JPH0477016B2 - - Google Patents
Info
- Publication number
- JPH0477016B2 JPH0477016B2 JP58088854A JP8885483A JPH0477016B2 JP H0477016 B2 JPH0477016 B2 JP H0477016B2 JP 58088854 A JP58088854 A JP 58088854A JP 8885483 A JP8885483 A JP 8885483A JP H0477016 B2 JPH0477016 B2 JP H0477016B2
- Authority
- JP
- Japan
- Prior art keywords
- silicone resin
- coupling agent
- silane coupling
- reaction
- weight
- 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 - Lifetime
Links
- 229920002050 silicone resin Polymers 0.000 claims description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 4
- -1 silanol compound Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000976 ink Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- URMCFMOUMIWRAH-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine;n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN.CO[Si](OC)(OC)CCCNCCN URMCFMOUMIWRAH-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明はシリコーン樹脂の変性方法に関し、さ
らに詳しくいえば、水酸基を有するシリコーン樹
脂にシランカツプリング剤を付加反応させること
により、ガラス質表面やクロムめつき表面に対す
る接着性を向上させるシリコーン樹脂の変性方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for modifying silicone resins, and more specifically, by adding a silane coupling agent to a silicone resin having hydroxyl groups, it is possible to modify glassy surfaces and chrome surfaces. The present invention relates to a method for modifying silicone resins to improve adhesion to matted surfaces.
従来の技術
シリコーン樹脂は、一般に耐熱性、耐寒性、耐
候性、耐水性に優れ、かつ、化学的に不活性で電
気的特性にも優れていることから、その他方の欠
点であるガラス質表面やクロムめつき表面に対す
る接着性が不十分であることや、他の樹脂に比べ
て高価であるにもかからわず、塗料、接着剤や各
種の結合剤などに広く使用されている。Conventional technology Silicone resins generally have excellent heat resistance, cold resistance, weather resistance, and water resistance, and are also chemically inert and have excellent electrical properties. Although it has insufficient adhesion to chrome-plated surfaces and is more expensive than other resins, it is widely used in paints, adhesives, and various binders.
上記した性質の欠点に関してはシランカツプリ
ング剤の助けをかりて改善されている。このシラ
ンカツプリング剤は１分子中に２個以上の異つた
反応基をもつ有機ケイ素系単量体であつて、それ
がもつ有機質材料や、無機質材料との化合的結合
性を利用したものである。特に、シリコーン樹脂
をガラス繊維への配合、合成樹脂へ直接混合する
ことによる強化プラスチツクの性能向上、また塗
料や接着剤等に使用するに際しては、このシラン
カツプリング剤をシリコーン樹脂に混合せしめて
初めて、その目的を達成していた。 The above-mentioned disadvantages in properties have been improved with the aid of silane coupling agents. This silane coupling agent is an organosilicon monomer that has two or more different reactive groups in one molecule, and utilizes its chemical bonding properties with organic and inorganic materials. be. In particular, the performance of reinforced plastics can be improved by blending silicone resin into glass fibers, directly mixing it with synthetic resins, and when using it in paints, adhesives, etc., it is necessary to mix this silane coupling agent with silicone resin. , had achieved its purpose.
また、このようにシリコーン樹脂にシランカツ
プリング剤を混在せしめても、なお所望の接着力
を得るには至つていない。 Moreover, even when a silane coupling agent is mixed with a silicone resin in this way, the desired adhesive strength is still not achieved.
基体上にシリコーン樹脂を積層するときに、基
体上にあらかじめシランカツプリング剤を被着せ
しめておく方法も知られているが、この方法にお
いては、シランカツプリング剤を被着するに際
し、加熱処理を必要とし、そのための装置と工程
は欠くことができず、工程数が多いばかりではな
く装置を必要とする欠点があつた。 When laminating silicone resin on a substrate, a method is also known in which a silane coupling agent is applied on the substrate in advance. , and the equipment and processes for that purpose are indispensable, and the disadvantage is that not only is there a large number of processes, but also equipment is required.
発明の目的
本発明者らは、シリコーン樹脂を変性すること
により、より大きな接着力を有する化合物を開発
すべく、鋭意研究を重ねた結果、本発明をなすに
至つた。Purpose of the Invention The present inventors have conducted extensive research in order to develop a compound with greater adhesive strength by modifying silicone resin, and as a result, have achieved the present invention.
発明の構成
本発明は、２個又は３個の水酸基を有する一般
式（）で表わされるシラノール化合物を、実質
的に脱水縮合反応して得られるシリコーン樹脂
と、一般式（）で表わされる化合物とをほぼ等
モル量の割合で反応させることからなる、シリコ
ーン樹脂の変性方法に関する。Structure of the Invention The present invention provides a silicone resin obtained by substantially dehydrating and condensing a silanol compound having two or three hydroxyl groups represented by the general formula (), and a compound represented by the general formula (). The present invention relates to a method for modifying silicone resins, which comprises reacting them in approximately equimolar proportions.
R4-oSi（OH）o （）
H2NC2H4NHC3H6SiR′p（OR′）q （）
（ただし、式中の
ｎは２又は３を示し、
ｐは０又は１を示し、
ｑは３−ｐの関係にあつて、しかも３又は２を
示し、
Ｒは低級アルキル基、アリール基又はビニル基
を示し、
R′は低級アルキル基を示す。）
（シリコーン樹脂）
本発明において変性の対象となる水酸基を有す
るシリコーン樹脂は、市販のものが利用でき、例
えば信越化学工業(株)製のシリコーンワニスKR−
112、212、213、214、215、216などを挙げること
ができる。R 4-o Si(OH) o () H 2 NC 2 H 4 NHC 3 H 6 SiR' p (OR') q () (However, n in the formula represents 2 or 3, and p represents 0 or 1. (Silicone resin) (Silicone resin) (Silicone resin) (Silicone resin) Commercially available silicone resins having hydroxyl groups to be modified in the invention can be used; for example, silicone varnish KR- manufactured by Shin-Etsu Chemical Co., Ltd.
Examples include 112, 212, 213, 214, 215, 216, etc.
（シランカツプリング剤）
また、一般式（）で表わされるシランカツプ
リング剤としては、R′が例えばメチル基、エチ
ル基、ｎ−プロピル基、ｎ−ブチル基などを挙げ
ることができるが、具体的には次のものが好まし
い。(Silan coupling agent) In addition, as for the silane coupling agent represented by the general formula (), R' can be, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc. The following are preferable.
Ｎ−β−アミノエチル−γ−アミノプロピルト
リメトキシシラン
Ｎ−β−アミノエチル−γ−アミノプロピルメ
チルジメトキシシラン
（変性反応）
シリコーン樹脂の変性は、一般に水酸基を有す
るシリコーン樹脂と一般式（）で表わされるシ
ランカツプリング剤とを、溶剤の存在下で攪拌混
合して行われる。この反応は、触媒なしでも混合
するだけで発熱を伴ない容易に進行して誘導体が
形成される。この反応式は次のとおりであり、脱
水を伴つて発熱する。 N-β-aminoethyl-γ-aminopropyltrimethoxysilane N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (modification reaction) In general, modification of silicone resin is performed using a silicone resin having a hydroxyl group and the general formula (). The above silane coupling agent is stirred and mixed in the presence of a solvent. This reaction easily proceeds with no heat generation even without a catalyst by simply mixing, and a derivative is formed. The reaction formula is as follows, and heat is generated along with dehydration.
≡SI−OH＋H2NC2H4NHC3H6SiR′p（OR′）q→
≡SiNHC2H4NHC3H6SiR′p（OR′）q＋H2O
この場合の溶剤としては例えばメタノール、エ
タノール、イソプロパノールの如きアルコール
類、トルエン、キシレンの如き芳香族炭化水素
類、アセトン、メチルエチルケトンの如きケトン
類などの単独又はこれらの混合溶剤が使用でき
る。ただ前記反応式からわかるように、反応で発
生した水がシランカツプリング剤のアルコキシ基
との間で加水分解反応を生ずることなく反応して
常に一定な反応生成物が得られることが必要であ
り、このため水に可溶な単独又は混合の溶剤を選
ぶか、若しくは生成する水を反応系外に取り除く
方がより望ましい。≡SI−OH＋H 2 NC 2 H 4 NHC 3 H 6 SiR′ p (OR′) q → ≡SiNHC 2 H 4 NHC 3 H 6 SiR′ p (OR′) q +H 2 O In this case, the solvent is, for example, methanol. , alcohols such as ethanol and isopropanol, aromatic hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, and the like can be used alone or in combination. However, as can be seen from the above reaction formula, it is necessary that the water generated in the reaction reacts with the alkoxy group of the silane coupling agent without causing a hydrolysis reaction, and a constant reaction product is always obtained. Therefore, it is more desirable to select a single or mixed solvent that is soluble in water, or to remove the generated water from the reaction system.
なお、反応温度は原料である水酸基を有するシ
リコーン樹脂及びシランカツプリング剤をそれぞ
れの種類、溶剤の種類その他の条件により必ずし
も一定しないが、通常は約25℃以上を選択する。 Although the reaction temperature is not necessarily constant depending on the types of silicone resin having a hydroxyl group and the silane coupling agent used as raw materials, the type of solvent, and other conditions, it is usually selected to be about 25°C or higher.
このようにして得られる変性シリコン樹脂は、
アルコキシ基と２個のイミノ基を分子中に適宜配
置した構造をとつているので、一般式（）と一
般式（）との組み合わせに左右されることな
く、同様の効果を奏することができる。 The modified silicone resin obtained in this way is
Since it has a structure in which an alkoxy group and two imino groups are appropriately arranged in the molecule, the same effect can be achieved regardless of the combination of general formula () and general formula ().
（変性生成物）
本発明の変性方法により得られる変性シリコー
ン樹脂は、いずれも文献未載の新規化合物であ
り、赤外線吸収スペクトルにより同定できる。す
なわち、反応の前後において、シランカツプリン
グ剤に帰因する900〜960cm-1における−NH2の
吸収が消失又は減少すること、3050cm-1附近にイ
ミノ基の吸収が現わられること、水酸基を有する
シリコーン樹脂とシランカツプリング剤を、溶剤
の存在下でほぼ等モル量反応させその溶剤を乾燥
させた時に、シリコーン樹脂に帰因する3200〜
3500cm-1附近に見られる水酸基の吸収が消失する
こと、などから明らかである。参考のため、シリ
コーン樹脂KR−214（商品名、信越化学工業(株)
製）、シランカツプリング剤KBM603（商品名、
信越化学工業(株)製、Ｎ−β−アミノエチル−γ−
アミノプロピルトリメトキシシラン）、KR−214
とKBM603との反応生成物の赤外線吸収スペク
トルをそれぞれ第１図ないし第３図に示す。第３
図のスペクトルは以下のように測定された。すな
わちブタノールとシランカツプリング剤を等グラ
ム数づつ混合した溶液を50℃で８時間攪拌した。
このときにKBM603のエトキシ基はブトキシ基
に交換される。そして室温まで温度を下げてか
ら、この反応液130ｇに対しKR−214を217ｇ混
合し50℃で６時間反応させることによつて完了す
る。(Modified product) The modified silicone resins obtained by the modification method of the present invention are all new compounds that have not been described in any literature, and can be identified by infrared absorption spectra. That is, before and after the reaction, -NH 2 absorption at 900 to 960 cm -1 due to the silane coupling agent disappears or decreases, imino group absorption appears around 3050 cm -1 , and hydroxyl group When the silicone resin and the silane coupling agent are reacted in approximately equimolar amounts in the presence of a solvent and the solvent is dried, the
This is clear from the fact that the absorption of hydroxyl groups observed around 3500 cm -1 disappears. For reference, silicone resin KR-214 (product name, Shin-Etsu Chemical Co., Ltd.)
), silane coupling agent KBM603 (product name,
Shin-Etsu Chemical Co., Ltd., N-β-aminoethyl-γ-
aminopropyltrimethoxysilane), KR-214
The infrared absorption spectra of the reaction products of KBM603 and KBM603 are shown in Figures 1 to 3, respectively. Third
The spectrum shown in the figure was measured as follows. That is, a solution in which equal grams of butanol and silane coupling agent were mixed was stirred at 50° C. for 8 hours.
At this time, the ethoxy group of KBM603 is exchanged with a butoxy group. After lowering the temperature to room temperature, 217 g of KR-214 was mixed with 130 g of this reaction solution, and the reaction was completed at 50° C. for 6 hours.
このようにして得られた反応液を岩塩板上に塗
り、乾燥させてのち、赤外線吸収スペクトルを測
定した。 The reaction solution thus obtained was applied onto a rock salt plate, dried, and then an infrared absorption spectrum was measured.
効果・用途
本発明の変性方法により得られる変性シリコー
ン樹脂は、末端のアルコキシ基が極性のある物質
例えばガラス質と直接作用し、かつイミノ基が水
素結合によつて被膜全体の強度をより強力にする
ものであり、又速乾性で、短時間で強固な接着が
可能であり、低温での接着性がよいので、イン
ク、塗料、ガラスのコーテイング剤、接着剤等多
くの用途が考えられる。Effects/Applications The modified silicone resin obtained by the modification method of the present invention has terminal alkoxy groups that interact directly with polar substances such as glass, and imino groups that increase the strength of the entire coating through hydrogen bonding. In addition, it dries quickly, enables strong adhesion in a short period of time, and has good adhesion at low temperatures, so it can be used in many applications such as inks, paints, glass coating agents, and adhesives.
なお本発明方法によつて得られる変性シリコー
ン樹脂は、アルコキシ基と２個のイミノ基を分子
中に適宜配置した構造をとつているので特にガラ
ス質またはクロムめつきした表面に対する接着力
が強固であるから例えば、これをインク組成物の
樹脂成分として用いた場合の印字体を指でこすつ
た程度の力では、印字体は容易に脱落することが
ないが、従来公知のインク組成物では容易に脱落
する。 The modified silicone resin obtained by the method of the present invention has a structure in which an alkoxy group and two imino groups are appropriately arranged in the molecule, so it has particularly strong adhesion to glassy or chromium-plated surfaces. For example, when this is used as the resin component of an ink composition, the printed material will not easily fall off when rubbed with a finger, but in conventional ink compositions, the printed material will not easily fall off. take off.
実施例
次に一般式（）の代表例としてシリコーン樹
脂、一般式（）の代表例としてＮ−β−アミノ
エチル−γ−アミノプロピルトリメトキシシラン
を使用した実施例を挙げて説明する。EXAMPLES Next, examples will be given and explained in which silicone resin is used as a representative example of general formula (), and N-β-aminoethyl-γ-aminopropyltrimethoxysilane is used as a representative example of general formula ().
実施例
溶剤としてメチルイソブチルケトン13重量部及
びイソプロピルアルコール57重量部、水酸基を有
するシリコーン樹脂としてKR−214（商品名、信
越化学工業(株)製、樹脂分70重量％、キシレン30重
量％）20重量部を混合し、これにシランカツプリ
ング剤としてKBM603（商品名、信越化学工業(株)
製、Ｎ−β−アミノエチル−γ−アミノプロピル
トリメトキシシラン）６重量部を室温で添加し反
応させた。得られた変性シリコーン樹脂溶液に、
電導性付与剤としてチオシアン酸ナトリウム
（NaSCN）1.8重量部、染料としてオイルブラツ
クHBB（商品名、オリエント化学工業社製）1.4
重量部、シリコーン界面活性剤としてKp−340
（商品名、信越化学工業(株)製）0.8重量部を添加、
溶解ないし混合した後フロロボア（孔径1μｍ、
住友電工(株)製）で濾過してインクジエツト記録用
インク組成物を作製した。液の特性は粘度
4.96cP、比重0.867、抵抗値1570Ω・cm、表面張
力25.7dyn／cmでインクジエツト記録用インクの
要求水準を満たしており、又日立IJプリンターＰ
型による印字テストでも独立微粒子となつて噴射
され鮮明な記録を形成した。このインクはガラス
板に印字後、短時間で乾燥し、ガラス面と強固に
密着し、非常に優れた効果を得た。Example 13 parts by weight of methyl isobutyl ketone and 57 parts by weight of isopropyl alcohol as a solvent, KR-214 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., resin content 70% by weight, xylene 30% by weight) as a silicone resin having a hydroxyl group 20 parts by weight, and KBM603 (trade name, Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent is mixed with this.
6 parts by weight of N-β-aminoethyl-γ-aminopropyltrimethoxysilane (manufactured by Manufacturer Co., Ltd.) were added at room temperature and allowed to react. To the obtained modified silicone resin solution,
1.8 parts by weight of sodium thiocyanate (NaSCN) as a conductivity imparting agent, and 1.4 parts by weight of Oil Black HBB (trade name, manufactured by Orient Chemical Industry Co., Ltd.) as a dye.
Parts by weight, Kp-340 as silicone surfactant
(Product name, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.8 parts by weight added,
After dissolving or mixing, fluorobore (pore size 1 μm,
An ink jet recording ink composition was prepared by filtration using a filter (manufactured by Sumitomo Electric Industries, Ltd.). The characteristic of liquid is viscosity
4.96cP, specific gravity 0.867, resistance value 1570Ω・cm, and surface tension 25.7dyn/cm, meeting the required standards for inkjet recording ink, and also compatible with Hitachi IJ Printer P.
Even in a printing test using a mold, it was sprayed as independent fine particles, forming a clear record. After printing on the glass plate, this ink dried in a short period of time, adhered firmly to the glass surface, and had excellent effects.
（比較例）
実施例におけるKR−214の20重量部とKBM−
603の６重量部の反応生成物を代えて、(1)KR−
214の20重量部のみ及び(2)KR−214の20重量部と
アミノ基を有しないカツプリング剤KBM−1003
｛信越化学工業(株)製）の５重量部の反応生成物を
それぞれのインク組成物を用い、素ガラス板に印
字して、指でこすつて、印字が脱落するに要する
回数を比較すると、上記(1)及び(2)の組成物におい
ては１回で、実施例の組成物においては10回で脱
落した。さらに素ガラス板表面をシランカツプリ
ング剤により処理した面に同様に印字して、脱落
するに要する回数をみたところ(1)及び(2)の組成物
においては３回、実施例の組成物においては15回
で脱落した。(Comparative example) 20 parts by weight of KR-214 and KBM- in the example
By replacing 6 parts by weight of the reaction product of 603, (1)KR-
Coupling agent KBM-1003 with only 20 parts by weight of 214 and (2) 20 parts by weight of KR-214 and no amino group
(Manufactured by Shin-Etsu Chemical Co., Ltd.) by printing 5 parts by weight of the reaction product using each ink composition on a plain glass plate, rubbing it with your finger, and comparing the number of times it takes for the print to fall off. In the compositions (1) and (2) above, it fell off once, and in the composition of Example, it fell off after 10 times. Furthermore, when printing was performed in the same manner on the surface of a raw glass plate treated with a silane coupling agent, and the number of times required for it to fall off was determined, it was printed 3 times for the compositions (1) and (2), and 3 times for the compositions of Examples. was eliminated after 15 innings.
第１図はシリコーン樹脂の赤外線吸収スペクト
ル、第２図はＮ−β−アミノエチル−γ−アミノ
プロピルトリメトキシシランの赤外線吸収スペク
トル、第３図はシリコーン樹脂とＮ−β−アミノ
エチル−γ−アミノプロピルトリメトキシシラン
との反応生成物の赤外線吸収スペクトルをそれぞ
れ表わす。
Figure 1 shows the infrared absorption spectrum of silicone resin, Figure 2 shows the infrared absorption spectrum of N-β-aminoethyl-γ-aminopropyltrimethoxysilane, and Figure 3 shows the infrared absorption spectrum of silicone resin and N-β-aminoethyl-γ- The infrared absorption spectra of the reaction products with aminopropyltrimethoxysilane are shown.
Claims (1)
で表わされるシラノール化合物を、実質的に脱水
縮合反応して得られるシリコーン樹脂と、一般式
（）で表わされる化合物とをほぼ等モル量の割
合で反応させることからなる、シリコーン樹脂の
変性方法。 R4-oSi（OH）o （） H2NC2H4NHC3H6SiR′p（OR′）q （） （ただし、式中の ｎは２又は３を示し、 ｐは０又は１を示し、 ｑは３−ｐの関係にあつて、しかも３又は２を
示し、 Ｒは低級アルキル基、アリール基又はビニル基
を示し、 R′は低級アルキル基を示す。）[Claims] 1 General formula () having 2 or 3 hydroxyl groups
A method for modifying a silicone resin, which comprises reacting a silicone resin obtained by substantially dehydrating and condensing a silanol compound represented by the formula () with a compound represented by the general formula () in approximately equimolar amounts. R 4-o Si(OH) o () H 2 NC 2 H 4 NHC 3 H 6 SiR' p (OR') q () (However, n in the formula represents 2 or 3, and p represents 0 or 1. , q has a 3-p relationship and represents 3 or 2, R represents a lower alkyl group, aryl group, or vinyl group, and R' represents a lower alkyl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8885483A JPS59215324A (en) | 1983-05-20 | 1983-05-20 | Modification of silicone resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8885483A JPS59215324A (en) | 1983-05-20 | 1983-05-20 | Modification of silicone resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59215324A JPS59215324A (en) | 1984-12-05 |
| JPH0477016B2 true JPH0477016B2 (en) | 1992-12-07 |
Family
ID=13954570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8885483A Granted JPS59215324A (en) | 1983-05-20 | 1983-05-20 | Modification of silicone resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59215324A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS501356A (en) * | 1973-05-11 | 1975-01-08 |
-
1983
- 1983-05-20 JP JP8885483A patent/JPS59215324A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS501356A (en) * | 1973-05-11 | 1975-01-08 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59215324A (en) | 1984-12-05 |
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