JP2023001307A5

JP2023001307A5 -

Info

Publication number: JP2023001307A5
Application number: JP2022179783A
Authority: JP
Filing date: 2022-11-09
Publication date: 2023-02-16
Anticipated expiration: 2038-10-23

Description

すなわち、本発明は以下のとおりである。
〔１〕
重量平均分子量Ｍｗが７５，０００～２００，０００であるメタクリル系樹脂（Ａ）１００質量部に対し、紫外線吸収剤（Ｂ）を０．０３～０．３質量部、リン酸系安定剤（Ｃ）を０．０３～０．３５質量部、ヒンダードフェノール系安定剤（Ｄ）、及び無機化合物の赤外線吸収剤（Ｅ）を０．０１２～０．０３５質量部含有し、ホスフィン系安定剤を含有しないメタクリル系樹脂組成物を、押出機で混練温度２００～２８０℃で溶融混練することを特徴とする、メタクリル系樹脂組成物の製造方法。
〔２〕
前記無機化合物の赤外線吸収剤（Ｅ）が、タングステン酸化物及び／又は六ホウ化ランタンである、〔１〕に記載のメタクリル系樹脂組成物の製造方法。
〔３〕
前記メタクリル系樹脂（Ａ）１００質量部に対し、前記ヒンダードフェノール系安定剤（Ｄ）を０．０３～０．５質量部含有する、〔１〕又は〔２〕に記載のメタクリル系樹脂組成物の製造方法。
〔４〕
前記紫外線吸収剤（Ｂ）の融点が９０℃以上１３７℃以下であり、前記リン酸系安定剤（Ｃ）の融点が９０℃以上１８０℃以下であり、及び前記ヒンダードフェノール系安定剤（Ｄ）の融点が９０℃以上１１０℃以下である、〔１〕～〔３〕のいずれかに記載に記載のメタクリル系樹脂組成物の製造方法。
〔５〕
〔１〕～〔４〕のいずれかに記載のメタクリル系樹脂組成物の製造方法により得られたメタクリル系樹脂組成物を、２２０～２５０℃で射出成形することを特徴とする、成形体の製造方法。 That is, the present invention is as follows.
[1]
0.03 to 0.3 parts by mass of an ultraviolet absorber (B), a phosphoric acid stabilizer ( C ) of 0.03 to 0.35 parts by mass , a hindered phenol stabilizer (D), and an inorganic compound infrared absorber (E) of 0.012 to 0.035 parts by mass , and a phosphine stabilizer A method for producing a methacrylic resin composition, comprising melt-kneading a methacrylic resin composition containing no methacrylic resin composition with an extruder at a kneading temperature of 200 to 280°C .
[2]
The method for producing a methacrylic resin composition according to [1] , wherein the inorganic infrared absorber (E) is tungsten oxide and/or lanthanum hexaboride.
[3]
The methacrylic resin according to [1] or [2] , which contains 0.03 to 0.5 parts by mass of the hindered phenol stabilizer (D) with respect to 100 parts by mass of the methacrylic resin (A). A method of making the composition.
[4]
The melting point of the ultraviolet absorber (B) is 90° C. or higher and 137° C. or lower , the melting point of the phosphoric acid stabilizer (C) is 90° C. or higher and 180° C. or lower , and the hindered phenol stabilizer (D ) has a melting point of 90 ° C. or higher and 110° C. or lower .
[5]
Production of a molded article, characterized by injection molding a methacrylic resin composition obtained by the method for producing a methacrylic resin composition according to any one of [1] to [4] at 220 to 250°C. Method.

〔実施例、参考例及び比較例において用いた原料〕
〈メタクリル系樹脂（Ａ）の原料〉
メタクリル系樹脂組成物の製造に用いたメタクリル系樹脂（Ａ）の原料は、下記のとおりである。
・メタクリル酸メチル（ＭＭＡ）：旭化成ケミカルズ製（重合禁止剤として中外貿易製２，４－ジメチル－６－ｔ－ブチルフェノールを２．５ｐｐｍ添加されているもの）
・アクリル酸メチル（ＭＡ）：三菱化学製（重合禁止剤として川口化学工業製４－メトキシフェノール（４－ｍｅｔｈｏｘｙｐｈｅｎｏｌ）が１４ｐｐｍ添加されているもの）
・アクリル酸エチル（ＥＡ）：三菱化学製
・ｎ－オクチルメルカプタン：アルケマ製
・ラウロイルパーオキサイド：日本油脂製
・第三リン酸カルシウム：日本化学工業製、懸濁剤として使用
・炭酸カルシウム：白石工業製、懸濁剤として使用
・ラウリル硫酸ナトリウム：和光純薬工業製、懸濁助剤として使用 [Raw materials used in Examples , Reference Examples and Comparative Examples]
<Raw material of methacrylic resin (A)>
The raw materials of the methacrylic resin (A) used in the production of the methacrylic resin composition are as follows.
・ Methyl methacrylate (MMA): manufactured by Asahi Kasei Chemicals (2.5 ppm of 2,4-dimethyl-6-t-butylphenol manufactured by Chugai Boeki is added as a polymerization inhibitor)
- Methyl acrylate (MA): manufactured by Mitsubishi Chemical (with 14 ppm of 4-methoxyphenol manufactured by Kawaguchi Chemical Industry Co., Ltd. added as a polymerization inhibitor)
・Ethyl acrylate (EA): manufactured by Mitsubishi Chemical ・n-octyl mercaptan: manufactured by Arkema ・Lauroyl peroxide: manufactured by NOF ・Calcium tertiary phosphate: manufactured by Nippon Chemical Industry, used as a suspension agent ・Calcium carbonate: manufactured by Shiraishi Kogyo, Used as a suspending agent ・Sodium lauryl sulfate: manufactured by Wako Pure Chemical Industries, used as a suspending aid

＜ＩＩＩ．赤外線吸収能＞
後述する実施例、参考例及び比較例で調製した平板試料の波長１０００ｎｍにおける透過率（％）を、島津製作所製ＵＶ－３１００ＰＣを用いて測定した。波長１０００ｎｍにおける透過率が６０％以下であれば良好な赤外線吸収能を有していると言える。 <III. Infrared Absorption Ability>
The transmittance (%) at a wavelength of 1000 nm of flat plate samples prepared in Examples , Reference Examples , and Comparative Examples, which will be described later, was measured using UV-3100PC manufactured by Shimadzu Corporation. If the transmittance at a wavelength of 1000 nm is 60% or less, it can be said to have a good infrared absorbing ability.

＜ＩＶ．長期耐熱安定性＞
後述する実施例、参考例及び比較例で調製した平板試料について、循環式熱風オーブン中に１００℃で１０００時間静置する前と後での波長１０００ｎｍにおける透過率（％）の変化を、島津製作所製ＵＶ－３１００ＰＣを用いて測定した。波長１０００ｎｍにおける透過率の変化が１５％以内であれば◎（優れる）、１５％超１８％以内であれば〇（良好）、１８％超２１％以内であれば△（可）、２１％超であれば×（不可）とした。透過率の変化が２１％以内であれば、実用上十分な長期耐熱安定性を有していると言える。 <IV. Long-term heat resistance stability>
For flat plate samples prepared in Examples , Reference Examples , and Comparative Examples, which will be described later, changes in transmittance (%) at a wavelength of 1000 nm before and after standing in a circulating hot air oven at 100 ° C. for 1000 hours were measured by Shimadzu Corporation. It was measured using UV-3100PC manufactured by ◎ (excellent) if the change in transmittance at a wavelength of 1000 nm is within 15%; If so, x (impossible). If the change in transmittance is within 21%, it can be said to have practically sufficient long-term heat resistance stability.

＜Ｖ．長期湿熱安定性＞
後述する実施例、参考例及び比較例で調製した平板試料について、エスペック社製恒温恒湿機を用いて温度８０℃、湿度９５％の環境下で１０００時間静置する前と後での波長１０００ｎｍにおける透過率（％）の変化を、島津製作所製ＵＶ－３１００ＰＣを用いて測定した。波長１０００ｎｍにおける透過率の変化が９．０％以内であれば◎（優れる）、９．０％超１０．０％以内であれば〇（良好）、１０．０％超１１．０％以内であれば△（可）、１１．０％超であれば×（不可）とした。透過率の変化が１１．０％未満であれば、実用上十分な長期湿熱安定性を有していると言える。 <V. Long-term wet heat stability>
The flat plate samples prepared in Examples , Reference Examples , and Comparative Examples, which will be described later, were left to stand for 1000 hours in an environment with a temperature of 80 ° C. and a humidity of 95% using a constant temperature and humidity machine manufactured by Espec. Change in transmittance (%) was measured using UV-3100PC manufactured by Shimadzu Corporation. ◎ (excellent) if the change in transmittance at a wavelength of 1000 nm is within 9.0%; If it was, it was evaluated as Δ (acceptable), and if it exceeded 11.0%, it was evaluated as × (impossible). If the change in transmittance is less than 11.0%, it can be said that the film has practically sufficient long-term moist heat stability.

＜ＶＩ．紫外線が当たる屋外環境に対する長期安定性＞
後述する実施例、参考例及び比較例で調製した平板試料について、スガ試験機製サンシャインウェザーメーター（ＳＷＯＭ）中に、照射６３℃で４時間、湿潤（結露）４０℃で４時間の条件で１０００時間連続して試験した平板試料の全光線透過率（％）の変化を、日本電色製１００１ＤＰを用いて測定した。また、波長１０００ｎｍにおける透過率（％）の変化を、島津製作所製ＵＶ－３１００ＰＣを用いて測定した。
全光線透過率の変化が２．０％以内ならば◎（優れる）、２．０％超２．５％以内ならば〇（良好）、２．５％超３．５％以内ならば△（可）、３．５％超は×（不可）とした。
また、波長１０００ｎｍにおける透過率の変化が６％以内ならば◎（優れる）、６％超７％以内ならば〇（良好）、７％超８％以内ならば△（可）、８％超ならば×（不可）とした。
全光線透過率の変化が３．５％以内でかつ、波長１０００ｎｍにおける透過率の変化が８％以内ならば、紫外線が当たる屋外環境に対する実用上十分な長期安定性を有していると言える。 <VI. Long-term stability against outdoor environments exposed to ultraviolet light>
The flat plate samples prepared in Examples , Reference Examples , and Comparative Examples, which will be described later, were placed in a Sunshine Weather Meter (SWOM) manufactured by Suga Test Instruments Co., Ltd. under the conditions of irradiation at 63°C for 4 hours and wetness (condensation) at 40°C for 4 hours for 1000 hours. Changes in the total light transmittance (%) of flat plate samples tested continuously were measured using Nippon Denshoku 1001DP. Also, change in transmittance (%) at a wavelength of 1000 nm was measured using UV-3100PC manufactured by Shimadzu Corporation.
◎ (excellent) if the change in total light transmittance is within 2.0%, ◯ (good) if over 2.0% and within 2.5%, and △ (if over 2.5% and within 3.5%) acceptable), and exceeding 3.5% was x (impossible).
Also, if the change in transmittance at a wavelength of 1000 nm is within 6%, ◎ (excellent), if it is more than 6% and within 7%, it is ◯ (good), if it is more than 7% and less than 8%, it is △ (acceptable), if it exceeds 8%. x (impossible).
If the change in total light transmittance is within 3.5% and the change in transmittance at a wavelength of 1000 nm is within 8%, it can be said that the film has practically sufficient long-term stability against outdoor environments exposed to ultraviolet rays.

〔メタクリル系樹脂組成物〕
後述する実施例、参考例及び比較例で、メタクリル系樹脂組成物の構成成分として用いたメタクリル系樹脂（Ａ）について、以下記載する。 [Methacrylic resin composition]
The methacrylic resin (A) used as a constituent component of the methacrylic resin composition in Examples , Reference Examples and Comparative Examples to be described later is described below.

〔実施例１、２、５、７、９、１１、１２、１４、１５〕〔参考例３、４、６、８、１０、１３、１６～１８〕〔比較例１～５〕
表１に記載の配合割合になるよう、メタクリル系樹脂（Ａ）、紫外線吸収剤（Ｂ）、リン酸系安定剤（Ｃ）、ヒンダードフェノール系安定剤（Ｄ）、赤外線吸収剤（Ｅ）、その他の添加剤をそれぞれ計量した後、ヘンシェルミキサーへ投入し、それらを撹拌によって混合した。十分撹拌によって混合させた後、φ２６ｍｍの二軸押出機にその混合原料を投入し、溶融混練（コンパウンド）してストランドを生成し、ウォーターバスでそのストランドを冷却した後、ペレタイザーで切断してペレットを得た。なお、コンパウンドの際、押出機のベント部に真空ラインを接続し、－０．０６ＭＰａの条件で水分やモノマー成分等の揮発成分を除去した。こうして、メタクリル系樹脂組成物を得た。なお、コンパウンド時の樹脂組成物の樹脂温度は、２５０～２７０℃であった。
なお、表１中の数値は、基材となるメタクリル系樹脂（Ａ）の質量を１００質量部としたときの配合部数（質量部）を表す。
[Examples 1 , 2, 5, 7, 9, 11, 12, 14, 15 ] [Reference Examples 3, 4, 6, 8, 10, 13, 16 to 18] [Comparative Examples 1 to 5]
A methacrylic resin (A), an ultraviolet absorber (B), a phosphoric acid stabilizer (C), a hindered phenol stabilizer (D), and an infrared absorber (E) so as to achieve the mixing ratios shown in Table 1. , and other additives were respectively weighed, put into a Henschel mixer, and mixed by stirring. After sufficiently stirring and mixing, the mixed raw material is put into a φ26 mm twin-screw extruder, melted and kneaded (compounded) to form a strand, cooled in a water bath, and cut with a pelletizer to form pellets. got During compounding, a vacuum line was connected to the vent portion of the extruder to remove volatile components such as moisture and monomer components under the condition of −0.06 MPa. Thus, a methacrylic resin composition was obtained. The resin temperature of the resin composition during compounding was 250 to 270°C.
The numerical values in Table 1 represent the number of parts (parts by mass) to be blended when the mass of the methacrylic resin (A) serving as the base material is 100 parts by mass.

実施例１、２、５、７、９、１１、１２、１４、１５、参考例３、４、６、８、１０、１３、１６～１８、比較例１～５において、良好な赤外線吸収能を達成することが出来た。しかし、比較例１においては、長期屋外環境安定性は良好であったが、ヒンダードフェノール系安定剤（Ｄ）が添加されていないため、長期耐熱安定性、長期湿熱安定性が良好でなかった。比較例２においては、リン酸系安定剤（Ｃ）が添加されていないため、長期耐熱安定性、長期湿熱安定性、長期屋外環境安定性のいずれも良好でなかった。比較例３においては、長期耐熱安定性は良好であったが、紫外線吸収剤（Ｂ）、ヒンダードフェノール系安定剤（Ｄ）、リン酸系安定剤（Ｃ）が添加されていないため、長期湿熱安定性、長期屋外環境安定性が良好でなかった。比較例４においては、長期屋外環境安定性は良好であったが、ヒンダードフェノール系安定剤（Ｄ）、リン酸系安定剤（Ｃ）が添加されていないため、長期耐熱安定性、長期湿熱安定性が良好でなかった。比較例５においては、実用上十分な長期屋外環境安定性有していたが、ヒンダードフェノール系安定剤（Ｄ）が添加されていなかったため、長期耐熱安定性、長期湿熱安定性が良好でなかった。
参考例１０においては、実用上十分ではあるが長期屋外環境安定性が実施例１、２、５、７、９、１１、１２、１４、１５、参考例３、４、６、８、１６～１８に比べやや劣っていた。
参考例１３においては、実用上十分ではあるが長期屋外環境安定性と長期湿熱安定性が、実施例１、２、５、７、９、１１、１２、１４、参考例３、４、６、８、１６～１８に比べやや劣っていた。
実施例１５においては、実用上十分ではあるが長期湿熱特性が実施例１、２、５、７、９、１１、１２、１４、参考例３、４、６、８、１０、１６～１８に比べやや劣っていた。 Good infrared absorption ability was able to achieve However, in Comparative Example 1, long-term outdoor environment stability was good, but long-term heat resistance stability and long-term moist heat stability were not good because the hindered phenol-based stabilizer (D) was not added. . In Comparative Example 2, since the phosphoric acid-based stabilizer (C) was not added, none of long-term heat resistance stability, long-term moist heat stability, and long-term outdoor environment stability was poor. In Comparative Example 3, the long-term heat resistance stability was good, but the ultraviolet absorber (B), the hindered phenol stabilizer (D), and the phosphoric acid stabilizer (C) were not added. Moist heat stability and long-term outdoor environment stability were not good. In Comparative Example 4, the long-term outdoor environmental stability was good, but since the hindered phenol-based stabilizer (D) and the phosphoric acid-based stabilizer (C) were not added, long-term heat resistance stability and long-term wet heat stability Stability was not good. In Comparative Example 5, although it had practically sufficient long-term outdoor environmental stability, since the hindered phenol-based stabilizer (D) was not added, long-term heat resistance stability and long-term wet heat stability were not good. rice field.
In Reference Example 10, although it is practically sufficient , long-term outdoor environmental stability Slightly worse than 18.
In Reference Example 13, although it is practically sufficient, the long-term outdoor environmental stability and long-term moist heat stability are inferior to Examples 1 , 2, 5, 7, 9, 11, 12, 14, Reference Examples 3, 4, 6, It was slightly inferior to 8 and 16-18.
In Example 15, although it is practically sufficient, the long-term moist heat characteristics are inferior to Examples 1 , 2, 5, 7, 9, 11, 12, 14, Reference Examples 3, 4, 6, 8, 10, 16-18. was slightly inferior.

Claims

0.03 to 0.3 parts by mass of an ultraviolet absorber (B), a phosphoric acid stabilizer ( C ) of 0.03 to 0.35 parts by mass , a hindered phenol stabilizer (D), and an inorganic compound infrared absorber (E) of 0.012 to 0.035 parts by mass , and a phosphine stabilizer A method for producing a methacrylic resin composition, comprising melt-kneading a methacrylic resin composition containing no methacrylic resin composition with an extruder at a kneading temperature of 200 to 280°C .

2. The method for producing a methacrylic resin composition according to claim 1 , wherein the inorganic infrared absorber (E) is tungsten oxide and/or lanthanum hexaboride.

3. The methacrylic resin composition according to claim 1 , which contains 0.03 to 0.5 parts by mass of the hindered phenol stabilizer (D) with respect to 100 parts by mass of the methacrylic resin (A). manufacturing method .

The melting point of the ultraviolet absorber (B) is 90° C. or higher and 137° C. or lower , the melting point of the phosphoric acid stabilizer (C) is 90° C. or higher and 180° C. or lower , and the hindered phenol stabilizer (D ) has a melting point of 90 ° C. or higher and 110° C. or lower .

Production of a molded article, characterized in that the methacrylic resin composition obtained by the method for producing a methacrylic resin composition according to any one of claims 1 to 4 is injection molded at 220 to 250 ° C. Method.