CN101616995A

CN101616995A - The organopolysiloxane composition of solvent-free formation solidified anti-stick coating and substrate with sheet-form of solidified anti-stick coating

Info

Publication number: CN101616995A
Application number: CN200780048222A
Authority: CN
Inventors: 堀诚司; 山田高照; D·A·里奇
Original assignee: Dow Corning Toray Co Ltd; Dow Corning Corp
Current assignee: DuPont Toray Specialty Materials KK; Dow Silicones Corp
Priority date: 2006-12-28
Filing date: 2007-12-20
Publication date: 2009-12-30
Anticipated expiration: 2027-12-20
Also published as: JP5420166B2; WO2008084747A3; CN101616995B; JP2008179782A; KR20090099078A; WO2008084747A2; KR101413028B1

Abstract

The organopolysiloxane composition of solvent-free formation solidified anti-stick coating, it comprises: (A) 100 weight parts have branched structure and comprise that (i) uses 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 organopolysiloxane fluid of the siloxane unit of expression; (B) 0.5-15 weight part average structure formula is R ^aR ^c ₂SiO (R ^bR ^cSiO _2/2) _N1(R ^c ₂SiO _2/2) _N2SiR ^c ₂R ^aDiorganopolysiloxaneand; (C) the organic radical hydrogen polysiloxanes of predetermined amount; (D) hydrosilylation reaction catalyst.In addition, the substrate that has the sheet-form of the solidified coating that obtains by this solvent-free organopolysiloxane composition that forms the solidified anti-stick coating.

Description

The organopolysiloxane composition of solvent-free formation solidified anti-stick coating and substrate with sheet-form of solidified anti-stick coating

Technical field

[0001] 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 provide good stripping performance with respect to viscous substance; With the surface treated with smooth sliding can be provided.The invention still further relates to the substrate of the sheet-form that has the solidified anti-stick coating that obtains by the curing said composition.

Background technology

[0002] by 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 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.

[0003] in JP47-032072A (references 1) and JP53-003979B (references 2), introduced the organopolysiloxane composition of the emulsion type that provides by emulsification addition reaction solidified nature organopolysiloxane composition in water and be the solvent-free organopolysiloxane composition that only contains low viscosity addition reaction solidified nature organopolysiloxane composition of liquid substitute at ambient temperature, and entered 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 JP2004-307691A (references 3), introduced the organopolysiloxane composition that forms the solvent-free solidified anti-stick coating of this class.

[0004] yet, has the low viscosity 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 paste kraft paper gummed tape on cardboard for example 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, and from the angle of technology, this may be the reason of quadratic problem.

[0005] in addition, when by 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.

[0006] 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 of 0.5-10.0mol%, with 2) 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 having viscosity is 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, be 50-10 because these compositions contain a large amount of viscosity, the straight chain diorganopolysiloxaneand of 000cps, therefore, solidified coating prepared therefrom can't provide the sliding that is entirely satisfactory.

[0007] 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 compositions and especially the composition exhibiting in references 8 and the references 9 go out good curability and solidify the coating that obtains to demonstrate the adhesivity good, good residual binding property etc. to substrate by their; Yet this solidified coating has big frictional coefficient, therefore considers from the angle of sliding, is not entirely satisfactory.

[0008] JP2001-064390A (references 8) and EP1070734A2 (references 9) have instructed the siloxanes release coating compositions can mix the poly-diorganosiloxane of alkenylation in addition, the for example ii) end capped poly-diorganosiloxane of alkenyl dialkyl group silyl and preferred end capped polydimethylsiloxane of dimethyl vinyl silyl and/or the end capped polydimethylsiloxane of dimethyl hexenyl silyl, wherein to be 25-85wt% and surplus be the ii) end capped poly-diorganosiloxane of alkenyl dialkyl group silyl 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

[0009] 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 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 described solidified coating demonstrates good adhesion to substrate and has good residual binding property and viscous substance is had improved stripping performance and has improved sliding.

[0010] 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,

(ii) use 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; With

(D) hydrosilylation reaction catalyst.

The invention still further relates to the substrate of sheet-form, described 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

[0011] can realize above-described purpose by following.

The organopolysiloxane composition of the solvent-free formation solidified of 1} 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 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 with average structure formula (1) expression and 25 ℃ of following viscosity:

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 ^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; With

(D) hydrosilylation reaction catalyst of catalytic amount.

The 2} basis 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 c8 carbon atom; And m=15-995).

The 3} basis 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, comprise in addition that the inhibitor of 0.001-5 weight part (E) hydrosilylation reactions and it are not solidified at ambient temperature but solidify 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, comprise in addition that the inhibitor of 0.001-5 weight part (E) hydrosilylation reactions and it are not solidified at ambient temperature but solidify applying under the heat.

[0012]

{ the basis of 8} by 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 by 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 glassine paper, clay coated, paper, thermoplastic resin film or the tinsel of laminated polyolefin.

[0013] 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, described 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.

Implement optimal mode of the present invention

[0014] organopolysiloxane composition of the solvent-free formation solidified of the present invention anti-stick coating is characterised in that and comprises:

(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 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);

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; Provide this component with n1+n2 and be at least 100 25 ℃ of following viscosity, the number of 000mPa.s);

(D) hydrosilylation reaction catalyst of catalytic amount.

[0015] 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 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 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.

[0016] 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 represented with following average siloxane unit formula (4):

[(R ^aR ₂SiO _1/2)(R ₂SiO _2/2) _m/4] ₄(SiO _4/2)????????????(4)

[0017] 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 siloxane unit polymer chain (ii) of expression is only on three directions or the molecule that extends on both direction.Organopolysiloxane with this branched structure can be represented with following average siloxane unit formula (2).

(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, it is possible mostly being 4 quantity most, but considers from the feature angle of organopolysiloxane, is preferably 1.

[0018] 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.

[0019] 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 _1/2The unit can exemplify Vi (Me ₂) SiO _1/2Unit, He (Me) ₂SiO _1/2Unit, (Me) ₃SiO _1/2Unit, ViMePhSiO _1/2Unit and (HO) (Me) ₂SiO _1/2(wherein Vi represents vinyl, and He represents hexenyl, and Me represents 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 _1/2Unit and (Me) ₃SiO _1/2The unit) combination also is possible.

R ₂SiO _2/2The unit can exemplify (Me) 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.

[0020] the more particularly available following average siloxane unit formula of this organopolysiloxane (5) with branched structure is represented:

[(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)

Represent with average siloxane unit formula (3) below the other usefulness:

[(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).

[0021] herein, 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 _1/2The unit can exemplify Vi (Me) ₂SiO _1/2Unit, He (Me) ₂SiO _1/2Unit and ViMePhSiO _1/2The unit.R ^dR ^c ₂SiO _1/2The unit can exemplify (Me) 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 _1/2Unit and (Me) ₃SiO _1/2The unit) combination is possible.

R ^bR ^cSiO _2/2The unit can exemplify ViMeSiO _2/2The unit.R ^c ₂SiO _2/2The unit can exemplify (Me) ₂SiO _2/2Unit and MePhSiO _2/2The unit.At same intramolecularly, these unitary combinations also are possible.

[0022], crosslinked with silicon bonded alkenyl experience in component (A) by interior and silicon bonded hydrogen atom generation hydrosilylation reactions 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 high viscosity 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 by hydrosilylation reactions.Because this mixes only a small amount of component (B) solidified coating with good sliding can be provided.

[0023] 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)

The a plurality of components (A) that differ from one another also can make together and be used for preparing same composition.

[0024] table 1 shows viscosity and the coefficient thereof that contains the organopolysiloxane of branched structure listed above concerning aforementioned siloxane unit formula (3).

Table 1

	?(4n+m1)	??(m1+m2)	Viscosity (mPa.s)
	?(4n+m1)	??(m1+m2)	Viscosity (mPa.s)	?(1)	?6	??56	??46
?(2)	?5.8	??104.8	??122	?(1)	?6	??56	??46
?(2)	?5.8	??104.8	??122	?(3)	?25.9	??157.9	??111
?(4)	?22.2	??203.2	??235	?(3)	?25.9	??157.9	??111
?(4)	?22.2	??203.2	??235	?(5)	?12.2	??218.2	??366
?(6)	?47.5	??285.5	??375	?(5)	?12.2	??218.2	??366
?(6)	?47.5	??285.5	??375	?(7)	?4	??56	??47
?(8)	?4	??180	??160	?(7)	?4	??56	??47

[0025] can produce this component (A) by referring to Patent Document 8 and refer to Patent Document the production method described in 9.For example, can be by 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 filtrate, remove low-boiling compound, thereby carry out the production of component (A).

Can analyze by introducing ratio, the NMR of initial siloxanes, measure the analysis of contents of ethylene etc., measure the average siloxane unit formula in the product.

[0026] component (B) plays and improves solidified coating to the rippability effect of viscous substance and also play the effect that the solidified coating sliding is provided, described component (B) is to be at least 100, the diorganopolysiloxaneand of 000mPa.s with average structure formula (1) expression and 25 ℃ of following viscosity:

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; Provide this component with n1+n2 and be at least 100 25 ℃ of following viscosity, the number of 000mPa.s).Component (B) rises to gradually when by component (A) with on the coating of the formation when take place solidifying of the hydrosilylation reactions (C), 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.

[0027] herein, 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 _1/2The unit can exemplify Vi (Me) 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 _2/2The unit can exemplify ViMeSiO _2/2The unit.

R ^c ₂SiO _2/2The unit can exemplify (Me) ₂SiO _2/2Unit and MePhSiO _2/2The unit.

At same intramolecularly, these unitary combinations are possible.

[0028] component (B) be included in intramolecularly have with the silicon bonded alkenyl and therefore can with the component of component (C) experience hydrosilylation reactions; 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); Not containing alkenyl does not contain silanol group yet and does not therefore have reactive component.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.

[0029] about has 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.Also can on the side chain position, have alkenyl in the component (B) that contains on the terminal position of molecular chain with the hydroxyl (silanol group) of silicon bonding.Alkenyl content is 0 (not comprising 0)-0.1mol% of the organic group of this intramolecularly and silicon bonding.

[0030] 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.

[0031] component (B) can exemplify dimethyl polysiloxane particularly, dimethyl siloxane Methyl Octyl silicone copolymers, dimethyl siloxane methyl ethylene silicone copolymers, dimethyl siloxane. methyl hexenyl silicone copolymers, dimethyl siloxane methylphenyl siloxane multipolymer, with dimethyl siloxane diphenyl siloxane multipolymer, under each situation, the place has dimethylvinylsiloxy at the molecular chain end group, the dimethyl-allyl siloxy-, dimethyl hexenyl siloxy-, present as dimethylhydroxysilox(, trimethylsiloxy or 3,5-dimethylphenyl siloxy-.

Also can use together and have different end group or different side chain or different end group and prepare same composition with the polysiloxane of different side chains.

[0032] under each situation,, mixes 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.

[0033] component (C) be 25 ℃ of following viscosity be 1-1000mPa.s and each molecule have at least two with silicon bonded hydrogen atom and alkyl or phenyl with 1-8 carbon atom as and the organic radical hydrogen polysiloxanes of the organic group of silicon bonding, it serves as the linking agent of component (A).By 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.

[0034] 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.

[0035] comprise phenyl with the organic group of silicon bonding and have the alkyl of 1-8 carbon atom, for example methyl, ethyl, propyl group, butyl, octyl group etc., preferably at least 50% of these organic group sums 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) exemplifies straight chain, side chain and ring-type.

[0036] viscosity of component (C) under 25 ℃ is 1-1000mPa.s and preferred 5-500mPa.s.Its basis is as described below: when the viscosity under 25 ℃ during less than 1mPa.s, component (C) volatilizes organopolysiloxane composition easily, and organopolysiloxane composition needs to spend long set time more than 1000mPa.s.

[0037] this component (C) can exemplify the end capped methylhydrogenpolysi,oxane of trimethylsiloxy, the end capped dimethylsiloxane methylhydrogensiloxacopolymer copolymer of trimethylsiloxy, 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.

The a plurality of components (C) that differ from one another can make together and be used for preparing same composition.

[0038] 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.

[0039] 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 by 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, (D) is not particularly limited to this component, and component (D) can exemplify platinum class catalyzer, for example Platinic chloride particularly, the Platinic chloride of alcohol modification, Platinic chloride/alkene complex, Platinic chloride/ketone complex compound, platinum/alkenyl siloxanes complex compound, Tetrachloroplatinum, the platinum micro mist, be carried on for example solid platinum on alumina powder or the SiO 2 powder of carrier, platinum black, the alkene complex of platinum, the carbonylcomplex of platinum, with the powder thermoplastic resin that mixes foregoing platinum class catalyzer (methyl-methacrylate resin for example, polycarbonate resin, polystyrene resin, silicone resin etc.).

[0040] other examples 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 hydrogen atom, chlorine atom, bromine atoms or iodine atom; Y is alkyl, CO or C ₈H ₁₄R ⁶Be alkyl, cycloalkyl 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).

[0041] considers 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.

[0042] 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), mix the component (D) of catalytic amount, usually mix 1-1000ppm and preferably mix 5-500ppm component (D).

[0043] except foregoing component, the organopolysiloxane composition of the solvent-free formation solidified of the present invention anti-stick coating preferably also contains hydrosilylation reactions inhibitor (E), so that make its thermofixation, by suppressing gelling at ambient temperature and curing, improve stability in storage simultaneously.This hydrosilylation reactions inhibitor can exemplify acetylene compound, alkene-alkine compounds, organic nitrogen compound, organo phosphorous compounds, and oxime compound, and can exemplify alkynol 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 inhibitor is usually in 0.001-5 weight part scope, 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 inhibitor, 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).

[0044] composition 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 damage purpose of the present invention and effect gets final product.But the coating based on composition in the substrate of sheet-form considers that the preferred as a whole range of viscosities under 25 ℃ of composition of the present invention is 50-2000mPa.s.

[0045] 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 composition of the present invention.The order of mixing each component is not particularly limited, yet when not using composition immediately after mixing, component (A), (B) and mixture (C) preferably are independent of component (D) storage and preferably just mixed these two before using.Under the situation of the composition that contains component (A)-(E), also preferred by selecting component (E) type and the composition that obtains of the incorporation of regulating component (E) do not experience at ambient temperature crosslinked, and the crosslinked and curing of experience when applying heat.

[0046] can be by at the substrate of any various sheet-forms glassine paper for example, cardboard, the paper of clay coated, the paper of laminated polyolefin and the especially paper of polyethylene lamination, thermoplastic resin film (for example, polyester film, polyethylene film, polypropylene screen, polyamide membrane), natural fabric, synthetic fabrics, tinsel (for example, aluminium foil) is coated with the organopolysiloxane composition of the solvent-free formation solidified of above-described the present invention anti-stick coating on etc. the surface equably, with be suitable for causing component (A) and (C) or component (A), (B) and (C) heat under the crosslinked condition of experience by 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.

[0047] 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 exemplify, pass long baking oven, perhaps use infrared lamp or halogen lamp irradiated heat at hot air circulate baking oven internal heating.Also can add thermal bond and be exposed under the ultraviolet radiation, be cured by use.When component (D) is platinum/alkenyl siloxanes complex compound catalyst, even the total amount of working as with composition is a benchmark, consumption in platinum, when this catalyzer mixes with the consumption of 50-200ppm, can be under 100-150 ℃, in the short time period, promptly 40-1 easily obtains the solidified coating that substrate to sheet-form demonstrates good adhesivity and demonstrates good stripping performance with respect to viscous substance in second.

[0048] the employed coating machine of organopolysiloxane composition that applies the solvent-free formation solidified of the present invention anti-stick coating on the surface of the substrate of sheet-form is not particularly limited, coating machine can exemplify roller coating machine, photogravure coating machine, air coating machine, curtain stream coating machine and offset printing and shift roller coating machine.About viscous substance, described viscous substance can be applied to by 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, this viscous substance can be for example any various pressure sensitive adhesives and various tackiness agent, the example is the acrylic resin pressure sensitive adhesive, the pressure sensitive adhesive of rubber type, pressure sensitive adhesive with the siloxanes type, and propylene resin tackiness agent, the pressure sensitive adhesive of synthetic rubber type, the tackiness agent of siloxanes type, the tackiness agent of the tackiness agent of Resins, epoxy type and urethane type.Other examples are pitch, viscous food product for example Herba Gonostegiae Hirtae (i.e. rice cake), glue and paste and bird lime.

[0049] composition of the present invention can be used for forming solidified coating, described 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 by solidifying the anti-stick coating that composition of the present invention forms is very suitable for especially being used for viscous substance and the technology paper of be clamminess material, pressure sensitive adhesive tape, pressure sensitive adhesive label etc., parcel or packing paper use.

Embodiment

[0050] provides embodiment and Comparative Examples below, so that describe the present invention particularly; Yet the present invention is unlimited on subsequently the embodiment.In embodiment and Comparative Examples subsequently, part is that weight part and ppm represent ppm by weight in all cases in all cases.Method by the following stated under 25 ℃ is measured viscosity and degree of moulding.In addition, by using the method for the following stated, measure down dynamic friction coefficients and antistripping values at 25 ℃ respectively, estimate the solidified coating that obtains by the solvent-free organopolysiloxane composition that forms the solidified anti-stick coating sliding and stripping performance viscous substance.

[0051] viscosity and degree of moulding

The viscometer that uses the numeral demonstration is (available from Shibaura Systems Co., 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.

[0052] antistripping value

Use printable tester (available from Akira Seisakusho Co., the model RI-2 of Ltd.), on the surface of the paper of polyethylene lamination or glassine paper 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 glassine paper of polyethylene lamination.The paper laminate body that obtains as mentioned above by cutting becomes the width of 2.5cm then, the preparation sample, and under above-described condition, peel off the measurement of desired power (N), different is that peeling rate is 100m/min.

[0053] dynamic friction coefficient

Use and the identical condition of above-described measurement antistripping value, form two solidified coatings.These solidified coatings that superpose then, its mode makes the solidified coating side contact with each other, then uses at a high speed and peels off tester, the condition tractive of working load=200g and draw rate=5m/min, and measure the desired power of tractive (g).The dynamic friction coefficient of the desired power of tractive/200 (g) expression solidified coating.

[0054] residual binding property

Lumilar 31B polyester tape (product of Nitto Denko Corporation) is adhered 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.

[0055] in an embodiment, the methylvinyl-polysiloxane that contains branched structure shown in the average siloxane unit formula is as component (A) below.Vi represents vinyl.

(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)

[0056] synthesis 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 stirred 6 hours under 80-90 ℃ temperature.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 filtrate 2 hours.The viscosity of the residue behind the stripping is that 46mPa.s and its contents of ethylene are 3.5wt%.

[0057] synthesis 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 stirred 6 hours under 80-90 ℃ temperature.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 filtrate 2 hours.The viscosity of the residue behind the stripping is that 122mPa.s and its contents of ethylene are 1.9wt%.

[0058] synthesis 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 stir 6 hours under 80-90 ℃ temperature.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 filtrate 2 hours.The viscosity of the residue behind the stripping is that 111mPa.s and its contents of ethylene are 5.6wt%.

[0059] synthesis 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 stirred 6 hours under 80-90 ℃ temperature.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 filtrate 2 hours.The viscosity of the residue behind the stripping is that 235mPa.s and its contents of ethylene are 3.8wt%.

[0060] synthesis 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 stirred 6 hours under 80-90 ℃ temperature.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 filtrate 2 hours.The viscosity of the residue behind the stripping is that 366mPa.s and its contents of ethylene are 2.0wt%.

[0061] synthesis 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 stirred 6 hours under 80-90 ℃ temperature.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 filtrate 2 hours.The viscosity of the residue behind the stripping is that 375mPa.s and its contents of ethylene are 5.8wt%.

[0062] synthesis 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 stirred 6 hours under 80-90 ℃ temperature.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 filtrate 2 hours.The viscosity of the residue behind the stripping is that 47mPa.s and its contents of ethylene are 2.4wt%.

[0063] synthesis 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 stirred 6 hours under 80-90 ℃ temperature.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 filtrate 2 hours.The viscosity of the residue behind the stripping is that 160mPa.s and its contents of ethylene are 0.90wt%.

[0064] 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 (the end capped dimethyl polysiloxane sizing material of dimethylvinylsiloxy (contents of ethylene=0.02wt%, 7.4 * 10 are all used in 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-1,1,3,3-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 by this organopolysiloxane composition on the paper that is solidificated in the polyethylene lamination, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.

[0065] embodiment 2-7

Mix 100 parts (A) with more than the methylvinyl-polysiloxane that contains branched structure, 3.0 parts of (B) molecule two ends shown in the average siloxane unit formula (2), (3), (4), (5), (6) or (7) that provide all use the end capped dimethyl polysiloxane sizing material of dimethylvinylsiloxy (contents of ethylene=0.02wt%, 7.4 * 10 ^-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-1,1,3,3-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 by these organopolysiloxane compositions on the paper that is solidificated in the polyethylene lamination, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.

[0066] embodiment 8

Under the condition identical, measure, but in this case, use glassine paper as the substrate of sheet-form rather than the paper of polyethylene lamination with embodiment 7; These results have been shown in the table 4.

Table 2

[0067] 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-1,1,3,3-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 by preceding method, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.

[0068] 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 (the end capped dimethyl siloxane methyl ethylene of dimethylvinylsiloxy silicone copolymers sizing material (contents of ethylene=0.063wt%, 2.3 * 10 are all used in 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-1,1,3,3-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 by preceding method, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.

[0069] 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-1,1,3,3-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 by preceding method, measure dynamic friction coefficient and antistripping value; These results have been shown in the table 4.

Table 3

[0071] Comparative Examples 1

Mix 100 parts of end capped dimethyl polysiloxanes of dimethylvinylsiloxy shown in the following average structure formula of usefulness (viscosity=60mPa.s):

3.0 the end capped dimethyl polysiloxane sizing material of dimethylvinylsiloxy (contents of ethylene=0.02wt%, 7.4 * 10 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-1,1,3,3-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.

[0072] Comparative Examples 2

Mix the 100 parts of end capped dimethyl siloxane methyl ethylene of dimethylvinylsiloxy silicone copolymers shown in the following average structure formula of usefulness (viscosity=70mPa.s):

3.0 the end capped dimethyl polysiloxane sizing material of dimethylvinylsiloxy (contents of ethylene=0.02wt%, 7.4 * 10 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-1,1,3,3-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.

[0073] Comparative Examples 3

Mix 100 parts of end capped dimethyl polysiloxanes of dimethylvinylsiloxy shown in the following average structure formula of usefulness (viscosity=400mPa.s):

1.0 part (B ¹) molecular end dimethylvinylsiloxy and the end capped dimethyl siloxane diphenyl siloxane of trimethylsiloxy multipolymer (diphenyl siloxane unit content=5wt%, 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-1,1,3,3-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.

[0074] Comparative Examples 4

(viscosity=20mPa.s is with the methylvinyl-polysiloxane that contains branched structure shown in the hydrogen richness of silicon bonding=1.6wt%) and 0.30 part of (E) 1-ethynyl-1-hexalin uniform mixing to 100 part (A) the 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.In this mixture, mix (D) Platinic chloride 1,3-divinyl-1,1,3,3-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.

[0075] Comparative Examples 5

(viscosity=20mPa.s is with the methylvinyl-polysiloxane that contains branched structure shown in the hydrogen richness of silicon bonding=1.6wt%) and 0.30 part of (E) 1-ethynyl-1-hexalin uniform mixing to 100 part (A) the 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.In this mixture, mix (D) Platinic chloride 1,3-divinyl-1,1,3,3-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.

[0076] table 4

[0077] 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.

[0078] 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 paper, pressure sensitive adhesive tape, Pressuresensitive Label etc.

Claims

1. the organopolysiloxane composition of solvent-free formation solidified anti-stick coating is characterized in that comprising:

(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 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;

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; Provide this component with n1+n2 and be at least 100 25 ℃ of following viscosity, the number of 000mPa.s;

(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 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, comprising the inhibitor of (E) 0.001-5 weight part hydrosilylation reactions and it does not in addition solidify at ambient temperature but solidifies when applying heat.

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 by 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 glassine paper, clay coated, paper, thermoplastic resin film or the tinsel of laminated polyolefin.