即ち、本発明は、環状不飽和多塩基酸および/又はアリルエーテル基を有するグリコールを構成成分とする不飽和ポリエステル樹脂(A)とビニルエステル樹脂(B)と反応性希釈剤として引火点が70℃以上のエチレン性不飽和二重結合を有する単量体(c−1)および分子中に尿素骨格を有する化合物(c−2)とを含んでなるラジカル重合性樹脂組成物、及びこれからなるゲルコート材及びこれを成形してなるFRP成形品を提供するものである。
That is, the present invention has a flash point of 70 as an unsaturated polyester resin (A) and vinyl ester resin (B) containing a cyclic unsaturated polybasic acid and / or glycol having an allyl ether group as a constituent component. Radical polymerizable resin composition comprising a monomer (c-1) having an ethylenically unsaturated double bond at ℃ or higher and a compound (c-2) having a urea skeleton in the molecule , and a gel coat comprising the same A material and an FRP molded product formed by molding the material are provided.
(比較例3)
参考例1で得られたビニルエステル樹脂(1)40部と参考例2で得られた空乾性不飽和ポリエステル樹脂(2)10部を、メタクリルモノマーBG(1,3−ブチレングリコールジメタクリレート、新中村化学社製、引火点(クリーブランド)100℃以上)を30部とメタクリルモノマーFA512MT(ジシクロペンテニルオキシエチルメタクリレート、日立化成社製、引火点(クリーブランド)100℃以上)30部添加し、予め加熱し溶解し易くした上記樹脂(1)および(2)に、上記メタクリルモノマーにて希釈溶解させラジカル重合性樹脂組成物(1)を得た。このラジカル重合性樹脂組成物(1)100部に、硬化促進剤として6%ナフテン酸コバルト(大日本インキ化学製)0.5部、ジメチルアニリン0.2部、チキソ付与材としてアエロジル#200(日本アエロジル製)1部、消泡剤、禁止剤を添加調合し、チキソ性を付与された樹脂組成物(A)を得た。ラジカル硬化剤として、パーメックN(日本油脂(株)製)1.0部を配合し、450g/m2チョップドストランドマット(日東紡(株)製)を用い、ガラス板の上に、上記ガラスマットを置き、その上からチキソ付与された樹脂組成物をかけ、含浸ローラーを用い、チョップドストランドマットに付着している気泡を取り除き、所謂ハンドレイアップ積層を行った。その上に、同様にチョップドストランドガラスマットを置き、この作業を繰り返し、ガラスマットが3層となる様、ハンドレイアップ積層成形を行い、硬化せしめて、厚みが3mmからなるFRP成形品を得た。
(実施例2)
比較例3で得られた樹脂組成物(A)100部にエチレン尿素を0.3部加えた後、加熱溶解させ、樹脂組成物(B)を得た。この樹脂組成物を用いて、比較例3と同様の操作を行い、FRP成形品を得た。
(比較例1)
参考例3で得られた不飽和ポリエステル樹脂(3)65部を、スチレン35部にて希釈した以外は、比較例3と同様に操作を行い、樹脂組成物を得た。この樹脂組成物は、スチレン(セタ密閉式引火点31℃)に由来する刺激臭が認められた。
この樹脂組成物を硬化せしめて、積層板および注型板を作成した。積層板からのホルムアルデヒド揮散量が、0.35mg/L以上確認された。また、スチレン放散速度は、スチレンに由来するピークが大きすぎ、検出オーバーであった。
(比較例2)
比較例3の空乾性ポリエステル樹脂を用いない以外は、比較例3と同様操作を行い、続いて積層板、注型板を作成した。
得られた積層板は、8時間後も表面がべとべとしていた。
[測定方法及び評価基準]
このラジカル重合性樹脂組成物及びこれを用いて得られる成形品について、空気乾燥性、ホルムアルデヒド放散量、スチレン揮散量及び耐水性について測定し評価した。測定方法及び評価基準は以下のとおりである。実施例2および比較例1〜3の結果は、表−1に示す。
(Comparative Example 3)
40 parts of the vinyl ester resin (1) obtained in Reference Example 1 and 10 parts of the air-drying unsaturated polyester resin (2) obtained in Reference Example 2 were mixed with methacrylic monomer BG (1,3-butylene glycol dimethacrylate, new Add 30 parts of flash point (Cleveland 100 ° C or higher) manufactured by Nakamura Chemical Co., Ltd. and 30 parts of methacrylic monomer FA512MT (dicyclopentenyloxyethyl methacrylate, Hitachi Chemical Co., Ltd., flashpoint (Cleveland) 100 ° C or higher) and heat in advance Then, the resin (1) and (2) that were easily dissolved were diluted and dissolved with the methacrylic monomer to obtain a radical polymerizable resin composition (1). To 100 parts of this radical polymerizable resin composition (1), 0.5 part of 6% cobalt naphthenate (manufactured by Dainippon Ink and Chemicals) as a curing accelerator, 0.2 part of dimethylaniline, Aerosil # 200 (as thixotropic agent) Nippon Aerosil Co., Ltd.) 1 part, an antifoaming agent and an inhibitor were added and prepared to obtain a resin composition (A) to which thixotropy was imparted. As a radical curing agent, 1.0 part of Parmek N (manufactured by Nippon Oil & Fats Co., Ltd.) is blended, and 450 g / m 2 chopped strand mat (manufactured by Nittobo Co., Ltd.) is used. Then, the resin composition provided with thixo was applied from above, the bubbles adhering to the chopped strand mat were removed using an impregnation roller, and so-called hand lay-up lamination was performed. On top of that, a chopped strand glass mat was similarly placed, and this operation was repeated to carry out hand lay-up lamination molding so that the glass mat had three layers, and cured to obtain an FRP molded product having a thickness of 3 mm. .
(Example 2)
After adding 0.3 parts of ethylene urea to 100 parts of the resin composition (A) obtained in Comparative Example 3 , the resin composition (B) was obtained by heating and dissolving. Using this resin composition, the same operation as in Comparative Example 3 was performed to obtain an FRP molded product.
(Comparative Example 1)
A resin composition was obtained in the same manner as in Comparative Example 3 except that 65 parts of the unsaturated polyester resin (3) obtained in Reference Example 3 was diluted with 35 parts of styrene. In this resin composition, an irritating odor derived from styrene (ceta closed flash point 31 ° C.) was observed.
This resin composition was cured to prepare a laminated plate and a cast plate. The amount of formaldehyde volatilized from the laminate was confirmed to be 0.35 mg / L or more. In addition, the styrene emission rate was over-detected because the peak derived from styrene was too large.
(Comparative Example 2)
Except not using the air-drying polyester resins of Comparative Example 3, the same operation as in Comparative Example 3, followed by laminate to prepare a cast plate.
The resulting laminate had a sticky surface even after 8 hours.
[Measurement method and evaluation criteria]
About this radically polymerizable resin composition and a molded article obtained using the same, air drying property, formaldehyde emission amount, styrene volatilization amount and water resistance were measured and evaluated. The measurement method and evaluation criteria are as follows. The results of Example 2 and Comparative Examples 1 to 3 are shown in Table-1.