CN1787900A

CN1787900A - Process for preparing UV curable sealing assemblies

Info

Publication number: CN1787900A
Application number: CN 200480013154
Authority: CN
Inventors: M·B·戈特里布; C·鲁平格
Original assignee: EI Du Pont de Nemours and Co
Current assignee: DuPont Performance Elastomers LLC; EIDP Inc
Priority date: 2003-05-16
Filing date: 2004-05-14
Publication date: 2006-06-14
Anticipated expiration: 2024-05-14
Also published as: CN100563986C

Abstract

Processes for preparation of seals and gaskets using cure-in-place techniques that incorporate a molding step, which is preferably an injection molding step, are provided. The process further comprises the steps of separating mold plates (12, 10, 34, 36, 60, 62, 76, 78) from a support member (22, 30, 48, 68) leaving an UV curable sealing composition adhered thereto and exposing said assembly to UV radiation to cure said UV curable elastomeric sealing composition. The processes are useful for preparing sealing assemblies that comprise compositions that are curable by UV radiation and that are adhered to a support member (22, 30, 48, 68).

Description

The method for preparing UV curable sealing assemblies

Invention field

The present invention relates to comprise the be bonded and sealed circle or the black box of packing ring type.Specifically, the present invention relates to comprise the preparation method of the goods of a pad and shaping, adhesion, uncured elastic packing composition.In addition, the present invention relates to prepare the method for black box with sticking to shaped resilient sealing compositions low-temperature setting on the pad.The invention still further relates to goods by the inventive method preparation.

Background of invention

Elastic washer and sealing ring wherein are directed to back hot pressing in the mould with the polymer that curing agent and other additive mix fully usually by preparing based on compression moulding, die casting or injection molding technology.The high temperature that uses in moulding process causes elastomer and curing agent chemically reactive, thereby produces cross-linked elastomer.As the result of the chemical reaction that takes place between polymer and curing agent, be to produce network structure in the cross-linking products at whole cured product.This network structure is given intensity and elasticity, makes the elasticity product have the feature capabilities at the pressure lower seal.

Under the normal condition, elastic seal ring by above-mentioned any molding technology preparation and packing ring are through manually being installed on the goods to be sealed.Perhaps, use adhesive that the curing seal is connected on the goods sometimes.In addition, packing ring can be for example in the production of axle envelope on metallic carrier molding.This joining technique can not be entirely satisfactory in all cases.Particularly, manual method is consuming time, and adhesive can influence the physical property of sealing ring, cycle time that molding need be grown on metallic carrier and high temperature.

The finished product sealing ring is commonly used for the sealing ring of trough of belt goods, for example be used for the sealing ring of rocker cover that automobile engine uses and air inlet pipe and in electronic equipment and treatment facility, use in conjunction with door assembly (bonded door assemblies).This channel members has complicated cross section usually, and sealing ring is fixed in the groove.The production that is used for the sealing ring of this groove relates to the design of the mould of corresponding complexity.In addition, elastic seal ring is inserted in the groove be one may be quite consuming time the component end item manufacture process in manual steps independently.Perhaps, this curing on the spot is also infeasible in some cases.

People have been familiar with relying on the use ultraviolet radiation but not heat causes the curing gasket techniques on the spot of chemistry.For example, United States Patent (USP) 6,346,300,6,472,452,6,495,213 and 6,506,460 have described and can use various elastomeric methods, and described elastomeric example has fluoroelastomer, ethene (methyl) acrylate elastomer, ethylene ' alpha '-olefin elastomer and chlorination elastomer.In similar approach, use the example of silicone elastomer to be disclosed in for example B.G.McClelland, Cure-In-Place Gasketing Offers Process And Quality Improvements As AWater Pump Flange Seal in Gaskets and Sealants For AutomotiveApplications, SAE Special Publications, 1235,47-51,1997.Though these methods obtain excellent result, but in some cases, this technology also is not suitable for, particularly when needing high precision and all the more so during than the obtainable more complicated sealing ring shape of the sealing of curing on the spot (the dispensed cure in placegasketing) technology of use disperseing.

Injection moulding is a kind ofly referred to be used to make all processable polymer technology of even complicated cross section members, and it is used for thermoplastic compounds, because they just easily flow through heating, and need not chemical crosslinking and handles.Injection moulding also is used to prepare the thermoplastic block elastic composition, and wherein the hypocrystalline composition of method of molding shaping is kept its shape by the crystallization of its hard block after cooling.This composition is easy to the demoulding.Use an example of thermoplastic elastic body method to be disclosed in United States Patent (USP) 5,618,488, it has described a kind of method of producing the roller bearing sealing ring.But, when this technology is used for thermo-setting elastomer, owing to required long process time of cross-linked elastomer and form the chip that can't reuse and cause uneconomical.It is that most of devices and mould can not see through ultraviolet light that UV curing method does not use another reason of injection molding machine usually, and therefore needs translucent mould.United States Patent (USP) 5,885,514 have described by the method that can form goods by the elastomer that action of ultraviolet light is solidified, and it is produced in the injection machine with the mould that can see through ultraviolet radiation.This technology can be used, but needs special equipment.

Curing technology carries out the benefit that packing ring production is brought because evenly fill the ability of mould in the injection moulding process and use on the spot, make the injection moulding process production that to use available conventional equipment stick to the forming and hardening sealing compositions on the holder, described composition can solidify the preparation goods on the spot, the physical property of the sealing compositions that solidifies is the elastomeric character of typical cross-linked thermal set, but wherein said method has short cycle time, and production does not produce a large amount of chips.

The invention summary

The present invention relates to be stated from a method of the curable sealing compositions that fills up,, be applied to a method of pad back curing sealing compositions and having goods that are stated from the sealing compositions assembly on the pad by the goods of this method preparation.

Specifically, the present invention relates to provide the method for the sealing compositions that is stated from the uV curable on the pad, the sealing compositions of wherein said uV curable comprises basic uncured elastomer, polyfunctional crosslinking agent and ultraviolet initiator, said method comprising the steps of:

A., first template and at least one other template relative with described first template with at least one injection channel are provided;

B., a pad with optional injection channel is provided;

C. described pad placed between described first template and described at least one other template, make that a) described pad contacts with described at least one other template with described first template, and b) form die cavity, described die cavity comprises the described injection channel of described first template and the surface of described pad;

D. the sealing compositions with described uV curable imports in the described die cavity, the feasible curing that the sealing compositions of described uV curable does not take place basically of described lead-in mode, and the sealing compositions of described uV curable contacts and is adhered on it with described pad; With

E. isolate described template from described pad, obtain being bonded in the sealing compositions of the described uV curable on the pad.

The present invention also relates to by the curable sealing compositions on the pad of method for preparing.

The invention still further relates to the method for preparing black box, said method comprising the steps of:

A., assembly is provided, at least one parts of wherein said assembly comprise the elastic packing composition that is adhered to the uV curable on the pad, described elastic packing composition comprises uncured elastomer, polyfunctional crosslinking agent and ultraviolet initiator basically, the wherein said method preparation of sealing compositions by may further comprise the steps that is adhered to the uV curable on the pad:

1. first template and at least one other templates relative with described first template with at least one injection channel are provided;

2. the pad with optional injection channel is provided;

3. described pad placed between described first template and described at least one other template, make that a) described pad contacts with described at least one other template with described first template, and b) form die cavity, described die cavity comprises described injection channel and described pad of described first template;

4. the sealing compositions with described uV curable imports in the described die cavity, the feasible curing that the sealing compositions of described uV curable does not take place basically of lead-in mode, and the sealing compositions of described uV curable contacts and is adhered on it with described pad; With

5. isolate described template from described pad, make the sealing compositions of described uV curable be bonded in the elastic packing composition that a pad is gone up and formation is bonded in described the uV curable on the pad thus; With

B. described assembly is exposed to the enough period of next section of ultraviolet radiation to solidify the elastic packing composition of described uV curable.

In addition, the present invention relates to black box by method for preparing.

Brief description of drawings

Fig. 1 is the longitudinal section of implementing the device embodiment of the inventive method, wherein props up pad 22 for trough of belt props up pad, and die cavity does not link to each other with all surface of groove.

Fig. 2 is the longitudinal section of implementing the device embodiment of the inventive method, wherein props up pad 30 and does not contain groove.

Fig. 3 is the longitudinal section of implementing the device embodiment of the inventive method, and wherein propping up pad 48 is that trough of belt props up pad, and wherein die cavity links to each other with all surface of groove.

Fig. 4 is the longitudinal section of implementing the device embodiment of the inventive method, wherein props up pad 68 and does not contain groove.

Detailed description of the present invention

The present invention relates on a pad and the sealing ring that in black box, solidifies on the spot. This The preparation of black box comprises two steps. In first method, the pad (common but non-must Must prop up pad for trough of belt) form die cavity with one or more templates. Ultraviolet light polymerization elasticity is close The envelope composition is directed in the die cavity, and the bar that does not basically solidify at described composition Keep wherein under the part, composition flows in the pad or stream is propping up on the pad. " basically not solid Change " refer to the elastic packing composition of the uV curable measured according to ASTMD-1646 Constant its initial value before importing to die cavity that remains on of Mooney viscosity ML1+4 (100 ℃) ± 50% in. To prop up then pad and separate with template or plate, and produce thus to have to be bonded in and prop up pad A pad of the substantially uncured elastic composition on surface. Substantially the uncured composition that refers to Viscosity remains in the front initial value of importing die cavity ± 50%. Prop up pad together with its bonding consolidating Changing sealing compositions is the useful products that can be used as the black box component. When being exposed to ultraviolet light During radiation, curable sealing compositions is cured and is transformed into thus sealing ring. Curing operation Can behind this production, carry out immediately. Obtain thus having a pad that solidifies sealing ring. Perhaps, the product of its uncured state can be used as the component that forms black box. Black box is logical Cross and to be exposed to ultraviolet radiation as a pad and its bonding elastic composition of component parts The lower time of enough solidifying will prepare. The method is produced has accurate deposition materials thickness Prop up pad and black box. The method also has the benefit that can implement at a lower temperature, thereby Improve efficiency and can seal on the spot thermoplastic and other base materials such as pottery, thermosetting Base material such as phenolic resins or epoxy resin or metal base. Cycle time in mold apparatus Shorter, be usually less than one minute, and the method there is not chip substantially.

The sealing compositions that can be used for uV curable of the present invention comprises substantially uncured Elastomer; Multifunctional crosslinking agent (normally acrylic crosslinking agent or metering system acid crosslinking agent or Triallyl cyanurate or triallyl isocyanurate); And ultraviolet initiator. Basically not The elastomer that solidifies refers to not have crosslinked or has the elastomer of low crosslinking degree, thus its can Up to extruding under 250 ℃ the temperature. Composition can solidify by the effect of ultraviolet radiation. This A little curable compositions can be used as sealing ring is applied to as another embodiment of the present invention Goods on the raw material of method. They be used for processing uncured elastomer blend as Mix or extrude under the temperature of operation thermally-stabilised. This temperature is generally 25-250 ℃. Heat is steady Surely refer to composition and unautogenous formation cross-linked network, i.e. their not premature setting or sulfurations. In other words, the viscosity of composition is being heated to molding temperature and when this temperature keeps 5 minutes Be held constant at initial value ± 50% in. The molding temperature that is fit to depends on concrete used ultraviolet The decomposition temperature of light trigger and multifunctional crosslinking agent. But molding temperature must Gao Zhike Cured elastomer composition can reach the required liquidity of production technology. This temperature is generally 25-250 ℃, preferred 90-170 ℃. Heating or during machining, as in screw extruder, In gear pump or the piston pump, composition energy viscoelastic fluid flow, and can import in the mould and shape Become to adhere to a curable form seal composition of pad. These are with curable seal combination A pad of thing is the goods that can solidify by being exposed to ultraviolet radiation.

The first kind of component that can be used for the thermostable composite of the inventive method is elastomer, and be logical Often be to have 1-150, ML1+4 (100 ℃) and preferred 1-70, the Mooney of ML1+4 (100 ℃) The thermo-setting elastomer of viscosity. Useful especially elastomer is former (namely uncured) of following type Elastomeric polymer: ethylene acrylate copolymer rubber, ethylene methyl acrylate copolymer Rubber, ACM, ethylene-vinyl ester elastomer, the bullet of diene and unsaturated nitrile Property copolymer (being nitrile rubber and hydrogenated nitrile rubber), polyurethane elastomer, polysiloxanes has The fluoroelastomer of the copolymerization units of iodate, bromination or chlorination cure site monomers has non-conjugated The fluoroelastomer of the copolymerization units of diene, comprise have chlorination, iodate or bromination comonomer Fluoroelastomer and have the elastomer of the fluoroelastomer of bromine or iodine atom in end position, chlorination alkene Olefin elastomer, chlorosulfonation olefin elastomer and epichlorohydrin elastomer, ethyleneα-olefincopolymer rubber Glue and butyl rubber.

A class ethylene copolymer rubber that can be used in the compositions and methods of the invention is described in United States Patent (USP) 6,472 is in 452. This type rubber is by two types vinyl ester copolymers group Become. First type comprises having acrylic acid C₁-C ₈The C of Arrcostab copolymerization units or methacrylic acid₁-C ₈The ethylene copolymer of Arrcostab copolymerization units. The second type comprises having C₂-C ₈The ethylene copolymer of the vinyl esters copolymerization units of carboxylic acid. Every type copolymer includes Dimer or more senior copolymer with other comonomer copolymerization units.

When described copolymer was dimer, the ethylene contents scope is about 20-85% weight, and was excellent Select 25-65% weight. The representative example of this composition comprises ethene and for example acrylic acid first Ester, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid 2-ethyl hexyl The copolymer of base ester, Hexyl 2-propenoate, and ethene and for example vinyl acetate, propionic acid second The copolymer of alkene ester and vinyl caproate. Also can use ethene and methyl methacrylate for example, EMA, isobutyl methacrylate, 2-Ethylhexyl Methacrylate, first The copolymer of base n-butyl acrylate or hexyl methacrylate, but optimal ethylene acrylate Copolymer and ethylene vinyl ester copolymers. Wherein, methyl acrylate, n-butyl acrylate With vinyl acetate be most preferred comonomer. Described copolymer has 1-60, ML usually 1+4 (100 ℃) and preferred 1-20, the Mooney viscosity of ML1+4 (100 ℃). Also can use dimerization The blend of thing.

Be fit to be used as in the method for the invention the aforementioned second of the more advanced types of polymers compositions The example of alkene elastocopolymer comprises a) ethene; B) alkyl acrylate, methacrylic acid alkane The vinyl esters of base ester or carboxylic acid; And c) copolymer of unsaturated acids. Object lesson comprises tool The terpolymer that following copolymerization units is arranged: a) ethene; B) acrylic acid C₁-C ₈The C of Arrcostab, methacrylic acid₁-C ₈Arrcostab or C₂-C ₈The vinyl esters of carboxylic acid and c) be selected from following The carboxylate of 3-12 carbon atom: α, β-unsaturated monocarboxylic acid; α, β-unsaturated binary carboxylic Acid; And α, the monoesters of β-unsaturated dicarboxylic acid. The ethylene contents scope of copolymer is about 25-70% weight, preferred 35-65% weight, α, β-unsaturated monobasic or dicarboxylic acids or α, β-insatiable hunger With the amount of acid monoester for being enough to provide 0.1-10% weight and preferred 0.5-5.0% weight carboxylic acid base Amount. α, the β that is fit to-unsaturated monobasic or dicarboxylic acids comprise monocarboxylic acid such as acrylic acid and first Base acrylic acid; Dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; With the monoesters of dicarboxylic acids as Ethyl maleate, monomethyl ester and the own ester of maleic acid single 2-ethyl. Preferred acrylic acid, Methacrylic acid and ethyl maleate. Alkyl acrylate or vinyl esters comonomer account for The 25-70% weight of polymer preferably accounts for 30-65% weight. Be applicable to the acrylic acid of polymer Arrcostab comprises acrylic acid C₁-C ₈Arrcostab, for example methyl esters, ethyl ester, positive butyl ester, isobutyl Ester, own ester and 2-Octyl Nitrite. Preferred acrylic acid methyl esters, ethyl ester and butyl ester. Most preferably Methyl acrylate. The vinyl esters that is applicable to the carboxylic acid of described polymer comprises having 2-8 carbon The vinyl esters of the carboxylic acid of atom is such as vinyl-acetic ester, vinyl propionate base ester, caproic acid second Alkenyl esters and 2 ethyl hexanoic acid vinyl esters. Preferred vinyl acetate. The door of these copolymers Buddhist nun's viscosity ML1+4 (100 ℃) is generally 1-50, preferred 1-20. The representative of these copolymers The property example comprises that ter-polymers and quadripolymer are such as ethylene/methyl acrylate/metering system Acid copolymer; Ethylene/methyl acrylate/ethyl maleate copolymer; Ethylene/acrylic acid/second The vinyl acetate copolymer; Ethylene/butyl acrylate/acrylic copolymer; Ethylene/vinyl acetate / methacrylic acid copolymer; Ethene/fumaric acid/methyl acrylate copolymer; Ethylene/acrylic acid Methyl esters/carbon monoxide/methacrylic acid copolymer; And ethene/ethyl maleate/carbon monoxide/ Vinyl acetate copolymer. Also can use copolymer blend or copolymer and other polymer Blend.

In addition, the copolymer considered of the present invention is those ethene (methyl) acrylate copolymers Skeleton is by using the copolymer such as reagent graft modifications such as sensitising agents. This composition Some examples be described in K.K.Dietliker, Photoinitiators for Free Radical and Cationic Polymerization, CHEMISTRY ﹠ TECHNOLOGY OF UV ﹠ EB FORMULATION FOR COATINGS, INKS ﹠ PAINTS, Vol.3,204-208 (P.K.T.Oldring ed., 1991).

Be applicable to another polymer type bag of implementing such elastic ethylene copolymer of the present invention Contain ethene, acrylate or vinyl esters, acrylic or methacrylic acid glycidyl ester, Copolymerization units with the carbon monoxide of choosing wantonly. In general, this composition comprises 30-70% The propylene of the acrylate of the ethene of weight, 25-65% weight or vinyl esters, 2-10% weight The carbon monoxide of acid or GMA and 0-15% weight, percentage by weight is total Count 100% weight. The copolymerization of optimal ethylene, acrylate and GMA Thing. Representational alkyl acrylate and comprise third as the alkyl acrylate of comonomer Olefin(e) acid methyl esters, ethyl acrylate, propyl acrylate, n-butyl acrylate, acrylic acid isobutyl Ester and Hexyl 2-propenoate. Representative copolymer comprises ethylene/methyl acrylate/methacrylic acid contracting Water glyceride; Positive butyl ester/the GMA of ethylene/acrylic acid; Ethylene/acetic acid second Alkene ester/GMA; And ethylene/methyl acrylate/carbon monoxide/methyl-prop The olefin(e) acid ethylene oxidic ester.

Be applicable to an again polymer type bag of implementing such elastic ethylene copolymer of the present invention Contain a) ethene; B) vinyl acetate, acrylic acid C₁-C ₈Arrcostab or methacrylic acid C₁-C ₈Arrcostab; And c) copolymerization units of carbon monoxide or sulfur dioxide. The vinyl acetate of copolymer Ester, alkyl acrylate or alkyl methacrylate content are generally 20-50% weight, one Carbonoxide or content of sulfur dioxide are generally 5-40% weight. The example of this copolymer comprises second Alkene/vinyl acetate/carbon monoxide; Positive butyl ester/the carbon monoxide of ethylene/acrylic acid; Ethylene/propene Acid methyl esters/carbon monoxide; And ethene/ethyl maleate/carbon monoxide/vinyl acetate.

Above-mentioned bipolymer and more senior copolymer exist by ethene and comonomer usually In the reactor that stirs, in the presence of at least a free-radical initiator, at about 100-300 ℃ temperature and the pressure of about 130-350MPa under continuously copolymerization prepare, common such as the U.S. Patent 3,883 is described in No. 472. Most preferably described copolymer is also at about 2-25% weight methyl alcohol Or the lower preparation of acetone existence, thereby reduce or eliminate the reactor dirt.

Described elastic component also can be selected from the ACM type, comprises acrylic acid C₁-C ₁₀The homopolymers of Arrcostab or copolymer. Preferred alkyl acrylate comprise ethyl acrylate, Butyl acrylate and 2-EHA. Acrylic ester copolymer rubber comprises and reaches 40% The copolymerization units of weight list vinyl monomer, for example styrene, acrylonitrile, vinyl butyl Ether, acrylic acid and be different from the acrylic acid C of main alkyl acrylate comonomer₁-C ₁₀Alkyl Ester. This copolymer can (can be available from Nippon available from for example Hytemp  ACM Zeon, the acrylate homopolymer of KK and copolymer rubber) and Toacron  AR-601 acrylic acid Ester rubber (polyethyl acrylate, can available from Toa Paint, KK).

In addition, described elastic component can be the copolymer of diene and unsaturated nitrile. Described two Alkene can be butadiene for example. Described nitrile is preferably acrylonitrile. This copolymer is called as fourth Nitrile rubber and commercialization. They have the acrylonitrile content of 18-50% weight usually. Hydrogenated nitrile rubber also is applicable to the inventive method.

The fluorubber that is suitable as the inventive method elastic component comprises and comprises following copolymerization units Fluoroelastomer: one or more fluorochemical monomers such as vinylidene fluoride, hexafluoropropene, 1-hydrogen Five fluorine propylene, 2-hydrogen five fluorine propylene, tetrafluoroethene, chlorotrifluoroethylene and perfluor (alkyl ethene Base) ether, and other not fluorine-containing monomers such as ethene and propylene. Such elastomer is retouched Be set forth in Logothetis, Chemistry of Fluorocarbon Elastomers, Prog.Polym.Sci., Vol.14,251-296 (1989). This polymer can by the monomer mixture that is fit to by means of Free radical produces initator to carry out polymerization and prepares, and can be polymerisation in bulk, atent solvent molten Liquid polymerization, aqueous emulsion polymerization or aqueous suspension polymerization. Described polymerization can be continuously, in batches Or semicontinuous mode is carried out. Article and the U.S. that conventional preparation method is described in Logothetis are special Sharp 4,281,092,3,682,872,4,035,565,5,824,755,5,789,509,3,051,677 With 2,968, in No. 649.

The object lesson of this fluorubber comprises vinylidene fluoride and hexafluoropropene and optional The copolymer of tetrafluoroethene; The copolymer of vinylidene fluoride and chlorotrifluoroethylene; 1,1-two The copolymer of PVF, hexafluoropropene, tetrafluoroethene and chlorotrifluoroethylene; Tetrafluoroethene and The copolymer of propylene; With tetrafluoroethene and perfluor (alkyl vinyl) ether [preferred perfluor (methyl second Thiazolinyl) ether] copolymer. The various fluorubber of the present composition also comprise come from exist non-common At least one halogenation solidification point or activity double key of the copolymerization units of yoke diene. The halogenation solidification point But can be copolymerization cure site monomers or the halogen atom that is present in fluorubber polymer end of the chain position. It is crosslinked that cure site monomers, activity double key or halogenation end group can react formation. Cure site monomers Be selected from bromination, chlorination or iodate alkene; Bromination, chlorination and iodate unsaturated ethers and non-conjugated Diene. The bromination cure site monomers can comprise other halogens, preferred fluorine. Example has bromine trifluoro second Alkene, 4-bromo-3,3,4,4-tetrafluoro butene-1 and other be such as bromine ethene, 1-bromo-2, the 2-difluoroethylene, Perfluor allyl bromide, bromoallylene, 4-bromo-1,1,2-trifluoro butylene, 4-bromo-1,1,3,3,4,4-hexafluoro butylene, 4-Bromo-3-chloro-1,1,3,4,4-five fluorine butylene, 6-bromo-5,5,6,6-tetrafluoro hexene, 4-bromine five fluorine butene-1s With 3,3-difluoro allyl bromide, bromoallylene. Can be used for bromination unsaturated ethers cure site monomers of the present invention comprises Ether, the CF of 2-bromo-perfluoroethyl perfluorovinyl base ether₂-Br-Rf-O-CF＝CF ₂The fluorinated compound of type such as CF₂BrCF ₂O-CF＝CF ₂And ROCF=CFBr or ROCBr=CF₂The fluorovinyl ether of type, wherein R is low alkyl group or fluoroalkyl such as CH₃OCH=CFBr or CF₃CH ₂OCF=CFBr. Iodate alkene also can be used as cure site monomers. The iodate monomer that is fit to The iodate alkene that comprises following formula: CHR=CH-Z-CH₂CR-I, wherein R be-H or-CH₃ Z is C₁-C ₁₈(entirely) fluoro alkylidene group, linearity or branch, optional comprise one or more Ether oxygen atom, or as at United States Patent (USP) 5,674, disclosed (entirely) fluorine polyoxy alkylidene in No. 959 Group. Other examples of useful iodate cure site monomers have the unsaturated ethers of following formula: I (CH₂CF ₂CF ₂) _nOCF＝CF ₂And ICH₂CF ₂O[CF(CF ₃)CF ₂O] _nCF＝CF ₂Deng, wherein N=1-3, such as being disclosed in United States Patent (USP) 5,717, the unsaturated ethers in No. 036. In addition, be fit to The iodate cure site monomers comprise iodoethylene, 4-iodo-3,3,4,4-tetrafluoro butene-1; The 3-chlorine-4-iodine-3,4,4-trifluoro butylene; 2-iodo-1,1,2,2-tetrafluoro-1-(vinyl oxygen) ethane; 2-iodo-1-(perfluor second Thiazolinyl oxygen)-1,1,2,2-tetrafluoroethene; 1,1,2,3,3,3-hexafluoro-2-iodo-1-(perfluorovinyl sulfide oxygen) third Alkane; 2-iodine ethyl vinyl ether; 3,3,4,5,5,5-hexafluoro-4-iodine amylene; With the iodine trifluoro-ethylene, It is disclosed in United States Patent (USP) 4,694, No. 045.

The example of non-conjugated diene cure site monomers comprises Isosorbide-5-Nitrae-pentadiene, 1,5-hexadiene, 1,7-Octadiene etc., such as being described in Canadian Patent 2,067, the example in 891. A kind of suitable Triolefin is 8-methyl-4-ethylidene-1, the 7-octadiene. In above-mentioned cure site monomers, preferred Compound comprises 4-bromo-3,3,4,4-trifluoro butene-1; 4-iodo-3,3,4,4-tetrafluoro butene-1 and bromine three PVF.

In addition, or as an alternative, owing to when fluorubber prepares, use chain-transferring agent or molecule The amount conditioning agent, iodine, bromine or its mixture can be present in the fluorubber end of the chain. This reagent comprises Contain iodine compound, it causes one or both ends at polymer molecule in conjunction with iodine. Diiodomethane, Isosorbide-5-Nitrae-diiodo perfluo normal butane and 1,6-, two iodo-3,3,4,4-tetrafluoro hexane is the representative of this reagent. Other iodinated chain transfer agents comprise 1,3-diiodo perfluo propane; Isosorbide-5-Nitrae-diiodo perfluo butane; 1,6-The diiodo perfluo hexane; 1,3-, two iodo-2-chlorine perfluoropropanes; 1,2-two (iodine difluoromethyl)-perfluor ring Butane; Single iodine hexafluoroethane; Single iodine perfluorinated butane; 2-iodo-1-hydrogen hexafluoroethane etc. Especially Diiodinated chain transfer agents preferably. The example of brominated chain transfer agents comprises 1-bromo-2-iodine perfluor Ethane; 1-bromo-3-iodine perfluoropropane; 1-iodo-2-bromo-1,1-Difluoroethane and for example be disclosed in the U.S. Patent 5,151, other brominated chain transfer agents in 492.

The copolymerization of ethene, tetrafluoroethene, perfluor (alkyl vinyl) ether and brominated cure site monomers Thing (such as disclosed copolymer in No. 4,694,045, the United States Patent (USP) of Moore) is applicable to this Invention. Also can use and usually comprise tetrafluoroethene and perfluor (the alkyl ethene of fluoridizing the nitrile solidification point Base) ether for example is disclosed in United States Patent (USP) 4,983, perfluor (8-cyano group-5-methyl-3,6-in No. 697 Dioxa-1-octene) etc. Other contain the available fluorubber of bromination or iodate alkene cure site monomers Be described in United States Patent (USP) 4,035,565,4,564,662,4,745,165,4,694,045,4,948,852 With 4,973, in No. 633. Other iodate cure site monomers are disclosed in FDA (Food and Drug Adminstration) Food Contact Nottification No.0017 (1999) and No. 4,962,236, United States Patent (USP).

Described each analog copolymer comprises binary polymer or the higher membered copolymer with other comonomer copolymerization units.

Have been found that to have 5-150, ML1+4 (121 ℃) and preferred 10-70, the former fluorubber of the Mooney viscosity of ML1+4 (121 ℃) is particularly useful in the method for the present invention.The composition that those fluorubber have a Mooney viscosity in preferable range shows the optimum balance of processability and draftability.

Have been found that also cure site monomers contained fluorubber, copolymerization unit shows the cure states of enhancing at the composition of 0.05-10.0% weight level.

Chlorinated olefin polymer also is suitable as the elastic component of the inventive method.Chlorinated olefin polymer specifically also comprises chlorosulfonated olefin polymers.Olefin polymer is meant C ₂-C ₈The homopolymers of α-monoolefine and copolymer comprise graft copolymer.Described copolymer can be binary polymer or more senior copolymer such as terpolymer or quadripolymer.But olefin polymer branch or branch not, and can be by the preparation of free radical method, Ziegler-Natta (Z-N) catalysis or use metallocene catalyst system catalysis, for example at United States Patent (USP) 5,272,236 and 5, carry out under the catalysis of disclosed catalyst in 278, No. 272.The example of useful especially olefin polymer comprises C ₂-C ₃The homopolymers of α-monoolefine, the copolymer of ethene and carbon monoxide, and the copolymer of ethene and at least a ethylenically unsaturated monomer, described ethylenically unsaturated monomer is selected from C ₃-C ₂₀α-monoolefine, unsaturated C ₃-C ₂₀The C of monocarboxylic acid ₁-C ₁₂Arrcostab, undersaturated C ₃-C ₂₀Monocarboxylic acid or dicarboxylic acids, unsaturated C ₄-C ₈The acid anhydrides of dicarboxylic acids, saturated C ₂-C ₁₈The vinyl esters of carboxylic acid.The object lesson of these polymer comprises polyethylene, polypropylene, EVAc, ethylene acrylic acid co polymer, ethylene methacrylic acid copolymer, ethylene methyl acrylate copolymer, the ethylene methacrylic acid methyl terpolymer, the positive butyl ester copolymer of ethylene methacrylic acid, the ethylene methacrylic acid glycidyl ester copolymer, the graft copolymer of ethene and maleic anhydride, the graft copolymer of propylene and maleic anhydride, and ethene and propylene, butylene, the 3-Methyl-1-pentene, the copolymer of hexene or octene.Preferred olefin polymer is polyethylene, ethylene propylene copolymer, ethylene-butylene copolymer, POE, ethylene and acrylic acid copolymer, copolymer from ethylene and methacrylic acid and ethene and vinyl acetate copolymer.Described olefin polymer has 1,000-300, and 000 number-average molecular weight preferably has 50,000-300,000 number-average molecular weight.Chlorination and chlorosulfonated olefin polymers have the chlorinity of about 15-70% weight.Chlorosulfonated olefin polymers has 0.5-10% weight, the sulfur content of preferred 1-3% weight.

Chlorination or chlorosulfonated olefin polymers can be prepared by olefin polymer by chlorination and the chlorosulfonation that free radical causes.The chlorination of olefin polymer can use gaseous chlorine to carry out under 50-150 ℃ temperature and 1-10 atmospheric pressure as chlorinating agent.In solution chlorination, reaction medium is atent solvent such as carbon tetrachloride, chlorobenzene, chloroform or fluorobenzene.Perhaps, can use slurry chlorination in water slurry or organic suspension liquid.Sulfuration bed process and melting method also are familiar with for people.The chlorosulfonation of olefinic polymerization raw material can use the mixture of gaseous chlorine and sulfur dioxide, sulfonic acid chloride or chlorine, sulfur dioxide and sulfonic acid chloride to carry out in solution under conditions of similarity.Commodity chlorination and chlorosulfonated olefin polymers comprise Tyrin  haloflex, Hypalon  chlorosulfonated polyethylene and Acsium  chlorosulfonated polyethylene, and they all can be available from DuPont Dow Elastomers L.L.C..

The epichlorohydrin elastomer that is applicable to the inventive method elastic component comprises Polyglycol 166-450 homopolymers and the copolymer that contains chloropropylene oxide and oxirane copolymerization units.Also can use the ter-polymers that contains solidification point unit such as allyl glycidyl ether.This composition comprises the chlorine of about 20-45% weight usually.Examples of commercial comprises the Daiso Epichlo Rubber Co. by Japan, the Epichlomer  rubber of Ltd. and by Japanese Nippon Zeon Co., the Hydrin  epichlorohydrin rubber that Ltd. produces.

In addition, ethylene ' alpha '-olefin elastomer such as ethene and be selected from propylene, 1-butylene, 1-hexene, 1-octene, 4-methyl-1-pentene and other C ₃-C ₂₀The elastocopolymer of alpha-olefin and EVA are the suitable elastic components in uV curable composition.Ethene, C ₃-C ₈The elastocopolymer of alkene and diene also can be used in the method for the present invention.These copolymers can be ethene/C ₃-C ₈The ter-polymers of alpha-olefin/diene type, quadripolymer or more senior copolymer elastomer.These elastomers are ethene, C ₃-C ₈The copolymer of alkene and at least a non-conjugated diene.In addition, they can comprise (be up to 10% weight usually) on a small quantity but at least a other diene or triolefin with the two keys of copolymerization.Preferred C ₃-C ₈Alpha-olefin is propylene and butylene.First type non-conjugated diene comprises 1,4-hexadiene, 2-methyl isophthalic acid, 5-hexadiene, vinyl norbornene, 8-methyl-4-ethylidene-1,7-octadiene, 1,9-18 carbon diene, dicyclopentadiene, three dicyclopentadienes, 5-ethylidene-2-ENB or 5-methylene-2-ENB.The diene that preferably has an activity double key is 1,4-hexadiene, dicyclopentadiene and ethylidene norbornene.Second type non-conjugated diene comprises norbornadiene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, 1,2-21 carbon diene or 5-(5-hexenyl)-2-ENB, preferred norbornadiene.These polymer prepare by polymerization in the presence of Ziegler-Natta catalyst or metallocene catalyst usually.Being used in the presence of metallocene catalyst the elastomeric technology of preparing of preparation ethylene ' alpha '-olefin can be referring to United States Patent (USP) 5,278, and 272 and 5,272,236.Typical ethylene and EPDM elastomer can Engage  polyolefin elastomer and the trade name of Nordel  hydrocarbon rubbers available from DuPont Dow ElastomersL.L.C..

The polyurethane rubber of uV curable is familiar with by people, for example referring to Japanese Laid-Open Patent Application 02-86680 and Japanese Laid-Open Patent Application 01-318028.The various polyurethane rubbers that polyurethane rubber such as tool is fit to Mooney viscosity all are applicable to the present invention.

As United States Patent (USP) 4,201, in 808 disclosed like that, silicone elastomer also can solidify in the presence of polyfunctional acrylic ester or dimethylacrylate and ultraviolet initiator.Other elastomers that this silicone elastomer or tool are fit to Mooney viscosity also are applicable to the present invention.

The elastic component that can be used for composition of the present invention can be elastomeric blend and single elastomer of planting.Described blend can be the mixture of polymers of same type, for example cyanogen bromide rubber and iodate fluorubber, and perhaps they can be the mixtures of the elastomer (for example chloridized polyolefin rubber and ethylene copolymer rubber) of more than one types.Have only a kind of elasticity physical efficiency also to be included among the present invention by the blend that is exposed to uv radiation curing.Blend composition is particularly useful for the balance physical property.For example, need by blend fluorubber and epichlorohydrin rubber balance solid state and oil resistivity.In another case, expensive polymer obtains being enough to satisfy the low combination that requires the performance of purposes usually with the blend of cheap polymer.In this article, the elastomeric blend of the blend of fluorubber and nitrile rubber or fluorubber and ethylene acrylate copolymer will be suitable as the elastic component in the inventive method.The Mooney viscosity of blend is preferably at 1-150, and ML1+4 (100 ℃) is because blend is applicable in the method for producing general purpose rubber goods such as sealing ring in this scope.The blend composition preferably clear, but for the most effective curing, can be translucent.

Except elastic component, can be used for curable compositions of the present invention and also comprise at least a multifunctional crosslinking agent.Preferred multifunctional crosslinking agent will be the acrylic or methacrylic acid crosslinking agent.In addition, multifunctional cyanurate or multifunctional chlorinated isocyanurates are such as triallyl isocyanurate, isocyanuric acid trimethyl allyl ester, triallyl cyanurate or isocyanuric acid trimethyl allyl ester.According to the elastomer difference, multifunctional crosslinking agent can be a polyalcohol.Multifunctional acrylic or methacrylic acid crosslinking agent is meant the ester of the product of polyol (normally polyhydroxy-alcohol) and acrylic or methacrylic acid, and wherein said crosslinking agent has at least two carbon-carbon double bonds.Be commonly referred to polyfunctional acrylic ester or multifunctional methacrylate in this composition this area.Typical polyfunctional acrylic ester and methacrylate have 150-1,000 molecular weight, and each molecule comprises at least two polymerizable unsaturated groups.

Representative multifunctional acrylic crosslinking agent comprises that acrylate and methacrylate are such as glycol diacrylate; Ethylene glycol dimethacrylate; 1, the 6-hexanediyl ester; 1, the 6-hexanediol dimethacrylate; 1, the 4-butanediol diacrylate; Pentaerythritol triacrylate; Tetramethylol methane tetraacrylate; Dipentaerythritol five acrylate; Methoxyl group-1,6-hexylene glycol pentaerythritol triacrylate; Trimethylolpropane triacrylate, tetraethylene glycol diacrylate, polyurethane polymethacrylate; Epoxy acrylate; Polyester acrylate monomer and oligomer; The propoxylation trimethylolpropane triacrylate; Poly-positive butylene oxide omega-diol diacrylate; With bisphenol-A alkylene oxide adduct diacrylate.Trimethylolpropane triacrylate and trimethylol-propane trimethacrylate are preferred cross-linking agents, because these compounds are easy to obtain.In addition, and contain the bifunctional acrylate such as diethyl glycol dimethylacrylate is compared, the compression set and the crosslink density that contain the composition of these crosslinking agents are enhanced.

Described multifunctional acrylic acid and metering system acid crosslinking agent can homopolymerizations when raying.Therefore, when the curable compositions that contains polyfunctional acrylic ester or methacrylate is used for the inventive method and described composition and is exposed to ultraviolet radiation, two kinds of reactions can take place simultaneously.Multifunctional crosslinking agent and elastomeric polymer component reaction form in interchain and the chain crosslinked, produce rubber mass.In addition, excessive multifunctional crosslinking agent can homopolymerization form interpenetrating networks, plays to strengthen the rubber mass effect, is very similar to filler and strengthens elastomeric mode.The hardness that therefore can be present in the final cured product of proportion control of multifunctional crosslinking agent in the curable compositions by adjusting.In general, the congener of high functionality compares with having more, and bifunctional acrylate and methacrylate are the crosslinking agents than poor efficiency.Therefore, with regard to purpose of the present invention, preferably has the more crosslinking agent type of high functionality.

Elastomeric material according to method compounding that is usually used in rubber processing and curing comprises carbon black or filler usually, is generally used for strengthening, but is used to strengthen other character sometimes.Intensity is the reflection such as character such as hardness, modulus and hot strengths.In general, the elastomeric of reinforcement is characterised in that nonlinear stress/strain concerns.On the contrary, the nonreinforcement elastic composition is characterised in that primary stress is assembled when low distortion, and it does not increase when higher distortion substantially.In addition, the nonreinforcement elastic composition can rupture under low ultimate tensile strength.

In the reaction that ultraviolet light causes, use filler it has been generally acknowledged that and to disturb the ultraviolet light polymerization process.But the inventive method can allow translucent composition solidify.Therefore, the composition that is used for the inventive method can comprise the filler of limiting the quantity of, usually the no more than 15 weight portion fillers of per 100 parts by weight polymer.Strengthen with formation the crosslinked of interpenetrating networks and carry out simultaneously.Compare with comprising not with the traditional elastic body of the filler of elastomeric matrices chemical bonding, the product that obtains shows more linear stress/strain behavior.

The amount that is present in the multifunctional crosslinking agent of the composition that is used for the inventive method depends on used concrete elastomer.In general, the scope of described amount is a 0.5-25% weight, decides according to weight, multifunctional crosslinking agent and the ultraviolet initiator of the polymer that mixes.

The third component that can be used for curable compositions of the present invention is a ultraviolet initiator.It can be selected from and be usually used in promoting by the intramolecular bond homolysis or by the intermolecular organic compound of taking the free radical of hydrogen formation ultraviolet light initiation by force.This reagent comprises the organic compound with aromatic carbonyl or uncle's amino.Wherein compounds suitable for use has benzophenone, acetophenone, benzil, benzaldehyde, o-chlorobenzaldehyde, xanthene ketone, thioxanthones, 9,10-anthraquinone, 1-hydroxy-cyclohexyl phenyl ketone, 2,2-diethoxy acetophenone, Dimethoxyphenyl acetophenone, methyl diethanolamine, dimethylaminobenzoic acid ester, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, 2,2-two sec-butoxy acetophenones, 2,2-dimethoxy-1,2-diphenyl second-1-ketone, benzil dimethyl acetal, benzoin methyl ether and phenyl glyoxal.After being exposed to ultraviolet radiation, various photochemical transformations can take place, for example ultraviolet initiator can form the free radical activity part, the acrylate end groups reaction of itself and multifunctional acrylic or methacrylic acid crosslinking agent.This has caused the homopolymerization of the crosslinked of polymer and acrylic or methacrylic acid crosslinking agent.A kind of preferred ultraviolet initiator is a 1-hydroxy-cyclohexyl phenyl ketone, because it produces free radical after being exposed to ultraviolet radiation fast.Also can use the mixture of ultraviolet initiator.Because it provides the production of more effective free radical in some cases, therefore often need to use mixture.In general, the amount of ultraviolet initiator accounts for the 0.1-10.0% weight of polymer, multifunctional crosslinking agent and ultraviolet initiator gross weight.But, the preferred ultraviolet initiator that uses based on the about 0.5-2.5% weight of the gross weight of polymer, multifunctional crosslinking agent and ultraviolet initiator, most preferably use the ultraviolet initiator of 0.5-1.0% weight, because the easy interference of high-caliber light trigger penetrates and basically whole crosslink density do not had effect.In the text scope of disclosure, concerning the combination of each concrete uncured gluey elastomer and crosslinking agent, there is the optimum level of a light trigger.These optimum levels can easily be recorded by those skilled in the art.For example, hydrogenated nitrile rubber needs higher levels of light trigger with common copolymer than ethene, methyl acrylate and ethyl maleate.Higher levels of light trigger has improved the crosslink density on hardening composition surface.Low-level light trigger can cause the compression set of several millimeters thick samples better (lower).

In addition, for the present invention, molding temperature must be no more than the temperature of ultraviolet initiator generation thermal degradation or inactivation.This in some cases degraded meeting is owing to forming the composition that free radical produces premature setting.This be because in process equipment the thermal induction of initator cracked cause elastomeric crosslinked too early.In other cases, will produce slow hardening composition owing to the inactivation of initator.The degradation temperature difference of each concrete ultraviolet initiator.According to the type of rubber and the consumption of additive, the molding temperature scope is 25-250 ℃.Be applicable to that elastic composition of the present invention is to stablize and can be applied in to reach 250 ℃ of compositions on the temperature base material.In practice, be the softening point that this temperature must be no more than the base material that elastic composition will apply to another restriction on the molding temperature.

Preferred described elastic component, multifunctional crosslinking agent component and ultraviolet initiator component are present in the composition that is used for the inventive method with concrete special ratios, and be different and different but the concrete effectively ratio of elastic component, crosslinking agent and ultraviolet initiator of one skilled in the art will realize that will be according to concrete selected elastomer, crosslinking agent and ultraviolet initiator.

For example, when the elastic component of composition is ethylene copolymer elastomer, ACM or nitrile rubber, based on the total weight of elastomer, crosslinking agent and ultraviolet initiator, the sealing compositions of uV curable preferably includes the elastomer of 75-95% weight.Multifunctional crosslinking agent preferably exists with the amount of the 2-24% weight that accounts for elastomer, crosslinking agent and ultraviolet initiator gross weight.At last, ultraviolet initiator preferably exists with the amount of the 0.2-5.0% weight that accounts for elastomer, crosslinking agent and ultraviolet initiator gross weight.Most preferably, elastic component exists with the amount of the 87-95% weight that accounts for elastomer, crosslinking agent and ultraviolet initiator gross weight.The level of crosslinking agent determines the withstand voltage compression set and the hardness of curable compositions of the present invention.If the amount of crosslinking agent is lower than 2% weight, may form the composition of soft and bad withstand voltage compression set.Crosslinking agent greater than 30% weight produces the composition of hardness greater than 70 Xiao A hardness.This composition is not suitable for sealing usually, particularly during the seal washer purposes.Therefore concrete selected constituent content scope will depend on the final use of intending consideration.According to the total weight of polymer, multifunctional crosslinking agent and ultraviolet initiator, preferred compositions comprises the multifunctional crosslinking agent of 5-20% weight, and most preferred composition comprises the multifunctional crosslinking agent of 5-15% weight.When the elastic component of composition was fluorubber, elastomer preferably existed with the amount of the 70-99% weight that accounts for elastomer, multifunctional crosslinking agent and ultraviolet initiator gross weight.Multifunctional crosslinking agent preferably exists with the amount of the 0.5-20% weight that accounts for elastomer, multifunctional crosslinking agent and ultraviolet initiator gross weight.At last, ultraviolet initiator preferably exists with the amount of the 0.1-10% weight that accounts for elastomer, multifunctional crosslinking agent and ultraviolet initiator gross weight.Most preferably elastic component exists with the amount of the 75-95% weight that accounts for elastomer, multifunctional crosslinking agent and ultraviolet initiator gross weight.The level of crosslinking agent determines the withstand voltage compression set and the hardness of curable compositions of the present invention.Multifunctional crosslinking agent preferably exists with the amount of the 4-15% weight that accounts for elastomer, multifunctional crosslinking agent and ultraviolet initiator gross weight.Selected concrete compositional range depends on the final use of specifically being considered.When chlorinated olefin polymer, chlorosulfonated olefin polymers or epichlorohydrin rubber were used as the elastic component of composition, elastomer preferably existed with the amount of the 80-97% weight that accounts for elastomer, multifunctional crosslinking agent and ultraviolet initiator gross weight.Multifunctional crosslinking agent preferably exists with the amount of the 2-19.5% weight that accounts for elastomer, multifunctional crosslinking agent and ultraviolet initiator gross weight.Ultraviolet initiator preferably exists with the amount of the 0.2-5.0 that accounts for elastomer, multifunctional crosslinking agent and ultraviolet initiator gross weight.Elastomer most preferably exists with the amount of the 85-95% weight that accounts for elastomer, multifunctional crosslinking agent and ultraviolet initiator gross weight.Multifunctional crosslinking agent preferably exists with the amount of the 3-15% weight that accounts for elastomer, multifunctional crosslinking agent and ultraviolet initiator gross weight.For other compositions that can be used for the inventive method, selected concrete compositional range will depend on the final use of being considered.

The various additives that are usually used in rubber compounding can be blended into and can be used in the composition of the present invention with modification, stable and strengthen these compositions.These additives preferably use with the amount of not disturbing uncured polymeric component cross-linking reaction basically.For example, if use a large amount of not fillers of saturating ultraviolet light, the composition through filling can not evenly solidify thoroughly, perhaps have only the surface of composition to be cured.Usually, the consumption of filler is up to per 100 parts of elastomers and uses about 15 parts of fillers.The exemplary of filler comprises non-black filler such as mineral or glass fibre.Also can use high polymer filler such as polytetrafluoroethylene (PTFE) and the aramid fibre of strengthening usefulness, but usually with low-level use.The existence of preferable additives can not rise to the viscosity that is used for the curable compositions of the inventive method the ML1+4 (100 ℃) greater than 150 or be reduced to and be lower than 1 ML1+4 (100 ℃).Composition beyond this scope also is not suitable for encapsulating method on the spot of the present invention.Except other additives, the elastic packing composition can comprise plasticizer and processing aid, and its addition is up to the about 15-20 part of per 100 parts of elastomers usually.

When polymeric component is fluorubber, can be used for the organotin hydride that preferred curable compositions of the present invention will comprise per 100 weight portion fluorubber 0.01-2.0 weight portions.Preferred per 100 weight portion fluorubber use 0.1-1 weight portion organotin hydride.Preferred hydrogenation three positive fourth tin.

When ethylene acrylate copolymer is used as polymers compositions, preferably can be used for the hear resistance and the non-oxidizability of composition of the present invention by sneaking into antioxidant enhancement.In general, use aromatics antioxidant, particularly arylamine.Because the radical crosslinking reaction that its protective effect, these compounds disturb ultraviolet radiation to cause to a certain extent.Do not having in the presence of the antioxidant, be exposed to several days time under 150 ℃ of temperature, composition is prone to surface checking.In antioxidant, 4,4 '-two (α, α-Er Jiajibianji) diphenylamines and 4 the most usefully, the blend of 4 '-two (α, α-Er Jiajibianji) diphenylamines and 4-(α-Er Jiajibianji) diphenylamines.Can use sterically hindered phenol, but they disturb curing reaction more than arylamine.Antioxidant is sneaked into the level of per 100 parts of polymer 0.5-2 parts usually.Also other additives can be blended into and can be used in the composition of the present invention, for example plasticizer, tackifier, fire retardant and be usually used in the processing aid of rubber chemical combination.

Owing in the production piece of acrylic or methacrylic acid crosslinking agent, have these additives, can be used for also can having a small amount of inhibitor in the composition of the present invention.Inhibitor for example is lower than 1500ppm (1,000,000/portion calculates based on crosslinking agent weight) usually to exist on a small quantity.The thermoinducible polymerization of crosslinking agent when they are used to prevent storage and transportation.

Method of the present invention is specially adapted to use us to be called the elastic seal ring that the technology of solidifying on the spot carries out and the production of packing ring.In general, according to this technology, curable elastic composition is heated to up to 250 ℃ and preferred 90-170 ℃ temperature.Composition is directed to die cavity then, thereby the uncured sealing ring of desired thickness is wanted bonding base material to constitute to form in its at least one surface on base material by sealing ring.Base material with uncured sealing compositions is exposed under the ultraviolet radiation subsequently, makes sealing compositions solidify.Therefore, on object to be sealed, directly form sealing ring on the spot.In general, uncured sealing forms 6-10mm, and the thickness of preferred 0.5-6mm usually with the thickness of the most about 20mm.

In an embodiment of the inventive method, will comprise that the curable compositions of low viscosity elastic component, multifunctional crosslinking agent and ultraviolet initiator imports in the injection machine.Composition soft and can extruding during heating.Curable compositions is directed to part by in the die cavity that the template of pad (curable compositions deposits thereon) and at least one injection machine forms.For example, curable compositions can import in the injection machine by extruder, piston pump, heated drum (heated drum) or any other feed arrangement.Curable compositions can be before importing to feed arrangement premix.For example, premix composition can be delivered in the feed arrangement by strip.Perhaps, each component can join in the feed arrangement respectively, thereby allows mixing and charging finish in an equipment, for example finishes in extruder or serial extruder.Like this, composition is applied to by precision control ground that groove is gone up or imported to a pad or by in one or more surperficial other chambeies that form of pad.Described pad can be such as metal, thermoplastic, glass or materials such as ceramic or fabric or film.When curing technology was used to form packing ring, the curable sealing compositions of sealing gasket shape for example still remained uncured bead in a pad groove when of the present invention on the spot.A pad of the sealing compositions of bonding uV curable is separated with template.A pad that has bonding sealing compositions can be exposed to the time that next section of ultraviolet radiation is enough to make its curing immediately, forms one type black box thus.Although what the condition of ultra-violet curing will be according to the type of institute's adhesive seal composition thickness and size, selected polymer and multifunctional crosslinking agent and ultraviolet initiator and ratio is different and different, the radiation of carrying out 2 seconds to 1.5 minutes with the UV source (400-250nm) of 200W/cm is enough to finish curing usually.Under the industrial production condition, usually by being cured by ultraviolet source at the uV curable composition that will stick on the conveyer belt on the pad.Perhaps, a pad can be subjected to ultraviolet radiation by storage, protection, is exposed to afterwards under the ultraviolet radiation so that the elastic packing composition is solidified.In addition, the parts that pad can be used as big assembly that prop up of uncured sealing compositions have been adhered to.In other words, it can form goods (being assembly) with miscellaneous part, is exposed to cause that elastic composition is solidified to form black box in the assembly behind the ultraviolet radiation.

The suitable temperature that one skilled in the art will realize that metering and molding will depend on the level of uncured elastomeric viscosity, uncured elastomeric molecular weight, crosslinking agent, the decomposition temperature of light trigger and the volatilization temperature of crosslinking agent, and select to be suitable for most the value of concrete condition in the scope that is up to 250 ℃.

Other embodiments of the inventive method comprise common injection moulding, and wherein a pad of adhesive composite is formed by thermoplastic in the first Shooting Technique step thereon.The base material of Xing Chenging is accepted the uV curable composition of the method according to this invention then in position like this.Other embodiments comprise compression moulding and die casting.

Encapsulating method of the present invention can be used for using curable elastic composition to prepare sealing ring and packing ring.

For the elastic property of the sealing ring of optimizing method for preparing, sealing compositions must be crosslinked (promptly solidifying).It is unactual to use the thermal activation curing system to finish quick cross-linking reaction in this method.Can bring the curable compositions crosslinked danger too early rambunctious when charging and molding that is used to form sealing ring like this.Specifically, along with curable compositions is heated or the temperature rising owing to machining, just can trigger cross-linking reaction.Import in the guided mode and the too early gelling (premature setting) during molding will be difficult to control.Because crosslinked composition does not flow fast, the process that produces cured product too early is undesirable.Therefore, the curing system that relies on the thermal induction cross-linking reaction is to the inventive method and be not suitable for.In addition, only depend on the prevailing homolysis of the thermal decomposition of peroxide, promptly the free radical cure method is not suitable for the inventive method yet.Curable compositions effectively solidifies by the free radical method that ultraviolet radiation is induced.

Use the ultraviolet light polymerization of the sealing compositions that method of the present invention carries out under room temperature or higher temperature, to finish.For example, in many cases, may after being applied to object to be sealed, uncured composition carry out photocuring immediately to avoid excess flow.Here, the temperature of composition may be up to 250 ℃.But, heating curable compositions and unnecessary also not to be in particular effective photocuring required.In addition, when composition was used for forming sealing ring on thermoplastic article, low-temperature setting had at utmost reduced the possibility of thermoplastic degraded or thermal deformation.In addition, may be best even in inert atmosphere, solidify, but be not that to carry out ultraviolet radiation institute essential.Curing reaction can carry out under the atmospheric conditions of adverse effect not having.In addition, have been found that also in some cases particularly when solidifying chlorination or chlorosulfonated polyolefin, preferred underwater curing because such heat is gathered is reduced.This has reduced the tendency that can cause the dehydrochlorination of depolymerization and variable color.

For the inventive method, the wave spectrum that is used to implement the radiation of curing reaction generally corresponds to the absorption maximum of ultraviolet initiator.Its scope is generally about 200-400nm.During comprising, the UV source that is fit to presses mercury vapor lamp, electrodeless lamp, xenon flash lamp and mixing xenon/mercury vapor lamp.A kind of preferred layout comprises that one or more lamps connect same reflector, and it is by the even propagate radiation of radiating surface.Dose of radiation must be enough to solidify polymeric compositions, promptly produces to have 90 or lower and preferred 50 or the lower compression set and the hardening composition of at least 100% extension at break.Every square centimeter is enough to carry out the best curing usually at least about 10 joules and preferred 20 joules dosage.Dosage is time of being exposed to ultraviolet radiation, from the function of the distance and the power of radiation source level of UV source.Required dose of radiation can easily be measured by the sample of cure curable compositions and physical property such as hot strength, compression set and the percentage elongation of measuring after solidifying.In most of the cases, acceptable curing degree can obtain by the lamp 30-300 that is exposed to about 80W/cm second.Have been found that the 200W/cm lamp is effective especially.According to the power of lamp, in the level of the filler of the level of the crosslinking agent of distribution, sample thickness and the polymers compositions of ultraviolet range output, existence and existence, can carry out suitable adjusting.For example, containing the ethylene acrylate copolymer rubber of filler will be than the longer hardening time of same combination needs that does not have filler.

Blowing agent can be blended into and can be used in the curable compositions of the present invention.In this case, when with described curable compositions by being exposed to ultra-violet radiation following time owing to simultaneously when being exposed to ultraviolet light induce the thermal decomposition of blowing agent, cause described curable compositions to form network because of heating.This heating phenomena can apply heat increase and control by the outside.Available typical blowing agent comprises p, the p '-two benzene sulfonyl hydrazides of oxygen connection, Celogen Az, p-toluenesulfonyl semicarbazides and dinitrosopentamethylene tetramine.Perhaps, the ultraviolet light polymerization reaction also can be finished by cooling, and curing and foaming occur in sequence, but not take place simultaneously.In other words, curable compositions is exposed under the ultra-violet radiation under cooling, and cured compositions causes foaming by hot-air channel then.Can prepare low-gravity hole-closing structure by this method.For example, can obtain 0.20-0.60g/cm ³The structure of proportion.

Further describe the present invention below with reference to the accompanying drawings.Referring to Fig. 1, the pad with injection channel 20 22 is placed on second template 10, and second template 10 has cavity 16, and cavity 16 has face 24 and 28 and the end 26.Prop up pad 22 and have groove 14, groove 14 has the end 6 and sidewall 4 and 8.First template 12 with injection canal 18 places a upper surface of pad 22, and the lower surface of the template 12 of winning is contacted with a upper surface of pad 22.Cavity 16 and injection canal 18 and 20 can respectively have any required form.Thereby first template 12 contact with a pad 22 passage 18 is contacted with injection canal 20 and continuous, the passage of supply UV curable elastic packing composition to cavity 16 is provided thus, is specially the composition that comprises uncured elastomer, multifunctional crosslinking agent and ultraviolet initiator.Like this, form the die cavity of determining by injection channel 18, injection channel 20 and cavity 16.Under the condition that takes place to solidify at the elastic packing composition that does not have uV curable basically, promptly the viscosity of composition when it is heated to molding temperature, be held constant at its initial value ± condition in 50% under, curable elastic composition is directed to chamber 16 by injection channel 18 and 20.Then second template 10 and first template 12 are disengaged with a pad 22 and the pad of curable elastic composition that produced adhesion with accurate shape.A pad that has adhered to elastic composition can be exposed under the ultra-violet radiation immediately, can store under its uncured state, or can form assembly with other components, then assembly is exposed under the ultraviolet radiation.The temperature of first or second template can make heat medium or the cooling medium passage (not shown) by one or two template change or control.The groove 5 of second template 10 is option features.

In another embodiment (not shown), first template, a pad and second template can respectively have a plurality of injection channels.In addition, propping up pad can contact and between one or more templates.

Another embodiment of the present invention illustrates by reference Fig. 2.Pad with injection channel 32 30 places on second template 34, and second template 34 has and comprises side 42 and 46 and the cavity 40 at the end 44.First template 36 with injection channel 38 places a upper surface of pad 30, thereby makes the upper surface of a lower surface contact pad 30 of first template 36.Cavity 40 and injection channel 32 and 38 respectively have optional required form.First template 36 contacts with a pad 30, thereby injection channel 38 is contacted with injection channel 32 and link to each other, the passage of supply UV curable elastic packing composition is provided thus, and described composition specifically comprises uncured elastomer, multifunctional crosslinking agent and ultraviolet initiator.Second template 34 contacts with a pad 30, makes the passage that is formed by injection channel 32 and 38 link to each other with cavity 40.Like this, form by injection channel 32 and 38 and the die cavity determined of cavity 40.Under the condition that takes place to solidify at the elastic packing composition that does not have uV curable basically, promptly the viscosity of composition when it is heated to molding temperature, be held constant at its initial value ± condition in 50% under, curable elastic composition is directed in the cavity 40 by injection channel 32 and 38.Second template 34 and first template 36 disengage with a pad 30 then, produce the accurate shape of tool adhesion a pad of curable elastic composition.

Referring to Fig. 3, the pad 48 with surface 54,56 and 58 is placed on second template 62.First template 60 with injection channel 50 places a upper surface of pad 48, thereby the lower surface of first template 60 is contacted with a upper surface of pad 48.Determine die cavity by cavity 52 (forming) and injection channel 50 by a surface 54,56 of pad 48 and the surface 64 and 64 of 58 and first template 60.Cavity 52 and injection channel 50 can respectively have optional required form.Then, under the condition that takes place to solidify at the elastic packing composition that does not have uV curable basically, promptly the viscosity of composition when it is heated to molding temperature, be held constant at its initial value ± condition in 50% under, UV curable elastic packing composition, specifically be the composition that comprises uncured elastomer, multifunctional crosslinking agent and ultraviolet initiator, import in the cavity 52 through injection channel 50.Then second template 62 and first template 60 are broken away from and the contacting an of pad 48, produce filling up of the curable elastic composition that is stained with accurate shape.The temperature of first or second template can change by heat medium or cooling medium through the passage (not shown) of one or two template or control.

Referring to Fig. 4, a pad 68 is placed on second template 76.First template 78 is positioned on the upper surface of pad 68, and the lower surface of first template 78 contacts with a upper surface of pad

68.By tool side

70 and 72 and the cavity 82 and the injection channel 80 at the end 74 form die cavity.But cavity 82 and any required form of injection channel 80 each tool.Then, under the condition that takes place to solidify at the elastic packing composition that does not have uV curable basically, promptly the viscosity of composition when it is heated to molding temperature, be held constant at its initial value ± condition in 50% under, the elastic packing composition of uV curable, specifically be exactly the composition that comprises uncured elastomer, multifunctional crosslinking agent and ultraviolet initiator, be directed in the cavity 82 through injection channel 80.Make contacting of

second template

76 and 78 disengagings of first template and a pad 68 then, produce the propping up of curable elastic composition that is stained with accurate shape and fill up.The temperature of first or second template can change by heat medium or cooling medium through the passage (not shown) of one or two template or control.

Molded plate can be made by various materials, but is made of metal usually.Prop up pad and also can comprise various materials, as thermoplastic, pottery, thermosets such as phenolic resins or epoxy resin, fabric or metal.

In another embodiment, can use a plurality of going up or lower bolster, for example main injection channel has by-path, and each by-path feeding is to each a group template and a pad.

In an embodiment more of the present invention, a surperficial available coating preliminary treatment of filling up that forms the part die cavity is to improve uncured elastic composition to an adhesiveness on pad surface.This coating is usually as adhesive.According to a cushion material and a uV curable composition, coating can be selected from silanes patent composition, for example can available from the Chemlock  rubber adhesive of Lord Corporation, can be available from the polymer-bonded system of Cilbond  of Chemical Innovation Ltd. and can be available from Rohm; The Thixon  adhesive of Haas Corporation and Megum  adhesive and can be available from the Chemosil  adhesive of Henkel KGaA.In addition, also be suitable for, such as can be available from the D-Ply-5-2 priming paint of Dongsung NSC and can be, the 9078X priming paint of Inc. available from H.P.Fuller by the priming paint of UV-activated.In another embodiment more of the present invention, the side 24 of the cavity 16 of Fig. 1 and 28 and the end 26 and second template 10 can use the coating preliminary treatment, reduce the bonding force of uncured elastic composition, make the propping up of uncured elastic composition that has adhesion fill up the easier demoulding the mould surface.This coating is included in the reagent of mould surface as lubricant or releasing agent, and they can be by spray, wiping or brush on the surface, and example has dimethyl silicone polymer.Perhaps, crosslinkable polymer such as polysiloxanes or the fluoropolymer used by solution or emulsion are such as can be available from various other TraSys of level of E.I.Du Pont de Nemours and Co. ^TMDemoulding system all is suitable for.These releasing agents that the back is one type comprise volatile vehicle and crosslinkable polymer.The hardening time that they need be lacked, during carrier volatilization, polymer-bonded to mould and be cross-linked to form thick uniform films.In addition, specialty metal alloy, polytetrafluoroethylene (PTFE) or metal and polytetrafluoroethylalloy alloy can be applied directly to the mould surface.

For easy removal, preferably before adhering to a curable compositions of pad, removal cools off second template.This can finish by staying for some time after curable compositions is imported to die cavity, perhaps can be for example by fluid is finished cooling by the raceway groove on the template.Other cooling means are familiar with by those skilled in the art.

Having propping up of curable sealing compositions of the present invention fills up in the goods that contain bonding on the spot sealing ring and packing ring that can be used on preparation example such as the LCD panel.The black box of curing of the present invention can be used as the automobile component of the packing of tool complicated shape, such as rocker lid (rockercovers), gear shift cover, food tray, water pump, air inlet pipe, radiator, headlight and rotating shaft sealing engine flange.The complicated shape packing also is used for injecting purposes such as fuel cell plate and battery pack.

Claims

1. one kind is provided at a method of the sealing compositions of the uV curable that fills up, and the sealing compositions of wherein said uV curable comprises uncured elastomer, multifunctional crosslinking agent and ultraviolet initiator basically, said method comprising the steps of:

B., a pad with optional injection channel is provided;

D. the sealing compositions with described uV curable imports in the described die cavity, the feasible curing that the sealing compositions of described uV curable does not take place basically of lead-in mode, and the sealing compositions of described uV curable contacts and is adhered on it with described pad; With

2. the method for claim 1, wherein said spacer has the injection channel, described injection channel links to each other with at least one injection channel of described first template, forms the die cavity on the surface of the described injection channel comprise the described injection channel of described first template, described pad and at least one other template thus.

3. the sealing compositions of the uV curable on the pad of the method for claim 1 preparation.

4. the sealing compositions of the uV curable on the pad of the method for claim 2 preparation.

5. the sealing compositions of the uV curable on the pad of the method for claim 1 preparation, the sealing compositions of wherein said uV curable comprises elastomer, and described elastomer is selected from ethylene acrylate copolymer rubber, ethylene methyl acrylate copolymer rubber, ACM, the ethylene-vinyl ester elastomer, the elastocopolymer of diene and unsaturated nitrile, the hydrogenation elastocopolymer of diene and unsaturated nitrile, polyurethane elastomer, polysiloxanes, has iodate, the fluoroelastomer of the copolymerization units of bromination or chlorination cure site monomers, fluoroelastomer with non-conjugated diene copolymerization units, fluoroelastomer, the chlorinated alkenes elastomer, the chlorosulfonation olefin elastomer, epichlorohydrin elastomer, ethylene rubber and butyl rubber.

6. the sealing compositions of the uV curable on the pad of the method for claim 1 preparation, wherein said pad comprises the material that is selected from metal, thermosets, thermoplastic and pottery.

7. the process of claim 1 wherein the described elastic packing composition that sticks to the uV curable on the pad is exposed to the time that next section of ultraviolet radiation is enough to make its curing.

8. the goods of the method for claim 7 preparation.

9. method for preparing black box said method comprising the steps of:

2. the pad with optional injection channel is provided;

10. the method for claim 9, wherein said spacer has the injection channel, described injection channel links to each other with at least one injection channel of described first template, forms the die cavity on the surface of the described injection channel comprise the described injection channel of described first template, described pad and at least one other template thus.

11. the black box of the method for claim 9 preparation.

12. the black box of the method for claim 10 preparation.

13. the black box of the method for claim 9 preparation, the sealing compositions of wherein said uV curable comprises elastomer, and described elastomer is selected from ethylene acrylate copolymer rubber, ethylene methyl acrylate copolymer rubber, ACM, the ethylene-vinyl ester elastomer, the elastocopolymer of diene and unsaturated nitrile, the hydrogenation elastocopolymer of diene and unsaturated nitrile, polyurethane elastomer, polysiloxanes, has iodate, the fluoroelastomer of the copolymerization units of bromination or chlorination cure site monomers, fluoroelastomer with non-conjugated diene copolymerization units, fluoroelastomer, the chlorinated alkenes elastomer, the chlorosulfonation olefin elastomer, epichlorohydrin elastomer, ethylene rubber and butyl rubber.

14. the black box of the method for claim 9 preparation, wherein said pad comprises the material that is selected from metal, thermosets, thermoplastic, fabric and pottery.

15. the process of claim 1 wherein the releasing agent preliminary treatment of described die cavity, to reduce the cohesive of uncured elastic composition to the mould surface.

16. the method for claim 9, the releasing agent preliminary treatment of wherein said die cavity is to reduce the cohesive of uncured elastic composition to the mould surface.