CN101616995B - Solventless cured release coating-forming organopolysiloxane composition and sheet-form substrate having cured release coating - Google Patents

Solventless cured release coating-forming organopolysiloxane composition and sheet-form substrate having cured release coating Download PDF

Info

Publication number
CN101616995B
CN101616995B CN2007800482229A CN200780048222A CN101616995B CN 101616995 B CN101616995 B CN 101616995B CN 2007800482229 A CN2007800482229 A CN 2007800482229A CN 200780048222 A CN200780048222 A CN 200780048222A CN 101616995 B CN101616995 B CN 101616995B
Authority
CN
China
Prior art keywords
sio
carbon atom
alkyl
alkenyl
solidified
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.)
Active
Application number
CN2007800482229A
Other languages
Chinese (zh)
Other versions
CN101616995A (en
Inventor
堀诚司
山田高照
D·A·里奇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont Toray Specialty Materials KK
Dow Silicones Corp
Original Assignee
Dow Corning Toray Co Ltd
Dow Corning Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Toray Co Ltd, Dow Corning Corp filed Critical Dow Corning Toray Co Ltd
Publication of CN101616995A publication Critical patent/CN101616995A/en
Application granted granted Critical
Publication of CN101616995B publication Critical patent/CN101616995B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/28—Presence of paper
    • C09J2400/283—Presence of paper in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)

Abstract

A solventless, cured release coating-forming organopolysiloxane composition comprising (A) 100 parts of an organopolysiloxane fluid having a branched structure and comprising (i) the siloxane unit represented by the formula SiO4/2, (ii) the siloxane unit represented by the general formula R2SiO2/2, and (iii) the siloxane unit represented by the general formula RaR2SiO1/2; (B) 0.5 to 15 parts of a diorganopolysiloxane with the average structural formula RaRc 2SiO(RbRcSiO2/2)n1(Rc2SiO2/2)n2SiRc2Ra; (c) a predetermined amount of organohydrogenpolysiloxane; and (D) a hydrosililatingreaction catalyst. In additon, the sheet-form substrate has the cured coating thereon.

Description

The organopolysiloxane composition of solvent-free formation solidified anti-stick coating and substrate with sheet-form of solidified anti-stick coating
Technical field
The present invention relates to the organopolysiloxane composition of solvent-free formation solidified anti-stick coating, said composition can for example form the solidified anti-stick coating on the surface of the paper, thermoplastic resin film, tinsel etc. of paper, laminated polyolefin in the substrate of sheet-form; Can good stripping performance be provided with respect to viscous substance; With the surface treated with smooth sliding property can be provided.The invention still further relates to the substrate of the sheet-form that has the solidified anti-stick coating that obtains through the curing said composition.
Background technology
Through being well-known at the organic solvent organopolysiloxane composition of solution type that for example dissolving contains the addition reaction solidified nature organopolysiloxane composition preparation of the functional diorganopolysiloxaneand sizing material of alkenyl, organic radical hydrogen polysiloxanes and hydrosilylation reaction catalyst in the toluene, and usually as on the surface of the for example various paper of the substrate of sheet-form, laminated paper opening and closing film forming, tinsel etc., forming the employed organopolysiloxane composition of solidified coating that demonstrates stripping performance with respect to viscous substance.
In JP47-032072A (references 1) and JP53-003979B (references 2), introduced the organopolysiloxane composition of the emulsion type that provides through emulsification addition reaction solidified nature organopolysiloxane composition in water and be the solvent-free organopolysiloxane composition that only contains LV addition reaction solidified nature organopolysiloxane composition of liquid substitute at ambient temperature, and got into actual use as the addition reaction solidified nature organopolysiloxane composition of above-described solution type.Based on safety and environmental consideration factor; In wide in range Application Areas, need the substitute of the organopolysiloxane composition of solvent-free formation solidified anti-stick coating in recent years as solution type; Reply with conduct, in JP 2004-307691A (references 3), introduced the organopolysiloxane composition that forms the solvent-free solidified anti-stick coating of this type.
Yet; Has the LV of about 50-1000cSt owing in the organopolysiloxane composition of existing solvent-free formation solidified anti-stick coating, be used as the diorganopolysiloxaneand of the vinyl functional of basic ingredient; Although therefore but these composition exhibiting go out good coating; But they obtain having the solidified coating of poor sliding, and shortcoming is that its application is limited to as a result.Therefore; When the diorganopolysiloxaneand with this low viscous vinyl functional is used stripper as the organopolysiloxane composition of the solvent-free formation solidified anti-stick coating of its basic ingredient as kraft paper gummed tape; The method that the gained solidified coating shows the sliding go on business and on cardboard for example, pastes kraft paper gummed tape can not be carried out smoothly; And pressure sensitive adhesive can not be bonding fully and can peel off.When on paper, lamination paper or plastic film, forming solidified coating; This solidified coating shows the sliding of going on business once more; This causes the problem such as adhesive tape infringement and adhesive tape can't rotate smoothly, sees that from the angle of technology this possibly be the reason of quadratic problem.
In addition; When through apply diorganopolysiloxaneand with this low viscous vinyl functional as the solvent-free addition reaction solidified nature organopolysiloxane composition of its basic ingredient on paper or plastic film and on paper or plastic film, form solidified coating; When preparation separate paper or antiadhesion barrier, the sliding of solidified coating difference causes damaging such as solidified coating, when being coated with viscous substance subsequently; Produce uneven release characteristics; With the problem of rolling separate paper or antiadhesion barrier and so on smoothly, the generation of these problems is because before separate paper or antiadhesion barrier rolling, and solidified coating and metal or plastic foil or plastic roller contact and cause.
In order to improve the sliding of solidified coating; JP61-159480A (references 4) has proposed to be used for the solvent-free addition reaction solidified nature organopolysiloxane composition that separate paper is used; Wherein basic ingredient is 1) viscosity is 50-100; 000cps and contents of ethylene are the straight chain organopolysiloxane and 2 of 0.5-10.0mol%) have low vinyl content and viscosity is at least 100, the straight chain organopolysiloxane of 000cps.JP61-264052A (references 5) has proposed to be used for the solvent-free addition reaction solidified nature silicone composition that separate paper is used; Its viscosity is 50-10; 000cps, and to have viscosity be 50-10,000cps and contents of ethylene are the straight chain organopolysiloxane of the 0.5-10.0% of whole organic groups; Be at least 100 with viscosity, 000cps and molecular end have the organopolysiloxane of straight chain basically of hydroxyl as basic ingredient.Yet, since these compsns to contain a large amount of viscosity be 50-10, therefore the straight chain diorganopolysiloxaneand of 000cps, can't provide the sliding that is entirely satisfactory by the solidified coating of its preparation.
On the other hand, in JP55-110155A (references 6) and JP2005-255928A (references 7), (it contains R to have proposed the organopolysiloxane composition of formation solidified coating of solvent-free addition reaction curing type 3SiO 1/2Unit (=M unit), R 2SiO 2/2Unit (=D unit) or RSiO 3/2Unit (=T unit) and SiO 4/2Unit (=Q unit) and each molecule have the multipolymer of at least two alkenyls) and the organopolysiloxane composition of the formation solidified anti-stick coating of solvent-free addition reaction curing type (it has the R of containing 3SiO 1/2Unit (=M unit) and SiO 4/2The organopolysiloxane resins of unit (=Q unit) is as its basic ingredient).In JP2001-064390A (references 8) and EP1070734A2 (references 9), hydrosilylation reactions solidified nature siloxanes release coating compositions has been proposed also; Wherein basic ingredient is to contain aforementioned Q unit, the functional side chain organopolysiloxane of the unitary alkenyl of specific quantity D unit and M.These compsns and especially references 8 go out good curability and solidify the coating that obtains to demonstrate the adhesivity good, good residual binding property etc. with composition exhibiting in the references 9 to substrate through their; Yet this solidified coating has big frictional coefficient, therefore considers from the angle of sliding, is not entirely satisfactory.
JP2001-064390A (references 8) and EP1070734A2 (references 9) have instructed the siloxanes release coating compositions can mix the diorganosiloxane that gathers of alkenylation in addition; For example ii) alkenyl dialkyl group silyl terminated gather diorganosiloxane and the YSR 3286 of preferred dimethylvinylsilyl-terminated and/or the YSR 3286 of dimethyl-hexenyl silyl terminated; Wherein to be 25-85wt% and surplus be the diorganosiloxane that gathers of ii) alkenyl dialkyl group silyl terminated to the side chain organopolysiloxane of preference chain alkenyl functional.Yet, do not recognize that the frictional coefficient of solidified coating descends and its sliding increase, do not mention the means that reduce the solidified coating frictional coefficient and increase its sliding yet.
Summary of the invention
In order to solve above-described problem; The present invention has been proposed; With the organopolysiloxane composition that the objective of the invention is to introduce solvent-free formation solidified anti-stick coating; When solidified, its forms substrate is demonstrated good adhesion property and has good residual binding property and viscous substance is had improved stripping performance and has the coating of improved sliding.Another purpose of the present invention provides the substrate of the sheet-form that has solidified coating, and said solidified coating demonstrates good adhesion property to substrate and has good residual binding property and viscous substance is had improved stripping performance and has improved sliding.
The present invention relates to the organopolysiloxane composition of solvent-free formation solidified anti-stick coating, it comprises: (A) 100 parts have branched structure and comprise following unitary organopolysiloxane fluid: (i) use chemical formula SiO 4/2The siloxane unit of expression is (ii) used general formula R 2SiO 2/2The expression siloxane unit and (iii) use general formula R aR 2SiO 1/2The siloxane unit of expression; (B) 0.5-15 part average structure formula is following diorganopolysiloxaneand: R aR c 2SiO (R bR cSiO 2/2) N1(R c 2SiO 2/2) N2SiR c 2R a(C) the organic radical hydrogen polysiloxanes of predetermined amount; (D) hydrosilylation reaction catalyst.The invention still further relates to the substrate of sheet-form, said substrate has the solidified coating that is obtained by this solvent-free organopolysiloxane composition that forms the solidified anti-stick coating.
Disclosure of the Invention
Can realize above-described purpose through following.{ the organopolysiloxane composition of the solvent-free formation solidified of 1} anti-stick coating; It is characterized in that comprising: (A) 100 weight parts have branched structure and are 10-1 25 ℃ of following viscosity; 000mPa.s, comprise the siloxane unit (i)-(iii) of the following stated and have containing a plurality of siloxane units linear fraction (ii); And the organopolysiloxane fluid that contains the branch point of siloxane unit (i), the end of wherein said linear fraction with siloxane unit (iii) end-blocking (i) use chemical formula SiO 4/2The siloxane unit of expression: one or more (ii) use general formula R 2SiO 2/2The siloxane unit of expression: 15-995 (iii) uses general formula R aR 2SiO 1/2The siloxane unit of expression (in these formulas, R aBe to be selected from alkyl, have the alkenyl of 2-8 carbon atom, phenyl with 1-8 carbon atom; Have the alkoxyl group of 1-8 carbon atom and the group and the R of hydroxyl and be selected from alkyl with 1-8 carbon atom; Alkenyl with 2-8 carbon atom, and phenyl groups, wherein intramolecularly R aWith among the R at least three is to have the alkenyl of 2-8 carbon atom and at this intramolecularly R aWith at least 50% of R sum be alkyl with 1-8 carbon atom); (B) the 0.5-15 weight part is at least 100, the diorganopolysiloxaneand of 000mPa.s: R with average structure formula (1) expression and 25 ℃ of following viscosity aR c 2SiO (R bR cSiO 2/2) N1(R c 2SiO 2/2) N2SiR c 2R a(1) (R wherein aBe to be selected from the alkyl with 1-8 carbon atom, have the alkenyl of 2-8 carbon atom, phenyl has the alkoxyl group of 1-8 carbon atom and the group of hydroxyl; R bIt is alkenyl with 2-8 carbon atom; R cIt is alkyl or phenyl with 1-8 carbon atom; At this intramolecularly R a, R bAnd R cThe 0-0.1% of sum is the alkenyl with 2-8 carbon atom; At this intramolecularly R a, R bAnd R cAt least 50% of sum is the alkyl with 1-8 carbon atom; N1 is that numerical value is at least 0 number; N2 is that numerical value is at least 1 number; Provide this component with n1+n2 and be at least 100 25 ℃ of following viscosity, the number of 000mPa.s); (C) be that 1-1000mPa.s and each molecule have at least two organic radical hydrogen polysiloxanes with the silicon bonded hydrogen atom 25 ℃ of following viscosity; Wherein the organic group with the silicon bonding is alkyl or the phenyl with 1-8 carbon atom, and it is 0.8: 1 to 5: 1 the mol ratio of alkenyl with silicon bonded hydrogen atom and component (A) and (B) in this organic radical hydrogen polysiloxanes that its consumption is enough to provide numerical value; (D) hydrosilylation reaction catalyst of catalytic amount.{ 2} is according to { organopolysiloxane composition of the solvent-free formation solidified anti-stick coating of 1} is characterized in that, component (A) is the organopolysiloxane that has branched structure and represent with following average siloxane unit formula (2): (R aR 2SiO 1/2) 4(R 2SiO 2/2) m(SiO 4/2) (2) (R wherein aBe to be selected from the alkyl with 1-8 carbon atom, have the alkenyl of 2-8 carbon atom, phenyl has the alkoxyl group of 1-8 carbon atom and the group of hydroxyl; R is selected from the alkyl with 1-8 carbon atom, has the alkenyl of 2-8 carbon atom, and phenyl groups; At this intramolecularly R aWith at least 3 of R be alkenyl with 2-8 carbon atom; At this intramolecularly R aWith at least 50% of R sum be alkyl with 1-8 carbon atom; And m=15-995).{ 3} is according to { organopolysiloxane composition of the solvent-free formation solidified anti-stick coating of 2} is characterized in that, component (A) is the organopolysiloxane that has branched structure and represent with following average siloxane unit formula (3): [(R bR c 2SiO 1/2) n(R dR c 2SiO 1/2) 1-n] 4(R bR cSiO 2/2) M1(R c 2SiO 2/2) M2(SiO 4/2) (3) (R wherein bIt is alkenyl with 2-8 carbon atom; R cBe alkyl or phenyl with 1-8 carbon atom; R dBe to be selected from alkyl, have the alkoxyl group of 1-8 carbon atom and the group of hydroxyl with 1-8 carbon atom; At this molecular memory at least three R bAt this intramolecularly, R b, R cAnd R dAt least 50% of sum is the alkyl with 1-8 carbon atom; N is 0 or 1; M1 is that numerical value is at least 0 number; M2 is that numerical value is at least 1 number; And m1+m2=15-995).{ 4} is according to { organopolysiloxane composition of the solvent-free formation solidified anti-stick coating of 2} is characterized in that, in average siloxane unit formula (2), R is a methyl, and R aIt is vinyl; In average structure formula (1), R aBe vinyl, methyl or hydroxyl, R bBe vinyl, and R cIt is methyl; With the alkyl in component (C) be methyl.The 5} basis organopolysiloxane composition of the solvent-free formation solidified anti-stick coating of 3} is characterized in that, and in average siloxane unit formula (3), R bBe vinyl, R cBe methyl, and n=1; In average structure formula (1), R aBe vinyl, methyl or hydroxyl, R bBe vinyl, and R cIt is methyl; Alkyl is a methyl in component (C).{ 6} is according to { any one the organopolysiloxane composition of solvent-free formation solidified anti-stick coating of 1}-{3} is characterized in that the said composition viscosity under 25 ℃ as a whole is 50-2000mPa.s.{ 6-1} is according to { 4} or { organopolysiloxane composition of the solvent-free formation solidified anti-stick coating of 5} is characterized in that, the said composition viscosity under 25 ℃ as a whole is 50-2000mPa.s.{ 7} is according to { any one the organopolysiloxane composition of solvent-free formation solidified anti-stick coating of 1}-{3}; It is characterized in that; Suppressor factor and it that comprises 0.001-5 weight part (E) hydrosilylation reactions is not in addition solidified at ambient temperature but is solidified applying under the heat.{ 7-1} is according to { the organopolysiloxane composition of the solvent-free formation solidified anti-stick coating of 6}; It is characterized in that; Suppressor factor and it that comprises 0.001-5 weight part (E) hydrosilylation reactions is not in addition solidified at ambient temperature but is solidified applying under the heat.
{ the basis of 8} through cured film form in the substrate of the sheet-form { substrate of the sheet-form that has the solidified anti-stick coating that any one the organopolysiloxane composition of solvent-free formation solidified anti-stick coating of 1}-{7} obtains.{ 8-1} is through the basis { substrate of the sheet-form that has the solidified anti-stick coating that the organopolysiloxane composition of the solvent-free formation solidified anti-stick coating of 7-1} obtains of cured film form in the substrate of sheet-form.{ 9} is according to { 8} or { substrate of the sheet-form that has the solidified anti-stick coating of 8-1}, the substrate that it is characterized in that sheet-form are the paper of zellglas, clay coated, paper, thermoplastic resin film or the tinsel of laminated polyolefin.
The organopolysiloxane composition of the solvent-free formation solidified of the present invention anti-stick coating forms coating when solidifying in the substrate at sheet-form; Said coating demonstrates good adhesivity and has good residual binding property the substrate of sheet-form, and viscous substance is also demonstrated improved stripping performance and has improved sliding.The substrate that has the sheet-form of solidified anti-stick coating of the present invention demonstrates good adhesivity and has good residual binding property substrate, and viscous substance is also demonstrated improved stripping performance and has improved sliding.
The optimal mode of embodiment of the present invention
The organopolysiloxane composition of the solvent-free formation solidified of the present invention anti-stick coating is characterised in that and comprises: (A) 100 weight parts have branched structure and are 10-1 25 ℃ of following viscosity; 000mPa.s; The siloxane unit (i)-(iii) that comprises the following stated; Contain a plurality of siloxane units linear fraction (ii) with having, and the organopolysiloxane fluid that contains the branch point of siloxane unit (i), the end of wherein said linear fraction with siloxane unit (iii) end-blocking (i) use chemical formula SiO 4/2The siloxane unit of expression: one or more (ii) use general formula R 2SiO 2/2The siloxane unit of expression: 15-995 (iii) uses general formula R aR 2SiO 1/2The siloxane unit of expression (in these general formulas, R aBe to be selected from alkyl, have the alkenyl of 2-8 carbon atom, phenyl with 1-8 carbon atom; Have the alkoxyl group of 1-8 carbon atom and the group and the R of hydroxyl and be selected from alkyl with 1-8 carbon atom; Alkenyl with 2-8 carbon atom, and phenyl groups, wherein intramolecularly R aWith among the R at least three is to have the alkenyl of 2-8 carbon atom and at this intramolecularly R aWith at least 50% of R sum be alkyl with 1-8 carbon atom); (B) the 0.5-15 weight part is at least 100, the diorganopolysiloxaneand of 000mPa.s: R with average structure formula (1) expression and 25 ℃ of following viscosity aR c 2SiO (R bR cSiO 2/2) N1(R c 2SiO 2/2) N2SiR c 2R a(1) (R wherein aBe to be selected from the alkyl with 1-8 carbon atom, have the alkenyl of 2-8 carbon atom, phenyl has the alkoxyl group of 1-8 carbon atom and the group of hydroxyl; R bIt is alkenyl with 2-8 carbon atom; R cBe alkyl or phenyl with 1-8 carbon atom; At this intramolecularly R a, R bAnd R cThe 0-0.1% of sum is the alkenyl with 2-8 carbon atom; At this intramolecularly R a, R bAnd R cAt least 50% of sum is the alkyl with 1-8 carbon atom; N1 is that numerical value is at least 0 number; N2 is that numerical value is at least 1 number; Provide this component with n1+n2 and be at least 100 25 ℃ of following viscosity, the number of 000mPa.s); (C) be that 1-1000mPa.s and each molecule have at least two organic radical hydrogen polysiloxanes with the silicon bonded hydrogen atom 25 ℃ of following viscosity; Wherein the organic group with the silicon bonding is alkyl or the phenyl with 1-8 carbon atom, and it is 0.8: 1 to 5: 1 the mol ratio of alkenyl with silicon bonded hydrogen atom and component (A) and (B) in this organic radical hydrogen polysiloxanes that its consumption is enough to provide numerical value; (D) hydrosilylation reaction catalyst of catalytic amount.
Component (A) is to have branched structure and is 10-1 25 ℃ of following viscosity; 000mPa.s; The siloxane unit (i)-(iii) that comprises the following stated; Contain a plurality of siloxane units linear fraction (ii) with having, and the organopolysiloxane fluid that contains the branch point of siloxane unit (i), the end of wherein said linear fraction with siloxane unit (iii) end-blocking (i) use chemical formula SiO 4/2The siloxane unit of expression: one or more (ii) use general formula R 2SiO 2/2The siloxane unit of expression: 15-995 (iii) uses general formula R aR 2SiO 1/2The siloxane unit of expression (in these general formulas, R aBe to be selected from alkyl, have the alkenyl of 2-8 carbon atom, phenyl with 1-8 carbon atom; Have the alkoxyl group of 1-8 carbon atom and the group and the R of hydroxyl and be selected from alkyl with 1-8 carbon atom; Alkenyl with 2-8 carbon atom, and phenyl groups, wherein intramolecularly R aWith among the R at least three is to have the alkenyl of 2-8 carbon atom and at this intramolecularly R aWith at least 50% of R sum be alkyl with 1-8 carbon atom).In this manual, use chemical formula SiO 4/2The siloxane unit (i) of expression is abbreviated as the Q unit in some cases; Use general formula R 2SiO 2/2The siloxane unit of expression (ii) is abbreviated as the D unit in some cases; With use general formula R aR 2SiO 1/2The siloxane unit of expression (iii) is abbreviated as the M unit under the certain situation.
Containing useful chemical formula SiO 4/2In the component (A) of a siloxane unit (i) of expression, SiO 4/2Serve as branch point and contain and use general formula R 2SiO 2/2The siloxane unit straight chain (ii) of expression therefrom extends and uses general formula R in 4 directions aR 2SiO 1/2The siloxane unit of expression (iii) is bonded on the end group of these straight chains.Therefore, in component (A), use general formula R aR 2SiO 1/2The siloxane unit quantity (iii) of expression equals the quantity of straight chain.Organopolysiloxane with this branched structure can be used following average siloxane unit formula (4) expression: [(R aR 2SiO 1/2) (R 2SiO 2/2) M/4] 4(SiO 4/2) (4)
In fact, because R aR 2SiO 1/2The unit is bonded directly to SiO 4/2On the unit, therefore, also can mix wherein to contain and use general formula R 2SiO 2/2The molecule that the siloxane unit that shows polymer chain (ii) only perhaps extends on both direction on three directions.Organopolysiloxane with this branched structure can be used following average siloxane unit formula (2) expression.(R aR 2SiO 1/2) 4(R 2SiO 2/2) m(SiO 4/2) (2) use chemical formula SiO 4/2The quantity of the siloxane unit (i) of expression is one or more.For example, be at most that 4 quantity is possible, but consider, be preferably 1 from the characteristic angle of organopolysiloxane.
In aforementioned formula, R aBe to be selected from the alkyl with 1-8 carbon atom, have the alkenyl of 2-8 carbon atom, phenyl has the alkoxyl group of 1-8 carbon atom and the group of hydroxyl; With R is to be selected from the alkyl with 1-8 carbon atom, has the alkenyl of 2-8 carbon atom and the group in the phenyl; Wherein at this intramolecularly R aWith at least 3 of R be alkenyl with 2-8 carbon atom; At this intramolecularly R aWith at least 50% of R sum be alkyl with 1-8 carbon atom; And m=15-995.In aforementioned formula (4) or aforementioned formula (2), each R aCan be identical or different and at same intramolecularly, each R can be identical or different.
Representative instance with this alkyl of 1-8 carbon atom is methyl, ethyl, propyl group etc., wherein preferable methyl.Representative instance with alkenyl of 2-8 carbon atom is vinyl, allyl group, hexenyl etc., wherein preferred vinyl.Alkoxyl group with 1-8 carbon atom can be methoxyl group, oxyethyl group etc.R aR 2SiO 1/2Vi (Me can give an example in the unit 2) SiO 1/2Unit, He (Me) 2SiO 1/2Unit, (Me) 3SiO 1/2Unit, ViMePhSiO 1/2Unit and (HO) (Me) 2SiO 1/2(wherein Vi representes vinyl, and He representes hexenyl, and Me representes that methyl and Ph represent phenyl in the unit; This also can be applicable to hereinafter).At same intramolecularly, these unit (Vi (Me for example 2) SiO 1/2The unit with (Me) 3SiO 1/2The unit) combination also is possible.R 2SiO 2/2(Me) can give an example in the unit 2SiO 2/2Unit, ViMeSiO 2/2Unit and MePhSiO 2/2The unit.At same intramolecularly, these unit (for example (Me) 2SiO 2/2Unit and ViMeSiO 2/2The unit) combination also is possible.In order to realize the adhesivity good to the substrate of sheet-form, in average siloxane unit formula (4) and average siloxane unit formula (2), R aR 2SiO 1/2The unit preferably contains the alkenyl with 2-8 carbon atom, for example Vi (Me) 2SiO 1/2Unit, He (Me) 2SiO 1/2Unit and ViMePhSiO 1/2The unit.
The more particularly available following average siloxane unit formula of this organopolysiloxane (5) expression with branched structure: [(R bR c 2SiO 1/2) n(R dR c 2SiO 1/2) 1-n(R bR cSiO 2/2) M1/4(R c 2SiO 2/2) M2/4] 4(SiO 4/2) (5) and represent with following average siloxane unit formula (3) in addition: [(R bR c 2SiO 1/2) n(R dR c 2SiO 1/2) 1-n] 4(R bR cSiO 2/2) M1(R c 2SiO 2/2) M2(SiO 4/2) (3) in aforementioned formula, R bIt is alkenyl with 2-8 carbon atom; R cBe alkyl or phenyl with 1-8 carbon atom; R dBe to be selected from alkyl, have the alkoxyl group of 1-8 carbon atom and the group of hydroxyl with 1-8 carbon atom; At this molecular memory at least three R bAt this intramolecularly, R b, R cAnd R dAt least 50% of sum is the alkyl with 1-8 carbon atom; N is 0 or 1; M1 is that numerical value is at least 0 number; M2 is that numerical value is at least 1 number; And m1+m2=15-995.In aforementioned formula (5) or aforementioned formula (3), at same intramolecularly, each R bCan be identical or different, each R cCan identical or different and each R dCan be identical or different.(R bR cSiO 2/2) unit and (R c 2SiO 2/2) unitary order chooses wantonly, but be that numerical value is under the situation more than or equal to 1 number at m1, normally random in aforementioned formula (5) or aforementioned formula (3).
Here, the representative instance with alkyl of 1-8 carbon atom is methyl, ethyl, propyl group etc., wherein preferable methyl.Representative instance with alkenyl of 2-8 carbon atom is vinyl, allyl group, hexenyl etc., wherein preferred vinyl.Alkoxyl group with 1-8 carbon atom can be methoxyl group, oxyethyl group etc.R bR c 2SiO 1/2Vi (Me) can give an example in the unit 2SiO 1/2Unit, He (Me) 2SiO 1/2Unit and ViMePhSiO 1/2The unit.R dR c 2SiO 1/2(Me) can give an example in the unit 3SiO 1/2Unit, (Me) 2PhSiO 1/2Unit, (HO) are (Me) 2SiO 1/2Unit and (MeO) (Me) 2SiO 1/2The unit.At same intramolecularly, these unit (Vi (Me for example 2) SiO 1/2The unit with (Me) 3SiO 1/2The unit) combination is possible.R bR cSiO 2/2ViMeSiO can give an example in the unit 2/2The unit.R c 2SiO 2/2(Me) can give an example in the unit 2SiO 2/2Unit and MePhSiO 2/2The unit.At same intramolecularly, these unitary combinations also are possible.
Through interior and silicon bonded hydrogen atom generation hydrosilylation reactions, crosslinked with silicon bonded alkenyl experience in component (A) with component (C).Therefore must be present in each intramolecularly by at least two alkenyls; Must be present in each intramolecularly by at least three alkenyls, so that the substrate of sheet-form is produced good adhesivity; Be present at least 4 terminal siloxane units with the preference chain thiazolinyl.Component (A) is the basal component of the organopolysiloxane composition of the solvent-free formation solidified coating of the present invention.Because it has the branched structure and the low polymerization degree, so it demonstrates and has linear chain structure and have the HV and the therefore low consistency of component (B) of high-polymerization degree.As a result, can induce component (B) effective mobility to the surface of the solidified coating that forms through hydrosilylation reactions.Because this, only mixing, minor components (B) can provide the solidified coating with good sliding.
But consider from performance perspective at the suprabasil coating of sheet-form and solidified coating, the component of being considered (A) the viscosity 25 ℃ under be 10-1000mPa.s and preferably the viscosity under 25 ℃ be 20-500mPa.s.The organopolysiloxane of representing with following average siloxane unit formula that contains branched structure is following specific examples.(1): (Vi (CH 3) 2SiO 1/2) 4(Vi (CH 3) SiO 2/2) 2((CH 3) 2SiO) 54(SiO 4/2) (2): (Vi (CH 3) 2SiO 1/2) 4(Vi (CH 3) SiO 2/2) 1.8((CH 3) 2SiO) 103(SiO 4/2) (3): (Vi (CH 3) 2SiO 1/2) 4(Vi (CH 3) SiO 2/2) 21.9((CH 3) 2SiO) 136(SiO 4/2) (4): (Vi (CH 3) 2SiO 1/2) 4(Vi (CH 3) SiO 2/2) 18.2((CH 3) 2SiO) 185(SiO 4/2) (5): (Vi (CH 3) 2SiO 1/2) 4(Vi (CH 3) SiO 2/2) 8.2((CH 3) 2SiO) 210(SiO 4/2) (6): (Vi (CH 3) 2SiO 1/2) 4(Vi (CH 3) SiO 2/2) 43.5((CH 3) 2SiO) 242(SiO 4/2) (7): (Vi (CH 3) 2SiO 1/2) 4((CH 3) 2SiO) 56(SiO 4/2) (8): (Vi (CH 3) 2SiO 1/2) 4((CH 3) 2SiO) 150(SiO 4/2) (9): (Vi (CH 3) 2SiO 1/2) 2((CH 3) 3SiO 1/2) 2(Vi (CH 3) SiO 2/2) 2((CH 3) 2SiO) 54(SiO 4/2) (10): (Vi (CH 3) 2SiO 1/2) 3((CH 3) 3SiO 1/2) ((CH 3) 2SiO) 150(SiO 4/2) a plurality of components (A) of differing from one another also can make together and be used for preparing same compsn.
The viscosity and the coefficient thereof of the organopolysiloxane that contains branched structure that table 1 is listed more than showing concerning aforementioned siloxane unit formula (3).Table 1
(4n+m1) (m1+m2) Viscosity (mPa.s)
(1) 6 56 46
(2) 5.8 104.8 122
(3) 25.9 157.9 111
(4) 22.2 203.2 235
(5) 12.2 218.2 366
(6) 47.5 285.5 375
(7) 4 56 47
(8) 4 180 160
Can produce this component (A) through referenced patent document 8 and the working method described in the referenced patent document 9.For example, can be through introducing predetermined amount [Vi (Me) 2SiO 1/2] 4SiO 4/2With the trifluoromethanesulfonic acid of octamethylcyclotetrasiloxane and/or tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and catalytic amount in reaction vessel; And in 80-90 ℃ of following stirred for several hour, then the catalyst neutralisation residue filters; And from filtrating, remove low-boiling compound, thereby carry out the production of component (A).Can analyze through introducing ratio, the NMR of initial siloxanes, measure the analysis of contents of ethylene etc., measure the average siloxane unit formula in the product.
Component (B) plays improves solidified coating to the rippability effect of viscous substance and also play the effect that the solidified coating sliding is provided; Said component (B) is to be at least 100, the diorganopolysiloxaneand of 000mPa.s: R with average structure formula (1) expression and 25 ℃ of following viscosity aR c 2SiO (R bR cSiO 2/2) N1(R c 2SiO 2/2) N2SiR c 2R a(1) (R wherein aBe to be selected from the alkyl with 1-8 carbon atom, have the alkenyl of 2-8 carbon atom, phenyl has the alkoxyl group of 1-8 carbon atom and the group of hydroxyl; R bIt is alkenyl with 2-8 carbon atom; R cBe alkyl or phenyl with 1-8 carbon atom; At this intramolecularly R a, R bAnd R cThe 0-0.1% of sum is the alkenyl with 2-8 carbon atom; At this intramolecularly R a, R bAnd R cAt least 50% of sum is the alkyl with 1-8 carbon atom; N1 is that numerical value is at least 0 number; N2 is that numerical value is at least 1 number; Provide this component with n1+n2 and be at least 100 25 ℃ of following viscosity, the number of 000mPa.s).Component (B) rises on the coating of formation when take place solidifying through component (A) and hydrosilylation reactions (C) gradually, and and then gives the surperficial good sliding of solidified coating.In aforementioned formula (1), at same intramolecularly, each R aCan be identical or different, each R bCan identical or different and each R cCan be identical or different.
Here, the representative instance with alkyl of 1-8 carbon atom is methyl, ethyl, propyl group etc., wherein preferable methyl.Representative instance with alkenyl of 2-8 carbon atom is vinyl, allyl group and hexenyl, wherein preferred vinyl.Alkoxyl group with 1-8 carbon atom can be for example methoxyl group, oxyethyl group etc.R aR c 2SiO 1/2Vi (Me) can give an example in the unit 2SiO 1/2Unit, He (Me) 2SiO 1/2Unit, ViMePhSiO 1/2Unit, (Me) 3SiO 1/2Unit, (Me) 2PhSiO 1/2Unit, (HO) are (Me) 2SiO 1/2Unit and (MeO) (Me) 2SiO 1/2The unit.R bR cSiO 2/2ViMeSiO can give an example in the unit 2/2The unit.R c 2SiO 2/2(Me) can give an example in the unit 2SiO 2/2Unit and MePhSiO 2/2The unit.At same intramolecularly, these unitary combinations are possible.
Component (B) is included in the component that intramolecularly has with the silicon bonded alkenyl and therefore can experience hydrosilylation reactions with component (C); On the terminal position of molecular chain, has the component that also therefore can experience condensation reaction with the hydroxyl (silanol group) of silicon bonding with component (C); Do not contain yet silane alcohol radical and therefore do not have reactive component not of alkenyl.Consider from the residual fusible angle relevant with solidified coating; Preferably intramolecularly have alkenyl and therefore can with the component (B) of component (C) experience hydrosilylation reactions, secondly on the terminal position of molecular chain, have with the hydroxyl (silanol group) of silicon bonding and therefore can with the component (B) of component (C) experience condensation reaction.
About have the component (B) that also therefore can experience hydrosilylation reactions with the silicon bonded alkenyl at intramolecularly with component (C); Too high alkenyl content causes stripping performance impaired; And 0 (not comprising 0)-0.1mol% that the sliding that causes solidified coating descends and therefore this content is the organic group of this intramolecularly and silicon bonding.Can be only exist with the silicon bonded alkenyl, only exist, perhaps position and exist endways simultaneously in the side chain position in the side chain position at the terminal position place of molecular chain.Component (B) containing on the terminal position of molecular chain with the hydroxyl (silanol group) of silicon bonding also can have alkenyl on the side chain position.Alkenyl content is 0 (not comprising 0)-0.1mol% of the organic group of this intramolecularly and silicon bonding.
The viscosity of component (B) under 25 ℃ is at least 100,000mPa.s, and considering from residual fusible angle, and its viscosity preferably at least 1,000,000mPa.s, and component (B) more preferably is sizing material at ambient temperature.When component (B) was the sizing material form, it had measurable degree of moulding and is evident as solid simultaneously, and when allowing its material to leave standstill, it descends highly gradually and spreads out in the zone on every side.
Component (B) can give an example particularly dimethyl polysiloxane, dimethyl siloxane Methyl Octyl silicone copolymers, dimethyl siloxane methyl ethylene silicone copolymers, dimethyl siloxane methyl hexenyl silicone copolymers, dimethyl siloxane methylphenyl siloxane multipolymer and dimethyl siloxane diphenyl siloxane multipolymer; Under each situation, have dimethylvinylsiloxy, dimethyl-allyl siloxy-, dimethyl-hexenyl siloxy-, present as dimethylhydroxysilox(, trimethylsiloxy or 3,5-dimethylphenyl siloxy-at molecular chain end group place.Also can use together and have different end group or different side chain or different end group and prepare same compsn with the ZGK 5 of different side chains.
Under each situation,, mix the component (B) of 0.5-15 weight part and preferred 1.0-8 weight part in 100 weight part aforementioned component (A).When mixing component (B) with the consumption less than aforementioned lower limit, the surface of solidified coating has insufficient sliding.When surpassing aforementioned going up in limited time, organopolysiloxane composition has too high viscosity, thereby causes the fracture in the substrate upper film coating of sheet-form.
Component (C) is to be that 1-1000mPa.s and each molecule have at least two with the silicon bonded hydrogen atom and have the alkyl or phenyl conduct of 1-8 carbon atom and the organic radical hydrogen polysiloxanes of the organic group of silicon bonding 25 ℃ of following viscosity, and it serves as the linking agent of component (A).Through in this component and in silicon bonded hydrogen atom and the component (A) and the hydrosilylation reactions between the silicon bonded alkenyl, take place crosslinked.When component (B) contains with the silicon bonded alkenyl, also participate in hydrosilylation reactions with the silicon bonded alkenyl in the component (B).As a result, each intramolecularly must exist at least two with the silicon bonded hydrogen atom and preferably each molecular memory at least three with the silicon bonded hydrogen atom.
Do not limit with the bonding position of silicon bonded hydrogen atom especially and for example they can be bonded in the terminal position, side chain position of molecular chain or in these two positions.Be preferably 0.1-20wt% and more preferably 0.5-18wt% with the content of silicon bonded hydrogen atom.
Comprise phenyl and alkyl with the organic group of silicon bonding with 1-8 carbon atom, for example methyl, ethyl, propyl group, butyl, octyl group etc., what preferably these organic groups were total at least 50% is the alkyl with 1-8 carbon atom.In the middle of these alkyl, consider preferable methyl from the angle of the easy degree of the performance of solidified coating and production.The molecular structure of component (C) give an example straight chain, side chain and ring-type.
The viscosity of component (C) under 25 ℃ is 1-1000mPa.s and preferred 5-500mPa.s.Its basis is described below: when the viscosity under 25 ℃ during less than 1mPa.s, component (C) volatilizes organopolysiloxane composition easily, and organopolysiloxane composition needs cost long set time more than 1000mPa.s.
This component (C) can give an example methylhydrogenpolysi,oxane, the dimethylsiloxane methylhydrogensiloxacopolymer copolymer of trimethylsiloxy-terminated, the end capped dimethylsiloxane methylhydrogensiloxacopolymer copolymer of dimethyl hydrogen siloxy-, ring-type methylhydrogenpolysi,oxane, ring-type methylhydrogenpolysi,oxane dimethylsiloxane copolymer, three (dimethyl hydrogen siloxy-) methyl-monosilane and four (dimethyl hydrogen siloxy-) silane of trimethylsiloxy-terminated.The a plurality of components (C) that differ from one another can make together and be used for preparing same compsn.
The incorporation of component (C) be enough to provide numerical value be 0.8: 1 to 5: 1 in component (C) with silicon bonded hydrogen atom and component (A) and (B) mol ratio of alkenyl and preferable amount to be enough to provide numerical value be this mol ratio of 0.9: 1 to 3: 1.Prescribe a time limit down less than above-described when this mol ratio, curability descends, and prescribes a time limit when surpassing described going up, and big stripper-resistance takes place, and can not get practical rippability.
Component (D) be promote in the component (C) with the silicon bonded hydrogen atom and component (A) is interior and the silicon bonded alkenyl between hydrosilylation reactions and play through component (A) and the addition reaction (C) causes crosslinked catalyzer.When component (B) when each intramolecularly contains one or more and silicon bonded alkenyl, this catalyzer also promote with component (B) in the hydrosilylation reactions of silicon bonded alkenyl.Except it is the employed catalyzer of hydrosilylation reactions; To the not special restriction of this component (D); And component (D) the platinum class catalyzer of can giving an example particularly, for example the Platinic chloride of Platinic chloride, pure modification, Platinic chloride/alkene complex, Platinic chloride/ketone complex compound, platinum/alkenyl siloxanes complex compound, Tetrachloroplatinum, platinum micro mist, be carried on carrier for example alkene complex, the platinum of the solid platinum on alumina powder or the SiO 2 powder, platinum black, platinum carbonylcomplex and mix the powder thermoplastic resin (for example methyl-methacrylate resin, polycarbonate resin, polystyrene resin, silicone resin etc.) of foregoing platinum class catalyzer.
Other instances are rhodium catalysts, for example [Rh (O 2CCH 3) 2] 2, Rh (O 2CCH 3) 3, Rh 2(C 8H 15O 2) 4, Rh (C 5H 7O 2) 3, Rh (C 5H 7O 2) (CO) 2, Rh (CO) [Ph 3P] (C 5H 7O 2), RhX 3[(R 6) 2S] 3, (R 7 3P) 2(CO) X, (R 7 3P) 2Rh (CO) H, Rh 2X 2Y 4, H aRh b(E) cCl dAnd Rh [O (CO) R 3] 3-n(OH) n(in these formulas, X is Wasserstoffatoms, chlorine atom, bromine atoms or iodine atom; Y is alkyl, CO or C 8H 14R 6Be alkyl, naphthenic base or aryl; R 7Be alkyl, aryl, alkoxyl group or aryloxy; E is an alkene; A is 0 or 1; B is 1 or 2; C is the integer of 1-4; D is 2,3 or 4; With n be 0 or 1), and iridium catalyst, for example Ir (OOCCH 3) 3, Ir (C 5H 7O 2) 3, [Ir (Z) (E) 2] 2[Ir (Z) (Dien)] 2(in these formulas, Z is chlorine atom, bromine atoms, iodine atom or alkoxyl group; E is that alkene and Dien are cyclooctadiene).
Consider from the ability angle of accelerated reaction; The alkene complex of preferred Platinic chloride, platinum/vinylsiloxane complex compound and platinum; Especially preferred Platinic chloride/divinyl tetramethyl disiloxane complex compound, Platinic chloride/tetramethyl-tetrem thiazolinyl cyclotetrasiloxane complex compound and platinum/alkenyl siloxanes complex compound, for example divinyl tetramethyl disiloxane platinum complex, platinum/tetramethyl-tetrem thiazolinyl cyclotetrasiloxane complex compound etc.
Under each situation; Gross weight with the organopolysiloxane composition of the solvent-free formation solidified of the present invention anti-stick coating is a benchmark, in the amount of metal in the component (D), the component (D) of mixing catalytic amount; Usually mix 1-1000ppm and preferably mix 5-500ppm component (D).
Except foregoing component; The organopolysiloxane composition of the solvent-free formation solidified of the present invention anti-stick coating preferably also contains hydrosilylation reactions suppressor factor (E); So that make its thermofixation, through suppressing gelling at ambient temperature and curing, improve stability in storage simultaneously.This hydrosilylation reactions suppressor factor acetylene compound of can giving an example; Alkene-alkine compounds, organic nitrogen compound, organo phosphorous compounds; And oxime compound; And the alkynol of can giving an example particularly, 3-methyl isophthalic acid-butine-3-alcohol, 3 for example, 5-dimethyl--1-hexin-3-alcohol, 3-methyl-1-pentene alkynes-3 alcohol, phenyl butynol etc.; With 3-methyl-pirylene, 3,5-dimethyl--1-hexin-3-alkene, benzotriazole, 1-ethynyl-1-hexalin and methyl ethylene cyclosiloxane.Under each situation; In 100 parts by weight of component (A); The incorporation of hydrosilylation reactions suppressor factor usually in 0.001-5 weight part scope and preferably in 0.01-2 weight part scope, and can be optionally according to the performance and the consumption of the type of hydrosilylation reactions suppressor factor, the hydrosilylation reaction catalyst of mixing; The consumption of the interior alkenyl of component (A), and select with the consumption of silicon bonded hydrogen atom in the component (C).
Compsn of the present invention comprises component (A)-(D) and other component (E) on optional basis, but also can mix the organopolysiloxane resins of vinyl functional, so that reduce the peeling force of solidified coating with respect to viscous substance.Also can mix thickening material, fine silica powder for example is so that increase the viscosity of coating fluid.Also can mix known additives, for example thermo-stabilizer, dyestuff, pigment etc., only otherwise infringement the object of the invention and effect get final product.But the coating that is based on compsn in the substrate of sheet-form considers that the preferred as a whole range of viscosities under 25 ℃ of compsn of the present invention is 50-2000mPa.s.
Can pass through to mix aforementioned component (A)-(D) or aforementioned component (A)-(E) or these components and any other optional component to even, thereby prepare compsn of the present invention.Mix not special qualification of order of each component, yet when after mixing, not using compsn immediately, component (A), (B) and mixture (C) are independent of preferably that component (D) stores and preferably just mix before this two in use.Under the situation of the compsn that contains component (A)-(E), the compsn that also preferred type and the incorporation of regulating component (E) through selecting component (E) obtains does not experience crosslinked at ambient temperature, and the crosslinked and curing of experience when applying heat.
Can through the substrate of any various sheet-forms for example paper and especially the Vilaterm lamination of paper, the laminated polyolefin of zellglas, cardboard, clay coated paper, thermoplastic resin film (for example; Polyester film, polyethylene film, polypropylene screen, PA membrane), natural fabric, synthetic fabrics, tinsel (for example; Aluminium foil) etc. be coated with the organopolysiloxane composition of the solvent-free formation solidified of above-described the present invention anti-stick coating on the surface equably; Be suitable for causing component (A) and (C) or component (A), (B) and (C) heat under the crosslinked condition of experience through hydrosilylation reactions, on the substrate surface of sheet-form, form the solidified coating that demonstrates good sliding and suitable antistripping value with respect to viscous substance.
Usually; Solidification value for the organopolysiloxane composition of the solvent-free formation solidified of the present invention anti-stick coating in the substrate of sheet-form; 50-200 ℃ is suitable, but when substrate has good thermotolerance, can use the solidification value more than 200 ℃.Do not limit heating means especially and can give an example, pass long baking oven, perhaps use ir lamp or halogen lamp irradiated heat at hot air circulate baking oven internal heating.Also can be exposed under the ultraviolet radiation, be cured through using heating combined.When component (D) is platinum/alkenyl siloxanes complex compound catalyst; Even the total amount of working as with compsn is a benchmark; In the consumption of platinum, when this catalyzer mixes with the consumption of 50-200ppm, can be under 100-150 ℃; In the short time period, promptly 40-1 obtains easily in second that substrate to sheet-form demonstrates good adhesivity and demonstrates the solidified coating of good stripping performance with respect to viscous substance.
To the not special restriction of the employed coating machine of organopolysiloxane composition that on the surface of the substrate of sheet-form, applies the solvent-free formation solidified of the present invention anti-stick coating, roller coating machine is shifted in can give an example roller coating machine, photogravure coating machine, air coating machine, curtain stream coating machine and offset printing of coating machine.About viscous substance, said viscous substance can be applied to through applying on the substrate surface of sheet-form and solidifying on the releasing sheet or film that the organopolysiloxane composition of the solvent-free formation solidified of the present invention anti-stick coating obtains, and this viscous substance can be for example any various pressure sensitive adhesives and various tackiness agent; The example is the acrylics pressure sensitive adhesive; The pressure sensitive adhesive of the pressure sensitive adhesive of rubber type and siloxanes type, and propylene resin tackiness agent; The pressure sensitive adhesive of viton type; The tackiness agent of siloxanes type, the tackiness agent of the tackiness agent of epoxy resin type and urethane type.Other instances are pitch, viscous food product for example Herba Gonostegiae Hirtae (i.e. rice cake), glue and paste and bird lime.
Compsn of the present invention can be used for forming solidified coating; Said solidified coating demonstrates good surperficial sliding and good stripping performance to viscous substance and the reagent of the formation solidified anti-stick coating that especially is very suitable for using as technology paper, asphalt packages paper and various plastic film.In addition, the substrate that has a sheet-form through solidifying the anti-stick coating that compsn of the present invention forms is very suitable for especially using being used for technology paper, parcel or the packing paper of viscous substance be clamminess material, pressure sensitive adhesive tape, pressure sensitive adhesive label etc.
Embodiment
Below provide embodiment and Comparative Examples, so that describe the present invention particularly; Yet the present invention is unlimited on the embodiment subsequently.In embodiment and Comparative Examples subsequently, part is that weight part and ppm represent ppm by weight in all cases in all cases.Method through the following stated under 25 ℃ is measured viscosity and degree of moulding.In addition; Through using the method for the following stated; Measure down dynamic friction coefficients and antistripping values at 25 ℃ respectively, the solidified coating that evaluation is obtained by the solvent-free organopolysiloxane composition that forms the solidified anti-stick coating is to the sliding and the stripping performance of viscous substance.
Viscosity uses the digital viscometer that shows (available from Shibaura Systems Co. with degree of moulding; Ltd. Vismetron model VDA2); Under the rotary speed of rotator of 30rpm; Adopt the #2 rotor of installing, 25 ℃ of viscosity of measuring the organopolysiloxane composition of organopolysiloxane and solvent-free formation solidified anti-stick coating down.According to JIS K 6249:2003, the Section 8 (plasticity testing) of " Test Method for uncured and curedsilicone rubber " uses parallel plate degree of moulding device, measures the degree of moulding of organopolysiloxane sizing material.
The antistripping value is used printable tester (available from Akira Seisakusho Co., the model RI-2 of Ltd.), on the surface of the paper of Vilaterm lamination or zellglas so that 1.0g/m to be provided 2The consumption of (in siloxanes) is coated with the organopolysiloxane composition of solvent-free formation solidified anti-stick coating, then in the hot air circulate baking oven, heats 30 seconds down at 120 ℃, forms solidified coating.Use applicator, on this solidified coating at 30g/m 2Under (in solid) equably coating solvent base acrylic pressure-sensitive adhesive (trade(brand)name: Oribain BPS-5127, available from ToyoInk Mfg.Co., Ltd.), and under 70 ℃, heated 2 minutes.On this acrylic pressure-sensitive adhesive, paste fine papers (weight=64g/m then 2), and cut the width that gained paper laminate body becomes 5cm, obtain sample.In air, kept this sample 20 hours under the temperature of the humidity 60% and 25 ℃.Then, use tester for elongation, in the opposite direction, under the peeling rate of 0.3m/min,, and measure the desired power (N) of peeling off with the angle tractive fine papers of 180 degree and the paper or the zellglas of Vilaterm lamination.The paper laminate body that obtains as stated through cutting then becomes the width of 2.5cm, the preparation sample, and under above-described condition, peel off the measurement of desired power (N), different is that peeling rate is 100m/min.
Dynamic friction coefficient uses and the identical condition of above-described measurement antistripping value, forms two solidified coatings.These solidified coatings that superpose then, its mode makes the solidified coating side contact with each other, and then uses at a high speed and peels off tester, the condition tractive of working load=200g and draw rate=5m/min, and the measurement desired power of tractive (g).The dynamic friction coefficient of the desired power of tractive/200 (g) expression solidified coating.
Residual binding property is adhered to Lumilar 31B polyester tape (product of Nitto Denko Corporation) on the surface of solidified coating of sample, then at the 20g/cm that is applied 2Load under, 70 ℃ aging 20 hours down.Peel off adhesive tape afterwards, and stick on the stainless steel sample.Then,, under the angle of 180 degree, under the peeling rate of 300mm/min, peel off this adhesive tape, and measure the desired power (g) of peeling off with respect to the surface of stainless steel sample.In addition, on polytetrafluoroethylsheet sheet, paste Lumilar 31B polyester tape (product of Nitto Denko Corporation) similarly, then at the 20g/cm that is applied 2Load under, 70 ℃ aging 20 hours down.Peel off adhesive tape afterwards, and stick on the stainless steel sample.Then,, under the angle of 180 degree, under the peeling rate of 300mm/min, peel off this adhesive tape, and measure the desired power (g) of peeling off with respect to the surface of stainless steel sample.Be used in the numerical value pasted on the polytetrafluoroethylsheet sheet as 100, will work as adhesive tape when having sticked on the surface of solidified coating desired power represent with percentage ratio and this percentage ratio is represented residual bounding force.
In an embodiment, the methylvinyl-polysiloxane that contains branched structure shown in the average siloxane unit formula is as component (A) below.Vi representes vinyl.(1)：(Vi(CH 3) 2SiO 1/2) 4(Vi(CH 3)SiO 2/2) 2((CH 3) 2SiO) 54(SiO 4/2)(2)：(Vi(CH 3) 2SiO 1/2) 4(Vi(CH 3)SiO 2/2) 1.8((CH 3) 2SiO) 103(SiO 4/2)(3)：(Vi(CH 3) 2SiO 1/2) 4(Vi(CH 3)SiO 2/2) 21.9((CH 3) 2SiO) 136(SiO 4/2)(4)：(Vi(CH 3) 2SiO 1/2) 4(Vi(CH 3)SiO 2/2) 18.2((CH 3) 2SiO) 185(SiO 4/2)(5)：(Vi(CH 3) 2SiO 1/2) 4(Vi(CH 3)SiO 2/2) 8.2((CH 3) 2SiO) 210(SiO 4/2)(6)：(Vi(CH 3) 2SiO 1/2) 4(Vi(CH 3)SiO 2/2) 43.5((CH 3) 2SiO) 242(SiO 4/2)(7)：(Vi(CH 3) 2SiO 1/2) 4((CH 3) 2SiO) 56(SiO 4/2)(8)：(Vi(CH 3) 2SiO 1/2) 4((CH 3) 2SiO) 150(SiO 4/2)
Synthetic example 1 synthetic (1): (Vi (CH 3) 2SiO 1/2) 4(Vi (CH 3) SiO 2/2) 2((CH 3) 2SiO) 54(SiO 4/2) with [Vi (CH 3) 2SiO 1/2] 4SiO 4/2(21.6g), tetramethyl-tetrem thiazolinyl cyclotetrasiloxane (8.60g), octamethylcyclotetrasiloxane (200g) and trifluoromethanesulfonic acid (1.2g) are incorporated in the reaction vessel, and under 80-90 ℃ temperature, stirred 6 hours.Cool off the gained reaction mixture then to room temperature.Calcium carbonate powders (1.0g) is joined in the refrigerative reaction mixture, then stirred 3 hours and filtered.Under the pressure of 40mbar (4000Pa) and about 150 ℃ temperature, stripping filtrating 2 hours.The viscosity of the residue behind the stripping is that 46mPa.s and its contents of ethylene are 3.5wt%.
Synthetic example 2 synthetic (2): (Vi (CH 3) 2SiO 1/2) 4(Vi (CH 3) SiO 2/2) 1.8((CH 3) 2SiO) 103(SiO 4/2) with [Vi (CH 3) 2SiO 1/2] 4SiO 4/2(21.6g), tetramethyl-tetrem thiazolinyl cyclotetrasiloxane (7.74g), octamethylcyclotetrasiloxane (381g) and trifluoromethanesulfonic acid (1.2g) are incorporated in the reaction vessel, and under 80-90 ℃ temperature, stirred 6 hours.Cool off the gained reaction mixture then to room temperature.Calcium carbonate powders (1.0g) is joined in the refrigerative reaction mixture, then stirred 3 hours and filtered.Under the pressure of 40mbar (4000Pa) and about 150 ℃ temperature, stripping filtrating 2 hours.The viscosity of the residue behind the stripping is that 122mPa.s and its contents of ethylene are 1.9wt%.
Synthetic example 3 synthetic (3): (Vi (CH 3) 2SiO 1/2) 4(Vi (CH 3) SiO 2/2) 21.9((CH 3) 2SiO) 136(SiO 4/2) with [Vi (CH 3) 2SiO 1/2] 4SiO 4/2(21.6g), tetramethyl-tetrem thiazolinyl cyclotetrasiloxane (94.2g), octamethylcyclotetrasiloxane (503g) and trifluoromethanesulfonic acid (1.2g) are incorporated in the reaction vessel, and under 80-90 ℃ temperature, stirred 6 hours.Cool off the gained reaction mixture then to room temperature.Calcium carbonate powders (1.0g) is joined in the refrigerative reaction mixture, then stirred 3 hours and filtered.Under the pressure of 40mbar (4000Pa) and about 150 ℃ temperature, stripping filtrating 2 hours.The viscosity of the residue behind the stripping is that 111mPa.s and its contents of ethylene are 5.6wt%.
Synthetic example 4 synthetic (4): (Vi (CH 3) 2SiO 1/2) 4(Vi (CH 3) SiO 2/2) 18.2((CH 3) 2SiO) 185(SiO 4/2) with [Vi (CH 3) 2SiO 1/2] 4SiO 4/2(21.6g), tetramethyl-tetrem thiazolinyl cyclotetrasiloxane (78.3g), octamethylcyclotetrasiloxane (685g) and trifluoromethanesulfonic acid (1.2g) are incorporated in the reaction vessel, and under 80-90 ℃ temperature, stirred 6 hours.Cool off the gained reaction mixture then to room temperature.Calcium carbonate powders (1.0g) is joined in the refrigerative reaction mixture, then stirred 3 hours and filtered.Under the pressure of 40mbar (4000Pa) and about 150 ℃ temperature, stripping filtrating 2 hours.The viscosity of the residue behind the stripping is that 235mPa.s and its contents of ethylene are 3.8wt%.
Synthetic example 5 synthetic (5): (Vi (CH 3) 2SiO 1/2) 4(Vi (CH 3) SiO 2/2) 8.2((CH 3) 2SiO) 210(SiO 4/2) with [Vi (CH 3) 2SiO 1/2] 4SiO 4/2(21.6g), tetramethyl-tetrem thiazolinyl cyclotetrasiloxane (35.3g), octamethylcyclotetrasiloxane (777g) and trifluoromethanesulfonic acid (1.2g) are incorporated in the reaction vessel, and under 80-90 ℃ temperature, stirred 6 hours.Cool off the gained reaction mixture then to room temperature.Calcium carbonate powders (1.0g) is joined in the refrigerative reaction mixture, then stirred 3 hours and filtered.Under the pressure of 40mbar (4000Pa) and about 150 ℃ temperature, stripping filtrating 2 hours.The viscosity of the residue behind the stripping is that 366mPa.s and its contents of ethylene are 2.0wt%.
Synthetic example 6 synthetic (6): (Vi (CH 3) 2SiO 1/2) 4(Vi (CH 3) SiO 2/2) 43.5((CH 3) 2SiO) 242(SiO 4/2) with [Vi (CH 3) 2SiO 1/2] 4SiO 4/2(21.6g), tetramethyl-tetrem thiazolinyl cyclotetrasiloxane (187g), octamethylcyclotetrasiloxane (895g) and trifluoromethanesulfonic acid (1.2g) are incorporated in the reaction vessel, and under 80-90 ℃ temperature, stirred 6 hours.Cool off the gained reaction mixture then to room temperature.Calcium carbonate powders (1.0g) is joined in the refrigerative reaction mixture, then stirred 3 hours and filtered.Under the pressure of 40mbar (4000Pa) and about 150 ℃ temperature, stripping filtrating 2 hours.The viscosity of the residue behind the stripping is that 375mPa.s and its contents of ethylene are 5.8wt%.
Synthetic example 7 synthetic (7): (Vi (CH 3) 2SiO 1/2) 4((CH 3) 2SiO) 56(SiO 4/2) with [Vi (CH 3) 2SiO 1/2] 4SiO 4/2(21.6g), octamethylcyclotetrasiloxane (207g) and trifluoromethanesulfonic acid (1.2g) are incorporated in the reaction vessel, and under 80-90 ℃ temperature, stirred 6 hours.Cool off the gained reaction mixture then to room temperature.Calcium carbonate powders (1.0g) is joined in the refrigerative reaction mixture, then stirred 3 hours and filtered.Under the pressure of 40mbar (4000Pa) and about 150 ℃ temperature, stripping filtrating 2 hours.The viscosity of the residue behind the stripping is that 47mPa.s and its contents of ethylene are 2.4wt%.
Synthetic example 8 synthetic (8): (Vi (CH 3) 2SiO 1/2) 4((CH 3) 2SiO) 150(SiO 4/2) with [Vi (CH 3) 2SiO 1/2] 4SiO 4/2(21.6g), octamethylcyclotetrasiloxane (555g) and trifluoromethanesulfonic acid (1.2g) are incorporated in the reaction vessel, and under 80-90 ℃ temperature, stirred 6 hours.Cool off the gained reaction mixture then to room temperature.Calcium carbonate powders (1.0g) is joined in the refrigerative reaction mixture, then stirred 3 hours and filtered.Under the pressure of 40mbar (4000Pa) and about 150 ℃ temperature, stripping filtrating 2 hours.The viscosity of the residue behind the stripping is that 160mPa.s and its contents of ethylene are 0.90wt%.
Embodiment 1 mix 100 parts (A) with more than the methylvinyl-polysiloxane that contains branched structure shown in the average siloxane unit formula (1) that provides (dimethyl polysiloxane sizing material (contents of ethylene=0.02wt%, 7.4 * 10 of dimethylvinylsiloxy-terminated are all used at viscosity=46mPa.s), 3.0 parts of (B) molecule two ends -4Mol%; Degree of moulding=140); 6.6 the methylhydrogenpolysi,oxane of part (C) capped at both thmolecular terminals with trimethylsiloxy groups (viscosity=25mPa.s, with the hydrogen richness of silicon bonding=1.6wt%) (with mol ratio=1.3 of silicon bonded hydrogen atom/vinyl) and 0.30 part of (E) 1-ethynyl-1-hexalin to even.In this mixture, mix (D) Platinic chloride 1; 3-divinyl-1; 1,3, and 3-tetramethyl disiloxane complex compound (platinum content=0.60wt%); Its consumption is enough to obtain the 100ppm platinum, thereby obtains the organopolysiloxane composition (viscosity=90mPa.s) of solvent-free formation solidified anti-stick coating.On the solidified coating that obtains through this organopolysiloxane composition on the paper that is solidificated in the Vilaterm lamination, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.
The methylvinyl-polysiloxane that contains branched structure shown in the average siloxane unit formula (2) that embodiment 2-7 mixing 100 parts (A) provides more than using, (3), (4), (5), (6) or (7), dimethyl polysiloxane sizing material (contents of ethylene=0.02wt%, 7.4 * 10 that dimethylvinylsiloxy-terminated is all used at 3.0 parts of (B) molecule two ends -4Mol%; Degree of moulding=140); (C) methylhydrogenpolysi,oxane (viscosity=25mPa.s of capped at both thmolecular terminals with trimethylsiloxy groups; With the hydrogen richness of silicon bonding=1.6wt%) (mol ratio that its umber is enough to obtain with silicon bonded hydrogen atom/vinyl is 1.3) and 0.30 part of (E) 1-ethynyl-1-hexalin to evenly.In this mixture, mix (D) Platinic chloride 1; 3-divinyl-1; 1,3, and 3-tetramethyl disiloxane complex compound (platinum content=0.60wt%); Its consumption is enough to obtain the 100ppm platinum, thereby obtains the organopolysiloxane composition of viscosity solvent-free formation solidified anti-stick coating as shown in table 2.On the solidified coating that obtains through these organopolysiloxane compositions on the paper that is solidificated in the Vilaterm lamination, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.
Embodiment 8 measures under the condition identical with embodiment 7, but under this situation, uses zellglas as the substrate of sheet-form rather than the paper of Vilaterm lamination; These results have been shown in the table 4.Table 2
Figure G2007800482229D00251
Embodiment 9 mix 100 parts (A) with more than (the dimethyl polysiloxane sizing material (degree of moulding=140) of viscosity=46mPa.s), 3.0 parts of (B) capped at both thmolecular terminals with trimethylsiloxy groups of the methylvinyl-polysiloxane that contains branched structure shown in the average siloxane unit formula (1) that provides; 6.6 the methylhydrogenpolysi,oxane of part (C) capped at both thmolecular terminals with trimethylsiloxy groups (viscosity=25mPa.s, with the hydrogen richness of silicon bonding=1.6wt%) and 0.30 part of (E) 1-ethynyl-1-hexalin to evenly.In this mixture, mix (D) Platinic chloride 1; 3-divinyl-1; 1,3, and 3-tetramethyl disiloxane complex compound (platinum content=0.60wt%); Its consumption is enough to obtain the 100ppm platinum, thereby obtains the organopolysiloxane composition of viscosity solvent-free formation solidified anti-stick coating as shown in table 2.On the solidified coating that solidifies this organopolysiloxane composition acquisition through preceding method, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.
Embodiment 10 mix 100 parts (A) with more than the methylvinyl-polysiloxane that contains branched structure shown in the average siloxane unit formula (1) that provides (dimethyl siloxane methyl ethylene silicone copolymers sizing material (contents of ethylene=0.063wt%, 2.3 * 10 of dimethylvinylsiloxy-terminated are all used at viscosity=46mPa.s), 3.0 parts of (B) molecule two ends -3Mol%; Degree of moulding=140), the methylhydrogenpolysi,oxane of 6.6 parts of (C) capped at both thmolecular terminals with trimethylsiloxy groups (viscosity=25mPa.s, with the hydrogen richness of silicon bonding=1.6wt%) and 0.30 part of (E) 1-ethynyl-1-hexalin to evenly.In this mixture, mix (D) Platinic chloride 1; 3-divinyl-1; 1,3, and 3-tetramethyl disiloxane complex compound (platinum content=0.60wt%); Its consumption is enough to obtain the 100ppm platinum, thereby obtains the organopolysiloxane composition of viscosity solvent-free formation solidified anti-stick coating as shown in table 3.On the solidified coating that solidifies this organopolysiloxane composition acquisition through preceding method, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.
Embodiment 11 mix 100 parts (A) with more than the methylvinyl-polysiloxane that contains branched structure shown in the average siloxane unit formula (1) that provides (the end capped dimethyl polysiloxane sizing material of silanol group (degree of moulding=140) is all used at viscosity=46mPa.s), 3.0 parts of (B) molecule two ends; 6.6 the methylhydrogenpolysi,oxane of part (C) capped at both thmolecular terminals with trimethylsiloxy groups (viscosity=25mPa.s, with the hydrogen richness of silicon bonding=1.6wt%) and 0.30 part of (E) 1-ethynyl-1-hexalin to evenly.In this mixture, mix (D) Platinic chloride 1; 3-divinyl-1; 1,3, and 3-tetramethyl disiloxane complex compound (platinum content=0.60wt%); Its consumption is enough to obtain the 100ppm platinum, thereby obtains the organopolysiloxane composition of viscosity solvent-free formation solidified anti-stick coating as shown in table 2.On the solidified coating that solidifies this organopolysiloxane composition acquisition through preceding method, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.Table 3
Figure G2007800482229D00271
The dimethyl polysiloxane of the dimethylvinylsiloxy-terminated shown in 100 parts of following average structure formulas of usefulness of Comparative Examples 1 mixing (viscosity=60mPa.s):
Figure G2007800482229D00272
3.0 dimethyl polysiloxane sizing material (contents of ethylene=0.02wt%, 7.4 * 10 of dimethylvinylsiloxy-terminated are all used in part (B) molecule two ends -4Mol%; Degree of moulding=140), the methylhydrogenpolysi,oxane of 4.8 parts of (C) capped at both thmolecular terminals with trimethylsiloxy groups (viscosity=20mPa.s, with the hydrogen richness of silicon bonding=1.6wt%) and 0.30 part of (E) 1-ethynyl-1-hexalin to evenly.In this mixture, mix (D) Platinic chloride 1; 3-divinyl-1; 1,3, and 3-tetramethyl disiloxane complex compound (platinum content=0.60wt%); Its consumption is enough to obtain the 100ppm platinum, thereby obtains the organopolysiloxane composition (viscosity=250mPa.s) of solvent-free formation solidified anti-stick coating.On resulting composition, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.
The dimethyl siloxane methyl ethylene silicone copolymers of the dimethylvinylsiloxy-terminated shown in 100 parts of following average structure formulas of usefulness of Comparative Examples 2 mixing (viscosity=70mPa.s):
Figure G2007800482229D00281
3.0 dimethyl polysiloxane sizing material (contents of ethylene=0.02wt%, 7.4 * 10 of dimethylvinylsiloxy-terminated are all used in part (B) molecule two ends -4Mol%; Degree of moulding=140), the methylhydrogenpolysi,oxane of 8.1 parts of (C) capped at both thmolecular terminals with trimethylsiloxy groups (viscosity=20mPa.s, with the hydrogen richness of silicon bonding=1.6wt%) and 0.30 part of (E) 1-ethynyl-1-hexalin to evenly.In this mixture, mix (D) Platinic chloride 1; 3-divinyl-1; 1,3, and 3-tetramethyl disiloxane complex compound (platinum content=0.60wt%); Its consumption is enough to obtain the 100ppm platinum, thereby obtains the organopolysiloxane composition (viscosity=200mPa.s) of solvent-free formation solidified anti-stick coating.On resulting composition, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.
The dimethyl polysiloxane of the dimethylvinylsiloxy-terminated shown in 100 parts of following average structure formulas of usefulness of Comparative Examples 3 mixing (viscosity=400mPa.s):
Figure G2007800482229D00282
1.0 part (B 1) molecular end is with dimethyl siloxane diphenyl siloxane multipolymer (the diphenyl siloxane unit content=5wt% of dimethylvinylsiloxy and trimethylsiloxy-terminated; Viscosity=50; 000mPa.s); 2.0 the methylhydrogenpolysi,oxane of part (C) capped at both thmolecular terminals with trimethylsiloxy groups (viscosity=20mPa.s, with the hydrogen richness of silicon bonding=1.6wt%) and 0.30 part of (E) 1-ethynyl-1-hexalin to evenly.In this mixture, mix (D) Platinic chloride 1; 3-divinyl-1; 1,3, and 3-tetramethyl disiloxane complex compound (platinum content=0.60wt%); Its consumption is enough to obtain the 100ppm platinum, thereby obtains the organopolysiloxane composition (viscosity=400mPa.s) of solvent-free formation solidified anti-stick coating.On resulting composition, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.
(viscosity=20mPa.s is with the hydrogen richness of silicon bonding=1.6wt%) and the methylvinyl-polysiloxane that contains branched structure shown in 0.30 part of (E) 1-ethynyl-1-hexalin uniform mixing to 100 part (A) aforementioned average siloxane unit formula (4) (in the viscosity=235mPa.s) with the methylhydrogenpolysi,oxane of 11.3 parts of (C) capped at both thmolecular terminals with trimethylsiloxy groups for Comparative Examples 4.In this mixture, mix (D) Platinic chloride 1; 3-divinyl-1; 1,3, and 3-tetramethyl disiloxane complex compound (platinum content=0.60wt%); Its consumption is enough to obtain the 100ppm platinum, thereby obtains the organopolysiloxane composition (viscosity=180mPa.s) of solvent-free formation solidified anti-stick coating.On resulting composition, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.
(viscosity=20mPa.s is with the hydrogen richness of silicon bonding=1.6wt%) and the methylvinyl-polysiloxane that contains branched structure shown in 0.30 part of (E) 1-ethynyl-1-hexalin uniform mixing to 100 part (A) aforementioned average siloxane unit formula (8) (in the viscosity=160mPa.s) with the methylhydrogenpolysi,oxane of 2.8 parts of (C) capped at both thmolecular terminals with trimethylsiloxy groups for Comparative Examples 5.In this mixture, mix (D) Platinic chloride 1; 3-divinyl-1; 1,3, and 3-tetramethyl disiloxane complex compound (platinum content=0.60wt%); Its consumption is enough to obtain the 100ppm platinum, thereby obtains the organopolysiloxane composition (viscosity=150mPa.s) of solvent-free formation solidified anti-stick coating.On resulting composition, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.
Table 4
Figure G2007800482229D00301
Above results reported shows, the solidified coating of embodiment 1-11 has than little dynamic friction coefficient of the solidified coating of Comparative Examples 1-5 and therefore sliding preferably.Show also, compare that the solidified coating of embodiment 1-11 has less antistripping value and therefore viscous substance had separability preferably in the high speed stripping process with the solidified coating of Comparative Examples 1-3.
The organopolysiloxane composition of the solvent-free formation solidified of the present invention anti-stick coating is used in and forms the solidified coating that viscous substance is demonstrated good sliding and good separability on the substrate surface of sheet-form.The substrate that has the sheet-form of the solidified coating that is obtained by foregoing of the present invention can be used for technology paper, parcel or packing viscous substance with paper, pressure sensitive adhesive tape, Pressuresensitive Label etc.

Claims (9)

1. the organopolysiloxane composition of solvent-free formation solidified anti-stick coating is characterized in that comprising:
(A) 100 weight parts have branched structure and are 10-1 25 ℃ of following viscosity; 000mPa.s; The siloxane unit (i)-(iii) that comprises the following stated; Contain a plurality of siloxane units linear fraction (ii) with having, and the organopolysiloxane fluid that contains the branch point of siloxane unit (i), the end of wherein said linear fraction is with (iii) end-blocking of siloxane unit
(i) use chemical formula SiO 4/2The siloxane unit of expression: one or more
(ii) use general formula R 2SiO 2/2The siloxane unit of expression: 15-995
(iii) use general formula R aR 2SiO 1/2The siloxane unit of expression
In these general formulas, R aBe to be selected from the alkyl with 1-8 carbon atom, have the alkenyl of 2-8 carbon atom, phenyl has the alkoxyl group of 1-8 carbon atom and the group of hydroxyl; R is selected from the alkyl with 1-8 carbon atom, has the alkenyl of 2-8 carbon atom, and phenyl groups; Intramolecularly R wherein aWith among the R at least three is to have the alkenyl of 2-8 carbon atom and at this intramolecularly R aWith at least 50% of R sum be alkyl with 1-8 carbon atom;
(B) the 0.5-15 weight part representes and is at ambient temperature the diorganopolysiloxaneand of sizing material form with average structure formula (1); This diorganopolysiloxaneand that is the sizing material form has measurable degree of moulding and is evident as solid; When allowing its material to leave standstill, it descends highly gradually and spreads out in the zone on every side:
R aR c 2SiO(R bR cSiO 2/2) n1(R c 2SiO 2/2) n2SiR c 2R a (1)
R wherein aBe to be selected from the alkyl with 1-8 carbon atom, have the alkenyl of 2-8 carbon atom, phenyl has the alkoxyl group of 1-8 carbon atom and the group of hydroxyl; R bIt is alkenyl with 2-8 carbon atom; R cBe alkyl or phenyl with 1-8 carbon atom; At this intramolecularly R a, R bAnd R cThe 0-0.1% of sum is the alkenyl with 2-8 carbon atom; At this intramolecularly R a, R bAnd R cAt least 50% of sum is the alkyl with 1-8 carbon atom; N1 is that numerical value is at least 0 number; N2 is that numerical value is at least 1 number; With n1+n2 provide this component be at ambient temperature have measurable degree of moulding and be evident as solid, when allowing its material to leave standstill its descend highly gradually and spread out around the zone in the number of sizing material form;
(C) be that 1-1000mPa.s and each molecule have at least two organic radical hydrogen polysiloxanes with the silicon bonded hydrogen atom 25 ℃ of following viscosity; Wherein the organic group with the silicon bonding is alkyl or the phenyl with 1-8 carbon atom, and it is 0.8: 1 to 5: 1 the mol ratio of alkenyl with silicon bonded hydrogen atom and component (A) and (B) in this organic radical hydrogen polysiloxanes that its consumption is enough to provide numerical value; With
(D) hydrosilylation reaction catalyst of catalytic amount.
2. the organopolysiloxane composition of the solvent-free formation solidified anti-stick coating of claim 1 is characterized in that, component (A) is the organopolysiloxane that has branched structure and represent with following average siloxane unit formula (2):
(R aR 2SiO 1/2) 4(R 2SiO 2/2) m(SiO 4/2) (2)
R wherein aBe to be selected from the alkyl with 1-8 carbon atom, have the alkenyl of 2-8 carbon atom, phenyl has the alkoxyl group of 1-8 carbon atom and the group of hydroxyl; R is selected from the alkyl with 1-8 carbon atom, has the alkenyl of 2-8 carbon atom, and phenyl groups; At this intramolecularly R aWith among the R at least 3 be alkenyl with 2-8 carbon atom; At this intramolecularly R aWith at least 50% of R sum be alkyl with 1-8 carbon atom; And m=15-995.
3. the organopolysiloxane composition of the solvent-free formation solidified anti-stick coating of claim 2 is characterized in that, component (A) is the organopolysiloxane that has branched structure and represent with following average siloxane unit formula (3):
[(R bR c 2SiO 1/2) n(R dR c 2SiO 1/2) 1-n] 4(R bR cSiO 2/2) m1(R c 2SiO 2/2) m2(SiO 4/2) (3)
R wherein bIt is alkenyl with 2-8 carbon atom; R cBe alkyl or phenyl with 1-8 carbon atom; R dBe to be selected from alkyl, have the alkoxyl group of 1-8 carbon atom and the group of hydroxyl with 1-8 carbon atom; At this molecular memory at least three R bAt this intramolecularly, R b, R cAnd R dAt least 50% of sum is the alkyl with 1-8 carbon atom; N is 0 or 1; M1 is that numerical value is at least 0 number; M2 is that numerical value is at least 1 number; And m1+m2=15-995.
4. the organopolysiloxane composition of the solvent-free formation solidified anti-stick coating of claim 2 is characterized in that, in average siloxane unit formula (2), R is a methyl, and R aIt is vinyl; In average structure formula (1), R aBe vinyl, methyl or hydroxyl, R bBe vinyl, and R cIt is methyl; With the alkyl in component (C) be methyl.
5. the organopolysiloxane composition of the solvent-free formation solidified anti-stick coating of claim 3 is characterized in that, in average siloxane unit formula (3), and R bBe vinyl, R cBe methyl, and n=1; In average structure formula (1), R aBe vinyl, methyl or hydroxyl, R bBe vinyl, and R cIt is methyl; Alkyl is a methyl in component (C).
6. any one the organopolysiloxane composition of solvent-free formation solidified anti-stick coating of claim 1-3 is characterized in that the said composition viscosity under 25 ℃ as a whole is 50-2000mPa.s.
7. any one the organopolysiloxane composition of solvent-free formation solidified anti-stick coating of claim 1-3; It is characterized in that; Suppressor factor and it that comprises (E) 0.001-5 weight part hydrosilylation reactions is not in addition solidified at ambient temperature but when applying heat, is solidified.
8. the substrate of the sheet-form that has the solidified anti-stick coating that obtains of any one the organopolysiloxane composition of solvent-free formation solidified anti-stick coating of the claim 1-7 through cured film form in the substrate of sheet-form.
9. the substrate of the sheet-form that has the solidified anti-stick coating of claim 8, the substrate that it is characterized in that sheet-form are the paper of zellglas, clay coated, paper, thermoplastic resin film or the tinsel of laminated polyolefin.
CN2007800482229A 2006-12-28 2007-12-20 Solventless cured release coating-forming organopolysiloxane composition and sheet-form substrate having cured release coating Active CN101616995B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2006356128 2006-12-28
JP356128/2006 2006-12-28
PCT/JP2007/075333 WO2008084747A2 (en) 2006-12-28 2007-12-20 Solventless cured release coating-forming organopolysiloxane composition and sheet-form substrate having cured release coating

Publications (2)

Publication Number Publication Date
CN101616995A CN101616995A (en) 2009-12-30
CN101616995B true CN101616995B (en) 2012-10-10

Family

ID=39283860

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007800482229A Active CN101616995B (en) 2006-12-28 2007-12-20 Solventless cured release coating-forming organopolysiloxane composition and sheet-form substrate having cured release coating

Country Status (4)

Country Link
JP (1) JP5420166B2 (en)
KR (1) KR101413028B1 (en)
CN (1) CN101616995B (en)
WO (1) WO2008084747A2 (en)

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2894591A1 (en) * 2005-12-09 2007-06-15 Rhodia Recherches & Tech ANTI-SOILING POLYADDITION SILICONE VARNISH, APPLICATION OF THIS VARNISH ON A SUBSTRATE AND SUBSTRATE THUS TREATED
WO2010061967A1 (en) * 2008-11-26 2010-06-03 Dow Corning Toray Co., Ltd. Solventless cured release coating-forming organopolysiloxane composition and sheet-form substrate having a cured release coating
JP5683848B2 (en) * 2009-07-01 2015-03-11 東レ・ダウコーニング株式会社 Curable organopolysiloxane composition, sheet-like article provided with a cured layer comprising the composition, and method for producing the same
EP2524954A4 (en) * 2010-01-13 2013-06-12 Dow Corning Toray Co Ltd Re-adherable silicone-based adhesive composition, sheet-shaped base material having re-adherable adhesive layer obtained by curing said composition, and use of said base material as protective film or affixing sheet
JP5343911B2 (en) * 2010-04-09 2013-11-13 信越化学工業株式会社 Release agent composition for solvent-free silicone adhesive and release sheet
DE102011004789A1 (en) 2011-02-25 2012-08-30 Wacker Chemie Ag Self-adhesive, elastomer-crosslinkable silicone compositions
CN102423929B (en) * 2011-09-01 2014-07-23 江阴新奇特塑胶制品有限公司 Solvent-free composite plastic film and composite technology thereof
JP5912600B2 (en) * 2011-09-16 2016-04-27 東レ・ダウコーニング株式会社 Curable silicone composition, cured product thereof, and optical semiconductor device
EP2812402A2 (en) * 2012-02-08 2014-12-17 Dow Corning Corporation Substrate in powder or fibre form
JP5999380B2 (en) * 2014-03-28 2016-09-28 ブラザー工業株式会社 Photocurable resin composition, container, three-dimensional model manufacturing apparatus, and three-dimensional model manufacturing method
TWI641669B (en) * 2013-10-25 2018-11-21 台灣道康寧股份有限公司 Solventless release coating organopolysiloxane composition and sheet-form substrate having cured release coating
WO2015058398A1 (en) * 2013-10-25 2015-04-30 Dow Corning (China) Holding Co., Ltd. Solventless release coating organopolysiloxane composition and sheet-form substrate having cured release coating
US20150307759A1 (en) * 2014-04-28 2015-10-29 Ames Rubber Corporation Solventless curable coating systems and uses thereof
US10155883B2 (en) 2014-06-27 2018-12-18 Dow Silicones Corporation Silicone release coating composition and low release force emulsion silicone release coating for films and papers having cured release coating
WO2016028783A1 (en) 2014-08-18 2016-02-25 Lord Corporation Method for low temperature bonding of elastomers
CN104817702B (en) * 2015-04-29 2018-11-09 中科院广州化学有限公司南雄材料生产基地 A kind of dendritic silicone macromolecule of spherical shape and the preparation method and application thereof
WO2018047756A1 (en) * 2016-09-07 2018-03-15 住友化学株式会社 Silicone resin composition, wavelength conversion material-containing silicone resin composition, and wavelength conversion material-containing sheet
EP3559132B1 (en) * 2016-12-23 2023-11-15 Dow (Shanghai) Holding Co., Ltd. Polyorganosiloxane release coating and method for its preparation and use
CN110997854A (en) * 2017-07-07 2020-04-10 道康宁东丽株式会社 Pressure-sensitive adhesive layer-forming organopolysiloxane composition and use thereof
KR20200115534A (en) * 2018-01-31 2020-10-07 다우 글로벌 테크놀로지스 엘엘씨 Polysiloxane resin composition
CN109266010B (en) * 2018-08-14 2021-04-23 山东圣佑高科新材料有限公司 Low-temperature-resistant transparent silicone gel composition for filling liquid crystal touch screen
WO2020232629A1 (en) * 2019-05-21 2020-11-26 Dow Silicones Corporation Polyorganosiloxane release coating and its preparation and use
WO2021113321A1 (en) * 2019-12-02 2021-06-10 Dow Silicones Corporation Composition for preparing a release coating
WO2021113058A1 (en) * 2019-12-02 2021-06-10 Dow Silicones Corporation Composition for preparing a release coating
KR102298512B1 (en) * 2020-02-24 2021-09-07 주식회사 케이씨씨실리콘 Addition-curable silicone composition
CN111718489B (en) * 2020-07-30 2022-07-12 万华化学集团股份有限公司 Polysiloxane copolymer and preparation method and application thereof
CN115704189B (en) * 2021-08-05 2024-05-31 杭州希力高新材料科技有限公司 Method for preparing antibacterial printed silica gel leather from high-transparency organic silicon coated fabric
CN113896894B (en) * 2021-11-03 2023-03-28 万华化学集团股份有限公司 Branched cross-linking agent, and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5080973A (en) * 1990-05-22 1992-01-14 Avery Dennison Corporation Low friction high release coatings for release tapes
CN1335344A (en) * 2000-05-26 2002-02-13 陶氏康宁东丽硅氧烷株式会社 Siloxane composition using for forming anti-adhesive coating

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2073765A (en) 1980-03-24 1981-10-21 Gen Electric Coating Composition for Use in a Transfer Adhesive System
JPS61159480A (en) * 1984-12-29 1986-07-19 Shin Etsu Chem Co Ltd Silicone composition for release paper
JPS61264052A (en) * 1985-05-17 1986-11-21 Shin Etsu Chem Co Ltd Silicone composition for release paper
GB9917372D0 (en) * 1999-07-23 1999-09-22 Dow Corning Silicone release coating compositions
US20050059776A1 (en) * 1999-07-23 2005-03-17 Cray Stephen Edward Silicone release coating compositions
GB0017468D0 (en) * 2000-07-18 2000-08-30 Dow Corning Silicone release coating compositions
JP3813467B2 (en) * 2001-05-31 2006-08-23 信越化学工業株式会社 Curable silicone release agent composition
JP3891260B2 (en) * 2001-10-24 2007-03-14 信越化学工業株式会社 Curable silicone release agent composition and release paper
CN1918256B (en) * 2003-12-23 2011-11-16 Ge拜尔硅股份有限公司 Curable siloxane composition with modified surface properties
JP4707531B2 (en) * 2004-10-29 2011-06-22 信越化学工業株式会社 Curable silicone release agent composition and release paper using the same
KR101165707B1 (en) * 2004-11-18 2012-07-18 다우 코닝 코포레이션 Silicone release coating compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5080973A (en) * 1990-05-22 1992-01-14 Avery Dennison Corporation Low friction high release coatings for release tapes
CN1335344A (en) * 2000-05-26 2002-02-13 陶氏康宁东丽硅氧烷株式会社 Siloxane composition using for forming anti-adhesive coating

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP昭56-155257A 1981.12.01

Also Published As

Publication number Publication date
JP5420166B2 (en) 2014-02-19
KR20090099078A (en) 2009-09-21
KR101413028B1 (en) 2014-07-02
WO2008084747A3 (en) 2008-12-04
CN101616995A (en) 2009-12-30
WO2008084747A2 (en) 2008-07-17
JP2008179782A (en) 2008-08-07

Similar Documents

Publication Publication Date Title
CN101616995B (en) Solventless cured release coating-forming organopolysiloxane composition and sheet-form substrate having cured release coating
CN102224188B (en) Solventless cured release coating-forming organopolysiloxane composition and sheet-form substrate having a cured release coating
CN102471578B (en) Curable organopolysiloxane composition and sheet-form article having a cured layer obtained therefrom
US4340647A (en) Vinyl gum cure accelerators for addition-cure silicone
CN106574168B (en) Release controlling agent, silicone release agent composition, release sheet and laminated body containing the release controlling agent
CN105705582B (en) Solvent-free release coating organopolysiloxane composition and with the sheet-form substrate for solidifying release coating
CN104685013A (en) Curable organopolysiloxane composition, sheet-like article having a cured layer formed from said composition, and laminate
GB2045788A (en) Method for coating a substrate using a curable silicone release composition
EP0446030A2 (en) Solventless silicone release coating
CN102344748A (en) Solventless releaser composition for use with silicone pressure-sensitive adhesives and release liner
CN101848972B (en) Solvent-based release coating-forming organopolysiloxane composition and release film or sheet
JP5138205B2 (en) Silicone composition for solvent-free release paper
CN101531868B (en) Organic silicon releasing coating mixture used in coating method with high solid content resolvent
USRE31727E (en) Vinyl gum cure accelerators for addition-cure silicone
WO1983003209A1 (en) Vinyl gum cure accelerators for condensation-cure silicone
EP0845511A2 (en) Silicone release coating compositions
EP0581285B1 (en) Organopolysiloxane composition for the formation of cured release films
JP2019099715A (en) Curable silicone release agent composition
WO2003029375A1 (en) Organohydrogenpolysiloxane mixture and silicone release coating composition
JP2003261855A (en) Silicone composition for forming peelable cured film
JP4233652B2 (en) Silicone composition for forming a peelable cured film
EP2906648B1 (en) Releasing laminate and production method thereof
US20060093835A1 (en) Curable silicone release composition and sheet having a releasability using the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CP03 Change of name, title or address

Address after: Tokyo, Japan, Japan

Co-patentee after: Dow organosilicon company

Patentee after: Dow Corning Toray Co., Ltd.

Address before: Tokyo, Japan

Co-patentee before: Dow Corning Corporation

Patentee before: Dow Corning Toray Co., Ltd.

CP03 Change of name, title or address