JPH0277469A - Ladder type silicone oligomer composition - Google Patents
Ladder type silicone oligomer compositionInfo
- Publication number
- JPH0277469A JPH0277469A JP24123088A JP24123088A JPH0277469A JP H0277469 A JPH0277469 A JP H0277469A JP 24123088 A JP24123088 A JP 24123088A JP 24123088 A JP24123088 A JP 24123088A JP H0277469 A JPH0277469 A JP H0277469A
- Authority
- JP
- Japan
- Prior art keywords
- ladder
- weight
- type silicone
- silicone oligomer
- silicone polymer
- 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
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 108
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 91
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 25
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 60
- 230000001070 adhesive effect Effects 0.000 abstract description 19
- 238000002156 mixing Methods 0.000 abstract description 18
- 239000000853 adhesive Substances 0.000 abstract description 16
- 238000005336 cracking Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 90
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 50
- 239000012046 mixed solvent Substances 0.000 description 27
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000000576 coating method Methods 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 229910000975 Carbon steel Inorganic materials 0.000 description 10
- 239000010962 carbon steel Substances 0.000 description 10
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical group N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- CNGFUKTUURDVOU-UHFFFAOYSA-N [C].CC(C)=O Chemical compound [C].CC(C)=O CNGFUKTUURDVOU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- -1 benzene and toluene Chemical compound 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐吸湿性、耐熱性、絶縁性、耐クラック性、
接着性、耐はく離性、耐溶剤性および耐水性等にすぐれ
たコーティング剤、接着剤等の材料として好適なラダー
型シリコーンオリゴマー組成物に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides moisture absorption resistance, heat resistance, insulation, crack resistance,
The present invention relates to a ladder-type silicone oligomer composition suitable as a material for coating agents, adhesives, etc., which has excellent adhesion, peel resistance, solvent resistance, water resistance, etc.
ラダー型シリコーンオリゴマーは、耐熱性、絶縁性、硬
度および耐水性等にすぐれているため、耐熱塗料、半導
体の絶縁コーティング等に用いられている。しかし、ラ
ダー型シリコーンオリゴマーから形成される皮膜には、
クラックが発生しやすく、脆弱であり、また接着性に劣
るという欠点を有する。このため、ラダー型シリコーン
オリゴマーに種々の添加剤を配合することが検討された
が、あるものはラダー型シリコーンオリゴマーとの混和
性が悪く、またあるものはよく混和するけれども温度を
上げると（たとえば２００〜２５０℃）蒸発してしまっ
たりして、現在まで有用な添加剤は見出されていない。Ladder-type silicone oligomers have excellent heat resistance, insulation, hardness, water resistance, etc., and are therefore used in heat-resistant paints, insulating coatings for semiconductors, and the like. However, the film formed from ladder-type silicone oligomers has
It has the drawbacks of being prone to cracks, being brittle, and having poor adhesive properties. For this reason, it has been considered to incorporate various additives into the ladder-type silicone oligomer, but some have poor miscibility with the ladder-type silicone oligomer, while others are miscible with the ladder-type silicone oligomer, but when the temperature is raised (for example, (200 to 250°C), and no useful additives have been found to date.
本発明の目的は、上記従来のラダー型シリコーンオリゴ
マーの欠点を克服して、接着性。The object of the present invention is to overcome the drawbacks of the conventional ladder-type silicone oligomers and improve adhesive properties.
耐吸湿性、耐熱性、絶縁性、耐水性、耐クラック性、耐
はく離性および耐溶剤性等にすぐれたラダー型シリコー
ンオリゴマー組成物を提供するにある。It is an object of the present invention to provide a ladder-type silicone oligomer composition having excellent moisture absorption resistance, heat resistance, insulation, water resistance, crack resistance, peeling resistance, solvent resistance, etc.
本発明によって、上記目的を達成し得るラダー型シリコ
ーンオリゴマー組成物が提供される。The present invention provides a ladder-type silicone oligomer composition that can achieve the above objects.
すなわち、本、発明は、
（Ａ）水酸基１〜１０重量％およびエトキシ基１〜１０
重量％を含有するラダー型シリコーンオリゴマー、（Ｂ
） （＜） 一般式 （Ｉ）
〔式中、Ｒ１は炭素数が１〜５のアルキル基またはフェ
ニル基、Ｒ２は炭素数が１〜５のアルキル基である〕
で示される化合物と
（ロ）一般式 （ｎ）
Ｒ４
〔式中、Ｒ３は炭素数が１〜５のアルキル基またはフェ
ニル基、Ｒ４は炭素数が１〜５のアルキル基である〕
で示される化合物とを、化合物ω対比合物（ロ）のモル
比が１対０．３〜９の範囲で反応させて得られる、分子
量５００〜ｔｏｏ、ｏｏｏのシリコーンポリマーおよび
（Ｃ）有機溶剤
とを主成分とするラダー型シリコーンオリゴマー組成物
に関する。That is, the present invention provides (A) 1 to 10% by weight of hydroxyl groups and 1 to 10% of ethoxy groups;
Ladder-type silicone oligomer containing % by weight (B
) (<) A compound represented by the general formula (I) [wherein R1 is an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R2 is an alkyl group having 1 to 5 carbon atoms] and (b) General formula (n) A ladder-type silicone oligomer composition containing as main components a silicone polymer with a molecular weight of 500 to too, ooo and an organic solvent (C) obtained by reacting the compound (B) at a molar ratio of 1:0.3 to 9. relating to things.
本発明において（Ａ）成分として使用されるラダー型シ
リコーンオリゴマーは、下記の一般式（ｍ）で表わされ
る構造を有するものである。The ladder type silicone oligomer used as component (A) in the present invention has a structure represented by the following general formula (m).
〔式中、Ｒ５はアルキル基、フェニル基または水酸基で
あり、末端はエトキシ基または水酸基である〕
ラダー型シリコーンオリゴマーを表わす上記の一般式（
ＩＩＩ）において、アルキル基はメチル基、プロピル基
およびブチル基などの炭素数が１〜５の低級アルキル基
が好ましい。[In the formula, R5 is an alkyl group, a phenyl group, or a hydroxyl group, and the terminal is an ethoxy group or a hydroxyl group] The above general formula representing a ladder-type silicone oligomer (
In III), the alkyl group is preferably a lower alkyl group having 1 to 5 carbon atoms, such as a methyl group, a propyl group, and a butyl group.
上記一般式（ｍ）で表わされるラダー型シリコーンオリ
ゴマー中のエトキシ基金Ｈ量は１〜ＩＯ重量％であり、
かつ水酸基含有量は側鎖の水酸基および末端の水酸基を
合わせて１〜ｌＯ重−％である。The amount of ethoxy group H in the ladder type silicone oligomer represented by the above general formula (m) is 1 to IO% by weight,
Moreover, the hydroxyl group content is 1 to 10% by weight, including the side chain hydroxyl groups and the terminal hydroxyl groups.
ラダー型シリ＝−ンオリゴマー中のエトキシ基と水酸基
の含有量がそれぞれ１重量％未満の場合には、基材にコ
ーティングまたは基材を接着した後、温度を上げても架
橋せず、接着性、耐水性。If the content of ethoxy groups and hydroxyl groups in the ladder-type silicone oligomer is less than 1% by weight each, it will not crosslink even if the temperature is raised after coating or adhering the substrate to the substrate, resulting in poor adhesive properties. ,water resistance.
耐溶剤性、耐食性および耐熱性に劣る。一方、ラダー型
シリコーンオリゴマー中のエトキシ基と水酸基の含有量
がそれぞれ１０重量％より多い場合には、接着性、耐水
性および耐溶剤性に劣る難点を有する。Poor solvent resistance, corrosion resistance and heat resistance. On the other hand, if the content of ethoxy groups and hydroxyl groups in the ladder-type silicone oligomer is each more than 10% by weight, the adhesiveness, water resistance, and solvent resistance are poor.
一般式（ｍ）で示されるラダー型シリコーンオリゴマー
は、分子量が３００〜１０．０００が望ましく、分子量
が３００より小さいと、加熱硬化過程においてラダー型
シリコーンオリゴマーの一部が分解揮発して満足すべき
皮膜や接着ができない。また、ラダー型シリコーンオリ
ゴマーの分子量が１０．０００を超えるときには、有機
溶剤に対する溶解性がよくないのみならず、〔Ｂ〕酸成
分して使用される一般式（ｉ）で示される化合物と一般
式（ＩＩ）で示される化合物とを反応させて得られるシ
リコーンポリマーとの混和性が十分でない。The ladder-type silicone oligomer represented by the general formula (m) preferably has a molecular weight of 300 to 10.000. If the molecular weight is less than 300, a part of the ladder-type silicone oligomer will decompose and volatilize during the heat curing process, making it unsatisfactory. Cannot be coated or bonded. In addition, when the molecular weight of the ladder type silicone oligomer exceeds 10.000, not only is the solubility in organic solvents poor, but also the compound represented by the general formula (i) used as the [B] acid component and the general formula The miscibility with the silicone polymer obtained by reacting the compound represented by (II) is insufficient.
また、本発明において（Ｂ）成分として使用されるシリ
コーンポリマーは、
ω 一般式（Ｉ）
〔式中、Ｒ１は炭素数が１〜５のアルキル基またはフェ
ニル基、Ｒ２は炭素数が１〜５のアルキル基である〕
で示される化合物と
（ロ）一般式 （ｎ）
Ｒ４
〔式中、Ｒ３は炭素数が１〜５のアルキル基またはフェ
ニル基、Ｒ４は炭素数が１〜５のアルキル基である〕
で示される化合物とを縮合反応させて得られる、下記の
一般式（ＩＶ）で示される構造を有するものである。In addition, the silicone polymer used as component (B) in the present invention has the general formula (I) [wherein R1 is an alkyl group or phenyl group having 1 to 5 carbon atoms, and R2 is an alkyl group having 1 to 5 carbon atoms] [In the formula, R3 is an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R4 is an alkyl group having 1 to 5 carbon atoms] It has a structure represented by the following general formula (IV), which is obtained by a condensation reaction with a compound represented by the formula (IV).
・・・−５ｉ −０−Ｓｉ −０−３Ｌ −０−３ｉ
−０−５ｉ−・・・−・・−Ｓｉ −０−Ｓｉ −０−
Ｓｉ −０−Ｓｉ −−−−Ｒａ Ｒａ Ｒｔ
Ｒｔ
このシリコーンポリマーは、有機溶剤に溶解し、ラダー
型シリコーンオリゴマーとよく混合して接着性、耐クラ
ツク性および耐はく離性などの向上に有効である。...-5i -0-Si -0-3L -0-3i
-0-5i-...--Si -0-Si -0-
Si -0-Si -----Ra Ra Rt
Rt This silicone polymer is dissolved in an organic solvent and mixed well with the ladder-type silicone oligomer, and is effective in improving adhesion, crack resistance, peeling resistance, etc.
一般式（ＩＶ）で示されるシリコーンポリマーを製造す
るには、前記一般式（Ｉ，）で示される化合物と一般式
（■）で示される化合物とを混合し、水中で、酸（たと
えば塩酸）またはアミン（たとえばトリエタノールアミ
ン）の存在下、加熱縮合する。一般式（Ｉ）で示される
化合物と一般式（ＩＩ）で示される化合物との混合比率
は、モル比で１対０６３〜９である。In order to produce the silicone polymer represented by the general formula (IV), the compound represented by the general formula (I,) and the compound represented by the general formula (■) are mixed, and an acid (for example, hydrochloric acid) is added to the mixture in water. Alternatively, thermal condensation is performed in the presence of an amine (eg triethanolamine). The mixing ratio of the compound represented by general formula (I) and the compound represented by general formula (II) is 1:063 to 9 in terms of molar ratio.
一般式（ＩＩ）で示される化合物の混合比率がモル比で
０゜３未満では、生成するシリコーンポリマーとラダー
型シリコーンオリゴマーとの相溶性が悪くなる。また、
一般式（ｎ）で示される化合物の混合比率がモル比で９
より多い場合は、生成するシリコーンポリマーを配合し
たラダー型シリコーンオリゴマー組成物から形成される
皮膜は脆く、耐クラツク性および接着性が乏しくなる。If the molar ratio of the compound represented by formula (II) is less than 0.3, the compatibility between the resulting silicone polymer and the ladder-type silicone oligomer will be poor. Also,
The mixing ratio of the compound represented by general formula (n) is 9 in molar ratio
If the amount is higher, the film formed from the ladder-type silicone oligomer composition blended with the resulting silicone polymer will be brittle and have poor crack resistance and adhesion.
シリコーンポリマーの分子量は、５００〜１００．００
０ 、好ましくは６００〜５０，０００、さらに好まし
くは７００〜ｉｏ、ｏｏｏがよく、分子量が５００未満
では耐溶剤性が不足であり、分子量が１００．０００を
超えるときはラダー型シリコーンオリゴマーとの混和性
が不十分である。The molecular weight of silicone polymer is 500-100.00
0, preferably 600 to 50,000, more preferably 700 to io, ooo. If the molecular weight is less than 500, solvent resistance is insufficient, and if the molecular weight is more than 100,000, it is miscible with ladder type silicone oligomers. Inadequate sex.
ラダー型シリコーンオリゴマーとシリコーンポリマーと
の混和性を良好にするためには、一般式（ＩＩＩ）で示
されるラダー型シリコーンオリゴマーのＲ５と一般式（
ＴＶ）で示されるシリコーンポリマーのＲおよびＲ３と
が同じか、または類似していることが望ましい。たとえ
ば一般式（ＩＩＩ）で示されるラダー型シリコーンオリ
ゴマーのＲ５がメチル基であれば、一般式（ＩＶ）で示
されるシリコーンポリマーのＲｔおよびＲ３もメチル基
、−般式（Ｉ［［）で示されるラダー型シリコーンオリ
ゴマーのＲ５がフェニル基であれば、一般式（ＩＶ）で
示されるシリコーンポリマーのＲ，およびＲ３もフェニ
ル基、一般式（ＩＩＩ）で示されるラダー型シリコーン
オリゴマーのＲ５がメチル基とフェニル基のモル比が２
＝１であれば一般式（ｒＶ）で示されるシリコーンポリ
マーのＲおよびＲ３もメチル基とフェニル基のモル比が
２：１であることが望ましい。In order to improve the miscibility between the ladder type silicone oligomer and the silicone polymer, R5 of the ladder type silicone oligomer represented by the general formula (III) and the general formula (
It is desirable that R and R3 of the silicone polymer represented by TV) are the same or similar. For example, if R5 of the ladder-type silicone oligomer represented by the general formula (III) is a methyl group, Rt and R3 of the silicone polymer represented by the general formula (IV) are also methyl groups; If R5 of the ladder-type silicone oligomer represented by the general formula (IV) is a phenyl group, R and R3 of the silicone polymer represented by the general formula (IV) are also phenyl groups, and R5 of the ladder-type silicone oligomer represented by the general formula (III) is a methyl group. and phenyl group molar ratio is 2
If =1, it is desirable that the molar ratio of methyl groups to phenyl groups in R and R3 of the silicone polymer represented by the general formula (rV) is 2:1.
さらに本発明において（Ｃ）成分として使用される有機
溶剤としては、酢酸エチル、酢酸ブチルのごときエステ
ル類、アセトン、メチルエチルヶトンのごときケトン類
、ベンゼン、トルエンのごとき芳香族炭化水素、セロソ
ルブアセテート、ブチルセロソルブのごときセロソルブ
類などがあげられる。Furthermore, the organic solvents used as component (C) in the present invention include esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl ethyl chloride, aromatic hydrocarbons such as benzene and toluene, and cellosolve acetate. , cellosolves such as butyl cellosolve.
本発明のラダー型シリコーンオリゴマー組成物は、〔Ａ
〕酸成分ラダー型シリコーンオリゴマーおよび（Ｂ）成
分のシリコーンポリマーを（Ｃ）成分の有機溶剤に溶解
することによって調整される。The ladder-type silicone oligomer composition of the present invention is [A
[Acid component] Prepared by dissolving the ladder-type silicone oligomer and the silicone polymer (B) in the organic solvent (C).
（Ａ）成分のラダー型シリコーンオリゴマーと（Ｂ）成
分のシリコーンポリマーの配合比率は、用途によって異
なるので一概には決められないが、一般には重量比で゛
１００対１〜２００である。The blending ratio of the ladder-type silicone oligomer (A) and the silicone polymer (B) varies depending on the application, but cannot be determined unconditionally, but is generally in the range of 100:1 to 200 by weight.
本発明のラダー型シリコーンオリゴマー組成物をコーテ
ィング剤として用いるとき、（Ａ）成分のラダー型シリ
コーンオリゴマーと〔Ｂ〕（イ）成分のシリコーンポリ
マーの配合比率は、＠量比で１００対１〜５０が望まし
い。（Ｂ）成分のシリコーンポリマーの配合比率が重量
比で１より少ない場合は皮膜の耐クラツク性が不十分で
あり、また［Ａ）成分のシリコーンポリマーの配合比率
が重量比で５０より多い場合は皮膜の硬度が小さいので
好ましくない。When the ladder-type silicone oligomer composition of the present invention is used as a coating agent, the blending ratio of the ladder-type silicone oligomer as the component (A) and the silicone polymer as the component (B) is 100:1 to 50 by weight. is desirable. If the weight ratio of the silicone polymer (B) is less than 1, the crack resistance of the film is insufficient; if the weight ratio of the silicone polymer (A) is more than 50, This is not preferred because the hardness of the film is low.
また、本発明のラダー型シリコーンオリゴマー組成物を
接着剤として用いるとき、（Ａ）成分のラダー型シリコ
ーンオリゴマーと〔Ｂ〕（イ）成分のシリコーンポリマ
ーの配合比率は、重量比で１００対２０〜２００が望ま
しい。〔Ｂ〕（イ）成分のシリコーンポリマーの配合比
率が重量比で２０より少ない場合は皮膜の耐はく離性が
不十分であり、また（Ａ）成分のシリコーンポリマーの
配合比率が重量比で２００より多い場合は皮膜の硬度が
小さいので好ましくない。Further, when the ladder-type silicone oligomer composition of the present invention is used as an adhesive, the blending ratio of the ladder-type silicone oligomer as the component (A) and the silicone polymer as the component [B] (A) is 100:20 to 20 by weight. 200 is desirable. [B] If the blending ratio of the silicone polymer of component (A) is less than 20 by weight, the peel resistance of the film is insufficient, and if the blending ratio of the silicone polymer of component (A) is less than 200 by weight If the amount is too large, the hardness of the film will be low, which is not preferable.
ラダー型シリコーンオリゴマー組成物中の（Ａ）成分の
ラダー型シリコーンオリゴマーおよび〔Ｂ〕（イ）成分
のシリコーンポリマーの合計濃度は、組成物の用途によ
って異なるので一概には決められないが、通常は５〜７
０重量％、好ましくは１０〜６０重量％である。The total concentration of the ladder-type silicone oligomer (A) component and the silicone polymer (B) component (A) in the ladder-type silicone oligomer composition varies depending on the use of the composition, but is usually 5-7
0% by weight, preferably 10-60% by weight.
本発明のラダー型シリコーンオリゴマー組成物には、必
要に応じて顔料、充填剤、増粘剤、レベリング剤、カッ
プリング剤、紫外線吸収剤、硬化触媒等を添加してもよ
い。Pigments, fillers, thickeners, leveling agents, coupling agents, ultraviolet absorbers, curing catalysts, etc. may be added to the ladder-type silicone oligomer composition of the present invention, if necessary.
上記のように調整された本発明のラダー型シリコーンオ
リゴマー組成物は、金属、セラミックス・プラスチック
、ガラスなどの基材のコーティング剤として有用である
。プラスチック、ガラスを基材とする場合は、これらの
表面を予めシランカップリング剤で処理しておくことが
望ましい。コーティング方法は、スプレーコーティング
、刷毛塗、浸漬コーティング、フローコーティング、ス
ピンコーティングなどいづれの方法も用いられる。The ladder-type silicone oligomer composition of the present invention prepared as described above is useful as a coating agent for substrates such as metals, ceramics/plastics, and glass. When using plastic or glass as a base material, it is desirable to treat the surfaces of these materials with a silane coupling agent in advance. As the coating method, any method such as spray coating, brush coating, dip coating, flow coating, or spin coating may be used.
本発明のラダー型シリコーンオリゴマーをコーティング
剤として用いるとき、この組成物を基材にコーテイング
後は、室温またはｔｏｏ’ｃ以下の温度に放置して有機
溶剤を蒸発させたのち、１６０〜２５０℃にて１０〜１
２０分間加熱して硬化せしめる。When using the ladder-type silicone oligomer of the present invention as a coating agent, after coating a substrate with this composition, leave it at room temperature or a temperature below too'C to evaporate the organic solvent, and then heat it to 160 to 250 °C. Te10-1
Heat for 20 minutes to harden.
これによって、硬度、耐熱性、耐水性、耐溶剤性にすぐ
れ、耐クラツク性の良好な塗膜が得られる。As a result, a coating film with excellent hardness, heat resistance, water resistance, solvent resistance, and good crack resistance can be obtained.
また、上記のように調整された本発明のラダー型シリコ
ーンオリゴマー組成物は、金属、セラミックス、ガラス
などの接着剤として有用である。Furthermore, the ladder-type silicone oligomer composition of the present invention prepared as described above is useful as an adhesive for metals, ceramics, glass, and the like.
ガラスを基材とする場合は、表面を予めシランカップリ
ング剤で処理しておくことが好ましい。接着剤を基材に
塗布する方法としては、刷毛塗、スプレーコーティング
、ローラーコーティングなどの方法が用いられる。When using glass as a base material, it is preferable to treat the surface with a silane coupling agent in advance. Methods such as brush coating, spray coating, and roller coating are used to apply the adhesive to the base material.
本発明のラダー型シリコーンオリゴマー組成物を接着剤
として用いるとき、この組成物を基材に塗布した後、基
材同士を貼り合わせ、室温または１００℃以下の温度に
放置して有機溶剤を蒸発させた後、 １６０〜２５０℃
で１０〜１２０分間加熱して硬化させる。これによって
、基材と接着剤層とが強固に結合した接着性、耐はく離
性、耐熱性、耐水性。When using the ladder-type silicone oligomer composition of the present invention as an adhesive, after applying this composition to a base material, the base materials are pasted together and left at room temperature or a temperature of 100°C or less to evaporate the organic solvent. After that, 160~250℃
Heat for 10 to 120 minutes to harden. As a result, the base material and the adhesive layer have strong bonding properties, peeling resistance, heat resistance, and water resistance.
耐溶剤性にすぐれた接着剤層が形成される。An adhesive layer with excellent solvent resistance is formed.
以下、実施例および比較例をあげて本発明をさらに詳細
に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
なお、ラダー型シリコーンオリゴマー組成物をコーティ
ング剤として用いたとき、実施例および比較例中の皮膜
の各物性値は、下記の方法に従って１ｔ）Ｉ定した。In addition, when the ladder-type silicone oligomer composition was used as a coating agent, each physical property value of the film in Examples and Comparative Examples was determined according to the following method.
（Ｉ） 耐クラツク性
コーティング板を４００℃で１時間加熱し、次いでｌＯ
℃／分の割合で室温にまで冷却し、コーテイング面のク
ラックを倍率１００倍の顕微鏡で観察した。クラックが
認められないものを０１僅かにクラックのあるものを△
、多数のクラックを認めたものを×とした。(I) The crack-resistant coated plate was heated at 400°C for 1 hour, then lO
It was cooled to room temperature at a rate of .degree. C./min, and cracks on the coating surface were observed using a microscope with a magnification of 100 times. Items with no cracks are 01 Items with slight cracks are △
, those in which many cracks were observed were rated x.
（２）耐水性
ＪＩＳ Ｋ５４００に準じ、加熱硬化させたコーティン
グ板を３０℃の水に２４時間浸漬して、塗膜の変化を肉
眼で観察した。(2) Water resistance According to JIS K5400, the heat-cured coated plate was immersed in 30°C water for 24 hours, and changes in the coating film were observed with the naked eye.
（３）耐溶剤性
加熱硬化させたコーティング板を３０℃のアセトン中に
２４時間浸漬し、溶出、塗膜のふくれ等を肉眼で観察し
た。(3) Solvent resistance The heat-cured coated plate was immersed in acetone at 30°C for 24 hours, and elution, blistering of the coating film, etc. were observed with the naked eye.
また、ラダー型シリコーンオリゴマー組成物を接着剤と
して用いたとき、実施例および比較例中の各物性値は、
下記の方法に従って測定した。In addition, when the ladder-type silicone oligomer composition was used as an adhesive, each physical property value in Examples and Comparative Examples was as follows:
It was measured according to the method below.
（Ｉ） 引張りせん断接者強さ
ＪＩＳ ＫＯ８５０（７）寸法の試料を用いて接着し、
同方法によって測定した。(I) Bonded using a sample with tensile shear strength JIS KO850 (7) dimensions,
It was measured by the same method.
（２） はく難接着強さ
ＪＩＳ ＫＯ８５４の寸法の試料を用いて接着し、同方
法によって測定した。(2) Peel-resistant adhesive strength Samples with dimensions of JIS KO854 were bonded and measured using the same method.
（３）耐熱性
接着した試料を２００℃に３０分間放置後、２００℃に
おいてＪＩＳ ＫＯ８５０に従いせん断接者強さを測定
した。(3) Heat Resistance After the bonded sample was left at 200°C for 30 minutes, the shear bond strength was measured at 200°C according to JIS KO850.
（４）耐水性、耐溶剤性
接着した試料を室温の水またはトルエン中に２４時間浸
漬後、ＪＩＳ ＫＯ３５０に従いせん断接若強さを測定
した。(4) Water resistance and solvent resistance After immersing the bonded samples in water or toluene at room temperature for 24 hours, the shear bond strength was measured according to JIS KO350.
実施例 １
前記一般式（ｍ）において、Ｒ５がメチル基であり、水
酸基含有量が４重量％、エトキシ基含有量が４重量％、
分子量が２．２００のラダー型シリコーンオリゴマー１
００重量部をトルエンと酢酸エチルの混合溶剤（重量比
２：１）２００重量部に溶解してラダー型シリコーンオ
リゴマー溶液を得た。Example 1 In the general formula (m), R5 is a methyl group, the hydroxyl group content is 4% by weight, the ethoxy group content is 4% by weight,
Ladder type silicone oligomer 1 with a molecular weight of 2.200
A ladder type silicone oligomer solution was obtained by dissolving 00 parts by weight in 200 parts by weight of a mixed solvent of toluene and ethyl acetate (weight ratio 2:1).
別に前記一般式（Ｉ）において、Ｒ１がメチル基、Ｒ２
がエチル基である化合物と前記一般式（ｎ）において、
Ｒがメチル基、Ｒ４がエチル基である化合物をモル比１
：２で縮合させて得られた分子量３，０００のシリコー
ンポリマ−１０ｖｆ量部をトルエンと酢酸エチルの混合
溶剤（重量比２：１）２０重量部に溶解してシリコーン
ポリマー溶液を得た。Separately, in the general formula (I), R1 is a methyl group, R2
is an ethyl group and in the general formula (n),
A compound in which R is a methyl group and R4 is an ethyl group at a molar ratio of 1
A silicone polymer solution was obtained by dissolving 10 parts by weight of a silicone polymer having a molecular weight of 3,000 obtained by condensation of 2:2 in 20 parts by weight of a mixed solvent of toluene and ethyl acetate (weight ratio 2:1).
ラダー型シリコーンオリゴマー溶液とシリコーンポリマ
ー溶液を混合してラダー型シリコーンオリゴマー組成物
を調整した。ラダー型シリコーンオリゴマー溶液とシリ
コーンポリマー溶液の混和性は良好であった。アセトン
で脱脂した７ｃａ＋Ｘ１５ｃｍの炭素鋼板に、上記組成
物を皮膜の乾燥膜厚が５ミクロンとなるようにスプレー
コートした。室温で３０分間、次いで９０℃で３０分間
放置して乾燥してから１８０℃で３０分間加熱して硬化
せしめた。硬化後、室温に冷却して諸物性を測定した。A ladder-type silicone oligomer composition was prepared by mixing a ladder-type silicone oligomer solution and a silicone polymer solution. The miscibility of the ladder-type silicone oligomer solution and the silicone polymer solution was good. The above composition was spray coated onto a 7ca+x15cm carbon steel plate that had been degreased with acetone so that the dry film thickness was 5 microns. It was dried by standing at room temperature for 30 minutes, then at 90°C for 30 minutes, and then heated at 180°C for 30 minutes to harden it. After curing, it was cooled to room temperature and various physical properties were measured.
結果を第１表に示す。The results are shown in Table 1.
比較例 １
実施例１で使用したラダー型シリコーンオリゴマーと同
じ構造のラダー型シリコーンオリゴマー１００重量部を
トルエンと酢酸エチルの混合溶剤（重量比２：１）２０
０重量部に溶解してラダー型シリコーンオリゴマー溶液
を得た。この溶液を実施例１と同じ操作により、炭素鋼
板に皮膜の厚さを乾燥膜厚にして５ミクロンになるよう
にスプレーコートした。室温で３０分間、９０℃で３０
分間放置して乾燥してから、１８０℃で３０分間加熱し
て硬化せしめた。硬化後、室温に冷却して物性を測定し
た。結果を第１表に示した。Comparative Example 1 100 parts by weight of a ladder-type silicone oligomer having the same structure as the ladder-type silicone oligomer used in Example 1 was mixed with a mixed solvent of toluene and ethyl acetate (weight ratio 2:1).
A ladder-type silicone oligomer solution was obtained by dissolving 0 parts by weight. This solution was spray coated onto a carbon steel plate by the same procedure as in Example 1 so that the dry film thickness was 5 microns. 30 min at room temperature, 30 min at 90°C
After being left to dry for a minute, it was heated at 180° C. for 30 minutes to harden it. After curing, it was cooled to room temperature and its physical properties were measured. The results are shown in Table 1.
第１表に示したように、シリコーンポリマーを配合しな
いと、皮膜の耐クラツク性が実施例１の耐クラツク性よ
り劣つた。As shown in Table 1, without the silicone polymer, the crack resistance of the coating was inferior to that of Example 1.
比較例 ２
前記一般式（ＩＩＩ）において、Ｒ５がメチル基であり
、水酸基金Ｈｊａが０．６ｆＩ量％、エトキシ基含有量
が０．８重量％、分子量が２．１００のラダー型シリコ
ーンオリゴマーをトルエンぶ酢酸エチルの混合溶剤（重
量比２：１）に溶解してラダー型シリコーンオリゴマー
濃度が３０重ｌ５のラダー型シリコーンオリゴマー溶液
を得た。この溶液１００重量部を実施例１と同様に調整
したシリコーンポリマー溶液と混合し、組成物を調整し
た。Comparative Example 2 In the general formula (III), R5 is a methyl group, a hydroxyl group Hja is 0.6 fI% by weight, an ethoxy group content is 0.8% by weight, and a molecular weight is 2.100. It was dissolved in a mixed solvent of toluene and ethyl acetate (weight ratio 2:1) to obtain a ladder-type silicone oligomer solution having a ladder-type silicone oligomer concentration of 30 parts by weight. 100 parts by weight of this solution was mixed with a silicone polymer solution prepared in the same manner as in Example 1 to prepare a composition.
この組成物を実施例１と同様に炭素鋼板に５ミクロンの
厚さにコーティングし、乾燥後１８０℃で３０分間加熱
して硬化させたのち、諸物性を測定した。結果を第１表
に示した。第１表から明らかなように、水酸基とエトキ
シ基の含有量が少いラダー型シリコーンオリゴマーを用
いたものは、皮膜の耐溶剤性が不良゛であった。This composition was coated on a carbon steel plate to a thickness of 5 microns in the same manner as in Example 1, dried and cured by heating at 180° C. for 30 minutes, and then various physical properties were measured. The results are shown in Table 1. As is clear from Table 1, the films using ladder-type silicone oligomers with a low content of hydroxyl groups and ethoxy groups had poor solvent resistance.
比較例 ３
前記一般式（ｍ）において、Ｒ５がメチル基であり、水
酸基含有量が１５重量％、エトキシ基含有量が１５１１
ｒ量％、分子量が２．１００のラダー型シリコーンオリ
ゴマーをトルエンと酢酸エチルの混合溶剤（重量比２：
１）に溶解してオリゴマー濃度が３０重量％のラダー型
シリコーンオリゴマー溶液を得た。これを実施例１と同
様に調整したシリコーンポリマー溶液と混合して組成物
を調整した。Comparative Example 3 In the general formula (m), R5 is a methyl group, the hydroxyl group content is 15% by weight, and the ethoxy group content is 1511
A ladder type silicone oligomer with a molecular weight of 2.100 and a molecular weight of 2.100 was dissolved in a mixed solvent of toluene and ethyl acetate (weight ratio 2:
1) to obtain a ladder-type silicone oligomer solution having an oligomer concentration of 30% by weight. This was mixed with a silicone polymer solution prepared in the same manner as in Example 1 to prepare a composition.
以下、実施例１にしたがってコーティング、硬化を行っ
た。物性は第１表に示したとおりであり、ラダー型シリ
コーンオリゴマーの水酸基とエトキシ基の含有量が共に
多いときには、皮膜の耐水性が不良であった。Thereafter, coating and curing were performed according to Example 1. The physical properties are as shown in Table 1, and when the content of both hydroxyl groups and ethoxy groups in the ladder-type silicone oligomer was high, the water resistance of the film was poor.
比較例 ４
前記一般式（Ｉ）において、Ｒ１がメチル基、Ｒ２がエ
チル基の化合物と、前記一般式（ｎ）においてＲ３がメ
チル基、Ｒ４がエチル基の化合物とをモル比が１対１０
で縮合させて、分子量２．７００のシリコーンポリマー
を製造した。このシリコーンポリマーをトルエンと酢酸
エチルの混合溶剤（重量比２：１）に溶解し、シリコー
ンポリマー濃度が３０重量％のシリコーンポリマー溶液
を調整した。この溶液を実施例１と同様に調整したラダ
ー型シリコーンオリゴマー溶液と重量比１：ｌＯで混合
し、組成物を調整した。実施例１と同じくコーティング
、硬化して物性を測定した。結果を第１表に示した。Comparative Example 4 A compound in which R1 is a methyl group and R2 is an ethyl group in the general formula (I) and a compound in which R3 is a methyl group and R4 is an ethyl group in the general formula (n) at a molar ratio of 1:10.
to produce a silicone polymer with a molecular weight of 2.700. This silicone polymer was dissolved in a mixed solvent of toluene and ethyl acetate (weight ratio 2:1) to prepare a silicone polymer solution having a silicone polymer concentration of 30% by weight. This solution was mixed with a ladder-type silicone oligomer solution prepared in the same manner as in Example 1 at a weight ratio of 1:1O to prepare a composition. It was coated and cured in the same manner as in Example 1, and its physical properties were measured. The results are shown in Table 1.
第１表に示したように、一般式（ＩＩ）で示される化合
物のモル比を本発明の範囲より多く用いて製造したシリ
コーンポリマーを用いたときは、皮膜の耐クラツク性の
改良にならなかった。As shown in Table 1, when using a silicone polymer manufactured using a molar ratio of the compound represented by general formula (II) greater than the range of the present invention, the crack resistance of the film was not improved. Ta.
比較例 ５
前記一般式（Ｉ）においてＲ１がメチル基、Ｒ２がエチ
ル基の化合物と、前記一般式（旧においてＲ３がメチル
基、Ｒ４がエチル基の化合物とをモル比が１：２で縮合
させて、分子量が３８０のシリコーンポリマーを製造し
た。このシリコーンポリマーをトルエンと酢酸エチルの
混合溶剤（重量比２：１）に溶解し、シリコーンポリマ
ー濃度が３０玉量％のシリコーンポリマー溶液を調整し
た。この溶液を実施例１と同様に調整したラダー型シリ
コーンオリゴマー溶液と重量比１：ｌＯで混合して組成
物を調整した。実施例１と同じくコーティング、硬化し
て物性を測定した。Comparative Example 5 A compound of the general formula (I) in which R1 is a methyl group and R2 is an ethyl group is condensed with a compound of the general formula (formerly, R3 is a methyl group and R4 is an ethyl group) at a molar ratio of 1:2. A silicone polymer with a molecular weight of 380 was produced.This silicone polymer was dissolved in a mixed solvent of toluene and ethyl acetate (weight ratio 2:1) to prepare a silicone polymer solution with a silicone polymer concentration of 30% by mass. A composition was prepared by mixing this solution with a ladder-type silicone oligomer solution prepared in the same manner as in Example 1 at a weight ratio of 1:1O.It was coated and cured in the same manner as in Example 1, and the physical properties were measured.
結果を第１表に示した。The results are shown in Table 1.
第１表に示したように、分子量の小さいシリコーンポリ
マーを併用したときは、皮膜の耐クラツク性の改良が不
十分であるばかりでなく、耐溶剤性が劣った。As shown in Table 1, when a silicone polymer with a low molecular weight was used in combination, not only the crack resistance of the film was insufficiently improved, but also the solvent resistance was poor.
第１表皮膜試験
比較例 ６
前記一般式（Ｉ）において、Ｒ１がメチル基、Ｒ２がエ
チル基である化合物と前記一般式（ＩＩ）において、Ｒ
３がメチル基、Ｒ４がエチル基である化合物をモル比１
： ０．２で縮合させて得られた分子ａｔ、ｏｏｏの
シリコーンポリマ−１１１Ｊａ部をトルエンと酢酸エチ
ルの混合溶剤（重量比２：１）２０重量部に溶解してシ
リコーンポリマー溶液を得た。この溶液を実施例１と同
様にして調整したラダー型シリコーンオリゴマー溶液に
加えて撹拌したところ、混和性が不十分であった。この
混和性の不十分な混合物をそのまま炭素鋼板にコーティ
ングしたが、むらが多く完全な皮膜ができなかった。First skin film test comparative example 6 In the general formula (I), R1 is a methyl group and R2 is an ethyl group, and in the general formula (II), R
A compound in which 3 is a methyl group and R4 is an ethyl group at a molar ratio of 1
A silicone polymer solution was obtained by dissolving 111 Ja parts of a silicone polymer having molecules at, ooo obtained by condensation with 0.2 in 20 parts by weight of a mixed solvent of toluene and ethyl acetate (weight ratio 2:1). When this solution was added to a ladder-type silicone oligomer solution prepared in the same manner as in Example 1 and stirred, miscibility was insufficient. This poorly miscible mixture was directly coated on a carbon steel plate, but it was uneven and a complete coating could not be formed.
比較例 ７
前記一般式（Ｉ）において、Ｒ１がメチル基、Ｒ２がエ
チル基である化合物と前記一般式（ｎ）において、Ｒ３
がメチル基、Ｒ４がエチル基である化合物をモル比１：
２で縮合させて得られた分子量１１０，０００のシリコ
ーンポリマ−１０ｆｆｉ量部をトルエンと酢酸エチルの
混合溶剤（ｆｆｉ量比２：１）２０ｆｆｉ量部に溶解し
てシリコーンポリマー溶液を得た。このシリコーンポリ
マー溶液を実施例１と同様にして調整したラダー型シリ
コーンオリゴマー溶液に加え撹拌したところ、混和性が
不十分であった。この混和性の不十分な混合物をそのま
ま炭素鋼板にコーティングしたが、むらが多く、完全な
皮膜ができなかった。Comparative Example 7 In the general formula (I), R1 is a methyl group and R2 is an ethyl group, and in the general formula (n), R3
is a methyl group and R4 is an ethyl group in a molar ratio of 1:
10ffi parts of the silicone polymer having a molecular weight of 110,000 obtained by condensation in step 2 were dissolved in 20ffi parts of a mixed solvent of toluene and ethyl acetate (ffi ratio 2:1) to obtain a silicone polymer solution. When this silicone polymer solution was added to a ladder-type silicone oligomer solution prepared in the same manner as in Example 1 and stirred, miscibility was insufficient. When this mixture with insufficient miscibility was directly coated on a carbon steel plate, it was uneven and a complete coating could not be formed.
実施例 ２
前記一般式（ＩＩＩ）においてＲ５がメチル基であり、
水酸基含有量が３重量％、エトキシ基含有量が５重量％
、分子量が２，０５０のラダー型シリコーンオリゴマー
１００重量部をトルエンとセロソルブアセテートの混合
溶剤（重量比３：１）２００重量部に溶解してラダー型
シリコーンオリゴマー溶液を得た。Example 2 In the general formula (III), R5 is a methyl group,
Hydroxyl group content is 3% by weight, ethoxy group content is 5% by weight
A ladder-type silicone oligomer solution was obtained by dissolving 100 parts by weight of a ladder-type silicone oligomer having a molecular weight of 2,050 in 200 parts by weight of a mixed solvent of toluene and cellosolve acetate (weight ratio 3:1).
別に前記一般式（Ｉ）において、Ｒ１がメチル基、Ｒ２
がエチル基である化合物と前記一般式（ｎ）において、
Ｒ３がメチル基、Ｒ４がエチル基である化合物をモル比
１：２で縮合させて得られた分子量２，７００のシリコ
ーンポリマ−１０ｆｆｌｕ部をトルエンとセロソルブア
セテートの混合溶剤（重量比３：１）２Ｏｆｆｉ量部に
溶解してシリコーンポリマー溶液を得た。Separately, in the general formula (I), R1 is a methyl group, R2
is an ethyl group and in the general formula (n),
10 fflu parts of a silicone polymer with a molecular weight of 2,700 obtained by condensing a compound in which R3 is a methyl group and R4 is an ethyl group at a molar ratio of 1:2 is mixed with a mixed solvent of toluene and cellosolve acetate (weight ratio of 3:1). A silicone polymer solution was obtained by dissolving in 2Offi parts.
ラダー型シリコーンオリゴマー溶液とシリコーンポリマ
ー溶液を混合して組成物を調整した。A composition was prepared by mixing a ladder-type silicone oligomer solution and a silicone polymer solution.
ラダー型シリコーンオリゴマー溶液とシリコーンポリマ
ー溶液との混和性は良好であった。The miscibility of the ladder-type silicone oligomer solution and the silicone polymer solution was good.
この組成物をシリコンウェファ−に回転数２．０００／
分でスピンコードした。室温で３０分間乾燥したのち、
２００℃で１時間硬化して仕上げた。厚さ０．９ミクロ
ンの均一な皮膜が得られた。塗面は４００℃に昇温し、
１０℃／分の割合で室温に冷却したがクラックは認めら
れなかった。This composition was applied to a silicon wafer at a rotational speed of 2,000/
Spincoded in minutes. After drying at room temperature for 30 minutes,
It was finished by curing at 200°C for 1 hour. A uniform film with a thickness of 0.9 microns was obtained. The temperature of the painted surface was raised to 400℃,
Although it was cooled to room temperature at a rate of 10° C./min, no cracks were observed.
実施例 ３
前記一般式（ＩＩＩ）においてＲ５がフェニル基であり
、水酸基含有量が４重量％、エトキシ基含有量が６重量
％、分子量が１，８００のラダー型シリコーンオリゴマ
ー１００重量部をトルエンとアセトンの混合溶剤（重量
比４：１）２００重量部に溶解してラダー型シリコーン
オリゴマー溶液を得た。Example 3 In the above general formula (III), R5 is a phenyl group, 100 parts by weight of a ladder-type silicone oligomer having a hydroxyl group content of 4% by weight, an ethoxy group content of 6% by weight, and a molecular weight of 1,800 was mixed with toluene. A ladder-type silicone oligomer solution was obtained by dissolving in 200 parts by weight of a mixed solvent of acetone (weight ratio 4:1).
別に前記一般式（Ｉ）においてＲ１がフェニル基、Ｒ２
がメチル基である化合物と、前記一般式（Ｉｔ）におい
てＲ３がフェニル基、Ｒ４がメチル基である化合物とを
モル比１：３で縮合させて得られた分子量２．１００の
シリコーンポリマ−１５ｉ量部をトルエンとアセトンの
混合溶剤（重量比４：１）３０重量部に溶解してシリコ
ーンポリマー溶液を得た。Separately, in the general formula (I), R1 is a phenyl group, R2
Silicone polymer 15i with a molecular weight of 2.100 obtained by condensing a compound in which is a methyl group and a compound in which R3 is a phenyl group and R4 is a methyl group in the general formula (It) at a molar ratio of 1:3. A certain amount was dissolved in 30 parts by weight of a mixed solvent of toluene and acetone (weight ratio 4:1) to obtain a silicone polymer solution.
ラダー型シリコーンオリゴマー溶液とシリコーンポリマ
ー溶液とを混合して組成物を調整した。ラダー型シリコ
ーンオリゴマー溶液とシリコーンポリマー溶液は、混和
性にすぐれていた。A composition was prepared by mixing a ladder-type silicone oligomer solution and a silicone polymer solution. The ladder-type silicone oligomer solution and silicone polymer solution had excellent miscibility.
この組成物浸漬コーティングにより５ｃｍＸ５ｃｍのア
ルミナ板にコーティングし、室温で３０分間、次いで９
０℃で１５分間乾燥してから２００℃で１時間加熱して
硬化させた。室温に冷却したのち、４５０℃の炉に１５
分間入れ、室温にとり出して１００倍の顕微鏡で観察し
たところ、皮膜にクラックは全く認められなかった。This composition was coated on a 5 cm x 5 cm alumina plate by dip coating for 30 minutes at room temperature and then for 9
It was dried at 0°C for 15 minutes and then heated at 200°C for 1 hour to cure. After cooling to room temperature, it was placed in a 450℃ oven for 15 minutes.
When the film was placed in the film for a minute, taken out to room temperature, and observed under a microscope with a magnification of 100 times, no cracks were observed in the film.
一方、シリコーンポリマー溶液を配合しないラダー型シ
リコーンオリゴマー溶液のみでコーティングした場合に
は、４５０℃に加熱し、室温に冷却したとき、皮膜に細
いクラックが認められた。On the other hand, when the film was coated with only a ladder-type silicone oligomer solution without a silicone polymer solution, thin cracks were observed in the film when it was heated to 450°C and cooled to room temperature.
実施例 ４
前記一般式（ＩＩＩ）においてＲ５がメチル基とフェニ
ル基からなり、メチル基とフェニル基とのモル比が２＝
１であり、水酸基含有量が３重量％、エトキシ基含有量
が５重量％、分子量が２．２００のラダー型シリコーン
オリゴマー１００重量部をトルエンと酢酸ブチルの混合
溶剤（重量比４：１）２００重量部に溶解してラダー型
シリコーンオリゴマー溶液を得た。Example 4 In the general formula (III), R5 consists of a methyl group and a phenyl group, and the molar ratio of the methyl group and the phenyl group is 2=
1, a hydroxyl group content of 3% by weight, an ethoxy group content of 5% by weight, and a molecular weight of 2.200, 100 parts by weight of a ladder type silicone oligomer was mixed with 200 parts by weight of a mixed solvent of toluene and butyl acetate (weight ratio 4:1). A ladder-type silicone oligomer solution was obtained by dissolving in parts by weight.
別に前記一般式（Ｉ）においてＲ１がメチル基とフェニ
ル基からなり、メチル基とフェニル基のモル比が２＝１
であり、Ｒ２がエチル基である化合物と、前記一般式（
ＩＩ）においてＲ３がメチル基とフェニル基からなり、
メチル基とフェニル基のモル比が２＝１であり、Ｒ４が
エチル基である化合物とをモル比１：５で縮合させて得
られる分子量が１．５００のシリコーンポリマー１０ｗ
瓜部をトルエンと酢酸ブチルの混合溶剤（重量比４二１
）２０重量部に溶解してシリコーンポリマー溶液を得た
。Separately, in the general formula (I), R1 consists of a methyl group and a phenyl group, and the molar ratio of the methyl group and phenyl group is 2=1.
and a compound in which R2 is an ethyl group, and a compound represented by the general formula (
In II), R3 consists of a methyl group and a phenyl group,
Silicone polymer 10w with a molecular weight of 1.500 obtained by condensing a compound in which the molar ratio of methyl groups and phenyl groups is 2 = 1 and R4 is an ethyl group at a molar ratio of 1:5
Melon part was mixed with a mixed solvent of toluene and butyl acetate (weight ratio 421
) to obtain a silicone polymer solution.
ラダー型シリコーンオリゴマー溶液とシリコーンポリマ
ー溶液とを混合して組成物を調整した。ラダー型シリコ
ーンオリゴマー溶液とシリコーンポリマー溶液は、混和
性にすぐれていた。A composition was prepared by mixing a ladder-type silicone oligomer solution and a silicone polymer solution. The ladder-type silicone oligomer solution and silicone polymer solution had excellent miscibility.
この組成物をスプレーコーティングにより、１０ｃｍＸ
１Ｏｃ＋ｎの一シランカップリング剤で処理したポリフ
ェニレンサルファイド板にコーティングし、室温で３０
分間、次いで９０℃で３０分間乾燥してから、１８０℃
で３０分間加熱して硬化させた。室温に冷却したのち、
２００℃に上昇し、室温に急冷して１００倍の顕＠鏡に
よってクラックを観察したところ、皮膜にクラックは全
く認められなかった。This composition was spray coated on a 10cm×
It was coated on a polyphenylene sulfide plate treated with 1Oc+n monosilane coupling agent and heated for 30 minutes at room temperature.
minutes, then dry at 90°C for 30 minutes, then at 180°C.
It was heated for 30 minutes to harden it. After cooling to room temperature,
When the temperature was raised to 200°C, the film was rapidly cooled to room temperature, and cracks were observed under a 100x microscope, no cracks were observed in the film.
一方、シリコーンポリマー溶液を配合しないラダー型シ
リコーンオリゴマー溶液のみでコーティングした場合に
は、２００℃に加熱して室温に急冷したとき、皮膜に細
いクラックが認められた。On the other hand, in the case of coating only with a ladder-type silicone oligomer solution without blending the silicone polymer solution, thin cracks were observed in the film when it was heated to 200° C. and rapidly cooled to room temperature.
実施例 ５
前記一般式（ｍ）において、Ｒ５がメチル基であり、水
酸基含有量が４ｆｆｉ量％、エトキシ基含有量が４重量
％、分子量が２．２００のラダー型シリコーンオリゴマ
ー１００重量部をトルエンと酢酸エチルの混合溶剤（重
量比２：１）５０重量部に溶解してラダー型シリコーン
オリゴマー溶液を得た。Example 5 In the above general formula (m), R5 is a methyl group, 100 parts by weight of a ladder type silicone oligomer having a hydroxyl group content of 4ffi%, an ethoxy group content of 4% by weight, and a molecular weight of 2.200 was added to toluene. and ethyl acetate (weight ratio: 2:1) to obtain a ladder-type silicone oligomer solution.
別に前記一般式（Ｉ）において、Ｒ，がメチル基、Ｒ２
がエチル基である化合物と前記一般式（ＩＩ）において
、Ｒがメチル基、Ｒ４がエチル基である化合物をモル比
１：２で縮合させて得られた分子ｆｆ１３．０００のシ
リコーンポリマー５０重量部をトルエンと酢酸エチルの
混合溶剤（重量比２：１）２０ｉｌＩ量部に溶解してシ
リコーンポリマー溶液を得た。Separately, in the general formula (I), R is a methyl group, R2
50 parts by weight of a silicone polymer with a molecule ff of 13.000 obtained by condensing a compound in which is an ethyl group and a compound in the general formula (II), in which R is a methyl group and R4 is an ethyl group at a molar ratio of 1:2. was dissolved in 20 parts of a mixed solvent of toluene and ethyl acetate (weight ratio 2:1) to obtain a silicone polymer solution.
ラダー型シリコーンオリゴマー溶液とシリコーンポリマ
ー溶液を混合して組成物を３３整した。A composition was prepared by mixing the ladder-type silicone oligomer solution and the silicone polymer solution.
ラダー型シリコーンオリゴマー溶液とシリコーンポリマ
ー溶液の混和性は良好であった。アセトンで脱脂したＪ
ＩＳ Ｋ８８５０の寸法の炭素鋼板同士を上記組成物を
用いて貼り合わせた。室温で２０時間、次いで９０℃で
３０分間放置して乾燥してから１８０℃で３０分間加熱
して硬化せしめた。硬化後、室温に冷却して諸物性を測
定した。次いで、ＪＩＳ ＫＢ８５４に従ってＴ型はく
離の試料をつくり、上記と同一条件で接着し、はく離接
着強さを測定した。結果を第１表に示す。The miscibility of the ladder-type silicone oligomer solution and the silicone polymer solution was good. J degreased with acetone
Carbon steel plates having dimensions of IS K8850 were bonded together using the above composition. It was dried at room temperature for 20 hours, then at 90°C for 30 minutes, and then heated at 180°C for 30 minutes to cure. After curing, it was cooled to room temperature and various physical properties were measured. Next, a T-peel sample was prepared in accordance with JIS KB854, adhered under the same conditions as above, and the peel adhesion strength was measured. The results are shown in Table 1.
比較例 ８
実施例１で使用したラダー型シリコーンオリゴマーと同
じ構造のラダー型シリコーンオリゴマー１００重量部を
トルエンと酢酸エチルの混合溶剤（重量比２：１）５０
ｆｆｌ量部に溶解してラダー型シリコーンオリゴマー溶
液を得た。この溶液を実施例５と同じ操作により、炭素
鋼板同士を接着した。Comparative Example 8 100 parts by weight of a ladder-type silicone oligomer having the same structure as the ladder-type silicone oligomer used in Example 1 was mixed with 50 parts by weight of a mixed solvent of toluene and ethyl acetate (weight ratio 2:1).
ffl amount part to obtain a ladder type silicone oligomer solution. Carbon steel plates were bonded together using this solution in the same manner as in Example 5.
室温で２０時間、９０℃で３０分間放置して乾燥してか
ら、１８０℃で３０分間加熱して硬化せしめた。硬化２
゜
後、室温に冷却して物性を測定した。結果を第壬表に示
した。After being left to dry at room temperature for 20 hours and at 90°C for 30 minutes, it was cured by heating at 180°C for 30 minutes. Hardening 2
After that time, it was cooled to room temperature and its physical properties were measured. The results are shown in Table 1.
第矛表に示したように、シリコーンポリマーを配合しな
いと、引張りせん断強さ、はく離接着強さ共に実施例５
より劣った。As shown in Table 1, when no silicone polymer is blended, both the tensile shear strength and peel adhesion strength of Example 5
Inferior.
比較例 ９
前記一般式（ＩＩＩ）において、Ｒ５がメチル基であり
、水酸基含有量が０．６ｆｆｉ量％、エトキシ基含有量
が０．８重量％、分子量が２．１００のラダー型シリコ
ーンオリゴマーをトルエンと酢酸エチルの混合溶剤（重
量比２：１）に溶解してラダー型シリコーンオリゴマー
濃度が７０重量％のラダー型シリコーンオリゴマー溶液
を得た。この溶液１００重量部を実施例５と同様に調整
したシリコーンポリマー溶液と混合し、組成物を調整し
た。Comparative Example 9 In the general formula (III), R5 is a methyl group, a ladder type silicone oligomer having a hydroxyl group content of 0.6 ffi%, an ethoxy group content of 0.8% by weight, and a molecular weight of 2.100. A ladder silicone oligomer solution having a ladder silicone oligomer concentration of 70% by weight was obtained by dissolving in a mixed solvent of toluene and ethyl acetate (weight ratio 2:1). 100 parts by weight of this solution was mixed with a silicone polymer solution prepared in the same manner as in Example 5 to prepare a composition.
この組成物を用いて実施例５と同様に炭素鋼板同士を貼
り合わせ、乾燥後１８０℃で３０分間加熱して硬化させ
たのち、諸物性を測定した。結果を第２表に示した。第
２表から明らかなように、水酸基とエトキシ基の含有量
が少いラダー型シリコーンオリゴマーを用いたものは、
接着物の耐熱性、耐溶剤性共に不良であった。Using this composition, carbon steel plates were bonded to each other in the same manner as in Example 5, and after drying, the composition was heated at 180° C. for 30 minutes to cure it, and then various physical properties were measured. The results are shown in Table 2. As is clear from Table 2, those using ladder-type silicone oligomers with a low content of hydroxyl groups and ethoxy groups are
Both the heat resistance and solvent resistance of the adhesive were poor.
比較例 ｌＯ
前記一般式（ＩＩＩ）において、Ｒ５がメチル基であり
、水酸基含有量が１５重量％、エトキシ基含有量が１５
重量％、分子量が２，１００のラダー型シリコーンオリ
ゴマーをトルエンと酢酸エチルの混合溶剤（重量比２：
１）に溶解してオリゴマー濃度が７０重量％のラダー型
シリコーンオリゴマー溶液を得た。これを実施例５と同
様に調整したシリコーンポリマー溶液と混合して組成物
を５！ｌ整した。Comparative Example lO In the general formula (III), R5 is a methyl group, the hydroxyl group content is 15% by weight, and the ethoxy group content is 15% by weight.
A ladder type silicone oligomer with a molecular weight of 2,100% by weight was mixed with a mixed solvent of toluene and ethyl acetate (weight ratio: 2:
1) to obtain a ladder-type silicone oligomer solution having an oligomer concentration of 70% by weight. This was mixed with a silicone polymer solution prepared in the same manner as in Example 5 to obtain a composition of 5! I've adjusted it.
以下、実施例５にしたがって貼り合わせ、硬化を行った
。物性は第２表に示したとおりであり、ラダー型シリコ
ーンオリゴマーの水酸基とエトキシ基の含有量が共に多
いときには、接着物のはく離接着強さ、耐水性が共に不
良であった。Thereafter, according to Example 5, bonding and curing were performed. The physical properties are as shown in Table 2, and when the content of both hydroxyl groups and ethoxy groups in the ladder type silicone oligomer was high, both the peel adhesion strength and water resistance of the adhesive were poor.
比較例 １１
前記一般式（Ｉ）において、Ｒ１がメチル基、Ｒ２がエ
チル基の化合物と、前記一般式（旧においてＲがメチル
Ｍ、Ｒ４がエチル基の化合物とをモル比が１対２０で縮
合させて、分子Ｒ２，７００のシリコーンポリマーを製
造した。このシリコーンポリマーをトルエンと酢酸エチ
ルの混合溶剤（重量比２：１）に溶解し、シリコーンポ
リマー濃度が７０重量％のシリコーンポリマー溶液を調
整した。この溶液を実施例５と同様に調整したラダー型
シリコーンオリゴマー溶液と重量比１：ｌＯで混合し、
組成物を調整した。実施例５と同じく貼り合わせ、硬化
して物性を測定した。結果を第２表に示した。Comparative Example 11 In the general formula (I), a compound in which R1 is a methyl group and R2 is an ethyl group, and a compound in the general formula (formerly, R is methyl M and R4 is an ethyl group) in a molar ratio of 1:20. A silicone polymer with a molecular R2,700 was produced by condensation.This silicone polymer was dissolved in a mixed solvent of toluene and ethyl acetate (weight ratio 2:1) to prepare a silicone polymer solution with a silicone polymer concentration of 70% by weight. This solution was mixed with a ladder-type silicone oligomer solution prepared in the same manner as in Example 5 at a weight ratio of 1:1O.
The composition was prepared. In the same manner as in Example 5, they were bonded together, cured, and their physical properties were measured. The results are shown in Table 2.
第２表に示したように、一般式（ｎ）で示される化合物
のモル比を本発明の範囲より多く用いて製造したシリコ
ーンポリマーを用いたときは、引張りせん断接着強さ、
はく離接石張さ共に小さく改良にならなかった。As shown in Table 2, when using a silicone polymer manufactured using a molar ratio of the compound represented by general formula (n) greater than the range of the present invention, the tensile shear adhesive strength,
Both spalling, contact and stone tension were small and did not improve.
比較例 １２
前記一般式（Ｉ）においてＲ１がメチル基、Ｒ２がエチ
ル基の化合物と、前記一般式（ＩＩ）においてＲがメチ
ル基、Ｒ４がエチル基の化合物とをモル比が１：２で縮
合させて、分子量が３８０のシリコーンポリマーを製造
した。このシリコーンポリマーをトルエンと酢酸エチル
の混合溶剤（重量比２：１）に溶解し、シリコーンポリ
マー濃度が７０重量％のシリコーンポリマー溶液を調整
した。この溶液を実施例５と同様に調整したラダー型シ
リコーンオリゴマー溶液と重量比１：２で混合して組成
物を調整した。実施例５と同じく貼り合わせ、硬化して
物性を測定した。結果を第２表に示した。Comparative Example 12 A compound in which R1 is a methyl group and R2 is an ethyl group in the general formula (I) and a compound in which R is a methyl group and R4 is an ethyl group in the general formula (II) at a molar ratio of 1:2. Condensation produced a silicone polymer with a molecular weight of 380. This silicone polymer was dissolved in a mixed solvent of toluene and ethyl acetate (weight ratio 2:1) to prepare a silicone polymer solution having a silicone polymer concentration of 70% by weight. This solution was mixed with a ladder type silicone oligomer solution prepared in the same manner as in Example 5 at a weight ratio of 1:2 to prepare a composition. In the same manner as in Example 5, they were bonded together, cured, and their physical properties were measured. The results are shown in Table 2.
第２表に示したように、分子量の小さいシリコーンポリ
マーを併用したときは、接着物のはく離接着強さが不十
分であるばかりでなく、耐溶剤性が劣った。As shown in Table 2, when a silicone polymer with a low molecular weight was used in combination, not only the peel adhesion strength of the adhesive was insufficient, but also the solvent resistance was poor.
（以下余白）
比較例 １３
前記一般式（Ｉ）において、Ｒ１がメチル基、Ｒ２がエ
チル基である化合物と前記一般式（ｎ）において、Ｒが
メチル＆、Ｒ４がエチル基である化合物をモル比１ ：
０．１で縮合させて得られた分子量１ 、０００のシ
リコーンポリマー４０重量部をトルエンと酢酸エチルの
混合溶剤（重量比２：１）２０ｆｆｉ量部に溶解してシ
リコーンポリマー溶液を得た。この溶液を実施例５と同
様にして調整したラダー型シリコーンオリゴマー溶液に
加えて撹拌したところ、混和性が不十分であった。この
混和性の不十分な混合物をそのまま炭素鋼板にコーティ
ングしたが、むらが多く均一に塗布ができなかったため
、接着試験は行なわなかった。(Leaving space below) Comparative Example 13 In the general formula (I), R1 is a methyl group and R2 is an ethyl group, and in the general formula (n), R is methyl &, R4 is an ethyl group. Ratio 1:
A silicone polymer solution was obtained by dissolving 40 parts by weight of a silicone polymer having a molecular weight of 1,000 obtained by condensation with a molecular weight of 0.1 in 20 ffi parts of a mixed solvent of toluene and ethyl acetate (weight ratio 2:1). When this solution was added to a ladder-type silicone oligomer solution prepared in the same manner as in Example 5 and stirred, miscibility was insufficient. This poorly miscible mixture was directly coated on a carbon steel plate, but because it was uneven and could not be coated uniformly, an adhesion test was not conducted.
比較例 １４
前記一般式（Ｉ）において、Ｒ１がメチル基、Ｒ２がエ
チル基である化合物と前記一般式（ｎ）において、Ｒが
メチル基、Ｒ４がエチル基である化合物をモル比１：２
で縮合させて得られた分子量１１０，０００のシリコー
ンポリマ−４０ｆｆｉ量部をトルエンと酢酸エチルの混
合溶剤（重量比２：１）２０′ｇＩＲ部に溶解してシリ
コーンポリマー溶液を得た。このシリコーンポリマー溶
液を実施例１と同様にして調整したラダー型シリコーン
オリゴマー溶液に加え撹拌したところ、混和性が不十分
であった。この混和性の不十分な混合物をそのまま炭素
鋼板にコーティングしたが、むらが多く、均一な塗布が
できなかったので接着試験は行なわなかった。Comparative Example 14 A compound in which R1 is a methyl group and R2 is an ethyl group in the general formula (I) and a compound in which R is a methyl group and R4 is an ethyl group in the general formula (n) at a molar ratio of 1:2.
A silicone polymer solution was obtained by dissolving 40ffi parts of the silicone polymer having a molecular weight of 110,000 obtained by condensation in 20g IR parts of a mixed solvent of toluene and ethyl acetate (weight ratio 2:1). When this silicone polymer solution was added to a ladder-type silicone oligomer solution prepared in the same manner as in Example 1 and stirred, miscibility was insufficient. This poorly miscible mixture was directly coated on a carbon steel plate, but it was uneven and could not be coated uniformly, so no adhesion tests were conducted.
実施例 ６
前記一般式（ＩＩＩ）においてＲ５がフェニル基であり
、水酸基含有量が４重量％、エトキシ基含有量が６重量
％、分子量が１．１１００のラダー型シリコーンオリゴ
マー１００重量部をトルエンとブタノールの混合溶剤（
重量比４：１）５０重量部に溶解してラダー型シリコー
ンオリゴマー溶液を得た。Example 6 In the general formula (III), R5 is a phenyl group, 100 parts by weight of a ladder type silicone oligomer having a hydroxyl group content of 4% by weight, an ethoxy group content of 6% by weight, and a molecular weight of 1.1100 was mixed with toluene. Butanol mixed solvent (
A ladder-type silicone oligomer solution was obtained by dissolving 50 parts by weight (weight ratio: 4:1).
別に前記一般式（Ｉ）においてＲ，がフェニル基、Ｒ２
がメチル基である化合物と、前記一般式（ｎ）において
Ｒがフェニル基、Ｒ４がメチル基である化合物とをモル
比１：３で縮合させて得られた分子ｍ２．１００のシリ
コーンポリマー８０重量部をトルエンとアセトンの混合
溶剤（重量比４：１）４０重量部に溶解してシリコーン
ポリマー溶液を得た。Separately, in the general formula (I), R is a phenyl group, R2
is a methyl group, and a compound in which R is a phenyl group and R4 is a methyl group in the general formula (n) at a molar ratio of 1:3, resulting in a silicone polymer having a molecular m2.100 of 80 weight. 1 part was dissolved in 40 parts by weight of a mixed solvent of toluene and acetone (weight ratio 4:1) to obtain a silicone polymer solution.
ラダー型シリコーンオリゴマー溶液とシリコーンポリマ
ー溶液とを混合したのち、微粉末の酸化けい素０．７重
量部を配合して組成物を調整した。この組成物を用いて
ＪＩＳ ＫＢ８５０の寸法のアルミナ板同士を貼り合わ
せた。室温で３０分間、次いで９０℃で１５分間乾燥し
てから、２５０℃で１時間加熱して硬化させた。接着強
さの測定結果は、引張りせん断接着強さ７７ｋｇ ｆ
／ ｃシ、耐熱性４８ｋｇ ｆ ／ｃ４゜耐水性７０ｋ
ｇｆ／ｃｊ、耐溶剤性４３ｋｇ ｆ ／ｃ−であった。After mixing the ladder-type silicone oligomer solution and the silicone polymer solution, 0.7 parts by weight of finely powdered silicon oxide was added to prepare a composition. Using this composition, alumina plates having dimensions of JIS KB850 were bonded together. It was dried at room temperature for 30 minutes, then at 90°C for 15 minutes, and then heated at 250°C for 1 hour to cure. The measurement result of adhesive strength is tensile shear adhesive strength 77 kg f
/c, heat resistance 48kg f/c4゜water resistance 70k
gf/cj and solvent resistance of 43 kg f/c-.
実施例 ７
前記一般式（ＤＩ）においてＲ５がメチル基とフェニル
基からなり、メチル基とフェニル基とのモル比が２：１
であり、水酸基含有量が３重量％、エトキシ基含有量が
５重量％、分子量が２．２００のラダー型シリコーンオ
リゴマーｔｏｏｉｍ部をトルエンと酢酸ブチルの混合溶
剤（重量比４：１）５０重量部に溶解してラダー型シリ
コーンオリゴマー溶液を得た。Example 7 In the general formula (DI), R5 consists of a methyl group and a phenyl group, and the molar ratio of the methyl group and the phenyl group is 2:1.
A tooim part of a ladder type silicone oligomer having a hydroxyl group content of 3% by weight, an ethoxy group content of 5% by weight, and a molecular weight of 2.200 was mixed with 50 parts by weight of a mixed solvent of toluene and butyl acetate (weight ratio 4:1). A ladder-type silicone oligomer solution was obtained.
別に前記一般式（Ｉ）においてＲ１がメチル基とフェニ
ル基からなり、メチル基とフェニル基のモル比が２＝１
であり、Ｒ２がエチル基である化合物と、前記一般式（
ＩＩ）においてＲ３がメチル基とフェニル基からなり、
メチル基とフェニル基のモル比が２：１であり、Ｒ４が
エチル基である化合物とをモル比１：５で縮合させて得
られる分子量が１．５００のシリコーンポリマー８０重
量部をトルエンと酢酸ブチルの混合溶剤（玉量比４：１
）４０重量部に溶解してシリコーンポリマー溶液を得た
。Separately, in the general formula (I), R1 consists of a methyl group and a phenyl group, and the molar ratio of the methyl group and phenyl group is 2=1.
and a compound in which R2 is an ethyl group, and a compound represented by the general formula (
In II), R3 consists of a methyl group and a phenyl group,
80 parts by weight of a silicone polymer with a molecular weight of 1.500 obtained by condensing a compound in which the molar ratio of methyl groups and phenyl groups is 2:1 and R4 is an ethyl group in a molar ratio of 1:5 is mixed with toluene and acetic acid. Butyl mixed solvent (ball ratio 4:1
) to obtain a silicone polymer solution.
ラダー型シリコーンオリゴマー溶液とシリコーンポリマ
ー溶液とを混合して組成物を調整した。ラダー型シリコ
ーンオリゴマー溶液とシリコーンポリマー溶液は、混和
性にすぐれていた。A composition was prepared by mixing a ladder-type silicone oligomer solution and a silicone polymer solution. The ladder-type silicone oligomer solution and silicone polymer solution had excellent miscibility.
この組成物を用いてＪＩＳ ＫＢ８５０の寸法のシラン
カップリング剤で処理したガラス板とカップリング剤処
理をしていないアルミニウム板とを貼り合わせた。室温
で２０時間、次いで９０℃で３０分間乾燥してから、１
８０℃で３０分間加熱して硬化させた。Using this composition, a glass plate treated with a silane coupling agent and having dimensions of JIS KB850 and an aluminum plate not treated with a coupling agent were bonded together. Dry at room temperature for 20 hours, then at 90°C for 30 minutes, then
It was cured by heating at 80° C. for 30 minutes.
接着強さの測定結果は、引張りせん断接石強さ５２ｋｇ
ｆ ／ ｃｄ、耐熱性３９ｋｇｆ／ｃｊ、耐水性４７
ｋｇ ｆ ／ｃｄ。The measurement result of adhesive strength is tensile shear contact strength of 52kg.
f/cd, heat resistance 39kgf/cj, water resistance 47
kgf/cd.
耐溶剤性３３ｋｇｆ／ｃ−であった。Solvent resistance was 33 kgf/c-.
一方、シリコーンポリマー溶液を配合しないラダー型シ
リコーンオリゴマー溶液のみで接着した場合には、接着
強さが低く、せん断接着強さ１１ｋｇｆ／ｃｊ、耐熱性
Ｏｋｇｆ／ｃｄ、耐水性７ｋｇｆ／ｃｄ１耐溶剤性３ｋ
ｇｆ／ｃ−であった。On the other hand, when bonding is done with only a ladder-type silicone oligomer solution that does not contain a silicone polymer solution, the bond strength is low, with a shear bond strength of 11 kgf/cj, heat resistance of Okgf/cd, water resistance of 7 kgf/cd, and solvent resistance of 3k.
It was gf/c-.
本発明のラダー型シリコーンオリゴマー組成物は、接着
性が良好であり、耐吸湿性、耐熱性、絶縁性、耐はく離
性、耐溶剤性および耐水性等にすぐれており、金属、セ
ラミックス、ガラス、プラスチック等のコーティング剤
、電子材料の絶縁コーティング剤、および金属、セラミ
ックス、ガラス等の接着剤として有用である。The ladder-type silicone oligomer composition of the present invention has good adhesion, moisture absorption resistance, heat resistance, insulation, peeling resistance, solvent resistance, water resistance, etc. It is useful as a coating agent for plastics, an insulating coating agent for electronic materials, and an adhesive for metals, ceramics, glass, etc.
Claims (1)
重量％を含有するラダー型シリコーンオリゴマー、 〔Ｂ〕（イ）一般式（ I ） ▲数式、化学式、表等があります▼（ I ） 〔式中、Ｒ＿１は炭素数が１〜５のアルキル基またはフ
ェニル基、Ｒ＿２は炭素数が１〜５のアルキル基である
〕 で示される化合物と （２）一般式（II） ▲数式、化学式、表等があります▼（II） 〔式中、Ｒ＿３は炭素数が１〜５のアルキル基またはフ
ェニル基、Ｒ＿４は炭素数が１〜５のアルキル基である
〕 で示される化合物とを、化合物（イ）対化合物（ロ）の
モル比が１対０．３〜９の範囲で反応させて得られる分
子量５００〜１００，０００のシリコーンポリマーおよ
び 〔Ｃ〕有機溶剤 とを主成分とするラダー型シリコーンオリゴマー組成物
。[Scope of Claims] [A] 1 to 10% by weight of hydroxyl groups and 1 to 10% of ethoxy groups
Ladder type silicone oligomer containing % by weight, [B] (a) General formula (I) ▲ Numerical formula, chemical formula, table, etc. are available ▼ (I) [In the formula, R_1 is an alkyl group having 1 to 5 carbon atoms or Phenyl group, R_2 is an alkyl group having 1 to 5 carbon atoms] Compounds represented by (2) General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) [In the formula, R_3 is carbon an alkyl group or phenyl group having 1 to 5 carbon atoms, R_4 is an alkyl group having 1 to 5 carbon atoms] at a molar ratio of compound (a) to compound (b) of 1:0. A ladder-type silicone oligomer composition containing as main components a silicone polymer having a molecular weight of 500 to 100,000 obtained by reaction in a range of 3 to 9, and [C] an organic solvent.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24123088A JP2632965B2 (en) | 1988-06-07 | 1988-09-27 | Ladder type silicone oligomer composition |
| US07/361,882 US5030699A (en) | 1988-06-07 | 1989-06-06 | Ladder silicone oligomer composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-140069 | 1988-06-07 | ||
| JP14006988 | 1988-06-07 | ||
| JP24123088A JP2632965B2 (en) | 1988-06-07 | 1988-09-27 | Ladder type silicone oligomer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0277469A true JPH0277469A (en) | 1990-03-16 |
| JP2632965B2 JP2632965B2 (en) | 1997-07-23 |
Family
ID=26472698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24123088A Expired - Lifetime JP2632965B2 (en) | 1988-06-07 | 1988-09-27 | Ladder type silicone oligomer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2632965B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0632341A (en) * | 1992-07-09 | 1994-02-08 | Asahi Breweries Ltd | Scratch shielding agent for container, and container which is shielded from scratch |
| US9388798B2 (en) | 2010-10-01 | 2016-07-12 | Lockheed Martin Corporation | Modular heat-exchange apparatus |
| US9541331B2 (en) | 2009-07-16 | 2017-01-10 | Lockheed Martin Corporation | Helical tube bundle arrangements for heat exchangers |
| JP2017014308A (en) * | 2015-06-26 | 2017-01-19 | Dic株式会社 | Adhesive tape, protective member and electronic equipment |
| US9670911B2 (en) | 2010-10-01 | 2017-06-06 | Lockheed Martin Corporation | Manifolding arrangement for a modular heat-exchange apparatus |
| US9777971B2 (en) | 2009-10-06 | 2017-10-03 | Lockheed Martin Corporation | Modular heat exchanger |
| US10209015B2 (en) | 2009-07-17 | 2019-02-19 | Lockheed Martin Corporation | Heat exchanger and method for making |
| CN113717637A (en) * | 2021-09-07 | 2021-11-30 | 河南三棵树新材料科技有限公司 | High-temperature-resistant anticorrosive paint and preparation method thereof |
-
1988
- 1988-09-27 JP JP24123088A patent/JP2632965B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0632341A (en) * | 1992-07-09 | 1994-02-08 | Asahi Breweries Ltd | Scratch shielding agent for container, and container which is shielded from scratch |
| US9541331B2 (en) | 2009-07-16 | 2017-01-10 | Lockheed Martin Corporation | Helical tube bundle arrangements for heat exchangers |
| US10209015B2 (en) | 2009-07-17 | 2019-02-19 | Lockheed Martin Corporation | Heat exchanger and method for making |
| US9777971B2 (en) | 2009-10-06 | 2017-10-03 | Lockheed Martin Corporation | Modular heat exchanger |
| US9388798B2 (en) | 2010-10-01 | 2016-07-12 | Lockheed Martin Corporation | Modular heat-exchange apparatus |
| US9670911B2 (en) | 2010-10-01 | 2017-06-06 | Lockheed Martin Corporation | Manifolding arrangement for a modular heat-exchange apparatus |
| JP2017014308A (en) * | 2015-06-26 | 2017-01-19 | Dic株式会社 | Adhesive tape, protective member and electronic equipment |
| CN113717637A (en) * | 2021-09-07 | 2021-11-30 | 河南三棵树新材料科技有限公司 | High-temperature-resistant anticorrosive paint and preparation method thereof |
| CN113717637B (en) * | 2021-09-07 | 2022-08-02 | 河南三棵树新材料科技有限公司 | High-temperature-resistant anticorrosive paint and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2632965B2 (en) | 1997-07-23 |
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