JPH0391565A - Releasable silicone composition - Google Patents
Releasable silicone compositionInfo
- Publication number
- JPH0391565A JPH0391565A JP22969089A JP22969089A JPH0391565A JP H0391565 A JPH0391565 A JP H0391565A JP 22969089 A JP22969089 A JP 22969089A JP 22969089 A JP22969089 A JP 22969089A JP H0391565 A JPH0391565 A JP H0391565A
- Authority
- JP
- Japan
- Prior art keywords
- composition
- organopolysiloxane
- parts
- cured film
- molecule
- 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 51
- 239000000203 mixture Substances 0.000 title description 49
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 239000012974 tin catalyst Substances 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- -1 siloxane units Chemical group 0.000 description 26
- 239000000123 paper Substances 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002655 kraft paper Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000013005 condensation curing Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、剥離性シリコーン組成物に関し、特に低温硬
化性、得られる硬化被膜の大気中での耐暴露性が良好で
ある縮合硬化型の剥離性シリコーン組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a releasable silicone composition, particularly a condensation-curable silicone composition that has good low-temperature curability and the resulting cured film has good resistance to exposure in the atmosphere. This invention relates to releasable silicone compositions.
従来、セルロース類、合成樹脂、合成繊維等からなるフ
ィルム、シート、不織布などの表面に、シリコーン組成
物を塗布して硬化させ、剥離性を有する硬化被膜を形成
することが行われている。BACKGROUND ART Conventionally, a silicone composition has been applied to the surface of a film, sheet, nonwoven fabric, etc. made of cellulose, synthetic resin, synthetic fiber, etc. and cured to form a cured film having releasability.
このような剥離性の硬化被膜を形成するシリコーン組成
物として、１分子中にケイ素原子に結合した水酸基を有
するオルガノポリシロキサンと、１分子中にケイ素原子
に結合した水素原子を有するオルガノポリシロキサンと
を含有し、硬化触媒として錫系触媒または白金系触媒を
配合してなる、いわゆる縮合硬化型のシリコーン組成物
；あるいは１分子中にケイ素原子に結合したビニル基を
有するオルガノポリシロキサンと、１分子中にケイ素原
子に結合した水素原子を有するオルガノポリシロキサン
とを含有し、硬化触媒として白金系触媒を配合してなる
、いわゆる付加硬化型のシリコーン組成物等が使用され
ている。Silicone compositions that form such a peelable cured film include organopolysiloxanes having a hydroxyl group bonded to a silicon atom in one molecule, and organopolysiloxanes having a hydrogen atom bonded to a silicon atom in one molecule. A so-called condensation-curing silicone composition containing a tin-based catalyst or a platinum-based catalyst as a curing catalyst; or an organopolysiloxane having a vinyl group bonded to a silicon atom in one molecule; So-called addition-curing silicone compositions are used, which contain an organopolysiloxane having a hydrogen atom bonded to a silicon atom, and a platinum-based catalyst as a curing catalyst.
しかし、前記従来の縮合型のシリコーン組成物は、一般
に１４０℃程度の温度で３０〜６０秒間加熱しなければ
硬化しないため、耐熱性が低い基材、例えば、紙、ポリ
エチレン、塩化ビニルなどの表面に硬化被膜を形成する
には適していない。一方、前記の付加型のシリコーン組
成物は、得られる硬化被膜を大気中に暴露すると剥離性
が低下し、また白金系触媒が被毒され易いため基材によ
っては硬化しないことがあり、用いる基材によってシリ
コーン組成物の硬化性に差があるなどの問題があった。However, the conventional condensation type silicone compositions generally do not cure unless heated at a temperature of about 140°C for 30 to 60 seconds. It is not suitable for forming a cured film on. On the other hand, the above-mentioned addition-type silicone compositions have a reduced releasability when the resulting cured film is exposed to the atmosphere, and the platinum-based catalyst is easily poisoned, so it may not cure depending on the substrate. There were problems such as differences in the curability of the silicone composition depending on the material.
そこで本発明の目的は、従来より低い温度で硬化させる
ことができ、基材による硬化性の差がなく、得られる硬
化被膜を大気中に暴露しても剥離性が低下しない縮合硬
化型の剥離性シリコーン組成物を提供することにある。Therefore, the purpose of the present invention is to provide a condensation-curing type peeling film that can be cured at a lower temperature than conventional methods, has no difference in curing properties depending on the base material, and does not reduce peelability even when the resulting cured film is exposed to the atmosphere. An object of the present invention is to provide a silicone composition with high compatibility.
すなわち、本発明は、
（Ａ）１分子中にケイ素原子に結合した水酸基を少なく
とも２個有するオルガノポリシロキサン、（Ｂ）１分子
中にケイ素原子に結合した水素原子を少なくとも２個有
するオルガノポリシロキサン、（Ｃ）錫系触媒
および
（ロ）白金系触媒
を含有してなる剥離性シリコーン組成物を提供するもの
である。That is, the present invention provides (A) an organopolysiloxane having at least two hydroxyl groups bonded to a silicon atom in one molecule, and (B) an organopolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule. , (C) a tin-based catalyst, and (b) a platinum-based catalyst.
本発明の組成物の（Ａ） ａ分であるオルガノポリシロ
キサンは、１分子中にケイ素原子に結合した水酸基を少
なくとも２個有するものである。この水酸基は、分子鎖
末端のケイ素原子に結合していても、分子鎖の途中のケ
イ素原子に結合していてもよい。このオルガノポリシロ
キサンとしては、例えば、下記平均単位式（■）：
（ＤＨ）−（Ｒ’）ｂｓｉＯ，＋ｋ（ｒ ）〔式中、Ｒ
１は置換または非置換の１価の炭化水素基であり、例え
ば、メチル基、エチル基、プロピル基等のアルキル基；
フェニル基、トリル基等のアリール基；シクロペンチル
基、シクロヘキシル基等のシクロアルキル基；並びにこ
れらの基の炭素原子に結合している水素原子の一部また
は全部がハロゲン原子、シアノ基等で置換されている基
、例えば、３．３．３−トリフルオロプロピル基、シア
ノエチル基などが挙げられる。ａは０．０００２〜０．
１の数、ｂは１．８〜２．１の数であり、ただし、ａ十
すは１．９〜２．２である〕
で表されるものが挙げられる。The organopolysiloxane (A) component a of the composition of the present invention has at least two hydroxyl groups bonded to a silicon atom in one molecule. This hydroxyl group may be bonded to a silicon atom at the end of the molecular chain, or may be bonded to a silicon atom in the middle of the molecular chain. As this organopolysiloxane, for example, the following average unit formula (■): (DH)-(R')bsiO,+k(r) [wherein R
1 is a substituted or unsubstituted monovalent hydrocarbon group, for example, an alkyl group such as a methyl group, ethyl group, or propyl group;
Aryl groups such as phenyl group and tolyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; and some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. Examples include 3.3.3-trifluoropropyl group, cyanoethyl group, and the like. a is 0.0002 to 0.
The number of 1, b is a number of 1.8 to 2.1, and a is a number of 1.9 to 2.2.
この（＾）ｊｄＥ分のオルガノポリシロキサンは、直鎮
状、分岐状のいずれのものであってもよい。実質的に直
鎮状のものが好ましい。直鎮
状のものとしては、例えば、下記一般式（■）：〔式中
、複数のＲ１は同一でも異なってもよく、前記式（１）
と同じであり、ｎは正、の整数、好ましくは６０以上の
整数である〕で表されるものが挙げられる。この一般式
（ｎ）で表されるもののうち、１分子中のケイ素原子に
結合した基Ｒ１の８０モル％以上がメチル基であるもの
が好ましい。This (^)jdE organopolysiloxane may be either straight or branched. Preferably, it is substantially straight-shaped. As for the straight-shaped one, for example, the following general formula (■): [In the formula, a plurality of R1 may be the same or different, and the formula (1)
and n is a positive integer, preferably an integer of 60 or more]. Among those represented by the general formula (n), those in which 80 mol% or more of the groups R1 bonded to silicon atoms in one molecule are methyl groups are preferred.
（Ａ） １分のオルガノポリシロキサンの２５℃におけ
る粘度は、通常、７００ｃＳｔ程度以上である。(A) The viscosity of organopolysiloxane for 1 minute at 25° C. is usually about 700 cSt or more.
本発明の組成物においては、これらのオルガノポリシロ
キサンを、（Ａ）成分として１種単独でも２種以上を組
合わせても用いられる。In the composition of the present invention, these organopolysiloxanes may be used singly or in combination of two or more as component (A).
本発明の組成物の（Ｂ）成分であるオルガノポリシロキ
サンは、１分子中にケイ素原子に結合した水素原子を少
なくとも２個有するものである。このオルガノポリシロ
キサンとして、例えば、下記平均単位式（■）：
（ＤＨ） ｃ（Ｒ’）ｄｓｉ吐イヨ（ＩＩＩ ）〔式中
、Ｒ１は前記式（１）と同じであり、好ましくはメチル
基である。Ｃは０．２〜１．０の数、ｄは１．０〜１．
８の数であり、ただし、ｃ＋ｄは１．８〜２．２である
。〕
で表されるものが挙げられる。The organopolysiloxane which is component (B) of the composition of the present invention has at least two silicon-bonded hydrogen atoms in one molecule. As this organopolysiloxane, for example, the following average unit formula (■): (DH) c(R') dsi (III) [wherein R1 is the same as the above formula (1), preferably a methyl group] It is. C is a number from 0.2 to 1.0, and d is a number from 1.0 to 1.
8, where c+d is 1.8 to 2.2. ] Examples include the following.
さらに具体的には、例えば、式：
％式％
位〔ここで、Ｒ’は前記のとおり〕
等の５ｉ−Ｈ結合を有するシロキサン単位のみからなる
もの；これらの単位の他に、式：
％式％
〔ここで、Ｒ″は前記のとおり〕
等のＳｉ −Ｈ結合を有しない単位も含むポリシロキサ
ンなどが例示され、これらは線状、環状、分岐状のいず
れでもよい。More specifically, for example, one consisting only of siloxane units having a 5i-H bond such as the formula: % [where R' is as described above]; Examples include polysiloxanes containing units having no Si--H bond, such as the formula % [Here, R'' is as defined above], and these may be linear, cyclic, or branched.
この（Ｂ） 成分のオルガノポリシロキサンは、直鎮状
、分岐状および環状のいずれのものであってもよい。The organopolysiloxane of component (B) may be straight, branched or cyclic.
（Ｂ）成分のすルガノボリシロキサンの２５℃における
粘度は、通常、１０〜５００ ｃＳｔ程度である。The viscosity of the component (B), sulfur polysiloxane, at 25° C. is usually about 10 to 500 cSt.
上記の（Ｂ） ｌ１１ｍ分のオルガノポリシロキサンは
１種単独でも２種以上を組み合わせても用いることがで
きる。The above organopolysiloxanes (B) 11m can be used alone or in combination of two or more.
（Ｂ）成分として、１分子中にケイ素原子に結合した水
素原子を２個有するオルガノポリシロキサンを５０重量
％以下含有し、残余が１分子中にケイ素原子に結合した
水素原子を３個以上含有するオルガノポリシロキサンか
らなる混合物を使用すると、得られる組成物の基材との
密着性が優れる点で好ましい。Component (B) contains 50% by weight or less of an organopolysiloxane having two hydrogen atoms bonded to silicon atoms in one molecule, and the remainder contains three or more hydrogen atoms bonded to silicon atoms in one molecule. It is preferable to use a mixture of organopolysiloxanes, since the resulting composition has excellent adhesion to the substrate.
本発明の組成物における（Ｂ）成分の配合量は、適度な
硬化性と剥離力が得られる点から、（Ａ）成分１００重
量部に対して０．５〜５０重量部が好ましく、さらに好
ましくは１〜１５重量部である。The blending amount of component (B) in the composition of the present invention is preferably 0.5 to 50 parts by weight, more preferably 0.5 to 50 parts by weight based on 100 parts by weight of component (A), in order to obtain appropriate curability and peeling force. is 1 to 15 parts by weight.
本発明の組成物の（Ｃ）成分である錫系触媒は、この種
のシリコーン組成物を硬化させるために通常使用される
ものでよく、特に制限されない。例えば、ジブチル錫ジ
アセテート、ジブチル錫ジオクトエート、ジブチル錫ジ
ラウレート等の有機錫化合物が挙げられる。The tin-based catalyst which is component (C) of the composition of the present invention may be one commonly used for curing this type of silicone composition, and is not particularly limited. For example, organic tin compounds such as dibutyltin diacetate, dibutyltin dioctoate, and dibutyltin dilaurate can be mentioned.
本発明の組成物における（Ｃ）成分の配合量は、通常、
（＾＞Ｊａ分１００重量部に対して、０．０１〜１０重
量部、好ましくは０．１〜５重量部である。The amount of component (C) in the composition of the present invention is usually
(^>0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of Ja).
本発明の組成物の（Ｄ）成分である白金系触媒は特に制
限されず、例えば、塩化第一白金酸、塩化第二白金酸等
の塩化白金酸；塩化白金酸のアルコール化合物またはア
ルデヒド化合物；塩化白金酸と各種オレフィンとの錯塩
などが挙げられる。The platinum-based catalyst that is component (D) of the composition of the present invention is not particularly limited, and examples include chloroplatinic acids such as chloroplatinic acid and chloroplatinic acid; alcohol compounds or aldehyde compounds of chloroplatinic acid; Examples include complex salts of chloroplatinic acid and various olefins.
本発明の組成物における（口）成分の配合量は、通常、
（＾）成分１０Ｇ重量部に対して、白金量として、通常
、０．０００１〜１．０重量部であり、経済性および得
られる硬化被膜が良好である点で０．００１〜０．１重
量部が好ましい。The amount of the (oral) component in the composition of the present invention is usually
(^) The amount of platinum is usually 0.0001 to 1.0 parts by weight per 10 G parts by weight of the component, and 0.001 to 0.1 parts by weight in terms of economical efficiency and good cured film. part is preferred.
本発明の組成物には、前記（＾） 、ＣＢ） 、（Ｃ）
および（Ｄ） 成分の他に、（Ｃ） を分の活性を抑制
して硬化反応を適度にするために、反応制御剤を必要に
応じて（＾）ｔｉ、分１００重量部に対して１０重量部
以下の量で配合してもよい。この反応制御剤としてハ、
例えば、アセチレンアルコール等のアセチレン系化合物
、あるいは有機窒素化合物、有機リン化合物、オキシム
化合物などが挙げられる。The composition of the present invention includes the above (^), CB), (C)
In addition to component (D), in order to suppress the activity of component (C) and moderate the curing reaction, a reaction control agent may be added as necessary (^)ti, 10 parts by weight per 100 parts by weight. It may be blended in an amount of less than parts by weight. As this reaction control agent,
Examples include acetylene compounds such as acetylene alcohol, organic nitrogen compounds, organic phosphorus compounds, and oxime compounds.
本発明の組成物は、いずれの材料からなる基材にも適用
可能であり、例えば、紙等のセルロース類、合成樹脂、
合成繊維、アルミ箔等に適用して剥離性の硬化被膜を形
成することができる。基材の形状も特に制限されず、フ
ィルム状、シート状、布状等のいずれのものでもよい。The composition of the present invention can be applied to a substrate made of any material, such as cellulose such as paper, synthetic resin,
It can be applied to synthetic fibers, aluminum foil, etc. to form a peelable cured film. The shape of the base material is not particularly limited either, and may be in the form of a film, sheet, cloth, or the like.
本発明の組成物を適用して剥離性の硬化被膜を基材の表
面に形成するためには、この組成物を基材の表面にその
まま塗布してもよいし、また組成物を適当な溶媒で希釈
して塗布してもよい。塗布後、加熱処理して剥離性を有
する硬化被膜を懲戒させることができる。希釈に用いら
れる溶媒としては、例えば、トルエン、キシレン、１．
１．１−）リクロロエタン、ヘキサン、ヘプタン等の有
機溶媒が挙げられる。また、加熱処理の温度は１００℃
以下で、加熱時間は４０秒以下で十分である。In order to form a removable cured film on the surface of a substrate by applying the composition of the present invention, the composition may be applied directly to the surface of the substrate, or the composition may be applied in a suitable solvent. It may be diluted and applied. After application, heat treatment can be performed to form a cured film that has peelability. Examples of the solvent used for dilution include toluene, xylene, 1.
1.1-) Organic solvents such as dichloroethane, hexane, and heptane can be mentioned. Also, the temperature of heat treatment is 100℃
Below, a heating time of 40 seconds or less is sufficient.
以下、実施例及び比較例を挙げて本発明の詳細な説明す
る。以下において、１部」は「重量部」を、粘度は２５
℃における値を示す。Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. In the following, "1 part" means "part by weight", and viscosity is 25
Values are shown in °C.
実施例１
両末端をジメチルヒドロキシシリル基で封鎖されたジメ
チルポリシロキサン生ゴム１００部と、両末端をトリメ
チルシリル基で封鎖されたメチルハイドロジエンポリシ
ロキサン（２５℃における粘度： ５０ｃＳｔ 、−分
子中に５ｉ−Ｈ結合を平均３８個含有）３部とを、トル
エン９００部に溶解して、オルガノポリシロキサン溶液
を調製した。次に、このオルガノポリシロキサン溶液に
、ジブチル錫ジアセテート３部、塩化白金酸−へキサメ
チルジビニルジシロキサン錯塩を白金として０．０３部
およびアセチレンアルコール０．８部を加えて剥離性シ
リコーン組成物を調製した。Example 1 100 parts of dimethylpolysiloxane crude rubber whose both ends were capped with dimethylhydroxysilyl groups and methylhydrodiene polysiloxane whose both ends were capped with trimethylsilyl groups (viscosity at 25°C: 50 cSt, 5i- in the molecule) (containing an average of 38 H bonds) was dissolved in 900 parts of toluene to prepare an organopolysiloxane solution. Next, 3 parts of dibutyltin diacetate, 0.03 parts of chloroplatinic acid-hexamethyldivinyldisiloxane complex salt as platinum, and 0.8 parts of acetylene alcohol were added to this organopolysiloxane solution to form a release silicone composition. was prepared.
得られ九組成物をポリエチレンラミネート紙の表面に、
ワイヤーバーを用いて塗布し、１００℃で３０秒間加熱
処理することによって硬化被膜を得ることができた。ま
た、この組成物について下記の方法にしたがって、硬化
性、剥離力、残留接着率および大気中にｎ露した後の剥
離性の変化（以下、「耐暴露性」という）を測定した。The resulting nine compositions were applied to the surface of polyethylene laminate paper,
A cured film could be obtained by coating using a wire bar and heat-treating at 100° C. for 30 seconds. Further, the curability, peeling force, residual adhesion rate, and change in peelability after exposure to air (hereinafter referred to as "exposure resistance") of this composition were measured according to the following methods.
結果を表１に示す。The results are shown in Table 1.
硬化性
オルガノポリシロキサン溶液に、ジブチル錫ジアセテー
ト３部、塩化白金酸−オレフィン錯塩を白金として０．
０３部およびアセチレンアルコール０．８部を加えて剥
離性シリコーン組成物を調製し、調製後１０分経過した
後に該組成物をポリエチレンラミネートクラフト紙の表
面に０．８ｇ／ｒｎ”の厚さに塗布した。このように組
成物を塗布したポリエチレンラミネートクラフト紙を、
１００℃の熱風循環式乾燥炉中で３０秒間加熱処理し、
シリコーン被膜を懲戒した。その後、得られた被膜の表
面を指で擦り、被膜が脱落せず、しかも曇らないときに
組成物が硬化したと判定した。Add 3 parts of dibutyltin diacetate and 0.0 parts of chloroplatinic acid-olefin complex salt as platinum to a curable organopolysiloxane solution.
A release silicone composition was prepared by adding 0.3 parts of 0.03 parts and 0.8 parts of acetylene alcohol, and 10 minutes after preparation, the composition was applied to the surface of polyethylene laminated kraft paper to a thickness of 0.8 g/rn''. Polyethylene laminated kraft paper coated with the composition in this way was
Heat treated for 30 seconds in a hot air circulation drying oven at 100°C,
Disciplined silicone coating. Thereafter, the surface of the resulting coating was rubbed with a finger, and the composition was determined to be cured when the coating did not fall off and did not become cloudy.
剥離力
組成物を、３片のポリエチレンラミネートクラフト紙（
縦２０ｃｍＸ横１０ｃｍ）の表面にそれぞれ０．８ｇ
／ ｍ’の量に塗布した。これを、１００℃の熱風循環
式乾燥炉中で３０秒間加熱して、表面に硬化被膜が形成
された３枚の紙片を得た。得られた３枚の紙片の硬化被
膜の表面に、ゴム系溶剤型粘着剤（東洋インキ製造■製
、オリパインＢＰＳ−２４１１）、アクリル系溶剤型粘
着剤（同社製、オリパインＢＰＳ−８１７０）まではア
クリル系エマルジョン型粘着剤（同社製、オリパインＢ
ＰＷ−３１１０Ｈ）を塗布後、１００℃で３分間加熱処
理して硬化被膜の上に粘着剤層を有する紙片を作製した
。次に、この紙片の粘着剤層に坪量６４ｇ／ｍ’の貼り
合わせ紙を貼り合わせ、室温で２０時間エイジングさせ
た。エイジング後、紙片を幅５ ｃＩＩＸ長さ１Ｏｃａ
＋に切断して試験片を作成し、引張試験機にかけて１８
０°の角度、剥離速度３００ｍａ＋／分で引張り、硬化
被膜が粘着剤層から剥離するのに要する力（８１５ｃｍ
幅）を測定した。The release force composition was applied to three pieces of polyethylene laminated kraft paper (
0.8g each on the surface (20cm long x 10cm wide)
/ m' was applied. This was heated for 30 seconds in a hot air circulation drying oven at 100° C. to obtain three pieces of paper with a cured film formed on the surface. Rubber-based solvent-based adhesive (Olipine BPS-2411, manufactured by Toyo Ink Manufacturing Co., Ltd.) and acrylic solvent-based adhesive (Olipine BPS-8170, manufactured by Toyo Ink Manufacturing Co., Ltd.) were applied to the surfaces of the cured films of the three pieces of paper obtained. Acrylic emulsion type adhesive (manufactured by the same company, Olipine B)
PW-3110H) was applied and then heat-treated at 100°C for 3 minutes to produce a piece of paper having an adhesive layer on the cured film. Next, a laminated paper having a basis weight of 64 g/m' was attached to the adhesive layer of this paper piece, and the paper was aged for 20 hours at room temperature. After aging, the paper strips are 5 cIIX in width and 1 Oca in length.
Create a test piece by cutting it at +, and put it in a tensile tester to test 18
The force required for the cured film to peel off from the adhesive layer (815 cm
width) was measured.
残留接着率
剥離力の測定の場合と同様にして、ポリエチレンラミネ
ートクラフト紙の表面に組成物の硬化被膜を形成させた
。その硬化被膜の表面にポリエステル粘着テープ（日東
電工■製、ルミラー３１Ｂ）を貼り合わせ、２０ｇ／ｃ
ａｒの荷重を掛けながら７０℃で２０時間加熱処理した
。加熱処理後、ポリエステル粘着テープをリエチレンラ
ミネート紙に硬化被膜から剥がし、ステンレス板の表面
に貼りつけた。A cured film of the composition was formed on the surface of polyethylene laminated kraft paper in the same manner as in the measurement of residual adhesion rate and peel force. A polyester adhesive tape (manufactured by Nitto Denko ■, Lumirror 31B) was attached to the surface of the cured film, and 20g/c
Heat treatment was performed at 70° C. for 20 hours while applying a load of ar. After the heat treatment, the polyester adhesive tape was peeled off from the cured film on a polyethylene laminate paper, and was attached to the surface of a stainless steel plate.
次に、この加熱処理されたポリエステル粘着テープをス
テンレス板から、１８Ｇ”の角度の方向に剥離速度３０
０ｍ／分で剥がし、剥離するのに要する力Ｗ（８１５ｃ
ｍ幅）を測定した。一方、加熱処理されていないポリエ
ステル粘着テープをステンレス板に貼りつけ、これを上
記と同様の条件でステンレス板から剥離するのに要する
力Ｗ−（ｇ／５ｃＩｌ１幅）を測定し、このＷｏに対す
るＷの比（Ｗ／Ｗ０）（百分率）を求めて残留接着率と
した。Next, this heat-treated polyester adhesive tape was peeled off from the stainless steel plate at a peeling speed of 30 G in the direction of an angle of 18 G.
Peeling at 0 m/min, force W required for peeling (815c
m width) was measured. On the other hand, an unheated polyester adhesive tape was attached to a stainless steel plate, and the force W-(g/5cIl1 width) required to peel it off from the stainless steel plate under the same conditions as above was measured. The ratio (W/W0) (percentage) was determined to be the residual adhesion rate.
耐ａ露性
剥離力の試験について記載したのと同様にして、組成物
をポリエチレンラミネートクラフト紙片の表面に０．８
ｇ／ｎ１″の量で塗布し、１００℃の熱風循環式乾燥炉
中で３０秒間加熱して、表面に硬化被膜を形成した。硬
化被膜を形成した紙片を大気中に２４時間暴露させた後
に剥離力の測定に供した以外は、前記と同様にして剥離
力を測定した。大気中に暴露後の紙片を用いた試験片の
剥離力が、！ＩＩ！しない紙片を用いた試験片の剥離力
に比して大きくならないものほど耐ａ露性が高い。The composition was applied to the surface of a piece of polyethylene laminated kraft paper in a manner similar to that described for the test of dew resistance peel strength.
g/n1" and heated for 30 seconds in a hot air circulation drying oven at 100°C to form a cured film on the surface. After exposing the paper strip with the cured film to the atmosphere for 24 hours, The peeling force was measured in the same manner as above, except that the peeling force was measured in the same manner as above.The peeling force of the test piece using the paper piece after exposure to the atmosphere was !II! The smaller the size compared to the force, the higher the atomization resistance.
比較例１
塩化白金酸−ヘキサメチルジビニルジシロキサン錯塩お
よびアセチレンアルコールを用いない以外は、実施例１
と同様にして組成物を製造した。Comparative Example 1 Example 1 except that chloroplatinic acid-hexamethyldivinyldisiloxane complex salt and acetylene alcohol were not used.
A composition was produced in the same manner as above.
得られた組成物を実施例１と同様にしてポリエチレンラ
ミネートクラフト紙の表面に塗布し、１００℃で３０秒
間加熱処理して硬化さ、せてみたが、得られた被膜は著
しく曇りを有するものであり、十分に硬化していないこ
とがわかった。The obtained composition was applied to the surface of polyethylene laminated kraft paper in the same manner as in Example 1, and cured by heat treatment at 100°C for 30 seconds, but the resulting film was significantly cloudy. It was found that it was not sufficiently cured.
この組成物について、硬化被膜を形成するときの加熱処
理を１６０℃、３０秒間の条件で行う以外は、実施例１
と同様にして処理し、剥離力、残留接着率および耐暴露
性を測定した。結果を表１に示す。Example 1 except that this composition was heat treated at 160°C for 30 seconds to form a cured film.
It was treated in the same manner as above, and the peel force, residual adhesion rate, and exposure resistance were measured. The results are shown in Table 1.
比較例２
ジブチル錫ジアセテートを用いない以外は、実施例１と
同様にして組成物を得た。Comparative Example 2 A composition was obtained in the same manner as in Example 1 except that dibutyltin diacetate was not used.
得られた組成物について、実施例１と同様にして硬化性
、剥離力、残留接着率および耐暴露性を測定した。結果
を表１に示す。The resulting composition was measured for curability, peel strength, residual adhesion rate, and exposure resistance in the same manner as in Example 1. The results are shown in Table 1.
比較例３
ジメチルビニルシリル基で末端が封鎖されたジメチル・
メチルビニルポリシロキサン生ゴム（ビニル基含有量＝
３モル％） １００部と、実施例１で用いたものと同じ
メチルハイドロジエンポリシロキサン３部とをトルエン
９００部に溶解して、オルガノポリシロキサン溶液を調
製した。次に、このオルガノポリシロキサン溶液に、ジ
ブチル錫ジアセテート３部、塩化白金酸−ヘキサメチル
ジビニルジシロキサン錯塩を白金として０．０３部およ
びアセチレンアルコール０．８部を加えて組成物を調製
した。Comparative Example 3 Dimethyl vinyl terminal-capped with dimethylvinylsilyl group
Methyl vinyl polysiloxane raw rubber (vinyl group content =
3 mol %) and 3 parts of the same methylhydrodiene polysiloxane used in Example 1 were dissolved in 900 parts of toluene to prepare an organopolysiloxane solution. Next, to this organopolysiloxane solution were added 3 parts of dibutyltin diacetate, 0.03 part of chloroplatinic acid-hexamethyldivinyldisiloxane complex salt as platinum, and 0.8 part of acetylene alcohol to prepare a composition.
得られた組成物をポリエチレンラミネートクラフト紙の
表面に、ワイヤーバーを用いて塗布し、１００℃で３０
秒間加熱処理することによって硬化被膜を得た。また、
この組成物について実施例１と同様にして硬化性、剥離
力、残留接着率および耐暴露性を測定した。結果を表１
に示す。The obtained composition was applied to the surface of polyethylene laminated kraft paper using a wire bar and heated at 100°C for 30 minutes.
A cured film was obtained by heat treatment for seconds. Also,
The curability, peel strength, residual adhesion rate, and exposure resistance of this composition were measured in the same manner as in Example 1. Table 1 shows the results.
Shown below.
本発明の剥離性シリコーン組成物は、従来の縮合硬化型
シリコーン組成物より低い温度で硬化させることができ
、適用する基材によって硬化性に差がなく、また大気中
に暴露されても剥離性が低下しない硬化被膜を得ること
ができる。そのため、本発明の組成物を用いれば、安定
な剥離性を有する紙、プラスチックのフィルム、シート
等の離型基材を高い生産性で製造することができる。The releasable silicone composition of the present invention can be cured at a lower temperature than conventional condensation-curing silicone compositions, has no difference in curability depending on the substrate to which it is applied, and has good releasability even when exposed to the atmosphere. It is possible to obtain a cured film with no decrease in . Therefore, by using the composition of the present invention, release substrates such as paper, plastic films, and sheets having stable releasability can be manufactured with high productivity.
Claims (1)
とも２個有するオルガノポリシロキサン、（Ｂ）１分子
中にケイ素原子に結合した水素原子を少なくとも２個有
するオルガノポリシロキサン、（Ｃ）錫系触媒 および （Ｄ）白金系触媒 を含有してなる剥離性シリコーン組成物。Scope of Claims: (A) Organopolysiloxane having at least two hydroxyl groups bonded to silicon atoms in one molecule; (B) Organopolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule , (C) a tin-based catalyst, and (D) a platinum-based catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22969089A JPH0655893B2 (en) | 1989-09-05 | 1989-09-05 | Peelable silicone composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22969089A JPH0655893B2 (en) | 1989-09-05 | 1989-09-05 | Peelable silicone composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0391565A true JPH0391565A (en) | 1991-04-17 |
| JPH0655893B2 JPH0655893B2 (en) | 1994-07-27 |
Family
ID=16896175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22969089A Expired - Fee Related JPH0655893B2 (en) | 1989-09-05 | 1989-09-05 | Peelable silicone composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0655893B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0522537U (en) * | 1991-09-05 | 1993-03-23 | リンテツク株式会社 | Double-sided release sheet |
| JP2003192897A (en) * | 2001-12-27 | 2003-07-09 | Dow Corning Toray Silicone Co Ltd | Organopolysiloxane composition for forming releasable cured film |
| JP2006144214A (en) * | 2004-10-22 | 2006-06-08 | Shin Etsu Chem Co Ltd | Silicone paper-treating agent |
-
1989
- 1989-09-05 JP JP22969089A patent/JPH0655893B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0522537U (en) * | 1991-09-05 | 1993-03-23 | リンテツク株式会社 | Double-sided release sheet |
| JP2003192897A (en) * | 2001-12-27 | 2003-07-09 | Dow Corning Toray Silicone Co Ltd | Organopolysiloxane composition for forming releasable cured film |
| JP2006144214A (en) * | 2004-10-22 | 2006-06-08 | Shin Etsu Chem Co Ltd | Silicone paper-treating agent |
| US7964062B2 (en) | 2004-10-22 | 2011-06-21 | Shin-Etsu Chemical Co., Ltd. | Paper treating agent comprising a silicone composition |
| JP4743757B2 (en) * | 2004-10-22 | 2011-08-10 | 信越化学工業株式会社 | Silicone paper treatment agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0655893B2 (en) | 1994-07-27 |
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