JP4779994B2 - Thermosetting resin composition and resin molded product thereof - Google Patents
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Description
本発明は、熱硬化性樹脂組成物とその樹脂成形品に関する。 The present invention relates to a thermosetting resin composition and a resin molded product thereof.
住設機器や建材等に用いられているカウンター、浴槽、洗面ボウル、シンク、テーブル等には意匠的に優れた人工大理石が用いられている。現在上市されている人工大理石には、大別すると不飽和ポリエステル樹脂系、アクリル樹脂系、ビニルエステル樹脂系、エポキシ樹脂系がある。このうちエポキシ樹脂系人工大理石については、液状エポキシ樹脂、酸無水物系硬化剤および硬化促進剤からなる配合物に無機充填材を添加してあるいは添加せずに、これら成分を含む樹脂組成物を成形して得る。ここで、無機充填材を添加する場合、通常液状配合物１００重量部に対し２００重量部程度添加するが、得られる樹脂成形品は透明感がなく機械的強度も低い。無機充填材を添加しない場合、得られる成形品が変色、あるいは発泡等が生じたり、表面平滑性が悪い等の問題があった。 Artificial marble with excellent design is used for counters, bathtubs, wash bowls, sinks, tables, etc. used in housing equipment and building materials. Artificial marble currently on the market can be broadly classified into unsaturated polyester resin, acrylic resin, vinyl ester resin, and epoxy resin. Among these, for epoxy resin-based artificial marble, a resin composition containing these components with or without the addition of an inorganic filler to a composition comprising a liquid epoxy resin, an acid anhydride-based curing agent, and a curing accelerator. Obtained by molding. Here, when adding an inorganic filler, about 200 weight part is normally added with respect to 100 weight part of liquid compounds, but the resin molded product obtained does not have transparency and has low mechanical strength. When the inorganic filler is not added, there is a problem that the obtained molded product is discolored or foamed, or the surface smoothness is poor.
以上の問題を解決するために、例えば、エポキシ樹脂と、酸無水物硬化剤と、第４級ホスホニウム塩または二環式アミジン化合物の有機酸塩もしくはこれらの混合物等の硬化促進剤と、ホスファイトを基本骨格に持つものあるいは前記ホスファイトの混合物からなる配合物を着色防止剤とするエポキシ樹脂組成物を用いて成形したものが提案されている（特許文献１参照）。
以上のエポキシ樹脂組成物は、成形時の従来の問題点である、変色、発泡、表面平滑性が悪い等の不具合を解決し、透明感のある意匠性に優れたエポキシ樹脂系人工大理石を実現している。しかしながら、用いる硬化促進剤や着色防止剤の種類、量が限られており、配合の自由度がなく、得られる成形品の用途が限定されるという問題があった。また、十分な機械的強度を有するものではなかった。 The above epoxy resin composition solves problems such as discoloration, foaming and poor surface smoothness, which are conventional problems during molding, and realizes an epoxy resin-based artificial marble with a transparent design and excellent design. is doing. However, there is a problem that the types and amounts of curing accelerators and coloring inhibitors used are limited, there is no degree of freedom in blending, and the use of the resulting molded product is limited. Moreover, it did not have sufficient mechanical strength.
本発明は、以上の通りの事情に鑑みてなされたものであり、硬化促進剤として第４級ホスホニウム塩または二環式アミジン化合物の有機酸塩もしくはこれらの混合物に限定されず、機械的強度を低下させることなく、発泡を抑え、表面平滑性に優れた、透明感のある樹脂成形品とするための熱硬化性樹脂組成物を提供することを課題としている。 The present invention has been made in view of the circumstances as described above, and is not limited to a quaternary phosphonium salt or an organic acid salt of a bicyclic amidine compound or a mixture thereof as a curing accelerator, and has a mechanical strength. An object of the present invention is to provide a thermosetting resin composition that suppresses foaming and is excellent in surface smoothness and has a transparent feeling without lowering.
本発明は、上記の課題を解決するために、以下のことを特徴としている。 The present invention is characterized by the following in order to solve the above problems.
第１に、本発明のエポキシ樹脂系人工大理石用熱硬化性樹脂組成物は、熱硬化性樹脂、硬化剤、硬化促進剤およびチクソ性付与剤を必須成分として含有し、充填材を含有せず、チクソトロビーインデックス（ＴＩ値）が１．１以上で、粘度が温度２５℃において１００００ｍＰａ・ｓ以下である熱硬化性樹脂組成物であって、前記熱硬化性樹脂が透明性を有するエポキシ樹脂である。 1stly, the thermosetting resin composition for epoxy resin type artificial marble of this invention contains a thermosetting resin, a hardening | curing agent, a hardening accelerator, and a thixotropy imparting agent as an essential component, and does not contain a filler. An epoxy resin having a thixotropic index (TI value) of 1.1 or more and a viscosity of 10,000 mPa · s or less at a temperature of 25 ° C. , wherein the thermosetting resin has transparency. It is .
第２に、本発明のエポキシ樹脂系人工大理石用熱硬化性樹脂組成物は、熱硬化性樹脂、硬化剤、硬化促進剤、チクソ性付与剤および充填材を必須成分として含有し、チクソトロビーインデックス（ＴＩ値）が１．１以上で、粘度が温度２５℃において１００００ｍＰａ・ｓ以下である熱硬化性樹脂組成物であって、前記熱硬化性樹脂が透明性を有するエポキシ樹脂であり、前記充填材は、前記熱硬化性樹脂と前記硬化剤と前記硬化促進剤との配合物１００重量部に対して１００重量部以下の範囲で含有されている。 Secondly, the thermosetting resin composition for epoxy resin-based artificial marble of the present invention contains a thermosetting resin, a curing agent, a curing accelerator, a thixotropic agent and a filler as essential components, and thixotropic lobby. A thermosetting resin composition having an index (TI value) of 1.1 or more and a viscosity of 10,000 mPa · s or less at a temperature of 25 ° C., wherein the thermosetting resin is a transparent epoxy resin, The filler is contained in the range of 100 parts by weight or less with respect to 100 parts by weight of the blend of the thermosetting resin, the curing agent, and the curing accelerator .
第３に、上記のエポキシ樹脂系人工大理石用熱硬化性樹脂組成物において、前記充填材は、水酸化アルミニウム、シリカまたはガラスフリットである。
第４に、上記のエポキシ樹脂系人工大理石用熱硬化性樹脂組成物において、前記硬化剤は、ヘキサヒドロ無水フタル酸またはメチルヘキサヒドロ無水フタル酸である。
第５に、本発明のエポキシ樹脂系人工大理石は、上記のエポキシ樹脂系人工大理石用熱硬化性樹脂組成物が加熱硬化されてなるものとする。
Third, in the above thermosetting resin composition for epoxy resin-based artificial marble, the filler is aluminum hydroxide, silica or glass frit.
Fourth, in the above-mentioned thermosetting resin composition for epoxy resin-based artificial marble, the curing agent is hexahydrophthalic anhydride or methylhexahydrophthalic anhydride.
Fifth, the epoxy resin-based artificial marble of the present invention is obtained by heat-curing the above-mentioned thermosetting resin composition for epoxy resin-based artificial marble .
上記第１−４の発明によれば、第４級ホスホニウム塩または二環式アミジン化合物の有機酸塩もしくはこれらの混合物の硬化促進剤に限定されず、機械的強度を低下させることなく、発泡を抑え、表面平滑性に優れた、透明感のあるものとすることができる。 According to the 1-4 of the invention is not limited to curing accelerator quaternary phosphonium salt or a bicyclic amidine compound organic acid salts or mixtures of these, without reducing the mechanical strength, the foam It is possible to suppress, to have excellent surface smoothness and to have a transparent feeling.
上記第２の発明によれば、より一層曲げ弾性率を向上させることができる。 According to the second aspect, the flexural modulus can be further improved.
以上の顕著な効果は、上記第５の発明のエポキシ樹脂系人工大理石として実現できる。 The above remarkable effects can be realized as the epoxy resin-based artificial marble of the fifth invention.
本発明は前記のとおりの特徴をもつものであるが、以下に、本発明を実施するための最良の形態を説明する。 The present invention has the features as described above, and the best mode for carrying out the present invention will be described below.
本発明の熱硬化性樹脂組成物は、前記のとおり、熱硬化性樹脂と硬化剤と硬化促進剤との配合物にチクソ性付与剤を必須成分として添加し、得られる熱硬化性樹脂組成物のＴＩ値を１．１以上に調整するとともに、熱硬化性樹脂組成物の粘度を温度２５℃において１００００ｍＰａ・ｓ以下としている。このチクソ性付与剤は、無機系のものあるいは有機系のものであってもよく、特に制限されるものではない。無機系のチクソ性付与剤としては、微粉シリカ系やベントナイト系等が挙げられるが透明性の点から微粉シリカ系が好ましい。有機系のチクソ性付与剤としては、ひまし油系やポリアマイド系が使用できる。チクソ性付与剤の添加量としては、熱硬化性樹脂、硬化剤、硬化促進剤の種類や量によって異なり、得られる熱硬化性樹脂組成物のＴＩ値が１．１以上で、かつ粘度が温度２５℃において１００００ｍＰａ・ｓ以下となるように適宜に設定される。例えば、後述する実施例では、熱硬化性樹脂としてビスフェノールＡジグリシジルエーテル型エポキシ樹脂が１００重量部、酸無水物硬化剤としてメチルヘキサヒドロ無水フタル酸が９３重量部、硬化促進剤として２エチル４メチルイミダゾールが２重量部の配合物に、チクソ性付与剤として微粉シリカの添加量を６重量部添加して、ＴＩ値を２．５、温度２５℃における粘度を５０００ｍＰａ・ｓとしている。 As described above, the thermosetting resin composition of the present invention is a thermosetting resin composition obtained by adding a thixotropic agent as an essential component to a blend of a thermosetting resin, a curing agent, and a curing accelerator. Is adjusted to 1.1 or more, and the viscosity of the thermosetting resin composition is 10000 mPa · s or less at a temperature of 25 ° C. The thixotropic agent may be inorganic or organic and is not particularly limited. Examples of the inorganic thixotropic agent include fine silica and bentonite, but fine silica is preferred from the viewpoint of transparency. As the organic thixotropic agent, castor oil or polyamide can be used. The addition amount of the thixotropic agent varies depending on the type and amount of the thermosetting resin, the curing agent, and the curing accelerator, the TI value of the obtained thermosetting resin composition is 1.1 or more, and the viscosity is the temperature. It is appropriately set so as to be 10,000 mPa · s or less at 25 ° C. For example, in the examples described later, 100 parts by weight of a bisphenol A diglycidyl ether type epoxy resin as a thermosetting resin, 93 parts by weight of methylhexahydrophthalic anhydride as an acid anhydride curing agent, and 2 ethyl 4 as a curing accelerator. 6 parts by weight of finely divided silica as a thixotropic agent is added to a composition containing 2 parts by weight of methylimidazole, the TI value is 2.5, and the viscosity at a temperature of 25 ° C. is 5000 mPa · s.
上記チクソ性付与剤を添加することにより、ぬれ性、流れ性、粘度が変わる。チクソ性付与剤を含有していない、樹脂主体の熱硬化性樹脂組成物は、それを成形材料として注型型を用いて成形すると、成形材料の硬化反応が開始する部分が金型の内壁面から離れた中心付近から開始することになり、引けが発生する。本発明は特に所定の粘度を維持しつつ、チクソ性を付与することで、成形時においてその成形材料が金型に面している表面より硬化を開始させることで、樹脂成形品の表面の発泡を抑えるとともに引けをなくしている。これにより、機械的強度を低下させずに表面平滑性に優れた樹脂成形品を得ることができる。ＴＩ値が１．１未満では、成形時において、いまだ成形材料の硬化反応が開始する部分が型の内壁面から離れた中心付近から開始するため、引けが発生してしまう。ＴＩ値の上限値としては、特に限定するものではないが、一般的にチクソ性が高くなると粘度も高くなって流れ性が悪くなり、これに伴い成形性が悪くなるので、例えば、５程度であることが考慮される。 By adding the thixotropic agent, wettability, flowability, and viscosity change. When a resin-based thermosetting resin composition containing no thixotropic agent is molded using a casting mold as a molding material, the part where the curing reaction of the molding material starts is the inner wall surface of the mold. It will start from the vicinity of the center away from, and close will occur. In particular, the present invention provides a thixotropy while maintaining a predetermined viscosity, and at the time of molding, the molding material starts curing from the surface facing the mold, thereby foaming the surface of the resin molded product. It suppresses and closes are lost. Thereby, the resin molded product excellent in surface smoothness can be obtained, without reducing mechanical strength. If the TI value is less than 1.1, at the time of molding, the part where the curing reaction of the molding material still starts from the vicinity of the center away from the inner wall surface of the mold, so that the shrinkage occurs. The upper limit of the TI value is not particularly limited, but generally, when the thixotropy is increased, the viscosity is also increased and the flowability is deteriorated. It is considered that there is.
なお、ＴＩ値は揺変度と呼ばれるもので、ＪＩＳ Ｋ６９０１に準拠して測定することができる。 Note that the TI value is called a fluctuation degree, and can be measured according to JIS K6901.
本発明は、上記熱硬化性樹脂組成物の粘度が、温度２５℃において１００００ｍＰａ・ｓ以下となるように、各成分の配合量を適宜に設定している。本発明は後述するように無機充填材を配合してもよいが、配合しなくてもチクソ性付与剤を添加することで上記粘度に調整可能である。これにより、透明感のある樹脂成形品を得ることができる。また、上記粘度とすることで、熱硬化性樹脂組成物の注型型への流れ性が良好となる。粘度の下限値は特に限定するものではないが、粘度が低すぎると成形性が悪くなるおそれがあるので、一般的には３０００程度であることが考慮される。温度２５℃における熱硬化性樹脂組成物の粘度が１００００ｍＰａ・ｓを超える場合には、注型型への流れ性が悪くなり、これに伴い成形性が悪くなる。 In the present invention, the blending amount of each component is appropriately set so that the viscosity of the thermosetting resin composition is 10,000 mPa · s or less at a temperature of 25 ° C. In the present invention, an inorganic filler may be blended as described later, but the viscosity can be adjusted by adding a thixotropic agent without blending. Thereby, a transparent resin molded product can be obtained. Moreover, the fluidity | liquidity to the casting type | mold of a thermosetting resin composition becomes favorable by setting it as the said viscosity. The lower limit of the viscosity is not particularly limited, but if the viscosity is too low, the moldability may be deteriorated, so that it is generally considered to be about 3000. When the viscosity of the thermosetting resin composition at a temperature of 25 ° C. exceeds 10,000 mPa · s, the flowability to the casting mold is deteriorated, and the moldability is deteriorated accordingly.
本発明は、熱硬化性樹脂としては、エポキシ樹脂、ポリイミド樹脂、フェノール樹脂、シリコン樹脂、不飽和ポリエステル樹脂、アクリル樹脂、ビニルエステル樹脂等が挙げられる。エポキシ樹脂を用いる場合には、具体的には、汎用のビスフェノールＡジグリシジルエーテルの他、水添ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、環状脂肪族エポキシ樹脂等の透明性を有する樹脂が挙げられる。コスト面を考慮すると、液状ビスフェノールＡジグリシジルエーテルが好適である。また種々の固形エポキシ樹脂や反応性希釈剤を本発明の所定の効果に影響を及ぼさない範囲内で適宜配合することができる。 In the present invention, examples of the thermosetting resin include an epoxy resin, a polyimide resin, a phenol resin, a silicon resin, an unsaturated polyester resin, an acrylic resin, and a vinyl ester resin. In the case of using an epoxy resin, specifically, in addition to general-purpose bisphenol A diglycidyl ether, there are transparent resins such as hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and cyclic aliphatic epoxy resins. Can be mentioned. In view of cost, liquid bisphenol A diglycidyl ether is preferred. Various solid epoxy resins and reactive diluents can be appropriately blended within a range that does not affect the predetermined effects of the present invention.
硬化剤および硬化促進剤は、熱硬化性樹脂に応じて適宜に選択される。例えば、エポキシ樹脂を熱硬化性樹脂として用いたときの硬化剤としては、無水フタル酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水トリメリット酸、無水ピロメリット酸、無水メチルハイミック酸、無水マレイン酸等の酸無水物硬化剤が挙げられる。着色性や耐候性を考慮すると２重結合がないヘキサヒドロ無水フタル酸またはメチルヘキサヒドロ無水フタル酸が好ましい。なお、両者を併用することも可能である。同様に、エポキシ樹脂を熱硬化性樹脂として用いたときの硬化促進剤としては、従来公知の化合物、第３級アミン類や第４級ホスホニウム塩、第４級アンモニウム塩、イミダゾール類、エポキシ−アミンダクト、尿素型アダクト等の潜在性硬化促進剤等が挙げられる。 The curing agent and the curing accelerator are appropriately selected according to the thermosetting resin. For example, curing agents when epoxy resin is used as thermosetting resin include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrotrimellitic anhydride, pyromellitic anhydride Acid anhydride curing agents such as acid, methyl hymic anhydride, and maleic anhydride are listed. In consideration of colorability and weather resistance, hexahydrophthalic anhydride or methylhexahydrophthalic anhydride having no double bond is preferable. In addition, it is also possible to use both together. Similarly, as a curing accelerator when an epoxy resin is used as a thermosetting resin, conventionally known compounds, tertiary amines, quaternary phosphonium salts, quaternary ammonium salts, imidazoles, epoxy-amines are used. Examples thereof include latent curing accelerators such as ducts and urea type adducts.
硬化剤および硬化促進剤の配合量は、熱硬化性樹脂組成物として一般的に用いられている範囲内で適宜に設定することができ、特に限定されるものではない。具体的には、熱硬化性樹脂１００重量部に対して硬化剤５０〜９５重量部、硬化促進剤０．５〜５重量部配合することができる。 The compounding amounts of the curing agent and the curing accelerator can be appropriately set within a range generally used as a thermosetting resin composition, and are not particularly limited. Specifically, 50 to 95 parts by weight of the curing agent and 0.5 to 5 parts by weight of the curing accelerator can be blended with 100 parts by weight of the thermosetting resin.
本発明は、必要に応じて、水酸化アルミニウム、シリカ、ガラスフリット等の充填材を添加してもよい。これにより、得られる樹脂成形品の曲げ弾性率を向上させることができる。その添加量としては、熱硬化性樹脂と硬化剤と硬化促進剤との配合物１００重量部に対して、１００重量部以下の範囲であることが考慮される。１００重量部を超えると、樹脂成形品の曲げ強度が劣り、透明感が損なわれてしまう場合があるので好ましくない。充填材の添加量の下限値としては、特に限定されるものではない。充填材の添加量が少ないほど樹脂成形品の透明感が向上し、曲げ強度が大きくなる傾向にある。なお、充填材の添加量が多ければ、その熱硬化性樹脂組成物の粘度が高くなる傾向にある。 In the present invention, a filler such as aluminum hydroxide, silica, or glass frit may be added as necessary. Thereby, the bending elastic modulus of the resin molded product obtained can be improved. The amount of addition is considered to be in the range of 100 parts by weight or less with respect to 100 parts by weight of the mixture of the thermosetting resin, the curing agent, and the curing accelerator. If it exceeds 100 parts by weight, the bending strength of the resin molded product is inferior and the transparency may be impaired, which is not preferable. It does not specifically limit as a lower limit of the addition amount of a filler. The smaller the amount of filler added, the better the transparency of the resin molded product and the greater the bending strength. In addition, if there is much addition amount of a filler, it exists in the tendency for the viscosity of the thermosetting resin composition to become high.
さらに必要に応じて酸化防止剤や紫外線吸収剤を添加することもできる。 Furthermore, antioxidants and ultraviolet absorbers can be added as necessary.
以上のような熱硬化性樹脂組成物を９０〜１５０℃程度の温度範囲で３０分〜３時間成形することで、目的の樹脂成形品を得ることができる。 By molding the thermosetting resin composition as described above in a temperature range of about 90 to 150 ° C. for 30 minutes to 3 hours, an intended resin molded product can be obtained.
以下に実施例を示し、さらに詳しく説明する。もちろん以下の例によって本発明が限定されることはない。 Hereinafter, examples will be shown and described in more detail. Of course, the present invention is not limited to the following examples.
＜実施例１＞
ビスフェノールＡジグリシジルエーテル型エポキシ樹脂（エポキシ当量１９０）１００重量部、メチルヘキサヒドロ無水フタル酸（酸無水物当量１６０）９３重量部、２エチル４メチルイミダゾ−ル２重量部とチクソ性付与剤として微粉シリカ（比表面積３８０ｍ２／ｇ）６重量部を混合し、減圧脱泡して得られた配合物を、２枚の厚み３ミリのステンレス板で１０ミリのスペーサーを挟んだ注型型に注型した。
<Example 1>
100 parts by weight of a bisphenol A diglycidyl ether type epoxy resin (epoxy equivalent 190), 93 parts by weight of methylhexahydrophthalic anhydride (acid anhydride equivalent 160), 2 parts by weight of 2-ethyl 4-methylimidazole and a thixotropic agent Mixing 6 parts by weight of finely divided silica (specific surface area 380 m 2 / g) and degassing the mixture into a casting mold with a 10 mm spacer sandwiched between two 3 mm thick stainless steel plates Cast.
この注型型を１００℃の熱風乾燥機に６０分、さらに１１０℃に昇温後３０分、さらに１３０℃に昇温後３０分放置し、取り出した後室温にて冷却し脱型して樹脂成形品を得た。この樹脂成形品は、機械的強度（曲げ強度、曲げ弾性率）に問題はなく、透明感が有り変色や発泡の無い表面平滑性の良いものであった。
＜実施例２＞
実施例１の配合物にさらに平均粒径１３ミクロンの結晶シリカを３０重量部添加し混合後減圧脱泡して得られた配合物を、２枚の厚み３ミリのステンレス板で１０ミリのスペーサーを挟んだ注型型に注型した。
This casting mold was left in a 100 ° C hot air dryer for 60 minutes, further raised to 110 ° C for 30 minutes, further raised to 130 ° C for 30 minutes, taken out, cooled at room temperature, demolded, and resin removed. A molded product was obtained. This resin molded article had no problem in mechanical strength (bending strength, flexural modulus), had a transparent feeling, and had good surface smoothness without discoloration or foaming.
<Example 2>
30 parts by weight of crystalline silica having an average particle size of 13 microns was further added to the composition of Example 1, mixed and then degassed under reduced pressure, and a 10 mm spacer was formed using two 3 mm thick stainless steel plates. It was cast into a casting mold that sandwiched it.
この注型型を１００℃の熱風乾燥機に６０分、さらに１１０℃に昇温後３０分、さらに１３０℃に昇温後３０分放置し、取り出した後室温にて冷却し脱型して樹脂成形品を得た。この樹脂成形品は、機械的強度に問題はなく、透明感が有り変色や発泡の無い表面平滑性の良いものであった。
＜比較例１＞
ビスフェノールＡジグリシジルエーテル型エポキシ樹脂（エポキシ当量１９０）１００重量部、メチルヘキサヒドロ無水フタル酸（酸無水物当量１６０）９３重量部、２エチル４メチルイミダゾ−ル２重量部とチクソ性付与剤として微粉シリカ（比表面積３８０ｍ２／ｇ）１重量部を混合し、減圧脱泡して得られた配合物を、２枚の厚み３ミリのステンレス板で１０ミリのスペーサーを挟んだ注型型に注型した。
This casting mold was left in a 100 ° C hot air dryer for 60 minutes, further raised to 110 ° C for 30 minutes, further raised to 130 ° C for 30 minutes, taken out, cooled at room temperature, demolded, and resin removed. A molded product was obtained. This resin molded article had no problem in mechanical strength, had a transparent feeling, and had good surface smoothness without discoloration or foaming.
<Comparative Example 1>
100 parts by weight of a bisphenol A diglycidyl ether type epoxy resin (epoxy equivalent 190), 93 parts by weight of methylhexahydrophthalic anhydride (acid anhydride equivalent 160), 2 parts by weight of 2-ethyl 4-methylimidazole and a thixotropic agent Mixing 1 part by weight of finely divided silica (specific surface area 380 m 2 / g) and degassing the mixture into a casting mold with a 10 mm spacer sandwiched between two 3 mm thick stainless steel plates Cast.
この注型型を１００℃の熱風乾燥機に６０分、さらに１１０℃に昇温後３０分、さらに１３０℃に昇温後３０分放置し，取り出した後室温にて冷却し脱型して樹脂成形品を得た。この樹脂成形品は透明感が有るものの、黄変や発泡が有り、表面平滑性も良くなかった。機械的強度は実施例１と同程度であった。
＜比較例２＞
ビスフェノールＡジグリシジルエーテル型エポキシ樹脂（エポキシ当量１９０）１００重量部、メチルヘキサヒドロ無水フタル酸（酸無水物当量１６０）９３重量部、２エチル４メチルイミダゾ−ル２重量部と平均粒径１０ミクロンの水酸化アルミニウム２５０重量部を混合し減圧脱泡して得られた配合物を、２枚の厚み３ミリのステンレス板で１０ミリのスペーサーを挟んだ注型型に注型した。
This casting mold is left in a hot air dryer at 100 ° C. for 60 minutes, further raised to 110 ° C. for 30 minutes, further raised to 130 ° C. for 30 minutes, taken out, cooled at room temperature, demolded, and resin removed. A molded product was obtained. Although this resin molded product had transparency, it had yellowing and foaming, and the surface smoothness was not good. The mechanical strength was similar to that in Example 1.
<Comparative example 2>
Bisphenol A diglycidyl ether type epoxy resin (epoxy equivalent 190) 100 parts by weight, methylhexahydrophthalic anhydride (acid anhydride equivalent 160) 93 parts by weight, 2 ethyl 4-methylimidazole 2 parts by weight and average particle size 10 microns A mixture obtained by mixing 250 parts by weight of aluminum hydroxide and degassing under reduced pressure was cast into a casting mold having two 10 mm spacers sandwiched between 3 mm thick stainless steel plates.
この注型型を１００℃の熱風乾燥機に６０分、さらに１１０℃に昇温後３０分、さらに１３０℃に昇温後３０分放置し、取り出した後室温にて冷却し脱型して樹脂成形品を得た。この樹脂成形品は変色や発泡も無く表面平滑性も良かったが、透明感が無く、曲げ強度が低かった。 This casting mold was left in a 100 ° C hot air dryer for 60 minutes, further raised to 110 ° C for 30 minutes, further raised to 130 ° C for 30 minutes, taken out, cooled at room temperature, demolded, and resin removed. A molded product was obtained. This resin molded article had no discoloration or foaming and good surface smoothness, but had no transparency and low bending strength.
表１に、実施例と比較例の配合と各種物性の評価結果を示した。 Table 1 shows the composition of Examples and Comparative Examples and the evaluation results of various physical properties.
なお、各種物性は以下のとおり評価した。
配合物粘度（ｍＰａ・ｓ／２５℃）：ビスコテスター ＶＴ５５０（メーカー：リオン）を用いて測定した。
ＴＩ値：ＪＩＳ Ｋ６９０１に準拠して測定した。
透明感：５ｍｍ厚の平板の樹脂成形品を形成し、以下の基準で評価した。
紙面上に樹脂成形品を配し、目視により紙面の印刷を確認し、文字が読めれば「○」、読みづらければ「△」、読めなければ「×」とした。
変色：樹脂成形品を目視により判断した。
発泡：樹脂成形品を目視により判断した。
表面平滑性：上記透明感の評価に使用したサンプルを定盤上に配し、ひけ（熱収縮により発生する凹み）の発生を確認した。
曲げ強度（ＭＰａ）：ＪＩＳ Ｋ７１７１に準拠して測定した。
曲げ弾性率（ＭＰａ）：ＪＩＳ Ｋ７１７１に準拠して測定した。
Various physical properties were evaluated as follows.
Formulation viscosity (mPa · s / 25 ° C.): Measured using a Bisco Tester VT550 (manufacturer: Rion).
TI value: Measured according to JIS K6901.
Transparency: A 5 mm thick flat resin molded product was formed and evaluated according to the following criteria.
A resin molded product was placed on the paper surface, and the printing of the paper surface was confirmed by visual observation. If the character could be read, it was “◯”, if it was difficult to read, “△”, and if it could not be read, “X”.
Discoloration: The resin molded product was judged visually.
Foaming: The resin molded product was judged visually.
Surface smoothness: The sample used for the evaluation of the transparency was placed on a surface plate, and the occurrence of sink marks (dents generated by heat shrinkage) was confirmed.
Bending strength (MPa): Measured according to JIS K7171.
Flexural modulus (MPa): Measured according to JIS K7171.
表１の結果より、熱硬化性樹脂、硬化剤、硬化促進剤とともにチクソ性付与剤を含有し、ＴＩ値が１．１以上で、粘度が温度２５℃において１００００ｍＰａ・ｓ以下である実施例１〜２の樹脂成形品は、いずれも変色や発泡がなく、表面平滑性に優れ透明感があり、機械的強度に問題がないことが確認できた。一方、ＴＩ値が１．１未満の比較例１の樹脂成形品、およびＴＩ値が１．１未満であって、粘度が温度２５℃において１００００ｍＰａ・ｓを超える比較例２の樹脂成形品は、変色や発泡があり表面平滑性に問題があるか、あるいは透明感がなく、曲げ強度が劣ることが確認できた。 From the results in Table 1, Example 1 containing a thixotropic agent together with a thermosetting resin, a curing agent and a curing accelerator, having a TI value of 1.1 or more and a viscosity of 10000 mPa · s or less at a temperature of 25 ° C. It was confirmed that none of the resin molded products of No. 2 had discoloration or foaming, had excellent surface smoothness and transparency, and had no problem in mechanical strength. On the other hand, the resin molded product of Comparative Example 1 having a TI value of less than 1.1 and the resin molded product of Comparative Example 2 having a TI value of less than 1.1 and a viscosity exceeding 10,000 mPa · s at a temperature of 25 ° C. It was confirmed that there was discoloration and foaming and there was a problem in surface smoothness, or there was no transparency and bending strength was inferior.
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