CN115521691A - UV cationic free radical hybrid curing adhesive and preparation method and application thereof - Google Patents
UV cationic free radical hybrid curing adhesive and preparation method and application thereof Download PDFInfo
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- CN115521691A CN115521691A CN202211349319.6A CN202211349319A CN115521691A CN 115521691 A CN115521691 A CN 115521691A CN 202211349319 A CN202211349319 A CN 202211349319A CN 115521691 A CN115521691 A CN 115521691A
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Abstract
The invention belongs to the field of adhesives, and particularly discloses a UV cation/free radical hybrid curing adhesive, and a preparation method and application thereof. The beneficial effects include: the glue film is easy to be solidified into a film, the strength of the glue film is still more than 14MPa after being soaked in acid-base solution, and the reduction amplitude is lower than 40 percent; the moisture absorption rate is lower than 4%, and the swelling effect is small; glass surface bonding is effectual, does not have the bulge to fall and glues abnormal phenomena such as, tears gluey normally not to have disconnected gluey, and glued membrane intensity, toughness are all better, and acid and alkali resistance is outstanding, enable glass attenuate to thinner to do not fall to glue disconnected gluey, remove gluey convenience.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a UV cation/free radical hybrid curing adhesive and a preparation method and application thereof.
Background
In recent years, electronic industries are rapidly developed, smart phones, tablet computers, televisions and the like are increasingly popularized, and the lightening and thinning are inevitable trends in the development of electronic display devices. A thin film transistor-liquid crystal display (TFT-LCD) is one of the electronic display devices widely used in the market, and thinning of a glass substrate is one of the most effective methods in the thinning process. The thinning process generally includes several steps: pure water cleaning, naOH/KOH solution alkali cleaning, concentrated H2SO4 pretreatment and HF or mixed acid etching. In the thinning process, the sealant needs to be coated around the glass in advance and cured to protect the liquid crystal inside, so as to prevent the product damage caused by the infiltration of acid-base solution into the liquid crystal in the thinning process.
The thinning thickness of common thinning glue in the current market is mainly about 0.5mm during design. However, the glass thinning thickness has been reduced to 0.3mm or even lower, and the etching time is longer, so the performance requirement for the encapsulation is higher. Common thinning glue in the market cannot meet the application requirement due to insufficient acid resistance, and the glue is easy to swell and fall off in the etching process to influence the subsequent processing; or the strength of the colloid is reduced, and the subsequent colloid removal is complicated.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the UV cation/free radical hybrid curing adhesive and the preparation method thereof, the adhesive has better acid and alkali resistance and better adhesion, and the thinning requirement of the liquid crystal display is met.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the first aspect of the invention provides a UV cation free radical hybrid curing adhesive, which comprises 5-20 parts of epoxy resin, 0-50 parts of dimer acid modified epoxy resin, 10-50 parts of epoxy resin capable of free radical reaction, 2-15 parts of adhesion promoting resin, 5-20 parts of epoxy diluent, 10-30 parts of monomer capable of free radical reaction, 1-6 parts of cation photoinitiator, 0.5-3 parts of free radical photoinitiator, 0.5-3 parts of coupling agent and 0-0.5 part of toner according to parts by weight;
specifically, the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin;
the dimer acid modified epoxy resin is one or more of dimer acid modified glycidyl ether type epoxy resin, dimer acid modified alicyclic epoxy resin and dimer acid modified oxetane; the structural general formula of the dimer acid modified epoxy resin is as follows,
wherein R is 1 Residue of dimer acid minus-COOH; r 2 Is the residue after the ring opening of the epoxy in the modified epoxy resin;
the dimer acid has the structural formula:
the structural formula of the glycidyl ether type epoxy resin is as follows:
the structural formula of the alicyclic epoxy resin is as follows:
the oxetane structure is:
the dimer acid modified epoxy resin is prepared by performing a carboxylic acid-epoxy ring-opening addition reaction on dimer acid and corresponding epoxy resin;
the reaction process of the other dimer acids with the epoxy resin is the same as above.
The epoxy resin capable of free radical reaction is one or more of 3,4-epoxy cyclohexyl methyl acrylate, epoxy polybutadiene and acrylic acid modified epoxy resin; the acrylic acid modified epoxy resin is a prepolymer of dimer acid modified epoxy resin and an acrylic compound,
the structural general formula of the acrylic acid modified epoxy resin is as follows:
wherein R is 1 、R 2 In accordance with the structure defined above; r 6 Is R 2 A residue of the structure following ring opening of an epoxy group;
the structural formula of the acrylic compound is as follows:
the prepolymer of the dimer acid modified epoxy resin and the acrylic compound is prepared by the ring-opening addition reaction of the prepared dimer acid modified epoxy resin and the acrylic compound through carboxylic acid-epoxy:
the reaction process of other dimer acid modified epoxy resin and acrylic acid compound is the same as above.
The dimer acid selected in the invention is obtained by polymerizing unsaturated fatty acid, and the molecular structure of the dimer acid has four alkane long-chain branches and one six-membered alicyclic ring, so that the dimer acid has the characteristics of low polarity, high flexibility and the like; but because the polarity difference between the modified epoxy resin and an epoxy system is too large and the compatibility is poor, the modified epoxy resin is modified by epoxy resin with lower molecular weight, so that the compatibility with the epoxy system is improved, and the reactivity of the modified resin is ensured.
Optionally, the adhesion promoting resin is a modified polyester compound.
Optionally, the epoxy diluent is one or more of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylformate, bis (7-oxabicyclo [4.1.0] ]3-heptamethyl) adipate, 1,4-butanediol diglycidyl ether, 3,3' - (oxybis-methylene) bis (3-ethyl) oxetane, 3-ethyl-3-oxetanemethanol.
Optionally, the free radically reactive monomer is one or more of a vinyl ether monomer, (meth) acrylate monomer, and allyl monomer. Further, it may be one or more of hydroxybutyl vinyl ether, triethylene glycol divinyl ether, benzyl vinyl ether, isobornyl methacrylate, isobornyl acrylate, 2-hydroxyethyl methacrylate, tricyclodecane dimethanol diacrylate, allyl glycidyl ether, glycerol monoallyl ether, trimethylolpropane diallyl ether.
Optionally, the cationic photoinitiator is one or more of iodonium salt and sulfonium salt. Further, the cationic photoinitiator is one or more of triaryl sulfonium hexafluoroantimonate, triaryl sulfonium hexafluorophosphate, diaryl iodonium hexafluoroantimonate and diaryl iodonium hexafluorophosphate.
Optionally, the free radical photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone.
Optionally, the coupling agent is one or more of 2- (3,4-epoxycyclohexylalkyl) ethyl trimethoxy silane, gamma-glycidoxypropyl trimethoxy silane, and vinyl trimethoxy silane.
Optionally, the toner is a dye or a pigment, the dye is an acid complex dye, and the pigment is a dispersed pigment.
In a second aspect of the present invention, a method for preparing a UV cation/radical hybrid curing adhesive comprises the following steps:
s1, weighing epoxy resin, dimer acid modified epoxy resin, free radical reactive resin, adhesion promoting resin, epoxy diluent and free radical reactive monomer according to a set weight ratio, putting into a reaction kettle, stirring at a rotating speed of 400r/min for 5 minutes, and then stirring at 1000r/min for 1 hour;
s2, weighing a cationic photoinitiator, a free radical photoinitiator, a coupling agent and toner, adding into the reaction kettle in the step S1, stirring for 30 minutes at a rotating speed of 800r/min and a vacuum degree of 0.05MPa, stopping stirring, and filtering by using a 200-mesh filter screen to obtain a finished product.
The third aspect of the invention provides an application of the UV cation/free radical hybrid curing adhesive, and the UV cation/free radical hybrid curing adhesive is applied to a thinning process of a glass substrate of a liquid crystal display.
According to the technical scheme, the invention has the beneficial effects that:
1. interpenetrating Polymer Networks (IPNs) are polymer blends of two or more crosslinked polymers entangled through molecular chains. According to the invention, the cationic epoxy system and the acrylate system are polymerized in situ to form an interpenetrating network structure, so that the crosslinking density and the tensile strength are obviously improved, the small molecule swelling effect is reduced, the adhesive film has excellent acid and alkali resistance, can resist acid and alkali soaking for a longer time in a thinning process, and can thin the glass to 0.3mm or even thinner.
2. The dimer acid has four long alkane chains in the structure, so that the dimer acid has the characteristics of low polarity, high flexibility and the like; dimer acid and epoxy resin are polymerized to improve the polarity of the dimer acid and introduced into an epoxy system, so that a cured adhesive film has good corrosion resistance and chemical resistance, the long-chain part in the structure can improve hydrophobicity, swelling is reduced, and the acid and alkali resistance of the adhesive film is more excellent; meanwhile, the Tg of the flexible chain segment in the structure can be reduced, the flexibility of a cured adhesive film is improved, and the adhesive removing performance is improved;
3. the surface of the curing adhesive film of the cation/free radical hybrid curing system is dry and comfortable, and the curing efficiency is high.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings used in the detailed description or the prior art description will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is a table of formulations for various embodiments of the present invention;
FIG. 2 is a table showing the results of the tests performed in the examples of the present invention and the control group.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
The raw material sources of the invention are as follows:
epoxy resin:
bisphenol a type epoxy resins available from Epikote828 (vastness), DER331 (dow chemical), NPEL128 (taiwan south asia, china);
bisphenol F type epoxy resins available from Epikote862 (hansen), DER354 (dow chemical), NPEF-170 (south asia, taiwan);
cycloaliphatic epoxy resins available from EHPE3150, EPOLEAD GT401 (xylonite);
free radical reactive epoxy resin:
epoxidized polybutadiene available from Poly bd 600E, poly bd 605E, poly bd 700 (g Lei Weili), EPOLEAD PB3600 (cellosolve);
3,4 epoxycyclohexylmethacrylate, available from CYCLOMER M100 (cellosolve);
adhesion promoting resins, available from AddBond LTH, addBond LTW (winning moraxel), ADP (modesty);
epoxy diluents, available from CELLOXIDE 2021P (celluloid), ARON OXETANE OXT-101, OXT-221 (east Asia Synthesis);
free radically reactive monomers:
vinyl ethers available from DVE-3, HBVE (BASF);
(meth) acrylate monomers, obtainable from SR506, SR508, SR833S (sartomer), EM-90 (changxing);
allyl monomers available from Neoallyl G, E-10, P-30 (Caoda);
dimer acid modified epoxy resin is prepared by ring-opening addition reaction of dimer acid and corresponding epoxy resin, and has the following structural formula:
the structural formula of dimer acid modified glycidyl ether type epoxy resin,
the structural formula of the dimer acid modified alicyclic epoxy resin,
the structural formula of dimer acid modified oxetane is shown in the specification,
dimer acid modified glycidyl ether type epoxy resin finished products are already on the market and thus available from DA323 (CVC), B-Tough A1, A2, A3 (poda);
dimer acid is available from Pripol 2033 (prochloraz);
acrylic compounds are available from MAA (mitsubishi chemical);
the dimer acid modified epoxy resin and the methacrylic acid prepolymer are prepared by ring-opening polymerization of corresponding dimer acid modified epoxy resin and methacrylic acid, and the structural formulas are respectively as follows;
dimer acid modified glycidyl ether type epoxy resin and methacrylic acid prepolymer,
dimer acid modified alicyclic epoxy resin and methacrylic acid prepolymer,
dimer acid-modified oxetane and methacrylic acid prepolymer,
the preparation method of the dimer acid modified epoxy resin comprises the following steps:
1. the weight portions of the raw materials in the total weight of the raw materials are as follows: epoxy resin =1:2 to 2.5, respectively weighing 47 to 52.6 parts of dimer acid and 47.4 to 53 parts of 3,4-epoxy cyclohexyl methyl 3,4-epoxy cyclohexyl formate (CELLOXIDE 2021P), putting into a reaction kettle, heating to 115 to 125 ℃, and stirring at the rotation speed of 800 to 1000r/min in a heat preservation way;
2. stopping stirring after reacting for 12 hours, sampling to test the acid value, if the test acid value is larger than 5mgKOH/g, continuing to keep the temperature and stir, and subsequently sampling every 1 hour to test the acid value until the acid value is smaller than 5mgKOH/g, and stopping stirring;
3. and cooling to 50-60 ℃, and discharging while the mixture is hot to obtain the dimer acid modified epoxy resin.
The preparation method of the dimer acid modified epoxy resin and methacrylic acid prepolymer comprises the following steps:
1. the dimer acid modified epoxy resin comprises the following raw materials in parts by weight: methacrylic acid =1:0.7 to 1, respectively weighing 92.5 to 94.2 parts of dimer acid modified alicyclic epoxy resin and 5.4 to 7.5 parts of methacrylic acid prepared in the steps, putting the weighed materials into a reaction kettle, heating to 80 to 90 ℃, and carrying out heat preservation and stirring at the rotating speed of 800 to 1000 r/min;
2. stopping stirring after 6 hours of reaction, sampling to test the acid value, continuing stirring at the constant temperature if the test acid value is more than 5mgKOH/g, sampling to measure the acid value every 1 hour subsequently, and stopping stirring until the acid value is less than 5 mgKOH/g;
3. and cooling to 50-60 ℃, and discharging while the mixture is hot to obtain the dimer acid modified epoxy resin and methacrylic acid prepolymer.
The invention makes a comparison experiment through a plurality of examples and two groups of comparative examples.
Example 1
1. Weighing 5 parts of bisphenol A type epoxy resin, 25 parts of dimer acid modified epoxy resin, 15 parts of epoxidized polybutadiene, 5 parts of dimer acid modified epoxy resin and methacrylic acid prepolymer, 10 parts of modified polyester compound, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl formate, 10 parts of 3,3' - (oxybispropylene) bis (3-ethyl) oxetane, 5 parts of triethylene glycol divinyl ether and 7 parts of isobornyl methacrylate, putting the raw materials into a reaction kettle, stirring the raw materials at a rotating speed of 400r/min for 5 minutes, and then stirring the raw materials at a rotating speed of 800-1000r/min for 1-2 hours;
2. weighing 4 parts of UVI6976 (cationic photoinitiator), 1 part of Irgacure 184 (free radical photoinitiator) and 3 parts of gamma-glycidyl ether oxypropyl trimethoxysilane, adding into the reaction kettle in the step 1, stirring at the rotating speed of 800-1000r/min and the vacuum degree of 0.05-0.09 MPa for 20-40 minutes, stopping stirring, and filtering by using a 200-mesh filter screen to obtain the finished product.
Example 2
1. Weighing 10 parts of bisphenol F type epoxy resin, 10 parts of alicyclic epoxy resin, 15 parts of dimer acid modified epoxy resin, 10 parts of epoxidized polybutadiene, 5 parts of dimer acid modified epoxy resin and methacrylic acid prepolymer, 5 parts of modified polyester compound, 10 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl formate, 5 parts of 3,3' - (oxybis methylene) bis (3-ethyl) oxetane, 10 parts of triethylene glycol divinyl ether, 10 parts of isobornyl methacrylate and 5 parts of allyl glycidyl ether according to the weight parts of the raw materials in the table of figure 1, putting the raw materials into a reaction kettle, stirring the raw materials at the rotating speed of 400r/min for 5 minutes, and then stirring the raw materials at the rotating speed of 800-1000r/min for 1-2 hours;
2. 3 parts of UVI6976 (cationic photoinitiator), 1 part of Irgacure 184 (free radical photoinitiator), 1 part of 2- (3,4-epoxycyclohexylalkyl) ethyltrimethoxysilane and 0.5 part of acid complex dye are weighed and added into the reaction kettle in the step 1, the stirring is stopped after 20-40 minutes at the rotating speed of 800-1000r/min and the vacuum degree of 0.05-0.09 MPa, and a 200-mesh filter screen is used for filtering, so that a finished product is obtained.
Example 3
1. Weighing 6 parts of alicyclic epoxy resin, 45 parts of dimer acid modified epoxy resin, 10 parts of dimer acid modified epoxy resin and methacrylic acid prepolymer, 5 parts of 3,4-epoxy cyclohexyl methacrylate, 2 parts of modified polyester compound, 5 parts of 3,4-epoxy cyclohexyl methyl 3,4-epoxy cyclohexyl formate, 15 parts of triethylene glycol divinyl ether and 5 parts of isobornyl methacrylate according to the parts by weight of the raw materials in the table of figure 1, putting the raw materials into a reaction kettle, stirring the raw materials at the rotating speed of 400r/min for 5 minutes, and then stirring the raw materials at the rotating speed of 800-1000r/min for 1-2 hours;
2. weighing 6 parts of UVI6976 (cationic photoinitiator), 1 part of Irgacure 184 (free radical photoinitiator), 1 part of gamma-glycidyl ether oxypropyltrimethoxysilane and 0.1 part of acid complex dye, adding into the reaction kettle in the step 1, stirring at the rotating speed of 800-1000r/min and the vacuum degree of 0.05-0.09 MPa for 20-40 minutes, stopping stirring, and filtering by using a 200-mesh filter screen to obtain the finished product.
Example 4
1. Weighing 5 parts of bisphenol F epoxy resin, 20 parts of epoxidized polybutadiene, 30 parts of dimer acid modified epoxy resin and methacrylic acid prepolymer, 10 parts of modified polyester compound, 10 parts of 3,3' - (oxybis-methylene) bis (3-ethyl) oxetane, 8 parts of triethylene glycol divinyl ether, 10 parts of isobornyl methacrylate and 3 parts of allyl glycidyl ether according to the weight parts of the raw materials in the table of figure 1, putting the raw materials into a reaction kettle, stirring the raw materials at the rotating speed of 400r/min for 5 minutes, and then stirring the raw materials at the rotating speed of 800-1000r/min for 1-2 hours;
2. weighing 1 part of UVI6976 (cationic photoinitiator), 2.5 parts of Irgacure 184 (free radical photoinitiator), 0.5 part of 2- (3,4-epoxycyclohexylalkyl) ethyl trimethoxy silane and 0.05 part of acid complex dye, adding into the reaction kettle in the step 1, stirring at the rotating speed of 800-1000r/min and the vacuum degree of 0.05-0.09 MPa for 20-40 minutes, stopping stirring, and filtering by using a 200-mesh filter screen to obtain the finished product.
Example 5
1. Weighing 10 parts of alicyclic epoxy resin, 34 parts of dimer acid modified epoxy resin, 10 parts of 3,4-epoxy cyclohexyl methacrylate, 15 parts of modified polyester compound, 3,4-epoxy cyclohexyl methyl 3,4-epoxy cyclohexyl formate, 10 parts of 3,3' - (oxybis methylene) bis (3-ethyl) oxetane and 10 parts of isobornyl methacrylate according to the parts by weight of the raw materials in the table of figure 1, putting the raw materials into a reaction kettle, stirring the raw materials at the rotating speed of 400r/min for 5 minutes, and then stirring the raw materials at the rotating speed of 800-1000r/min for 1-2 hours;
2. 3 parts of UVI6976 (cationic photoinitiator), 0.5 part of Irgacure 184 (free radical photoinitiator), 1 part of gamma-glycidyl ether oxypropyl trimethoxy silane, 1 part of 2- (3,4-epoxycyclohexylalkyl) ethyl trimethoxy silane and 0.1 part of acid complex dye are weighed and added into the reaction kettle in the step 1, the stirring is stopped after 20-40 minutes at the rotating speed of 800-1000r/min and the vacuum degree of 0.05-0.09 MPa, and a 200-mesh filter screen is used for filtering, so that a finished product is obtained.
Example 6
1. Weighing 10 parts of alicyclic epoxy resin, 21 parts of dimer acid modified epoxy resin, 15 parts of dimer acid modified epoxy resin and methacrylic acid prepolymer, 10 parts of modified polyester compound, 5 parts of 3,3' - (oxybis methylene) bis (3-ethyl) oxetane, 10 parts of triethylene glycol divinyl ether and 20 parts of isobornyl methacrylate according to the parts by weight of the raw materials in the table in figure 1, putting the raw materials into a reaction kettle, stirring the raw materials at the rotating speed of 400r/min for 5 minutes, and then stirring the raw materials at the rotating speed of 800-1000r/min for 1-2 hours;
2. 3 parts of UVI6976 (cationic photoinitiator), 2 parts of Irgacure 184 (free radical photoinitiator), 2 parts of 2- (3,4-epoxycyclohexylalkyl) ethyltrimethoxysilane and 0.1 part of acid complex dye are weighed and added into the reaction kettle in the step 1, stirring is stopped after 20-40 minutes at the rotating speed of 800-1000r/min and the vacuum degree of 0.05-0.09 MPa, and a 200-mesh filter screen is used for filtering, so that a finished product is obtained.
The preparation process of the present invention is further described in detail below with reference to several examples.
In an embodiment of the present invention,
in order to obtain representative data, regarding the epoxy resin, the bisphenol A type epoxy resin adopts Vast Epikote828; the bisphenol F type epoxy resin adopts Vast Epikote862; the cycloaliphatic epoxy resin is selected from the group consisting of xylonite EHPE3150, but the present invention is not limited thereto.
For representative data, CVC DA323 was used as the dimer acid-modified epoxy resin, but the present invention is not limited thereto.
In order to obtain representative data and can perform free radical reaction on epoxy resin, the epoxidized polybutadiene is selected from xylonite PB3600; the acrylate modified epoxy resin is prepared from new Zhongcun chemical EA1010LC;3,4-epoxy cyclohexyl methacrylate, xylonite CYCLOMER M100 is selected, but the invention is not limited thereto.
For representative data, addBond LTH was chosen as the adhesion promoting resin, but the invention is not limited thereto.
For representative data, epoxy diluent 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl formate xylonite 2021P is selected; 3,3' - (oxybis-methylene) bis (3-ethyl) oxetane was chosen for the east Asia synthesis of OXT-221, but the invention is not limited thereto.
In order to obtain representative data, in the aspect of free radical reactive monomers, the vinyl ether is Basfov DVE-3; methacrylate ester is Changxing EM-90; the allyl monomer is Caoda Neoallyl G, but the invention is not limited thereto.
For representative data, the cationic photoinitiator was chosen to be the dow UVI6976, but the invention is not limited thereto.
To obtain representative data, the radical photoinitiator was chosen to be basf Irgacure 184, but the invention is not limited thereto.
To obtain representative data, the coupling agents are selected from FIGS. A-186 and A-187, but the invention is not limited thereto.
To obtain representative data, the other component sources in the comparative examples are as follows: the polyester polyol flexibilizer is xylonite PCL305; polyurethane acrylate is Changxing 6118; the 2-hydroxyethyl methacrylate is prepared from HEMA (hexa chemical engineering); 2,4,6-trimethylbenzoyldiphenylphosphine oxide is Pasteff Irgacure TPO; the vinyltrimethoxysilane is shown in the A-171.
Comparative example 1:
1. weighing 20 parts of bisphenol A epoxy resin, 20 parts of alicyclic epoxy resin, 15 parts of polyester polyol toughening agent, 5 parts of adhesion promoting resin, 25 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl formate and 10 parts of 3,3' - (oxybispropylene) bis (3-ethyl) oxetane according to the weight parts of the raw materials based on the total weight of the raw materials, putting the raw materials into a reaction kettle, stirring the raw materials at the rotating speed of 400r/min for 5 minutes, and then stirring the raw materials at the rotating speed of 800-1000r/min for 1-2 hours;
2. 4 parts of UVI6976 (cationic photoinitiator), 1 part of gamma-glycidyl ether oxypropyltrimethoxysilane and 0.1 part of toner are weighed, added into the reaction kettle in the step 1, stirred for 20-40 minutes at the rotating speed of 800-1000r/min and the vacuum degree of 0.05-0.09 MPa, and then stopped, and filtered by a 200-mesh filter screen to obtain a finished product.
Comparative example 2:
1. weighing 40 parts of urethane acrylate, 25 parts of acrylate modified epoxy resin, 15 parts of 2-hydroxyethyl methacrylate and 15 parts of isobornyl methacrylate according to the weight parts of the raw materials in the total weight, putting the raw materials into a reaction kettle, firstly stirring at the rotating speed of 400r/min for 5 minutes, and then stirring at the rotating speed of 800-1000r/min for 1-2 hours;
2. weighing 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (free radical photoinitiator) 2.5 parts, vinyl trimethoxy silane 2 parts and toner 0.5 part, adding into the reaction kettle in the step 1, stirring at the rotating speed of 800-1000r/min and the vacuum degree of 0.05-0.09 MPa for 20-40 minutes, stopping, and filtering with a 200-mesh filter screen to obtain the finished product.
The adhesives prepared in the above examples 1-6 and comparative examples 1-2 were cured under 365nm UV-LED lamp with curing energy of 3000mJ/cm2, respectively, and various performance tests were performed. The test results are tabulated in fig. 2.
1. The adhesive film hardness is as follows: type D Shore durometer.
2. Testing acid and alkali resistance of the adhesive film: a sample is prepared according to GBT13022-1991 plastic film tensile property test method, and is placed for 1h at room temperature, and then is soaked in KOH solution with mass fraction of 20% at 45 ℃ for 1h, concentrated sulfuric acid with mass fraction of 50% at 45 ℃ for 1h, HF solution with mass fraction of 20% at 45 ℃ for 10h in sequence, and the tensile strength is tested after washing.
3. Testing the acid and alkali resistance and moisture absorption rate of the adhesive film: curing a glue film with the thickness of 0.3mm, standing for 1h at room temperature, weighing, sequentially soaking in KOH solution with the mass fraction of 20% at 45 ℃ for 1h, concentrated sulfuric acid with the mass fraction of 50% at 45 ℃ for 1h, and HF solution with the mass fraction of 20% at 45 ℃ for 10h, washing with water, wiping, weighing, and calculating the acid-base soaking moisture absorption rate.
4. Acid and alkali resistance bonding test: after the coating is scraped on glass and cured, the glass is placed for 1h at room temperature, is soaked in KOH solution with the mass fraction of 20% at the temperature of 45 ℃ for 1h and is soaked in concentrated sulfuric acid with the mass fraction of 50% at the temperature of 45 ℃ for 10h, and whether the adhesive film falls off or is abnormal is observed.
5. And (3) tearing the glue: after the glass is coated by a scraper and solidified, the glass is placed for 1h at room temperature, and is sequentially soaked in KOH solution with the mass fraction of 20% at 45 ℃ for 1h, concentrated sulfuric acid with the mass fraction of 50% at 45 ℃ for 1h, and HF solution with the mass fraction of 20% at 45 ℃ for 45min, the glass is taken out and washed, the edge of the glue film is picked up to tear the glue, and if the whole glue film can be torn off without fracture, the OK is obtained.
According to the detection result and test data, the cation/free radical hybrid curing adhesive is cured into a film, the strength of the adhesive film is still greater than 14MPa after being soaked in an acid-base solution, and the reduction amplitude is lower than 40%; the moisture absorption rate is lower than 4%, and the swelling effect is small; the glass surface has good bonding effect, no abnormal phenomena such as swelling, glue falling and the like, and the glue is torn normally without glue breaking. The cation/free radical hybrid curing adhesive disclosed by the invention has the advantages that the adhesive film after curing is better in strength and toughness and excellent in acid and alkali resistance, glass can be thinned to be thinner, no adhesive is dropped or broken, and the adhesive is convenient to remove.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being covered by the appended claims and their equivalents.
Claims (10)
1. The UV cationic free radical hybrid curing adhesive is characterized by comprising, by weight, 5-20 parts of epoxy resin, 0-50 parts of dimer acid modified epoxy resin, 10-50 parts of free radical reactive epoxy resin, 2-15 parts of adhesion promoting resin, 5-20 parts of epoxy diluent, 10-30 parts of free radical reactive monomer, 1-6 parts of cationic photoinitiator, 0.5-3 parts of free radical photoinitiator, 0.5-3 parts of coupling agent and 0-0.5 part of toner.
2. The UV cationic free-radical hybrid curing adhesive of claim 1, wherein:
the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin;
the dimer acid modified epoxy resin is one or more of dimer acid modified glycidyl ether type epoxy resin, dimer acid modified alicyclic epoxy resin and dimer acid modified oxetane; the structural general formula of the dimer acid modified epoxy resin is as follows,
wherein R is 1 Residue of dimer acid minus-COOH; r is 2 Is the residue after the ring opening of the epoxy in the modified epoxy resin;
the dimer acid has the structural formula:
the structural formula of the glycidyl ether type epoxy resin is as follows:
the structural formula of the alicyclic epoxy resin is as follows:
the oxetane structure is:
the dimer acid modified epoxy resin is prepared by performing a carboxylic acid-epoxy ring-opening addition reaction on dimer acid and corresponding epoxy resin;
the epoxy resin capable of free radical reaction is one or more of 3,4-epoxy cyclohexyl methacrylate, epoxy polybutadiene and acrylic acid modified epoxy resin; the acrylic acid modified epoxy resin is a prepolymer of dimer acid modified epoxy resin and an acrylic compound,
the structural general formula of the acrylic acid modified epoxy resin is as follows:
wherein R is 1 、R 2 In accordance with the structure defined above; r is 6 Is R 2 A residue of the structure following ring opening of an epoxy group;
the structural formula of the acrylic compound is as follows:
the prepolymer of the dimer acid modified epoxy resin and the acrylic compound is prepared by the ring-opening addition reaction of the prepared dimer acid modified epoxy resin and the acrylic compound through carboxylic acid-epoxy;
the adhesion promoting resin is a modified polyester compound.
3. The UV cationic free-radical hybrid curing adhesive of claim 1, wherein: the epoxy diluent is one or more of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl formate, bis (7-oxabicyclo [4.1.0] -3-heptamethyl) adipate, 1,4-butanediol diglycidyl ether, 3,3' - (oxybis methylene) bis (3-ethyl) oxetane and 3-ethyl-3-oxetanyl methanol.
4. The UV cationic free-radical hybrid curing adhesive of claim 1, wherein: the free radical reactive monomer is one or more of hydroxybutyl vinyl ether, triethylene glycol divinyl ether, benzyl vinyl ether, isobornyl methacrylate, isobornyl acrylate, 2-hydroxyethyl methacrylate, tricyclodecane dimethanol diacrylate, allyl glycidyl ether, glycerol monoallyl ether and trimethylolpropane diallyl ether.
5. The UV cationic free-radical hybrid curing adhesive of claim 1, wherein: the cationic photoinitiator is one or more of triaryl hexafluoroantimonate sulfonium salt, diaryl hexafluoroantimonate iodonium salt and diaryl hexafluoroantimonate iodonium salt.
6. The UV cationic free-radical hybrid curing adhesive of claim 1, wherein: the free radical photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl acetone.
7. The UV cationic free-radical hybrid curing adhesive of claim 1, wherein: the coupling agent is one or more of 2- (3,4-epoxycyclohexylalkyl) ethyl trimethoxy silane, gamma-glycidoxypropyl trimethoxy silane and vinyl trimethoxy silane.
8. The UV cationic free-radical hybrid curing adhesive of claim 1, wherein: the toner is dye or pigment, the dye is acid complex dye, and the pigment is dispersed pigment.
9. A preparation method of a UV cation/free radical hybrid curing adhesive comprises the following steps:
s1, weighing epoxy resin, dimer acid modified epoxy resin, free radical reactive resin, adhesion promoting resin, epoxy diluent and free radical reactive monomer according to a set weight ratio, putting into a reaction kettle, stirring at a rotating speed of 400r/min for 5 minutes, and then stirring at 1000r/min for 1 hour;
s2, weighing a cationic photoinitiator, a free radical photoinitiator, a coupling agent and toner, adding into the reaction kettle in the step S1, stirring for 30 minutes at a rotating speed of 800r/min and a vacuum degree of 0.05MPa, stopping stirring, and filtering by using a 200-mesh filter screen to obtain a finished product.
10. The application of the UV cation/free radical hybrid curing adhesive is characterized in that: use of the UV cation/free radical hybrid curing adhesive of any one of claims 1-8 in a process for thinning a glass substrate of a liquid crystal display.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401706A (en) * | 2018-10-31 | 2019-03-01 | 深圳广恒威科技有限公司 | One kind can quick-setting high reliability filling glue |
| JP2019151716A (en) * | 2018-03-01 | 2019-09-12 | 味の素株式会社 | Sealing resin composition |
| CN114096583A (en) * | 2019-07-09 | 2022-02-25 | 汉高股份有限及两合公司 | Two-component (2K) compositions based on modified epoxy resins |
| CN114621719A (en) * | 2020-12-11 | 2022-06-14 | 日本化药株式会社 | Liquid crystal sealant for liquid crystal dropping method |
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- 2022-10-31 CN CN202211349319.6A patent/CN115521691A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019151716A (en) * | 2018-03-01 | 2019-09-12 | 味の素株式会社 | Sealing resin composition |
| CN109401706A (en) * | 2018-10-31 | 2019-03-01 | 深圳广恒威科技有限公司 | One kind can quick-setting high reliability filling glue |
| CN114096583A (en) * | 2019-07-09 | 2022-02-25 | 汉高股份有限及两合公司 | Two-component (2K) compositions based on modified epoxy resins |
| CN114621719A (en) * | 2020-12-11 | 2022-06-14 | 日本化药株式会社 | Liquid crystal sealant for liquid crystal dropping method |
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