JPH02124916A - Unsaturated polyester resin composition - Google Patents

Unsaturated polyester resin composition

Info

Publication number
JPH02124916A
JPH02124916A JP27904988A JP27904988A JPH02124916A JP H02124916 A JPH02124916 A JP H02124916A JP 27904988 A JP27904988 A JP 27904988A JP 27904988 A JP27904988 A JP 27904988A JP H02124916 A JPH02124916 A JP H02124916A
Authority
JP
Japan
Prior art keywords
acid
oil fatty
polybasic acid
polyester resin
unsaturated polyester
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.)
Pending
Application number
JP27904988A
Other languages
Japanese (ja)
Inventor
Kiyoji Makino
牧野 喜代次
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyocera Chemical Corp
Original Assignee
Toshiba Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toshiba Chemical Corp filed Critical Toshiba Chemical Corp
Priority to JP27904988A priority Critical patent/JPH02124916A/en
Publication of JPH02124916A publication Critical patent/JPH02124916A/en
Pending legal-status Critical Current

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  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

PURPOSE:To improve flexibility and to reduce change in hardness with time by compounding an unsatd. polybasic acid contg. a specified amt. of tall oil fatty acid, a satd. polybasic acid, a polyhydric alcohol and a copolymerizable monomer. CONSTITUTION:An unsatd. polybasic acid (A) (e.g., maleic anhydride) contg. 15-30 equivalent % tall oil fatty acid, a satd. polybasic acid (B) (e.g., tetrahydrophthalic anhydride) and a polyhydric alcohol (C) (e.g., glycerin) are compounded in such a way that tall oil fatty acid in component A is 40-60wt.% based on the sum of the components A-C and the mixture is reacted. A copolymerizable monomer (D) (e.g., styrene) is furthermore compounded therein.

Description

【発明の詳細な説明】 [発明の目的] (産業上の利用分野) 本発明は、柔軟性に優れ、しかも経時変化に対して硬度
変化の少ない不飽和ポリエステル樹脂組成物に関する。
DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to an unsaturated polyester resin composition that has excellent flexibility and shows little change in hardness over time.

(従来の技術) 不飽和ポリエステルは、無水マレイン酸等の不飽和多塩
基酸、あるいはその一部を無水フタル酸等の飽和多塩基
酸で置換したものと、エチレングリコール等の多価アル
コールとをエステル化反応させて得られ、この不飽和ポ
リエステルにスチレン等σ)共重合性単量体を添加して
架橋反応の可能な不飽和ポリエステル樹脂組成物とし、
建材、注型物、塗料等に広く利用されている。
(Prior art) Unsaturated polyester is a combination of an unsaturated polybasic acid such as maleic anhydride, or a part thereof replaced with a saturated polybasic acid such as phthalic anhydride, and a polyhydric alcohol such as ethylene glycol. A copolymerizable monomer (sigma) such as styrene is added to this unsaturated polyester obtained by an esterification reaction to obtain an unsaturated polyester resin composition capable of a crosslinking reaction,
It is widely used in building materials, cast materials, paints, etc.

しかしながら、これらの不飽和ポリエステル樹脂組成物
は、−数的に硬く、また軟かいものでもその硬度の経時
変化が大きい等の欠点があった。
However, these unsaturated polyester resin compositions have disadvantages in that they are numerically hard, and even if they are soft, their hardness changes significantly over time.

これを改善するため、従来、各種の脂肪酸を変性剤とし
て使用しているが、初期的には柔軟性は改善されるもの
の経時変化をさせると硬度変化が大きいという欠点は改
良できなかった。
In order to improve this, various fatty acids have been used as modifiers in the past, but although the flexibility is initially improved, the drawback of large changes in hardness over time cannot be improved.

(発明が解決しようとする課題) 本発明は、上記の欠点を解消するためになされたもので
、柔軟性のよい硬化物を与え、かつ経時変化が少なく、
安定性に優れた不飽和ポリエステル樹脂組成物を提供し
ようとするものである。
(Problems to be Solved by the Invention) The present invention has been made in order to eliminate the above-mentioned drawbacks, and provides a cured product with good flexibility, and has little change over time.
The object is to provide an unsaturated polyester resin composition with excellent stability.

[発明の構成] (課題を解決するための手段) 本発明者は、上記の目的を達成しようと鋭意研究を重ね
た結果、樹脂中の不飽和多塩基酸の含有量を制限し、ま
た、脂肪酸としてトール油脂肪酸を用いたことによって
硬化物の経時変化の少ない不飽和ポリエステル樹脂組成
物が得られることを見いだし、本発明を完成したもので
ある。
[Structure of the Invention] (Means for Solving the Problems) As a result of extensive research in an attempt to achieve the above object, the present inventor limited the content of unsaturated polybasic acids in the resin, and The present invention was completed based on the discovery that by using tall oil fatty acid as the fatty acid, an unsaturated polyester resin composition in which the cured product changes less over time can be obtained.

すなわち、本発明は、 (A)不飽和多塩基酸、 (B)飽和多塩基酸。That is, the present invention (A) unsaturated polybasic acid, (B) Saturated polybasic acid.

(C)多価アルコール及び (D)共重合性単量体 を主成分とする不飽和ポリエステル樹脂組成物において
、不飽和多塩基酸としてトール油脂肪酸を前記<A)の
不飽和多塩基酸に対して15〜30当量%、かつ樹脂[
(A)+ (B)+ (C)]に対して40〜60重量
%含有することを特徴とする不飽和ポリエステル樹脂組
成物である。
In an unsaturated polyester resin composition containing (C) a polyhydric alcohol and (D) a copolymerizable monomer as the main components, tall oil fatty acid is used as the unsaturated polybasic acid in <A) as the unsaturated polybasic acid. 15 to 30 equivalent% to the resin [
(A) + (B) + (C)] is an unsaturated polyester resin composition characterized by containing 40 to 60% by weight.

本発明に用いる(A)不飽和多塩基酸としては、例えば
無水マレイン酸、フマール酸、イタコン酸、シトラコン
酸等が挙げられ、通常不飽和ポリエステル樹脂の原料と
して使用されるものはすべて使用できる。 これらの不
飽和多塩基酸は単独又は2種以上混合して使用する。
Examples of the unsaturated polybasic acid (A) used in the present invention include maleic anhydride, fumaric acid, itaconic acid, and citraconic acid, and all those commonly used as raw materials for unsaturated polyester resins can be used. These unsaturated polybasic acids may be used alone or in combination of two or more.

本発明に用いるトール油脂肪酸は、二重結合の比較的少
ないもので通常半乾性油といわれるもめである。 大豆
油脂肪酸では硬さの経時変化が大きく好ましくない、 
またヤシ油脂肪酸の場合には硬化物の表面の粘着性が除
去できず好ましくない、 トール油脂肪酸を、前述した
不飽和多塩基酸の一部を置換して使用する。 この場合
のトール油脂肪酸の配合割合は、全不飽和多塩基酸に対
して15〜30当量%含有するように配合することが好
ましい、 配合量が15重量%未満では硬化性が悪く、
また30当量%を超えると硬化物の硬度が上り柔軟性が
なくなり好ましくない、 またトール油脂肪酸の配合割
合は不飽和ポリエステル樹脂[(A)+ (B)+ (
C)]に対して40〜60重量%であることが望ましい
、 配合量が40重量%未満では初期硬度が大きくて柔
軟性に乏しいため好ましくない、60重量%を超えると
硬化性が悪くなり好ましくない。
The tall oil fatty acid used in the present invention has relatively few double bonds and is usually referred to as a semi-drying oil. Soybean oil fatty acids have a large change in hardness over time, which is undesirable.
In the case of coconut oil fatty acids, tall oil fatty acids, which are undesirable because they cannot remove the tackiness of the surface of the cured product, are used to partially replace the aforementioned unsaturated polybasic acids. In this case, the blending ratio of tall oil fatty acid is preferably 15 to 30 equivalent% based on the total unsaturated polybasic acid. If the blending ratio is less than 15% by weight, the curability is poor;
Moreover, if it exceeds 30 equivalent %, the hardness of the cured product increases and the flexibility decreases, which is undesirable.
C)] is preferably 40 to 60% by weight. If the amount is less than 40% by weight, the initial hardness will be large and flexibility will be poor, which is undesirable. If it exceeds 60% by weight, the curability will deteriorate and it is not desirable. do not have.

本発明に用いる(B)飽和多塩基酸としては、例えば無
水フタル酸、イソフタル酸、アジピン酸、コハク酸、セ
バシン酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無
水フタル酸、エンドメチレンテトラヒドロ無水フタル酸
等が挙げられ、これらは単独又は2種以上混合して使用
する。 飽和多塩基酸は、要求される不飽和ポリエステ
ル樹脂の特性等に応じて、不飽和多塩基酸の一部を置換
して反応させるものである。
Examples of the saturated polybasic acid (B) used in the present invention include phthalic anhydride, isophthalic acid, adipic acid, succinic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, etc. These can be used alone or in a mixture of two or more. The saturated polybasic acid is used to partially substitute and react the unsaturated polybasic acid depending on the required characteristics of the unsaturated polyester resin.

本発明に用いる(C)多価アルコールとしては。(C) Polyhydric alcohol used in the present invention.

例えばエチレングリコール、プロピレングリコール、ジ
エチレングリコール、1.3−ブタンジオール、1.6
−ヘキサンジオール、グリセリン、ペンタエリスリトー
ル、ネオペンチルグリコール等が挙げられ、これらは単
独又は2種以上混合して使用する。
For example, ethylene glycol, propylene glycol, diethylene glycol, 1.3-butanediol, 1.6
-hexanediol, glycerin, pentaerythritol, neopentyl glycol, etc., which may be used alone or in combination of two or more.

本発明に用いるCD)重合性単量体としては、スチレン
、ビニルトルエン、ジビニルベンゼン、ジアリルフタレ
ート、メタクリル酸メチル、アクリル酸メチル、アクリ
ル酸エチル等が挙げられ、これらは単独又は2種以上混
合して使用する。
Examples of the polymerizable monomer (CD) used in the present invention include styrene, vinyltoluene, divinylbenzene, diallyl phthalate, methyl methacrylate, methyl acrylate, and ethyl acrylate, which may be used alone or in combination of two or more. and use it.

本発明の不飽和ポリエステル樹脂組成物は1段反応でト
ール油脂肪酸と多価アルコールを反応させ、次いで2段
反応で不飽和多塩基酸、飽和多塩基酸、多価アルコール
を反応させ、その後単量体を加えて不飽和ポリエステル
樹脂組成物をつくることができる。 こうして製造した
組成物は、水銀灯、蛍光灯等のチョークトランスの充填
用などに使用することができる。
The unsaturated polyester resin composition of the present invention is produced by reacting a tall oil fatty acid and a polyhydric alcohol in a one-stage reaction, then reacting an unsaturated polybasic acid, a saturated polybasic acid, and a polyhydric alcohol in a two-stage reaction, and then reacting a polyhydric alcohol with a tall oil fatty acid in a two-stage reaction. polymers can be added to create unsaturated polyester resin compositions. The composition thus produced can be used for filling choke transformers such as mercury lamps and fluorescent lamps.

(作用) 本発明で、トール油脂肪酸を使用して不飽和多塩基酸の
量を減らすことにより、硬化物の硬度(柔軟性)をよく
制御でき、またトール油脂肪酸そのものの不飽和度と、
その所定量の配合によって、初期の硬度が経時変化後の
硬度に対してあまり変らない柔軟性の不飽和ポリエステ
ル樹脂組成物を得ることができる。
(Function) In the present invention, by using tall oil fatty acids to reduce the amount of unsaturated polybasic acids, the hardness (flexibility) of the cured product can be well controlled.
By blending it in a predetermined amount, it is possible to obtain a flexible unsaturated polyester resin composition whose initial hardness does not change much with respect to the hardness after aging.

(実施例) 次に本発明を実施例によって説明する。 以下の実施例
及び比較例において「部」とは「重量部Jを意味する。
(Example) Next, the present invention will be explained by referring to an example. In the following Examples and Comparative Examples, "parts" means "parts by weight J."

実施例 1 撹拌機、温度計、窒素ガス導入管および冷却器を付けた
反応容器に、グリセリン55.2部 およびハードルF
A−20(措置化成社製商品名、トール油脂肪酸)16
8部を仕込み、璧索ガスを通しながら加熱を始め180
〜210°Cで所定量の水をとり、酸価4,2の中間体
をつくって 100”Cに冷却する。
Example 1 55.2 parts of glycerin and hurdle F were placed in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a condenser.
A-20 (trade name manufactured by Seikatsu Kasei Co., Ltd., tall oil fatty acid) 16
Pour in 8 parts and start heating while passing gas to 180 ml.
A predetermined amount of water is taken at ~210°C, an intermediate with an acid value of 4.2 is prepared, and the mixture is cooled to 100''C.

100℃になったところで、ジエチレングリコール79
、11、無水マレインfi11.8部、およびテトラヒ
ドロ無水フタル1fi88゜2部を添加し、さらに全体
量に対して0.05重量%量の重合防止剤ハイドロキノ
ンを添加配合し、加熱を再開し徐々に温度を上げて20
0〜210″Cでエステル化反応を進め、酸価21を反
応終点とした。 その後100℃に冷却し、200部の
スチレンを加えて60%溶液とした。
When the temperature reached 100℃, diethylene glycol 79
, 11. Add 11.8 parts of anhydrous maleic fi and 88.2 parts of tetrahydrophthalic anhydride 1 fi, further add and blend the polymerization inhibitor hydroquinone in an amount of 0.05% by weight based on the total amount, restart heating and gradually Raise the temperature to 20
The esterification reaction was carried out at 0 to 210"C, and the reaction end point was an acid value of 21. Thereafter, the mixture was cooled to 100C, and 200 parts of styrene was added to form a 60% solution.

実施例 2 実施例1においてハードルFA−20の代わりにハード
ルF−1(措置化成社製商品名)のトール油脂肪酸を用
いた以外はすべて実施例1と同様に反応させて酸価23
を反応終点とし、これを100゛Cに冷却した後、20
0部のスチレンを加えて60%溶液とした。
Example 2 The reaction was carried out in the same manner as in Example 1 except that tall oil fatty acid of Hurdle F-1 (trade name manufactured by Seikatsu Kasei Co., Ltd.) was used instead of Hurdle FA-20 in Example 1, and the acid value was 23.
is the end point of the reaction, and after cooling to 100°C, 20
0 parts of styrene was added to make a 60% solution.

実施例 3 実施例1において、ジエチレングリコール19.1部、
無水マレイン酸20,6部、テトラヒドロフタル無水フ
タル酸68.4部とし、また酸価終点を18とした以外
はすべて実施例1と同様にして60%溶液とした。
Example 3 In Example 1, 19.1 parts of diethylene glycol,
A 60% solution was prepared in the same manner as in Example 1 except that 20.6 parts of maleic anhydride and 68.4 parts of tetrahydrophthalic anhydride were used, and the acid value end point was changed to 18.

比較例 1 実施例1においてトール油脂肪酸の代わりに大豆油脂肪
酸を用いた以外は、すべて実施例1と同様にして60%
溶液とした。
Comparative Example 1 Same as Example 1 except that soybean oil fatty acid was used instead of tall oil fatty acid in Example 1, but 60%
It was made into a solution.

比較例 2 実施例1においてトール油脂肪酸の代わりにヤシ油脂肪
酸を用いた以外は、すべて実施例1と同様にして60%
溶液とした。
Comparative Example 2 Same as Example 1 except that coconut oil fatty acid was used instead of tall oil fatty acid in Example 1, but 60%
It was made into a solution.

実施例1〜3及び比較例1〜2で得られた不飽和ポリエ
ステル樹脂組成物の硬化状況及び硬度を試験したので、
その結果を第1表に示した。 実施例1〜3の組成物は
硬化状況か良好で100″C50Heの硬度も柔らかい
ものであり、本発明の効(単位) *1 *2 :MEKパーオキサイドを2%と、コバルト系金属塩を
0.2%添加し、80℃XIHで硬化させた。
Since the curing status and hardness of the unsaturated polyester resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 2 were tested,
The results are shown in Table 1. The compositions of Examples 1 to 3 were cured well and had a soft hardness of 100''C50He, and the effect of the present invention (unit) *1 *2: 2% MEK peroxide and cobalt metal salt. 0.2% was added and cured at 80°C XIH.

:○印・・粘着なし、×印・・・粘着有り。: ○ mark: No adhesive, × mark: Adhesive.

[発明の効果] 以上の説明および第1表から明らかなように、本発明の
不飽和ポリエステル樹脂組成物は、硬化初期の表面状態
が良好で、経時変化しても潰れた柔軟性を有するととも
に、安定性の優れたもので、水銀灯、蛍光灯等のチョー
クコイルにおける充填用として好適なものである。
[Effects of the Invention] As is clear from the above explanation and Table 1, the unsaturated polyester resin composition of the present invention has a good surface condition at the initial stage of curing, remains flexible even when changed over time, and has excellent flexibility. It has excellent stability and is suitable for filling choke coils in mercury lamps, fluorescent lamps, etc.

特許出願人 東芝ケミカル株式会社Patent applicant: Toshiba Chemical Corporation

Claims (1)

【特許請求の範囲】 1(A)不飽和多塩基酸、 (B)飽和多塩基酸、 (C)多価アルコール及び (D)共重合性単量体 を主成分とする不飽和ポリエステル樹脂組成物において
、不飽和多塩基酸としてトール油脂肪酸を、前記(A)
の不飽和多塩基酸に対して15〜30当量%、かつ樹脂
[(A)+(B)+(C)]に対して40〜60重量%
含有することを特徴とする不飽和ポリエステル樹脂組成
物。
[Claims] 1. An unsaturated polyester resin composition whose main components are (A) an unsaturated polybasic acid, (B) a saturated polybasic acid, (C) a polyhydric alcohol, and (D) a copolymerizable monomer. In the above-mentioned (A), tall oil fatty acid is used as the unsaturated polybasic acid.
15 to 30 equivalent % with respect to the unsaturated polybasic acid, and 40 to 60 weight % with respect to the resin [(A) + (B) + (C)]
An unsaturated polyester resin composition comprising:
JP27904988A 1988-11-04 1988-11-04 Unsaturated polyester resin composition Pending JPH02124916A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP27904988A JPH02124916A (en) 1988-11-04 1988-11-04 Unsaturated polyester resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP27904988A JPH02124916A (en) 1988-11-04 1988-11-04 Unsaturated polyester resin composition

Publications (1)

Publication Number Publication Date
JPH02124916A true JPH02124916A (en) 1990-05-14

Family

ID=17605687

Family Applications (1)

Application Number Title Priority Date Filing Date
JP27904988A Pending JPH02124916A (en) 1988-11-04 1988-11-04 Unsaturated polyester resin composition

Country Status (1)

Country Link
JP (1) JPH02124916A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008239906A (en) * 2007-03-29 2008-10-09 Matsushita Electric Ind Co Ltd Unsaturated polyester resin and molded article
CN102219882A (en) * 2011-05-04 2011-10-19 肇庆福田化学工业有限公司 Method for synthesizing unsaturated polyester resin by utilizing glycerol

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55143014A (en) * 1979-04-25 1980-11-08 Toshiba Chem Corp Impedance device
JPS55144014A (en) * 1979-04-02 1980-11-10 Hitachi Chem Co Ltd Unsaturated polyester resin composition for casting electrical equipment
JPS55144013A (en) * 1979-04-02 1980-11-10 Hitachi Chem Co Ltd Unsaturated polyester resin composition for casting electrical equipment
JPS55145718A (en) * 1979-04-30 1980-11-13 Toshiba Chem Corp Curable resin composition and preparation thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55144014A (en) * 1979-04-02 1980-11-10 Hitachi Chem Co Ltd Unsaturated polyester resin composition for casting electrical equipment
JPS55144013A (en) * 1979-04-02 1980-11-10 Hitachi Chem Co Ltd Unsaturated polyester resin composition for casting electrical equipment
JPS55143014A (en) * 1979-04-25 1980-11-08 Toshiba Chem Corp Impedance device
JPS55145718A (en) * 1979-04-30 1980-11-13 Toshiba Chem Corp Curable resin composition and preparation thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008239906A (en) * 2007-03-29 2008-10-09 Matsushita Electric Ind Co Ltd Unsaturated polyester resin and molded article
CN102219882A (en) * 2011-05-04 2011-10-19 肇庆福田化学工业有限公司 Method for synthesizing unsaturated polyester resin by utilizing glycerol

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