JPH0220542A - Light-screening molding - Google Patents

Light-screening molding

Info

Publication number
JPH0220542A
JPH0220542A JP16879088A JP16879088A JPH0220542A JP H0220542 A JPH0220542 A JP H0220542A JP 16879088 A JP16879088 A JP 16879088A JP 16879088 A JP16879088 A JP 16879088A JP H0220542 A JPH0220542 A JP H0220542A
Authority
JP
Japan
Prior art keywords
weight
parts
aromatic vinyl
copolymer
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP16879088A
Other languages
Japanese (ja)
Other versions
JP2793597B2 (en
Inventor
Ketsuo Ookubo
大久保 傑夫
Norio Yagi
則夫 八木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Denka Co Ltd
Original Assignee
Denki Kagaku Kogyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Denki Kagaku Kogyo KK filed Critical Denki Kagaku Kogyo KK
Priority to JP63168790A priority Critical patent/JP2793597B2/en
Publication of JPH0220542A publication Critical patent/JPH0220542A/en
Application granted granted Critical
Publication of JP2793597B2 publication Critical patent/JP2793597B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE:To obtain a light-screening molding of excellent heat resistance and dimensional stability by using a thermoplastic resin containing a specified aromatic vinyl/unsaturated dicarboxylic imide copolymer, a specified graft copolymer and titanium oxide. CONSTITUTION:This light-screening molding is formed of a thermoplastic resin containing 10-80wt.% copolymer containing 35-80wt.% aromatic vinyl monomer residues and 20-65wt.% unsaturated dicarboxylic imide residues, 0-60wt.% graft copolymer formed by grafting 30-90pts.wt. monomer mixture comprising 40-85wt.% aromatic vinyl monomer and 15-40wt.% vinyl cyanide monomer onto 10-70pts.wt. rubberlike polymer and 5-20wt.% titanium oxide.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は芳香族ビニル・不飽和ジカルボン酸イミド共重
合体を含有する熱可塑性樹脂よりなる光遮蔽成形物に関
する。
DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a light shielding molded article made of a thermoplastic resin containing an aromatic vinyl/unsaturated dicarboxylic acid imide copolymer.

(従来の技術及びその問題点) 従来光遮蔽部品はアルミダイキャストやブリキ板等が使
用されていたが、次第にプラスチック成形物が使用され
てきた。しかしながら最近は光源の高出力化および成形
物の小型化のため、プラスチック成形物に対する耐熱性
及び寸法安定性のさらに一層の改善が要求されている。
(Prior art and its problems) Conventionally, aluminum die-casting, tin plate, etc. have been used for light shielding parts, but plastic moldings are gradually being used. However, in recent years, there has been a demand for further improvements in the heat resistance and dimensional stability of plastic molded products due to the increase in the output of light sources and the miniaturization of molded products.

これら要求を満たすためには従来用いられているABS
樹脂や変性PPO樹脂では耐熱性の点で十分でなく、ま
たナイロンやPBT樹脂は結晶性のため寸法安定性が十
分でなく、ポリカーボネート樹脂は成形性及び耐薬品性
が十分でないという問題点があった。
In order to meet these requirements, conventionally used ABS
Resins and modified PPO resins do not have sufficient heat resistance, nylon and PBT resins do not have sufficient dimensional stability due to their crystallinity, and polycarbonate resins have problems such as insufficient moldability and chemical resistance. Ta.

(問題点を解決するための手段) 本発明はこれら問題点を改良すべく鋭意研究を行った結
果、芳香族ビニル単量体残基35〜80重量%および不
飽和ジカルボン酸イミド誘導体残基20〜65重量%を
含む共重合体(以下しばしば「芳香族ビニル・不飽和ジ
カルボン酸イミド共重合体」という)10〜80重量%
、ゴム状重合体10〜70重量部に芳香族ビニル単量体
40〜85重量%、シアン化ビニル単量体15〜40重
量%およびこれらと共重合可能なビニル単量体O〜40
重量%からなる単量体混合物30〜90重量部をグラフ
ト重合させたグラフト共重合体O〜60重量%、および
酸化チタン5〜20重量%を含有する熱可塑性樹脂より
なる光遮蔽成形物は、耐熱性および寸法安定性に優れた
ものであることがわかり、本発明が完成した。
(Means for Solving the Problems) As a result of extensive research aimed at improving these problems, the present invention has revealed that 35 to 80% by weight of aromatic vinyl monomer residues and 20% by weight of unsaturated dicarboxylic acid imide derivative residues. ~65% by weight (hereinafter often referred to as "aromatic vinyl/unsaturated dicarboxylic acid imide copolymer") 10 to 80% by weight
, 10 to 70 parts by weight of a rubbery polymer, 40 to 85% by weight of an aromatic vinyl monomer, 15 to 40% by weight of a vinyl cyanide monomer, and O to 40 parts by weight of a vinyl monomer copolymerizable with these.
A light-shielding molded article made of a thermoplastic resin containing 5 to 20 weight % of titanium oxide and a graft copolymer O to 60 weight % obtained by graft polymerization of 30 to 90 weight % of a monomer mixture consisting of It was found that it had excellent heat resistance and dimensional stability, and the present invention was completed.

本発明に用いる熱可塑性樹脂は芳香族ビニル・不飽和ジ
カルボン酸イミド共重合体と酸化チタンのみからなるも
のであってもよいが、これよりなる成形物の衝撃強度を
更に一層改良するためにゴム状重合体に芳香族ビニル単
量体、シアン化ビニル単量体およびこれらと共重合可能
なビニル単量体をグラフト重合させたグラフト共重合体
を60重量%まで含有することが好ましい。また本発明
に用いる熱可塑性樹脂には更にアクリロニトリル−スチ
レン共重合体、アクリロニトリル−α−メチルスチレン
共重合体、メチルメタクリレートブタジェン−スチレン
共重合体、芳香族ポリカーボネート、ポリエチレンテレ
フタレート、ポリブチレンテレフタレート、ナイロン−
6、ナイロン−6,6、ボリアリレート、ポリフェニレ
ンサルファイド、ポリフェニレンオキサイド、ポリエー
テルイミド、ポリエーテルスルホンおよびポリスルホン
等の熱可塑性樹脂を混合してもよい。
The thermoplastic resin used in the present invention may consist only of an aromatic vinyl/unsaturated dicarboxylic acid imide copolymer and titanium oxide, but in order to further improve the impact strength of molded products made of this, It is preferable to contain up to 60% by weight of a graft copolymer obtained by graft-polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer, and a vinyl monomer copolymerizable with these into the polyester. In addition, the thermoplastic resin used in the present invention further includes acrylonitrile-styrene copolymer, acrylonitrile-α-methylstyrene copolymer, methyl methacrylate butadiene-styrene copolymer, aromatic polycarbonate, polyethylene terephthalate, polybutylene terephthalate, nylon −
Thermoplastic resins such as 6, nylon-6,6, polyarylate, polyphenylene sulfide, polyphenylene oxide, polyetherimide, polyether sulfone, and polysulfone may be mixed.

ここで本発明に用いられる芳香族ビニル・不飽和ジカル
ボン酸イミド共重合体およびその製法について説明する
。共重合体を構成する芳香族ビニル単量体としてスチレ
ン、α−メチルスチレン、ビニルトルエン、t−ブチル
スチレン、クロロスチレン等のスチレン単量体およびそ
の置換体があり、これらの中でスチレンが特に好ましい
。不飽和ジカルボン酸イミド誘導体は不飽和ジカルボン
酸無水物を芳香族ビニルと共重合させた後アンモニアお
よび/又は第1級アミンと反応させてイミド誘導体にし
ても、又はマレイミド、N−メチルマレイミド、N−エ
チルマレイミド、N−シクロへキシルマレイミド、N−
フェニルマレイミド、N−ナフチルマレイミド等のマレ
イミド単量体を直接芳香族ビニル単量体と共重合させた
ものでもよい。しかしながらこれら共重合体を製造する
方法としては前者、すなわち不飽和ジカルボン酸無水物
を芳香族ビニルと共重合させた後にイミド化する方法が
共重合性および経済性の点でより好ましい。不飽和ジカ
ルボン酸無水物としてはマレイン酸、イタコン酸、シト
ラコン酸、アコニット酸等の無水物があり、マレイン酸
無水物が特に好ましい。イミド化反応に用いる第1級ア
ミンとしてはメチルアミン、エチルアミン、プロピルア
ミン、シクロヘキシルアミン等のアルキルアミン、およ
びこれらのクロル又はブロム置換アルキルアミン、アニ
リン、トリルアミン、ナフチルアミン等の芳香族アミン
およびクロル又はブロム置換芳香族アミンがあげられる
Here, the aromatic vinyl/unsaturated dicarboxylic acid imide copolymer used in the present invention and its production method will be explained. The aromatic vinyl monomers constituting the copolymer include styrene monomers and substituted products thereof, such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, among which styrene is particularly preferable. Unsaturated dicarboxylic acid imide derivatives can be obtained by copolymerizing unsaturated dicarboxylic acid anhydride with aromatic vinyl and then reacting with ammonia and/or primary amine to obtain imide derivatives, or maleimide, N-methylmaleimide, N -ethylmaleimide, N-cyclohexylmaleimide, N-
A maleimide monomer such as phenylmaleimide or N-naphthylmaleimide may be directly copolymerized with an aromatic vinyl monomer. However, as a method for producing these copolymers, the former method, that is, a method in which an unsaturated dicarboxylic acid anhydride is copolymerized with an aromatic vinyl and then imidized, is more preferable in terms of copolymerizability and economy. Examples of the unsaturated dicarboxylic anhydride include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, with maleic anhydride being particularly preferred. Primary amines used in the imidization reaction include alkyl amines such as methylamine, ethylamine, propylamine, and cyclohexylamine; and aromatic amines such as chloro- or bromine-substituted alkyl amines, aniline, tolylamine, and naphthylamine; Examples include substituted aromatic amines.

イミド化反応は溶液状態又は懸濁状態で行う場合は通常
の反応容器、例えばオートクレーブなどを用いるのが好
ましく、塊状溶融状態で行う場合は脱揮装置の付いた押
出機を用いてもよい。イミド化反応の温度は約80〜3
50℃であり、り子ましくは100〜300℃である。
When the imidization reaction is carried out in a solution or suspension state, it is preferable to use an ordinary reaction vessel such as an autoclave, and when carried out in a bulk molten state, an extruder equipped with a devolatilization device may be used. The temperature of the imidization reaction is about 80-3
The temperature is 50°C, preferably 100 to 300°C.

80℃未満の場合には反応速度が遅く、反応に長時間を
要し実用的でない。一方350℃を越える場合には重合
体の熱分解による物性低下をきたす。またイミド化反応
には触媒を用いてもよく、その場合には第3級アミン、
例えばトリエチルアミンが好ましく用いられる。
If the temperature is lower than 80°C, the reaction rate is slow and the reaction takes a long time, which is not practical. On the other hand, if the temperature exceeds 350°C, the physical properties will deteriorate due to thermal decomposition of the polymer. In addition, a catalyst may be used for the imidization reaction, in which case a tertiary amine,
For example, triethylamine is preferably used.

本発明における芳香族ビニル単量体・不飽和ジカルボン
酸イミド共重合体において芳香族ビニル単量体残基は3
5〜805〜80重量、芳香族ビニル単量体残基の含有
量が35重量%未満であると芳香族ビニル化合物の特徴
である成形性、寸法安定性が失なわれる。また不飽和ジ
カルボン酸イミド誘導体残基が20重量%未満では耐熱
性および耐薬品性が十分でない。
In the aromatic vinyl monomer/unsaturated dicarboxylic acid imide copolymer of the present invention, the number of aromatic vinyl monomer residues is 3.
If the content of aromatic vinyl monomer residues is less than 35% by weight, moldability and dimensional stability, which are characteristics of aromatic vinyl compounds, will be lost. Furthermore, if the unsaturated dicarboxylic acid imide derivative residue is less than 20% by weight, heat resistance and chemical resistance are insufficient.

一方該イミド誘導体残基が65重量%を越えると共重合
体がもろくなり、成形性も著しく悪くなる。
On the other hand, if the imide derivative residue exceeds 65% by weight, the copolymer becomes brittle and its moldability becomes extremely poor.

本発明に用いる芳香族ビニル単量体・不飽和ジカルボン
酸イミド共重合体には0〜40重量%のゴム状重合体お
よび/又は芳香族ビニル単量体と不飽和ジカルボン酸無
水物および/又は不飽和ジカルボン酸イミド誘導体と共
重合可能な単量体残基を0〜40重量%含有することが
できる。ゴム状重合体としてはブタジェン重合体、ブタ
ジェンと共重合可能なビニル単量体との共重合体、エチ
レン−プロピレン共重合体、エチレン−プロピレン−ジ
エン共重合体、ブタジェンと芳香族ビニルとのブロック
共重合体、アクリル酸エステル重合体およびアクリル酸
エステルとこれと共重合可能なビニル単量体との共重合
体等が用いられる。芳香族ビニル単量体と不飽和ジカル
ボン酸無水物および/又は不飽和ジカルボン酸イミド誘
導体と共重合可能な単量体としてはアクリロニトリル、
メタクリロニトリル、α−クロロアクリロニトリル等の
シアン化ビニル単量体、メチルアクリル酸エステル、エ
チルアクリル酸エステル、ブチルアクリル酸エステル等
のアクリル酸エステル単量体、メチルメタクリル酸エス
テル、エチルメタクリル酸エステル等のメタクリル酸エ
ステル単量体、アクリル酸、メタクリル酸等のビニルカ
ルボン酸単量体、アクリル酸アミドおよびメタクリル酸
アミド等がある。
The aromatic vinyl monomer/unsaturated dicarboxylic acid imide copolymer used in the present invention contains 0 to 40% by weight of a rubbery polymer and/or aromatic vinyl monomer and an unsaturated dicarboxylic anhydride and/or It can contain 0 to 40% by weight of monomer residues copolymerizable with the unsaturated dicarboxylic acid imide derivative. Examples of rubbery polymers include butadiene polymers, copolymers of butadiene and copolymerizable vinyl monomers, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, and blocks of butadiene and aromatic vinyl. Copolymers, acrylic ester polymers, copolymers of acrylic esters and vinyl monomers copolymerizable therewith, and the like are used. Monomers that can be copolymerized with aromatic vinyl monomers and unsaturated dicarboxylic anhydrides and/or unsaturated dicarboxylic acid imide derivatives include acrylonitrile,
Vinyl cyanide monomers such as methacrylonitrile and α-chloroacrylonitrile, acrylic acid ester monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate, methyl methacrylate, ethyl methacrylate, etc. Examples include methacrylic acid ester monomers, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide and methacrylic acid amide.

また本発明に使用できるグラフト共重合体について説明
する。グラフト共重合体において用いられるゴム状重合
体はブタジェン重合体、ブタジェンと共重合可能なビニ
ル単量体との共重合体、エチレンーフロヒレン共重合体
、エチレン−プロピレン−ジエン共重合体、ブタジェン
と芳香族ビニルとのブロック共重合体、アクリル酸エス
テル重合体およびアクリル酸エステルとこれと共重合可
能なビニル単量体との共重合体等がある。また芳香族ビ
ニル単量体としてはスチレン、α−メチルスチレン、ビ
ニルトルエン、t−ブチルスチレン、クロロスチレン等
のスチレン単量体およびその置換41体でありこれらの
中でスチレンおよびα−メチルスチレン単量体が特に好
ましい。シアン化ビニル単量体としてはアクリロニトリ
ル、メタクリロニトリル、α−クロロアクリロニトリル
等があり、特にアクリロニトリルが好ましい。またこれ
らと共重合可能なビニル単量体としてはメチルメタクリ
ル酸エステル、エチルメタクリル酸エステル等のメタク
リル酸エステル、アクリル酸、メタクリル酸等のビニル
カルボン酸単量体があげられる。
Also, the graft copolymer that can be used in the present invention will be explained. Rubbery polymers used in the graft copolymer include butadiene polymers, copolymers of butadiene and copolymerizable vinyl monomers, ethylene-fluorohene copolymers, ethylene-propylene-diene copolymers, and butadiene copolymers. and aromatic vinyl, acrylic ester polymers, and copolymers of acrylic esters and vinyl monomers copolymerizable therewith. Examples of aromatic vinyl monomers include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, and 41 substituted monomers thereof. Among these, styrene and α-methylstyrene monomers mer is particularly preferred. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile being particularly preferred. Examples of vinyl monomers that can be copolymerized with these include methacrylic acid esters such as methyl methacrylic acid ester and ethyl methacrylic acid ester, and vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid.

グラフト共重合体の製法は、ゴム状重合体10〜70.
ill!i部存在下に芳香族ビニル単量体40〜85重
量%、シアン化ビニル単量体15〜40重憧%、および
必要に応じこれらと共重合可能なビニル単量体0〜40
重量%からなる単量体混合物30〜90重量部を重合し
て得られる。このグラフト重合体の製造に当っては一般
に公知のいずれの重合技術も採用可能であって、例えば
懸濁重合、乳化重合の如き水性不均一重合、塊状重合、
溶液重合および生成重合体の非溶媒中での沈殿重合その
他又はこれらの組合せ等がある。
The method for producing the graft copolymer includes rubbery polymers 10 to 70.
ill! In the presence of part i, 40 to 85% by weight of an aromatic vinyl monomer, 15 to 40% by weight of a vinyl cyanide monomer, and 0 to 40% by weight of a vinyl monomer copolymerizable with these if necessary.
It is obtained by polymerizing 30 to 90 parts by weight of a monomer mixture consisting of % by weight. In producing this graft polymer, any generally known polymerization technique can be employed, such as suspension polymerization, aqueous heterogeneous polymerization such as emulsion polymerization, bulk polymerization,
Examples include solution polymerization, precipitation polymerization of the produced polymer in a non-solvent, and others, or a combination thereof.

本発明の光遮蔽部品のプラスチック成形物は芳香族ビニ
ル・不飽和ジカルボン酸イミド共重合体を必須成分とし
た熱可塑性樹脂よりなるものであるが、この熱可塑性樹
脂にガラス、カーボン、アラミド等の繊維や難燃剤、安
定剤、可塑剤、滑剤、紫外線吸収剤、着色剤および酸化
チタンの他にタルク、シリカ、クレー、マイカ、炭酸カ
ルシウム、硫酸バリウム等の充填剤などを添加すること
も可能である。
The plastic molded product of the light shielding component of the present invention is made of a thermoplastic resin containing an aromatic vinyl/unsaturated dicarboxylic acid imide copolymer as an essential component. In addition to fibers, flame retardants, stabilizers, plasticizers, lubricants, ultraviolet absorbers, colorants, and titanium oxide, it is also possible to add fillers such as talc, silica, clay, mica, calcium carbonate, and barium sulfate. be.

(実施例) 以下本発明をさらに実施例によって説明するが、本発明
はその要旨を越えない限り、以下の実施例に限定される
ものではない。なお実施例中の部、%はいずれも重量基
準で表わした。
(Examples) The present invention will be further explained below with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. Note that all parts and percentages in the examples are expressed on a weight basis.

実験例(11 攪拌機を備えたオートクレーブ中にスチレン60部、メ
チルエチルケトン100部を仕込み、系内を窒素ガスで
置換した後、温度を83℃に昇温し、無水マレイン酸4
0部とベンゾイルパーオキサイド0.15部をメチルエ
チルケトン200部に溶解した溶液を8時間で連続的に
添加した。添加後さらに3時間温度を83℃に保った。
Experimental Example (11) 60 parts of styrene and 100 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, and after purging the system with nitrogen gas, the temperature was raised to 83°C, and maleic anhydride 4
A solution of 0 parts of benzoyl peroxide and 0.15 parts of benzoyl peroxide dissolved in 200 parts of methyl ethyl ketone was continuously added over 8 hours. The temperature was maintained at 83° C. for an additional 3 hours after the addition.

語調な反応液の一部をサンプリングしてガスクロマトグ
ラフィーにより未反応単量体の定量を行った結果、重合
率はスチレン96%、無水マレイン酸98%であった。
A portion of the reaction solution was sampled and the amount of unreacted monomer was determined by gas chromatography. As a result, the polymerization rate was 96% for styrene and 98% for maleic anhydride.

ここで得られた共重合体溶液に無水マレイン酸に対し当
量のアニリン38部、トリエチルアミン0.3部を加え
140℃で7時間反応させた。
To the copolymer solution obtained here, 38 parts of aniline and 0.3 parts of triethylamine, which were equivalent to maleic anhydride, were added and reacted at 140° C. for 7 hours.

反応溶液にメチルエチルケトン200部を加え、室温ま
で冷却し、激しく攪拌したメタノール1500部に注ぎ
、析出、濾別、乾燥レイミド化共重合体を得た。C−C
−13部分析より酸無水物基のイミド基への転化率は9
8%であった。このイミド化共重合体は不飽和ジカルボ
ン酸イミド誘導体残基としてのN−フェニルマレイミド
単位を54%含む共重合体であり、これを重合体Aとし
た。
200 parts of methyl ethyl ketone was added to the reaction solution, cooled to room temperature, poured into 1,500 parts of vigorously stirred methanol, precipitated, separated by filtration, and a dried leimidized copolymer was obtained. C-C
-13 part analysis shows that the conversion rate of acid anhydride groups to imide groups is 9
It was 8%. This imidized copolymer was a copolymer containing 54% of N-phenylmaleimide units as unsaturated dicarboxylic acid imide derivative residues, and was designated as Polymer A.

実験例(2) 実験例(1)と同様のオートクレーブ中にスチレン60
部、メチルエチルケトン50部、小片状に切断したポリ
ブタジェン10部を仕込み、室温で一昼夜攪拌しゴム溶
解した後、系内を窒素ガスで置換し温度を83℃に昇温
した。無水マレイン酸40部とベンゾイルパーオキサイ
ド0.075部およびアゾビスイソブチロニトリル0.
075部をメチルエチルケトン250部に溶解した溶液
を8時間で連続的に添加した。これ以降は実験例(1)
と全く同じ操作を行った。重合率はスチレン97%、無
水マレイン酸99%であった。酸無水物基のイミド基へ
の転化率は98%であった。このイミド化共重合体は不
飽和ジカルボン酸イミド誘導体残基としてのN−フェニ
ルマレイミド単位を50%含む共重合体でありこれを重
合体Bとした。
Experimental Example (2) Styrene 60 was placed in the same autoclave as Experimental Example (1).
1, 50 parts of methyl ethyl ketone, and 10 parts of polybutadiene cut into small pieces were charged, and after stirring at room temperature all day and night to dissolve the rubber, the inside of the system was purged with nitrogen gas and the temperature was raised to 83°C. 40 parts of maleic anhydride, 0.075 parts of benzoyl peroxide, and 0.0 parts of azobisisobutyronitrile.
A solution of 075 parts of methyl ethyl ketone dissolved in 250 parts of methyl ethyl ketone was added continuously over 8 hours. From here on, experiment example (1)
performed the exact same operation. The polymerization rate was 97% for styrene and 99% for maleic anhydride. The conversion rate of acid anhydride groups to imide groups was 98%. This imidized copolymer was a copolymer containing 50% of N-phenylmaleimide units as unsaturated dicarboxylic acid imide derivative residues, and was designated as Polymer B.

実験例(3) ポリブタジェンラテックス143部(固形分35%、重
量平均粒径0.35μ、ゲル含率90%)、ステアリン
酸カリウム1部、ソジウムホルムアルデヒドスルホキシ
レート0.1部、テトラソジウムエチレンジアミンテト
ラアセチソクアシッド0.03部、硫酸第1鉄0. O
O3部および水150部を50℃に加熱し、これにスチ
レン70%およびアクリロニトリル30%よりなる単量
体混合物50部、t−ドデシルメルカプタン0.2部、
キュメンハイドロパーオキサイド0.15部を6時間で
連続添加し、さらに添加後65℃に昇温し2時間重合し
た。
Experimental example (3) 143 parts of polybutadiene latex (solid content 35%, weight average particle size 0.35μ, gel content 90%), 1 part potassium stearate, 0.1 part sodium formaldehyde sulfoxylate, tetra 0.03 parts of sodium ethylenediaminetetraacetysoquacid, 0.03 parts of ferrous sulfate. O
3 parts of O and 150 parts of water are heated to 50°C, and to this are added 50 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile, 0.2 part of t-dodecylmercaptan,
0.15 part of cumene hydroperoxide was continuously added over 6 hours, and after the addition, the temperature was raised to 65°C and polymerization was carried out for 2 hours.

重合率はガスクロマトグラフィー分析よりスチレン98
%、アクリロニトリル98%であった。得られたラテッ
クスに酸化防止剤を添加した後、塩化カルシウムで凝固
、水洗、乾燥し白色粉末としてグラフト共重合体を得た
。これを重合体Cとした。
The polymerization rate was determined to be styrene 98% by gas chromatography analysis.
%, acrylonitrile 98%. After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water, and dried to obtain a graft copolymer as a white powder. This was designated as Polymer C.

実施例1 実験例(1)で得られた重合体AS0部、実験例(3)
で得られた重合体40部、アクリロニトリル・スチレン
(AS)樹脂(電気化学社製、AS−H)10部、およ
びこれら重合体100部に対し酸化チタン10部、オク
タデシル3− (3,5−ジターシャリブチル−4−ヒ
ドロキシフェニル)−プロピオネート0.5部をヘンシ
ェルミキサーにより混合後、ベント付押出機で押出しペ
レット化した。
Example 1 0 parts of polymer AS obtained in Experimental Example (1), Experimental Example (3)
40 parts of the polymer obtained above, 10 parts of acrylonitrile styrene (AS) resin (manufactured by Denki Kagaku Co., Ltd., AS-H), and 10 parts of titanium oxide, octadecyl 3- (3,5- After mixing 0.5 parts of di-tert-butyl-4-hydroxyphenyl-propionate using a Henschel mixer, the mixture was extruded into pellets using a vented extruder.

このペレットを射出成形機により縦×横×深さ約I Q
cmX 6c11X 5C11,厚み2寵のボックスを
280℃で射出成形した。この成形物を150℃に保っ
たオーブン中に2時間放置した後、その外形寸法を測定
した。縦、横、深さとも寸法はほとんど変化しておらず
、元の寸法に比べて変形率はすべて1%以内であった。
This pellet is molded using an injection molding machine to a length x width x depth of approximately IQ.
A box measuring cm x 6c11 x 5c11 and 2 mm thick was injection molded at 280°C. After this molded product was left in an oven kept at 150° C. for 2 hours, its external dimensions were measured. There was almost no change in the vertical, horizontal, and depth dimensions, and the deformation rates were all within 1% compared to the original dimensions.

またプレス成形により厚み0、5 tmの板を作成し、
遮光程度を測定したところ全光線透過率で0.8%であ
った。
In addition, a plate with a thickness of 0.5 tm was created by press forming,
When the degree of light shielding was measured, the total light transmittance was 0.8%.

実施例2 実験例(2)で得られた重合体850部、実験例(3)
で得られた重合体C40部およびAS樹脂10部を酸化
チタン15部、オクタデシル3− (3,5−ジターシ
ャリブチル−4−ヒドロキシフェニル)−プロピオネー
ト0.5部とともに実施例1と同様の方法で混合、ペレ
ット化し、ボックスを成形した。この成形物を実施例1
と同様にオーブン中で熱処理した。オーブン中での熱処
理による外形寸法はほとんど変化しておらず変形率は縦
、横、深さとも1%以内であった。また厚み0.5 鰭
の板の全光線透過率は0.2%であった。
Example 2 850 parts of the polymer obtained in Experimental Example (2), Experimental Example (3)
In the same manner as in Example 1, 40 parts of the polymer C obtained in 1 and 10 parts of the AS resin were mixed with 15 parts of titanium oxide and 0.5 parts of octadecyl 3-(3,5-ditertiarybutyl-4-hydroxyphenyl)-propionate. The mixture was mixed, pelletized, and formed into boxes. Example 1
Heat treated in the oven in the same manner as above. The external dimensions were hardly changed by the heat treatment in the oven, and the deformation rate was within 1% in length, width, and depth. The total light transmittance of the 0.5-thick fin plate was 0.2%.

特許出願人  電気化学工業株式会社Patent applicant: Denki Kagaku Kogyo Co., Ltd.

Claims (1)

【特許請求の範囲】[Claims]  芳香族ビニル単量体残基35〜80重量%および不飽
和ジカルボン酸イミド誘導体残基20〜65重量%を含
む共重合体10〜80重量%、ゴム状重合体10〜70
重量部に芳香族ビニル単量体40〜85重量%、シアン
化ビニル単量体15〜40重量%およびこれらと共重合
可能なビニル単量体0〜40重量%からなる単量体混合
物30〜90重量部をグラフト重合させたグラフト共重
合体0〜60重量%、および酸化チタン5〜20重量%
を含有する熱可塑性樹脂よりなる光遮蔽成形物。
10-80% by weight of a copolymer containing 35-80% by weight of aromatic vinyl monomer residues and 20-65% by weight of unsaturated dicarboxylic acid imide derivative residues, 10-70% by weight of a rubbery polymer.
A monomer mixture consisting of 40 to 85% by weight of an aromatic vinyl monomer, 15 to 40% by weight of a vinyl cyanide monomer, and 0 to 40% by weight of a vinyl monomer copolymerizable with these, 30 to 30% by weight. 0 to 60% by weight of a graft copolymer obtained by graft polymerization of 90 parts by weight, and 5 to 20% by weight of titanium oxide.
A light shielding molded product made of thermoplastic resin containing.
JP63168790A 1988-07-08 1988-07-08 Light shielding molding Expired - Fee Related JP2793597B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP63168790A JP2793597B2 (en) 1988-07-08 1988-07-08 Light shielding molding

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63168790A JP2793597B2 (en) 1988-07-08 1988-07-08 Light shielding molding

Publications (2)

Publication Number Publication Date
JPH0220542A true JPH0220542A (en) 1990-01-24
JP2793597B2 JP2793597B2 (en) 1998-09-03

Family

ID=15874522

Family Applications (1)

Application Number Title Priority Date Filing Date
JP63168790A Expired - Fee Related JP2793597B2 (en) 1988-07-08 1988-07-08 Light shielding molding

Country Status (1)

Country Link
JP (1) JP2793597B2 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59202241A (en) * 1983-05-04 1984-11-16 Showa Denko Kk Thermoplastic resin composition
JPS60214597A (en) * 1984-04-10 1985-10-26 電気化学工業株式会社 Electromagnetic wave shielding resin composition
JPS6286045A (en) * 1985-10-11 1987-04-20 Denki Kagaku Kogyo Kk Plastic molding

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59202241A (en) * 1983-05-04 1984-11-16 Showa Denko Kk Thermoplastic resin composition
JPS60214597A (en) * 1984-04-10 1985-10-26 電気化学工業株式会社 Electromagnetic wave shielding resin composition
JPS6286045A (en) * 1985-10-11 1987-04-20 Denki Kagaku Kogyo Kk Plastic molding

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Publication number Publication date
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