JPH01317720A - Production of molded product - Google Patents
Production of molded productInfo
- Publication number
- JPH01317720A JPH01317720A JP15015888A JP15015888A JPH01317720A JP H01317720 A JPH01317720 A JP H01317720A JP 15015888 A JP15015888 A JP 15015888A JP 15015888 A JP15015888 A JP 15015888A JP H01317720 A JPH01317720 A JP H01317720A
- Authority
- JP
- Japan
- Prior art keywords
- gel coat
- layer
- curing
- org
- side chain
- 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
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract 2
- 238000005266 casting Methods 0.000 claims description 19
- -1 organic acid salt Chemical class 0.000 claims description 7
- 150000001451 organic peroxides Chemical class 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 150000002978 peroxides Chemical class 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 2
- 238000005336 cracking Methods 0.000 abstract 2
- 238000002347 injection Methods 0.000 abstract 2
- 239000007924 injection Substances 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 2
- 238000001723 curing Methods 0.000 description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920001567 vinyl ester resin Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 125000005609 naphthenate group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PVCVRLMCLUQGBT-UHFFFAOYSA-N (1-tert-butylcyclohexyl) (1-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CCCCC1(C(C)(C)C)OC(=O)OOC(=O)OC1(C(C)(C)C)CCCCC1 PVCVRLMCLUQGBT-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002928 artificial marble Substances 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
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000005076 polymer ester Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は主として浴槽、テーブルトップ、洗面化粧台等
の美感を要求される成形品の製造に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention mainly relates to the production of molded products that require aesthetic appeal, such as bathtubs, table tops, washstands, and the like.
ラジカル硬化型樹脂、例えばポリエステル樹脂、ビニル
エステル樹脂は、加熱により硬化させること・ができる
が、工業的にこれを行おうとすると、大きな加熱装置を
必要とし、コストもかかるので可能な限り低温で、でき
れば常温で硬化させる方法が求められている。しかしな
がら、これらの硬化型の樹脂を常温またはこれに近い温
度で硬化させるには、硬化剤として有機過酸化物例えば
ケトンパーオキサイドを用い、硬化促進剤として例えば
コバルトの有機酸塩(ナフテン酸塩、オクチル酸塩)を
併用する必要がある。Radical-curable resins, such as polyester resins and vinyl ester resins, can be cured by heating, but if this is attempted on an industrial scale, large heating equipment is required and costs are high, so they must be cured at the lowest possible temperature. If possible, a method of curing at room temperature is required. However, in order to cure these curable resins at or near room temperature, an organic peroxide such as ketone peroxide is used as a curing agent, and an organic acid salt of cobalt (naphthenate, naphthenate, etc.) is used as a curing accelerator. octylate) must be used in combination.
しかし、例えばナフテン酸コバルトを利用した場合、成
形品、塗膜が時の経過とともに黄変するという、望まし
くない欠点を有する。However, when cobalt naphthenate is used, for example, it has the undesirable drawback that molded products and coatings yellow over time.
例えば、きわめて淡色が求められている人造大理石など
にあっては、使用中に変色することはその商品価値を大
きく下落させるので、好ましいことではない、とくにゲ
ルコートは、樹脂成形品の表面層を構成するものである
ので、この層の変色は避けなければならない。For example, when it comes to artificial marble, which is required to have an extremely light color, discoloration during use is not desirable because it greatly reduces its commercial value. Therefore, discoloration of this layer must be avoided.
しかしながら、このようにコバルト塩の使用は、樹脂の
黄変という面からすると望ましくないことではあるが、
今まではこれを用いないと、樹脂の効果的な常温ないし
低温硬化はできなかっなのである。However, although the use of cobalt salts is undesirable in terms of yellowing of the resin,
Until now, effective room temperature or low temperature curing of resins has not been possible without this.
またゲルコート層の耐水性も従来の樹脂では、必ずしも
十分ではなく、注型部の耐クラツク性や透明感のある外
観の面でも、いまだ不十分であった。Furthermore, the water resistance of the gel coat layer is not necessarily sufficient with conventional resins, and the crack resistance of the cast part and the transparent appearance are still insufficient.
〔課題を解決するための手段および作用〕本発明者らは
、コバルト塩の使用を避けるために幾多の試みを行った
結果、常温硬化で着色させないためには、パーオキサイ
ド系硬化剤の硬化促進剤であるコバルトの有機酸塩を使
用しないで、光硬化法を用いることが最適であることを
知り、本発明に至った。[Means and effects for solving the problem] The present inventors have made numerous attempts to avoid the use of cobalt salts, and have found that in order to prevent coloring during curing at room temperature, it is necessary to accelerate the curing of peroxide-based curing agents. We found that it is optimal to use a photocuring method without using an organic acid salt of cobalt as a cobalt agent, leading to the present invention.
光硬化法は、ゲルコートの硬化には非常に有効であった
が、別な欠点も見出された。それは、ゲルコートとして
十分な物性を示すように完全に光硬化させると、次のF
RP積層、または注型層との間に剥離を生じ易いことで
あった。ゲルコートを研摩して密着性を高めれば、この
欠点は防止できるが、工数が著しく増大し生産的には不
利となる。Although the photocuring method was very effective in curing gel coats, other drawbacks were also discovered. When it is fully photocured to exhibit sufficient physical properties as a gel coat, the following F
Peeling was likely to occur between the RP laminate or the cast layer. This drawback can be prevented by polishing the gel coat to improve its adhesion, but this significantly increases the number of man-hours and is disadvantageous in terms of productivity.
従って、この欠点を避けるためには、光硬化で完全に硬
化させるのではなく、光硬化は中間の硬・化段階に迄硬
化を進行させるために用い、最後の完全硬化(キュア)
は有機過酸化物で行わせることで目的を達成できること
を見出した。Therefore, in order to avoid this drawback, instead of completely curing with light curing, light curing is used to advance the curing to an intermediate curing stage, and the final complete curing (curing)
found that their objective could be achieved by using organic peroxides.
丈な(1)のゲルコート層とく夏1)の注型層に、分子
量5000以上の側鎖に(メタ)アクロイル基を1個以
上有するラジカル硬化可能なポリマーを使用したので、
ゲルコート層の耐水性ならびに注型層の耐クラツク性、
外観透明感も向上した。Since we used a radically curable polymer with a molecular weight of 5000 or more and one or more (meth)acroyl groups in the side chain for the gel coat layer in (1) and the casting layer in summer 1),
The water resistance of the gel coat layer and the crack resistance of the cast layer,
The appearance transparency has also been improved.
本発明の(I)工程における光による硬化のコントロー
ルは、容易に行えるので、必要な程度までゲルコートま
たはその次の積層部分の硬化調節を行うことができる。Since the curing by light in step (I) of the present invention can be easily controlled, the curing of the gel coat or the subsequent laminated portion can be adjusted to the required degree.
ゲルコート層、或は必要に応じて積層部分進光硬化させ
た後は、ラジカル硬化剤を配合したラジカル硬化型樹脂
を用いて注型を行い、ゲルコート層とともにこれを加熱
硬化させる。これにより注型部とゲルコート部は一体に
硬化接着されて、剥離のない強固な成形体を得ることが
できる。硬化のための加熱温度は、100℃以下、好ま
しくは70〜80℃程度である。After the gel coat layer or, if necessary, the laminated portion has been light-cured, casting is performed using a radical curing resin containing a radical curing agent, and this is heated and cured together with the gel coat layer. As a result, the casting part and the gel coat part are cured and bonded together, and a strong molded product without peeling can be obtained. The heating temperature for curing is 100°C or less, preferably about 70 to 80°C.
ゲルコートには、光硬化が可能で、有機過酸化物による
硬化が行えるラジカル硬化型樹脂が用いられる。とくに
本発明においては、分子量が5000以上のポリマー側
鎖に(メタ)アクリロイル基を1個以上有するラジカル
硬化可能なポリマーのモノマー溶液の形のものが好適で
ある。このポリマーを選択することにより、ゲルコート
層の耐水性を向上させることができる。The gel coat uses a radical curing resin that can be photocured and cured with organic peroxide. In particular, in the present invention, a monomer solution of a radically curable polymer having one or more (meth)acryloyl groups in the polymer side chain having a molecular weight of 5,000 or more is suitable. By selecting this polymer, the water resistance of the gel coat layer can be improved.
この側鎖に(メタ)アクリロイル基を有する不飽和ポリ
マー(以下単に不飽和ポリマーと略称する)は、次の方
法で合成される。This unsaturated polymer having a (meth)acryloyl group in its side chain (hereinafter simply referred to as unsaturated polymer) is synthesized by the following method.
(i)側鎖にヒドロキシル基を有するポリマーに、メタ
アクリロイル基を有する不飽和イソシアナートを反応さ
せる。(i) A polymer having a hydroxyl group in its side chain is reacted with an unsaturated isocyanate having a methacryloyl group.
(ii>側鎖にエポキシ基を有するポリマーに、(メタ
)アクリル酸を反応、
(iii)側鎖に酸無水物基を有するポリマーに(メタ
)アクリロイル基を有する不飽和アルコールを反応させ
る。(ii> Reacting a polymer having an epoxy group in a side chain with (meth)acrylic acid; (iii) Reacting a polymer having an acid anhydride group in a side chain with an unsaturated alcohol having a (meth)acryloyl group.
このことを、以下に式で示す。This is shown in the formula below.
(イ)ウレタン型不飽和ボリマー
(ロ)ビニルエステル型下飽和ポリマー側鎖エポキシ基
ポリマー メタクリル酸ビニルエステル型不飽和ポリ
マー
(ハ)エステル型不飽和ポリマー
エステル型不飽和ポリマー
不飽和ポリマーの原料となる各ポリマーは、いづれもモ
ノマーの重合により合成されるが、ウレタン型不飽和ポ
リマーは側鎖ヒドロキシルポリマー、例えばセルローズ
誘導体も利用し得るが、コスト、耐煮沸性といった点が
ちとニルモノマーの重合タイプが好適といえる6重合は
既存の方法が採用されるが後の工程の取扱いを考えれば
、直接重合法が便利である。(a) Urethane type unsaturated polymer (b) Vinyl ester type lower saturated polymer Side chain epoxy group polymer Methacrylic acid vinyl ester type unsaturated polymer (c) Ester type unsaturated polymer Ester type unsaturated polymer Serves as raw material for unsaturated polymer Each polymer is synthesized by polymerization of monomers, but for urethane-type unsaturated polymers, side-chain hydroxyl polymers such as cellulose derivatives can also be used, but polymerization of nil monomers is preferable in terms of cost and boiling resistance. Existing methods can be used for hexapolymerization, but the direct polymerization method is convenient when considering the handling of subsequent steps.
これら注型用不飽和ポリマーは、モノマー溶液例えばス
チレンモノマーとの混合物として使用される。混合割合
は、不飽和ポリマーの濃度で30〜70%、好ましくは
40〜60%である。These casting unsaturated polymers are used as a mixture with a monomer solution, for example styrene monomer. The mixing ratio is 30 to 70%, preferably 40 to 60% in terms of concentration of unsaturated polymer.
以上の不飽和ポリマーは、(1)工程におけるゲルコー
トにも、また(II)工程における注型層にも利用され
る。またポリエステル樹脂、ビニルエステル樹脂も必要
に応じ併用することもできる。The above unsaturated polymers are used for the gel coat in step (1) and the casting layer in step (II). Further, polyester resins and vinyl ester resins can also be used in combination if necessary.
これらラジカル硬化型不飽和ポリマーを、本発明のゲル
コート用樹脂として光硬化型とするためには、光重合開
始剤を併用することかが必要である。光重合開始剤には
各種のものが利用可能であるが、硬化ゲルコート層の着
色を避ける意味からは、水素引抜き型でアミン類を併用
するタイプは適当ではなく、開裂型のラジカル発生源が
良い。In order to make these radically curable unsaturated polymers photocurable as the gel coat resin of the present invention, it is necessary to use a photopolymerization initiator together. Various types of photopolymerization initiators can be used, but from the perspective of avoiding coloring of the cured gel coat layer, hydrogen abstraction types that use amines in combination are not suitable, and cleavage type radical generators are preferable. .
それらの例には、
(イ)アセトフェノン誘導体、例えば、2−ヒドロキシ
−2−メチル−1−フェニルプロパン−1−オン(メル
ク社”Daroeure#1173”)(ロ)ベンジル
ケタール類、例えば、ヒドロキシ−シクロへキシル−フ
ェニルケトン(チバ社”Irgaeure#184″)
があげられる。Examples of these include (a) acetophenone derivatives, such as 2-hydroxy-2-methyl-1-phenylpropan-1-one (Merck & Co., Ltd. "Daroeure #1173"); (b) benzyl ketals, such as hydroxy- Cyclohexyl-phenylketone (Ciba “Irgaeure #184”)
can be given.
本発明のゲルコート樹脂は、最終の完全硬化のために有
機過酸化物を併用する。これに使用される有機過酸化物
は、特にその種類が特定されるわけではないが、実際に
は注型層を形成させる操作が100℃以下で行われるこ
とが多いことがら、比較的低温例えば80℃以下で分解
するタイプが望ましい。The gel coat resin of the present invention uses an organic peroxide in combination for final complete curing. The type of organic peroxide used for this is not particularly specified, but in reality, the operation to form a cast layer is often carried out at 100°C or lower, so the temperature is relatively low, e.g. A type that decomposes at 80°C or lower is desirable.
1例として、半減期10時間を得るための分解温度が1
20℃以下のケトンパーオキシド、パーオキシケタール
、パーオキシカーボネート、ジアシルパーオキシド、パ
ーオキシエステルがあげられ、なかでもパーオキシカー
ボネート、パーオキシエステル類が有利であって、硬化
温度が適切なことと取扱上の安全性を併せ考慮するなら
ば、ビス(t−ブチルシクロヘキシル)パーオキシジカ
ーボネート(化薬ヌーリー社″パーカドックス#16”
)が適当である。他の過酸化物との併用も可能である。As an example, to obtain a half-life of 10 hours, the decomposition temperature is 1
Examples include ketone peroxide, peroxyketal, peroxycarbonate, diacyl peroxide, and peroxyester at a temperature of 20°C or less. Among them, peroxycarbonate and peroxyester are advantageous, and the curing temperature is appropriate. Considering handling safety, bis(t-butylcyclohexyl) peroxydicarbonate (Kayaku Nury Co., Ltd. "Perkadox #16")
) is appropriate. Combination use with other peroxides is also possible.
樹脂の注型、硬化にあたっては、通常注型用樹脂にフィ
ラーを併用し、適度の透明感を出し、併せて硬化成形時
の発熱によるクラックを防止することが行われている。When casting and curing the resin, a filler is usually used in combination with the casting resin to provide a suitable degree of transparency and to prevent cracks caused by heat generation during curing and molding.
併用さ′れるフィラーとしては、ガラス粉、水酸化アル
ミニウム等が一般的である。また本発明の組成物および
方法においては、必要に応じて着色剤、離型剤、チクソ
トロピー付与剤、熱可塑性ポリマー等を併用できること
は勿論である。Glass powder, aluminum hydroxide, etc. are commonly used as fillers. Furthermore, in the composition and method of the present invention, it is of course possible to use a coloring agent, a mold release agent, a thixotropy imparting agent, a thermoplastic polymer, etc. in combination, if necessary.
次に本発明をさらに説明するために、以下に実施例を示
す。Next, in order to further explain the present invention, Examples are shown below.
実施例1
(ゲルコート用樹脂(A)(ウレタン型不飽和ポリマー
A)の合成)
撹拌機、還流コンデンサー、ガス導入管、温度計を付し
た21セパラブルフラスコに、スチレン936g、2−
ヒドロキシエチルメタクリレート(HEMA)130g
を秤取し、窒素気流中120℃で6時間加熱すると、反
応率は約42%に達し、遊離のHEMAはガスクロマト
グラフ分析の結果約当初仕込量の14%になったものと
判断された。Example 1 (Synthesis of gel coat resin (A) (urethane type unsaturated polymer A)) 936 g of styrene, 2-
Hydroxyethyl methacrylate (HEMA) 130g
When the sample was weighed and heated at 120° C. for 6 hours in a nitrogen stream, the reaction rate reached about 42%, and as a result of gas chromatography analysis, it was determined that the amount of free HEMA was about 14% of the initially charged amount.
ハイドロキノン0.2gを加え温度を70℃に下げ、空
気気流に切替えてイソシアナートエチルメタクリレ−)
140.、ジブチル錫ジラウレート3gを加え70℃で
5時間反応すると、赤外分析の結果遊離のイソシアナー
トは消滅したことが確認された。Add 0.2 g of hydroquinone, lower the temperature to 70°C, and switch to air flow.
140. , dibutyltin dilaurate (3 g) was added and reacted at 70° C. for 5 hours, and as a result of infrared analysis, it was confirmed that free isocyanate had disappeared.
ハーゼン色数30、粘度11.4ポイズのウレタン型不
飽和ポリマー(A)が得られた。A urethane-type unsaturated polymer (A) having a Hazen color number of 30 and a viscosity of 11.4 poise was obtained.
(注型用樹脂(B)(ビニルエステル型不飽和ポリマー
B)の製造)
撹拌機、還流コンデンサー、温度計、ガス導入管を付し
た21セパラブルフラスコに、スチレン936g、グリ
シジルメタクリレート142gを仕込み、窒素気流中1
20〜122℃で6時間加熱すると、重合体はほぼ43
%に達し、グリシジルメタクリレートの仕込み量に対す
る残存率は約16%になった。(Production of casting resin (B) (vinyl ester type unsaturated polymer B)) 936 g of styrene and 142 g of glycidyl methacrylate were charged into a 21 separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a gas introduction tube. In nitrogen stream 1
When heated at 20-122°C for 6 hours, the polymer becomes approximately 43
%, and the residual ratio of glycidyl methacrylate to the charged amount was about 16%.
これにハイドロキノン0,3g、メタクリル酸95g、
トリメチルベンジルアンモニウムクロライド5gを加え
、温度を100〜105℃に下げ、空気気流中で12時
間反応した。To this, 0.3 g of hydroquinone, 95 g of methacrylic acid,
5 g of trimethylbenzylammonium chloride was added, the temperature was lowered to 100-105° C., and the reaction was carried out for 12 hours in an air stream.
赤外分析の結果エポキシ基の吸収は消失したものと判断
された。As a result of infrared analysis, it was determined that the absorption of epoxy groups had disappeared.
これに、エチレングリコールジメタクリレート130g
加え、ハーゼン色数100、粘度14.1ポイズの注型
用樹脂(B)が得られた。Add to this 130g of ethylene glycol dimethacrylate
In addition, a casting resin (B) having a Hazen color number of 100 and a viscosity of 14.1 poise was obtained.
(ゲルコート層の形成)
不飽和ポリマー(A)を100部、エチレングリコール
ジメタクリレートを10部、エロジルト200を3部、
シランカップリング剤(信越化学(株)KBM−503
)を0.5部、光開始剤としてメルク社(株)“Dar
oeure#1173”を2部、有機過酸化物(化薬ヌ
ーリー(株)“バー力ドックス#16”)を1部加え、
ロール混練して光硬化型ゲルコート用組成物(a)を得
た。(Formation of gel coat layer) 100 parts of unsaturated polymer (A), 10 parts of ethylene glycol dimethacrylate, 3 parts of Elozilt 200,
Silane coupling agent (Shin-Etsu Chemical Co., Ltd. KBM-503)
) and 0.5 part of Merck & Co., Ltd. “Dar” as a photoinitiator.
oeure #1173” and 1 part of an organic peroxide (Kayaku Noury Co., Ltd. “Barriki Dox #16”) were added.
A photocurable gel coat composition (a) was obtained by roll kneading.
比較例として、不飽和ポリマー(A)100部にさらに
ナフテン酸コバルト(6%Co)0.1部を加えたもの
をゲルコート用組成物(b)とした。As a comparative example, a gel coat composition (b) was prepared by adding 0.1 part of cobalt naphthenate (6% Co) to 100 parts of the unsaturated polymer (A).
離型剤を塗布した3 0ciX 30ciX 5ggの
ガラス板上に、ゲルコートを厚さ0.5gmになるよう
にバーコーターで塗装し、塗面が均一になるのを待って
、出力250Wのサンランプ(スタンレー電気(株)製
)下30cmで約15分照射したところ、ゲルコート層
は指触乾燥程度に硬化した。On a 30ciX 30ciX 5gg glass plate coated with a mold release agent, apply gel coat to a thickness of 0.5gm using a bar coater, wait until the coated surface is uniform, and apply a 250W sun lamp ( When the gel coat layer was irradiated for about 15 minutes at a distance of 30 cm below (manufactured by Stanley Electric Co., Ltd.), the gel coat layer was hardened to the extent that it was dry to the touch.
(注型および加熱、硬化)
硬化したゲルコート層を一方の側とし、別に厚さ2mg
で白く着色したガラスマット使用のFRPを置き、その
間隔を10%gとして、この間に、注型用樹脂(B)を
100部、日本フェロ−製フリットB−10を200部
、日本油脂(株)パーブチルpvを1.5部、混合しと
ものを、脱泡注型の上、70℃で2時閉、80℃で2時
間硬化させた。(Casting, heating, and curing) The cured gel coat layer is on one side, and a separate layer with a thickness of 2 mg is
FRP using glass mat colored white was placed, and the interval between them was set to 10% g. During this time, 100 parts of casting resin (B), 200 parts of Nippon Ferro Frit B-10, and Nippon Oil & Fats Co., Ltd. ) 1.5 parts of Perbutyl PV was mixed therewith, and after defoaming casting, the mixture was closed at 70°C for 2 hours and cured at 80°C for 2 hours.
ゲルコート用組成物(a)を使用した成形品を成形品(
a)、ゲルコート用組成物(b)を使用した成形品を成
形品(b)とした6
両成形品を15ciX 15cmで切断し、直径10c
1の円形開孔部を片面で4ケ所有する耐煮沸テスト容器
に、ゲルコート層が内側になるように敷設し、温度98
〜99℃で煮沸テストを行った。結果を第1表に示す、
この表から判るように、ナフテン酸コバルトを用いない
本発明は、極めて優れた性能を示した。A molded product using the gel coat composition (a) is a molded product (
a), a molded product using the gel coat composition (b) was used as molded product (b) 6 Both molded products were cut at 15 ci x 15 cm, and a diameter of 10 cm was obtained.
The gel coat layer was placed on the inside of a boiling test container with 4 circular holes on one side, and the temperature was 98°C.
Boiling tests were conducted at ~99°C. The results are shown in Table 1.
As can be seen from this table, the present invention, which does not use cobalt naphthenate, showed extremely excellent performance.
第 1 表
実施例2
実施例1で注型に用いたビニルエステル樹脂型不飽和ポ
リマー(B)をゲルコートに用いた。ポリマー(B)1
00部、エコジル3部、カップリング剤0.5部、光重
合開始剤としてチバ社の“Irgaeure#181″
を2部、バーブチルpvを1部を混練し、ゲルコート用
組成物(e)とした。Table 1 Example 2 The vinyl ester resin type unsaturated polymer (B) used for casting in Example 1 was used for gel coat. Polymer (B) 1
00 parts, Ecosil 3 parts, coupling agent 0.5 parts, Ciba's "Irgaeure #181" as a photopolymerization initiator
2 parts of barbutyl pv and 1 part of barbutyl pv were kneaded to obtain a gel coat composition (e).
(注型用樹脂(C)(エステル型不飽和ポリマー)の合
成)
撹拌機、加温滴下ロート、還流コンデンサー、ガス導入
管付温度計を付した21セパラブルフラスコに、スチレ
ン936gを仕込み、温度120℃で溶融無水マレイン
酸98gを3時間にわたって滴下した後、さらに1.5
時間同温度に保つ。(Synthesis of casting resin (C) (ester-type unsaturated polymer)) 936 g of styrene was charged into a 21 separable flask equipped with a stirrer, a heating dropping funnel, a reflux condenser, and a thermometer with a gas introduction tube, and the temperature After dropping 98 g of molten maleic anhydride at 120°C over 3 hours, an additional 1.5
Keep at the same temperature for the time.
次いで、2−ヒドロキシエチルメタクリレート200g
、ジプチル錫ジオキサイド5g、ハイドロキノン0.1
gを加え、85〜90℃で22時間反応した。ハーゼン
色数50、粘度5.9ボイズの注型用樹脂(C)が得ら
れた。赤外分析の結果、酸無水物基の約80%は開環し
たものと判断された。Next, 200 g of 2-hydroxyethyl methacrylate
, diptyltin dioxide 5g, hydroquinone 0.1
g and reacted at 85 to 90°C for 22 hours. A casting resin (C) having a Hazen color number of 50 and a viscosity of 5.9 voids was obtained. As a result of infrared analysis, it was determined that about 80% of the acid anhydride groups were ring-opened.
(ゲルコート層の形成および注型、加熱、硬化)ゲルコ
ート用組成物(e)を実施例1と同一条件で塗布、光硬
化させた後、さらに#360のシラン処理ガラスマット
を置き、ゲルコート用組成物(c)を含浸、脱泡した後
、同様に光硬化させた。(Formation, casting, heating, and curing of gel coat layer) After applying and photocuring the gel coat composition (e) under the same conditions as in Example 1, a #360 silane-treated glass mat was further placed, and the gel coat composition After impregnating and defoaming material (c), it was photocured in the same manner.
これを白く着色したFRPを裏打ち層とし、注型用樹脂
(C)100部、フリット180部、日本油脂(株)製
パーキュア0(t−ブチルパーオキシ−2=エチルヘキ
サネート)2部を混練したものを、厚さ1Qiu+に注
型し、当初80℃2時間で硬化させた後、脱型した。FRP colored white is used as a backing layer, and 100 parts of casting resin (C), 180 parts of frit, and 2 parts of Percure 0 (t-butylperoxy-2=ethylhexanate) manufactured by NOF Corporation are kneaded. The molded product was cast to a thickness of 1 Qiu+, initially cured at 80° C. for 2 hours, and then demolded.
これを切断し、実施例1と同様に耐煮沸テストを実施し
た。1000時間煮沸テスト後も、表面ゲルコート層の
外見にはなんらの異常も認められなかった。This was cut and a boiling resistance test was conducted in the same manner as in Example 1. Even after the 1000 hour boiling test, no abnormality was observed in the appearance of the surface gel coat layer.
Claims (1)
ル基を1個以上有するラジカル硬化可能なポリマー (ロ)光重合開始剤 (ハ)有機過酸化物 を混合してなり、かつコバルトの有機酸塩を実質的に含
有しない組成物を、ゲルコートとして型に施し、これに
光照射して所望の硬化度までゲルコートを硬化させ、 (II)ガラス繊維を用いて裏打ちを行うかまたは行わず
に、分子量5000以上の側鎖に(メタ)アクリロイル
基を1個以上有するラジカル硬化可能なポリマーのモノ
マー溶液を注型し、しかる後ゲルコート層および注型層
を加熱硬化することよりなる成形品の製造方法。[Scope of Claims] (I) (1) Photocurable resin (a) Radically curable polymer having one or more (meth)acryloyl groups in the side chain with a molecular weight of 5,000 or more (b) Photopolymerization initiator (c) A composition mixed with an organic peroxide and containing substantially no organic acid salt of cobalt is applied to a mold as a gel coat, and the gel coat is cured to a desired degree of hardening by irradiating it with light. (II) casting a monomer solution of a radically curable polymer having one or more (meth)acryloyl groups in the side chain with a molecular weight of 5000 or more with or without backing with glass fiber; A method for producing a molded article, which comprises heating and curing a gel coat layer and a casting layer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15015888A JPH01317720A (en) | 1988-06-20 | 1988-06-20 | Production of molded product |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15015888A JPH01317720A (en) | 1988-06-20 | 1988-06-20 | Production of molded product |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01317720A true JPH01317720A (en) | 1989-12-22 |
JPH0542930B2 JPH0542930B2 (en) | 1993-06-30 |
Family
ID=15490771
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15015888A Granted JPH01317720A (en) | 1988-06-20 | 1988-06-20 | Production of molded product |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01317720A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004039856A1 (en) * | 2002-10-31 | 2004-05-13 | Kyoeisha Chemical Co.,Ltd. | Resin composition, transfer material and process for producing shaped item |
JP2010530455A (en) * | 2007-06-19 | 2010-09-09 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Reactive mixture for coating a molded body by reaction injection molding and coated molded body |
JP5242170B2 (en) * | 2005-12-28 | 2013-07-24 | 株式会社カネカ | Photo radical curing / thermal radical curing combined curable composition |
-
1988
- 1988-06-20 JP JP15015888A patent/JPH01317720A/en active Granted
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004039856A1 (en) * | 2002-10-31 | 2004-05-13 | Kyoeisha Chemical Co.,Ltd. | Resin composition, transfer material and process for producing shaped item |
JP4758647B2 (en) * | 2002-10-31 | 2011-08-31 | 共栄社化学株式会社 | Resin composition, transfer material and method for producing molded product |
JP5242170B2 (en) * | 2005-12-28 | 2013-07-24 | 株式会社カネカ | Photo radical curing / thermal radical curing combined curable composition |
JP2010530455A (en) * | 2007-06-19 | 2010-09-09 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Reactive mixture for coating a molded body by reaction injection molding and coated molded body |
JP2014012850A (en) * | 2007-06-19 | 2014-01-23 | Evonik Roehm Gmbh | Molding coated with reactive mixture |
KR101432348B1 (en) * | 2007-06-19 | 2014-08-21 | 에보니크 룀 게엠베하 | Reactive Mixture for Coating Molded Objects by means of Reaction Injection Molding and Coated Molded Object |
US9062211B2 (en) | 2007-06-19 | 2015-06-23 | Evonik Roehm Gmbh | Reactive mixture for coating molded objects by means of reaction injection molding and coated molded object |
Also Published As
Publication number | Publication date |
---|---|
JPH0542930B2 (en) | 1993-06-30 |
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