CN115466593A - Ultraviolet light curing adhesive - Google Patents

Ultraviolet light curing adhesive Download PDF

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Publication number
CN115466593A
CN115466593A CN202211072870.0A CN202211072870A CN115466593A CN 115466593 A CN115466593 A CN 115466593A CN 202211072870 A CN202211072870 A CN 202211072870A CN 115466593 A CN115466593 A CN 115466593A
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Prior art keywords
diisocyanate
weight
fluorine
parts
hydroxyl
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Chinese (zh)
Inventor
欧阳亮
林武
王攀
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Shenzhen Holeo New Material Technology Co ltd
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Shenzhen Holeo New Material Technology Co ltd
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Priority to CN202211072870.0A priority Critical patent/CN115466593A/en
Publication of CN115466593A publication Critical patent/CN115466593A/en
Priority to CN202310971336.1A priority patent/CN117004361A/en
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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
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4607—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen having halogens
    • C—CHEMISTRY; METALLURGY
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present disclosure relates to an ultraviolet light curing adhesive, which is characterized by comprising 100 parts by weight of fluorine-modified urethane acrylate resin, 10-60 parts by weight of acrylate monomer, 1-15 parts by weight of photoinitiator, and 1-30 parts by weight of auxiliary agent. The ultraviolet curing adhesive disclosed by the invention can adjust the refractive index to a required value (such as 1.36-1.38) through reasonable formula design, has excellent adhesive applying performance and good curing effect, meets requirements on various properties after curing, and has controllable cost.

Description

Ultraviolet light curing adhesive
Technical Field
The disclosure relates to the field of polymer material synthesis, in particular to an ultraviolet light curing adhesive.
Background
With the development of technology, optical fiber communication is increasingly applied to aspects of people's life. The principle of optical fiber communication is that modulated optical signals containing specific information are transmitted to a receiving end through an optical fiber at a transmitting end and are finally converted into electric signals to be read. The optical fiber used in optical fiber transmission generally consists of a high-refractive-index fiber core, a low-refractive-index inner coating and an outer protective layer. The transmission of light in the optical fiber is the total reflection of signal light formed by the refractive index difference between the fiber core and the inner coating, so that information is effectively transmitted with extremely weak signal loss. The refractive index of the inner coating is typically between 1.36 and 1.38. The inner layer coating has specific requirements on refractive index, and also has the characteristics of good weather resistance, good stability, water resistance, oil resistance and the like.
In practice, fusion splicing of optical fibers to optical fibers is often involved, such as fusion splicing of single fibers to single fibers, and fusion splicing of single fibers to multiple fibers (e.g., fiber splitter and combiner (PBS/PBC)). After fusion splicing, the fused optical fiber is generally coated and firmly bonded to the substrate by using glue with the same refractive index as that of the inner coating. This type of glue requires not only good adhesion properties, but also good properties of weather resistance, stability, corrosion resistance, water and oil resistance.
The comprehensive performance of the glue applicable to optical fiber fusion bonding in the prior art is yet to be improved.
Disclosure of Invention
The purpose of the present disclosure is to provide an ultraviolet light curing adhesive, which has excellent performance.
In order to achieve the above object, the present disclosure provides an ultraviolet-curable adhesive, which includes a fluorine-modified urethane acrylate resin, an acrylate monomer, a photoinitiator and an auxiliary agent, wherein 100 parts by weight of the fluorine-modified urethane acrylate resin is used as a reference, the acrylate monomer is 10 to 60 parts by weight, the photoinitiator is 1 to 15 parts by weight, and the auxiliary agent is 1 to 30 parts by weight;
wherein the fluorine modified polyurethane acrylate resin has a chemical structural formula as follows:
Figure BDA0003829865160000021
wherein X is any natural number between 1 and 100; y is any natural number between 1 and 100; ra is a group containing CH 2 (CF 2 ) n CH 2 N is any natural number between 4 and 20; rb is (CF) 2 ) m M is any natural number between 2 and 20; rc is di-isoAn alkyl group, a cycloalkyl group or an aryl group of cyanate ester; rf is an acrylate group or a vinyl ether group having photoreaction activity.
Optionally, based on 100 parts by weight of the fluorine-modified urethane acrylate resin, the content of the acrylate monomer is 15 to 50 parts by weight, the content of the photoinitiator is 2 to 10 parts by weight, and the content of the auxiliary agent is 2 to 20 parts by weight.
Optionally, the preparation of the fluorine-modified urethane acrylate resin comprises the following steps:
a. contacting fluorine-containing dihydric alcohol, fluorine-containing dibasic acid and a first catalyst for esterification reaction to obtain hydroxyl-terminated perfluoro polyester;
b. and (2) contacting the hydroxyl-terminated perfluoro polyester and diisocyanate with a second catalyst, carrying out chain extension reaction in the presence of a solvent, and then adding a blocking agent for blocking.
Optionally, in the step a, the molar ratio of the fluorine-containing diol to the fluorine-containing diacid is (1-2): 1;
the weight ratio of the total amount of the fluorine-containing dihydric alcohol and the fluorine-containing dibasic acid to the first catalyst is 100: (0.01 to 0.1);
the esterification reaction conditions include: stirring at 100-300 r/min, 140-180 deg.c, pressure of-1 MPa to-0.01 MPa and time of 2-4 hr;
the weight average molecular weight of the hydroxyl-terminated perfluoro polyester is 500-10000.
Optionally, in step b, the molar ratio of the hydroxyl-terminated perfluoro polyester to the diisocyanate is (0.5-1): 1, wherein the hydroxyl-terminated perfluoropolyester is calculated as-OH and the diisocyanate is calculated as-NCO;
the weight ratio of the hydroxyl-terminated perfluoropolyester to the second catalyst is 100: (0.01 to 0.1);
the conditions of the chain extension reaction include: the stirring speed is 150-250 r/min, the temperature is 60-70 ℃, and the time is 2-3 hours;
the end-capping conditions include: the stirring speed is controlled to be 150-250 r/min, the temperature is controlled to be 70-80 ℃, and the time is 2-4 hours.
Alternatively, the fluorine-containing diol is selected from the group consisting of 2,2,3,3-tetrafluoro-1, 4-butanediol, 2,2,3,3,4,4-hexafluoro-1, 5-pentanediol, 2,2,3,3,4,5,5-octafluoro-1, 6-hexanediol, a diol having a specific structure, and a diol having a specific structure one or more of hexadecafluoro-1, 10-decanediol and 1H, 12H-eicosafluoro-1, 12-dodecanediol;
the fluorine-containing binary acid is one or more selected from tetrafluorosuccinic acid, hexafluoroglutaric acid, octafluoro adipic acid, perfluoro suberic acid, perfluoro azelaic acid and hexadecafluoro sebacic acid;
the first catalyst is one or more selected from ethylene glycol antimony, antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate, p-toluenesulfonic acid and zinc acetate;
the diisocyanate is one or more selected from hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 4' -dicyclohexylmethane diisocyanate, toluene diisocyanate, methylcyclohexane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, cyclohexane dimethylene diisocyanate, 1, 4-cyclohexane diisocyanate, o-xylylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethyl-m-xylylene diisocyanate, norbornane diisocyanate, dimethyl biphenyl diisocyanate, L-lysine diisocyanate, 1, 5-naphthalene diisocyanate;
the second catalyst is one or more selected from triethylene diamine, dimethylethanolamine, stannous octoate, lead octoate, dibutyltin dilaurate, zinc octoate, bismuth isooctanoate and bismuth naphthenate;
the end-capping reagent is a hydroxyl-containing acrylate monomer or a hydroxyl-containing vinyl ether monomer, and is one or more selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl 2-methacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate and 4-hydroxybutyl vinyl ether;
the solvent is one or more selected from toluene, xylene, cyclohexane, cyclohexanone, butyl acetate, N-dimethylformamide, N-dimethylacetamide, acetone, butanone and N-methylpyrrolidone.
<xnotran> , , ,2,2,2- ,2,2,3,3- ,2,2,3,3,3- ,1,1,1,3,3,3- ,1,1,1,3,3,3- , , ,2,2,3,3,4,4,4- ,2,2,3,3,4,4,4- , , , , ,1H,1H,2H,2H- ,1H,1H- ,1H,1H,2H,2H- ,2- ( ) , ,2- -2- -3,3,5- , , ,1,6- , , , . </xnotran>
Optionally, the photoinitiator is one or more selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylphenyl acetone, (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, benzophenone, isooctyl p-dimethylaminobenzoate, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinobenzylphenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -propan-1-one, 2-isopropylthioxanthone, ethyl 4-dimethylaminobenzoate, benzoin bismethyl ether, methyl 2-benzoylbenzoate, 4-chlorobenzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, and 2, 4-diethylthiazolone.
Optionally, the delivered auxiliary agent comprises a silane coupling agent and a leveling agent, and the silane coupling agent is contained in an amount of 0.5 to 15 parts by weight and the leveling agent is contained in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the fluorine-modified urethane acrylate resin.
Optionally, the silane coupling agent is one or more selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, tris (2-methoxyethoxy) vinylsilane, 3-aminopropyltriethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane.
Optionally, the leveling agent is selected from
Figure BDA0003829865160000051
FL 3277、
Figure BDA0003829865160000052
FL 3600、
Figure BDA0003829865160000053
FL 3670、
Figure BDA0003829865160000054
WE 3370、
Figure BDA0003829865160000055
WE 3500、DOWSILTM402LS、 DOWSILTM67、
Figure BDA0003829865160000056
346 and
Figure BDA0003829865160000057
354, respectively.
Through the technical scheme, the refractive index of the ultraviolet curing adhesive can be adjusted to a required value (such as 1.36-1.38) through reasonable formula design, the ultraviolet curing adhesive has excellent gluing performance and good curing effect, various properties after curing meet requirements, and the cost is controllable.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
Specific embodiments of the present disclosure are described in detail below. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The invention provides an ultraviolet curing adhesive (UV adhesive), which comprises fluorine modified polyurethane acrylate resin, acrylate monomer, photoinitiator and auxiliary agent, wherein 100 parts by weight of the fluorine modified polyurethane acrylate resin is taken as a reference, the content of the acrylate monomer is 10-60 parts by weight, the content of the photoinitiator is 1-15 parts by weight, and the content of the auxiliary agent is 1-30 parts by weight;
wherein the fluorine modified polyurethane acrylate resin has a chemical structural formula as follows:
Figure BDA0003829865160000058
wherein X is any natural number between 1 and 100, preferably 1 to 50; y is any natural number between 1 and 100, preferably any natural number between 1 and 50; ra is a group containing CH 2 (CF 2 ) n CH 2 N is any natural number between 4 and 20; rb is (CF) 2 ) m M is any natural number between 2 and 20; rc is an alkyl group, a cycloalkyl group or an aryl group of diisocyanate;
rf is an acrylate group or a vinyl ether group with photoreaction activity, in particular a (methyl) acrylate group or a vinyl ether group of a blocking agent adopted after chain extension is finished, and the structural formula of the group can comprise
Figure BDA0003829865160000061
Wherein Rg has a structure represented by the formulaIs composed of
Figure BDA0003829865160000062
T can be any natural number between 1 and 10, and Z can be any natural number between 1 and 10; rh may be H or CH 3 。
The weight average molecular weight of the fluorine-modified urethane acrylate resin may be 1000 to 100000, and preferably 5000 to 50000.
The ultraviolet curing adhesive disclosed by the invention is prepared by adopting a special modified polyurethane acrylate resin with a fluorine-containing main chain structure, an acrylate monomer and an auxiliary agent, and the refractive index can be adjusted to a required value (such as 1.36-1.38) through reasonable formula design. The ultraviolet curing adhesive has excellent sizing performance and good curing effect, various properties after curing meet the requirements, and the cost is controllable.
Further, the content of the acrylate monomer may be 15 to 50 parts by weight, the content of the photoinitiator may be 2 to 10 parts by weight, and the content of the auxiliary may be 2 to 20 parts by weight, based on 100 parts by weight of the fluorine-modified urethane acrylate resin. The ultraviolet curing adhesive in the formula range has more excellent comprehensive performance.
In the present disclosure, the preparation step of the fluorine-modified urethane acrylate resin may include:
a. contacting fluorine-containing dihydric alcohol, fluorine-containing dibasic acid and a first catalyst for esterification reaction to obtain hydroxyl-terminated perfluoro polyester;
b. and (2) contacting the hydroxyl-terminated perfluoro polyester and diisocyanate with a second catalyst, carrying out chain extension reaction in the presence of a solvent, and then adding a blocking agent for blocking.
Wherein, the following reaction formula can be referred to in step a:
Figure BDA0003829865160000071
wherein X is any natural number between 1 and 100; ra is a group containing CH 2 (CF 2 ) n CH 2 N is any natural number between 4 and 20; rb is (CF) 2 ) m And m is any natural number between 2 and 20.
Further, the molar ratio of the fluorine-containing diol to the fluorine-containing dibasic acid may be (1 to 2): 1, preferably (1.2 to 1.6): 1. the weight ratio of the total usage amount of the fluorine-containing dihydric alcohol and the fluorine-containing dibasic acid to the first catalyst is 100: (0.01 to 0.1), preferably 100: (0.01-0.05). The esterification reaction conditions may include: the stirring speed is 100-300 r/min, preferably 150-200 r/min; the temperature is 140-180 ℃, preferably 140-160 ℃; the pressure is-1 MPa to-0.01 MPa, preferably-0.05 MPa to-0.1 MPa; the time is 2 to 4 hours, preferably 2 to 3 hours. The esterification reaction may be performed under oil bath conditions.
Further, the air conditioner is provided with a fan, the fluorine-containing diol may be one or more selected from the group consisting of 2,2,3,3-tetrafluoro-1, 4-butanediol, 2,2,3,3,4,4-hexafluoro-1, 5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1, 6-hexanediol, hexadecafluoro-1, 10-decanediol and 1H, 12H-icosafluoro-1, 12-dodecanediol, preferably 1H, 12H-icosano-1, 12-dodecanediol.
The fluorine-containing dibasic acid may be one or more selected from tetrafluorosuccinic acid, hexafluoroglutaric acid, octafluoroadipic acid, perfluorosuberic acid, perfluoroazelaic acid and hexadecafluorodecanesebacic acid, and is preferably decahexafluorosebacic acid.
The first catalyst can be one or more selected from ethylene glycol antimony, antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate, p-toluenesulfonic acid and zinc acetate, and tetrabutyl titanate is preferred.
The weight average molecular weight of the hydroxyl-terminated perfluoropolyester prepared in step a may be 500 to 10000, preferably 2000 to 6000.
Wherein, the chain extension reaction in the step b can refer to the following reaction formula:
Figure BDA0003829865160000072
wherein Y is any of 1 to 100A natural number; rc is an alkyl group, a cycloalkyl group or an aryl group of the diisocyanate; rd is
Figure BDA0003829865160000081
X is any natural number between 1 and 100.
Further, the molar ratio of the hydroxyl-terminated perfluoropolyester to the diisocyanate may be (0.5 to 1): 1, preferably (0.6 to 0.9): 1, wherein the hydroxyl terminated perfluoropolyester is calculated as-OH and the diisocyanate is calculated as-NCO. The weight ratio of the hydroxyl-terminated perfluoropolyester to the second catalyst may be 100: (0.01 to 0.1), preferably 100: (0.01-0.05). The conditions of the chain extension reaction include: the stirring speed is 150-250 r/min, preferably 200-250 r/min; the temperature is 60-70 ℃, preferably 65-70 ℃; the time is 2 to 3 hours, preferably 2.5 to 3 hours. The chain extension reaction can be carried out under the protection of nitrogen and under the condition of oil bath.
Further, the diisocyanate may be one or more selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 4' -dicyclohexylmethane diisocyanate, toluene diisocyanate, methylcyclohexane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, cyclohexane dimethylene diisocyanate, 1, 4-cyclohexane diisocyanate, o-xylylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethyl-m-xylylene diisocyanate, norbornane diisocyanate, dimethyl biphenyl diisocyanate, L-lysine diisocyanate, 1, 5-naphthalene diisocyanate, preferably isophorone diisocyanate.
The second catalyst may be one or more selected from the group consisting of triethylenediamine, dimethylethanolamine, stannous octoate, lead octoate, dibutyltin dilaurate, zinc octoate, bismuth isooctanoate, and bismuth naphthenate, and preferably bismuth isooctanoate.
The solvent may be one or more selected from the group consisting of toluene, xylene, cyclohexane, cyclohexanone, butyl acetate, N-dimethylformamide, N-dimethylacetamide, acetone, butanone, and N-methylpyrrolidone, and is preferably butyl acetate. The amount of the solvent to be used is not particularly limited, and may be adjusted according to the dissolution of the raw material, and may be, for example, 60 to 100% by weight based on the total amount of the raw material to be used. The solvent may be removed by conventional means (e.g., by applying a vacuum) after the subsequent capping is complete.
The end capping in step b can be referred to the following reaction scheme:
Figure BDA0003829865160000091
wherein Re is
Figure BDA0003829865160000092
Y is any natural number between 1 and 100; rf is a (meth) acrylate group or a vinyl ether group of the blocking agent.
Further, the end-capping conditions may include: controlling the stirring speed to be 150-250 r/min, preferably 200-250 r/min; the temperature is 70-80 ℃, preferably 75-80 ℃; the time is 2 to 4 hours, preferably 3 to 3.5 hours. The capping may be performed under oil bath conditions.
The end-capping agent may be a hydroxyl-containing acrylate monomer or a hydroxyl-containing vinyl ether monomer. Further, the blocking agent may be one or more selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl 2-methacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, 4-hydroxybutyl vinyl ether, preferably hydroxypropyl acrylate. The amount of the blocking agent to be used may be adjusted depending on the reaction condition of the diisocyanate, and for example, the molar ratio of the blocking agent to the unreacted diisocyanate may be (1 to 1.0005): 1, wherein the diisocyanate is calculated as-NCO.
The weight average molecular weight of the fluorine-modified urethane acrylate resin prepared in step b may be 1000 to 100000, preferably 5000 to 50000.
In the ultraviolet curing adhesive of the present disclosure, the acrylate monomer may be a fluorine-containing acrylate monomer, a monofunctional acrylate monomer, a difunctional acrylate monomer, or a polyfunctional acrylate monomer. <xnotran> , , ,2,2,2- ,2,2,3,3- ,2,2,3,3,3- ,1,1,1,3,3,3- ,1,1,1,3,3,3- , , ,2,2,3,3,4,4,4- ,2,2,3,3,4,4,4- , , , , ,1H,1H,2H,2H- ,1H,1H- ,1H,1H,2H,2H- , </xnotran> <xnotran> 2- ( ) , ,2- -2- -3,3,5- , , ,1,6- , , , , , ,2,2,3,3,4,4,4- , ,1H,1H,2H,2H- ,1H,1H- ,1H,1H,2H,2H- , , , . </xnotran>
In the uv curable adhesive of the present disclosure, further, the photoinitiator may be one or more selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylphenyl acetone, (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, benzophenone, isooctyl p-dimethylaminobenzoate, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -propan-1-one, 2-isopropylthioxanthone, ethyl 4-dimethylaminobenzoate, benzoin bismethyl ether, methyl 2-benzoylbenzoate, 4-chlorobenzophenone, 4-methylbenzophenone, 4-phenylbenzophenone and 2, 4-diethylthiazolone.
Further, in the uv curable adhesive of the present disclosure, the delivered auxiliary agent may include a silane coupling agent and a leveling agent. The silane coupling agent may be contained in an amount of 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the fluorine-modified urethane acrylate resin; the content of the leveling agent may be 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight.
The silane coupling agent may be one or more selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, tris (2-methoxyethoxy) vinylsilane, 3-aminopropyltriethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane and 3-mercaptopropyltriethoxysilane, and is preferably one or more of vinyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane and 3- (methacryloyloxy) propyltrimethoxysilane.
The leveling agent may be selected from
Figure BDA0003829865160000111
FL 3277、
Figure BDA0003829865160000112
FL 3600、
Figure BDA0003829865160000113
FL 3670、
Figure BDA0003829865160000114
WE 3370、
Figure BDA0003829865160000115
WE 3500、DOWSIL TM 402LS、 DOWSIL TM 67、
Figure BDA0003829865160000116
346 and (b) and
Figure BDA0003829865160000117
354, preferably one or more of 354
Figure BDA0003829865160000118
FL 3600、
Figure BDA0003829865160000119
WE 3370、DOWSIL TM 402LS、
Figure BDA00038298651600001110
346、
Figure BDA00038298651600001111
354. One or more of (a). The leveling agent is commercially available under the trade name of "leveling agent".
The preparation method of the ultraviolet curing adhesive is simple, and the raw materials are uniformly mixed and dispersed according to the formula, for example, the mixing can be carried out in a stirring pot, the stirring speed can be 800-1000 r/min, the mixing and dispersing time can be 20-50 minutes, and the temperature can be controlled within 35 ℃ by adopting cooling water in the whole mixing process.
The present disclosure is further described with reference to the following examples, but the present disclosure is not limited to the scope of the following examples.
Examples 1 to 4 are provided to illustrate the preparation process of the fluorine modified urethane acrylate resin used in the uv curable adhesive of the present disclosure.
Example 1
1, 1H,1 2H-icosyl-1, 12-dodecanediol and hexadecafluoro sebacic acid are mixed according to a molar ratio of 1.25:1, placing the mixture into a reaction kettle, and adding the mixture into the reaction kettle in a nitrogen protection manner according to the weight ratio of the total dosage of the raw materials as 100:0.03 adding tetrabutyl titanate, carrying out esterification reaction, controlling the stirring speed to be 150-200 r/min, heating in an oil bath and keeping the temperature to be 140-160 ℃, reducing the internal pressure of the reaction kettle to-0.1 MPa by utilizing a vacuum dewatering device, and reacting for 3 hours to obtain the hydroxyl-terminated perfluoropolyester with the weight-average molecular weight of 4800.
And (2) mixing the hydroxyl-terminated perfluoro polyester and isophorone diisocyanate obtained in the previous step according to a molar ratio of 0.8: 1. adding the mixture into a reaction kettle, and adding the mixture into the reaction kettle in a nitrogen protection manner according to the weight ratio of the total dosage of the raw materials as 100:0.03 adding bismuth isooctanoate, adding solvent butyl acetate with the same weight part as the total material, controlling the stirring speed to be 200-250 r/min, heating in an oil bath, and keeping the temperature to be 65-70 ℃ for chain extension reaction for 2.5 hours; then the molar ratio of the unreacted-NCO groups to the remaining unreacted-NCO groups was 1.0005:1, adding hydroxypropyl acrylate, controlling the stirring speed to be 200-250 r/min, heating in an oil bath and keeping the temperature to be 75-85 ℃, and carrying out end capping reaction for 3 hours; and finally, vacuumizing to remove the solvent to obtain the fluorine modified urethane acrylate resin A with the weight-average molecular weight of 20000, wherein the chemical structural formula of the fluorine modified urethane acrylate resin A is as follows:
Figure BDA0003829865160000121
wherein X1 is more than or equal to 1, and Y1 is more than or equal to 1; r 1 Is CH 2 (CF 2 ) 10 CH 2 ；R 2 Is (CF) 2 ) 8 ；R 3 Is composed of
Figure BDA0003829865160000122
Example 2
1, 1H,1 2H-icosyl-1, 12-dodecanediol and hexadecafluoro sebacic acid are mixed according to the molar ratio of 1.4:1, putting the mixture into a reaction kettle, and adding the mixture into the reaction kettle in a nitrogen protection manner according to the weight ratio of the total consumption of the raw materials as 100: 0.04, adding tetrabutyl titanate, carrying out esterification reaction, controlling the stirring speed to be 150-200 r/min, heating in an oil bath and keeping the temperature to be 140-160 ℃, reducing the internal pressure of the reaction kettle to-0.1 MPa by utilizing a vacuum dewatering device, and reacting for 3 hours to obtain the hydroxyl-terminated perfluoropolyester with the weight-average molecular weight of 3200.
And (2) mixing the hydroxyl-terminated perfluoro polyester and isophorone diisocyanate obtained in the previous step according to a molar ratio of 0.7: 1. adding the mixture into a reaction kettle, and adding the mixture into the reaction kettle in a nitrogen protection manner according to the weight ratio of the total dosage of the raw materials as 100:0.03 adding bismuth isooctanoate, adding solvent butyl acetate with the same weight part as the total material, controlling the stirring speed to be 150-250 r/min, heating in an oil bath, and keeping the temperature to be 65-70 ℃ to carry out chain extension reaction for 2.5 hours; then the molar ratio of the unreacted-NCO groups to the remaining unreacted-NCO groups was 1.0005:1, adding hydroxypropyl acrylate, controlling the stirring speed to be 150-250 r/min, heating in an oil bath and keeping the temperature to be 75-85 ℃, and carrying out end capping reaction for 3 hours; finally, vacuumizing to remove the solvent to obtain the fluorine modified urethane acrylate resin B with the weight-average molecular weight of 8500, wherein the chemical structural formula of the fluorine modified urethane acrylate resin B is shown in the specification
Figure BDA0003829865160000123
Wherein X2 is more than or equal to 1, and Y2 is more than or equal to 1; r 1 Is CH 2 (CF 2 ) 10 CH 2 ；R 2 Is (CF) 2 ) 8 ；R 3 Is composed of
Figure BDA0003829865160000124
Example 3
2, 3-tetrafluoro-1, 4-butanediol and tetrafluorosuccinic acid are mixed according to the mol ratio of 1.7:1, putting the mixture into a reaction kettle, and adding the mixture into the reaction kettle in a nitrogen protection manner according to the weight ratio of the total consumption of the raw materials as 100:0.06 of tetrabutyl titanate is added for esterification reaction, the stirring speed is controlled to be 150-200 r/min, the mixture is heated in an oil bath and is kept at 140-160 ℃, the internal pressure of the reaction kettle is reduced to-0.1 MPa by utilizing a vacuum dewatering device, and the reaction is carried out for 3 hours, so that the hydroxyl-terminated perfluoropolyester with the weight-average molecular weight of 700 is obtained.
And (2) mixing the hydroxyl-terminated perfluoro polyester obtained in the step (a) and hexamethylene diisocyanate in a molar ratio of 0.55: 1, adding the mixture into a reaction kettle, and adding the mixture into the reaction kettle in a nitrogen protection manner according to the weight ratio of the total dosage of the raw materials as 100:0.06 Adding triethylene diamine, adding acetone solvent with the same weight part as the total material, controlling the stirring speed to be 150-250 r/min, heating in an oil bath, and keeping the temperature to be 65-70 ℃ for chain extension reaction for 2.5 hours; then the molar ratio of the unreacted-NCO groups to the remaining unreacted-NCO groups was 1.0005:1, adding hydroxyethyl methacrylate, controlling the stirring speed to be 150-250 r/min, heating in an oil bath and keeping the temperature to be 75-85 ℃, and carrying out end capping reaction for 3 hours; finally, vacuumizing to remove the solvent to obtain the fluorine modified urethane acrylate resin C with the weight-average molecular weight of 1500, wherein the chemical structural formula of the fluorine modified urethane acrylate resin C is shown in the specification
Figure BDA0003829865160000131
Wherein X3 is more than or equal to 1, and Y3 is more than or equal to 1; r 4 Is CH 2 (CF 2 ) 2 CH 2 ；R 5 Is (CF) 2 ) 2 ；R 6 Is (CH) 2 ) 6 。
Example 4
Decahexafluoro-1, 10-decanediol, perfluoroazelaic acid in a molar ratio of 1.15:1, putting the mixture into a reaction kettle, and adding the mixture into the reaction kettle in a nitrogen protection manner according to the weight ratio of the total consumption of the raw materials as 100:0.1 adding tetrabutyl titanate to carry out esterification reaction, controlling the stirring speed to be 150-200 r/min, heating in an oil bath and keeping the temperature to be 140-160 ℃, reducing the internal pressure of the reaction kettle to-0.1 MPa by utilizing a vacuum dewatering device, and reacting for 3 hours to obtain the hydroxyl-terminated perfluoropolyester with the weight-average molecular weight of 6500.
And (2) mixing the hydroxyl-terminated perfluoro polyester obtained in the step (a) and toluene diisocyanate according to a molar ratio of 0.92:1, adding the raw materials into a reaction kettle, and adding the raw materials into the reaction kettle in a weight ratio of 100:0.1 adding stannous octoate, adding solvent toluene with the same weight parts as the total material, controlling the stirring speed to be 150-250 r/min, heating in an oil bath, and keeping the temperature to be 65-70 ℃ to carry out chain extension reaction for 2.5 hours; then the molar ratio of the unreacted-NCO groups to the remaining unreacted-NCO groups was 1.0005:1 adding pentaerythritol triacrylate, controlling the stirring speed to be 150-250 r/min, heating in an oil bath and keeping the temperature to be 75-85 ℃, and carrying out end capping reaction for 3 hours; finally, vacuumizing to remove the solvent to obtain the fluorine modified urethane acrylate resin D with the weight average molecular weight of 60000, wherein the chemical structural formula of the fluorine modified urethane acrylate resin D is shown in the specification
Figure BDA0003829865160000141
Wherein X4 is more than or equal to 1, and Y4 is more than or equal to 1; r 7 Is CH 2 (CF 2 ) 8 CH 2 ；R 8 Is (CF) 2 ) 7 ；R 9 Is composed of
Figure BDA0003829865160000142
Or
Figure BDA0003829865160000143
Examples 5 to 10 are for illustrating the uv curable paste of the present disclosure.
Example 5
The ultraviolet curing adhesive of the embodiment is prepared from the following raw materials:
Figure BDA0003829865160000144
the raw materials are added into a stainless steel stirring pot, dispersed for 30 minutes at the rotating speed of 800-1000 r/min until the raw materials are completely and uniformly dispersed, and the temperature is controlled within 35 ℃ by adopting cooling water in the whole process, so that the ultraviolet curing adhesive prepared by the embodiment is obtained.
Example 6
The ultraviolet curing adhesive of the embodiment is prepared from the following raw materials:
Figure BDA0003829865160000151
the raw materials are added into a stainless steel stirring pot, dispersed for 30 minutes at the rotating speed of 800-1000 r/min until the raw materials are completely and uniformly dispersed, and the temperature is controlled within 35 ℃ by adopting cooling water in the whole process, so that the ultraviolet curing adhesive prepared by the embodiment is obtained.
Example 7
The ultraviolet curing adhesive of the embodiment is prepared from the following raw materials:
Figure BDA0003829865160000152
the raw materials are added into a stainless steel stirring pot, dispersed for 30 minutes at the rotating speed of 800-1000 r/min until the raw materials are completely and uniformly dispersed, and the temperature is controlled within 35 ℃ by adopting cooling water in the whole process, so that the ultraviolet curing adhesive prepared by the embodiment is obtained.
Example 8
The ultraviolet curing adhesive of the embodiment is prepared from the following raw materials:
Figure BDA0003829865160000161
the raw materials are added into a stainless steel stirring pot, dispersed for 30 minutes at the rotating speed of 800-1000 r/min until the raw materials are completely and uniformly dispersed, and the temperature of the whole process is controlled within 35 ℃ by adopting cooling water, so that the ultraviolet curing adhesive prepared by the embodiment is obtained.
Comparative example 1
Compared with the example 5, the ultraviolet curing adhesive of the comparative example adopts the purchased low-refractive-index light curing resin CHEMITON CHTL2009 to replace the fluorine modified polyurethane acrylate resin, and other raw materials are unchanged and are prepared according to the following formula:
Figure BDA0003829865160000162
and (3) adding the raw materials into a stainless steel stirring pot, dispersing for 30 minutes at the rotating speed of 800-1000 r/min until the raw materials are completely and uniformly dispersed, and controlling the temperature within 35 ℃ by adopting cooling water in the whole process to obtain the ultraviolet curing adhesive prepared by the comparative example.
Comparative example 2
Compared with the example 5, the ultraviolet curing adhesive of the comparative example adopts the purchased modified acrylate SARTOMER CN966J75NS to replace the fluorine modified urethane acrylate resin, and other raw materials are unchanged and are prepared according to the following formula:
Figure BDA0003829865160000171
and (3) adding the raw materials into a stainless steel stirring pot, dispersing for 30 minutes at the rotating speed of 800-1000 r/min until the raw materials are completely and uniformly dispersed, and controlling the temperature within 35 ℃ by adopting cooling water in the whole process to obtain the ultraviolet curing adhesive prepared by the comparative example.
Comparative example 3
Compared with the example 5, the ultraviolet curing adhesive of the comparative example adopts outsourced Jettida DSP-552F to replace the fluorine modified polyurethane acrylate resin, and other raw materials are unchanged and are prepared according to the following formula:
Figure BDA0003829865160000172
and (3) adding the raw materials into a stainless steel stirring pot, dispersing for 30 minutes at the rotating speed of 800-1000 r/min until the raw materials are completely and uniformly dispersed, and controlling the temperature within 35 ℃ by adopting cooling water in the whole process to obtain the ultraviolet curing adhesive prepared by the comparative example.
Test example
The UV curable adhesives of examples 5-8 and comparative examples 1-3 were tested for their performance. The viscosity test method comprises the following steps: GB/T2794-2013; the method for testing the refractive index of the glue solution comprises the following steps: GB/T6488-2008; the method for testing the refractive index of the adhesive film comprises the following steps: GB/T6488-2008 (bromonaphthalene process); the hardness test method comprises the following steps: GB/T531.1-2008; the test method of the tensile shear strength comprises the following steps: GB/T7124-2008; the test method of the cold-hot impact cycle comprises the following steps: GB/T2423.22-2002; the test method of the high temperature and high humidity test comprises the following steps: GB/T2423.50-1999; the test method for the high-voltage accelerated aging life test comprises the following steps: GB/T2423.40-2013; the method for testing the light transmittance comprises the following steps: GB/T2410-2008; the test method of the elongation at break comprises the following steps: GB/T528-2009. The test results are as follows.
Figure BDA0003829865160000181
The ultraviolet curing adhesive can be used for bonding the surface coating of the optical fiber, has excellent performance and good weather resistance, has the characteristics of chemical corrosion resistance, water resistance, oil resistance and the like, and is suitable for being used in long-term complex harsh environments. In addition, the ultraviolet curing adhesive disclosed by the invention is a product with 100% solid content and zero VOC (volatile organic compounds), can be cured by ultraviolet lamp irradiation, and is low in energy consumption, green and environment-friendly. Compared with the existing known products, the product has excellent comprehensive performance.
The preferred embodiments of the present disclosure have been described above in detail, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (10)

1. An ultraviolet light curing adhesive is characterized by comprising fluorine modified polyurethane acrylate resin, acrylate monomer, photoinitiator and auxiliary agent, wherein 100 parts by weight of the fluorine modified polyurethane acrylate resin is taken as a reference, the content of the acrylate monomer is 10-60 parts by weight, the content of the photoinitiator is 1-15 parts by weight, and the content of the auxiliary agent is 1-30 parts by weight;
wherein the fluorine modified polyurethane acrylate resin has a chemical structural formula as follows:
Figure FDA0003829865150000011
wherein X is any natural number between 1 and 100; y is any natural number between 1 and 100; ra is a group containing CH 2 (CF 2 ) n CH 2 N is any natural number between 4 and 20; rb is (CF) 2 ) m M is any natural number between 2 and 20; rc is an alkyl group, a cycloalkyl group or an aryl group of the diisocyanate; rf is an acrylate group or a vinyl ether group having photoreaction activity.
2. The ultraviolet curing adhesive according to claim 1, wherein the content of the acrylate monomer is 15 to 50 parts by weight, the content of the photoinitiator is 2 to 10 parts by weight, and the content of the auxiliary agent is 2 to 20 parts by weight, based on 100 parts by weight of the fluorine-modified urethane acrylate resin.
3. The ultraviolet curing adhesive according to claim 1 or 2, wherein the preparation of the fluorine-modified urethane acrylate resin comprises the following steps:
a. contacting fluorine-containing dihydric alcohol, fluorine-containing dibasic acid and a first catalyst for esterification reaction to obtain hydroxyl-terminated perfluoro polyester;
b. and (2) contacting the hydroxyl-terminated perfluoro polyester and diisocyanate with a second catalyst, carrying out chain extension reaction in the presence of a solvent, and then adding a blocking agent for blocking.
4. The ultraviolet light curing adhesive according to claim 3, wherein in the step a, the molar ratio of the fluorine-containing diol to the fluorine-containing diacid is (1-2): 1;
the weight ratio of the total usage amount of the fluorine-containing dihydric alcohol and the fluorine-containing dibasic acid to the first catalyst is 100: (0.01 to 0.1);
the esterification reaction conditions include: stirring at 100-300 r/min, 140-180 deg.c, pressure of-1 MPa to-0.01 MPa and time of 2-4 hr;
the weight average molecular weight of the hydroxyl-terminated perfluoro polyester is 500-10000.
5. The ultraviolet light curing adhesive according to claim 3, wherein in the step b, the molar ratio of the hydroxyl-terminated perfluoro polyester to the diisocyanate is (0.5-1): 1, wherein the hydroxyl-terminated perfluoropolyester is calculated as-OH and the diisocyanate is calculated as-NCO;
the weight ratio of the hydroxyl-terminated perfluoro polyester to the second catalyst is 100: (0.01 to 0.1);
the conditions of the chain extension reaction include: the stirring speed is 150-250 r/min, the temperature is 60-70 ℃, and the time is 2-3 hours;
the end-capping conditions include: the stirring speed is controlled to be 150-250 r/min, the temperature is controlled to be 70-80 ℃, and the time is 2-4 hours.
6. The UV-curable adhesive according to claim 3, wherein the fluorine-containing diol is one or more selected from the group consisting of 2,2,3,3-tetrafluoro-1, 4-butanediol, 2,2,3,3,4,4-hexafluoro-1, 5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1, 6-hexanediol, hexadecafluoro-1, 10-decanediol, and 1H, 12H-icosano-1, 12-dodecanediol;
the fluorine-containing dibasic acid is one or more selected from tetrafluorosuccinic acid, hexafluoroglutaric acid, octafluoro adipic acid, perfluoro suberic acid, perfluoro azelaic acid and hexadecafluoro sebacic acid;
the first catalyst is one or more selected from ethylene glycol antimony, antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate, p-toluenesulfonic acid and zinc acetate;
the diisocyanate is one or more selected from hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 4' -dicyclohexylmethane diisocyanate, toluene diisocyanate, methylcyclohexane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, cyclohexane dimethylene diisocyanate, 1, 4-cyclohexane diisocyanate, o-xylylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethyl-m-xylylene diisocyanate, norbornane diisocyanate, dimethyl biphenyl diisocyanate, L-lysine diisocyanate, 1, 5-naphthalene diisocyanate;
the second catalyst is one or more selected from triethylene diamine, dimethylethanolamine, stannous octoate, lead octoate, dibutyltin dilaurate, zinc octoate, bismuth isooctanoate and bismuth naphthenate;
the end-capping reagent is a hydroxyl-containing acrylate monomer or a hydroxyl-containing vinyl ether monomer, and is one or more selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl 2-methacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate and 4-hydroxybutyl vinyl ether;
the solvent is one or more selected from toluene, xylene, cyclohexane, cyclohexanone, butyl acetate, N-dimethylformamide, N-dimethylacetamide, acetone, butanone and N-methylpyrrolidone.
7. <xnotran> 1 2 , , , ,2,2,2- ,2,2,3,3- ,2,2,3,3,3- ,1,1,1,3,3,3- ,1,1,1,3,3,3- , , ,2,2,3,3,4,4,4- ,2,2,3,3,4,4,4- , , , , ,1H,1H,2H,2H- ,1H,1H- ,1H,1H,2H,2H- ,2- ( ) , ,2- -2- -3,3,5- , , ,1,6- , , , ; </xnotran>
The photoinitiator is one or more selected from 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylphenyl acetone, (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, benzophenone, isooctyl p-dimethylaminobenzoate and 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinobenzylphenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -propan-1-one, 2-isopropylthioxanthone, ethyl 4-dimethylaminobenzoate, benzoin bismethyl ether, methyl 2-benzoylbenzoate, 4-chlorobenzophenone, 4-methylbenzophenone, 4-phenylbenzophenone and 2, 4-diethylthiazolone.
8. The ultraviolet curing adhesive according to claim 1 or 2, wherein the auxiliary agent comprises a silane coupling agent and a leveling agent, and the silane coupling agent is contained in an amount of 0.5 to 15 parts by weight and the leveling agent is contained in an amount of 0.5 to 15 parts by weight, based on 100 parts by weight of the fluorine-modified urethane acrylate resin.
9. The UV-curable adhesive according to claim 8, wherein the silane coupling agent is one or more selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, tris (2-methoxyethoxy) vinylsilane, 3-aminopropyltriethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.
10. The UV curable adhesive according to claim 8, wherein the leveling agent is selected from
Figure FDA0003829865150000041
FL 3277、
Figure FDA0003829865150000042
FL 3600、
Figure FDA0003829865150000043
FL 3670、
Figure FDA0003829865150000044
WE 3370、
Figure FDA0003829865150000045
WE 3500、DOWSIL TM 402LS、DOWSIL TM 67、
Figure FDA0003829865150000046
346 and
Figure FDA0003829865150000047
354, respectively.
CN202211072870.0A 2022-09-02 2022-09-02 Ultraviolet light curing adhesive Pending CN115466593A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116023836A (en) * 2023-02-09 2023-04-28 安徽省林田光电科技有限公司 Synthesis method of aqueous fluorine release agent and application of aqueous fluorine release agent in PET film
CN117025122A (en) * 2023-10-08 2023-11-10 汕头市恒顺包装材料有限公司 Lens cold-stamping film and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11349646A (en) * 1998-06-12 1999-12-21 Nippon Kayaku Co Ltd Resin composition and cured product
CN105273613A (en) * 2015-11-11 2016-01-27 武汉长盈通光电技术有限公司 Low-refractive optical fiber coating resin
CN111187568A (en) * 2020-02-26 2020-05-22 上海维凯光电新材料有限公司 Low-refractive-index optical fiber inner layer coating and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11349646A (en) * 1998-06-12 1999-12-21 Nippon Kayaku Co Ltd Resin composition and cured product
CN105273613A (en) * 2015-11-11 2016-01-27 武汉长盈通光电技术有限公司 Low-refractive optical fiber coating resin
CN111187568A (en) * 2020-02-26 2020-05-22 上海维凯光电新材料有限公司 Low-refractive-index optical fiber inner layer coating and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116023836A (en) * 2023-02-09 2023-04-28 安徽省林田光电科技有限公司 Synthesis method of aqueous fluorine release agent and application of aqueous fluorine release agent in PET film
CN117025122A (en) * 2023-10-08 2023-11-10 汕头市恒顺包装材料有限公司 Lens cold-stamping film and preparation method thereof
CN117025122B (en) * 2023-10-08 2024-02-06 汕头市恒顺包装材料有限公司 Lens cold-stamping film and preparation method thereof

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