CN108611033A - A kind of UV visbreakings glue - Google Patents

A kind of UV visbreakings glue Download PDF

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Publication number
CN108611033A
CN108611033A CN201611171314.3A CN201611171314A CN108611033A CN 108611033 A CN108611033 A CN 108611033A CN 201611171314 A CN201611171314 A CN 201611171314A CN 108611033 A CN108611033 A CN 108611033A
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CN
China
Prior art keywords
visbreakings
solvent
combination
aging agent
initiator
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Pending
Application number
CN201611171314.3A
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Chinese (zh)
Inventor
黄志萍
熊琰
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Individual
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Individual
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Priority to CN201611171314.3A priority Critical patent/CN108611033A/en
Publication of CN108611033A publication Critical patent/CN108611033A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12Homopolymers or copolymers of methyl methacrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate

Abstract

A kind of UV visbreakings glue, including reaction monomers 30% 60%, reactive diluent 30% 50%, initiator 0.01% 5%, crosslinking agent 1% 5%, thermal curing agents 0.05% 5%, anti-aging agent 0.1% 5%, solvent 0 30%.UV visbreakings glue of the present invention, which has, just glues sufficiently low, good fluidity, and acidproof, oil resistant, solvent-proof advantage.Applied to UV protective films, have that peeling force is high, solar radiation not visbreaking, visbreaking after UV illumination, and the advantage that peeling force is low.

Description

A kind of UV visbreakings glue
Technical field
The invention belongs to macromolecule adhesives to develop field.
Background technology
Semiconductor is the critical component of household digital product and electronic device.Large scale integrated circuit manufacture and partly lead In the manufacture process of body device, essential basic material is semiconductor chip.Semiconductor chip is with monocrystalline silicon piece It is process, monocrystalline silicon piece abbreviation wafer.Wafer material is cut, grinding when, need with a kind of special Protective film is adhesively fixed.After completion of processing, then the wafer coupons processed are completely exfoliated from fixed glued membrane, no Influence wafer material itself.Crystal (ambetti) is applied to the daily lifes such as lamps and lanterns, dress ornament, and optical glass is applied to optics Instrument is also required to, by cutting and grinding, protective film be also needed in process and is fixed, after processing is completed easily stripping again From.Since ultraviolet light (UV) solidified pressure-sensitive solidification rate is fast, save the energy, cost-effective, curing apparatus is simple, floor space It is small, it is therefore got the attention using the UV visbreakings protective film of ultraviolet light (UV) solidified pressure-sensitive.UV visbreakings protective film in addition to Outside having the advantages that UV-light solidified pressure-sensitive has, it can be completely exfoliated, be occurred by " viscous " to " no with being realized in the short time It is viscous " transformation.Such as disclosure(Bulletin)Number be CN105778806A patent《Heat resistant type UV visbreakings glue composition and the protection of UV visbreakings Film》, disclose poly- using polyfunctionality oligomer or polyfunctional monomer or combinations thereof object 1%~25%, solvent type high temperature resistant Acrylic Pressure Sensitive Adhesive 30%~50%, crosslinking agent A 0.5%~1.5%, photoinitiator 0.3%~1.5%, solvent 35%~60% heat resistant type UV visbreaking protective films prepared are resistant to 120 DEG C of high temperature, and big, the UV light with peeling force before UV illumination It is low and the advantages of do not stay residue glue according to rear peeling force.It is open(Bulletin)Number be CN105602316A patent《A kind of peelable gel coating Composition, peelable gel coating and its application》, using 80~120 parts of acrylate quasi-oligomer, 8~20 parts of dilution list It is prepared by body, 2.5~12.5 parts of low surface tension compatibility auxiliary agent, 2~12 parts of initiator and 70~140 parts of organic solvent Peelable glue coating composition after heat cure or UV solidifications the peelable gel coating that is formed have surface adhesion good, when need by When peelable gel coating is removed from article surface, and it is easily peeled off without the advantages of article surface forms residue.It is open(It is public It accuses)Number be CN104479436A patent《Peelable glue coating composition, peelable gel coating, peelable gel coating preparation method and Using》, using 80~120 parts of acrylate quasi-oligomer, 8~20 parts of diluent monomers, 0.1~1.5 part of peeling force It is formed after peelable glue coating composition solidification prepared by modifying agent, 2~12 parts of initiator and 30~50 parts of organic solvent Coating has higher high temperature resistance and higher removability.Above-mentioned formula uses a large amount of organic solvents, in film When need to remove solvent, can be to the larger pollution of environment, and recycling design then has higher requirements to equipment.It is open(Bulletin)Number The patent of CN105086730A《A kind of bi-component UV curing visbreaking glue》, component A is with hydroxyl, or solidified resin containing carboxyl 35~60 parts, 22~45 parts of Photosensitive monomers, 2~10 parts of Photoepolymerizationinitiater initiater, 2~15 parts of diluent, 2~10 parts of groups of auxiliary agent At;Component B is that NCO content is 12.5~23.5%, the NCO curing agent and polymercaptan containing sulfydryl that molecular weight is 200~600, Middle sulfhydryl content is 5~15%;The weight of component B is the 5%~20% of component A weight.Bi-component prepared by the invention is solid Changing after UV dehesions glue cures plastic at normal temperatures has initial bonding strength height, has peeling effect good after UV irradiates visbreaking, not residual The advantages of glue.But the formula cures at normal temperatures, when for film there are viscosity increase it is too fast, operable time is too short to ask Topic.In addition, the UV visbreaking protective films of domestic production there are in fact, initial peeling force is not high enough, and initial viscosity is excessive, after film forming Not plus the irradiation of UV light is automatic visbreaking, uses the problem that the term of validity is too short.
Invention content
It is an object of the invention to overcome, UV visbreakings glue initial viscosity is excessive in existing domestic technique, is initially removed after film forming Power is not high enough, and not plus the irradiation of UV light is automatic visbreaking problem, and invention is a kind of just viscous sufficiently low, there is good mobility, acidproof, resistance to Oil, solvent resistant, peeling force is sufficiently high after film forming, and visbreaking, UV irradiations are not the UV visbreaking glue of visbreaking to solar radiation.
The present invention also aims to provide the preparation method of above-mentioned UV visbreakings glue.
The present invention also aims to provide above-mentioned UV visbreakings glue in glass and semiconductor machining UV visbreaking protective films Using.
The technical scheme is that:It is characterized in that including the component of following masses percentage:
Reaction monomers 30%-60%, reactive diluent 30%-50%, initiator 0.01%-5%, crosslinking agent 1%-5%, thermal curing agents 0.05%-5%, anti-aging agent 0.1%-5%, solvent 0-30%.
The present invention preferred ingredient be:
Reaction monomers 40%-55%, reactive diluent 30%-40%, initiator 0.05%-2%, crosslinking agent 2%-3%, thermal curing agents 0.5%-2%, anti-aging agent 0.1%-1%, solvent 1%-10%.
Reaction monomers are methyl methacrylate (MMA), acrylic acid (AA), ethyl methacrylate, acrylic acid methoxy second Ester, butyl acrylate (BA), acrylic acid ethoxy ethyl ester and one kind in diisooctyl maleate (DOM) or combination.
Reactive diluent uses diethylene glycol divinyl ether, tri (propylene glycol) diacrylate isoreactivity monomer A kind of or combination.
Initiator is dibenzoyl peroxide, 1- hydroxycyclohexan Benzophenones, 2- hydroxy-2-methyl -1- phenylacetones, Azodiisobutyronitrile, cumyl peroxide, one kind in fluorinated diphenyl titanium cyclopentadienyl etc. or combination.
Crosslinking agent pentaerythritol triacrylate, diethylene glycol divinyl ether, in tri (propylene glycol) diacrylate One kind or combination.
Thermal curing agents are IPDI, one kind in HDI, N-100 or combination.
Anti-aging agent is bisphenol-A, anti-aging agent RD, antioxidant A W, antioxidant 264, one kind in anti-aging agent 445 or combination.
Solvent is ethyl acetate, acetone, one kind in petroleum ether or combination.
The manufacturing process of UV visbreakings glue of the present invention is:By UV photoreactive monomers, crosslinking agent mixes in proportion, first adds Enter part initiator initiated polymerization, heat and control temperature at 60 ~ 100 DEG C, is stirred to react 0.5 ~ 2h.Residue is added to draw Send out agent the reaction was continued 0.5 ~ 2h.The reaction was complete, addition reactive diluent, anti-aging agent inhibit glue autohemagglutination, and are added after cooling Thermal curing agents and solvent, stir evenly.Thermal curing agents and solvent can also independent mixing, when film adds.
Application of the UV visbreakings glue of the present invention in UV visbreaking protective films.
UV visbreakings glue of the present invention, which has, just to be glued sufficiently low, and good fluidity, solvent is few, small excellent of environmental pollution Point.Its superiority also resides in, and when it is uniformly coated on special base material, is become after drying tunnel is dried and has extra-high stripping Power and hold viscosity, low just viscous UV visbreaking protective films.Protective film has acidproof, oil resistant, solvent resistant, and peeling force is high, solar radiation Not visbreaking, the low advantage of peeling force after UV visbreakings.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Example 1
Methyl methacrylate 35%, acrylic acid 6%, diisooctyl maleate 5%, acrylic acid methoxy ethyl ester 5%, crosslinking agent Ji Wusi Alcohol triacrylate 1%, diethylene glycol divinyl ether 1%, initiator dibenzoyl peroxide 1%.It heats and controls temperature and exist 80 DEG C, it is stirred to react 0.5h.Fluorinated diphenyl titanium cyclopentadienyl 1% is added, the reaction was continued 1h.It is bisphenol-A that anti-aging agent is added after cooling 0.5%, anti-aging agent RD 0.5%, reactive diluent diethylene glycol divinyl ether 35%, thermal curing agents IPDI 4%, solvent is acetic acid Ethyl ester 5%.Use it as the UV protective films of adhesive, initial peeling force is for peeling force after 15.95 N/25 mm, UV illumination 0.04N/25 mm。
Example 2
Ethyl methacrylate 40%, butyl acrylate 10%, acrylic acid ethoxy ethyl ester 5%, crosslinking agent pentaerythritol triacrylate 1%, tri (propylene glycol) diacrylate 1%, initiator azodiisobutyronitrile 0.5% heats and controls temperature at 70 DEG C, stirs React 1h.2- hydroxy-2-methyl -1- phenylacetones 1% are added, the reaction was continued 1.5h.It is added after cooling, antioxidant 264 1.5%, reactive diluent tri (propylene glycol) diacrylate 37%, thermal curing agents HDI 3%.It is used to be protected as the UV of adhesive Cuticula, initial peeling force are that peeling force is 0.13N/25 mm after 14.82 N/25 mm, UV illumination.
Example 3
Methyl methacrylate 30%, butyl acrylate 15%, diisooctyl maleate 2%, three acrylic acid of crosslinking agent pentaerythrite Ester 1%, initiator cumyl peroxide 2% heat and control temperature at 60 DEG C, be stirred to react 1.5h.Add 1- hydroxyl rings Hexane Benzophenone 0.5%, the reaction was continued 1h.Anti-aging agent 445 0.5%, antioxidant A W 1%, reactive diluent two are added after cooling Contracting tripropylene glycol diacrylate 35%, thermal curing agents N-100 3%, HDI 1%, solvent acetone 4%, petroleum ether 5%.Use its as The UV protective films of adhesive, initial peeling force are that peeling force is 0.08N/25 mm after 15.48 N/25 mm, UV illumination.
Example 4
Methyl methacrylate 28%, butyl acrylate 8%, acrylic acid 6%, diisooctyl maleate 5%, crosslinking agent pentaerythrite three Acrylate 2%, initiator dibenzoyl peroxide 1% heat and control temperature at 80 DEG C, be stirred to react 1h.Add initiation Agent dibenzoyl peroxide 1%, the reaction was continued 1h.Anti-aging agent RD 1%, reactive diluent tripropylene glycol two are added after cooling Acrylate 35%.Thermal curing agents N-100 4%, solvent petroleum ether 9% are added in film.It is used to be protected as the UV of adhesive Film, initial peeling force are that peeling force is 0.06N/25 mm after 15.28 N/25 mm, UV illumination.

Claims (10)

1. a kind of UV visbreakings glue, it is characterised in that include the raw material of following mass percent:
Reaction monomers 30%-60%, reactive diluent 30%-50%, initiator 0.01%-5%, crosslinking agent 1%-5%, thermal curing agents 0.05%-5%, anti-aging agent 0.1%-5%, solvent 0-30%;
Its preferred ingredient is:
Reaction monomers 40%-55%, reactive diluent 30%-40%, initiator 0.05%-2%, crosslinking agent 2%-3%, thermal curing agents 0.5%-2%, anti-aging agent 0.1%-1%, solvent 1%-10%.
2. UV visbreakings glue according to claim 1, it is characterised in that:The reaction monomers are methyl methacrylate (MMA), Acrylic acid (AA), ethyl methacrylate, acrylic acid methoxy ethyl ester, butyl acrylate (BA), acrylic acid ethoxy ethyl ester, and One kind in diisooctyl maleate (DOM) or combination.
3. UV visbreakings glue according to claim 1, it is characterised in that:The reactive diluent uses diethylene glycol divinyl base Ether, one kind of tri (propylene glycol) diacrylate isoreactivity monomer or combination.
4. UV visbreakings glue according to claim 1, it is characterised in that:The crosslinking agent pentaerythritol triacrylate, diethyl Divinyl ether, one kind in tri (propylene glycol) diacrylate or combination.
5. UV visbreakings glue according to claim 1, it is characterised in that:The initiator is dibenzoyl peroxide, 1- hydroxyls Hexamethylene Benzophenone, 2- hydroxy-2-methyl -1- phenylacetones, azodiisobutyronitrile, cumyl peroxide, fluorinated diphenyl One kind in titanium cyclopentadienyl etc. or combination.
6. UV visbreakings glue according to claim 1, it is characterised in that:The thermal curing agents are IPDI, one in HDI, N-100 Kind or combination.
7. UV visbreakings glue according to claim 1, it is characterised in that:The anti-aging agent is bisphenol-A, anti-aging agent RD, anti-aging agent AW, antioxidant 264, one kind in anti-aging agent 445 or combination.
8. UV visbreakings glue according to claim 1, it is characterised in that:The solvent is ethyl acetate, acetone, in petroleum ether A kind of or combination.
9. a kind of manufacturing process of UV visbreakings glue described in claim 1, it is characterised in that:By reaction monomers, crosslinking agent press than Example mixing, is first added part initiator initiated polymerization, heats and control temperature at 60 ~ 100 DEG C, be stirred to react 0.5 ~ 2h; Add remaining initiator the reaction was continued 0.5 ~ 2h;Terminate in reaction, reactive diluent is added after cooling, anti-aging agent inhibits glue Autohemagglutination, and thermal curing agents and solvent are added, it stirs evenly;Thermal curing agents and solvent can also independent mixing, when film adds.
10. a kind of application of the UV visbreakings glue described in claim 1 in UV visbreaking protective films.
CN201611171314.3A 2016-12-17 2016-12-17 A kind of UV visbreakings glue Pending CN108611033A (en)

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Application Number Priority Date Filing Date Title
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109659419A (en) * 2018-10-30 2019-04-19 东莞市谷麦光学科技有限公司 A kind of LED light sealing printing technology
CN109735256A (en) * 2019-01-28 2019-05-10 苏州世华新材料科技股份有限公司 A kind of preparation method of the UV visbreaking protective film of the one pack system of resistance to visible light
CN110205043A (en) * 2019-06-21 2019-09-06 广东硕成科技有限公司 A kind of semiconductor material processing dicing tape and preparation method thereof
CN110283537A (en) * 2019-07-04 2019-09-27 四川羽玺新材料股份有限公司 A kind of UV solves viscous pressure sensitive adhesive and preparation method thereof
CN110484150A (en) * 2019-08-28 2019-11-22 昆山博益鑫成高分子材料有限公司 A kind of high temperature resistant UV visbreaking adhesive tape
CN111117523A (en) * 2020-01-08 2020-05-08 南京工业大学 Emulsion type diene-based copolymer UV visbreaking adhesive and preparation method thereof
CN112375518A (en) * 2020-11-16 2021-02-19 中山市皇冠胶粘制品有限公司 Ultra-low viscosity acrylate pressure-sensitive adhesive, protective film adhesive tape, and preparation method and application thereof
CN113088209A (en) * 2021-04-07 2021-07-09 广东硕成科技有限公司 Easily-stripped UV (ultraviolet) anti-adhesion protective film and preparation method thereof
CN113897168A (en) * 2021-10-26 2022-01-07 湖北大学 UV (ultraviolet) viscosity-reducing glue solution, single-side UV viscosity-reducing protective film and preparation method
CN115197663A (en) * 2022-08-15 2022-10-18 芊惠半导体科技(苏州)有限公司 UV (ultraviolet) viscosity reducing adhesive for wafer, preparation method of UV viscosity reducing adhesive and UV viscosity reducing adhesive tape for wafer

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109659419A (en) * 2018-10-30 2019-04-19 东莞市谷麦光学科技有限公司 A kind of LED light sealing printing technology
CN109735256A (en) * 2019-01-28 2019-05-10 苏州世华新材料科技股份有限公司 A kind of preparation method of the UV visbreaking protective film of the one pack system of resistance to visible light
CN110205043B (en) * 2019-06-21 2021-07-16 广东硕成科技有限公司 Cutting adhesive tape for processing semiconductor material and preparation method thereof
CN110205043A (en) * 2019-06-21 2019-09-06 广东硕成科技有限公司 A kind of semiconductor material processing dicing tape and preparation method thereof
CN110283537A (en) * 2019-07-04 2019-09-27 四川羽玺新材料股份有限公司 A kind of UV solves viscous pressure sensitive adhesive and preparation method thereof
CN110283537B (en) * 2019-07-04 2021-06-04 四川羽玺新材料股份有限公司 UV (ultraviolet) debonding pressure-sensitive adhesive and preparation method thereof
CN110484150A (en) * 2019-08-28 2019-11-22 昆山博益鑫成高分子材料有限公司 A kind of high temperature resistant UV visbreaking adhesive tape
CN111117523A (en) * 2020-01-08 2020-05-08 南京工业大学 Emulsion type diene-based copolymer UV visbreaking adhesive and preparation method thereof
CN112375518A (en) * 2020-11-16 2021-02-19 中山市皇冠胶粘制品有限公司 Ultra-low viscosity acrylate pressure-sensitive adhesive, protective film adhesive tape, and preparation method and application thereof
CN113088209A (en) * 2021-04-07 2021-07-09 广东硕成科技有限公司 Easily-stripped UV (ultraviolet) anti-adhesion protective film and preparation method thereof
CN113088209B (en) * 2021-04-07 2021-12-03 广东硕成科技有限公司 Easily-stripped UV (ultraviolet) anti-adhesion protective film and preparation method thereof
CN113897168A (en) * 2021-10-26 2022-01-07 湖北大学 UV (ultraviolet) viscosity-reducing glue solution, single-side UV viscosity-reducing protective film and preparation method
CN115197663A (en) * 2022-08-15 2022-10-18 芊惠半导体科技(苏州)有限公司 UV (ultraviolet) viscosity reducing adhesive for wafer, preparation method of UV viscosity reducing adhesive and UV viscosity reducing adhesive tape for wafer

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Application publication date: 20181002