JP3197263B2 - Resin modifier - Google Patents
Resin modifierInfo
- Publication number
- JP3197263B2 JP3197263B2 JP2000380464A JP2000380464A JP3197263B2 JP 3197263 B2 JP3197263 B2 JP 3197263B2 JP 2000380464 A JP2000380464 A JP 2000380464A JP 2000380464 A JP2000380464 A JP 2000380464A JP 3197263 B2 JP3197263 B2 JP 3197263B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- resin modifier
- sio
- present
- fluorosilicone
- 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 - Fee Related
Links
Landscapes
- Silicon Polymers (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明はフルオロシリコーン
共重合体からなる樹脂改質剤に関する。The present invention relates to a resin modifier comprising a fluorosilicone copolymer.
【０００２】[0002]
【従来の技術】従来、耐熱・耐寒性に優れた合成油とし
てジメチルシリコーンオイル、その耐油・耐溶剤性を改
良したグレードとしてケイ素上の１つの置換基をトリフ
ルオロプロピル基とするフルオロシリコーンオイルが知
られている。2. Description of the Related Art Conventionally, dimethyl silicone oil has been used as a synthetic oil having excellent heat and cold resistance, and fluorosilicone oil having one substituent on silicon as a trifluoropropyl group has been used as a grade having improved oil and solvent resistance. Are known.
【０００３】一方、近年シリコーンオイルの産業上での
使用分野が拡大するにつれて、オイルの諸物性（屈折
率、表面張力、有機溶剤に対する溶解性等）を幅広い範
囲にわたり厳密にコントロールし、個々の用途に対応す
る必要が生じてきた。On the other hand, as the field of use of silicone oils in the industrial field has expanded in recent years, various properties of the oils (refractive index, surface tension, solubility in organic solvents, etc.) have been strictly controlled over a wide range, and individual applications have been studied. The need to respond has arisen.
【０００４】上記既存オイルは基本的にホモポリマーで
あるため、このような要求に応えられなかった。また、
ジメチルシロキサン単位とトリフルオロプロピルメチル
シロキサン単位からなる共重合体オイルも知られている
が、トリフルオロプロピル基自体の物性が不充分なた
め、オイル物性を変えうる範囲はわずかであった。[0004] Since the above-mentioned existing oils are basically homopolymers, such demands have not been met. Also,
Copolymer oils composed of dimethylsiloxane units and trifluoropropylmethylsiloxane units are also known, but the physical properties of the trifluoropropyl groups themselves are insufficient, so that the range in which the oil properties can be changed is small.
【０００５】さらに特開昭５９−１８９９３３には、ジ
メチルシロキサン単位と長鎖パーフルオロアルキルエチ
ルメチルシロキサン単位からなるコポリマーを、オキシ
アルキレン基とパーフルオロアルキル基とを有するオル
ガノポリシロキサンと併用すると消泡効果・自己乳化性
に優れることが記載されているが、コポリマー単品とし
ての評価についてはなんら記載がない。Further, JP-A-59-189933 discloses that a copolymer comprising a dimethylsiloxane unit and a long-chain perfluoroalkylethylmethylsiloxane unit is defoamed when used in combination with an organopolysiloxane having an oxyalkylene group and a perfluoroalkyl group. It is described that the effect and the self-emulsifying property are excellent, but there is no description about the evaluation as a copolymer alone.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、ジメ
チルシロキサン単位と長鎖パーフルオロアルキルエチル
メチルシロキサン単位からなる共重合オイルよりなる樹
脂改質剤を提供することにより、上記要求に応えようと
するものである。SUMMARY OF THE INVENTION An object of the present invention is to meet the above-mentioned demand by providing a resin modifier comprising a copolymerized oil comprising a dimethylsiloxane unit and a long-chain perfluoroalkylethylmethylsiloxane unit. It is assumed that.
【０００７】[0007]
【課題を解決するための手段】本発明は、下記式１で表
されるフルオロシリコーン共重合体オイルからなる樹脂
改質剤を提供する。ただし、式１中、Ｒfは炭素数４〜
９のパーフルオロアルキル基、ＲFはＣＨ3−またはＲf
ＣＨ2ＣＨ2−、ｎ≧１、ｍ≧１である。SUMMARY OF THE INVENTION The present invention provides a resin modifier comprising a fluorosilicone copolymer oil represented by the following formula 1. However, in the formula 1, R f has 4 to 4 carbon atoms.
9, R F is CH 3 — or R f
CH 2 CH 2 —, n ≧ 1, and m ≧ 1.
【０００８】[0008]
【化２】 Embedded image
【０００９】本発明において、式１中のＲfは炭素数４
〜９のパーフルオロアルキル基であり、ＲFはＣＨ3−ま
たはＲfＣＨ2ＣＨ2−である。このような長鎖パーフル
オロアルキル基含有フルオロシリコーン共重合体オイル
は、通常、連鎖移動剤ＲF（ＣＨ3）2ＳｉＯＳｉ（Ｃ
Ｈ3）2ＲFの存在下に［（ＲfＣＨ2ＣＨ2）（ＣＨ3）Ｓ
ｉＯ］3および［（ＣＨ3）2ＳｉＯ］p（ｐは３または
４）を適当な触媒下に開環重合させて製造される。In the present invention, R f in the formula 1 represents 4 carbon atoms.
And R F is CH 3 — or R f CH 2 CH 2 —. Such a long chain perfluoroalkyl group-containing fluorosilicone copolymer oil is generally used as a chain transfer agent R F (CH 3 ) 2 SiOSi (C
H 3) 2 in the presence of R F [(R f CH 2 CH 2) (CH 3) S
It is produced by ring-opening polymerization of iO] 3 and [(CH 3 ) 2 SiO] p (p is 3 or 4) in the presence of a suitable catalyst.
【００１０】Ｒfが長鎖になるにつれて［ＲfＣＨ2ＣＨ2
（ＣＨ3）ＳｉＯ］3の製造が困難になるため、好ましい
Ｒfはパーフルオロブチル基である。一方、ＲFは原料入
手の容易さからメチル基が特に好ましい。また、ｎ≧
１、ｍ≧１であり、ｎおよびｍの値は該範囲を満たせば
特に限定されず、本オイルの用途によって決定されるべ
き数値である。As R f becomes longer, [R f CH 2 CH 2
Preferred production of (CH 3 ) SiO] 3 makes it difficult to produce R f is a perfluorobutyl group. On the other hand, R F is particularly preferably a methyl group because of availability of raw materials. Also, n ≧
1, m ≧ 1, and the values of n and m are not particularly limited as long as they satisfy the range, and are values to be determined according to the use of the present oil.
【００１１】本発明に係るオイルは、後に示すように共
重合組成を変えることによりその表面張力・屈折率等の
諸物性を精度良く変えうる。したがって細分化されたシ
リコーンオイルの利用分野における様々な諸物性を有す
るフルオロシリコーンオイルを製造でき、その使用条件
を特に限定することなく使用できる。The properties of the oil according to the present invention, such as surface tension and refractive index, can be accurately changed by changing the copolymer composition as described later. Therefore, a fluorosilicone oil having various physical properties in the application field of the finely divided silicone oil can be produced, and can be used without any particular limitation on its use conditions.
【００１２】本発明に係るオイルは、耐熱性・耐寒性・
酸化安定性・潤滑性・柔軟性等を利用して樹脂の改質剤
に使用する。また本発明に係るフルオロシリコーン共重
合体オイルは、動粘度が１００００センチストークス
（以下、ｃＳｔと略す）程度以下であることが好まし
い。動粘度があまりに高すぎると、流動性、特に低温で
の流動性が低下するため好ましくない。The oil according to the present invention has heat resistance, cold resistance,
It is used as a resin modifier by utilizing its oxidation stability, lubricity and flexibility. Further, the fluorosilicone copolymer oil according to the present invention preferably has a kinematic viscosity of about 10,000 centistokes (hereinafter abbreviated to cSt). If the kinematic viscosity is too high, the fluidity, particularly the fluidity at low temperatures, is not preferred.
【００１３】[0013]
【作用】本発明において長鎖パーフルオロアルキル基
は、フッ素に由来する各種性能（耐油・耐溶剤、低表面
張力、低屈折率）をオイルに付与する。そこで（ＲfＣ
Ｈ2ＣＨ2）（ＣＨ3）ＳｉＯ2/2と（ＣＨ3）2ＳｉＯ2/2
の共重合比を変えることによりオイルの諸物性を幅広い
範囲にわたり厳密にコントロールでき、オイルの各種用
途に対応できる。In the present invention, the long-chain perfluoroalkyl group imparts various properties (oil resistance / solvent resistance, low surface tension, low refractive index) derived from fluorine to oil. Then (R f C
H 2 CH 2 ) (CH 3 ) SiO 2/2 and (CH 3 ) 2 SiO 2/2
By changing the copolymerization ratio of, various physical properties of the oil can be strictly controlled over a wide range, and can be used for various uses of the oil.
【００１４】[0014]
【実施例】［製造例１］ 撹拌器・還流冷却器・温度計のついた４つ口フラスコを
アルゴンによりパージし、［（Ｃ4 Ｆ 9Ｃ2Ｈ4）（Ｃ
Ｈ3）ＳｉＯ］3の１５ｇ、［（ＣＨ3）2ＳｉＯ］3の１
５ｇ、（ＣＨ3）3ＳｉＯＳｉ（ＣＨ3）3の１ｇを仕込ん
だ。内温を７５℃に上昇せしめ、トリフルオロメタンス
ルホン酸４８ｍｇをマイクロシリンジによりフラスコ内
に導入した。EXAMPLES [Production Example 1] A four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was purged with argon, and [(C 4 F 9 C 2 H 4 ) (C
15 g of [H 3 ) SiO] 3 and 1 of [(CH 3 ) 2 SiO] 3
5 g and 1 g of (CH 3 ) 3 SiOSi (CH 3 ) 3 were charged. The internal temperature was raised to 75 ° C., and 48 mg of trifluoromethanesulfonic acid was introduced into the flask with a micro syringe.
【００１５】６時間後にモノマーが完全に消費されたこ
とを確認した。生成物を５％重曹水および水により連続
洗浄した後、２００℃にて低沸分を除去し、動粘度１１
２ｃＳｔのフルオロシリコーンオイル２７．９ｇ（９０
％）を得た。このオイルは1Ｈ−ＮＭＲ、ＩＲにより下
記構造を有することを確認した。After 6 hours, it was confirmed that the monomer was completely consumed. The product was washed successively with 5% aqueous sodium bicarbonate and water, then low boiling components were removed at 200 ° C.
27.9 g of 2cSt fluorosilicone oil (90
%). The oil was confirmed to have the following structure by 1 H-NMR and IR.
【００１６】[0016]
【化３】 Embedded image
【００１７】［製造例２］ ［（Ｃ4 Ｆ 9Ｃ2Ｈ4）（ＣＨ3）ＳｉＯ］3を６．１ｇ、
［（ＣＨ3）2ＳｉＯ］3を１４．１ｇ、（ＣＨ3）3Ｓｉ
ＯＳｉ（ＣＨ3）3を０．８５ｇ、トリフルオロメタンス
ルホン酸を２６ｍｇ、に変更した他は製造例１と同様に
して動粘度１０４ｃＳｔのフルオロシリコーンオイル１
８．７ｇ（８８．９％）を得た。このオイルは1Ｈ−Ｎ
ＭＲ、ＩＲにより下記構造を有することを確認した。[Production Example 2] 6.1 g of [(C 4 F 9 C 2 H 4 ) (CH 3 ) SiO] 3 was prepared.
14.1 g of [(CH 3 ) 2 SiO] 3 and (CH 3 ) 3 Si
Fluorosilicone oil 1 having a kinematic viscosity of 104 cSt was prepared in the same manner as in Production Example 1, except that 0.85 g of OSi (CH 3 ) 3 and 26 mg of trifluoromethanesulfonic acid were used.
8.7 g (88.9%) were obtained. This oil is 1 H-N
It was confirmed by MR and IR that it had the following structure.
【００１８】[0018]
【化４】 Embedded image
【００１９】［実施例］ 〈共重合組成を変えることによりオイルの物性を調整で
きることの証明〉本発明に係るオイルは（ＲfＣＨ2ＣＨ
2）（ＣＨ3）ＳｉＯ2/2と（ＣＨ3）2ＳｉＯ2/2の共重合
比を変えることによりオイルの諸物性を幅広い範囲にわ
たりコントロールできる。ＲfをＣ4Ｆ9とした場合の共
重合組成と物性の関係を表１に示す。表１において動粘
度は２５℃における値、比重は２０℃における値、ゲル
化時間は２００℃における値、誘電率は２５℃、６０Ｈ
ｚにおける値、誘電正接は２５℃、６０Ｈｚにおける値
である。[Example] <Proof that physical properties of oil can be adjusted by changing copolymer composition> The oil according to the present invention is (R f CH 2 CH).
2 ) By changing the copolymerization ratio of (CH 3 ) SiO 2/2 and (CH 3 ) 2 SiO 2/2 , various physical properties of the oil can be controlled over a wide range. Table 1 shows the relationship between the copolymer composition and the physical properties when R f is C 4 F 9 . In Table 1, kinematic viscosity is a value at 25 ° C., specific gravity is a value at 20 ° C., gel time is a value at 200 ° C., dielectric constant is 25 ° C., 60H
The value at z and the dielectric loss tangent are the values at 25 ° C. and 60 Hz.
【００２０】[0020]
【表１】 [Table 1]
【００２１】〈樹脂改質剤への応用〉小型ニーダーを使
用し、ポリアセタール樹脂（ポリプラ社製）１００部と
表２に示すオイル１部を、温度２００℃で１０分間溶融
混練したのち、温度２００℃、圧力１００ｋｇ／ｃｍ2
の条件で圧縮成形し、厚さ２ｍｍのシートを作製した。
このシートについて次の評価方法で外観、摩擦係数、流
動性を調べたところ、表２に示す結果を得た。表２から
本発明品は樹脂の改質に優れることがわかる。<Application to Resin Modifier> Using a small kneader, 100 parts of a polyacetal resin (manufactured by Polypla Co.) and 1 part of an oil shown in Table 2 were melt-kneaded at a temperature of 200 ° C. for 10 minutes, and then heated to a temperature of 200 ° C. ° C, pressure 100kg / cm 2
Under the following conditions to produce a sheet having a thickness of 2 mm.
The sheet was examined for appearance, coefficient of friction, and fluidity by the following evaluation methods, and the results shown in Table 2 were obtained. Table 2 shows that the product of the present invention is excellent in resin modification.
【００２２】外観：肉眼で観察。 摩擦係数：ＨＥＩＤＥＮ−１４型測定機を使用し、荷重
１００ｇ、速度５０ｍｍ／分、温度２５℃の条件で測
定。 流動性：高化式フローテスターを用い２００℃、荷重１
０ｋｇ、Ｌ／Ｄ＝１ｍｍ／１ｍｍの条件下での流出速度
（Ｑ値、単位：×１０-2ｍｌ／秒）を測定。Appearance: Observed with the naked eye. Coefficient of friction: Measured using a HEIDEN-14 type measuring instrument under the conditions of a load of 100 g, a speed of 50 mm / min, and a temperature of 25 ° C. Fluidity: 200 ° C, load 1 using a Koka type flow tester
The outflow speed (Q value, unit: × 10 -2 ml / sec) was measured under the conditions of 0 kg and L / D = 1 mm / 1 mm.
【００２３】[0023]
【表２】 [Table 2]
【００２４】[0024]
【発明の効果】本発明に係るオイルはパーフルオロアル
キル基の存在により耐熱・潤滑性に優れる。さらにジメ
チルシリコーンとの共重合割合を調整することにより、
オイルの諸物性をコントロールできる効果も認められ、
樹脂改質剤として適する。The oil according to the present invention is excellent in heat resistance and lubricity due to the presence of the perfluoroalkyl group. Furthermore, by adjusting the copolymerization ratio with dimethyl silicone,
The effect of controlling various physical properties of oil is also recognized,
Suitable as a resin modifier.
Claims (3)
重合体オイルからなることを特徴とする樹脂改質剤。た
だし、式１中、Ｒfは炭素数４〜９のパーフルオロアル
キル基、ＲFはＣＨ3−またはＲfＣＨ2ＣＨ2−、ｎ≧
１、ｍ≧１である。 【化１】 1. A resin modifier comprising a fluorosilicone copolymer oil represented by the following formula 1. However, in Formula 1, R f is a perfluoroalkyl group having 4 to 9 carbon atoms, R F is CH 3 — or R f CH 2 CH 2 —, and n ≧
1, m ≧ 1. Embedded image
メチル基である請求項１に記載の樹脂改質剤。2. The resin modifier according to claim 1, wherein R f is a perfluorobutyl group, and R F is a methyl group.
量に対する（ＲfＣ2Ｈ4）（ＣＨ3）ＳｉＯ2/2単位の全
重量の比が、５０／５０〜１０／９０である請求項１ま
たは２に記載の樹脂改質剤。3. The ratio of the total weight of (R f C 2 H 4 ) (CH 3 ) SiO 2/2 units to the total weight of (CH 3 ) 2 SiO 2/2 units in the formula 1 is 50/50. The resin modifier according to claim 1, wherein the ratio is from 10/90 to 10/90.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000380464A JP3197263B2 (en) | 2000-12-14 | 2000-12-14 | Resin modifier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000380464A JP3197263B2 (en) | 2000-12-14 | 2000-12-14 | Resin modifier |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12215299A Division JP3197255B2 (en) | 1999-04-28 | 1999-04-28 | Release agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001158822A JP2001158822A (en) | 2001-06-12 |
| JP3197263B2 true JP3197263B2 (en) | 2001-08-13 |
Family
ID=18848643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000380464A Expired - Fee Related JP3197263B2 (en) | 2000-12-14 | 2000-12-14 | Resin modifier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3197263B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111446B (en) * | 2015-09-17 | 2017-10-20 | 华南理工大学 | A kind of fluorine-containing phenyl hydrogen-containing silicon oil crosslinking agent and preparation method thereof |
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2000
- 2000-12-14 JP JP2000380464A patent/JP3197263B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001158822A (en) | 2001-06-12 |
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