JP2005146143A - Ultraviolet-curing heat-ray-shielding hard coat composition - Google Patents
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本発明は建築物や自動車、鉄道等の窓表面に形成する熱線遮蔽ハードコート用組成物に関する。詳しくは、耐擦傷性や密着性を有し、短時間で硬化膜が形成できる熱線遮蔽ハードコート用組成物である。 The present invention relates to a composition for heat ray shielding hard coat formed on the window surface of buildings, automobiles, railways and the like. Specifically, it is a composition for heat ray shielding hard coat having scratch resistance and adhesion and capable of forming a cured film in a short time.
太陽光等の熱線による影響を抑制するために、建築物や自動車、鉄道等の窓表面には、アンチモンドープ酸化スズ（以下、ＡＴＯとする）、スズドープ酸化インジウム（以下、ＩＴＯとする）等の金属酸化物の薄膜を設けている。しかし、これらの薄膜の形成は真空蒸着法やスパッタリング法等の物理成膜法によるため大掛かりな設備を必要とし、また広面積の基材に対する薄膜形成が困難である等の欠点がある。 In order to suppress the influence of heat rays such as sunlight, windows such as buildings, automobiles, railways, etc. have antimony-doped tin oxide (hereinafter referred to as ATO), tin-doped indium oxide (hereinafter referred to as ITO), etc. A metal oxide thin film is provided. However, since these thin films are formed by a physical film forming method such as a vacuum vapor deposition method or a sputtering method, a large facility is required, and there is a drawback that it is difficult to form a thin film on a substrate having a large area.
この欠点を解決するための簡便な薄膜形成方法として、上記金属酸化物を微粒子として溶媒に分散させ、熱可塑性樹脂や熱硬化性樹脂等の合成樹脂をバインダーとして用いた塗工液を塗布、硬化する方法がある。しかし、塗工液によって形成された膜は物理成膜された膜と比較して熱線遮蔽率が低い。また、ＡＴＯやＩＴＯ等の金属酸化物は８００ｎｍ〜１１００ｎｍの近赤外域での遮蔽能が弱いことから、該塗工液による硬化膜の熱線遮蔽効果が小さいという欠点がある。熱線遮蔽率を向上させる方法としては、従来の金属酸化物微粒子に６ホウ化物微粒子を加えた塗工液がある（特許文献１）。 As a simple thin film formation method for solving this drawback, the above metal oxide is dispersed in a solvent as fine particles, and a coating liquid using a synthetic resin such as a thermoplastic resin or a thermosetting resin as a binder is applied and cured. There is a way to do it. However, the film formed by the coating liquid has a lower heat ray shielding rate than the film formed by physical film formation. Further, since metal oxides such as ATO and ITO have a weak shielding ability in the near infrared region of 800 nm to 1100 nm, there is a drawback that the heat ray shielding effect of the cured film by the coating solution is small. As a method for improving the heat ray shielding rate, there is a coating solution in which hexaboride fine particles are added to conventional metal oxide fine particles (Patent Document 1).
また、塗工液による方法はバインダーとして用いる樹脂によっては好ましくない結果をもたらす。例えば、熱可塑性樹脂を用いた場合には膜の耐擦傷性が低くなり、熱硬化性樹脂では膜の硬化に長時間を要するためゴミや埃などが付着しやすく、且つ、生産性が低くなる等の欠点がある。 Moreover, the method using a coating solution brings about an undesirable result depending on the resin used as a binder. For example, when a thermoplastic resin is used, the scratch resistance of the film is low, and with a thermosetting resin, it takes a long time to cure the film, so dust and dust are likely to adhere, and productivity is low. There are disadvantages such as.
一方、膜の硬化時間を短縮するために紫外線硬化性樹脂をバインダーに用いる方法も検討された。紫外線硬化性樹脂の場合には４００ｎｍ以下の紫外線を照射して硬化させるが、この際、用いる微粒子によっては塗工液が紫外域の波長を吸収してしまい、硬化性が著しく低下するため硬化に長時間を要し、生産性が低く、基材が劣化するという欠点がある。また、近赤外線の遮蔽能向上には無機微粒子を膜中に多く含有させる必要があり、このため十分な耐擦傷性が得られないという欠点がある。耐擦傷性を改善する方法として、熱線遮蔽層、粘着剤層及びハードコート層からなる熱線遮蔽フィルムがある（特許文献２）。
特許文献１では、６ホウ化物微粒子をＡＴＯ微粒子又はＩＴＯ微粒子と併用することで近赤外線遮蔽効果は得られているが、これらの無機微粒子は溶媒やバインダーへの分散性に問題があり、また可視領域や紫外域にも吸収があるため多量に添加できない。通常量での使用の場合でも紫外線硬化に１分間程度の時間を必要とし、硬化時間を短縮するために過剰の紫外線を照射すると基材や膜の劣化を生じ、十分な硬度が得られない。一方、無機微粒子が少量であると膜の耐候性が不十分となる課題がある。特許文献２は、熱線遮蔽無機微粒子としてＡＴＯ微粒子やＩＴＯ微粒子を熱線遮蔽層に用いたものであり、耐候性や耐擦傷性は向上したが熱線遮蔽効果は満足できるものではない。 In Patent Document 1, a near-infrared shielding effect is obtained by using hexaboride fine particles in combination with ATO fine particles or ITO fine particles. However, these inorganic fine particles have a problem in dispersibility in solvents and binders, and are visible. A large amount cannot be added because there is also absorption in the region and ultraviolet region. Even when used in a normal amount, ultraviolet curing requires a time of about 1 minute. When excessive ultraviolet rays are irradiated to shorten the curing time, the base material and film are deteriorated, and sufficient hardness cannot be obtained. On the other hand, if the amount of inorganic fine particles is small, there is a problem that the weather resistance of the film becomes insufficient. Patent Document 2 uses ATO fine particles or ITO fine particles as heat ray shielding inorganic fine particles in a heat ray shielding layer. Although the weather resistance and scratch resistance are improved, the heat ray shielding effect is not satisfactory.
以上のように塗工液による方法は、無機微粒子を分散させて用いるため、添加した微粒子同士やバインダーとの相互作用で分散性、安定性を低下させるという欠点がある。そのため、十分な熱線遮蔽率を得るための必要量を添加できない課題がある。また、従来から用いられるＡＴＯ微粒子、ＩＴＯ微粒子は熱線遮蔽率、可視光透過率に優れるが、近赤外域の８００ｎｍ〜１１００ｎｍの遮蔽能に乏しい。さらに、６ホウ化物微粒子を用いる場合は、金属酸化物微粒子やバインダーとの相溶性が十分でないことや、６ホウ化物微粒子自体が可視領域に吸収を有するので添加量が制限されることなど課題を有する。 As described above, since the method using the coating liquid is used by dispersing inorganic fine particles, there is a drawback that the dispersibility and stability are lowered due to the interaction between the added fine particles and the binder. Therefore, there is a problem that a necessary amount for obtaining a sufficient heat ray shielding rate cannot be added. Conventionally used ATO fine particles and ITO fine particles are excellent in heat ray shielding rate and visible light transmittance, but have poor shielding ability in the near infrared region of 800 nm to 1100 nm. Further, when hexaboride fine particles are used, the compatibility with the metal oxide fine particles and the binder is not sufficient, and the addition amount is limited because the hexaboride fine particles themselves absorb in the visible region. Have.
そこで本発明の目的は、耐擦傷性や密着性に優れ、短時間で硬化膜が形成できる、紫外線硬化性熱線遮蔽ハードコート用組成物を提供することである。 Accordingly, an object of the present invention is to provide an ultraviolet curable heat ray shielding hard coat composition which is excellent in scratch resistance and adhesion and can form a cured film in a short time.
（１）本発明は、有機色素としてフタロシアニン錯体又はジチオレン錯体、無機微粒子、バインダーとして（メタ）アクリル基を有するモノマー、紫外線吸収剤を含有する紫外線硬化性熱線遮蔽ハードコート用組成物である。 (1) The present invention is an ultraviolet curable heat ray shielding hard coat composition containing a phthalocyanine complex or dithiolene complex as an organic dye, inorganic fine particles, a monomer having a (meth) acryl group as a binder, and an ultraviolet absorber.
（２）また、本発明は、上記無機微粒子が、金属酸化物微粒子及び６ホウ化物微粒子の一方または両方であることを特徴とする上記（１）の紫外線硬化性熱線遮蔽ハードコート用組成物である。 (2) The present invention also provides the ultraviolet curable heat ray shielding hard coat composition according to (1) above, wherein the inorganic fine particles are one or both of metal oxide fine particles and hexaboride fine particles. is there.
（３）また、本発明は、上記（メタ）アクリル基を有するモノマーが、１分子中に少なくとも３つ以上の（メタ）アクリル基を有するモノマー（Ａ）と１分子中に１つ又は２つの（メタ）アクリル基を有するモノマー（Ｂ）からなり、（Ａ）と（Ｂ）の重量比が９９／１〜５０／５０であることを特徴とする上記（１）又は（２）の紫外線硬化性熱線遮蔽ハードコート用組成物である。 (3) Further, in the present invention, the monomer having the (meth) acrylic group includes the monomer (A) having at least three (meth) acrylic groups in one molecule and one or two monomers in one molecule. The ultraviolet curing according to (1) or (2) above, comprising a monomer (B) having a (meth) acrylic group, wherein the weight ratio of (A) to (B) is 99/1 to 50/50. It is a composition for a heat-shielding hard coat.
（４）また、本発明は、（１）〜（３）のいずれかの紫外線硬化性熱線遮蔽ハードコート用組成物を硬化する際に、光開始剤として分子内に（ビス）アシルフォスフィンオキサイド構造を有する化合物を用いることを特徴とする上記（１）〜（３）のいずれかの硬化膜形成方法である。 (4) In addition, the present invention provides (bis) acylphosphine oxide as a photoinitiator in the molecule when the ultraviolet curable heat ray shielding hard coat composition according to any one of (1) to (3) is cured. The method for forming a cured film according to any one of (1) to (3) above, wherein a compound having a structure is used.
本発明によれば、耐擦傷性や密着性に優れ、短時間で硬化膜が形成でき、８００ｎｍ〜１１００ｎｍの領域の遮蔽能及び耐候性を有する熱線遮蔽ハードコート用組成物が提供できる。 ADVANTAGE OF THE INVENTION According to this invention, it is excellent in abrasion resistance and adhesiveness, can form a cured film in a short time, and can provide the composition for heat ray shielding hard-coats which has the shielding ability and weather resistance of a 800 nm-1100 nm area | region.
本発明者らは無機微粒子に好適な金属錯体を見出すことで本発明に到り、さらに無機微粒子と特定の金属錯体との相乗効果により、無機微粒子量をコントロールすることを可能とし、本発明に至ったものである。 The present inventors have arrived at the present invention by finding a metal complex suitable for inorganic fine particles, and further, it is possible to control the amount of inorganic fine particles by the synergistic effect of the inorganic fine particles and a specific metal complex. It has come.
本発明で使用されるフタロシアニン錯体又はジチオレン錯体は、８００ｎｍ〜１１００ｎｍに吸収極大波長を有する。フタロシアニン錯体として具体的には、下式（１）で示されるものが挙げられ、例えばＡｖｅｃｉａ社製ＰＲＯＪＥＴの８００ＮＰ、８３０ＮＰ、９００ＮＰ、９２５ＮＰ、日本触媒社製イーエクスカラーのＩＲ−１０Ａ、ＩＲ−１２、ＩＲ−１４、９０６Ｂ、９１０Ｂとして入手できる。 The phthalocyanine complex or dithiolene complex used in the present invention has an absorption maximum wavelength at 800 nm to 1100 nm. Specific examples of the phthalocyanine complex include those represented by the following formula (1). For example, Avecia PROJET 800NP, 830NP, 900NP, 925NP, Nippon Shokubai EEX Color IR-10A, IR-12 , IR-14, 906B, 910B.
ただし、式中、Ｘ１〜Ｘ１６は、独立して水素原子、ハロゲン原子、−ＳＲ１または−ＯＲ２、−ＮＨＲ３を表し、Ｒ１、Ｒ２、Ｒ３はそれぞれ独立して、置換基を有していてもよいフェニル基または炭素原子数１〜２０個のアルキル基を表し、Ｍは無金属、金属、金属酸化物または金属ハロゲン化物を表す。 However, in the formula, X 1 to X 16 independently represent a hydrogen atom, a halogen atom, —SR 1 or —OR 2 , —NHR 3 , and R 1 , R 2 , and R 3 are each independently substituted. A phenyl group which may have a group or an alkyl group having 1 to 20 carbon atoms is represented, and M represents a metal-free, metal, metal oxide or metal halide.
フタロシアニン錯体の中心のＭは、無金属、金属、金属酸化物または金属ハロゲン化物を表わす。無金属とは、金属以外の原子、例えば、２個の水素原子であることを意味する。金属としては、鉄、マグネシウム、ニッケル、コバルト、銅、パラジウム、亜鉛、バナジウム、チタン、インジウム、スズ等が挙げられる。金属酸化物としては、チタニル、バナジル等が挙げられる。金属ハロゲン化物としては、塩化アルミニウム、塩化インジウム、塩化ゲルマニウム、塩化スズ（ＩＩ）、塩化スズ（ＩＶ）、塩化ケイ素等が挙げられる。好ましくは、金属、金属酸化物または金属ハロゲン化物であり、具体的には、銅、亜鉛、コバルト、ニッケル、鉄、バナジル、チタニル、塩化インジウム、塩化スズ（ＩＩ）である。 M at the center of the phthalocyanine complex represents a metal-free, metal, metal oxide or metal halide. Metal-free means an atom other than a metal, for example, two hydrogen atoms. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride. Preferably, it is a metal, a metal oxide, or a metal halide, specifically, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, or tin (II) chloride.
置換基を有するフェニル基としては、炭素原子数１〜４個のアルキル基で１〜３個置換されたフェニル基、炭素原子数１〜４個のアルコキシ基で１〜２個置換されたフェニル基、あるいは塩素、フッ素等のハロゲン原子で１〜５個置換されたフェニル基等が挙げられる。 Examples of the phenyl group having a substituent include a phenyl group substituted by 1 to 3 alkyl groups having 1 to 4 carbon atoms, and a phenyl group substituted by 1 to 2 alkoxy groups having 1 to 4 carbon atoms. Or a phenyl group substituted with 1 to 5 halogen atoms such as chlorine and fluorine.
また、ジチオレン錯体として具体的には、下式（２）で示されるものが挙げられ、例えばエポリン社製Ｅｐｏｌｉｇｈｔ３０６３、Ｅｐｏｌｉｇｈｔ４０１９、Ｅｐｏｌｉｇｈｔ４１２１、Ｅｐｏｌｉｇｈｔ４１２９、みどり化学社製のＭＩＲ−１０１、ＭＩＲ−１１１、ＭＩＲ−１２１、ＭＩＲ−１０２、ＭＩＲ−１０５として入手できる。 Specific examples of the dithiolene complex include those represented by the following formula (2). For example, Epolight 3063, Epolight 4019, Epolight 4121, Epolight 4129 manufactured by Eporin, MIR-101, MIR-111, MIR- manufactured by Midori Chemical Co., Ltd. 121, MIR-102, and MIR-105.
ただし、式中、Ｒ１〜Ｒ４は独立して置換基を有していてもよいフェニル基または炭素原子数１〜２０のアルキル基を表し、Ｍは金属を表す。 However, wherein, R 1 to R 4 represents an alkyl group of independent number phenyl group or a carbon atom which may have a substituent 1 to 20, M represents a metal.
ジチオレン錯体の中心のＭは、ニッケル、白金、パラジウム、銅、モリブデン等の金属を表す。 M at the center of the dithiolene complex represents a metal such as nickel, platinum, palladium, copper, or molybdenum.
置換基を有するフェニル基としては、炭素原子数１〜４個のアルキル基で１〜３個置換されたフェニル基、炭素原子数１〜４個のアルコキシ基で１〜２個置換されたフェニル基、あるいは塩素、フッ素等のハロゲン原子で１〜５個置換されたフェニル基等が挙げられる。 Examples of the phenyl group having a substituent include a phenyl group substituted by 1 to 3 alkyl groups having 1 to 4 carbon atoms, and a phenyl group substituted by 1 to 2 alkoxy groups having 1 to 4 carbon atoms. Or a phenyl group substituted with 1 to 5 halogen atoms such as chlorine and fluorine.
ジチオレン錯体中のＳはＳｅでも良く、ジセレノレン錯体を用いることもできる。 S in the dithiolene complex may be Se, and a diselenolene complex can also be used.
これら錯体は可視領域で透過率が高いので、８００ｎｍ〜１１００ｎｍの遮蔽効果に劣るＡＴＯ微粒子やＩＴＯ微粒子と併用することで良好な熱線遮蔽ハードコート用組成物が得られる。このフタロシアニン錯体又はジチオレン錯体は溶媒やバインダーへの溶解性が非常に高く、微粒子の分散性が良好であり、近赤外線遮蔽に必要な量を用いることができ、さらに、得られた硬化膜も耐候性に優れるという特徴を有する。このフタロシアニン錯体又はジチオレン錯体を用いることで、ＡＴＯ微粒子やＩＴＯ微粒子の欠点を解消でき、６ホウ化物微粒子を用いる場合には、その使用量を必要最小量にすることができる。該フタロシアニン錯体又はジチオレン錯体は所望に応じて少なくとも１種以上を組み合わせることができ、使用量は全微粒子に対して０．１〜２０重量％が好ましい。２０重量％より多いと可視透過率が低下する傾向があり、０．１重量％より少ないと近赤外領域８００ｎｍ〜１１００ｎｍの吸収が不十分になる傾向がある。 Since these complexes have high transmittance in the visible region, a good composition for heat ray shielding hard coat can be obtained by using in combination with ATO fine particles or ITO fine particles which are inferior in the shielding effect of 800 nm to 1100 nm. This phthalocyanine complex or dithiolene complex has very high solubility in solvents and binders, good dispersibility of fine particles, and can be used in an amount necessary for shielding near infrared rays. It has the characteristic that it is excellent in property. By using this phthalocyanine complex or dithiolene complex, the disadvantages of ATO fine particles and ITO fine particles can be eliminated, and when hexaboride fine particles are used, the amount used can be reduced to a necessary minimum amount. The phthalocyanine complex or dithiolene complex can be combined with at least one or more as desired, and the amount used is preferably 0.1 to 20% by weight based on the total fine particles. If it exceeds 20% by weight, the visible transmittance tends to decrease, and if it is less than 0.1% by weight, the absorption in the near infrared region 800 nm to 1100 nm tends to be insufficient.
本発明に使用される無機微粒子とは、ＡＴＯ微粒子、ＩＴＯ微粒子等や、６ホウ化物微粒子が挙げられる。これらは、熱線遮蔽率の制御や塗工液の生産を簡便にするために、溶媒に分散させた状態で用いることが好ましい。なお、微粒子を分散させる際には必要に応じて添加剤や分散剤を加えることもできる。該微粒子の平均粒径は好ましくは２００ｎｍ以下、より好ましくは１００ｎｍ以下である。２００ｎｍより大きくなると、微粒子の凝集が起きやすく、ヘイズが発生して膜の透明性が失われるため好ましくない。 Examples of the inorganic fine particles used in the present invention include ATO fine particles, ITO fine particles, and hexaboride fine particles. These are preferably used in a state where they are dispersed in a solvent in order to control the heat ray shielding rate and simplify the production of the coating liquid. In addition, when dispersing fine particles, an additive and a dispersing agent can also be added as needed. The average particle size of the fine particles is preferably 200 nm or less, more preferably 100 nm or less. If it exceeds 200 nm, the aggregation of fine particles tends to occur, haze is generated, and the transparency of the film is lost.
本発明に使用されるバインダーは、１分子中に（メタ）アクリル基を３つ以上有する紫外線硬化性モノマーと１分子中に（メタ）アクリル基を１つ又は２つ有する紫外線硬化性モノマーを９９／１〜５０／５０の重量比で含有することが好ましい。 The binder used in the present invention is composed of an ultraviolet curable monomer having 3 or more (meth) acrylic groups in one molecule and an ultraviolet curable monomer having one or two (meth) acrylic groups in one molecule. It is preferable to contain by the weight ratio of / 1-50 / 50.
１分子中に（メタ）アクリル基を３つ以上有する紫外線硬化性モノマーとしては、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートとヘキサメチレンジイソシアネートのウレタンプレポリマー、ペンタエリスリトールトリ（メタ）アクリレートとトリレンジイソシアネートのウレタンプレポリマー、ペンタエリスリトールトリ（メタ）アクリレートとイソホロンジイソシアネートのウレタンプレポリマー等が挙げられる。これら３官能以上の紫外線硬化性モノマーは１種以上組み合わせてもよく、所望の膜物性に応じて選択する。使用量はバインダー中５０〜９９重量％である。５０重量％より少ない場合には膜の架橋密度が低く、耐擦傷性が低下する。 Examples of ultraviolet curable monomers having three or more (meth) acrylic groups in one molecule include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa. Urethane prepolymer of (meth) acrylate, pentaerythritol tri (meth) acrylate and hexamethylene diisocyanate, urethane prepolymer of pentaerythritol tri (meth) acrylate and tolylene diisocyanate, urethane prepolymer of pentaerythritol tri (meth) acrylate and isophorone diisocyanate Examples thereof include polymers. One or more of these tri- or higher functional UV-curable monomers may be combined and selected according to desired film properties. The amount used is 50 to 99% by weight in the binder. When the amount is less than 50% by weight, the cross-linking density of the film is low, and the scratch resistance is lowered.
１分子中に（メタ）アクリル基を１つ又は２つ有する紫外線硬化性モノマーとしては、分子中にさらに水酸基やアミド基、カルボキシル基、リン酸基等の極性基を有すると基材への膜密着性が向上する。具体的には、（メタ）アクリル酸、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、２−（メタ）アクリロイロキシエチルアシッドホスフェート、コハク酸水素（メタ）アクリロイルオキシエチル、フタル酸水素（メタ）アクリロイルオキシエチル、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド、Ｎ，Ｎ−ジメチルアミノエチルアクリルアミド、ジメチルアミノエチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、ビスフェノールＡ型ジグリシジルエーテルの（メタ）アクリル酸付加物、ビスフェノールＦ型ジグリシジルエーテルの（メタ）アクリル酸付加物、エトキシ化ビスフェノールＡ型ジ（メタ）アクリレート、エトキシ化ビスフェノールＦ型ジ（メタ）アクリレート、臭素付加ビスフェノールＡ型ジグリシジルエーテルの（メタ）アクリル酸付加物、臭素付加ビスフェノールＦ型ジグリシジルエーテルの（メタ）アクリル酸付加物等が挙げられる。これらのうちベンゼン骨格やビスフェノールＡ骨格、ビスフェノールＦ骨格、臭素付加ビスフェノールＡ骨格、臭素付加ビスフェノールＦ骨格、イソシアヌル酸骨格等を有するモノマーを用いる場合には硬化性のさらなる向上が期待できる。これら紫外線硬化性モノマーは少なくとも１種類以上を適宜選択して用いる。使用量はバインダー中１〜５０重量％である。５０重量％より多い場合には膜の架橋密度が低く、所望する耐擦傷性が得られない。１重量％より少ない場合には密着性を向上させる効果が得られない。 As an ultraviolet curable monomer having one or two (meth) acrylic groups in one molecule, a film on a substrate when a polar group such as a hydroxyl group, an amide group, a carboxyl group, or a phosphoric acid group is further contained in the molecule. Adhesion is improved. Specifically, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, Hydrogen (meth) acryloyloxyethyl succinate, hydrogen (meth) acryloyloxyethyl phthalate, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminoethylacrylamide, dimethylaminoethyl (meth) ) Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, (meth) acrylic acid adduct of bisphenol A type diglycidyl ether, (meth) acrylic acid adduct of bisphenol F type diglycidyl ether, (Meth) acrylic acid adduct of xylated bisphenol A type di (meth) acrylate, ethoxylated bisphenol F type di (meth) acrylate, brominated bisphenol A type diglycidyl ether, (meta) of brominated bisphenol F type diglycidyl ether ) Acrylic acid adduct and the like. Among these, when a monomer having a benzene skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a bromine-added bisphenol A skeleton, a bromine-added bisphenol F skeleton, an isocyanuric acid skeleton, or the like is used, further improvement in curability can be expected. These ultraviolet curable monomers are used by appropriately selecting at least one kind or more. The amount used is 1 to 50% by weight in the binder. If it exceeds 50% by weight, the cross-linking density of the film is low, and the desired scratch resistance cannot be obtained. When it is less than 1% by weight, the effect of improving the adhesion cannot be obtained.
本発明に使用される光開始剤は、（ビス）アシルフォスフィンオキサイド構造を有する光開始剤が好ましい。この光開始剤は紫外領域から可視領域４４０ｎｍ付近まで吸収を持ち、且つアシルフォスフィンオキサイド部分を有する化合物であるので紫外線吸収剤や無機微粒子などの紫外線を吸収する他成分による硬化阻害が起こらない。具体的には２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチル−ペンチルフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド等が挙げられる。所望するバインダーの硬化性に応じて、前記光開始剤を２種以上組み合わせたり、アセトフェノン系やＯ-アシルオキシム系等の他のラジカル光開始剤と組み合わせることもできる。使用量は、バインダーに対して０．１〜１０重量％の範囲が好ましい。光開始剤の使用量が０．１重量％より少ない場合にはバインダーの硬化性が低下し、硬化に長時間を要するため好ましくない。１０重量％より多い場合には光開始剤過剰のため、塗工液が高粘度化しやすくポットライフが短くなってしまう。 The photoinitiator used in the present invention is preferably a photoinitiator having a (bis) acylphosphine oxide structure. Since this photoinitiator is a compound having absorption from the ultraviolet region to the vicinity of the visible region of 440 nm and having an acylphosphine oxide portion, curing inhibition by other components that absorb ultraviolet rays such as an ultraviolet absorber and inorganic fine particles does not occur. Specifically, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6- And trimethylbenzoyl) -phenylphosphine oxide. Depending on the desired curability of the binder, two or more photoinitiators can be combined, or other radical photoinitiators such as acetophenone or O-acyloxime can be combined. The amount used is preferably in the range of 0.1 to 10% by weight based on the binder. When the amount of the photoinitiator used is less than 0.1% by weight, the curability of the binder is lowered and it takes a long time for curing, which is not preferable. When the amount is more than 10% by weight, the photoinitiator is excessive, so that the viscosity of the coating liquid is easily increased and the pot life is shortened.
バインダーと無機微粒子の重量割合は、硬化膜中で１０／９０〜７０／３０、好ましくは２０／８０〜５０／５０である。バインダーが７０重量％より多くなると、硬化膜の熱線遮蔽率が低くなるため高膜厚化の必要が生じる。バインダーが１０重量％未満では、結合成分が少なくなるため硬化膜が脆弱になってしまう。 The weight ratio of the binder and the inorganic fine particles is 10/90 to 70/30, preferably 20/80 to 50/50 in the cured film. When the amount of the binder exceeds 70% by weight, the heat ray shielding rate of the cured film is lowered, so that it is necessary to increase the film thickness. If the binder is less than 10% by weight, the cured component becomes brittle because the binding components are reduced.
本発明のハードコート組成物は基材への塗布方法、所望する膜厚に応じて、溶媒希釈による粘度調製を行うことができる。使用できる溶媒は、バインダー、使用する微粒子の分散液との相溶性や分散性を失わないものであれば使用可能である。具体的にはメタノール、エタノール、プロパノール、ブタノール等のアルコール類や、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン等のケトン類、酢酸エチルや酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート等のエステル類、セロソルブ、メチルセロソルブ、プロピレングリコールモノメチルエーテル、メチルカルビトール、ブチルセロソルブ等のエーテル類、トルエン、キシレン、シクロヘキサン等の炭化水素類が挙げられ、少なくとも１種以上の溶媒を組み合わせることで、塗工液の揮発性を制御して白化を防止したり、成膜性を向上させることができる。 The viscosity of the hard coat composition of the present invention can be adjusted by solvent dilution according to the coating method on the substrate and the desired film thickness. The solvent which can be used can be used as long as it does not lose the compatibility and dispersibility with the binder and the dispersion of the fine particles to be used. Specifically, alcohols such as methanol, ethanol, propanol, butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, etc. Esters, cellosolve, methyl cellosolve, propylene glycol monomethyl ether, ethers such as methyl carbitol, butyl cellosolve, and hydrocarbons such as toluene, xylene, cyclohexane, and the like. By controlling the volatility of the working liquid, it is possible to prevent whitening or improve the film formability.
本発明のハードコート組成物には硬化膜の耐候性をさらに向上させるために紫外線吸収剤を添加することが好ましい。紫外線吸収剤としては溶解性が良く、使用する微粒子の分散性を失わせないものを用い、光開始剤の作用を妨害しない範囲の量を添加する。例えば、ベンゾトリアゾール系、トリアジン系、ベンゾフェノン系紫外線吸収剤、具体的には２−（２−ヒドロキシ−５−メチルフェニル）−２Ｈ−ベンゾトリアゾール、５−クロロ−２−（３，５−ジ−ｔｅｒｔ−ブチル−２−ヒドロキシフェニル）−２Ｈ−ベンゾトリアゾール、２−（３−ｔｅｒｔ−ブチル−２−ヒドロキシ−５−メチルフェニル）−５−クロロ−２Ｈ−ベンゾトリアゾール、２−（３，５−ジ−ｔｅｒｔ−ペンチル−２−ヒドロキシフェニル）−２Ｈ−ベンゾトリアゾール、２−（３，５−ジ−ｔｅｒｔ−ブチル−２−ヒドロキシフェニル）−２Ｈ−ベンゾトリアゾール、２−（２−ヒドロキシ−４−オクチルオキシフェニル）−２Ｈ−ベンゾトリアゾール、２−（２−ヒドロキシ−５−ｔｅｒｔ−オクチルフェニル）−２Ｈ−ベンゾトリアゾール、１，４−ビス（４−ベンゾイル−３−ヒドロキシフェニルオキシ）−ブタン、２−[４−[（２−ヒドロキシ−３−ドデシルオキシプロピル）オキシ]−２−ヒドロキシフェニル]−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン、２−[４−[（２−ヒドロキシ−３−トリデシルオキシプロピル）オキシ]−２−ヒドロキシフェニル]−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン、２，４−ビス（２，４−ジメチルフェニル）−６−（２−ヒドロキシ−４−ｉｓｏ−オクチルオキシフェニル）−ｓ−トリアジン、２，４−ジヒドロキシベンゾフェノン、２，−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン−５−スルホン酸トリハイドレート、２−ヒドロキシ−４−オクチルオキシベンゾフェノン、４−ドデシルオキシ−２−ヒドロキシベンゾフェノン、４−ベンジルオキシ−２−ヒドロキシベンゾフェノン、２，２，４，４−テトラヒドロキシベンゾフェノン、２，２−ジヒドロキシ−４，４−ジメトキシベンゾフェノン等を硬化膜中で０．０１〜１０重量％の範囲内、好ましくは０．０５〜５重量％の範囲内になるように調製して用いればよい。 In order to further improve the weather resistance of the cured film, it is preferable to add an ultraviolet absorber to the hard coat composition of the present invention. As the ultraviolet absorber, one that has good solubility and does not lose the dispersibility of the fine particles to be used is added, and an amount in a range that does not interfere with the action of the photoinitiator is added. For example, benzotriazole series, triazine series, benzophenone series UV absorbers, specifically 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 5-chloro-2- (3,5-di- tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5- Di-tert-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-4- Octyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 1,4-bis (4-benzoyl-3-hydroxyphenyloxy) -butane, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl]- 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-iso-octyloxyphenyl) ) -S-triazine, 2,4-dihydroxybenzophenone, 2, -hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfone Acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2,4,4-tetrahydroxybenzophenone, 2,2 -Dihydroxy-4,4-dimethoxybenzophenone or the like may be prepared and used in the cured film in a range of 0.01 to 10% by weight, preferably in a range of 0.05 to 5% by weight.
本発明の熱線遮蔽ハードコート用組成物の塗布方法は特に限定されることはなく、基材に対して均一に塗布できる方法であればよい。例えば、フローコート法、スプレーコート法、ディッピング法、バーコート法、スピンコート法、ロールコート法、グラビアコート法、スクリーン印刷法、ブレードコート法等が挙げられる。 The method for applying the composition for heat ray shielding hard coat of the present invention is not particularly limited as long as it can be uniformly applied to a substrate. Examples thereof include a flow coating method, a spray coating method, a dipping method, a bar coating method, a spin coating method, a roll coating method, a gravure coating method, a screen printing method, and a blade coating method.
本発明の熱線遮蔽膜を形成する基材としては、フィルム状及びシート状、板状の何れでもよい。例えば、ポリエチレンテレフタレートやポリカーボネート、ポリメタクリレート、ポリエチレン、ポリプロピレン、ポリアミド、ポリ塩化ビニル、ポリ酢酸ビニル、ポリビニルアルコール等が挙げられる。また、これら基材との密着性を向上させるために、表面処理を施すことが可能で、例えば、プラズマ処理やコロナ処理等を行うこともできる。 The substrate for forming the heat ray shielding film of the present invention may be any of a film shape, a sheet shape, and a plate shape. Examples thereof include polyethylene terephthalate, polycarbonate, polymethacrylate, polyethylene, polypropylene, polyamide, polyvinyl chloride, polyvinyl acetate, and polyvinyl alcohol. Moreover, in order to improve adhesiveness with these base materials, it is possible to perform a surface treatment, for example, a plasma treatment, a corona treatment, etc. can also be performed.
熱線遮蔽ハードコート組成物を塗布した基材は、加熱して溶媒を乾燥した後に、紫外線等で硬化させることが好ましい。光源としては、メタルハライドランプ、高圧水銀ランプ、超高圧水銀ランプ、紫外線レーザー、キセノンランプ等が挙げられ、特に好ましくは、メタルハライドランプ、高圧水銀ランプで、２００ｎｍ〜５００ｎｍの波長を照射する。 The substrate coated with the heat ray-shielding hard coat composition is preferably cured with ultraviolet light after heating to dry the solvent. Examples of the light source include a metal halide lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an ultraviolet laser, and a xenon lamp. Particularly preferably, the metal halide lamp and the high-pressure mercury lamp irradiate a wavelength of 200 nm to 500 nm.
次に、本発明を詳しく説明するが、本発明はこれらの実施例に限定されるものではない。なお、熱線遮蔽ハードコートを施された基材の評価は下記の方法で実施した。 Next, the present invention will be described in detail, but the present invention is not limited to these examples. In addition, the following method evaluated the base material with which the heat ray shielding hard coat was given.
（１）分光特性
島津製作所製の分光光度計ＵＶ３１５０を用いて２００ｎｍ〜２０００ｎｍの透過率を測定した。日射遮蔽効果として、８００ｎｍ〜１１００ｎｍの近赤外線透過率の平均値、１１００ｎｍ〜２０００ｎｍの熱線透過率の平均値を算出した。８００ｎｍ〜１１００ｎｍの平均透過率が３５％以下、且つ１１００ｎｍ〜２０００ｎｍの平均透過率が１０％以下のものを◎、８００ｎｍ〜１１００ｎｍの平均透過率が３５％を越え５０％以下、且つ１１００ｎｍ〜２０００ｎｍの平均透過率が１０％を越え２０％以下のものを○、これら以外のものを×とした。
(1) Spectral characteristics The transmittance of 200 nm to 2000 nm was measured using a spectrophotometer UV3150 manufactured by Shimadzu Corporation. As a solar radiation shielding effect, an average value of near-infrared transmittance of 800 nm to 1100 nm and an average value of heat ray transmittance of 1100 nm to 2000 nm were calculated. The average transmittance of 800 nm to 1100 nm is 35% or less, and the average transmittance of 1100 nm to 2000 nm is 10% or less. The average transmittance of 800 nm to 1100 nm is more than 35% to 50% or less, and 1100 nm to 2000 nm. A sample having an average transmittance of more than 10% and not more than 20% was marked with ◯, and other than these were marked with ×.
（２）耐擦傷性
１２０Ｗ／ｃｍメタルハライドランプで塗布基材から１０ｃｍの距離で１０秒間紫外線照射して、形成された硬化膜に♯００００のスチールウールを１平方センチメートルあたり２００ｇの荷重をかけて水平方向に１０往復させて、発生した傷を目視で評価した。発生した傷の本数が０〜５本の状態をＡ、６〜１５本の状態をＢ、１６本以上をＣと区分して３段階で評価した。
(2) Scratch resistance A 120 W / cm metal halide lamp was irradiated with ultraviolet rays at a distance of 10 cm from the coated substrate for 10 seconds, and a # 0000 steel wool was applied to the formed cured film at a load of 200 g per square centimeter in the horizontal direction. The resulting scratches were visually evaluated. A state in which the number of generated scratches was 0 to 5 was divided into A, 6 to 15 states were divided into B, and 16 or more pieces were divided into C and evaluated in three stages.
（３）密着性
熱線遮蔽膜を形成した基材樹脂にカッターナイフで１ｍｍ×１ｍｍのマス目を１００個付け、粘着テープ（ニチバン製業務用セロテープ）を貼り付けた後、素早く剥がして硬化膜の剥れ具合を観察し、硬化膜が全く剥れなかった状態をＡ、一部剥れた状態をＢ、全て剥れた状態をＣと区分して３段階で評価した。
(3) Adhesion After attaching 100 squares of 1 mm x 1 mm to the base resin on which the heat ray shielding film has been formed with a cutter knife and affixing an adhesive tape (Nichiban's commercial cello tape), it is quickly removed to remove the cured film. The state of peeling was observed, and the state where the cured film was not peeled at all was classified as A, the state where it was partially peeled was classified as B, and the state where it was completely peeled was classified as C, and evaluated in three stages.
（バインダー液の調製）
ペンタエリスリトールテトラアクリレート３５重量部、ビスフェノールＡ型ジグリシジルエーテルのアクリル酸付加物１５重量部、メチルエチルケトン１５０重量部、シクロペンタノン４７．９重量部、レベリング剤ＢＹＫ３００（ＢＹＫＣｈｅｍｉｅ社製）０．１重量部、紫外線吸収剤としてＴＩＮＵＶＩＮ３８４−２（チバスペシャルティケミカルズ社製）０．０５重量部、（ビス）アシルフォスフィンオキサイド構造を有する光開始剤としてイルガキュア１８５０（チバスペシャルティケミカルズ社製）２重量部を攪拌、混合した液をバインダーＡ液とした。
(Preparation of binder liquid)
Pentaerythritol tetraacrylate 35 parts by weight, acrylic acid adduct of bisphenol A type diglycidyl ether 15 parts by weight, methyl ethyl ketone 150 parts by weight, cyclopentanone 47.9 parts by weight, leveling agent BYK300 (manufactured by BYK Chemie) 0.1 part by weight , 0.05 part by weight of TINUVIN 384-2 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber, and 2 parts by weight of Irgacure 1850 (manufactured by Ciba Specialty Chemicals) as a photoinitiator having a (bis) acylphosphine oxide structure, The mixed liquid was designated as a binder A liquid.
［実施例１］
メチルエチルケトンに分散した濃度４０％のＩＴＯ分散液６５重量部とフタロシアニン錯体（Ａｖｅｃｉａ社製 商品名ＰＲＯＪＥＴ９００ＮＰ）１重量部を攪拌、混合した液にＡ液２５重量部を加えて攪拌し、熱線遮蔽ハードコート液とした。
[Example 1]
65 parts by weight of ITO dispersion having a concentration of 40% dispersed in methyl ethyl ketone and 1 part by weight of a phthalocyanine complex (trade name PROJET900NP manufactured by Avecia) were stirred and mixed. Liquid.
透明樹脂基材に帝人デュポン社製ポリエチレンテレフタレートフィルムを使用した。♯１６のバーコータで塗工液を塗布し、１００℃で３０秒の熱乾燥の後、１２０Ｗ／ｃｍのメタルハライドランプで１０秒照射して硬化膜を得た。得られた硬化膜の性能評価を表１に示した。 A polyethylene terephthalate film manufactured by Teijin DuPont was used as the transparent resin substrate. The coating solution was applied with a # 16 bar coater, dried at 100 ° C. for 30 seconds, and then irradiated with a 120 W / cm metal halide lamp for 10 seconds to obtain a cured film. Table 1 shows the performance evaluation of the obtained cured film.
［実施例２］
メチルエチルケトンに分散した濃度４０％のＡＴＯ分散液１０重量部、フタロシアニン錯体（Ａｖｅｃｉａ社製 商品名ＰＲＯＪＥＴ９００ＮＰ）１重量部を混合した液にバインダーＡ液３９重量部を加えて攪拌、混合して熱線遮蔽ハードコート液とした。
[Example 2]
Heat ray shielding hard by adding 39 parts by weight of binder A liquid to a liquid obtained by mixing 10 parts by weight of an ATO dispersion having a concentration of 40% dispersed in methyl ethyl ketone and 1 part by weight of a phthalocyanine complex (trade name PROJET900NP manufactured by Avecia). A coating solution was obtained.
該塗工液を用いて、実施例１と同様にして硬化膜を得た。得られた硬化膜の性能評価を表１に示した。 Using the coating solution, a cured film was obtained in the same manner as in Example 1. Table 1 shows the performance evaluation of the obtained cured film.
［実施例３］
メチルエチルケトンに分散した濃度４０％のＩＴＯ分散液６５重量部とジチオレン錯体（みどり化学社製 商品名ＭＩＲ−１０１）１重量部を攪拌、混合した液にＡ液２５重量部を加えて攪拌し、熱線遮蔽ハードコート液とした。該塗工液を用いて、実施例１と同様にして硬化膜を得た。得られた硬化膜の性能評価を表１に示した。
[Example 3]
65 parts by weight of ITO dispersion having a concentration of 40% dispersed in methyl ethyl ketone and 1 part by weight of a dithiolene complex (trade name MIR-101, manufactured by Midori Chemical Co., Ltd.) are stirred and mixed. A shielding hard coat solution was obtained. Using the coating solution, a cured film was obtained in the same manner as in Example 1. Table 1 shows the performance evaluation of the obtained cured film.
［実施例４］
メチルエチルケトンに分散した濃度４０％のＩＴＯ分散液６５重量部とフタロシアニン錯体（日本触媒社製 商品名ＴＸ−ＥＸ−９１０Ｂ）１重量部、トルエンに分散した濃度１．８５％の６ホウ化物微粒子分散液（住友金属鉱山社製 商品名ＫＨＦ−７Ａ）３重量部を攪拌、混合した液にＡ液２５重量部を加えて攪拌し、熱線遮蔽ハードコート液とした。該塗工液を用いて、実施例１と同様にして硬化膜を得た。得られた硬化膜の性能評価を表１に示した。
[Example 4]
65 parts by weight of ITO dispersion having a concentration of 40% dispersed in methyl ethyl ketone and 1 part by weight of a phthalocyanine complex (trade name TX-EX-910B manufactured by Nippon Shokubai Co., Ltd.), 1.85% concentration of hexaboride fine particle dispersion dispersed in toluene (Product name KHF-7A, manufactured by Sumitomo Metal Mining Co., Ltd.) 3 parts by weight was stirred and mixed, and A part 25 parts by weight was added and stirred to obtain a heat ray shielding hard coat liquid. Using the coating solution, a cured film was obtained in the same manner as in Example 1. Table 1 shows the performance evaluation of the obtained cured film.
［実施例５］
メチルエチルケトンに分散した濃度４０％のＩＴＯ分散液１５．４重量部とジチオレン錯体（みどり化学社製 商品名ＭＩＲ−１０１）０．５重量部、トルエンに分散した濃度１．８５％の６ホウ化物微粒子分散液（住友金属鉱山社製 商品名ＫＨＦ−７Ａ）３．７重量部を攪拌、混合した液にＡ液３０．８重量部を加えて攪拌し、熱線遮蔽ハードコート液とした。該塗工液を用いて、実施例１と同様にして硬化膜を得た。得られた硬化膜の性能評価を表１に示した。
[Example 5]
15.4 parts by weight of ITO dispersion having a concentration of 40% dispersed in methyl ethyl ketone, 0.5 part by weight of a dithiolene complex (trade name MIR-101, manufactured by Midori Chemical Co., Ltd.), hexaboride fine particles having a concentration of 1.85% dispersed in toluene A dispersion (Sumitomo Metal Mining Co., Ltd., trade name KHF-7A) of 3.7 parts by weight was stirred and mixed, and 30.8 parts by weight of Liquid A was added and stirred to obtain a heat ray shielding hard coat liquid. Using the coating solution, a cured film was obtained in the same manner as in Example 1. Table 1 shows the performance evaluation of the obtained cured film.
［実施例６］
メチルエチルケトンに分散した濃度４０％のＡＴＯ分散液９．４重量部とジチオレン錯体（みどり化学社製 商品名ＭＩＲ−１０１）０．６重量部、トルエンに分散した濃度１．８５％の６ホウ化物微粒子分散液（住友金属鉱山社製 商品名ＫＨＦ−７Ａ）１．５重量部を攪拌、混合した液にＡ液３９重量部を加えて攪拌し、熱線遮蔽ハードコート液とした。該塗工液を用いて、実施例１と同様にして硬化膜を得た。得られた硬化膜の性能評価を表１に示した。
[Example 6]
9.4 parts by weight of ATO dispersion having a concentration of 40% dispersed in methyl ethyl ketone and 0.6 part by weight of a dithiolene complex (trade name MIR-101, manufactured by Midori Chemical Co., Ltd.), hexaboride fine particles having a concentration of 1.85% dispersed in toluene The dispersion (Sumitomo Metal Mining Co., Ltd., trade name KHF-7A) 1.5 parts by weight was stirred and mixed, and 39 parts by weight of Liquid A was added and stirred to obtain a heat ray shielding hard coat liquid. Using the coating solution, a cured film was obtained in the same manner as in Example 1. Table 1 shows the performance evaluation of the obtained cured film.
Claims (4)
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| CN104479436A (en) * | 2014-11-28 | 2015-04-01 | 张家港康得新光电材料有限公司 | Peelable glue coating composition and peelable glue coating as well as preparation method and application of peelable glue coating |
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