JPH04277545A - Methacrylic resin composition excellent in solvent resistance - Google Patents
Methacrylic resin composition excellent in solvent resistanceInfo
- Publication number
- JPH04277545A JPH04277545A JP3874491A JP3874491A JPH04277545A JP H04277545 A JPH04277545 A JP H04277545A JP 3874491 A JP3874491 A JP 3874491A JP 3874491 A JP3874491 A JP 3874491A JP H04277545 A JPH04277545 A JP H04277545A
- Authority
- JP
- Japan
- Prior art keywords
- methacrylic resin
- weight
- resin composition
- solvent resistance
- copolymer
- 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.)
- Withdrawn
Links
- 239000000113 methacrylic resin Substances 0.000 title claims abstract description 35
- 239000002904 solvent Substances 0.000 title claims description 23
- 239000000203 mixture Substances 0.000 title claims description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 12
- 239000011342 resin composition Substances 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は 耐溶剤性、成形性、
に優れたメタクリル樹脂に関するものである。[Industrial Application Field] The present invention is characterized by solvent resistance, moldability,
The invention relates to methacrylic resins with excellent properties.
【０００２】0002
【従来の技術】メタクリル樹脂は 透明性、耐候性、
機械的強度、等の性質に優れる為広く利用されている。
この様に産業上利用価値の高い材料であるが、メタクリ
ル樹脂成形体は有機溶剤と接触することによりクラック
、クレイズ、の発生する場合もあり致命的な欠陥になる
ことがある。このような有機溶剤によるクラック、クレ
イズの発生を抑制する方法として、通常、成形体をガラ
ス転移温度近辺で熱処理する方法があるが、熱処理に長
時間要し生産性が悪い。又、樹脂の平均分子量を大きく
する方法もあるが、この場合、耐溶剤性は改良されるも
のの成形性に劣るという新たな問題点が発生する。上記
以外に、耐溶剤性を改良する手段として、いくつかの方
法が提案されている。■アクリル樹脂へアイオノマ−樹
脂を少量添加し耐溶剤性を改良する方法〔特開昭６３−
１７０４４２号公報〕、■アクリル酸アルキルエステル
を共重合させることにより耐溶剤性を改良する方法〔特
公昭５４−３２６６９号公報〕、■メタクリル酸メチル
をグラフト共重合したアクリル酸アルキルエステル系架
橋重合体とメタクリル樹脂を混合することにより耐溶剤
性や成形加工性を改良する方法〔特公昭−４９１２８９
３号公報〕、■メタクリル樹脂へ屈折率を合わせたアク
リル系重合体を混合することにより耐溶剤性や成形加工
性を改良する方法〔特開平１−２６１４４７号公報〕、
などがある。[Prior art] Methacrylic resin has transparency, weather resistance,
It is widely used because of its excellent properties such as mechanical strength. Although it is a material with high industrial value, methacrylic resin moldings may develop cracks or crazes when they come into contact with organic solvents, which can lead to fatal defects. As a method of suppressing the occurrence of cracks and crazes caused by such organic solvents, there is usually a method of heat-treating the molded product at around the glass transition temperature, but the heat treatment requires a long time and is poor in productivity. There is also a method of increasing the average molecular weight of the resin, but in this case, although solvent resistance is improved, a new problem arises in that moldability is poor. In addition to the above, several methods have been proposed as means for improving solvent resistance. ■Method of improving solvent resistance by adding a small amount of ionomer resin to acrylic resin [JP-A-63-
No. 170442], ■ Method for improving solvent resistance by copolymerizing acrylic acid alkyl ester [Japanese Patent Publication No. 170442], ■ Acrylic acid alkyl ester crosslinked polymer obtained by graft copolymerization of methyl methacrylate A method for improving solvent resistance and molding processability by mixing methacrylic resin with
3], ■ A method for improving solvent resistance and moldability by mixing an acrylic polymer with a matched refractive index into a methacrylic resin [JP-A-1-261447],
and so on.
【０００３】しかし、■では耐溶剤性に改良効果は認め
られるものの透明性が低下し問題であった。■では流動
性は向上し成形加工性はよくなるものの熱変形温度が低
くなるという問題があった。■では流動性、加工性の向
上は認められず又透明性が低下し問題があった。■では
流動性はあまり向上せず耐候性に劣り問題であった。こ
のように、メタクリル樹脂本来の優れた性質を維持した
まま耐溶剤性及び成形性が改良されたメタクリル樹脂は
得られていない。[0003] However, although the effect of improving solvent resistance was recognized in the case of (1), the transparency was lowered, which was a problem. In case (2), although the fluidity is improved and the moldability is improved, there is a problem that the heat distortion temperature becomes low. In case (2), no improvement in fluidity or processability was observed, and there was a problem in that transparency decreased. In case (3), the fluidity did not improve much and the weather resistance was poor. As described above, a methacrylic resin with improved solvent resistance and moldability while maintaining the original excellent properties of methacrylic resin has not been obtained.
【０００４】0004
【発明が解決しようとする課題】耐溶剤性、成形性、生
産性、に優れかつメタクリル樹脂本来の性質をもった樹
脂を提供することにある。OBJECTS OF THE INVENTION It is an object of the invention to provide a resin which is excellent in solvent resistance, moldability and productivity, and which has the properties inherent to methacrylic resin.
【０００５】[0005]
【課題を解決する為の手段】本発明はメタクリル樹脂〔
Ａ〕へ特定のアクリル系共重合体〔Ｂ〕を特定量含有さ
せる事を最大の特徴とする。本発明のメタクリル樹脂組
成物は、メタクリル樹脂〔Ａ〕８０．０〜９９．５重量
部と、メタクリル酸メチル単位３５．０〜８０．０重量
％、炭素数が１〜８のアルキル基を有すアクリル酸アル
キルエステル単位２０．０〜６５．０重量％で構成され
る分子量２．０〜１５．０万の共重合体〔Ｂ〕０．５〜
２０．０重量部とからなることを特徴とする耐溶剤性に
優れたメタクリル樹脂組成物である。この共重合体〔Ｂ
〕を用いることにより、従来あった問題をすべて解決し
、耐溶剤性、成形性、生産性の優れた樹脂を発明するに
到った。共重合体〔Ｂ〕で用いられるアクリル酸アルキ
ルエステルは炭素数１〜８のアクリル酸アルキルエステ
ルである。好ましくは、炭素数１〜４のアクリル酸アル
キルエステルである。更に好ましくは、メタクリル樹脂
〔Ａ〕のアクリル酸アルキルエステル単位と同一種類の
物である。[Means for solving the problems] The present invention provides methacrylic resin [
The biggest feature is that A] contains a specific amount of a specific acrylic copolymer [B]. The methacrylic resin composition of the present invention contains 80.0 to 99.5 parts by weight of methacrylic resin [A], 35.0 to 80.0% by weight of methyl methacrylate units, and an alkyl group having 1 to 8 carbon atoms. Copolymer with a molecular weight of 2.0 to 150,000 [B] 0.5 to 150,000, composed of 20.0 to 65.0% by weight of acrylic acid alkyl ester units
This is a methacrylic resin composition with excellent solvent resistance, characterized by comprising 20.0 parts by weight. This copolymer [B
], we solved all the conventional problems and invented a resin with excellent solvent resistance, moldability, and productivity. The acrylic acid alkyl ester used in the copolymer [B] is an acrylic acid alkyl ester having 1 to 8 carbon atoms. Preferably, it is an acrylic acid alkyl ester having 1 to 4 carbon atoms. More preferably, it is the same type of acrylic acid alkyl ester unit of the methacrylic resin [A].
【０００６】又、アクリル酸アルキルエステル量の範囲
は２０．０〜６５．０重量％である。アクリル酸アルキ
ルエステルの量が６５．０重量％を超える場合にはメタ
クリル樹脂組成物の透明性が著しく低下し、２０．０重
量％未満の場合にはメタクリル樹脂組成物の耐溶剤性が
実質向上しない。好ましいアクリル酸エステル量の範囲
は２５．０〜６０．０重量％である。更に、好ましいア
クリル酸エステル量の範囲は２５．０〜５５．０重量％
である。共重合体〔Ｂ〕の分子量の範囲は２．０〜１５
．０万である。共重合体〔Ｂ〕の分子量が１５．０万を
超える場合には、メタクリル樹脂組成物の流動性が低下
し成形性が向上せず、２．０万未満の場合には、メタク
リル樹脂組成物の機械的強度が低下する。好ましい共重
合体〔Ｂ〕の分子量の範囲は２．０〜１３．０万である
。更に、好ましい共重合体〔Ｂ〕の分子量の範囲は２．
０万〜９．０万である。[0006]The range of the amount of acrylic acid alkyl ester is 20.0 to 65.0% by weight. When the amount of acrylic acid alkyl ester exceeds 65.0% by weight, the transparency of the methacrylic resin composition is significantly reduced, and when it is less than 20.0% by weight, the solvent resistance of the methacrylic resin composition is substantially improved. do not. The preferred amount of acrylic ester is in the range of 25.0 to 60.0% by weight. Furthermore, the preferable range of the amount of acrylic acid ester is 25.0 to 55.0% by weight.
It is. The molecular weight range of copolymer [B] is 2.0 to 15
．． It is 00,000. When the molecular weight of the copolymer [B] exceeds 150,000, the fluidity of the methacrylic resin composition decreases and the moldability does not improve, and when it is less than 20,000, the methacrylic resin composition mechanical strength decreases. The preferred molecular weight range of copolymer [B] is 20,000 to 130,000. Furthermore, the preferred molecular weight range of copolymer [B] is 2.
It is 00,000 to 90,000.
【０００７】メタクリル樹脂組成物中で、共重合体〔Ｂ
〕の含有量の範囲は０．５〜２０．０重量％である。共
重合体〔Ｂ〕の含有量が、２０．０重量％を超える場合
にはメタクリル樹脂組成物の熱変形温度が著しく低下し
、０．５重量％未満の場合にはメタクリル樹脂組成物の
耐溶剤性、流動性が実質向上しない。好ましい共重合体
〔Ｂ〕の含有量の範囲は１．０〜１８．０重量％である
。更に、好ましい共重合体〔Ｂ〕の含有量の範囲は１．
０〜１５．０重量％である。該樹脂組成物中で共重合体
〔Ｂ〕の含有量はゲルパ−ミレ−ションクロマトグラフ
ィ−（ＧＰＣ）で分取した重合体の分析で求められる。[0007] In the methacrylic resin composition, copolymer [B
] The content range is 0.5 to 20.0% by weight. If the content of copolymer [B] exceeds 20.0% by weight, the heat distortion temperature of the methacrylic resin composition will decrease significantly, and if it is less than 0.5% by weight, the resistance of the methacrylic resin composition will decrease. Solvent properties and fluidity are not substantially improved. The preferred content range of copolymer [B] is 1.0 to 18.0% by weight. Furthermore, the preferred content range of copolymer [B] is 1.
It is 0 to 15.0% by weight. The content of copolymer [B] in the resin composition can be determined by analyzing a polymer fractioned by gel permeation chromatography (GPC).
【０００８】本発明に供するメタクリル樹脂〔Ａ〕とは
一般に用いられているもので特に限定しないが、好まし
くはメタクリル酸メチル単位８０．０〜９９．５重量％
と炭素数１〜８のアルキル基を有すアクリル酸アルキル
エステル単位０．５〜１５．０重量％で分子量７．０〜
２５．０万の重合体である。本発明のメタクリル樹脂組
成物おいて、耐溶剤性向上の理由は明らかでないが、メ
タクリル樹脂〔Ａ〕と共重合体〔Ｂ〕とに極性の差があ
るため、該樹脂組成物中で共重合体〔Ｂ〕がミクロ分散
し射出成形体の成形歪み（内部応力）が緩和され、溶剤
によるダメ−ジが低下したと推定される。The methacrylic resin [A] used in the present invention is commonly used and is not particularly limited, but preferably contains 80.0 to 99.5% by weight of methyl methacrylate units.
and 0.5 to 15.0% by weight of acrylic acid alkyl ester units having an alkyl group having 1 to 8 carbon atoms and a molecular weight of 7.0 to 7.0.
250,000 polymers. Although the reason for the improvement in solvent resistance in the methacrylic resin composition of the present invention is not clear, since there is a difference in polarity between the methacrylic resin [A] and the copolymer [B], copolymerization is possible in the resin composition. It is presumed that the coalescence [B] was microdispersed, the molding strain (internal stress) of the injection molded article was alleviated, and the damage caused by the solvent was reduced.
【０００９】本発明の樹脂組成物を製造する場合には公
知の重合法、重合条件、重合開始剤、分子量調整剤、を
用いる事ができる。共重合体〔Ｂ〕とメタクリル樹脂〔
Ａ〕との混合は公知の混練法を用いる事ができ、必要に
応じて、共重合体〔Ｂ〕をモノマ−溶液へ溶解混合し重
合して該樹脂組成物を得る事もできる。When producing the resin composition of the present invention, known polymerization methods, polymerization conditions, polymerization initiators, and molecular weight regulators can be used. Copolymer [B] and methacrylic resin [
A known kneading method can be used for mixing with A], and if necessary, the resin composition can also be obtained by dissolving and mixing copolymer [B] in a monomer solution and polymerizing it.
【００１０】本発明の樹脂組成物はメタクリル樹脂本来
の特性を損なわない範囲で可塑剤、紫外線吸収剤、滑剤
、熱安定剤、離型剤、等の添加剤を含有してもよい。The resin composition of the present invention may contain additives such as plasticizers, ultraviolet absorbers, lubricants, heat stabilizers, mold release agents, etc., to the extent that the inherent properties of the methacrylic resin are not impaired.
【００１１】[0011]
【実施例】次に実施例、比較例、によって本発明を詳細
に説明する。なお共重合体〔Ｂ〕、メタクリル樹脂〔Ａ
〕、メタクリル樹脂組成物の物性の測定法及び評価法は
次の通りである。
（１）分子量：ここでは粘度平均分子量をいう、すなわ
ちクロロホルムを溶剤として２５℃で極限粘度を測定し
次式に従って求めたものである。[Examples] Next, the present invention will be explained in detail with reference to Examples and Comparative Examples. Copolymer [B], methacrylic resin [A]
], The methods for measuring and evaluating the physical properties of the methacrylic resin composition are as follows. (1) Molecular weight: Here, it refers to the viscosity average molecular weight, that is, the intrinsic viscosity was measured at 25° C. using chloroform as a solvent and determined according to the following formula.
【００１２】
Ｍ０８ ＝〔η〕／４．８５×１０−６ （ｌ／ｇ
）ただしＭは粘度平均分子量であり、〔η〕はクロロホ
ルム溶媒２５℃における極限粘度である。
（２）重合体中のアルキルアクリレ−ト量：ガスクロ法
で温度４５０℃で熱分解して求めたものである。M08 = [η]/4.85×10-6 (l/g
) However, M is the viscosity average molecular weight, and [η] is the intrinsic viscosity of the chloroform solvent at 25°C. (2) Amount of alkyl acrylate in the polymer: Determined by thermal decomposition at a temperature of 450° C. using a gas chromatography method.
【００１３】（３）耐溶剤性： 射出成形体（ＡＳＴ
Ｍ、ＴＹＰＥ−Ｉダンベル、厚さ３．１８ｍｍ）をもち
いて温度２３℃、相対湿度６０％で２４時間状態調節し
たのち温度２０℃のエタノ−ル及びキシレン中へ１分間
浸漬しクラック、クレイズの発生状態を観察する。優劣
判定は次のようにして示した。○はクラック、クレイズ
が発生しない。△は小さいクラック、クレイズが数個発
生する。×はクラック、クレイズが多数発生する。(3) Solvent resistance: Injection molded product (AST
M, TYPE-I dumbbells, thickness 3.18 mm) were conditioned for 24 hours at a temperature of 23°C and a relative humidity of 60%, and then immersed in ethanol and xylene at a temperature of 20°C for 1 minute to remove cracks and crazes. Observe the state of occurrence. The superiority/inferiority judgment was made as follows. ○ indicates that no cracks or crazes occur. △: Several small cracks and crazes occur. × indicates that many cracks and crazes occur.
【００１４】（４）流動性：同一成形温度でのショ−ト
ショット射出圧を流動性の指標にした。ここでは、ＩＳ
−７５型射出成形機（東芝機械製）でシリンダ−温度２
４０℃、金型温度５０℃での金型内部を樹脂で充分に満
たす充填下限圧をショ−トショト射出圧とし、物性試験
片（ＡＳＴＭ、ＴＹＰＥ−Ｉダンベル、厚さ３．１８ｍ
ｍ）成形時の射出圧で示したものである。(4) Fluidity: The short shot injection pressure at the same molding temperature was used as an index of fluidity. Here, IS
- Cylinder temperature 2 using a 75-type injection molding machine (manufactured by Toshiba Machine)
The lower limit filling pressure to sufficiently fill the inside of the mold with resin at 40°C and mold temperature of 50°C was taken as the short-shot injection pressure, and a physical property test piece (ASTM, TYPE-I dumbbell, thickness 3.18 m) was prepared.
m) It is indicated by the injection pressure during molding.
【００１５】（５）曇価：ＡＳＴＭＤ−１００３で測定
する。
（６）引張強度：ＡＳＴＭＤ−６３８で測定する。
（７）熱変形温度：ＡＳＴＭＤ−６４８で測定する。
（１８．２ｋｇ／ｃｍ２）(5) Haze value: Measured according to ASTM D-1003. (6) Tensile strength: Measured according to ASTM D-638. (7) Heat distortion temperature: Measured according to ASTM D-648. (18.2kg/cm2)
【００１６】[0016]
【実施例−１】２００リットルの反応機にメタクリル酸
メチル３０ｋｇ、アクリル酸メチル２０ｋｇ、ラウリル
パ−オキサイド０．２ｋｇ、ｎ−ドデシルメルカプタン
０．５ｋｇ、を溶解した溶液と、脱イオン水１００ｋｇ
、ポリメタクリル酸カリウム７５ｇ、硫酸ナトリウム５
０ｇ、を溶解した溶液とを仕込んで重合温度７５℃で通
常の懸濁重合をおこなった。最大発熱ピ−クの終了後、
９０℃、６０分間、後重合して反応を完結した。しかる
のち常法通りロ過、洗浄、した後 乾燥して共重合体
〔Ｂ〕を得た。共重合体〔Ｂ〕は 分子量４万、アク
リル酸メチルの含有量３９．４重量％であった。[Example-1] A solution of 30 kg of methyl methacrylate, 20 kg of methyl acrylate, 0.2 kg of lauryl peroxide, and 0.5 kg of n-dodecyl mercaptan was placed in a 200-liter reactor, and 100 kg of deionized water was added.
, potassium polymethacrylate 75g, sodium sulfate 5g
A solution in which 0 g of 0.0 g was dissolved was charged, and normal suspension polymerization was carried out at a polymerization temperature of 75°C. After the end of the maximum heat generation peak,
The reaction was completed by post-polymerization at 90° C. for 60 minutes. Thereafter, the mixture was filtered, washed, and dried in the usual manner to obtain copolymer [B]. Copolymer [B] had a molecular weight of 40,000 and a methyl acrylate content of 39.4% by weight.
【００１７】アクリル酸メチル含有量が４重量％で分子
量１２万のメタクリル樹脂〔Ａ〕９５重量部と、共重合
体〔Ｂ〕５重量部とを、混合しベント付二軸押出機でペ
レット化した。得た樹脂組成物の一部をもちいて射出成
形したところ、このもののショ−トショット圧は３８０
ｋｇ／ｃｍ２を示し、又、射出圧をショ−トショット圧
プラス１００ｋｇ／ｃｍ２で得た成形体は発泡、銀状痕
、ヒケ、等が全く認められなかった。この成形体をエタ
ノ−ル中に浸漬したところクラック、クレイズは全く発
生しなかった。又、溶剤をキシレンにかえて浸漬したが
クラック、クレイズは全く発生しなかった。[0017] 95 parts by weight of methacrylic resin [A] having a methyl acrylate content of 4% by weight and a molecular weight of 120,000 and 5 parts by weight of copolymer [B] were mixed and pelletized using a vented twin-screw extruder. did. When injection molding was performed using a part of the obtained resin composition, the short shot pressure of this product was 380.
kg/cm2, and no foaming, silver marks, sink marks, etc. were observed in the molded product obtained under the injection pressure of short shot pressure plus 100 kg/cm2. When this molded article was immersed in ethanol, no cracks or crazes occurred. In addition, even though the solvent was changed to xylene for immersion, no cracks or crazes occurred.
【００１８】この樹脂組成物の物性は曇価０．４％、熱
変形温度９６℃、引張強度７５０ｋｇ／ｃｍ２、を示し
、又、サンシャインウェザ−メ−タ−で２５００時間照
射したが着色、光沢、等の外観に全く変化は認められな
かった。結果を表２に示す。The physical properties of this resin composition were a haze value of 0.4%, a heat deformation temperature of 96°C, and a tensile strength of 750 kg/cm2.Also, when irradiated with a sunshine weather meter for 2500 hours, there was no coloration or gloss. , etc. No changes were observed in the appearance. The results are shown in Table 2.
【００１９】[0019]
【比較例−１】アクリル酸メチル含有量６重量％、分子
量１１．５万のメタクリル樹脂ペレットで、実施例−１
と同様にして射出成形したところ、このもののショ−ト
ショット圧は４２０ｋｇ／ｃｍ２を示した。成形体をエ
タノ−ル中に浸漬したところクラックが多数発生したが
、８５℃で熱処理した成形体で同じ試験をするとクラッ
ク、クレイズは全く発生しなかった。この樹脂の物性は
曇価０．４％、熱変形温度９６℃、引張強度７５０ｋｇ
／ｃｍ２、であった。結果を表３に示す。[Comparative Example-1] Using methacrylic resin pellets with a methyl acrylate content of 6% by weight and a molecular weight of 115,000, Example-1
When injection molded in the same manner as above, the short shot pressure of this product was 420 kg/cm2. When the molded product was immersed in ethanol, many cracks occurred, but when the same test was performed on a molded product heat-treated at 85° C., no cracks or crazes occurred at all. The physical properties of this resin are haze value 0.4%, heat distortion temperature 96℃, and tensile strength 750kg.
/cm2. The results are shown in Table 3.
【００２０】[0020]
【実施例−２〜−９】表１に示す樹脂組成物を用いて押
出機でペレット化した以外は実施例−１と同様にして行
った、結果を表２に示す。[Examples 2 to 9] The same procedure as in Example 1 was conducted except that the resin compositions shown in Table 1 were pelletized using an extruder. The results are shown in Table 2.
【００２１】[0021]
【比較例−２〜−１０】表１に示す樹脂組成物を用いて
、押出機でペレット化した以外は実施例−１と同様にし
て行った、結果を表３に示す。Comparative Examples 2 to 10 The resin compositions shown in Table 1 were used in the same manner as in Example 1 except that they were pelletized using an extruder. The results are shown in Table 3.
【００２２】[0022]
【表１】[Table 1]
【００２３】[0023]
【表２】[Table 2]
【００２４】[0024]
【表３】[Table 3]
【００２５】[0025]
【発明の効果】本発明によれば 耐溶剤性、成形性に
優れかつメタクリル樹脂本来の性質を維持した従来にな
い新規なメタクリル樹脂がえられる。しかも熱処理を必
要としない為生産性に優れており産業上利用価値が高い
。[Effects of the Invention] According to the present invention, a novel methacrylic resin which has excellent solvent resistance and moldability and maintains the original properties of methacrylic resin can be obtained. Furthermore, since no heat treatment is required, productivity is excellent and industrial use value is high.
Claims (1)
．５重量部と、メタクリル酸メチル単位３５．０〜８０
．０重量％と炭素数が１〜８のアルキル基を有すアクリ
ル酸アルキルエステル単位２０．０〜６５．０重量％で
構成される分子量２．０〜１５．０万の共重合体〔Ｂ〕
０．５〜２０．０重量部とからなる事を特徴とする耐溶
剤性に優れたメタクリル樹脂組成物。[Claim 1] Methacrylic resin [A] 80.0-99
．． 5 parts by weight and 35.0 to 80 methyl methacrylate units
．． Copolymer with a molecular weight of 2.0 to 150,000 [B] composed of 0% by weight and 20.0 to 65.0% by weight of acrylic acid alkyl ester units having an alkyl group having 1 to 8 carbon atoms.
0.5 to 20.0 parts by weight of a methacrylic resin composition having excellent solvent resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3874491A JPH04277545A (en) | 1991-03-05 | 1991-03-05 | Methacrylic resin composition excellent in solvent resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3874491A JPH04277545A (en) | 1991-03-05 | 1991-03-05 | Methacrylic resin composition excellent in solvent resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04277545A true JPH04277545A (en) | 1992-10-02 |
Family
ID=12533826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3874491A Withdrawn JPH04277545A (en) | 1991-03-05 | 1991-03-05 | Methacrylic resin composition excellent in solvent resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04277545A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011049203A1 (en) | 2009-10-22 | 2011-04-28 | 旭化成ケミカルズ株式会社 | Methacrylic resin, molded body thereof, and method for producing methacrylic resin |
| US7964690B2 (en) | 2005-11-24 | 2011-06-21 | Asahi Kasei Chemicals Corporation | Methacrylic resin and process for producing thererof |
| JP2012012564A (en) * | 2009-12-25 | 2012-01-19 | Asahi Kasei Chemicals Corp | Methacrylic resin for melt molding, methacrylic resin composition for melt molding, manufacturing methods for the same, and molded article |
-
1991
- 1991-03-05 JP JP3874491A patent/JPH04277545A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7964690B2 (en) | 2005-11-24 | 2011-06-21 | Asahi Kasei Chemicals Corporation | Methacrylic resin and process for producing thererof |
| JP2012132032A (en) * | 2005-11-24 | 2012-07-12 | Asahi Kasei Chemicals Corp | Methacrylic resin and method of manufacturing the same |
| JP2013189652A (en) * | 2005-11-24 | 2013-09-26 | Asahi Kasei Chemicals Corp | Methacrylic resin and method for producing the same |
| JP5623693B2 (en) * | 2005-11-24 | 2014-11-12 | 旭化成ケミカルズ株式会社 | Methacrylic resin and method for producing the same |
| WO2011049203A1 (en) | 2009-10-22 | 2011-04-28 | 旭化成ケミカルズ株式会社 | Methacrylic resin, molded body thereof, and method for producing methacrylic resin |
| US8617708B2 (en) | 2009-10-22 | 2013-12-31 | Asahi Kasei Chemicals Corporation | Methacrylic resin, molded article thereof, and method for producing methacrylic resin |
| JP2012012564A (en) * | 2009-12-25 | 2012-01-19 | Asahi Kasei Chemicals Corp | Methacrylic resin for melt molding, methacrylic resin composition for melt molding, manufacturing methods for the same, and molded article |
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| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980514 |