CN105602515B - A kind of ultraviolet curing transfer adhesive and preparation method and application - Google Patents
A kind of ultraviolet curing transfer adhesive and preparation method and application Download PDFInfo
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- CN105602515B CN105602515B CN201610031144.2A CN201610031144A CN105602515B CN 105602515 B CN105602515 B CN 105602515B CN 201610031144 A CN201610031144 A CN 201610031144A CN 105602515 B CN105602515 B CN 105602515B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a kind of transfer film ultraviolet curing transfer adhesive compositions, the ultraviolet light transfer glue composition includes 20~40 parts of modification acrylates, 20~40 parts of epoxy resin, 10~30 portions of reactive diluents, 3~8 parts of photoinitiators, 5~15 parts of adhesion promoters, 2~5 parts of silane coupling agents, 0~1 part of auxiliary agent, and the modification acrylate is by the polyurethane containing isocyano to by methyl methacrylate（MMA）, n-butyl acrylate（n‑BA）, hydroxy propyl methacrylate（HMPA）, acrylic acid（AA）And Isooctyl acrylate monomer（EHA）It is modified and is prepared by the five-membered copolymer of free-radical polymerized preparation.The ultraviolet curing transfer adhesive of preparation has glass baseplate good adhesion, and the water-tolerant of transfer glue, and tensile strength is high, transferring effect is excellent.
Description
Technical field
The present invention relates to ultraviolet photo-curing cementing agent field, more particularly, to a kind of transfer film transfer glue.
Background technology
Glue-line adhesive used in transfer film industry is based on hot melt adhesive.Hot melt adhesive is at normal temperatures in solid-state, heating melting
It can complete to be bonded after being coated with and pressing.Hot melt adhesive substance based on thermoplastic resin or rubber at present, then
A series of auxiliary agents such as plasticizer, antioxidant, fire retardant, filler are equipped with, it is a kind of multicomponent mixture.Common hot melt adhesive
Stick matrix resin have polyethylene, ethylene-vinyl acetate, polyamide, polyurethane, polyester etc. and styrene-butadiene-
The elastomers such as styrene, styrene-isoprene-phenylethene.
Although current hot melt adhesive application is very extensive, there is also some shortcomings for it：Heat resistance is inadequate, adhesive strength
Not high, resistance to chemical reagents is poor, hardening time is long, has a small amount of VOC to discharge, not environmentally；Special equipment such as hot melt gun etc. need to be equipped with
Melting, sizing, inconvenient to use etc..
Ultraviolet photo-curing cementing agent is under the jurisdiction of the adhesive of environmentally protective class, since it can be effectively reduced the row of VOC
It puts and the advantages that low energy consumption, room temperature curing, fast curing rate, is widely used in each field, esters of acrylic acid gluing
The research of agent is particularly, active.The advantages of acrylate copolymer is that have good film forming and light fastness, but due to third
On olefin(e) acid resin side chain the reason of ester bond, make its water resistance and heat resistance, wearability, solvent resistance poor, so as to make curing
The glossiness and adhesion-tight degree of film are not ideal enough, influence to decorate performance and application value.Polyurethane modified acrylic resin can
With assign the good mechanical endurance of resin, film it is plentiful it is bright, chemical resistance is good etc..Polyurethane-acrylate resin has both
There is the advantages of acrylate and polyurethane, hydrogen bond can be formed between high-polymer molecular, so as to make the wearability of cured film and resistance to
Chemically obtain larger raising.However ultraviolet photo-curing cementing agent in transfer film field using less, this is mainly due to routines
Ultraviolet photo-curing cementing agent is insufficient to glass baseplate adhesive force, and water resistance is poor, and is difficult to realize surface drying at normal temperatures, so as to
It cannot function as transfer glue.
Invention content
The defects of the present invention is directed to overcome the above-mentioned prior art, provides a kind of transfer film and is combined with ultraviolet curing transfer adhesive
Object.The composition has glass baseplate good adhesion, and the water-tolerant of transfer glue, and tensile strength is high, transferring effect is excellent.
It is another object of the present invention to above-mentioned ultraviolet curing transfer adhesive composition is applied to the thermal transfer of glass baseplate.
The present invention is achieved through the following technical solutions foregoing invention purpose.
The invention discloses a kind of UV transfer glue composition, UV transfer glue composition is calculated by weight by following
Component forms：
20~40 parts of modification acrylate；
20~40 parts of epoxy resin；
10~30 parts of reactive diluent；
3~8 parts of photoinitiator；
5~15 parts of adhesion promoter；
2~5 parts of silane coupling agent
0~1 part of auxiliary agent；
Wherein, the modification acrylate reacts preparation by the polyurethane containing isocyano with five yuan of acrylate copolymers
It forms；
Five yuan of acrylate copolymers are by methyl methacrylate (MMA), butyl acrylate (n-BA), metering system
Five kinds of sour hydroxypropyl acrylate (HPMA), acrylic acid (AA), Isooctyl acrylate monomer (EHA) acrylic ester monomers pass through radical copolymerization
It prepares, structural unit, wherein a shown in structural formula 1 is included in structure:b:c:d:E is 49~61:14~18:12~16:6~
8:4~6；
The number-average molecular weight of five yuan of acrylate copolymers is 5000~7000；
The polyurethane containing isocyano is reacted by diisocyanate with acrylic acid monohydroxy ester to be prepared；
The molar ratio of the polyurethane and hydroxy propyl methacrylate containing isocyano is 0.8~1.
Preferably, the molar ratio of the diisocyanate and acrylic acid monohydroxy ester is 1:1.
MMA, n-BA, HMPA, AA and EHA is selected to polymerize according to the above ratio as comonomer, five yuan third of preparation can be made
Olefin(e) acid ester copolymer has higher glass transition temperature.Five yuan of acrylate copolymers change through the polyurethane containing isocyano
Property, gained modification acrylate still has higher glass transition temperature, surface drying can be realized under room temperature.When with the modification
When resin prepares adhesive based on acrylate, the adhesive after the completion of coating without ultraviolet light before it is just presented
Dry film glue state, so as to as thermal transfer glue.Acrylate introduces photoactivatable groups after polyurethane-modified, so as into
Row ultraviolet light cures.In addition, ammonia ester bond and urea ester bond have higher cohesive energy in modification acrylate, and glass is a kind of
The material of high surface energy causes modification acrylate that can form the higher adhesive layer of surface tension on the glass surface.
The hydroxyl and ehter bond of epoxy resin are all polar groups, have preferable cohesive force, and asphalt mixtures modified by epoxy resin to glass baseplate
Fat water-tolerant mixes the water resistance that can significantly improve acrylic ester resin with acrylic ester resin.Acrylic ester tree
Fat is also very good with epoxy-resin systems compatibility, and mixed resin is still clarified, is transparent, is uniform.By epoxy resin and modification
Acrylate is used cooperatively, and the transfer glue adhesive force and water resistance that can make preparation are obviously improved.
Further, in above-mentioned UV transfers glue composition, the weight ratio of modification acrylate and epoxy resin is 1~3:
1~3.Modification acrylate is excessive, then transfer glue declines the adhesive force of glass baseplate, and water resistance is also deteriorated；Epoxy resin mistake
More, then transfer glue carries out cured required overlong time or is difficult to completion of cure, and the easy xanthochromia of glue-line.
Preferably, UV transfers glue composition described above, the adhesion promoter are PN-700, PN-701 or PN-
702。
Preferably, the preparation of five yuan of acrylate copolymers uses radical copolymerization, during radical copolymerization
Chain-transferring agent is added, the addition of the chain-transferring agent is the 1%~6% of acrylic ester monomer gross mass, adds in chain and turns
It moves agent and is conducive to control reaction, prevent implode.
Preferably, in the UV transfers glue composition, the diisocyanate is isophorone diisocyanate
(IPDI), toluene di-isocyanate(TDI) (TDI) or methyl diphenylene diisocyanate (MDI).
Preferably, the acrylic acid monohydroxy ester for hydroxyethyl methacrylate (HEMA), hydroxy-ethyl acrylate (HEA),
Hydroxypropyl acrylate (HPA) or hydroxy propyl methacrylate (HPMA).
Modification acrylate in UV transfer glue compositions is prepared via a method which：
S1. diisocyanate with acrylic acid monohydroxy ester is reacted, obtains the polyurethane containing isocyano；
S2., MMA, n-BA, HMPA, AA and EHA are prepared to five yuan of acrylic acid as shown in structural formula 1 by free radical polymerization
Ester copolymer；
S3. the polyurethane containing isocyano is added dropwise in five yuan of acrylate copolymers.
Preferably, step S2 is：Cause MMA, n-BA, HMPA, AA and EHA polymerization with the initiator of total amount 60%~70%
1~2h is reacted, then adds remaining 4~5h of initiator for reaction.
Preferably, the reaction temperature of step S2 is 70~75 DEG C.
It is highly preferred that the reaction temperature of step S1 is 65~70 DEG C, the reaction temperature of step S2 is 70~75 DEG C, step S3
Reaction temperature be 65~70 DEG C.
Specifically, the preparation process of the modification acrylate is as follows：
S1. diisocyanate and solvent are added in into the flask of reaction system 1, controls 45~50 DEG C of temperature, will with it is two different
The acrylic acid monohydroxy ester of the amount of the substances such as cyanate is uniformly mixed with catalyst, polymerization inhibitor, solvent, and mixing is added dropwise into flask
Liquid increases temperature to 65~70 DEG C, reacts 1.5~2h, obtain the polyurethane containing isocyano after dripping；
S2. MMA, n-BA, HMPA, AA and EHA and initiator azo-bis-isobutyl cyanide (AIBN), chain-transferring agent and solvent are mixed
It closes and uniformly obtains mixed liquor, control mixed liquor is added dropwise completely in two hours.After mixed liquor is added dropwise to complete, then will be remaining
/ 3rd AIBN is added drop-wise in reaction vessel, and control system temperature is in 70~75 DEG C of isothermal reaction 5h.Go out after reaction
Material, obtains hydroxy acrylate copolymer (MMA-co-BA-co-HMPA-co-AA-co-EHA)；
S3. the polyurethane containing isocyano, solvent and catalyst, controlling reaction temperature 65~70 are added dropwise into S2 systems
DEG C, react 2~3h.
The invention also discloses application of the UV transfer glue compositions as transfer glue on the glass substrate.By the UV
Transfer glue composition is dissolved in mixed solvent (ethyl acetate and ethyl alcohol), is configured to the glue used.Glue is coated in
Have on the PET transfer films of ink layer, using heat transfer machine, the pattern on heat transfer film can be transferred on glass plate, then carry out
Ultraviolet light cures.
Compared with prior art, the present invention has the advantages that：
The present invention is synthesized five yuan of acrylate copolymers, is passed through using MMA, n-BA, HMPA, AA and EHA as comonomer
The higher acrylate of glass transition temperature has been prepared in the selection of monomer and the allotment of ratio；Using containing isocyano
Polyurethane is modified the acrylate, makes double containing ammonia ester bond and photoactivatable groups carbon carbon on modified acroleic acid ester side chain
Key, prepared modification acrylate can carry out UV curings, and glass transition temperature is higher, at ambient temperature can table
It is dry；The modification acrylate and epoxy resin are compounded so that the transfer glue of preparation have simultaneously polyacrylate it is good into
The advantages of good water resistance of film property, light fastness and epoxy resin, by the modification acrylate of preparation and epoxy resin, activity
Diluent, photoinitiator, additive compound are prepared into transfer glue, and prepared transfer glue water-tolerant, tensile shear strength are high, right
Glass baseplate adhesive force is good and transferring effect is excellent.
Specific embodiment
The present invention is described in further details with reference to specific embodiment, but embodiment the present invention is not done it is any
The restriction of form.Unless stated otherwise, source chemicals used in the embodiment of the present invention are conventional source chemicals purchased in market.
Embodiment 1
To with condenser pipe, thermometer, blender, nitrogen conduit four-hole boiling flask in add in 30.8gIPDI and 20mL second
Acetoacetic ester controls 45~50 DEG C of temperature, and 18.1gHEMA, 0.3g catalyst dibutyltin dilaurylate (DBTDL), 0.04g are hindered
Poly- agent 2,2,6,6- tetramethyl piperidine -1- oxygen radicals (TEMPO), MMA, n-BA, HMPA, AA and EHA and 20mL ethyl acetate
It is uniformly mixed, mixed liquor is added dropwise into flask, temperature is increased after dripping to 65~70 DEG C, reacts 1.5~2h, is obtained containing isocyanide
The polyurethane of acid group；By 55g MMA, 20g n-BA, 20g HPMA, 5g AA, 10g HEA and 1g AIBN, 2g dodecyl sulphur
Alcohol (NDM) and 50mL solvents are uniformly mixed to obtain mixed liquor, and control mixed liquor is added dropwise completely in two hours.In mixing drop
After the completion of adding, 0.5g AIBN are added drop-wise in reaction vessel, control system temperature obtains five yuan of propylene in 72 DEG C of isothermal reaction 5h
Acid ester copolymer, number-average molecular weight 6200；The above-mentioned poly- ammonia containing isocyano is added dropwise toward five yuan of acrylate copolymer kinds
The mixed solution of ester, 0.3g catalyst DBTDL, 20mL ethyl acetate, 65~70 DEG C of controlling reaction temperature are reacted 3h, are changed
Property acrylate.
Prepolymer and epoxy resin 601, reactive diluent, photoinitiator, auxiliary agent etc. are prepared into (being shown in Table 1) by formula ratio,
Resin formula is dissolved in mixed solvent (ethyl acetate:Ethyl alcohol=7:3) in, it is configured to the glue used.Glue is coated in
It is coated on the PET transfer films of ink layer, coating thickness is 4 μm, observes the whether dry and comfortable viscous hand of glued membrane of formation.Use thermal transfer
Machine, transfer temperature are 160 DEG C, the pattern on heat transfer film are transferred on glass plate, then with uv cure machine hardening with radiation.
Embodiment 2
To with condenser pipe, thermometer, blender, nitrogen conduit four-hole boiling flask in add in 24g TDI and 20mL acetic acid
Ethyl ester controls 45~50 DEG C of temperature, by 16g HEA and 0.3g catalyst DBTDL, 0.04g polymerization inhibitor TEMPO, 20mL acetic acid second
Ester is uniformly mixed, mixed liquor is added dropwise into flask, and temperature is increased after dripping to 65~70 DEG C, 1.5~2h is reacted, is contained
The polyurethane of isocyano；By 50g MMA, 18g n-BA, 20g HPMA, 5g AA, 9g EHA and 1.5g AIBN, 3g NDM and
50mL solvents are uniformly mixed to obtain mixed liquor, and control mixed liquor is added dropwise completely in two hours.After mixed liquor is added dropwise to complete,
0.5g AIBN are added drop-wise in reaction vessel, control system temperature obtains five yuan of acrylic ester copolymers in 72 DEG C of isothermal reaction 5h
Object, number-average molecular weight 6000；Toward the above-mentioned polyurethane containing isocyano is added dropwise in five yuan of acrylate copolymer kinds, 0.3g is urged
The mixed solution of agent DBTDL, 20mL ethyl acetate, 65~70 DEG C of controlling reaction temperature react 3h, obtain modified acroleic acid
Ester.
Prepolymer and epoxy resin 601, reactive diluent, photoinitiator, auxiliary agent etc. are prepared into (being shown in Table 1) by formula ratio,
Resin formula is dissolved in mixed solvent (ethyl acetate:Ethyl alcohol=7:3) in, it is configured to the glue used.Glue is coated in
It is coated on the PET transfer films of ink layer, coating thickness is 4 μm, observes the whether dry and comfortable viscous hand of glued membrane of formation.Use thermal transfer
Machine, transfer temperature are 160 DEG C, the pattern on heat transfer film are transferred on glass plate, then with uv cure machine hardening with radiation.
Embodiment 3
To with condenser pipe, thermometer, blender, nitrogen conduit 1 four-hole boiling flask in add in 25.9g IPDI and 20mL
Ethyl acetate controls 45~50 DEG C of temperature, by 13.5g HEA and 0.3g catalyst DBTDL, 0.04g polymerization inhibitors TEMPO, 20mL
Ethyl acetate is uniformly mixed, mixed liquor is added dropwise into flask, and temperature is increased after dripping to 65~70 DEG C, reacts 1.5~2h,
Obtain the polyurethane containing isocyano；By 60g MMA, 22g BA, 21g HPMA, 5g AA, 11g EHA and 2g AIBN, 4g
NDM and 50mL solvents are uniformly mixed to obtain mixed liquor, and control mixed liquor is added dropwise completely in two hours.It is dripped in mixed liquor
0.5g AIBN are added drop-wise in reaction vessel by Cheng Hou, and control system temperature obtains five yuan of acrylate in 72 DEG C of isothermal reaction 5h
Copolymer, number-average molecular weight 5300；Toward five yuan of acrylate copolymer kinds be added dropwise the above-mentioned polyurethane containing isocyano,
The mixed solution of 0.03g catalyst dibutyltins dilaurylate, 20mL ethyl acetate, 65~70 DEG C of controlling reaction temperature, reaction 2
~3h, obtains modification acrylate.
Prepolymer and epoxy resin 601, reactive diluent, photoinitiator, auxiliary agent etc. are prepared into (being shown in Table 1) by formula ratio,
Resin formula is dissolved in mixed solvent (ethyl acetate:Ethyl alcohol=7:3) in, it is configured to the glue used.Glue is coated in
It is coated on the PET transfer films of ink layer, coating thickness is 4 μm, observes the whether dry and comfortable viscous hand of glued membrane of formation.Use thermal transfer
Machine, transfer temperature are 160 DEG C, the pattern on heat transfer film are transferred on glass plate, then with uv cure machine hardening with radiation.
Comparative example 1
Prepare modified acrylic ester resin by the experimental procedure of embodiment 1, by modification acrylate and epoxy resin 601,
Reactive diluent, photoinitiator, adhesive force promote machine, auxiliary agent etc. to prepare (being shown in Table 1) by formula ratio, resin formula are dissolved in mixed
Bonding solvent (ethyl acetate:Ethyl alcohol=7:3) in, it is configured to the glue used.The PET that glue is coated with to ink layer is transferred
On film, coating thickness is 4 μm, observes the whether dry and comfortable viscous hand of glued membrane of formation.Using heat transfer machine, transfer temperature is 160 DEG C, will
Pattern on heat transfer film is transferred on glass plate, then with uv cure machine hardening with radiation.
Comparative example 2
Prepare modified acrylic ester resin by the experimental procedure of embodiment 1, by modification acrylate and epoxy resin 601,
Reactive diluent, photoinitiator, auxiliary agent etc. prepare (being shown in Table 1) by formula ratio, and resin formula is dissolved in mixed solvent (acetic acid second
Ester:Ethyl alcohol=7:3) in, it is configured to the glue used.Glue is coated on the PET transfer films of ink layer, coating thickness
It is 4 μm, observes the whether dry and comfortable viscous hand of glued membrane of formation.Using heat transfer machine, transfer temperature is 160 DEG C, will be on heat transfer film
Pattern is transferred on glass plate, then with uv cure machine hardening with radiation.
Comparative example 3
To with condenser pipe, thermometer, blender, nitrogen conduit 1 four-hole boiling flask in add in 30.8g IPDI and 20mL
Ethyl acetate controls 45~50 DEG C of temperature, by 18.1g HEMA and 0.3g catalyst DBTDL, 0.04g polymerization inhibitors TEMPO, 20mL
Ethyl acetate is uniformly mixed, mixed liquor is added dropwise into flask, and temperature is increased after dripping to 65~70 DEG C, reacts 1.5~2h,
Obtain the polyurethane containing isocyano；By 45g MMA, 25g n-BA, 20g HPMA, 5g AA, 15g EHA and 1.5g AIBN,
2g NDM and 50mL solvents are uniformly mixed to obtain mixed liquor, and control mixed liquor is added dropwise completely in two hours.In mixing drop
After the completion of adding, remaining 0.5gAIBN is added drop-wise in reaction vessel, control system temperature obtains five in 72 DEG C of isothermal reaction 5h
First acrylate copolymer, number-average molecular weight 5200；It is added dropwise toward five yuan of acrylate copolymers above-mentioned containing isocyano
The mixed solution of polyurethane, 0.3g catalyst DBTDL, 20mL ethyl acetate, 65~70 DEG C of controlling reaction temperature are reacted 3h, are obtained
To modification acrylate.
Prepolymer and epoxy resin 601, reactive diluent, photoinitiator, auxiliary agent etc. are prepared by 1 formula ratio of embodiment
Resin formula is dissolved in mixed solvent (ethyl acetate by (being shown in Table 1):Ethyl alcohol=7:3) in, it is configured to the glue used.By glue
Liquid is coated on the PET transfer films of ink layer, and coating thickness is 4 μm, observes the whether dry and comfortable viscous hand of glued membrane of formation.It uses
Heat transfer machine, transfer temperature are 160 DEG C, the pattern on heat transfer film are transferred on glass plate, then with uv cure machine spoke
According to curing.
Comparative example 4
To with condenser pipe, thermometer, blender, nitrogen conduit 1 four-hole boiling flask in add in 30.8g IPDI and 20mL
Ethyl acetate controls 45~50 DEG C of temperature, will with 18.1g HEMA and 0.3g catalyst DBTDL, 0.04g polymerization inhibitors TEMPO,
20mL ethyl acetate is uniformly mixed, mixed liquor is added dropwise into flask, and temperature is increased after dripping to 65~70 DEG C, and reaction 1.5~
2h obtains the polyurethane containing isocyano；By 55gMMA, 20g n-BA, 20g HPMA, 5g AA, 10g EHA and 1.5g
AIBN, 10g NDM and 50mL solvents are uniformly mixed to obtain mixed liquor, and control mixed liquor is added dropwise completely in two hours.Mixed
After conjunction liquid is added dropwise to complete, remaining 0.5g AIBN are added drop-wise in reaction vessel, control system temperature is in 72 DEG C of isothermal reaction 5h
Obtain five yuan of acrylate copolymers, number-average molecular weight 3200；It is added dropwise toward five yuan of acrylate copolymers above-mentioned containing isocyanide
The polyurethane of acid group, the mixed solution of 0.3g catalyst DBTDL, 20mL ethyl acetate, 65~70 DEG C of controlling reaction temperature, reaction
3h obtains modification acrylate.
Prepolymer and epoxy resin 601, reactive diluent, photoinitiator, auxiliary agent etc. are prepared by 1 formula ratio of embodiment
Resin formula is dissolved in mixed solvent (ethyl acetate by (being shown in Table 1):Ethyl alcohol=7:3) in, it is configured to the glue used.By glue
Liquid is coated on the PET transfer films of ink layer, observes the whether dry and comfortable viscous hand of glued membrane of formation.It, will be hot using heat transfer machine
Pattern on transfer film is transferred on glass plate, then with uv cure machine hardening with radiation.
The formula dosage of 1 embodiment of table and comparative example
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Polyurethane-modified polyacrylate/g | 30 | 36 | 40 | 50 | 10 | 30 | 30 |
| Epoxy resin 601/g | 30 | 24 | 20 | 10 | 50 | 30 | 30 |
| Darocur-1173/g | 4 | 6 | 6 | 4 | 6 | 4 | 4 |
| IBOA/g | 20 | 18 | 30 | 20 | 18 | 20 | 20 |
| PN-700/g | 10 | 10 | 15 | 10 | 10 | 10 | 10 |
| KH-560/g | 5 | 5 | 2 | 5 | 5 | 5 | 5 |
| Antifoaming agent/g | 1 | 1 | 0.5 | 1 | 1 | 1 | 1 |
The test result of 2 embodiment performance of table
Remarks：Transferring effect：The transfer pattern on glass plate is torn using 3M adhesive tapes, checks the effect of transfer：3M adhesive tapes
It is 1 grade to glue pattern when pulling one time to be all stained with adhesive tape；It is 2 grades that 2-5 pattern, which is glued adhesive tape,；5-10 times less than 30% pattern quilt
It is 3 grades to be stained with adhesive tape；It is 4 grades to be less than 10% after 5-10 times；It is 5 grades that 10 times or more viscous, which pulls pattern and be not stripped, and series is got over
It is better to represent transferring effect for height.
It is dry-ness：The glued membrane of coating is placed 7 days, has seen whether to after-tack phenomenon.
According to the test result of each embodiment it is found that being compounded using polyurethane-modified acrylic ester and epoxy resin, by formula
Amount debugging, the UV transfer glue strong adhesive forces of preparation can reach 0 grade, water-tolerant, can reach 1 grade, good transferring effect, and thermosetting
The change time is short, no more than 20min.
According to the comparison of the test result of comparative example 1 and embodiment 1 it is found that when modification acrylate in UV transfer glue compositions
Amount is excessive and when the amount of epoxy resin is very few, the adhesive force and water resistance of transfer glue decline, and tensile shear strength also declines；
It is compared according to the test result of comparative example 2 and embodiment 2 it is found that being modified when transfer glue composition epoxy resin content is excessive
When acrylate content is very few, the thermal transfer time of transfer glue significantly lengthens, thermal transfer effect slightly declines, tensile shear strength
Decline；According to the test result of comparative example 3 and embodiment 1 compare it is found that only when methyl methacrylate, butyl acrylate,
This five kinds of acrylic ester monomers of hydroxy propyl methacrylate, acrylic acid, Isooctyl acrylate monomer prepare acrylic acid according to a certain ratio
Ester copolymer, prepared transfer glue can be only achieved good transferring effect and realize surface drying in room temperature；According to comparative example 4 and in fact
The test result comparison of example 1 is applied it is found that when five yuan of acrylate number-average molecular weights for preparing modification acrylate are too low, is transferred
Poor effect.
Claims (10)
1. a kind of UV transfers glue composition, which is characterized in that the UV transfers glue composition by the following group calculated by weight
Part composition：
20~40 parts of modification acrylate；
20~40 parts of epoxy resin；
10~30 parts of reactive diluent；
3~8 parts of photoinitiator；
5~15 parts of adhesion promoter；
2~5 parts of silane coupling agent
0~1 part of auxiliary agent；
Wherein, the modification acrylate reacted by the polyurethane containing isocyano with five yuan of acrylate copolymers preparation and
Into；
Five yuan of acrylate copolymers are by methyl methacrylate, n-butyl acrylate, hydroxy propyl methacrylate, third
Five kinds of acrylic ester monomers of olefin(e) acid and Isooctyl acrylate monomer are prepared by radical copolymerization, and structure is included in backbone structure
Structural unit shown in formula 1, wherein a:b:c:d:E is 49~61:14~18:12~16:6~8:4~6；
The number-average molecular weight of five yuan of acrylate copolymers is 5000~7000；
The polyurethane containing isocyano is reacted by diisocyanate with acrylic acid monohydroxy ester to be prepared；
The molar ratio of the polyurethane and hydroxy propyl methacrylate containing isocyano is 0.8~1.
2. UV transfers glue composition according to claim 1, which is characterized in that the modification acrylate and epoxy resin
Weight ratio be 1~3:1~3.
3. UV transfers glue composition according to claim 1, it is characterised in that the adhesion promoter is PN-700, PN-
701 or PN-702.
4. UV transfers glue composition according to claim 1, which is characterized in that is added in the radical polymerization process
Chain-transferring agent, the addition of the chain-transferring agent are the 1%~6% of acrylic ester monomer gross mass.
5. UV transfers glue composition according to claim 1, which is characterized in that the diisocyanate is isophorone two
Isocyanates, toluene di-isocyanate(TDI) or methyl diphenylene diisocyanate.
6. UV transfers glue composition according to claim 1, which is characterized in that the acrylic acid monohydroxy ester is methyl-prop
Olefin(e) acid hydroxyl ethyl ester, hydroxy-ethyl acrylate, hydroxypropyl acrylate or hydroxy propyl methacrylate.
7. UV transfers glue composition according to claim 1, which is characterized in that the modification acrylate passes through such as lower section
It is prepared by method：
S1. diisocyanate with acrylic acid monohydroxy ester is reacted, obtains the polyurethane containing isocyano；
S2. methyl methacrylate, n-butyl acrylate, hydroxy propyl methacrylate, acrylic acid and Isooctyl acrylate monomer are led to
Cross five yuan acrylate copolymers of the radical copolymerization preparation as shown in structural formula 1；
S3. the polyurethane containing isocyano is added dropwise in five yuan of acrylate copolymers.
8. UV transfers glue composition according to claim 7, which is characterized in that the step S2 is：With total amount 60%~
It is different that 70% initiator causes methyl methacrylate, n-butyl acrylate, hydroxy propyl methacrylate, acrylic acid, acrylic acid
Monooctyl ester 1~2h of polymerisation, then add remaining 4~5h of initiator for reaction.
9. UV transfers glue composition according to claim 8, which is characterized in that the reaction temperature of the step S2 for 70~
75℃。
10. described in claim 1~6 any one claim UV transfer glue composition as transfer glue on the glass substrate
Application.
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| CN107474216B (en) * | 2017-09-19 | 2020-10-02 | 立邦工业涂料(上海)有限公司 | Water-soluble polyurethane modified acrylic polymer, preparation method and application thereof |
| CN108822788A (en) * | 2018-06-13 | 2018-11-16 | 上海昀通电子科技有限公司 | Ultraviolet cured adhesive composition, preparation method and its usage |
| CN109294512B (en) * | 2018-10-11 | 2021-08-27 | 江苏卫星新材料股份有限公司 | High-transferability UV (ultraviolet) photocuring adhesive and preparation method and application thereof |
| CN110128996B (en) * | 2019-06-06 | 2021-08-20 | 杭州之江新材料有限公司 | Sealant, preparation method and application thereof and vehicle |
| CN112126402B (en) * | 2020-09-24 | 2022-06-07 | 广东普赛达密封粘胶有限公司 | Photo-curing adhesive and preparation method and application thereof |
| CN115322518A (en) * | 2021-05-10 | 2022-11-11 | 财团法人工业技术研究院 | Resin composition, package structure and method for forming resin composition |
| TWI788839B (en) * | 2021-05-10 | 2023-01-01 | 財團法人工業技術研究院 | Resin composition, encapsulation structure, and method for manufacturing resin composition |
| CN114933886B (en) * | 2021-06-04 | 2024-04-02 | 东莞市瑞辉新材料技术有限公司 | High-flexibility UV transfer printing adhesive and preparation method and application thereof |
| CN114085411B (en) * | 2021-12-14 | 2023-04-25 | 金万正(广东)新材料有限公司 | Embossing photoresist release film material with exhaust function and preparation method and application thereof |
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| US5164473A (en) * | 1990-01-16 | 1992-11-17 | Miles Inc. | Two-component polyurethane adhesive |
| CN103613698A (en) * | 2013-11-26 | 2014-03-05 | 王鹏飞 | Thermosetting acrylic resin for powder coating as well as synthesis method and applications of thermosetting acrylic resin |
| CN104829776A (en) * | 2015-04-29 | 2015-08-12 | 华南理工大学 | Resin for UV-cured strippable protection film, preparation method and applications thereof |
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| US5164473A (en) * | 1990-01-16 | 1992-11-17 | Miles Inc. | Two-component polyurethane adhesive |
| CN103613698A (en) * | 2013-11-26 | 2014-03-05 | 王鹏飞 | Thermosetting acrylic resin for powder coating as well as synthesis method and applications of thermosetting acrylic resin |
| CN104829776A (en) * | 2015-04-29 | 2015-08-12 | 华南理工大学 | Resin for UV-cured strippable protection film, preparation method and applications thereof |
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