JPS644976B2 - - Google Patents
Info
- Publication number
- JPS644976B2 JPS644976B2 JP20921083A JP20921083A JPS644976B2 JP S644976 B2 JPS644976 B2 JP S644976B2 JP 20921083 A JP20921083 A JP 20921083A JP 20921083 A JP20921083 A JP 20921083A JP S644976 B2 JPS644976 B2 JP S644976B2
- Authority
- JP
- Japan
- Prior art keywords
- syrup
- weight
- methyl methacrylate
- aluminum hydroxide
- curing
- 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.)
- Expired
Links
- 239000006188 syrup Substances 0.000 claims description 26
- 235000020357 syrup Nutrition 0.000 claims description 26
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 20
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000001451 organic peroxides Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 13
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 7
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- -1 peroxy compound Chemical class 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical class OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical class CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 239000002928 artificial marble Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- PXFDQFDPXWHEEP-UHFFFAOYSA-M benzyl-dimethyl-octylazanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(C)CC1=CC=CC=C1 PXFDQFDPXWHEEP-UHFFFAOYSA-M 0.000 description 1
- BNDXNEVHWSOJGV-UHFFFAOYSA-M benzyl-hexyl-dimethylazanium;chloride Chemical compound [Cl-].CCCCCC[N+](C)(C)CC1=CC=CC=C1 BNDXNEVHWSOJGV-UHFFFAOYSA-M 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UKRVECBFDMVBPU-UHFFFAOYSA-N ethyl 3-oxoheptanoate Chemical compound CCCCC(=O)CC(=O)OCC UKRVECBFDMVBPU-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FZCCKDYTOZQJJR-UHFFFAOYSA-M hexyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCC[N+](C)(C)C FZCCKDYTOZQJJR-UHFFFAOYSA-M 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical class CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- AQZSPJRLCJSOED-UHFFFAOYSA-M trimethyl(octyl)azanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(C)C AQZSPJRLCJSOED-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
メチルメタアクリレート系予備重合体シロツプ
に水酸化アルミニウムを混合して該シロツプ用硬
化剤を加えて硬化せしめた大理石調物品はよく知
られている。
但しこの硬化に際しては、水酸化アルミニウム
の付着水分の除去が困難なために混合物中の水分
が多くなり、重合阻害作用を受けるのが普通であ
る。従つて、これを改善するための種々な方法が
提案されている。
その一例はマレイン酸のヘミパーエステルのよ
うな水溶性パーオキシ化合物またはその金属塩と
メルカプタン系連鎖移動剤を用いる方法であり、
他の一例は有機過酸化物と有機三級アミンの組合
せによる方法である。しかし、前者の方法で用い
られるマレイン酸のヘミパーエステル類は非常に
不安定な化合物で通常入手が困難であり、大量に
取扱うのは容易でない。後者の方法では例えば過
酸化ベンゾイルとジメチルアニリンとの組合せな
どが最も一般的であり硬化促進の効果はあるが、
着色が大であり且つ変色もするので、人工大理石
のような美しさが要求され変色を嫌うような用途
には適切な方法とは言い難い。
本発明はこれらの問題点を解消する有効な方法
を提供するものである。即ち本発明は、メチルメ
タアクリレート系予備重合体シロツプ80〜10重量
％と水酸化アルミニウム20〜90重量％とを混合し
て（但し、両者の合計は100重量％である。）、シ
ロツプ用硬化剤を加え固化せしめて人工大理石調
物品を製造する方法において、硬化剤として有機
過酸化物と一般式
Marble-like articles prepared by mixing aluminum hydroxide with methyl methacrylate prepolymer syrup and curing the syrup by adding a curing agent for the syrup are well known. However, during this curing, since it is difficult to remove moisture adhering to aluminum hydroxide, the mixture usually contains a large amount of moisture, which inhibits polymerization. Therefore, various methods have been proposed to improve this. One example is a method using a water-soluble peroxy compound such as hemiperester of maleic acid or a metal salt thereof and a mercaptan chain transfer agent,
Another example is a method using a combination of an organic peroxide and an organic tertiary amine. However, hemiperesters of maleic acid used in the former method are very unstable compounds and are usually difficult to obtain, and it is not easy to handle them in large quantities. In the latter method, the most common method is a combination of benzoyl peroxide and dimethylaniline, which has the effect of accelerating curing, but
Since it is highly colored and discolored, it is difficult to say that it is an appropriate method for applications where beauty such as artificial marble is required and discoloration is disliked. The present invention provides an effective method for solving these problems. That is, in the present invention, 80 to 10% by weight of methyl methacrylate prepolymer syrup and 20 to 90% by weight of aluminum hydroxide are mixed (however, the total of both is 100% by weight), and a curing agent for syrup is prepared. In the method of manufacturing artificial marble-like articles by adding a curing agent and solidifying it, organic peroxide and the general formula
【式】で示される
四級アンモニウム塩を用いるか必要により更に有
機溶媒に可溶性の有機酸金属塩を併用して、60℃
以下の温度で硬化せしめることを特徴とする人造
大理石調物品の製造に関するものである。
本発明に用い得るメチルメタアクリレート系予
備重合体シロツプは、メチルメタアクリレートモ
ノマーに必要粘度を与えるだけのポリメチルメタ
アクリレートを溶解するか、メチルメタアクリレ
ートモノマーに重合開始剤と連鎖移動剤を加えて
加熱重合を行い希望の重合率に達したならば重合
停止剤を含む冷たいメチルメタアクリレートモノ
マーを加えるなどの方法で反応系を急冷して重合
を停止するなどの通常の方法で得られたものであ
る。水酸化アルミニウムは平均粒子径が３〜50μ
ｍで実質的に有機物質を含まない白度の高いもの
が良い。粒子の大なるものは透明感を大にするが
沈降を起こし易くなり、小なるものはシロツプと
の混合において粘度が高くなるために混入量を多
くできないなどの障害を生ずる。
硬化剤の有機過酸化物としてはメチルエチルケ
トンパーオキサイド、メチルイソブチルケトンパ
ーオキサイド、シクロヘキサノンパーオキサイド
などがある。四級アンモニウム塩は一般式が
Using a quaternary ammonium salt represented by the formula or, if necessary, an organic acid metal salt soluble in an organic solvent, at 60°C.
The present invention relates to the production of an artificial marble-like article characterized by being cured at the following temperature. The methyl methacrylate prepolymer syrup that can be used in the present invention can be prepared by dissolving enough polymethyl methacrylate to give the methyl methacrylate monomer the necessary viscosity, or by adding a polymerization initiator and a chain transfer agent to the methyl methacrylate monomer. It is obtained by the usual method of heating the polymerization and once the desired polymerization rate is reached, the reaction system is rapidly cooled by adding cold methyl methacrylate monomer containing a polymerization terminator to stop the polymerization. be. Aluminum hydroxide has an average particle size of 3 to 50μ
A material with a high whiteness and substantially free of organic substances is preferable. Large particles increase transparency but tend to cause sedimentation, while small particles cause problems such as the inability to increase the amount of mixed syrup due to the increased viscosity when mixed with syrup. Examples of organic peroxides used as curing agents include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, and cyclohexanone peroxide. The general formula for quaternary ammonium salts is
【式】で示される化合物である。こ
こでＸはCl、Br又はＩ；R1は炭素数６〜18の炭
化水素基；R2はメチル、エチル、ラウリル、又
はステアリル基；R3、R4はメチル基、エチル基
又はベンジル基である。具体的にはオクチルトリ
メチルアンモニウムクロライド、オクチルベンジ
ルジメチルアンモニウムクロライド、ヘキシルト
リメチルアンモニウムクロライド、ヘキシルベン
ジルジメチルアンモニウムクロライド、ラウリル
トリメチルアンモニウムクロライドなどが好適で
ある。金属石けんとしてはナフテン酸やオクチル
酸のCo、Mn、Fe、Cu、Caなどの塩の単独又は
組合せで用いるのが適当である。
本発明を実施するにはメチルメタアクリレート
系シロツプ100重量部に対して四級アンモニウム
塩0.01〜２重量部をよく混合しておき、次いで有
機過酸化物を0.5〜2.0重量部の割合で加えてよく
撹拌し、必要ならば有機酸金属塩を金属分として
0.001〜0.05重量部となる量を予じめシロツプ中
に溶解して硬化剤含有シロツプを調製する。次
に、硬化剤含有シロツプが80〜10重量％、水酸化
アルミニウムが20〜90重量％になるように配合し
てよく混練し、脱泡後、注形用型に注入して60℃
以下の温度で硬化せしめる。この段階で60℃を越
える温度で硬化させると本発明の優れた人工大理
石調物品が得られない。60℃以下の温度で硬化せ
しめたのち、若し必要ならば80゜〜100℃の温度で
後硬化をし、徐冷をして歪のないようにして硬化
を完了する。このようにすることによつて、分厚
い注形品もクラツクの発生なしにしかも経済的な
時間内で硬化を行うことが出来、好ましからざる
着色のない美麗な物品を得ることができる。以
下、実施例を用いて詳細に説明するが、これらは
本発明の全てを包含するものではない。尚、例中
の％は重量％を示すものとする。
実施例 １
メチルメタアクリレート14Kgを加熱し、30分間
で85℃まで昇温し、その間雰囲気をN2ガス置換
して脱酸素した。85℃になつた時点でチオグリコ
ール酸50ｇを加え、引続きアゾイソブチロニトリ
ル６ｇを加えて重合を開始し、内温を１℃〜1.5
℃／分で90℃まで昇温させ、そのまま保持して開
始剤添加後60分後にMMA5Kgを２分間で加えて
冷却して重合を停止させ、不揮発分30％、粘度
420センチポイズのメチルメタアクリレートのシ
ロツプを得た。このシロツプ１Kgに、イソプロパ
ノールに溶解したラウリルトリメチルアンモニウ
ムクロライド（濃度約60％）10ｇを加えてよく撹
拌し、次いでシクロヘキサノンパーオキサイド10
ｇを加えよく溶解した。次いでこの樹脂組成物に
平均粒径が6.5〜9.5ミクロンの水酸化アルミニウ
ム２Kgを加えてよく混合し、脱気後、30cm×40cm
×1.5cmの内容のあるガラス板を組立てた型に注
入し、室温（約20℃）で静置した。内容物は4.5
時間後から5.5時間位の間で発熱を終り、硬化を
完了した。固化物は白色半透明で耐炎性を有する
美麗な板であつた。
実施例 ２
実施例１で得たメチルメタアクリレートの
シロツプ（不揮発分30％） １Kg
ラウリルトリメチルアンモニウムクロライド
（濃度約60％） 10ｇ
メチルイソブチルケトンパーオキサイド
（濃度約60％） 10ｇ
水酸化アルミニウム
（粒径6.5〜9.5ミクロン） ２Kg
上記の組成で実施例１と同様にして室温で硬化
させたところ、３〜４時間で硬化が完了し、耐炎
性を有する美麗な白色半透明板が得られた。
実施例 ３
実施例１で得たメチルメタアクリレートの
シロツプ（不揮発分30％） １Kg
ラウリルトリメチルアンモニウムクロライド
（濃度約60％） ３ｇ
オクテン酸マンガン
（マンガン分約0.5％） ３ｇ
シクロヘキサノンパーオキサイド
（濃度約60％） 10ｇ
水酸化アルミニウム
（粒径6.5〜9.5ミクロン） ２Kg
上記の組成で実施例１と同様にして室温で硬化
させたところ、６〜７時間で硬化が完了し、耐炎
性を示する美麗な白色半透明板が得られた。
比較例 １
実施例１において、四級アンモニウム塩である
ラウリルトリメチルアンモニウムクロライドを用
いない他は実施例１と同様にして注型し、室温下
に放置したが、３日後もゲル化していなかつた。
比較例 ２
実施例２において、四級アンモニウム塩である
ラウリルトリメチルアンモニウムクロライドを用
いない他は実施例２と同様にして注型し、室温下
に放置したが、２日後もゲル化していなかつた。
比較例 ３
実施例３において、四級アンモニウム塩である
ラウリルトリメチルアンモニウムクロライドを用
いない他は実施例３と同様にして注型し、室温下
に放置したが、５日後もゲル化していなかつた。
実施例 ４
実施例１で得たメチルメタアクリレートの
シロツプ（不揮発分30％） １Kg
ステアリルトリメチルアンモニウムクロライド
（濃度約60％） 10ｇ
メチルイソブチルケトンパーオキサイド
（濃度約60％） 10ｇ
水酸化アルミニウム
（粒径6.5〜9.5ミクロン） ２Kg
上記の組成で実施例１と同様にして室温で硬化
させたところ、５〜６時間で硬化が完了し、耐炎
性を有する美麗な白色半透明板が得られた。
実施例 ５
実施例１で得たメチルメタアクリレートの
シロツプ（不揮発分30％） １Kg
ジステアリルジメチルアンモニウムクロライド
（濃度約60％） 10ｇ
メチルエチルケトンパーオキサイド
（濃度約55％） 10ｇ
水酸化アルミニウム
（粒径6.5〜9.5ミクロン） ２Kg
上記の組成で実施例１と同様にして室温で硬化
させたところ、６〜７時間で硬化が完了し、耐炎
性を有する美麗な白色半透明板が得られた。
比較例 ４
実施例１で得たメチルメタアクリレートの
シロツプ（不揮発分30％） １Kg
ジメチルアニリン 0.3ｇ
ベンゾイルパーオキサイド
（50％ペースト） 10ｇ
水酸化アルミニウム
（粒径6.5〜9.5ミクロン） ２Kg
上記の組成で実施例１と同様にして室温で硬化
させたところ、４〜５時間で硬化が完了したが、
得られたものは淡黄色に着色した半透明板であつ
た。
実施例 ６
実施例１で得たメチルメタアクリレートのシロツ
プ
（不揮発分30％） 2100ｇ
ラウリルトリメチルアンモニウムクロライド
（濃度60％） ２ｇ
シクロヘキサノンパーオキサイド
（濃度約60％） 13ｇ
水酸化アルミニウム
（粒径3.5ミクロン） 700ｇ
上記の組成で実施例１と同様にして硬化させた
ところ、８〜10時間で硬化が完了し、耐炎性のあ
る白色透明性に富んだ美麗な板が得られた。
実施例 ７
実施例１で得たメチルメタアクリレートのシロツ
プ
（不揮発分30％） 750ｇ
ラウリルトリメチルアンモニウムクロライド
（濃度約60％） ５ｇ
シクロヘキサノンパーオキサイド
（濃度約60％） 30ｇ
水酸化アルミニウム
（粒径200〜325メツシユ86％） 3000ｇ
（平均粒径16ミクロン） 1250ｇ
上記の組成で混練押出機でよく混練し、脱泡し
て型内に押出し注入して、50℃で２〜３時間で硬
化させた。硬化物は透明感のある耐炎、白色、美
麗な板であつた。
比較例 ５
実施例１で得たメチルメタアクリレートのシロツ
プ
（不揮発分30％） １Kg
ベンゾイル、パーオキサイド
（50％ペースト） 60ｇ
水酸化アルミニウム
（粒径6.5〜9.5ミクロン） ２Kg
上記の組成で30cm×40cm×1.5cmのセルに注入
し、80℃の空気浴中で硬化させた。硬化物は白色
で透明感が少なく、部分的に大きな気泡が入つて
いた。It is a compound represented by the formula: Here, X is Cl, Br, or I; R 1 is a hydrocarbon group having 6 to 18 carbon atoms; R 2 is methyl, ethyl, lauryl, or stearyl group; R 3 and R 4 are methyl, ethyl, or benzyl groups. It is. Specifically, octyltrimethylammonium chloride, octylbenzyldimethylammonium chloride, hexyltrimethylammonium chloride, hexylbenzyldimethylammonium chloride, lauryltrimethylammonium chloride, etc. are suitable. As the metal soap, it is appropriate to use salts of naphthenic acid or octylic acid such as Co, Mn, Fe, Cu, Ca, etc. alone or in combination. To carry out the present invention, 0.01 to 2 parts by weight of a quaternary ammonium salt is thoroughly mixed with 100 parts by weight of methyl methacrylate syrup, and then an organic peroxide is added in a proportion of 0.5 to 2.0 parts by weight. Stir well and add organic acid metal salt as a metal component if necessary.
A hardener-containing syrup is prepared by dissolving in advance an amount of 0.001 to 0.05 parts by weight in the syrup. Next, the hardening agent-containing syrup is 80-10% by weight and the aluminum hydroxide is 20-90% by weight, mixed well, and after defoaming, poured into a casting mold and heated to 60°C.
Cure at the following temperatures. If it is cured at a temperature exceeding 60°C at this stage, the excellent artificial marble-like article of the present invention cannot be obtained. After curing at a temperature of 60°C or lower, if necessary, post-curing is performed at a temperature of 80° to 100°C, followed by slow cooling to complete curing without distortion. By doing so, thick cast articles can be cured without cracking and within an economical time, and beautiful articles without undesirable coloring can be obtained. Hereinafter, the present invention will be explained in detail using Examples, but these do not include all of the present invention. Note that % in the examples indicates weight %. Example 1 14 kg of methyl methacrylate was heated and the temperature was raised to 85° C. in 30 minutes, during which time the atmosphere was replaced with N 2 gas to remove oxygen. When the temperature reached 85°C, 50g of thioglycolic acid was added, followed by 6g of azoisobutyronitrile to start polymerization, and the internal temperature was raised to 1°C to 1.5°C.
The temperature was raised to 90℃ at a rate of ℃/min, held at that temperature, and 60 minutes after adding the initiator, 5 kg of MMA was added over 2 minutes to cool down and stop the polymerization.
A syrup of 420 centipoise methyl methacrylate was obtained. To 1 kg of this syrup, add 10 g of lauryltrimethylammonium chloride (concentration approximately 60%) dissolved in isopropanol, stir well, and then add 10 g of cyclohexanone peroxide.
g was added and dissolved well. Next, 2 kg of aluminum hydroxide with an average particle size of 6.5 to 9.5 microns was added to this resin composition, mixed well, and after degassing, a 30 cm x 40 cm
A glass plate with a content of 1.5 cm was poured into the assembled mold and left at room temperature (approximately 20°C). The contents are 4.5
After about 5.5 hours, the heat generation stopped and curing was completed. The solidified product was a beautiful, white, translucent, flame-resistant plate. Example 2 Methyl methacrylate syrup obtained in Example 1 (nonvolatile content 30%) 1Kg Lauryltrimethylammonium chloride (Concentration approximately 60%) 10g Methyl isobutyl ketone peroxide (Concentration approximately 60%) 10g Aluminum hydroxide (Particle size 6.5 to 9.5 microns) 2Kg When the above composition was cured at room temperature in the same manner as in Example 1, curing was completed in 3 to 4 hours, and a beautiful white translucent plate with flame resistance was obtained. Example 3 Methyl methacrylate syrup obtained in Example 1 (non-volatile content: 30%) 1 kg Lauryltrimethylammonium chloride (concentration: approx. 60%) 3 g Manganese octoate (manganese content: approx. 0.5%) 3 g cyclohexanone peroxide (concentration: approx. 60%) %) 10g Aluminum hydroxide (particle size 6.5-9.5 microns) 2Kg When the above composition was cured at room temperature in the same manner as in Example 1, curing was completed in 6-7 hours and a beautiful flame-resistant product was obtained. A white translucent plate was obtained. Comparative Example 1 Casting was performed in the same manner as in Example 1 except that lauryltrimethylammonium chloride, which is a quaternary ammonium salt, was not used, and the molding was left at room temperature, but gelation did not occur even after 3 days. Comparative Example 2 Casting was performed in the same manner as in Example 2 except that lauryltrimethylammonium chloride, which is a quaternary ammonium salt, was not used, and the molding was left at room temperature, but gelation did not occur even after 2 days. Comparative Example 3 Casting was carried out in the same manner as in Example 3 except that lauryltrimethylammonium chloride, which is a quaternary ammonium salt, was not used, and the molding was left at room temperature, but gelation did not occur even after 5 days. Example 4 Methyl methacrylate syrup obtained in Example 1 (non-volatile content 30%) 1 kg Stearyltrimethylammonium chloride (concentration approximately 60%) 10 g Methyl isobutyl ketone peroxide (concentration approximately 60%) 10 g Aluminum hydroxide (particle size 6.5 to 9.5 microns) 2Kg When the above composition was cured at room temperature in the same manner as in Example 1, curing was completed in 5 to 6 hours, and a beautiful white translucent plate with flame resistance was obtained. Example 5 Methyl methacrylate syrup obtained in Example 1 (non-volatile content 30%) 1 kg Distearyldimethylammonium chloride (concentration approximately 60%) 10 g Methyl ethyl ketone peroxide (concentration approximately 55%) 10 g Aluminum hydroxide (particle size 6.5 ~9.5 microns) 2Kg When the above composition was cured at room temperature in the same manner as in Example 1, curing was completed in 6 to 7 hours, and a beautiful white translucent plate with flame resistance was obtained. Comparative Example 4 Methyl methacrylate syrup obtained in Example 1 (non-volatile content 30%) 1Kg Dimethylaniline 0.3g Benzoyl peroxide (50% paste) 10g Aluminum hydroxide (particle size 6.5-9.5 microns) 2Kg With the above composition When it was cured at room temperature in the same manner as in Example 1, curing was completed in 4 to 5 hours, but
What was obtained was a semi-transparent plate colored pale yellow. Example 6 Methyl methacrylate syrup obtained in Example 1 (non-volatile content 30%) 2100g lauryltrimethylammonium chloride (concentration 60%) 2g cyclohexanone peroxide (concentration approximately 60%) 13g aluminum hydroxide (particle size 3.5 microns) 700g When the above composition was cured in the same manner as in Example 1, curing was completed in 8 to 10 hours, and a beautiful white board with flame resistance and high transparency was obtained. Example 7 Methyl methacrylate syrup obtained in Example 1 (nonvolatile content 30%) 750g Lauryltrimethylammonium chloride (concentration approximately 60%) 5g cyclohexanone peroxide (concentration approximately 60%) 30g Aluminum hydroxide (particle size 200~ 325 mesh 86%) 3000g (average particle size 16 microns) 1250g The above composition was thoroughly kneaded in a kneading extruder, defoamed, extruded into a mold, and cured at 50°C for 2 to 3 hours. The cured product was a transparent, flame-resistant, white, and beautiful board. Comparative Example 5 Methyl methacrylate syrup obtained in Example 1 (nonvolatile content 30%) 1Kg Benzoyl, peroxide (50% paste) 60g Aluminum hydroxide (particle size 6.5-9.5 microns) 2Kg 30cm x 40cm with the above composition It was injected into a 1.5 cm x 1.5 cm cell and cured in an 80°C air bath. The cured product was white with little transparency and contained large bubbles in some areas.
Claims (1)
プ80〜10重量％と水酸化アルミニウム20〜90重量
％とを混合して（但し、両者の合計は100重量％
である。）、シロツプ用硬化剤を加え固化せしめて
人工大理石調物品を製造する方法において、硬化
剤として有機過酸化物と一般式
【式】で示される四級アンモニウム 塩を用い、60℃以下の温度で硬化せしめることを
特徴とする方法。 ２ メチルメタアクリレート系予備重合体シロツ
プ80〜10重量％と水酸化アルミニウム20〜90重量
％とを混合して（但し、両者の合計は100重量％
である。）、シロツプ用硬化剤を加え固化せしめて
人工大理石調物品を製造する方法において、硬化
剤として有機過酸化物と一般式
【式】で示される四級アンモニウム 塩と有機溶媒可溶性の有機酸金属塩を併用し、60
℃以下の温度で硬化せしめることを特徴とする方
法。[Claims] 1. 80 to 10% by weight of methyl methacrylate prepolymer syrup and 20 to 90% by weight of aluminum hydroxide are mixed (however, the total of both is 100% by weight).
It is. ), a method of manufacturing artificial marble-like articles by adding and solidifying a hardening agent for syrup, using an organic peroxide and a quaternary ammonium salt represented by the general formula [formula] as the hardening agent, at a temperature of 60°C or less. A method characterized by hardening. 2 Mix 80 to 10% by weight of methyl methacrylate prepolymer syrup and 20 to 90% by weight of aluminum hydroxide (however, the total of both is 100% by weight).
It is. ), a method of manufacturing an artificial marble-like article by adding and solidifying a hardening agent for syrup, in which an organic peroxide is used as a hardening agent, a quaternary ammonium salt represented by the general formula [formula], and an organic acid metal salt soluble in an organic solvent. 60
A method characterized by curing at a temperature below ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20921083A JPS60103065A (en) | 1983-11-09 | 1983-11-09 | Manufacture of artificial marble article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20921083A JPS60103065A (en) | 1983-11-09 | 1983-11-09 | Manufacture of artificial marble article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60103065A JPS60103065A (en) | 1985-06-07 |
| JPS644976B2 true JPS644976B2 (en) | 1989-01-27 |
Family
ID=16569172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20921083A Granted JPS60103065A (en) | 1983-11-09 | 1983-11-09 | Manufacture of artificial marble article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60103065A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4734452A (en) * | 1985-08-07 | 1988-03-29 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Curable composition, method for manufacturing thereof, and uses thereof |
| JPH075345B2 (en) * | 1989-11-24 | 1995-01-25 | 日本植生株式会社 | Method of manufacturing artificial marble |
| US5243003A (en) * | 1992-06-25 | 1993-09-07 | Edwards Bill R | Acrylic/carbonate resin compositions |
| WO2001038407A1 (en) * | 1999-11-19 | 2001-05-31 | Mitsubishi Rayon Co., Ltd. | Resin composition |
| JP2005272175A (en) * | 2004-03-23 | 2005-10-06 | Kuraray Co Ltd | Acrylic-based artificial marble excellent in transparency feeling |
| JP6285164B2 (en) * | 2013-12-05 | 2018-02-28 | デクセリアルズ株式会社 | Compound, thermosetting resin composition, and thermosetting sheet |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5022586A (en) * | 1973-06-27 | 1975-03-11 | ||
| US4197215A (en) * | 1975-09-22 | 1980-04-08 | E. I. Du Pont De Nemours And Company | Composition for polymerizing and curing methyl methacrylate monomer-polymer syrups in the presence of metal salts of hemi-peresters of maleic acid |
| JPS5411188A (en) * | 1977-06-28 | 1979-01-27 | Denki Kagaku Kogyo Kk | Polymerization of acrylates and/or methacrylates |
-
1983
- 1983-11-09 JP JP20921083A patent/JPS60103065A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60103065A (en) | 1985-06-07 |
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