JP6932965B2 - Resin composition, manufacturing method of resin composition, molded body and vehicle parts - Google Patents
Resin composition, manufacturing method of resin composition, molded body and vehicle parts Download PDFInfo
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Description
本発明は、樹脂組成物、樹脂組成物の製造方法、成形体及び車両用部品に関する。 The present invention relates to a resin composition, a method for producing a resin composition, a molded product, and vehicle parts.
ポリメチルメタクリレートやポリカーボネートは、優れた透明性や寸法安定性から、光学材料、車両用部品、照明用材料、建築用材料等、様々な分野で幅広く用いられている。
近年、ポリメチルメタクリレートやポリカーボネートの成形体は、部品の薄肉化や細密化に伴い、より高性能化が求められている。その性能として、耐熱性と金型からの離型性が挙げられる。特に、テールランプやヘッドランプ等の車両用部品は、高温で金型成形された後、自動車等の車両が高温多湿下でも用いられるため、より優れた耐熱性と金型からの離型性が求められている。
Polymethylmethacrylate and polycarbonate are widely used in various fields such as optical materials, vehicle parts, lighting materials, and building materials because of their excellent transparency and dimensional stability.
In recent years, molded products of polymethylmethacrylate and polycarbonate are required to have higher performance as parts become thinner and finer. Its performance includes heat resistance and mold releasability. In particular, vehicle parts such as tail lamps and headlamps are required to have better heat resistance and mold releasability because vehicles such as automobiles are used even under high temperature and high humidity after being molded at high temperature. Has been done.
しかしながら、ポリメチルメタクリレートは、優れた透明性や耐候性を有するものの、耐熱性や金型からの離型性が十分ではなかった。また、ポリカーボネートは、優れた耐熱性や耐衝撃性を有するものの、光学的歪みである複屈折率が大きく成形体に光学的異方性が生じる、また、成形加工性や耐傷性や耐油性に著しく劣る。 However, although polymethylmethacrylate has excellent transparency and weather resistance, its heat resistance and mold releasability are not sufficient. In addition, although polycarbonate has excellent heat resistance and impact resistance, it has a large birefringence, which is an optical strain, and causes optical anisotropy in the molded product, and also has excellent molding processability, scratch resistance, and oil resistance. Remarkably inferior.
そのため、ポリメチルメタクリレートに代表されるアクリル樹脂の金型からの離型性と耐熱性を改善する検討が行われている。例えば、特許文献１には、離型性を改善するため、ステアリン酸や、ステアリン酸金属塩などの高級脂肪酸及びその金属塩を使用する方法が提案されているが、耐熱性が十分ではなかった。特許文献２には、耐熱性を改善するため、メチルメタクリレート単位とメタクリル酸単位とグルタル酸無水物単位を有する樹脂組成物が提案されている。 Therefore, studies have been conducted to improve the mold releasability and heat resistance of acrylic resins typified by polymethylmethacrylate. For example, Patent Document 1 proposes a method of using a higher fatty acid such as stearic acid or a metal stearic acid salt and a metal salt thereof in order to improve the releasability, but the heat resistance is not sufficient. .. Patent Document 2 proposes a resin composition having a methyl methacrylate unit, a methacrylic acid unit, and a glutaric anhydride unit in order to improve heat resistance.
しかしながら、特許文献２で提案されている樹脂組成物は、高温成形時にポリマー中のメタクリル酸残基と多官能離型剤が反応して一部架橋構造を形成し、流動性の低下を引き起こす。 However, in the resin composition proposed in Patent Document 2, the methacrylic acid residue in the polymer reacts with the polyfunctional release agent during high-temperature molding to form a partially crosslinked structure, which causes a decrease in fluidity.
そこで、本発明の目的は、耐熱性、離型性、流動性に優れた樹脂組成物を提供することにある。また、本発明の目的は、得られる樹脂組成物の耐熱性、離型性、流動性に優れる樹脂組成物の製造方法を提供することにある。 Therefore, an object of the present invention is to provide a resin composition having excellent heat resistance, releasability, and fluidity. Another object of the present invention is to provide a method for producing a resin composition having excellent heat resistance, releasability, and fluidity of the obtained resin composition.
（１）メチル（メタ）アクリレート単位（Ａ１）及び（メタ）アクリル酸単位（Ａ２）を含む共重合体（Ａ）と、官能基が１つの有機物である離型剤（Ｂ）とを含む、樹脂組成物。
（２）官能基が１つの有機物である離型剤（Ｂ）の官能基が、カルボニル基、ヒドロキシル基、カルボキシル基、アミノ基、アミド基からなる群より選ばれる少なくとも１種である、前記の樹脂組成物。
（３）官能基が１つの有機物である離型剤（Ｂ）の分子量が、１００〜５００である、前記の樹脂組成物。
（４）官能基が１つの有機物である離型剤（Ｂ）が、ステアリン酸、パルチミン酸、ベヘニン酸、モンタン酸、ステアリルアルコール、ステアルアミド、流動パラフィンおよびワックスからなる群より選ばれる少なくとも１種である、前記の樹脂組成物。
（５）官能基が１つの有機物である離型剤（Ｂ）の含有量が、共重合体（Ａ）１００質量部に対して、０．０１〜１質量部である、前記の樹脂組成物。
（６）共重合体（Ａ）が、更に、無水グルタル酸単位（Ａ３）を含む、前記の樹脂組成物。
（７）共重合体（Ａ）を構成する単位において、メチル（メタ）アクリレート単位（Ａ１）が８０ｍｏｌ％以上、（メタ）アクリル酸由来の繰り返し単位（Ａ２）が１ｍｏｌ％〜１５ｍｏｌ％、及び無水グルタル酸単位（Ａ３）が５ｍｏｌ％以下である、前記の樹脂組成物。
（８）下記式（１’）で示すグルタル酸無水物単位（Ａ３）への変換率が、０．１％〜３０％である、前記の樹脂組成物。
グルタル酸無水物単位（Ａ３）への変換率（％）＝｛［共重合体中のグルタル酸無水物単位（Ａ３）の割合（ｍｏｌ％）］／（［共重合体中の（メタ）アクリル酸単位（Ａ２）の割合（ｍｏｌ％）］＋［共重合体中のグルタル酸無水物単位（Ａ３）の割合（ｍｏｌ％）］）｝×１００・・・（１’）
(1) include methyl (meth) acrylate unit (A1) and (meth) copolymers containing acrylic acid units (A2) and (A), releasing agent functional group is one organics and (B) , Resin composition.
(2) the functional group of the functional group releasing agent is one organic (B) is at least one carbonyl group, a hydroxyl group, a carboxyl group, an amino group, selected from the group consisting of an amide group, wherein Resin composition.
(3) The above-mentioned resin composition, wherein the release agent (B), which is an organic substance having one functional group, has a molecular weight of 100 to 500.
(4) At least one mold release agent (B) having one functional group selected from the group consisting of stearic acid, palmitic acid, behenic acid, montanic acid, stearyl alcohol, stealamide, liquid paraffin and wax. The above-mentioned resin composition.
(5) The above-mentioned resin composition in which the content of the release agent (B), which is an organic substance having one functional group, is 0.01 to 1 part by mass with respect to 100 parts by mass of the copolymer (A). thing.
(6) The above-mentioned resin composition, wherein the copolymer (A) further contains a glutaric anhydride unit (A3).
(7) Among the units constituting the copolymer (A), the methyl (meth) acrylate unit (A1) is 80 mol% or more, the repeating unit (A2) derived from (meth) acrylic acid is 1 mol% to 15 mol%, and anhydrous. The resin composition having a glutaric acid unit (A3) of 5 mol% or less.
(8) The resin composition described above, wherein the conversion rate to the glutaric acid anhydride unit (A3) represented by the following formula (1') is 0.1% to 30%.
Conversion rate to glutaric acid anhydride unit (A3) (%) = {[Ratio of glutaric acid anhydride unit (A3) in copolymer (mol%)] / ([(Meta) acrylic in copolymer Ratio of acid unit (A2) (mol%)] + [Ratio of glutaric anhydride unit (A3) in copolymer (mol%)])} × 100 ... (1')
（９）メチル（メタ）アクリレート（ａ１）及び（メタ）アクリル酸（ａ２）を含む単量体を重合して前駆体を得て、得られた前駆体と官能基が１つ以下の有機物である離型剤（Ｂ）とを溶融混練する、樹脂組成物の製造方法。
（１０）重合方法が、懸濁重合である、前記の樹脂組成物の製造方法。
（１１）官能基が１つ以下の離型剤（Ｂ）の含有量が、前駆体１００質量部に対して、０．０１〜１質量部である、前記の樹脂組成物の製造方法。
（１２）溶融混練温度が、１５０℃〜２７０℃である、前記の樹脂組成物の製造方法。
(9) A precursor is obtained by polymerizing a monomer containing methyl (meth) acrylate (a1) and (meth) acrylic acid (a2), and the obtained precursor and an organic substance having one or less functional groups are used. A method for producing a resin composition, in which a certain mold release agent (B) is melt-kneaded.
(10) The method for producing the above-mentioned resin composition, wherein the polymerization method is suspension polymerization.
(11) The method for producing a resin composition, wherein the content of the release agent (B) having one or less functional groups is 0.01 to 1 part by mass with respect to 100 parts by mass of the precursor.
(12) The method for producing a resin composition, wherein the melt-kneading temperature is 150 ° C to 270 ° C.
（１３）前記の樹脂組成物を成形した成形体。
（１４）前記の成形体を含む車両用部品。
(13) A molded product obtained by molding the above resin composition.
(14) Vehicle parts including the molded body.
（１５）メチル（メタ）アクリレート単位（Ａ１）及び（メタ）アクリル酸単位（Ａ２）を含む共重合体であり、下記条件（２’）を満たす樹脂組成物
積分分子量分布より求めた２５０℃、１時間加熱後のｌｏｇ［２Ｍｗ］以上の割合％／積分分子量分布より求めた加熱前のｌｏｇ［２Ｍｗ］以上の割合％≦１．５・・・（２’）
(15) A resin composition which is a copolymer containing a methyl (meth) acrylate unit (A1) and a (meth) acrylic acid unit (A2) and satisfies the following condition (2').
Ratio% of log [2Mw] or more after heating at 250 ° C. for 1 hour obtained from the integrated molecular weight distribution / Ratio% of log [2Mw] or more before heating obtained from the integrated molecular weight distribution% ≤ 1.5 ... (2') )
本発明の樹脂組成物は、耐熱性、離型性、流動性に優れる。
また、本発明の樹脂組成物の製造方法は、得られる樹脂組成物の耐熱性、離型性、流動性に優れる。
更に、本発明の成形体は、耐熱性、離型性、流動性に優れる。
The resin composition of the present invention is excellent in heat resistance, mold releasability, and fluidity.
In addition, the method for producing a resin composition of the present invention is excellent in heat resistance, mold releasability, and fluidity of the obtained resin composition.
Further, the molded product of the present invention is excellent in heat resistance, mold releasability, and fluidity.
本発明の樹脂組成物における共重合体（Ａ）は、メチル（メタ）アクリレート単位（Ａ１）及び（メタ）アクリル酸単位（Ａ２）（以下、単に「単位（Ａ１）」、「単位（Ａ２）」ということがある。）を含む。 Copolymer in the resin composition of the present invention (A) are methyl (meth) acrylate unit (A1) and (meth) acrylic acid unit (A2) (hereinafter, simply "unit (A1)", "unit (A2 ) ”Is included.)
単位（Ａ１）及び単位（Ａ２）を含む共重合体中の単位（Ａ１）の含有率は、共重合体１００ｍｏｌ％中、８０ｍｏｌ％以上９９ｍｏｌ％以下がより好ましく、９０ｍｏｌ％以上９８ｍｏｌ％以下が更に好ましい。単位（Ａ１）の含有率が８０ｍｏｌ％以上であると、特に、外観、低吸水性、成形性の観点で、アクリル樹脂本来の性能を損なわない。また、単位（Ａ１）の含有率が９９ｍｏｌ％以下であると、共重合体の耐熱性、機械特性に優れる。
尚、本明細書において、共重合体中の各単位の含有率は、１Ｈ−ＮＭＲ測定から算出した値とする。
The content of the unit (A1) in the copolymer containing the unit (A1) and the unit (A2) is more preferably 80 mol% or more and 99 mol% or less, and further preferably 90 mol% or more and 98 mol% or less in 100 mol% of the copolymer. preferable. When the content of the unit (A1) is 80 mol% or more, the original performance of the acrylic resin is not impaired, particularly from the viewpoint of appearance, low water absorption, and moldability. Further, when the content of the unit (A1) is 99 mol% or less, the heat resistance and mechanical properties of the copolymer are excellent.
In the present specification, the content of each unit in the copolymer is a value calculated from 1 1 H-NMR measurement.
単位（Ａ１）及び単位（Ａ２）を含む共重合体中の単位（Ａ２）の含有率は、共重合体１００ｍｏｌ％中、０．４５ｍｏｌ％以上７ｍｏｌ％以下が好ましく、０．５ｍｏｌ％以上６ｍｏｌ％以下がより好ましい。単位（Ａ２）の含有率が０．４５ｍｏｌ％以上であると、共重合体の耐熱性、機械特性に優れる。また、単位（Ａ２）の含有率が７ｍｏｌ％以下であると、特に、外観、低吸水性、成形性の観点で、アクリル樹脂本来の性能を損なわない。 The content of the unit (A2) in the copolymer containing the unit (A1) and the unit (A2) is preferably 0.45 mol% or more and 7 mol% or less, and 0.5 mol% or more and 6 mol% in 100 mol% of the copolymer. The following is more preferable. When the content of the unit (A2) is 0.45 mol% or more, the heat resistance and mechanical properties of the copolymer are excellent. Further, when the content of the unit (A2) is 7 mol% or less, the original performance of the acrylic resin is not impaired, particularly from the viewpoint of appearance, low water absorption and moldability.
本発明に記載の離型剤とは、金型成形後に金型から剥離しやすくするために添加する成分である。
離型剤（Ｂ）は官能基が１つ以下の有機物である。すなわち官能基が１つ及び官能基が無い有機物の内の少なくともいずれかである。中でも官能基が１つの有機物であることがより好ましい。官能基が１つ以下であると、溶融混練や溶融成形の際に共重合体（Ａ）の反応性官能基との架橋反応による高分子量化が起こらず、流動性が低下しない。ここで言う官能基としては、特に限定されないが例えばカルボニル基、ヒドロキシル基、カルボキシル基、アミノ基、アミド基などが挙げられる。
The mold release agent described in the present invention is a component added to facilitate peeling from the mold after molding the mold.
The release agent (B) is an organic substance having one or less functional groups. That is, it is at least one of an organic substance having one functional group and no functional group. Above all, it is more preferable that the functional group is one organic substance. When the number of functional groups is one or less, the copolymer (A) does not increase in molecular weight due to the cross-linking reaction with the reactive functional group during melt kneading or melt molding, and the fluidity does not decrease. The functional group referred to here is not particularly limited, and examples thereof include a carbonyl group, a hydroxyl group, a carboxyl group, an amino group, and an amide group.
離型剤（Ｂ）の分子量は１００〜５００が好ましく、２００〜４００がより好ましい。分子量が１００より大きいと揮発性が低いため、金型クモリに対して十分な効果が得られる。一方、分子量が５００より小さいとメタクリル樹脂との相溶性が高いため、離型時に金型への残存が少なく、金型汚れ、成形品のクモリが発生しにくい。 The molecular weight of the release agent (B) is preferably 100 to 500, more preferably 200 to 400. When the molecular weight is larger than 100, the volatility is low, so that a sufficient effect can be obtained on the mold spider. On the other hand, when the molecular weight is smaller than 500, the compatibility with the methacrylic resin is high, so that the residue on the mold is small at the time of mold release, and the mold is less likely to be soiled and the molded product is less likely to become cloudy.
官能基が１つの有機物である離型剤（Ｂ）としては例えば、ステアリン酸、パルチミン酸、ベヘニン酸、モンタン酸およびその塩、そのエステル、そのハーフエステル、ステアリルアルコール、ステアルアミドが挙げられる。官能基が無い離型剤（Ｂ）としては例えば、ワックス、流動パラフィンなどが挙げられる。これらを単独で、又は組み合わせて使用することができる。 Examples of the release agent (B) in which the functional group is an organic substance include stearic acid, partiminic acid, behenic acid, montanic acid and salts thereof, esters thereof, half esters thereof, stearyl alcohol, and stealamide . Examples of the release agent (B) having no functional group include wax and liquid paraffin. These can be used alone or in combination.
離型剤（Ｂ）の含有量は、共重合体（Ａ）１００質量部に対して、０．０１〜１質量部が好ましく、０．１〜０．３質量部がより好ましい。含有量が０．０１質量部より多いと離型性が向上し、１質量部より少ないと添加剤のブリードによる金型汚染の影響が少ない。 The content of the release agent (B) is preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.3 parts by mass with respect to 100 parts by mass of the copolymer (A). If the content is more than 0.01 part by mass, the releasability is improved, and if it is less than 1 part by mass, the influence of mold contamination due to the bleeding of the additive is small.
単位（Ａ１）、単位（Ａ２）及び無水グルタル酸単位（Ａ３）（以下、単に「単位（Ａ３）」ということがある。）を含む共重合体中の単位（Ａ３）の含有率は、共重合体１００ｍｏｌ％中、０．００１ｍｏｌ％以上０．２５ｍｏｌ％以下が好ましく、０．００１ｍｏｌ％以上０．１５ｍｏｌ％以下がより好ましい。単位（Ａ３）の含有率が０．００１ｍｏｌ％以上であると、共重合体の耐熱性、機械特性に優れる。また、単位（Ａ３）の含有率が０．２５ｍｏｌ％以下であると、特に、外観、低吸水性、成形性の観点で、アクリル樹脂本来の性能を損なわない。 The content of the unit (A3) in the copolymer including the unit (A1), the unit (A2) and the glutaric anhydride unit (A3) (hereinafter, may be simply referred to as "unit (A3)") is the same. Of the 100 mol% of the polymer, 0.001 mol% or more and 0.25 mol% or less is preferable, and 0.001 mol% or more and 0.15 mol% or less is more preferable. When the content of the unit (A3) is 0.001 mol% or more, the heat resistance and mechanical properties of the copolymer are excellent. Further, when the content of the unit (A3) is 0.25 mol% or less, the original performance of the acrylic resin is not impaired, particularly from the viewpoint of appearance, low water absorption and moldability.
無水グルタル酸単位（Ａ３）への変換率（％）は、下記式（１’）より得ることができる。
無水グルタル酸単位（Ａ３）への変換率（％）＝｛［共重合体中の無水グルタル酸単位（Ａ３）の割合（ｍｏｌ％）］／（［共重合体中の（メタ）アクリル酸単位（Ａ２）の割合（ｍｏｌ％）］＋［共重合体中の無水グルタル酸単位（Ａ３）の割合（ｍｏｌ％）］）｝×１００・・・（１’）
無水グルタル酸単位（Ａ３）への変換率は、０．１％以上５％以下が好ましく、０．１％以上３％以下がより好ましい。無水グルタル酸単位（Ａ３）への変換率が０．１％以上であると、共重合体の耐熱性に優れる。また、無水グルタル酸単位（Ａ３）への変換率が５％以下であると、特に、外観の観点で、アクリル樹脂本来の性能を損なわない。
The conversion rate (%) to the glutaric anhydride unit (A3) can be obtained from the following formula (1').
Conversion rate to glutaric anhydride unit (A3) (%) = {[Ratio of glutaric anhydride unit (A3) in copolymer (mol%)] / ([(Meta) acrylic acid unit in copolymer (A2) ratio (mol%)] + [ratio of glutaric anhydride unit (A3) in copolymer (mol%)])} × 100 ... (1')
The conversion rate to the glutaric anhydride unit (A3) is preferably 0.1% or more and 5% or less, and more preferably 0.1% or more and 3% or less. When the conversion rate to the glutaric anhydride unit (A3) is 0.1% or more, the heat resistance of the copolymer is excellent. Further, when the conversion rate to the glutaric anhydride unit (A3) is 5% or less, the original performance of the acrylic resin is not impaired, especially from the viewpoint of appearance.
単位（Ａ１）８０ｍｏｌ％以上、単位（Ａ２）０．４５ｍｏｌ％以上７ｍｏｌ％以下及び単位（Ａ３）０．００１ｍｏｌ％以上０．２５ｍｏｌ％以下を含む共重合体を得るには、メチル（メタ）アクリレート（ａ１）８０ｍｏｌ％以上及び（メタ）アクリル酸（ａ２）０．７ｍｏｌ％以上７ｍｏｌ％以下を含む単量体混合物を重合して前駆体を得て、得られた前駆体を押出機等により加熱溶融混練し、前駆体中の単位（Ａ１）と単位（Ａ２）を反応させ、単位（Ａ３）を形成させればよい。 To obtain a copolymer containing 80 mol% or more of the unit (A1), 0.45 mol% or more and 7 mol% or less of the unit (A2), and 0.001 mol% or more and 0.25 mol% or less of the unit (A3), methyl (meth) acrylate A monomer mixture containing (a1) 80 mol% or more and (meth) acrylic acid (a2) 0.7 mol% or more and 7 mol% or less is polymerized to obtain a precursor, and the obtained precursor is heated by an extruder or the like. The unit (A1) and the unit (A2) in the precursor may be reacted by melt-kneading to form the unit (A3).
加熱温度は、２００℃以上２７０℃以下が好ましく、２１０℃以上２６０℃以下がより好ましい。加熱温度が２００℃以上であると、共重合体の流動性に優れ、共重合体や樹脂組成物の生産性に優れる。また、加熱温度が２７０℃以下であると、共重合体の熱劣化を抑制することができる。 The heating temperature is preferably 200 ° C. or higher and 270 ° C. or lower, and more preferably 210 ° C. or higher and 260 ° C. or lower. When the heating temperature is 200 ° C. or higher, the fluidity of the copolymer is excellent, and the productivity of the copolymer and the resin composition is excellent. Further, when the heating temperature is 270 ° C. or lower, thermal deterioration of the copolymer can be suppressed.
加熱時間は、１秒以上２４００秒以下が好ましく、５秒以上１８００秒以下がより好ましく、１０秒以上１２００秒以下が更に好ましい。加熱時間が１秒以上であると、共重合体や樹脂組成物を十分混合することができる。また、加熱時間が２４００秒以下であると、共重合体の熱劣化を抑制することができる。 The heating time is preferably 1 second or more and 2400 seconds or less, more preferably 5 seconds or more and 1800 seconds or less, and further preferably 10 seconds or more and 1200 seconds or less. When the heating time is 1 second or more, the copolymer and the resin composition can be sufficiently mixed. Further, when the heating time is 2400 seconds or less, the thermal deterioration of the copolymer can be suppressed.
本発明の共重合体は、単位（Ａ１）、単位（Ａ２）、単位（Ａ３）以外にも、他の単量体単位（Ａ４）（以下、単に「単位（Ａ４）」ということがある。）を含んでもよい。 In addition to the unit (A1), the unit (A2), and the unit (A3), the copolymer of the present invention may be referred to as another monomer unit (A4) (hereinafter, simply "unit (A4)". ) May be included.
単位（Ａ４）の含有率は、樹脂組成物がアクリル樹脂本来の性能を損なわないことから、共重合体１００ｍｏｌ％中、１５ｍｏｌ％以下が好ましく、５ｍｏｌ％以下がより好ましい。 The content of the unit (A4) is preferably 15 mol% or less, more preferably 5 mol% or less, based on 100 mol% of the copolymer, because the resin composition does not impair the original performance of the acrylic resin.
単位（Ａ４）を構成する単量体としては、例えば、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、グリシジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、テトラシクロドデカニル（メタ）アクリレート、シクロヘキサンジメタノールモノ（メタ）アクリレート等の（メタ）アクリレート類；スチレン、α−メチルスチレン等の芳香族ビニル単量体等が挙げられる。 Examples of the monomer constituting the unit (A4) include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and sec. -Butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate , Tridecyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, etc. (Meta) Acrylates; Examples thereof include aromatic vinyl monomers such as styrene and α-methylstyrene.
メチル（メタ）アクリレートは、メチルメタクリレート、メチルアクリレート又はその両者をいう。
メチル（メタ）アクリレート（ａ１）の中でも、共重合体の外観、機械特性に優れることから、メチルメタクリレートが主成分であることが好ましい。また、共重合体の耐熱分解性を向上させる観点で、メチルアクリレートをメチルメタクリレートと共に用いることがより好ましい。
単位（Ａ１）も同様に、共重合体の外観、機械特性に優れることから、メチルメタクリレート単位が主成分であることが好ましい。また、共重合体の耐熱分解性を向上させる観点で、メチルアクリレート単位がメチルメタクリレート単位と共に含まれることがより好ましい。
Methyl (meth) acrylate refers to methyl methacrylate, methyl acrylate, or both.
Among the methyl (meth) acrylates (a1), it is preferable that methyl methacrylate is the main component because the copolymer is excellent in appearance and mechanical properties. Further, from the viewpoint of improving the thermostable decomposition property of the copolymer, it is more preferable to use methyl acrylate together with methyl methacrylate.
Similarly, the unit (A1) is preferably a methyl methacrylate unit as a main component because it is excellent in appearance and mechanical properties of the copolymer. Further, from the viewpoint of improving the thermostable decomposition property of the copolymer, it is more preferable that the methyl acrylate unit is contained together with the methyl methacrylate unit.
（メタ）アクリル酸は、アクリル酸、メタクリル酸又はその両者をいう。
（メタ）アクリル酸（ａ２）の中でも、共重合体の耐熱性に優れることから、メタクリル酸が好ましい。
単位（Ａ２）も同様に、共重合体の耐熱性に優れることから、メタクリル酸単位が好ましい。
(Meta) acrylic acid refers to acrylic acid, methacrylic acid, or both.
Among the (meth) acrylic acids (a2), methacrylic acid is preferable because the copolymer has excellent heat resistance.
Similarly, the unit (A2) is preferably a methacrylic acid unit because it is excellent in heat resistance of the copolymer.
メチル（メタ）アクリレート（ａ１）及び（メタ）アクリル酸（ａ２）を含む単量体混合物中のメチル（メタ）アクリレート（ａ１）の含有率は、単量体混合物１００ｍｏｌ％中、８０ｍｏｌ％以上が好ましく、８０ｍｏｌ％以上９９．５ｍｏｌ％以下がより好ましく、９０ｍｏｌ％以上９９ｍｏｌ％以下が更に好ましい。メチル（メタ）アクリレート（ａ１）の含有率が８０ｍｏｌ％以上であると、特に、外観、低吸水性、成形性の観点で、アクリル樹脂本来の性能を損なわない。また、メチル（メタ）アクリレート（ａ１）の含有率が９９．５ｍｏｌ％以下であると、共重合体の耐熱性、機械特性に優れる。 The content of methyl (meth) acrylate (a1) in the monomer mixture containing methyl (meth) acrylate (a1) and (meth) acrylic acid (a2) is 80 mol% or more in 100 mol% of the monomer mixture. It is preferable that 80 mol% or more and 99.5 mol% or less is more preferable, and 90 mol% or more and 99 mol% or less is further preferable. When the content of the methyl (meth) acrylate (a1) is 80 mol% or more, the original performance of the acrylic resin is not impaired, particularly from the viewpoint of appearance, low water absorption and moldability. Further, when the content of methyl (meth) acrylate (a1) is 99.5 mol% or less, the heat resistance and mechanical properties of the copolymer are excellent.
メチル（メタ）アクリレート（ａ１）及び（メタ）アクリル酸（ａ２）を含む単量体混合物中の（メタ）アクリル酸（ａ２）の含有率は、単量体混合物１００ｍｏｌ％中、０．７ｍｏｌ％以上７ｍｏｌ％以下が好ましく、１ｍｏｌ％以上６ｍｏｌ％以下がより好ましい。（メタ）アクリル酸（ａ２）の含有率が０．７ｍｏｌ％以上であると、共重合体の耐熱性、機械特性に優れる。また、（メタ）アクリル酸（ａ２）の含有率が７ｍｏｌ％以下であると、特に、外観、低吸水性、成形性の観点で、アクリル樹脂本来の性能を損なわない。 The content of (meth) acrylic acid (a2) in the monomer mixture containing methyl (meth) acrylate (a1) and (meth) acrylic acid (a2) was 0.7 mol% in 100 mol% of the monomer mixture. More than 7 mol% is preferable, and 1 mol% or more and 6 mol% or less is more preferable. When the content of (meth) acrylic acid (a2) is 0.7 mol% or more, the heat resistance and mechanical properties of the copolymer are excellent. Further, when the content of the (meth) acrylic acid (a2) is 7 mol% or less, the original performance of the acrylic resin is not impaired, particularly from the viewpoint of appearance, low water absorption and moldability.
単量体混合物は、メチル（メタ）アクリレート（ａ１）、（メタ）アクリル酸（ａ２）以外にも、他の単量体（ａ４）を含んでもよい。
他の単量体（ａ４）は、メチル（メタ）アクリレート（ａ１）、（メタ）アクリル酸（ａ２）と共重合が可能なものであればよい。
The monomer mixture may contain other monomers (a4) in addition to methyl (meth) acrylate (a1) and (meth) acrylic acid (a2).
The other monomer (a4) may be any one capable of copolymerizing with methyl (meth) acrylate (a1) and (meth) acrylic acid (a2).
他の単量体（ａ４）の含有率は、樹脂組成物がアクリル樹脂本来の性能を損なわないことから、単量体混合物１００ｍｏｌ％中、１５ｍｏｌ％以下が好ましく、５ｍｏｌ％以下がより好ましい。 The content of the other monomer (a4) is preferably 15 mol% or less, more preferably 5 mol% or less, based on 100 mol% of the monomer mixture, because the resin composition does not impair the original performance of the acrylic resin.
他の単量体（ａ４）としては、例えば、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、グリシジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、テトラシクロドデカニル（メタ）アクリレート、シクロヘキサンジメタノールモノ（メタ）アクリレート等の（メタ）アクリレート類；スチレン、α−メチルスチレン等の芳香族ビニル単量体等が挙げられる。 Examples of the other monomer (a4) include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl. (Meta) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (Meta) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (Meta) such as norbornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, etc. ) Acrylates; examples include aromatic vinyl monomers such as styrene and α-methylstyrene.
単量体混合物の重合方法としては、例えば、塊状重合、溶液重合、懸濁重合、乳化重合等が挙げられる。これらの単量体混合物の重合方法の中でも、単量体混合物の反応効率に優れることから、塊状重合、溶液重合、懸濁重合が好ましい。 Examples of the polymerization method of the monomer mixture include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like. Among these polymerization methods of the monomer mixture, bulk polymerization, solution polymerization and suspension polymerization are preferable because the reaction efficiency of the monomer mixture is excellent.
単量体混合物の重合において、重合温度、重合開始剤種類、重合開始剤量等は、重合方法や得ようとする共重合体に応じて、適宜設定すればよい。 In the polymerization of the monomer mixture, the polymerization temperature, the type of the polymerization initiator, the amount of the polymerization initiator and the like may be appropriately set according to the polymerization method and the copolymer to be obtained.
共重合体（Ａ）の質量平均分子量は、５０，０００以上１５０，０００以下であり、７０，０００以上１３０，０００以下が好ましい。共重合体の質量平均分子量が５０，０００以上であると、共重合体の機械特性に優れる。また、共重合体の質量平均分子量が１５０，０００以下であると、共重合体の流動性に優れる。
尚、本明細書において、質量平均分子量は、標準試料として標準ポリスチレンを用い、ゲルパーミエーションクロマトグラフィーを用いて測定した値とする。
The mass average molecular weight of the copolymer (A) is 50,000 or more and 150,000 or less, preferably 70,000 or more and 130,000 or less. When the mass average molecular weight of the copolymer is 50,000 or more, the mechanical properties of the copolymer are excellent. Further, when the mass average molecular weight of the copolymer is 150,000 or less, the fluidity of the copolymer is excellent.
In the present specification, the mass average molecular weight is a value measured by using standard polystyrene as a standard sample and using gel permeation chromatography.
前記共重合体の質量平均分子量を制御するためには、単量体混合物の重合において連鎖移動剤の量を調整することが好ましい。
単量体混合物の重合における連鎖移動剤の含有量は、所望の共重合体の質量平均分子量とすることができることから、単量体混合物１００質量部に対して、０．１質量部以上０．５質量部以下が好ましく、０．１５質量部以上０．４質量部以下がより好ましい。
In order to control the mass average molecular weight of the copolymer, it is preferable to adjust the amount of the chain transfer agent in the polymerization of the monomer mixture.
Since the content of the chain transfer agent in the polymerization of the monomer mixture can be set to the mass average molecular weight of the desired copolymer, 0.1 parts by mass or more and 0 parts by mass or more with respect to 100 parts by mass of the monomer mixture. It is preferably 5 parts by mass or less, and more preferably 0.15 parts by mass or more and 0.4 parts by mass or less.
前記共重合体のビカット軟化温度は、１１５℃以上が好ましく、また１２５℃以下が好ましい。共重合体のビカット軟化温度が１１５℃以上であると、共重合体の耐熱性に優れる。また、共重合体のビカット軟化温度が１２５℃以下であると、共重合体の流動性に優れる。
尚、本明細書において、ビカット軟化温度は、ＩＳＯ３０６のＡ５０法に準拠して測定した値とする。
The Vicat softening temperature of the copolymer is preferably 115 ° C. or higher, and preferably 125 ° C. or lower. When the Vicat softening temperature of the copolymer is 115 ° C. or higher, the heat resistance of the copolymer is excellent. Further, when the Vicat softening temperature of the copolymer is 125 ° C. or lower, the fluidity of the copolymer is excellent.
In this specification, the Vicat softening temperature is a value measured according to the A50 method of ISO306.
本発明の樹脂組成物は、前記共重合体を含む。 The resin composition of the present invention contains the above-mentioned copolymer.
本発明の樹脂組成物は、前記共重合体以外に、他の添加剤を含んでもよい。
他の添加剤としては、例えば、紫外線吸収剤、酸化防止剤、可塑剤、光拡散剤、艶消剤、滑剤、帯電防止剤、顔料等の着色剤等が挙げられる。これらの他の添加剤は、１種を単独で用いてもよく、２種以上を併用してもよい。
日光等の紫外線による共重合体の劣化を抑制することから、樹脂組成物中に紫外線吸収剤を含むことが好ましい。
溶融混練や溶融成形の際に共重合体の熱劣化を抑制することから、樹脂組成物中に酸化防止剤を含むことが好ましい。
The resin composition of the present invention may contain other additives in addition to the copolymer.
Examples of other additives include ultraviolet absorbers, antioxidants, plasticizers, light diffusing agents, matting agents, lubricants, antistatic agents, colorants such as pigments, and the like. These other additives may be used alone or in combination of two or more.
It is preferable to include an ultraviolet absorber in the resin composition because it suppresses deterioration of the copolymer due to ultraviolet rays such as sunlight.
It is preferable to include an antioxidant in the resin composition because it suppresses thermal deterioration of the copolymer during melt kneading and melt molding.
共重合体と他の添加剤とを混合する方法としては、例えば、二軸押出機等の装置を用いて溶融混練する方法等が挙げられる。また、前駆体と他の添加剤とを加熱溶融混練し、単位（Ａ３）を形成させて共重合体を得ると共に、他の添加剤と混合してもよい。 Examples of the method of mixing the copolymer and other additives include a method of melt-kneading using an apparatus such as a twin-screw extruder. Further, the precursor and other additives may be heat-melted and kneaded to form a unit (A3) to obtain a copolymer, and may be mixed with other additives.
本発明の成形体は、本発明の樹脂組成物を成形して得られる。 The molded product of the present invention is obtained by molding the resin composition of the present invention.
成形体を得るための成形方法としては、例えば、射出成形、押出成形、加圧成形等が挙げられる。また、得られた成形体を、更に圧空成形や真空成形等の二次成形してもよい。 Examples of the molding method for obtaining a molded body include injection molding, extrusion molding, pressure molding and the like. Further, the obtained molded product may be further subjected to secondary molding such as compressed air molding or vacuum molding.
成形温度は、２００℃以上２７０℃以下が好ましく、２１０℃以上２６０℃以下がより好ましい。成形温度が２００℃以上であると、樹脂組成物の流動性に優れ、成形体の外観に優れる。また、成形温度が２７０℃以下であると、共重合体の熱劣化を抑制することができる。 The molding temperature is preferably 200 ° C. or higher and 270 ° C. or lower, and more preferably 210 ° C. or higher and 260 ° C. or lower. When the molding temperature is 200 ° C. or higher, the fluidity of the resin composition is excellent and the appearance of the molded product is excellent. Further, when the molding temperature is 270 ° C. or lower, thermal deterioration of the copolymer can be suppressed.
成形時間は、３０秒以上１２００秒以下が好ましく、４５秒以上９００秒以下がより好ましく、６０秒以上６００秒以下が更に好ましい。成形時間が３０秒以上であると、樹脂組成物の流動性に優れ、成形体の外観に優れる。また、成形時間が１２００秒以下であると、共重合体の熱劣化を抑制することができる。 The molding time is preferably 30 seconds or more and 1200 seconds or less, more preferably 45 seconds or more and 900 seconds or less, and further preferably 60 seconds or more and 600 seconds or less. When the molding time is 30 seconds or more, the fluidity of the resin composition is excellent and the appearance of the molded body is excellent. Further, when the molding time is 1200 seconds or less, the thermal deterioration of the copolymer can be suppressed.
本発明の成形体は、耐熱性、機械特性、外観に優れることから、光学材料、車両用部品、照明用材料、建築用材料等に用いることができ、特に、自動車の車両用部品に好適である。
自動車の車両用部品としては、例えば、リアランプアウターカバー、リアランプ内部の光学部材、ヘッドライト用のインナーレンズ（プロジェクターレンズやＰＥＳレンズと称される場合がある）、メーターカバー、ドアミラーハウジング、ピラーカバー（サッシュカバー）、ライセンスガーニッシュ、フロントグリル、フォグガーニッシュ、エンブレム等が挙げられる。
Since the molded product of the present invention is excellent in heat resistance, mechanical properties, and appearance, it can be used for optical materials, vehicle parts, lighting materials, building materials, etc., and is particularly suitable for automobile vehicle parts. be.
Examples of automobile vehicle parts include a rear lamp outer cover, an optical member inside the rear lamp, an inner lens for headlights (sometimes referred to as a projector lens or a PES lens), a meter cover, a door mirror housing, and a pillar cover ( Sash cover), licensed garnish, front grill, fog garnish, emblem, etc.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
（共重合体中の各単位の含有率）
実施例・比較例で得られた共重合体及び重ジメチルスルホキシドを、撹拌子を備えた２０ｍｌのシュレンク管に供給し、撹拌しながら８０℃に加熱し、共重合体を溶解させた。その後、２３℃まで冷却し、ベンジルアミンをシュレンク管に供給し、撹拌しながら８０℃に加熱した。１時間反応させた後、反応溶液を抜き取り、核磁気共鳴装置（ｖａｒｉａｎ社製、２７０ＭＨｚ）を用い、測定温度８０℃、積算回数３２回の条件で、１Ｈ−ＮＭＲ測定を行った。
得られた１Ｈ−ＮＭＲ測定結果から、３．７ｐｐｍ付近に存在するシングレットピークの未反応ベンジルアミンのベンジルプロトンの積分値と、４．２ｐｐｍ付近に存在するシングレットピークのグルタル酸ベンジルアミドのベンジルプロトンの積分値との比から、共重合体中の単位（Ａ３）の含有率を算出した。また、３．５ｐｐｍ付近に存在するシングレットピークの単位（Ａ１）由来のプロトンの積分値、０．５ｐｐｍ以上２．５ｐｐｍ以下付近に存在する単位（Ａ１）と単位（Ａ２）由来のプロトンの積分値をそれぞれ、３．７ｐｐｍ付近に存在するシングレットピークの未反応ベンジルアミンのベンジルプロトンの積分値と比をとることで、共重合体中の単位（Ａ１）及び単位（Ａ２）の含有率を算出した。
(Content rate of each unit in the copolymer)
The copolymer and deuterated dimethylsulfoxide obtained in Examples and Comparative Examples were supplied to a 20 ml Schlenk tube equipped with a stirrer and heated to 80 ° C. with stirring to dissolve the copolymer. Then, the mixture was cooled to 23 ° C., benzylamine was supplied to a Schlenk tube, and the mixture was heated to 80 ° C. with stirring. After reacting for 1 hour, the reaction solution was withdrawn, and 1H-NMR measurement was carried out using a nuclear magnetic resonance apparatus (manufactured by Varian, 270 MHz) under the conditions of a measurement temperature of 80 ° C. and an integration frequency of 32 times.
From the obtained 1H-NMR measurement results, the integrated value of the benzyl proton of the unreacted benzylamine of the singlet peak present at around 3.7 ppm and the benzyl proton of the glutaric benzylamide of the singlet peak present at the vicinity of 4.2 ppm. The content of the unit (A3) in the copolymer was calculated from the ratio with the integrated value. In addition, the integrated value of the proton derived from the unit (A1) of the singlet peak existing near 3.5 ppm, and the integrated value of the protons derived from the unit (A1) and the unit (A2) existing near 0.5 ppm or more and 2.5 ppm or less. The content of the unit (A1) and the unit (A2) in the copolymer was calculated by taking the ratio with the integral value of the benzyl proton of the unreacted benzylamine of the singlet peak existing in the vicinity of 3.7 ppm, respectively. ..
（質量平均分子量）
実施例・比較例で得られた共重合体２０ｍｇを、１０ｍｌのテトラヒドロフランに溶解し、０．２μｍメンブレンフィルターで濾過して、試料溶液を得た。得られた試料溶液について、ゲルパーミエーションクロマトグラフィー（機種名「ＨＬＣ−８３２０ ＧＰＣ Ｅｃｏ ＳＥＣ」、東ソー（株）製）を用い、質量平均分子量を測定した。分離カラムとして「ＴＳＫｇｅｌ ＳｕｐｅｒＨＭ−Ｈ」（商品名、東ソー（株）製、内径６．０ｍｍ×長さ１５ｃｍ）を２本直列にしたもの、溶媒としてテトラヒドロフラン、検出器として示差屈折計、標準試料として標準ポリスチレンを用い、流量０．６ｍｌ／分、測定温度４０℃、注入量０．０１ｍｌの条件とした。
(Mass average molecular weight)
20 mg of the copolymer obtained in Examples and Comparative Examples was dissolved in 10 ml of tetrahydrofuran and filtered through a 0.2 μm membrane filter to obtain a sample solution. The mass average molecular weight of the obtained sample solution was measured using gel permeation chromatography (model name "HLC-8320 GPC Eco SEC", manufactured by Tosoh Corporation). Two "TSKgel SuperHM-H" (trade name, manufactured by Toso Co., Ltd., inner diameter 6.0 mm x length 15 cm) in series as a separation column, tetrahydrofuran as a solvent, differential refractometer as a detector, and a standard sample. Using standard polystyrene, the conditions were a flow rate of 0.6 ml / min, a measurement temperature of 40 ° C., and an injection volume of 0.01 ml.
（流動性）
実施例・比較例で得られた樹脂組成物の質量平均分子量（Ｍｗ）および積分分子量分布を、ゲルパーミエーションクロマトグラフィーを用い、測定した。次に、実施例・比較例で得られた樹脂組成物を、２５０℃に加熱した乾燥機（機種名「ＤＲＶ３２０ＤＡ」、アドバンテック東洋（株）製）中で１時間加熱した後、ゲルパーミエーションクロマトグラフィーを用い、積分分子量分布を測定した。測定条件は、前記（質量平均分子量）の項に記載している条件と同条件とした。下記式（２’）の条件を満たす樹脂組成物の流動性を「○」、満たさない樹脂組成物のそれを「×」とした。
積分分子量分布より求めた加熱後のｌｏｇ［２Ｍｗ］以上の割合％／積分分子量分布より求めた加熱前のｌｏｇ［２Ｍｗ］以上の割合％≦１．５・・・（２’）
加熱による高分子量体の増加率（式（２’））は、０．８以上１．５以下が好ましく、０．９以上１．１以下がより好ましい。高分子量体の増加率が０．８以上であると、共重合体の熱分解による発泡が抑えられ、外観に優れる。また、高分子量体の増加率が１．５以下であると、流動性に優れる。
(Liquidity)
The mass average molecular weight (Mw) and the integrated molecular weight distribution of the resin compositions obtained in Examples and Comparative Examples were measured using gel permeation chromatography. Next, the resin compositions obtained in Examples and Comparative Examples were heated in a dryer (model name "DRV320DA", manufactured by Advantech Toyo Co., Ltd.) heated to 250 ° C. for 1 hour, and then gel permeation chromatography was performed. The integrated molecular weight distribution was measured using chromatography. The measurement conditions were the same as those described in the above section (mass average molecular weight). The fluidity of the resin composition satisfying the condition of the following formula (2') was designated as "○", and that of the resin composition not satisfying the condition was designated as "x".
Percentage% of log [2Mw] or more after heating obtained from the integrated molecular weight distribution / Percentage% of log [2Mw] or more before heating obtained from the integrated molecular weight distribution% ≤ 1.5 ... (2')
The rate of increase of the high molecular weight substance by heating (formula (2')) is preferably 0.8 or more and 1.5 or less, and more preferably 0.9 or more and 1.1 or less. When the rate of increase of the high molecular weight polymer is 0.8 or more, foaming due to thermal decomposition of the copolymer is suppressed, and the appearance is excellent. Further, when the rate of increase of the high molecular weight substance is 1.5 or less, the fluidity is excellent.
（耐熱性評価）
実施例・比較例で得られた樹脂組成物を、射出成形機（機種名「ＩＳ−１００」、東芝機械（株）製）を用い、成形温度２５０℃、成形時間３６０秒の条件で射出成形し、８０ｍｍ×８ｍｍ×４ｍｍの成形体を得た。得られた８０ｍｍ×８ｍｍ×４ｍｍの成形体を切断し、４０ｍｍ×８ｍｍ×４ｍｍの成形体を得た後、８０℃で１６時間アニールを行い、得られた成形体を耐熱性評価の試験片として用いた。
耐熱性評価として、ＨＤＴ／ＶＩＣＡＴ試験機（機種名「Ｎｏ．１４８−ＨＡＤ ヒートデストーションテスター」、（株）安田精機製作所製）を用い、ＩＳＯ３０６のＡ５０法に準拠し、ビカット軟化温度試験を行い、ビカット軟化温度を測定した。
尚、各共重合体３回ビカット軟化温度試験を行い、その平均値をビカット軟化温度とした。
(Heat resistance evaluation)
The resin composition obtained in Examples and Comparative Examples is injection-molded using an injection molding machine (model name "IS-100", manufactured by Toshiba Machine Co., Ltd.) under the conditions of a molding temperature of 250 ° C. and a molding time of 360 seconds. Then, a molded product having a size of 80 mm × 8 mm × 4 mm was obtained. The obtained 80 mm × 8 mm × 4 mm molded product was cut to obtain a 40 mm × 8 mm × 4 mm molded product, which was then annealed at 80 ° C. for 16 hours, and the obtained molded product was used as a test piece for heat resistance evaluation. Using.
As a heat resistance evaluation, an HDT / VICAT tester (model name "No. 148-HAD heat distortion tester", manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was used to perform a Vicut softening temperature test in accordance with the A50 method of ISO306. , The Vicat softening temperature was measured.
The Vicat softening temperature test was performed three times for each copolymer, and the average value was taken as the Vicat softening temperature.
（離型性評価）
実施例・比較例で得られた樹脂組成物を射出成形機（機種名「ＩＳ−１００」、東芝機械（株）製）を用い、成形温度２５０℃、成形時間３６０秒の条件で射出成形し、１００ｍｍ×５０ｍｍ×２ｍｍの成形体を得た。
いずれも安定的に剥離したものを「○」、剥離し難いものがあったものを「×」と評価した。
(Evaluation of releasability)
The resin composition obtained in Examples and Comparative Examples was injection-molded using an injection molding machine (model name "IS-100", manufactured by Toshiba Machine Co., Ltd.) under the conditions of a molding temperature of 250 ° C. and a molding time of 360 seconds. , A molded product having a size of 100 mm × 50 mm × 2 mm was obtained.
In each case, those that were stably peeled off were evaluated as "○", and those that were difficult to peel off were evaluated as "x".
［製造例０］
脱イオン水９００質量部、メタクリル酸２−スルホエチルナトリウム６０質量部、メタクリル酸カリウム１０質量部及びメチルメタクリレート１２質量部を、撹拌機、温度計及び冷却管を備えたフラスコに供給し、窒素を放流しながら、フラスコの内温が５０℃になるよう加熱した。その後、２，２’−アゾビス（２−メチルプロピオンアミジン）二塩酸塩０．０８質量部を供給し、フラスコの内温が６０℃になるよう加熱した。その後、滴下ポンプを用いて、メチルメタクリレートを０．２４質量部／分の速度で７５分間滴下した。その後、６時間保持し、分散剤（固形分１０質量％）を得た。
[Manufacturing Example 0]
900 parts by mass of deionized water, 60 parts by mass of 2-sulfoethyl sodium methacrylate, 10 parts by mass of potassium methacrylate and 12 parts by mass of methyl methacrylate were supplied to a flask equipped with a stirrer, a thermometer and a cooling tube to add nitrogen. While discharging, the flask was heated so that the internal temperature of the flask was 50 ° C. Then, 0.08 parts by mass of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was supplied, and the flask was heated so that the internal temperature of the flask was 60 ° C. Then, using a dropping pump, methyl methacrylate was added dropwise at a rate of 0.24 parts by mass / min for 75 minutes. Then, it was held for 6 hours to obtain a dispersant (solid content 10% by mass).
［製造例１］
脱イオン水２０００質量部及び硫酸ナトリウム４．２質量部を、攪拌機、温度計、冷却管及び窒素ガス導入管を備えたセパラブルフラスコに供給し、３２０ｒｐｍの撹拌速度で１５分間撹拌した。その後、メチルメタクリレート（９５ｍｏｌ％）（商品名「アクリエステルＭ」、三菱レイヨン（株）製）１３３９．４質量部、メタクリル酸（５ｍｏｌ％）６０．６質量部、２，２’−アゾビス−２−メチルブチロニトリル（重合開始剤、商品名「Ｖ−５９」、和光純薬工業（株）製）２．８質量部、ｎ−オクチルメルカプタン（連鎖移動剤、東京化成工業（株）製）４．２質量部（単量体合計１００質量部に対する含有量が０．３質量部）及びステアリン酸２．８質量部（単量体合計１００質量部に対する含有量が０．２質量部）をセパラブルフラスコに供給し、５分間撹拌した。その後、製造例０で製造した分散剤６．７２質量部をセパラブルフラスコに供給し、撹拌し、セパラブルフラスコ中の単量体混合物を水中に分散させた。その後、窒素ガスを１５分間放流した。
その後、セパラブルフラスコの内温が７５℃になるよう加熱し、重合発熱ピークが観測されるまでその温度を保持した。重合発熱ピークが観測された後、セパラブルフラスコの内温が９０℃になるよう加熱し、６０分間保持し、重合を完了させた。その後、セパラブルフラスコ内の混合物を濾過し、濾過物を脱イオン水で洗浄し、８０℃で１６時間乾燥し、ビーズ状の前駆体（１）を得た。
[Manufacturing Example 1]
2000 parts by mass of deionized water and 4.2 parts by mass of sodium sulfate were supplied to a separable flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas introduction tube, and stirred at a stirring rate of 320 rpm for 15 minutes. After that, methyl methacrylate (95 mol%) (trade name "Acryester M", manufactured by Mitsubishi Rayon Co., Ltd.) 1339.4 parts by mass, methacrylic acid (5 mol%) 60.6 parts by mass, 2,2'-azobis-2. -Methylbutyronitrile (polymerization initiator, trade name "V-59", manufactured by Wako Pure Chemical Industries, Ltd.) 2.8 parts by mass, n-octyl mercaptan (chain transfer agent, manufactured by Tokyo Kasei Kogyo Co., Ltd.) 4.2 parts by mass (content for 100 parts by mass of total monomer is 0.3 parts by mass) and 2.8 parts by mass of stearate (content for 100 parts by mass of total monomer is 0.2 parts by mass) It was fed into a separable flask and stirred for 5 minutes. Then, 6.72 parts by mass of the dispersant produced in Production Example 0 was supplied to the separable flask and stirred to disperse the monomer mixture in the separable flask in water. Then, nitrogen gas was discharged for 15 minutes.
Then, the temperature of the separable flask was heated to 75 ° C., and the temperature was maintained until the peak of heat generation of polymerization was observed. After the polymerization exothermic peak was observed, the flask was heated so that the internal temperature of the separable flask was 90 ° C. and held for 60 minutes to complete the polymerization. Then, the mixture in the separable flask was filtered, the filtrate was washed with deionized water, and dried at 80 ° C. for 16 hours to obtain a beaded precursor (1).
［製造例２〜４］
単量体混合物中のメチル（メタ）アクリレート（ａ１）、（メタ）アクリル酸（ａ２）の含有率及びステアリン酸（離型剤）を表１のように無添加またはリケマールＳ−１００Ａ（離型剤、理研ビタミン（株）製）に変更したこと以外は製造例１と同様の操作を行い、ビーズ状の前駆体（２）〜（４）を得た。
[Manufacturing Examples 2 to 4]
The content of methyl (meth) acrylate (a1) and (meth) acrylic acid (a2) in the monomer mixture and stearic acid ( release agent ) were not added as shown in Table 1 or Rikemar S-100A (release). The same operation as in Production Example 1 was carried out except that the agent was changed to RIKEN Vitamin Co., Ltd.) to obtain beaded precursors (2) to (4).
[実施例１]
得られたビーズ状の前駆体（１）を、二軸混練押出機（Ｗｅｒｎｅｒ＆Ｐｆｌｅｉｄｅｒｅｒ社製、３０ｍｍφ）を用い、混練温度２５０℃、混練時間６０秒で溶融混練し、グルタル酸無水物単位（Ａ３）を形成させ、ペレット状の樹脂組成物を得た。
[Example 1]
The obtained bead-shaped precursor (1) was melt-kneaded using a twin-screw kneading extruder (manufactured by Werner & Pfleiderer, 30 mmφ) at a kneading temperature of 250 ° C. and a kneading time of 60 seconds. Was formed to obtain a pellet-shaped resin composition.
[比較例１〜３]
用いる前駆体を前駆体（２）〜（４）とすること以外は実施例１と同様の操作を行い、ペレット状の樹脂組成物を得た。
得られた樹脂組成物の評価結果を、表２に示す。
[Comparative Examples 1 to 3]
The same operation as in Example 1 was carried out except that the precursors used were the precursors (2) to (4), to obtain a pellet-shaped resin composition.
The evaluation results of the obtained resin composition are shown in Table 2.
実施例１で得られた樹脂組成物は、耐熱性、離型性、流動性に優れた。
一方、比較例１で得られた樹脂組成物は、離型性に劣り、比較例２で得られた樹脂組成物は、加熱後に高分子量化しており流動性に劣った。また、比較例３で得られた樹脂組成物は、耐熱性に劣った。
The resin composition obtained in Example 1 was excellent in heat resistance, releasability, and fluidity.
On the other hand, the resin composition obtained in Comparative Example 1 was inferior in releasability, and the resin composition obtained in Comparative Example 2 had a high molecular weight after heating and was inferior in fluidity. Moreover, the resin composition obtained in Comparative Example 3 was inferior in heat resistance.
本発明の成形体は、耐熱性、離型性、流動性、機械特性、外観、低吸水性、成形性に優れることから、光学材料、車両用部品、照明用材料、建築用材料等に用いることができ、特に、自動車等の車両用部品に好適である。 Since the molded body of the present invention is excellent in heat resistance, mold releasability, fluidity, mechanical properties, appearance, low water absorption, and moldability, it is used for optical materials, vehicle parts, lighting materials, building materials, and the like. It can be used, and is particularly suitable for vehicle parts such as automobiles.
Claims (16)
共重合体（Ａ）が、更に、無水グルタル酸単位（Ａ３）を含み、
官能基が１つの有機物である離型剤（Ｂ）の官能基が、カルボキシル基、アミノ基、アミド基からなる群より選ばれる少なくとも１種である、樹脂組成物。 A copolymer (A) containing 80 mol% or more of a methyl (meth) acrylate unit (A1) and 1 mol% to 15 mol% of a (meth) acrylic acid unit (A2), and a release agent (B) in which a functional group is an organic substance. ) And
The copolymer (A) further comprises a glutaric anhydride unit (A3).
A resin composition in which the functional group of the release agent (B), which is an organic substance having one functional group, is at least one selected from the group consisting of a carboxyl group, an amino group, and an amide group.
グルタル酸無水物単位（Ａ３）への変換率（％）＝｛［共重合体中のグルタル酸無水物単位（Ａ３）の割合（ｍｏｌ％）］／（［共重合体中の（メタ）アクリル酸単位（Ａ２）の割合（ｍｏｌ％）］＋［共重合体中のグルタル酸無水物単位（Ａ３）の割合（ｍｏｌ％）］）｝×１００・・・（１’） The resin composition according to claim 5 or 6 , wherein the conversion rate to the glutaric anhydride unit (A3) represented by the following formula (1') is 0.1% to 30%.
Conversion rate to glutaric acid anhydride unit (A3) (%) = {[Ratio of glutaric acid anhydride unit (A3) in copolymer (mol%)] / ([(Meta) acrylic in copolymer Ratio of acid unit (A2) (mol%)] + [Ratio of glutaric anhydride unit (A3) in copolymer (mol%)])} × 100 ... (1')
積分分子量分布より求めた２５０℃、１時間加熱後のｌｏｇ［２Ｍｗ］以上の割合％／積分分子量分布より求めた加熱前のｌｏｇ［２Ｍｗ］以上の割合％≦１．５・・・（２’） The resin composition according to any one of claims 1 to 7 , which satisfies the following condition (2').
Ratio% of log [2Mw] or more after heating at 250 ° C. for 1 hour obtained from the integrated molecular weight distribution / Ratio% of log [2Mw] or more before heating obtained from the integrated molecular weight distribution% ≤ 1.5 ... (2') )
メチル（メタ）アクリレート（ａ１）及び（メタ）アクリル酸（ａ２）を含む単量体を重合して前駆体を得て、得られた前駆体と官能基が１つの有機物である離型剤（Ｂ）とを溶融混練する、樹脂組成物の製造方法。 The method for producing a resin composition according to any one of claims 1 to 8.
A mold release agent (a release agent in which a precursor and a functional group are one organic substance is obtained by polymerizing a monomer containing methyl (meth) acrylate (a1) and (meth) acrylic acid (a2) to obtain a precursor. A method for producing a resin composition, which is melt-kneaded with B).
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