy acrylate of CDMDG was 75% by mass (silver powder was 25% by mass), and screen printing was performed in the same manner as in Example 1 to obtain a test piece. Since the amount of filler was too small, the stickiness was so bad that the film thickness could not be measured.
実施例１と同様にしてパルス光を１Ｈｚで１００回照射した結果、べたつきがひどくＣＤＭＤＧのエポキシアクリレートは硬化が不十分であった。 As in Example 1, pulse light was irradiated 100 times at 1 Hz. As a result, CDMDG epoxy acrylate was not sufficiently cured.
これらの比較例では、光を吸収して発熱するフィラーが含まれていない（比較例１）か少なすぎる（比較例２）ために、パルス光を照射しても十分な発熱が得られず、ＣＤＭＤＧのエポキシアクリレートを重合させるほどの熱エネルギーを確保できなかったため、ＣＤＭＤＧのエポキシアクリレートを硬化させることができなかった。 In these comparative examples, since the filler that generates heat by absorbing light is not included (Comparative Example 1) or too little (Comparative Example 2), sufficient heat generation cannot be obtained even when irradiated with pulsed light. Since the thermal energy sufficient to polymerize the epoxy acrylate of CDMDG could not be secured, the epoxy acrylate of CDMDG could not be cured.
比較例３．
ＣＤＭＤＧのエポキシアクリレートの割合を５質量％（銀粉を９５質量％）にして、実施例１と同様に遊星型真空攪拌装置で混合しようとしたが、フィラー量が多すぎてうまく混合することができなかった。また、得られたものも不均一な上に流動性が全くなく、スクリーン印刷を行うことも出来なかった。
Comparative Example 3
The proportion of the epoxy acrylate of CDMDG was 5% by mass (95% by mass of silver powder), and an attempt was made to mix with a planetary vacuum stirrer as in Example 1. There wasn't. Further, the obtained product was not uniform and had no fluidity, and screen printing could not be performed.
実施例２．
ＣＤＭＤＧのエポキシアクリレートに光を吸収して発熱するフィラーとして銀粉ＡｇＣ−ＧＳ（福田金属箔粉工業製、球状粉、レーザ回折・散乱法で測定した平均粒子径４．２μｍを、エポキシアクリレート：銀粉＝２０質量％：８０質量％となるように加え、実施例１と同様にしてよく混合してインクサンプルを調製した。このサンプルを、基板として東レ（株）社製両面易接着ポリエステルフィルム：ルミラー（登録商標）１２５Ｕ９８（厚み１２５μｍ）上に、２０ｍｍ×２０ｍｍのベタ状に約２５μｍ厚になるようにスクリーン印刷し、試験片とした。
Example 2
Silver powder AgC-GS (made by Fukuda Metal Foil Powder Industry, spherical powder, average particle diameter of 4.2 μm measured by laser diffraction / scattering method) is used as epoxy acrylate: silver powder = 20% by mass: 80% by mass and mixed well in the same manner as in Example 1 to prepare an ink sample, which was used as a substrate as a double-sided easily adhesive polyester film manufactured by Toray Industries, Inc .: Lumirror ( On the registered trademark 125U98 (thickness 125 μm), a 20 mm × 20 mm solid was screen-printed to a thickness of about 25 μm to obtain a test piece.
この試験片を実施例１と同様に１Ｈｚでパルス光を１０回照射した。光照射した結果、ＣＤＭＤＧのエポキシアクリレートが硬化し、タックフリーであり、アセトン拭き取り試験も合格した（拭き取れなかった）。 This test piece was irradiated with pulsed light 10 times at 1 Hz in the same manner as in Example 1. As a result of light irradiation, the epoxy acrylate of CDMDG was cured, was tack-free, and passed the acetone wiping test (not wiped off).
実施例３．
光を吸収して発熱するフィラーとして銀粉の代わりに、銅粉１１００Ｙ（三井金属鉱業社製、球状粉、レーザ回折・散乱法で測定した平均粒子径１．２μｍ）を使用した以外は実施例１と同様に試験片を作製し、光照射した結果、ＣＤＭＤＧのエポキシアクリレートが硬化し、タックフリーであり、アセトン拭き取り試験も合格した。
Example 3
Example 1 except that copper powder 1100Y (manufactured by Mitsui Mining & Smelting Co., Ltd., spherical powder, average particle diameter 1.2 μm measured by laser diffraction / scattering method) was used instead of silver powder as a filler that absorbs light and generates heat. As a result of producing a test piece and irradiating with light, the epoxy acrylate of CDMDG was cured, was tack-free, and passed the acetone wiping test.
実施例４−６．
ビスフェノール−Ａタイプのエポキシアクリレート樹脂(Ｒｉｐｏｘｙ（登録商標）ＳＰ−１５０７、昭和電工（株）製)に、銀粉ＡｇＣ−２３９（福田金属、扁平粉、レーザ回折・散乱法で測定した平均粒子径３．０μｍ)をそれぞれ８０、８５、９０質量％混合し、遊星型真空攪拌装置(ＡＲＶ−３１０、（株）シンキー製)にて最大攪拌速度２０００ｒｐｍでよく混合してサンプルとした。ガラス基板(縦５０ｍｍ、横１０ｍｍ、厚み１ｍｍ)上へ各サンプルを５０μｍ厚のテープ(Ｓｃｏｔｃｈ、３Ｍ社製)でマスク印刷した。印刷後の導電性フィルムは、５ｍｍ×５ｍｍ×０．０５ｍｍのサイズであった。このガラス基板上のフィルムに、Ｎｏｖａｃｅｎｔｒｉｘ社製ＰｕｌｓｅＦｏｒｇｅ３３００を用いて２２０Ｖ、照射時間１４００μｓｅｃ、照射間隔９９８．６ｍｓｅｃ、２．３８Ｊ／ｃｍ２でフィルム全体を硬化させるために、１Ｈｚの間隔で１００回光照射した。照射後、導電体（導電性フィルム）の抵抗率は、それぞれ、８０質量％混合インクで１．８５×１０−５Ωｃｍ、８５質量％混合インクで１．４１×１０−５Ωｃｍ、９０質量％混合インクでは７．５４×１０−６Ωｃｍの値を示した。いずれの導電性フィルムの表面もタックフリーであり、アセトン拭き取り試験も合格した。
Example 4-6.
Bisphenol-A type epoxy acrylate resin (Ripoxy (registered trademark) SP-1507, manufactured by Showa Denko KK) and silver powder AgC-239 (Fukuda Metal, flat powder, average particle diameter measured by laser diffraction / scattering method 3 0.0 μm) were mixed at 80%, 85% and 90% by mass, respectively, and mixed well with a planetary vacuum stirrer (ARV-310, manufactured by Sinky Corporation) at a maximum stirring speed of 2000 rpm to prepare a sample. Each sample was mask-printed on a glass substrate (length 50 mm, width 10 mm,
実施例７．
光を吸収して発熱するフィラーとして銀粉の代わりに、球状の酸化銅ナノ粉末（Ｎａｎｏｔｅｋ社製 Ｎａｎｏｔｅｋ ＣｕＯ：球状、メーカー分析値：平均粒子径４８ｎｍ）を５０質量％使用した以外は実施例４と同様に試験片を作製し、光照射した結果、ビスフェノール−Ａタイプのエポキシアクリレート樹脂が硬化し、タックフリーであり、アセトン拭き取り試験も合格した。
Example 7
Example 4 except that 50% by mass of spherical copper oxide nanopowder (Nanotek CuO: spherical, manufacturer analysis value: average particle size 48 nm) manufactured by Nanotek as a filler that absorbs light and generates heat is used instead of silver powder. Similarly, as a result of producing a test piece and irradiating it with light, the bisphenol-A type epoxy acrylate resin was cured, was tack-free, and passed the acetone wiping test.
実施例８．
光を吸収して発熱するフィラーとして銀粉の代わりに、チタン酸バリウムナノ粉末（和光純薬工業 ３２２−４３４３２：メーカー分析値：平均粒子径約１００ｎｍ）を５０質量％使用した以外は実施例４−６と同様に試験片を作製し、１Ｈｚの間隔で３００回光照射した。光照射した結果、ビスフェノール−Ａタイプのエポキシアクリレート樹脂が硬化し、タックフリーであり、アセトン拭き取り試験も合格した。
Example 8 FIG.
Example 4 except that 50% by mass of barium titanate nanopowder (Wako Pure Chemical Industries, Ltd. 322-43432: manufacturer analysis value: average particle diameter of about 100 nm) was used as a filler that absorbs light and generates heat instead of silver powder. A test piece was prepared in the same manner as 6 and irradiated with light 300 times at intervals of 1 Hz. As a result of the light irradiation, the bisphenol-A type epoxy acrylate resin was cured, was tack-free, and passed the acetone wiping test.
実施例９
光を吸収して発熱するフィラーとして銀粉の代わりに、シリコンカーバイトナノ粉末（Ｎａｎｏｍａｋｅｒｓ社製Ｆｉ−ＮＩＴＥ（登録商標） メーカー分析値：平均粒子径＜１００ｎｍ）を５０質量％使用した以外は実施例４−６と同様に試験片を作製し、１Ｈｚの間隔で３００回光照射した結果、ビスフェノール−Ａタイプのエポキシアクリレート樹脂が硬化し、タックフリーであり、アセトン拭き取り試験も合格した。
Example 9
Example except that 50% by mass of silicon carbide nanopowder (Nanomakers Fi-NITE (registered trademark) manufacturer analysis value: average particle size <100 nm) was used in place of silver powder as a filler that absorbs light and generates heat. A test piece was prepared in the same manner as in 4-6 and irradiated with light 300 times at an interval of 1 Hz. As a result, the bisphenol-A type epoxy acrylate resin was cured, was tack-free, and passed the acetone wiping test.
実施例１０
光を吸収して発熱するフィラーとして銀粉の代わりに、人造黒鉛微粉末ＵＦ−Ｇ１０（昭和電工（株）製 レーザ回折・散乱法で測定した平均粒子径３．９μｍ）を３０質量％使用した以外は実施例４−６と同様に試験片を作製し、１Ｈｚの間隔で９００回光照射した。光照射した結果、ビスフェノール−Ａタイプのエポキシアクリレート樹脂が硬化し、タックフリーであり、アセトン拭き取り試験も合格した。
Example 10
Except for using 30% by mass of artificial graphite fine powder UF-G10 (average particle diameter 3.9 μm measured by laser diffraction / scattering method, manufactured by Showa Denko KK) instead of silver powder as a filler that generates heat by absorbing light. A test piece was prepared in the same manner as in Example 4-6, and irradiated with light 900 times at an interval of 1 Hz. As a result of the light irradiation, the bisphenol-A type epoxy acrylate resin was cured, was tack-free, and passed the acetone wiping test.
実施例１１．
熱硬化性樹脂としてエポキシアクリレート樹脂の代わりに、ビスフェノール系エポキシ樹脂(ｊＥＲ−８２８三菱化学（株）製)にキュアゾール２ＭＺ−ＣＮ(四国化成（株）製イミダゾール系硬化剤)１０質量部を混合したものを使用し、銀粉ＡｇＣ−２３９、福田金属、扁平粉)を６０質量％混合した以外は実施例４−６と同様に試験片を作製し、１Ｈｚの間隔で９００回光照射した。光照射した結果、ビスフェノール−系エポキシ樹脂が硬化し、タックフリーであり、アセトン拭き取り試験も合格した。
Example 11
Instead of an epoxy acrylate resin as a thermosetting resin, 10 parts by mass of CURSOL 2MZ-CN (an imidazole curing agent manufactured by Shikoku Kasei Co., Ltd.) was mixed with a bisphenol epoxy resin (manufactured by Mitsubishi Chemical Corporation). A test piece was prepared in the same manner as in Example 4-6 except that 60% by mass of silver powder (AgC-239, Fukuda metal, flat powder) was mixed and irradiated with light 900 times at an interval of 1 Hz. As a result of the light irradiation, the bisphenol-based epoxy resin was cured, was tack-free, and passed the acetone wiping test.
以上の各実施例及び比較例の結果を表１に示す。
表１に示されるように、３０質量％以上９０質量％以下含有する樹脂組成物にパルス光を照射することによりタックフリー、すなわち十分硬化した硬化物が得られることがわかる。なお、アセトン拭き取り試験にも合格している。 As shown in Table 1, it can be seen that a tack-free, that is, a sufficiently cured product can be obtained by irradiating a resin composition containing 30% by mass or more and 90% by mass or less with pulsed light. In addition, it passed the acetone wiping test.
一方、フィラーを含有しない比較例１では樹脂が硬化しなかった。また、フィラーの含有率が２５質量%であった比較例２でも樹脂が硬化せず、９５質量%であった比較例３では樹脂とフィラーとの混合ができなかった。 On the other hand, in Comparative Example 1 containing no filler, the resin was not cured. Further, in Comparative Example 2 in which the filler content was 25% by mass, the resin was not cured, and in Comparative Example 3 in which the content was 95% by mass, the resin and the filler could not be mixed.
Claims (5)
The method for producing a cured resin product according to any one of claims 1 to 4, wherein the pulsed light is irradiated from a light source including a flash lamp.
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