CN101089106A - Coating composite and method for coating carrier - Google Patents

Abstract

The present invention discloses sheet carrier coating process, which includes the first coating (methyl) acrylate modified organic polysiloxane capable of being cured onto the surface of the carrier, and the subsequent curing the modified organic polysiloxane by means of polymerizing high energy radiation. Therefore, polysiloxane with functional hydroxyl radical is adopted, and the polysiloxane is prepared with (methyl) acrylic acid with hydroxyl radical in 0.4-0.9 molar weight and monobasic carboxylic acid without double bond in up to 0.6 molar weight, and through mixing and reaction.

Description

The method of coating composition and coating carrier

Technical field

Present invention relates in general to coating procedure, particularly, the method that relates to a kind of coating carrier in the following manner (sheet-like support): the curable organopolysiloxane of (methyl) acrylate-based modification is coated on the carrier surface, and the energy-rich radiation by polymerization is solidified the modification organopolysiloxane then.Term " (methyl) is acrylate-based " has both comprised acrylate-based, also comprises methacrylate based.

On the other hand, the invention also discloses new coating composition.

Background technology

The unsticking coating composition is used for particularly applying flaky material on a large scale, to reduce the adhesion tendency of viscous product to its surface.The unsticking coating composition is used for, and for example, applies paper or film as the Pressuresensitive Label carrier.Label with pressure sensitive adhesive is bonded on the coated surface, and its bondability is enough to make and can operates the carrier film that has Pressuresensitive Label.Yet, must label be peeled off from coated carrier film, simultaneously bounding force that again can the remarkably influenced label is to treat follow-up use.Other of unsticking coating composition used also has wrapping paper, especially for the wrapping paper of packing adhesive article.This unsticking paper or unsticking film are used for, for example, and wrap food or Industrial products, for example packaged asphalt.

The organopolysiloxane of this (methyl) acrylate-based modification also can be used for applying the printed circuit board (PCB) that is equipped with electronic component.In this application, the main effect of described organopolysiloxane is to make circuit card avoid the influence of mechanical influence and corrosive gases or steam.

German patent DE 2,948, disclose in 708 a kind of from organochlorine for polysiloxane preparation method by the organopolysiloxane of pentaerythritol triacrylate or pentaerythritol acrylate trimethyl modification, wherein optional (HCl-binding) neutralizing agent that adds the HCl associativity.In this patent, the organopolysiloxane molecular formula is as follows:

(R ¹Alkyl, vinyl and/or the phenyl of=1 to 4 carbon atom, prerequisite are the R of at least 90 molar percentages ¹Base is a methyl; A is 1.8 to 2.2; B is 0.004 to 0.5), at first based on the dialkylamine reaction with at least 2 moles of SiCl base, the alkyl of described dialkylamine respectively has 3 to 5 carbon atoms to this organopolysiloxane, and the carbon atom that closes on nitrogen respectively has hydrogen atom at the most.Reaction product and the pentaerythritol triacrylate or the tetramethylolmethane methacrylic ester of equimolar amount are at least reacted, from the solids component that suspends, isolate final product by currently known methods at last.

Coating composition by this method preparation shows unsticking preferably.Kept its bounding force largely with the contacted sealing tape of coating composition to the substrate of being untreated.Yet, fixedly be that this unsticking performance should be got in touch the chemical constitution of tackiness agent and structure all the time and considered and estimate, and is at this adhesive exhibits unsticking performance and apply agent.Therefore, with regard to German patent DE 2,948, disclosed unsticking coating in 708 is because its performance can't allocate at different tackiness agents, so this unsticking coating can't all can provide gratifying effect in all cases.

Show improved performance by (methyl) acrylate modified organopolysiloxane mixture: the feature of described mixture is to have following formation: on average have＞the equilibrated organopolysiloxane of 25 to＜200 Siliciumatoms and the organopolysiloxane that 2 to 25 Siliciumatoms are on average arranged of 2 to 30 weight %, and the organopolysiloxane that 200 to 2,000 Siliciumatoms are on average arranged of 2 to 30 weight %.The organopolysiloxane that contains in the above-mentioned tertiary mixture is born different tasks.The task of low molecular weight part mainly is to guarantee that coating composition is bonded in the substrate.On the other hand, the effect of high molecular part mainly is to make coating composition have required unsticking performance.Middle portion is a curable matrix, particularly determines the physicals of coating composition.What those of ordinary skills will understand is, more than only be the concise and to the point description of the performance and the task of three kinds of different pieces, this be because unsticking coating the complicated performance that must have have only joint efforts to realize by three kinds of compositions.By German patent DE 3,426,087 modification organopolysiloxane mixture had become already and possible is, on the one hand, improved the unsticking performance of mixture to viscous surface, on the other hand, improved for coating applying and the adhesive performance of solidified substrate thereon.Yet even this coating compound, its performance also can't fully be allocated at different tackiness agents.

But narrated a kind of liquid coating of electrocuring among the open text EP 0159683 in Europe.Described coating comprises following component:

1.60 to 95 parts organopolysiloxane, wherein, contain 25 siloxaness of having an appointment in the described polysiloxane per molecule, and each molecule contain 2 to 10 parts reaction methanol-based (carbinol), other substituting group of silicon is the alkyl of 1 to 20 carbon atom; The implication of the methanol-based that term anti has been answered is interpreted as the ester of vinylformic acid, methacrylic acid or its mixture, or the ether of these sour hydroxy alkyl esters, and described alkyl comprises 2 to 4 carbon atoms; The unreacted methanol base should not have basically again, so that hydroxyl value is less than 10;

2.3 to the polyester of 25 parts polyvalent alcohols and vinylformic acid, methacrylic acid or its mixture, wherein, the described polyvalent alcohol of per molecule contains 2 to 4 hydroxyls, and the molecular weight of described polyvalent alcohol is less than 1,200;

3.1 to 10 parts vinylformic acid, methacrylic acid or these sour mixtures.

The additional use of polyvalent alcohol (methyl) acrylate has improved solidification rate; Yet the increase of organic moiety is but to the flexibility and the unsticking generation adverse influence of coating.Containing free acrylic or methacrylic acid composition is the another one defective, and this is because it can produce a kind of disgusting smell, also can make product is coated on operational difficulty on the material to be coated.

Can be cured by radiation with acrylate-based organopolysiloxane, therefore report a series of other purposes of this organopolysiloxane.For example, the organopolysiloxane of acrylate-based modification as japanning, is poured in electrical element or the electronic component and is poured over around it, also can be in order to the modeling goods.The open text of below quoting, authorization text (Auslegeschriften) and patent relate to the possible structure of the organopolysiloxane of described acrylate-based modification.

Germany's authorization text 2,335,118 relates to the acrylate-based organopolysiloxane that contains of the following optional replacement of a kind of general formula,

(the monovalence alkyl of R=hydrogen or 1 to 12 carbon atom; The monovalence alkyl or the Qing Wanji of R '=optional halogenated 1 to 8 carbon atom; R " the bivalent hydrocarbon radical of=1 to 18 carbon atom or contain the bivalent hydrocarbon radical of C-O-C key; R =R  ' O _0.5Or R ' ₃SiO _0.5Z=OR  ', R  ' or OSiR ' ₃R  '=1 is to the alkyl of 12 carbon atoms; A and b represent numeral 1 to 20,000 respectively; C is a numeral 0 to 3; E is a numeral 0 to 2; At least one Z base is OR  ' when c=0).Described siloxane polymer can be used as the intermediate of synthetic a kind of multipolymer, and described multipolymer contains the organopolysiloxane segment, and has found that this multipolymer can be used as coating composition.In addition, this acrylate functional siloxane polymer also can be used as the spreading mass and the protective coating compositions of paper and fabric.Yet this product is not suitable for preparing unsticking coating.In addition, Germany's authorization text 2,335, the group that has alkoxyl group in 118 the linear diacrylate modified polyorganosiloxane by its definition, these groups are can be by hydrolysis separated and cause that polysiloxane is further crosslinked to destroy its elasticity, and elasticity is very important for coating composition.

Disclose a kind of polysiloxane with pendant acrylate groups in the open text 3,044,237 of Germany, described polysiloxane can synthesize by the epoxy-functional siloxanes and the vinylformic acid reaction of ad hoc structure.The product radiation-hardenable that obtains.This polysiloxane can be used as the low viscosity lacquer that uses by conventional oil-based ink form.Yet, a hydroxyl is arranged owing to each is acrylate-based, bigger limitation is arranged when therefore above-mentioned product is as the unsticking coating composition.

U.S. Pat P 4,568, narrated a kind of curable silicone goods that comprise following component in 566:

A) molecular formula of 75 to 100 molar percentages is R ₃SiO _0.5, RSiO _1.5And SiO ₂Chemically combined (chemically bound) siloxy units; And

B) R of 0 to 25 molar percentage ₂The SiO unit, wherein a plurality of R unit has following structure

R wherein ¹Be the alkyl of hydrogen or 1 to 12 carbon atom, R ²Be bivalent hydrocarbon radical or alkylidene oxide.Described curable product is used in particular for applying electronic component, also can be used as optical fiber coating.Yet, because R ₂The unitary content of SiO is too low, so these goods are not suitable for the unsticking coating as chip carrier.

The open text EP 0152179 in Europe provides a kind of curable formation elastomeric polysiloxane goods.These goods comprise a) a kind of silicone resin of linear structure, contain on average at least 150 siloxane units, also contain the vinylformic acid end group, and wherein the zone between two end groups does not have acrylic; B) light trigger at least 10% high dispersing silicon-dioxide, and c).This material is as tackiness agent and casting die compound (casting compound).

At last, with reference to the open text EP 0169592 in Europe, wherein relate to a kind of optical glass fibre that has the synthetic resins tectum, include glass fibre and synthetic rubber integument, wherein the specific refractory power of synthetic rubber integument is greater than the outer field specific refractory power of glass fibre, described synthetic rubber is formed by the curable compound resin composition that contains multipolymer, and described multipolymer comprises dimethyl siloxane and at least a siloxanes that is selected from tolyl siloxanes and diphenyl siloxane, as monomeric unit.Comprise in the described silicone copolymers per molecule at least two acrylate-based.The prominent feature of described curable compound resin composition is, also additionally contains molecular-weight average in the said composition and be 3,000 urethane acrylate.The polysiloxane that its claim proposed can have following molecular formula:

A primary condition is that described polysiloxane should have the phenyl that links to each other with silicon.This phenyl composition is to make the specific refractory power of coating composition approach the prerequisite of glass fiber specific refractory power.Yet, be used for applying the purposes of optical glass fibre from above-mentioned and urethane acrylate bonded siloxanes, can not draw the conclusion that this compound also can be used as the unsticking coating composition.

At publication " polymer chemistry " (Makromolekulare Chemie) (MacromolecularChemistry, Rapid Communication), 7, (1986) have reported the method for the linear methyl polysiloxane of anamorphic zone methacrylate end-groups in the 703rd to 707 page.This reaction in, the allyl group glycidyl ethers at first in the presence of Platinic chloride with α, ω-hydrogen dimethylamino based polysiloxane generation addition reaction.Formed di-epoxide in the presence of di-isopropyl Whitfield's ointment chromium with the methacrylic acid-respons, generate required methacrylic ester.Described ester can two kinds of isomer form exist:

(alpha-isomer)

(β-isomer)

If (methyl) acrylate passes through the method for prior art by the initial preparation of epoxy-functional siloxanes, then epoxy group(ing) is reacted with (methyl) vinylformic acid.In this reaction,, generate (methyl) acrylic monoester that contains vicinal hydroxyl groups by the open loop of epoxide.

Summary of the invention

An object of the present invention is to provide a kind of unsticking coating composition based on (methyl) acrylate modified organopolysiloxane, coating composition known in the performance of described composition and the industry has been compared improvement.

More specifically, an object of the present invention is to provide a kind of coating composition that can allocate at different viscous products (tackiness agent).

Especially, required (methyl) acrylate-based modification organopolysiloxane combination that should have following performance:

1. to the gratifying clinging power of specific carrier to be coated

2. at carrier or suprabasil high solidification rate

3. solidify the chemistry and the physical stability of back coating

4. solidify the high flexibility of back coating

5. to the unsticking performance of viscous product, but and unsticking coating to the adaptation ability of adhesive chemistry characteristic

6. the adjustable characteristic of required unsticking degree.

In addition, this modification organopolysiloxane also should be suitable for applying the printed circuit board (PCB) and the similar electronic component of electronic assemblies.

The characteristics of the inventive method are to have used curable organopolysiloxane, described organopolysiloxane be by the polysiloxane that average general formula is following with based on (methyl) vinylformic acid hydroxyl, 0.4 to 0.9 molar weight and be up to not reacting of 0.6 molar weight and make with the monocarboxylic acid of polymerizable double bond, the summation of the molar weight of wherein said acid is not more than 1.0

Wherein

R ¹Group is identical or different, and represents the low molecular weight alkyl or the phenyl of 1 to 4 carbon atom,

R ²Group is

(a) molecular formula is-CH ₂(CR ³ ₂) _n-(OCH ₂CHR ⁴) _m-OH ,-CH=CH-CR ₂ ³The hydroxy-functional group of-OH and/or the following group of molecular formula

R wherein ³Base is identical or different, and represents the alkyl of hydrogen or 1 to 4 carbon atom,

R ⁴Base is identical or different, represents the alkyl of hydrogen or 1 to 10 carbon atom separately, and

Subscript

N=0 to 10 and

M=0 to 40 and

(b) the not substituted alkyl of 2 to 20 carbon atoms or substituted alkyl and/or hydrogen, and

(c) R ¹Base,

Prerequisite is to comprise at least 1.8 hydroxy-functional R in the mean molecule ²Base (a),

A be numerical value 1 to 1,000 and

B is a numerical value 0 to 10.

This is reflected under the common enzymatic synthesis condition and carries out.

Necessary is to have at least 1.8 hydroxy-functional R in the mean molecule ²Base (a), but also can have more amount.In fact, R ²Base can all be a hydroxy-functional.Yet, in case satisfy the hydroxy-functional R that has 1.8 (a) classes ²The condition of base, then remaining R ²Base can be (b) class and/or can be R ¹If there is the R of (b) class ²Base then is suitable for supplementary condition, i.e. hydroxy-functional R ²Base (a) and (b) class R ²The lower value of the ratio of base must not be lower than 70: 30.

General formula I is the average mark minor of the required hydroxy-functional organopolysiloxane of this reaction.Independent structural unit (in statistical mode) is randomly dispersed in the polymeric blends.

Functional unit [R ¹R ²SiO-] summation be 2a+b * a.Trifunctional units [R ¹SiO _3/2-] number provide by subscript b.A is a numerical value 1 to 1,000, preferred value 5 to 200, and b is a numerical value 0 to 10, preferred 0 to 2.If b equals 0, then the hydroxy-functional organopolysiloxane exists with the chain form with linear structure.Even after the hydroxy-functional organopolysiloxane that is limited by subscript a and b reacted with (methyl) vinylformic acid and other monocarboxylic acid, its structure was still constant.

In polymerizable molecular, R ¹Can be identical or different, open and represent a low alkyl group or a phenyl with 1 to 4 carbon atom.This alkyl can be straight chain or branched.Preferably, at least 90% R ¹Base is a methyl.

R ²Base can partly have R ¹The implication of base.Remaining R ²In the base, 70 to 100% R ²Base is molecular formula-CH ₂(CR ³ ₂) _n-(OCH ₂CHR ⁴) _mThe hydroxy-functional group of-OH and/or the following group of molecular formula,

30 to 0% R ²Base is optional substituted alkyl and/or hydrogen with 2 to 20 carbon atoms.

In the described group, R ³Be identical or different, and represent the alkyl of hydrogen or 1 to 4 carbon atom, this alkyl preferable methyl.

R ⁴Be identical or different, and represent the alkyl of hydrogen or 1 to 10 carbon atom, preferred straight chained alkyl.

N is a numerical value 0 to 10, but considers that from accessible angle then preferred value 2 to 10.

M is a numerical value 0 to 40; But m preferably equals zero.

If with R ³And R ⁴The implication of base and following target value substitution-CH ₂(CR ₂ ³) _n-(OCH ₂CHR ⁴) _mIn-OH base or the following group,

Then its result is-CH ₂(CR ₂ ³) _nPart or norcamphyl have the implication of bridging element, and wherein this hydroxy-functional group links to each other with the Siliciumatom of siloxane backbone by described bridging element.Preferably, bridging part-CH ₂(CR ₂ ³) _nImplication be-(CH ₂) ₃Or

Or-(CH ₂) ₁₁

R ²Base between bridging element and OH end group, molecular formula is-(OCH ₂CHR ⁴) _mPart have the implication of ether or polyether-based.This group can omit (m=0).

Preferably, R ⁴Be hydrogen or methyl.But R ⁴It also can be the chain alkyl that is up to 10 carbon atoms.Described alkyl is preferably unbranched.

Preferred hydroxy-functional R ²Base is-CH ₂OH ,-(CH ₂) ₃OH ,-(CH ₂) ₄OH ,-(CH ₂) ₁₁OH ,-CH ₂CH (CH ₃) CH ₂OH ,-CH ₂CH (CH ₃) CH ₂CH ₂OH ,-CH ₂CH ₂C (CH ₃) ₂OH ,-CH ₂CH ₂C (CH ₃) HOH and-CH=CH-CH ₂OH.

Be up to 30% R ²Base can be the alkyl or the hydrogen of 2 to 20 carbon atoms.Alkyl can be chosen wantonly by halogen or phenyl and replace.The preferred R that is fit to ²The example of alkyl comprises ethyl, propyl group, normal-butyl, isobutyl-, hexyl, octyl group, dodecyl, octadecyl, 2-phenyl propyl and 3-chloropropyl.

Be R ²When base is selected different implication, should note satisfying at least 1.8 R in the mean molecule ²Base is the condition of hydroxy-functional group.Numerical value 1.8 is considered to the mathematical mean of mixture of polymers.

Necessary is that at least 1.8 hydroxy-functional R should be arranged in the mean molecule ²Base (a), but also more amount can be arranged.In fact, R ²Base can all be a hydroxy-functional.Yet, have 1.8 (a) class hydroxy-functional R in case satisfy ²The condition of base, then remaining R ²Base can be (b) class and/or can be R ¹If there is (b) class R ²Base then is suitable for supplementary condition, i.e. hydroxy-functional R ²Base (a) and (b) class R ²The lower value of the ratio of base must not be lower than 70: 30.

Employed organopolysiloxane can make by following reaction in the inventive method, the hydroxy-functional organopolysiloxane that is about to general formula I and (methyl) vinylformic acid and optional not reacting with the monocarboxylic acid of polymerizable double bond of adding in addition.Wording (methyl) vinylformic acid is the mixture that is used to represent to adopt acrylic or methacrylic acid or two kinds of acid.

A crucial prerequisite of the present invention is, based on hydroxyl, what (methyl) vinylformic acid of 0.4 to 0.9 molar weight should be arranged and be up to 0.6 molar weight other does not react with the monocarboxylic acid of polymerizable double bond.Yet based on hydroxyl, the integral molar quantity of acid can not surpass 1.0.

Preferably, all hydroxyl is all esterified in the employed polysiloxane.

Alkyl carboxylic acid and phenylformic acid are considered to not be with the monocarboxylic acid of polymerizable double bond.As alkyl carboxylic acid, the alkyl carboxylic acid of preferred 2 to 11 carbon atoms.This monocarboxylic example includes acetate, propionic acid, butyric acid, valeric acid, PIVALIC ACID CRUDE (25), 2,2-acid dimethyl, 2,2-dimethyl valeric acid, etheric acid, octane-iso carboxylic acid, isodecane carboxylic acid, Sorbic Acid and undecylenic acid.

Especially preferred monocarboxylic acid is an acetate.

In the employed organopolysiloxane of the inventive method, the hydroxy-functional R of 40 to 90 molar percentages ²Base exists with the form of its (methyl) acrylate.The hydroxy-functional R that is up to 60 molar percentages ²The existence form of base can be not to be with the monocarboxylic ester of polymerizable double bond.In addition, according to the monocarboxylic ratio in order to esterification, the form that the hydroxy-functional group can not change yet exists.By the R that has (methyl) acrylate-based and monocarboxylic acid ester group ²The resulting group of base is with unaltered hydroxy-functional R ²Ratio between the base depends on character and consumption thereof in order to (methyl) vinylformic acid/monocarboxylic acid mixture of esterification.

By these means, those of ordinary skill in the art has had an operational method, regulates the performance of employed organopolysiloxane among the present invention by required mode with this:

1. after organopolysiloxane used in the present invention solidified, its unsticking increased along with (methyl) acrylate-based number in the polymer molecule.When cross-linking density increased, the second-order transition temperature of solidifying back coating raise, and the flexibility of paint coatings reduces.Simultaneously, solidify the chemistry and the physical stability increase of back coating.

2. when not increasing with the monocarboxylic ratio of polymerizable double bond, this unsticking performance reduces and the clinging power of carrier is improved.The reduction of this unsticking performance also can be by the optional unreacted hydroxy-functional R that exists ²Hydroxyl in the base and extra the reinforcement.By these means, this unsticking coating is allocated at the chemical property of tackiness agent.

Therefore, employed organopolysiloxane is particularly suitable for corresponding specific purposes and regulates and allocate in the inventive method.Therefore, described organopolysiloxane is particularly suited for the unsticking coating material as radiation-hardenable, perhaps is used for applying to electrical element or electronic component.

Hereinafter provided the example with polysiloxane of (methyl) acrylate-based and optional monocarboxylic acid base used in the present invention, wherein said (methyl) is acrylate-based to be connected by the SiC base.

Compound 1

m＝0，8，

n＝0，2，

R ⁶＝CH ₃， H

Compound 2

A ¹, A ², n and m such as compound 1 definition.

Compound 3

m＝0，8

n＝0，1，

p＝0，1，

Compound 4

q＝0，9，

r＝0，1，

R ⁶＝H，CH ₃

Compound 5

s＝0，7，

t＝0，1，

u＝0，2，

R ⁶＝H，CH ₃

A ¹⁰＝-(CH ₂) ₅-CH ₃

Organopolysiloxane used in the present invention is synthetic by approach well known.For example, with regard to the hydroxy-functional organopolysiloxane of molecular formula I synthetic, can use hydrogen polysiloxanes, wherein R ¹Represent hydrogen.Above-mentioned hydrogen siloxane also with R ^2*Addition reaction takes place in base.R ^2*The corresponding R of base ²Base, but plan with end that Siliciumatom links to each other on have an alkene pair keys.In this reaction, may keep unreacted SiH base in the product, therefore polysiloxane of the present invention can comprise a spot of hydrogen as R ²Base.The hydroxyl of the hydroxy-functional organopolysiloxane of molecular formula I is by known method and (methyl) vinylformic acid and other monocarboxylic acid generation esterification.Should understand this means that esterification preferably carries out under 80 to 150 ℃ temperature, and optionally have a kind of solvent.Preferably, this solvent should form azeotrope with the water that disengages in the esterification process.Suggestion adds a kind of esterifying catalyst, for example sulfuric acid, sulfonic acid or metal-salt in reaction mixture.

If desired, also can add known stopper with significant quantity in esterification process, for example quinhydrones takes place too early to prevent polymerization.

The modification organopolysiloxane can be directly used in the method for the present invention.Only under UV solidified situation, just need add radical initiator in modified polyorganosiloxane, the add-on of initiator is 2 to 5 weight % of siloxanes.

The selection of radical initiator should be based on the wavelength spectrum of the source of radiation that is adopted in solidifying.Described radical initiator is known.The example of described radical initiator comprises benzophenone, diphenyl-ketoxime or benzoin ether.

Can carry out modification by adding other product to the coating composition that obtains thus in a known manner.

Described known properties-correcting agent is the siloxanes of tape base group, and described group is attached in the coating composition with chemical mode when coating composition solidifies.Particularly suitable properties-correcting agent is to have the siloxanes that is connected the hydrogen atom on the Siliciumatom.One of producible effect of described properties-correcting agent is to reduce the viscosity of coating composition, therefore improves the coating performance on chip carrier.

Also can in coating, add additive again.These additives are sealed by coating composition as inert substance in solidification process.The example that is distributed in this material in the coating composition comprises, the silicon-dioxide of high dispersing or the polymkeric substance of fluorinated hydrocarbons.

In following examples, narrated the preparation method and the application performance thereof of employed modified polyorganosiloxane in the inventive method.

Embodiment 1

Under 100 ℃, the 116g in the 4L three-necked flask (2mol) vinyl carbinol, 200g toluene and 4mg H ₂PtCl ₆H ₂O is dissolved in the 40mL solution of 3mL glycol dimethyl ether, splashes into the following polydimethylsiloxane that contains the SiH base of 1170g (1mol) average mark minor.

100 ℃ after following 8 hours, in the following hydroxy-functional polydimethylsiloxane of resulting average mark minor, in 30 ℃ of sulfuric acid and 200g toluene that add 116g (1.6mol) vinylformic acid, 24g (0.4mol) acetate, 0.3g toluhydroquinone, 2.5g 98%.

A ¹¹＝-(CH ₂) ₃-OH

Subsequently reaction mixture is heated to boiling point, azeotropic boils off the reaction water that obtains.After 15 hours, boil off the water of 36g theoretical amount.Unnecessary acid NaHCO ₃Neutralization.Distillation (100 ℃, 40mbar), filter after, obtain the moderately viscous oily matter of 1320g (theoretical amount 95%), foundation ¹The H-NMR spectrum, its general formula is as follows,

A ¹And A ²As compound 1 (R ⁶=H) definition

m＝0.8

n＝0.2。

Embodiment 2

As embodiment 1, the following polydimethylsiloxane that contains the SiH base of 11.6g (0.2mol) vinyl carbinol and 441.9g (0.05mol) average mark minor is reacted,

Generate the following hydroxy-functional polydimethylsiloxane of average mark minor,

A ¹¹＝-(CH ₂) ₃-OH

Make the polydimethylsiloxane and 11.6g (0.16mol) vinylformic acid and 2.4g (40mmol) the acetate generation esterification that obtain subsequently.After 30 hours, with reaction mixture neutralization, filter and distillation, obtain 431g (theoretical amount 93%) the medium-viscosity oily matter that the average mark minor is following,

Wherein

A ¹, A ²As compound 1 (R ⁶=H) definition

n＝0.8

m＝0.2。

Embodiment 3

As embodiment 1, to the following ethoxylation 2-Norborneol of 96.8g (0.4mol) average mark minor,

In the mixture of 100g toluene and 8ml catalyst solution, splash into the following polydimethylsiloxane that contains the SiH base of 200g (0.1mol) average mark minor.

100 ℃ after following 7 hours, reaction mixture is cooled to room temperature, and adds the sulfuric acid of 100g toluene, 2.9g (40mmol) propionic acid, 23.1g (320mmol) vinylformic acid and 0.8g 98%.Be warming up to boiling point subsequently, azeotropic boils off reaction water.Carry out similar aftertreatment after 24 hours, obtain the following oily matter of 310g (96%) average mark minor,

Wherein

A ³, A ⁴, A ⁵As compound 3 (R ⁶=H) definition

m＝0.8

n＝0.1

p＝0.1。

Embodiment 4

As embodiment 1, by the following polyethers of 1447g (1.8mol) general formula,

26.3g (0.2mol) the following polydimethylsiloxane that contains the SiH base of alpha-methyl styrene and 1170g (1mol) average mark minor,

The following hydroxy-functional polydimethylsiloxane of preparation average mark minor,

Wherein

A ⁷As compound 4 definition

A ¹¹＝

m＝0.9

n＝0.1。

As embodiment 1, make this product and 116g (1.6mol) vinylformic acid generation esterification.After 30 hours, carry out similar aftertreatment, obtain 2591g (theoretical amount 95%) reddish-brown oily matter, foundation ¹H-NMR, its average mark minor is as follows,

Wherein

A ⁶, A ⁷As compound 4 (R ⁶=H) definition

A ¹¹＝

m＝0.8

n＝0.1

p＝0.1。

Embodiment 5

As embodiment 1, by 14.0g (0.24mol) vinyl carbinol, 5.0g (0.06mol) 1-hexene and the following polydimethylsiloxane that contains the SiH base of 440.5g (0.05mol) average mark minor,

The following hydroxy-functional polydimethylsiloxane of preparation average mark minor,

Wherein

A ¹⁰＝-(CH ₂) ₅-CH ₃，

A ¹¹＝-(CH ₂) ₃-OH，

m＝0.2

n＝0.8。

Make the polydimethylsiloxane and 13.0g (0.18mol) vinylformic acid and 11.0g (0.06mol) the undecylenic acid generation esterification that obtain subsequently.After 34 hours, with reaction mixture neutralization, filter and distillation, obtain 465g (theoretical amount 98%) medium-viscosity oily matter, foundation ¹The H-NMR spectrum, its average mark minor is as follows,

Wherein

A ²As compound 1 (R ⁶=H) definition

A ¹⁰As compound 5 definition

A ¹²＝

m＝0.7

n＝0.2

p＝0.1。

Application testing

For detecting the application performance of polysiloxane used in the present invention, the product of embodiment 1 to 5 is coated on the different chip carrier (polypropylene oriented film, supercalendered paper), under the effect of 1.5Mrad electron beam, solidify.Each about 1.1g/m of the glue spread of each situation ²

In simultaneous test, adopt the following different wide sealing tape of 30mm: two kinds of Tesa by name ^(R)154 and Tesa ^(R)970 commercially available sealing tape scribbles acrylic binder on the sealing tape, and a kind of Tesa by name ^(R)969 commercially available sealing tape scribbles rubber adhesive on the sealing tape.

For measuring unsticking, above-mentioned sealing tape is spread in the substrate, store the acrylate sealing tape down for 70 ℃ then, store the rubber sealing tape down for 40 ℃.After 24 hours, the peel angle of sealing tape with 180 ° pulled from substrate, to measure required power.This power is called as separating force (releaseforce).In addition, also with firmly scraping of thumb, to measure the clinging power of modified dimethyl polysiloxane to substrate.If clinging power is not enough, will form elastomeric chip (being that what is called is wiped test (" rub-off " test)).

Table

Modified siloxane embodiment	Supercalendered paper				The polypropylene oriented film
									Tesa (R) 154	Tesa (R) 970	Tesa (R) 969	Wipe test	Tesa (R) 154	Tesa (R) 970	Tesa (R) 969	Wipe test
	Separating force [N]			Separating force [N]
							1	1.0	2.0	1.8	Do not have		0.9	1.8	1.6		Do not have
2	0.15	0.4	0.3	Do not have	0.1	0.3						0.3				Do not have
							3	3	6	8	Do not have		3	4	7		Do not have
4	4	6	6	Do not have	2	5						5				Do not have
							5	0.1	0.4	0.3	Do not have		0.05	0.2	0.2		Do not have

From last table, know and find out that organopolysiloxane used in the present invention has required application performance; Described polysiloxane is attached on the coated carrier, can be on carrier fast setting, and show unsticking preferably to the different tackiness agent of chemical.

Claims (12)

1. method of coating carrier in the following manner: a kind of curable organopolysiloxane of (methyl) acrylate-based modification is coated on the carrier surface, effect by the polymerizability energy-rich radiation is solidified this modification organopolysiloxane, it is characterized in that, described curable organopolysiloxane is following (A) and the reaction product (B) under the enzymatic synthesis condition

(A) the following polysiloxane of a kind of average general formula

Wherein

R ¹Base is identical or different, and represents the low molecular weight alkyl or the phenyl of 1 to 4 carbon atom,

R ²Base is selected from following group

(a) molecular formula is-CH ₂(CR ³ ₂) _n-(OCH ₂CHR ⁴) _m-OH ,-CH=CH-CR ³ ₂The hydroxy-functional group of-OH and the following group of molecular formula

R wherein ³Base is identical or different, and represents a hydrogen or the alkyl with 1 to 4 carbon atom,

R ⁴Base is identical or different, and represents a hydrogen or have the alkyl of 1 to 10 carbon atom,

Subscript

N=0 to 10

M=0 to 40,

(b) the not replacement of 2 to 20 carbon atoms or substituted alkyl and hydrogen, and

(c) R ¹Base,

A is a numerical value 1 to 1,000

B is a numerical value 0 to 10,

Prerequisite is

(i) comprise at least 1.8 hydroxy-functional R in the mean molecule ²Base (a),

(ii) remaining R ²Base is type (a) and (b) or (c),

(iii) (a) class hydroxy-functional R ²Base and (b) class R ²The lower value of the ratio of base was not less than 70: 30, and

(B) based on hydroxyl, (methyl) vinylformic acid of 0.4 to 0.9 molar weight and be up to a kind of of 0.6 molar weight not with the monocarboxylic acid of polymerizable double bond, the summation of described these sour molar weights is not more than 1.0.

2. coating composition, its main composition or comprise composition and be that the curable organopolysiloxane by (methyl) acrylate-based modification of significant quantity, described organopolysiloxane are following (A) and (B) reaction product,

(A) the average following a kind of polysiloxane of general formula

Wherein

R ¹Base is identical or different, and represents the low molecular weight alkyl or the phenyl of 1 to 4 carbon atom,

R ²Base is selected from following group

(a) molecular formula is-CH ₂(CR ³ ₂) _n-(OCH ₂CHR ⁴) _m-OH ,-CH=CH-CR ³ ₂The hydroxy-functional group of-OH and the following group of molecular formula

R wherein ³Base is identical or different, and represents a hydrogen or the alkyl with 1 to 4 carbon atom,

R ⁴Base is identical or different, represents a hydrogen or the alkyl with 1 to 10 carbon atom separately, and

Subscript

N=0 to 10

M=0 to 40,

(b) the not replacement of 2 to 20 carbon atoms or substituted alkyl and hydrogen, and

(c) R ¹Base,

A is a numerical value 1 to 1,000

B is a numerical value 0 to 10,

Prerequisite is

(i) comprise at least 1.8 hydroxy-functional R in the mean molecule ²Base (a),

(ii) remaining R ²Base is type (a) and (b) or (c),

(iii) (a) class hydroxy-functional R ²Base and (b) class R ²The lower value of the ratio of base was not less than 70: 30,

(B) based on hydroxyl, (methyl) vinylformic acid of 0.4 to 0.9 molar weight and be up to a kind of of 0.6 molar weight not with the monocarboxylic acid of polymerizable double bond, the summation of described these sour molar weights is not more than 1.0.

3. the coating composition of claim 2, wherein said curable organopolysiloxane be formula I polysiloxane and (methyl) vinylformic acid with not with the reaction product of two monocarboxylic mixtures of key, the ratio of described polysiloxane and described mixture makes the whole esterifications of all hydroxyls of the polysiloxane of general formula I.

4. the coating composition of claim 2, wherein said curable organopolysiloxane be formula I polysiloxane and (methyl) vinylformic acid with 2 to 10 carbon atoms not with the reaction product of pair monocarboxylic mixtures of key.

5. the coating composition of claim 4, wherein said curable organopolysiloxane are the reaction product of the mixture of formula I polysiloxane and (methyl) vinylformic acid and acetate.

6. the coating composition of claim 2, the subscript a in the curable organopolysiloxane of wherein said formula I is a numerical value 5 to 200, and subscript b is a numerical value 0 to 2.

7. the coating composition of claim 2, the subscript b in the curable organopolysiloxane of wherein said formula I is a numerical value 0.

8. the coating composition of claim 2, the R that the curable organopolysiloxane of wherein said formula I comprises ¹At least 90% is methyl in the base.

9. the coating composition of claim 2, the m=0 in the curable organopolysiloxane of wherein said formula I.

10. the coating composition of claim 2, the hydroxy-functional R that the curable organopolysiloxane of wherein said formula I is included ²Base (a) is selected from-CH ₂OH ,-(CH ₂) ₃OH ,-CH ₂-CH (CH ₃) CH ₂OH ,-(CH ₂) ₄OH ,-CH ₂CH (CH ₃) CH ₂-CH ₂OH ,-CH ₂CH ₂C (CH ₃) ₂OH and CH ₂CH ₂C (CH ₃) HOH.

11. the coating composition of claim 2, (b) class R that the curable organopolysiloxane of wherein said formula I is included ²Base is selected from ethyl, propyl group, 1-butyl, hexyl, octyl group, dodecyl, octadecyl, 2-phenyl propyl and 3-chloropropyl.

12. the coated product that the method by claim 1 makes.