CN114369439A - Toughening type light-curable adhesive and preparation method and application thereof - Google Patents
Toughening type light-curable adhesive and preparation method and application thereof Download PDFInfo
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- CN114369439A CN114369439A CN202111434594.3A CN202111434594A CN114369439A CN 114369439 A CN114369439 A CN 114369439A CN 202111434594 A CN202111434594 A CN 202111434594A CN 114369439 A CN114369439 A CN 114369439A
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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
- C09J163/10—Epoxy resins modified by unsaturated compounds
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention relates to a toughening type light-curable adhesive and a preparation method and application thereof; the adhesive comprises a first component and a second component, wherein the raw materials of the first component are epoxy acrylic resin, hydroxy acrylic resin, an acrylate monomer, reactive nitrile rubber, a photoinitiator and an auxiliary agent; the adhesive prepared by mixing the two specific components can realize normal-temperature UV rapid curing, has good deep curing effect, good durability and crack resistance, and excellent high and low temperature impact resistance; solves the problems of long primary curing time, large brittleness of cured products, poor durability and easy cracking of the traditional epoxy resin adhesive.
Description
Technical Field
The invention belongs to the field of adhesive materials, and relates to a toughened light-curable adhesive, and a preparation method and application thereof.
Background
The glue joint has the advantages of light weight, uniform stress distribution, no damage to the continuity of a glued joint part and the like, so that the glue joint is widely applied; the epoxy resin adhesive is a common adhesive and is a curing system prepared by epoxy resin and a curing agent according to a certain proportion.
The molecular structure of the epoxy resin is characterized in that a molecular chain contains active epoxy groups, and the epoxy groups can be positioned at the tail end and in the middle of the molecular chain. Because the molecular structure contains active epoxy groups, the epoxy groups can generate cross-linking reaction with a curing agent to form insoluble high polymer with a net structure, thereby achieving the bonding effect; the traditional epoxy resin adhesive generally adopts a thermosetting mode, when the epoxy resin adhesive is applied to the gluing of electronic components, the components are easily damaged by heating, the packaging efficiency is influenced, the initial curing speed is low, and the production efficiency is low.
The light curing mode can avoid the heat damage to components and base materials in the gluing process, but the influence of the composition of an adhesive system is large, and the problems of insufficient deep curing and incapability of curing a shadow area exist; in addition, the photo-cured epoxy resin has the problems of high brittleness, impact and vibration resistance and easy cracking; when the adhesive is applied to the bonding process of an electronic component and a base material, the problems leave great hidden dangers for the durability of the bonding part of the component and the base material.
Therefore, the development of an adhesive which has excellent durability and cracking resistance and can realize normal-temperature photocuring, deep curing and good shadow area curing effect is still significant.
Disclosure of Invention
The invention aims to provide a toughening type light-curable adhesive and a preparation method and application thereof; the adhesive comprises a first component and a second component, wherein the raw materials of the first component are epoxy acrylic resin, hydroxy acrylic resin, an acrylate monomer, reactive nitrile rubber, a photoinitiator and an auxiliary agent; the adhesive prepared by mixing the two specific components can realize normal-temperature UV rapid curing, has good deep curing effect, good durability and crack resistance, and excellent high and low temperature impact resistance; solves the problems of long primary curing time, large brittleness of cured products, poor durability and easy cracking of the traditional epoxy resin adhesive.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a toughened, photocurable adhesive comprising a first component and a second component;
the composition comprises a first component and a second component, wherein the first component comprises the following raw materials in percentage by mass based on 100% of the first component:
the second component comprises an isocyanate-based curing agent.
The toughened photocurable adhesive comprises two components, wherein the raw materials of the first component comprise 20-60 wt% of epoxy acrylic resin, such as 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt%, 38 wt%, 40 wt%, 42 wt%, 45 wt%, 48 wt%, 50 wt%, 52 wt%, 55 wt% or 58 wt%, etc., 20-60 wt% of hydroxy acrylic resin, such as 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt%, 38 wt%, 40 wt%, 42 wt%, 45 wt%, 48 wt%, 50 wt%, 52 wt%, 55 wt% or 58 wt%, etc., 10-20 wt% of acrylate monomer, such as 12 wt%, 14 wt%, 15 wt%, 16 wt% or 18 wt%, etc., the mass percentage of the reactive nitrile rubber is 6-30 wt%, such as 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt% or 28 wt%, etc., the mass percentage of the photoinitiator is 0.5-3 wt%, such as 1 wt%, 1.5 wt%, 2 wt% or 2.5 wt%, etc., and the mass percentage of the auxiliary agent is 0-1 wt%, such as 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt% or 0.9 wt%.
The traditional epoxy resin adhesive has the defects of long primary curing time, insufficient photocuring depth, incapability of curing in a shadow area, high brittleness, impact and vibration resistance and easiness in cracking of a cured product, and great hidden danger in durability of a bonding part; in order to overcome the technical problems, the invention develops the adhesive which has the advantages of high normal-temperature photocuring speed, good deep curing effect, good shadow area curing, excellent durability and excellent anti-cracking performance, and the obtained adhesive has excellent high-low temperature cycle impact performance; the first component of the adhesive disclosed by the invention adopts epoxy acrylic resin, hydroxy acrylic resin, an acrylate monomer, reactive nitrile rubber, a photoinitiator and an auxiliary agent, the components are matched according to a specific proportion for use, so that the obtained adhesive has a rapid photocuring performance at normal temperature, the required curing energy is low, and the hydroxyl-containing acrylic resin and the monomer in the first component are matched with an isocyanate curing agent in the second component, so that a good curing effect at normal temperature is realized, and the curing depth and the curing effect of a shadow area are further ensured; in addition, the addition of the reactive nitrile rubber in the first component and the mutual cooperation of the components ensure good photocuring effect, namely, the rapid curing of normal-temperature UV light, good photocuring depth and shadow area curing are realized, and meanwhile, the durability and cracking resistance of a bonding part in the using process of the adhesive are further improved, and the high-temperature and low-temperature impact resistance of the adhesive is effectively improved.
The adhesive can be used for encapsulation, structural bonding, coating and the like; the adhesive is particularly suitable for the fields of encapsulation and structural bonding, and solves the problems of incomplete deep curing and low-temperature cracking of the traditional adhesive.
The hydroxyl acrylic resin in the first component of the adhesive is matched with the isocyanate curing agent in the second component, so that the normal-temperature light rapid curing is realized, and the deep curing and shadow area curing effects are ensured; and the reactive nitrile rubber in the first component is matched with the epoxy acrylic resin and the hydroxy acrylic resin, so that the durability, the cracking resistance and the high-low cycle impact resistance of the adhesive are further improved while the photocuring effect is ensured.
The adhesive has the advantages that the photocuring rate at normal temperature can reach 3s positioning (namely surface drying is realized), the curing depth can reach more than 20mm, the curing effect of a shadow area is complete, and the shear strength of the cured adhesive to glass is more than 13 MPa.
Preferably, the mass ratio of the first component to the second component is 1 (0.1 to 1), for example 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8 or 1:0.9, etc., preferably 1 (0.45 to 0.65), for example 1:0.5, 1:0.55 or 1:0.6, etc., and more preferably 1 (0.5 to 0.6).
In the adhesive, the proportion of the first component and the second component meets the range, so that the normal-temperature light rapid curing is realized, and the curing depth and the curing effect of a shadow area can be ensured; and can meet the performance requirements of durability, cracking resistance and high and low temperature impact resistance. And further preferably, the mass ratio of the first component to the second component is 1 (0.45-0.65); within this range, the curing effect is more excellent, and the durability, crack resistance and high and low temperature impact resistance are better.
Preferably, the hydroxy acrylic resin is selected from any one of or a combination of at least two of solid thermoplastic hydroxy acrylates, hydroxy-containing polyurethane acrylates or hydroxy-containing polyester acrylates, preferably hydroxy-containing polyurethane acrylates.
The hydroxyl acrylic resin adopted in the adhesive is beneficial to realizing normal-temperature photocuring and ensuring the curing depth, and has important significance in improving the durability, cracking resistance and high-low temperature impact resistance of the adhesive; in the present invention, the hydroxy acrylic resin is preferably selected from the three types described above, and the durability, cracking resistance and high/low temperature impact resistance of the corresponding bonding part are most excellent. And the hydroxyl-containing polyurethane acrylate is further preferably selected, so that the adhesive has the advantages of good weather resistance, strong adhesive force, good toughness and strong plasticity, and can effectively improve the impact resistance, weather resistance and low-temperature cracking resistance of the adhesive by being matched with other components in the adhesive, thereby ensuring the requirement on the durability of the bonding part.
The bi-component adhesive composition provided by the invention has good flexibility and impact resistance under normal temperature and low temperature conditions. After 10 times of cycles at the high temperature and the low temperature of-40 to 80 ℃, the cracking phenomenon does not occur, and the impact resistance tensile strength can reach more than 3.5 MPa; the tensile elongation at the low temperature of minus 40 ℃ can reach more than 150 percent.
Preferably, the solid thermoplastic hydroxy acrylate is a solid hydroxy acrylate having good miscibility with the photocurable monomer and the resin, preferably an ester-soluble solid hydroxy acrylate, and more preferably at least one of german martes AC160, AC162, AC169, japan mitsubishi BR113 and BR 106.
Preferably, the hydroxyl-containing polyurethane acrylate is a UV polyurethane resin containing hydroxyl and an acrylate structure, and preferably any one or a combination of at least two of the blue kohlenite L-8468, the blue kohlenite L-6906 and the bayer dual-curing UV resin LS 2396.
Preferably, the hydroxyl-containing polyester acrylate is a modified UV polyester resin, preferably, the blue chrysol L-8460 and/or the Coding AD 7001.
Preferably, the acrylate monomer is a hydroxy acrylate.
The acrylate monomer in the adhesive is preferably hydroxyl acrylate, and is matched with hydroxyl acrylic resin and an isocyanate curing agent in the second component, so that the adhesive has important significance for improving the normal-temperature photocuring effect and is beneficial to ensuring deep curing; the obtained adhesive has better durability, cracking resistance and high and low temperature impact resistance.
Preferably, the hydroxyl acrylate includes any one of or a combination of at least two of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, trimethylolpropane diacrylate or pentaerythritol triacrylate, and the combination illustratively includes a combination of hydroxyethyl acrylate and hydroxyethyl methacrylate, a combination of hydroxybutyl acrylate and trimethylolpropane diacrylate or a combination of pentaerythritol triacrylate and hydroxyethyl acrylate, and the like.
Preferably, the reactive nitrile rubber comprises any one of carboxyl-terminated nitrile rubber (CTBN), amino-terminated nitrile rubber (ATBN), epoxy-terminated nitrile rubber (ETBN) or vinyl-terminated nitrile rubber (VTBN), or a combination of at least two thereof; exemplary combinations include a combination of carboxyl-terminated nitrile rubber and amino-terminated nitrile rubber, a combination of epoxy-terminated nitrile rubber and vinyl-terminated nitrile rubber, and the like; preferably carboxyl-terminated nitrile rubber and/or vinyl-terminated nitrile rubber.
The reactive nitrile rubber is preferably selected from the components, and has important significance for realizing excellent durability, cracking resistance and high and low temperature cycle impact resistance of the adhesive; the adhesive is matched with other components in the adhesive, so that not only can excellent normal-temperature photocuring performance be realized, but also the curing depth effect is good, and the obtained adhesive has good durability, cracking resistance and high-low temperature cycle impact resistance; and further preferably carboxyl-terminated nitrile rubber and/or vinyl-terminated nitrile rubber.
Preferably, the epoxy acrylic resin is selected from any one of or a combination of at least two of bisphenol a epoxy acrylate, acid-modified epoxy acrylate or amine-modified epoxy acrylate, and the combination exemplarily comprises a combination of bisphenol a epoxy acrylate and acid-modified epoxy acrylate or a combination of bisphenol a epoxy acrylate and amine-modified epoxy acrylate, and the like; preferably an acid-modified epoxy acrylate and/or an amine-modified epoxy acrylate.
In the adhesive, the epoxy acrylic resin is used in combination with other components, so that the normal-temperature photocuring effect, the curing depth and the curing effect of a shadow area are better, the durability, the cracking resistance and the high-low temperature cycle impact resistance of the adhesive are better, and acid-modified epoxy acrylate and/or amine-modified epoxy acrylate are further preferred.
Preferably, the acid-modified epoxy acrylate is any one of succinic acid-modified epoxy acrylate, glutaric acid-modified epoxy acrylate and adipic acid-modified epoxy acrylate or a combination of at least two of the succinic acid-modified epoxy acrylate, the glutaric acid-modified epoxy acrylate and the adipic acid-modified epoxy acrylate.
Preferably, the amine-modified epoxy acrylate is an aliphatic amine-modified epoxy acrylate, preferably any one or a combination of at least two of kotian 4100, zhongshan qian leaf UV1101 and bosch B151.
Preferably, the content of the auxiliary agent is 0.1 to 1% by mass, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, etc., preferably 0.3 to 0.8%, based on 100% by mass of the first component.
Preferably, the auxiliary agent is a silane coupling agent.
The adhesive is added with a silane coupling agent as an auxiliary agent, the silane coupling agent can simultaneously generate certain bonding force with polar substances and nonpolar substances, the adhesive is characterized in that molecules simultaneously have polar parts and nonpolar parts, a 'molecular bridge' can be erected between interfaces of inorganic substances and organic substances by using the silane coupling agent to connect two materials with completely different properties, so that the bonding strength of the interface layers is effectively improved, and the addition of the auxiliary agent has an obvious promoting effect on improving the durability and the anti-cracking performance of the adhesive in the light-curable adhesive system.
Preferably, the silane coupling agent includes any one of or a combination of at least two of gamma-aminopropyltriethoxysilane (KH-550), gamma-methacryloxypropyltrimethoxysilane HDI (KH-570), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), vinyltriethoxysilane (A-151), or vinyltrimethoxysilane (A-171).
Preferably, the photoinitiator is selected from any one or a combination of at least two of 1173, 184, BP, TPO, 819, ITX or EDB, preferably the photoinitiator ITX.
Preferably, the isocyanate-based curing agent includes any one of or a combination of at least two of TDI, HDI, IPDI, HDI trimer or HDI biuret.
The second component in the adhesive provided by the invention adopts the isocyanate curing agent, and the isocyanate curing agent has the effects of reacting with the resin containing hydroxyl and the monomer in the first component, so that normal-temperature curing can be realized, the curing depth and the curing effect of a shadow area are good, the toughness of the adhesive is good, and the requirements of durability, cracking resistance and high and low temperature impact resistance are met.
In a second aspect, the present invention provides a method for preparing the toughened photocurable adhesive according to the first aspect, the method comprising:
a first component preparation comprising: sequentially adding epoxy acrylic resin, hydroxyl acrylic resin, reactive nitrile rubber and an acrylate monomer into a mixer, starting vacuum, stirring, and controlling the temperature to be less than or equal to 60 ℃ in the stirring process; then stopping stirring and cooling, adding a photoinitiator and an auxiliary agent under the irradiation of a light source with the wavelength of more than 500nm, and stirring to obtain a first component;
a second component preparation comprising: and defoaming the isocyanate curing agent to obtain a second component.
In a third aspect, the present invention provides a method of using the adhesive of the first aspect, the method comprising: the first component and the second component were mixed and then coated on a substrate and radiation cured under the illumination of a mercury lamp.
Preferably, the substrate comprises glass or plastic.
In a fourth aspect, the present invention provides the use of the toughened photocurable adhesive according to the first aspect in the field of potting, structural bonding or thick coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) the adhesive comprises a first component and a second component, and the two specific components are mixed to enable the adhesive to realize normal-temperature light rapid curing, wherein the deep curing can reach more than 20 mm;
(2) the adhesive has good high and low temperature cycle impact resistance, and solves the problems of poor brittleness, poor durability and easy cracking of the traditional epoxy resin cured product.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a toughening type photo-curable adhesive which comprises a first component and a second component in a mass ratio of 1: 0.5;
the composition comprises a first component and a second component, wherein the first component comprises the following raw materials in percentage by mass based on 100% of the first component:
the second component is TDI;
the components are as follows: the bisphenol A epoxy acrylate is bosch B-100M;
the hydroxyl-containing polyurethane acrylate is erythroxylol L-8468;
carboxyl terminated nitrile butadiene rubber (CTBN) is available from dow chemical company;
2-isopropyl thioxanthone ITX is selected from Tianjin Jieshi New materials, Inc.;
KH-550 is selected from Nanjing Quanxi chemical Co., Ltd;
TDI was selected from Cangzhou Daghnized GmbH.
The preparation method of the adhesive comprises the following steps:
preparation of a first component: the method comprises the following steps: sequentially adding bisphenol A epoxy acrylate, hydroxyl-containing polyurethane acrylate, carboxyl-terminated butadiene-acrylonitrile rubber (CTBN) and hydroxyethyl acrylate into a double-planet vacuum mixer, starting vacuum, and stirring at a high speed for 80min, wherein the temperature is controlled to be not more than 60 ℃; stopping stirring, cooling the glue solution to 20-25 ℃, turning off a lighting fluorescent lamp and an equipment window observation lamp, starting a long-wavelength light source with the wavelength of more than 500nm, adding 2-isopropyl thioxanthone ITX and KH-550, stirring for 80min in vacuum, controlling the temperature to be 20-25 ℃, and uniformly stirring to obtain a first component;
preparation of a second component: defoaming the isocyanate curing agent, and canning into a dry anhydrous container.
Example 2
The difference between the present example and example 1 is that the raw materials of the first component are:
wherein the succinic acid modified epoxy acrylate is selected from Guangzhou Boxing new material science and technology limited; the solid thermoplastic hydroxyacrylate is selected from the group consisting of Mateiss, Germany AC 160; the photoinitiator ITX is selected from New Tianjin materials GmbH; KH-560 is selected from Nanjing Quanxi chemical Co.
Example 3
The difference between the present example and example 1 is that the raw materials of the first component are:
wherein the amine modified epoxy acrylate is selected from Kotian 4100, the hydroxyl-containing polyester acrylate is selected from erythroxylol L-8460, the hydroxyethyl methacrylate is selected from Jiangsu Yucorridor chemical industry Co., Ltd, the epoxy-terminated nitrile rubber is selected from Beijing Deorth chemical CHX100, 2-isopropyl thioxanthone ITX and A-151 is selected from Tianjin Jiu New materials Co., Ltd.
Example 4
This example is different from example 1 in that the hydroxyl group-containing urethane acrylate and the like are replaced with a solid thermoplastic type hydroxyl acrylate, and other parameters and conditions are exactly the same as those in example 1.
Wherein the solid thermoplastic hydroxyacrylate is selected from the German Mateiss AC 160.
Example 5
This example differs from example 1 in that the photoinitiator ITX and the like was replaced by the photoinitiator EDB, and the other parameters and conditions were exactly the same as in example 1.
Wherein the photoinitiator EDB is selected from New Tianjin Material Co.
Example 6
This example is different from example 1 in that hydroxyethyl acrylate and the like are replaced by pentaerythritol triacrylate, and other parameters and conditions are exactly the same as in example 1.
Wherein the pentaerythritol triacrylate is selected from Changxing chemical industries, Inc.
Example 7
This example differs from example 1 in that the mass of carboxyl-terminated nitrile rubber (CTBN) was replaced by amino-terminated nitrile rubber (ATBN), and the other parameters and conditions were exactly the same as in example 1.
Wherein the amino-terminated nitrile butadiene rubber (ATBN) is selected from BFGoodrich.
Example 8
The difference between this example and example 1 is that KH-550 is replaced by bisphenol A epoxy acrylate, i.e. no auxiliary agent is contained in the adhesive, and other parameters and conditions are exactly the same as those in example 1.
Example 9
This example differs from example 1 in that the equimolar amount of TDI in the second component was replaced by HDI and the other parameters and conditions were exactly the same as in example 1.
Wherein HDI is selected from Vanhua chemical group, Inc.
Example 10
This example differs from example 1 in that the hydroxyethyl acrylate monomer is replaced by an ethyl acrylate monomer, i.e. the monomer does not contain a hydroxyl group, and the other parameters and conditions are exactly the same as in example 1.
Example 11
This comparative example is different from example 1 in that hydroxyethyl acrylate and the like are replaced by hydroxypropyl acrylate, and other parameters and conditions are exactly the same as those in example 1.
Wherein the hydroxypropyl acrylate is selected from Jiangsu Yucorridor chemical industry Co.
Comparative example 1
This comparative example is different from example 1 in that the hydroxyl group-containing urethane acrylate was replaced with bisphenol A epoxy acrylate in the same amount, that is, the hydroxyl group-containing urethane acrylate was not added, and other parameters and conditions were exactly the same as those in example 1.
Comparative example 2
This comparative example is different from example 1 in that the quality of bisphenol A epoxy acrylate was replaced with hydroxyl group-containing urethane acrylate, that is, bisphenol A epoxy acrylate was not added, and other parameters and conditions were exactly the same as those in example 1.
Comparative example 3
The comparative example is different from example 1 in that the carboxyl-terminated nitrile butadiene rubber (CTBN) and other qualities are replaced by nano titanium dioxide, and other parameters and conditions are completely the same as those in example 1.
Wherein, the nano titanium dioxide is selected from Yingchuang.
And (3) performance testing:
and testing the UV deep curing effect, wherein the testing method comprises the following steps: casting the test sample in a tubular container, irradiating with mercury lamp, and drying with curing energy of 5000MJ/cm2Standing at normal temperature for 12h, and testing the curing depth; the test results are shown in table 1; normal temperature in the test here means 25 ℃;
crack resistance test: and (2) taking each group of adhesives, casting the adhesives by using a mold, completely curing the adhesives under the irradiation of a mercury lamp to obtain a strip-shaped sample with the width multiplied by the thickness of 10mm multiplied by 2mm, correspondingly manufacturing 4 samples for each group of adhesives, putting the samples into a cold and heat impact testing machine, circulating the samples at a high temperature of 80 degrees multiplied by 1h and a low temperature of-40 degrees multiplied by 1h for 10 times, and taking out the samples to observe whether the appearance of the samples has a cracking phenomenon or not.
Testing the high and low temperature impact tensile strength: and taking each group of adhesives, casting the adhesives by using a mold, completely curing the adhesives under the irradiation of a mercury lamp to obtain strip-shaped samples with the width multiplied by the thickness of 10mm multiplied by 2mm, correspondingly manufacturing 4 samples for each group of adhesives, putting the samples into a cold and heat impact testing machine, circulating the samples at the high temperature of 80 degrees multiplied by 1h and the low temperature of-40 degrees multiplied by 1h for 10 times, taking the samples out, placing the samples at the normal temperature, and testing the tensile strength by using a tensile machine. The experimental results are expressed as the arithmetic mean of the tensile strengths.
TABLE 1
| Depth of cure thickness, mm | High and low temperature impact tensile strength, MPa | Whether cracking occurs after 10 cycles of high and low temperature | |
| Example 1 | >20mm | 3.5 | Whether or not |
| Example 2 | >20mm | 3.8 | Whether or not |
| Example 3 | 15mm | 3.9 | Whether or not |
| Example 4 | >20mm | 3.3 | Whether or not |
| Example 5 | 17mm | 3.5 | Whether or not |
| Example 6 | 16mm | 3.0 | Whether or not |
| Example 7 | >20mm | 3.6 | Whether or not |
| Example 8 | >20mm | 3.0 | Whether or not |
| Example 9 | >20mm | 3.9 | Whether or not |
| Example 10 | 15mm | 2.8 | Whether or not |
| Example 11 | >20mm | 3.2 | Whether or not |
| Comparative example 1 | 10mm | 2.5 | Whether or not |
| Comparative example 2 | 18mm | 2.1 | Is that |
| Comparative example 3 | 18mm | 1.9 | Is that |
As can be seen from the test results in the table above, the adhesive disclosed by the invention has the characteristics of good deep curing effect and excellent durability, cracking resistance and high and low temperature impact resistance, and on the contrary, the test results in comparative examples 1-3 do not have the characteristics.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A toughened, photocurable adhesive comprising a first component and a second component;
the composition comprises a first component and a second component, wherein the first component comprises the following raw materials in percentage by mass based on 100% of the first component:
the second component comprises an isocyanate-based curing agent.
2. The toughened photocurable adhesive according to claim 1, wherein the mass ratio of the first component to the second component is 1 (0.1-1), preferably 1 (0.45-0.65), and more preferably 1 (0.5-0.6).
3. The toughened photocurable adhesive according to claim 1 or 2, wherein the hydroxy acrylic resin is selected from any one of or a combination of at least two of solid thermoplastic hydroxy acrylates, hydroxy-containing polyurethane acrylates or hydroxy-containing polyester acrylates, preferably hydroxy-containing polyurethane acrylates.
4. The toughened photocurable adhesive according to any of claims 1-3 wherein the acrylate monomer is a hydroxy acrylate;
preferably, the hydroxyl acrylate comprises any one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, trimethylolpropane diacrylate or pentaerythritol triacrylate or a combination of at least two thereof.
5. The toughened photocurable adhesive according to any of claims 1-4 wherein the reactive nitrile rubber comprises any one or a combination of at least two of carboxyl-terminated nitrile rubber, amino-terminated nitrile rubber, epoxy-terminated nitrile rubber or vinyl-terminated nitrile rubber; preferably carboxyl-terminated nitrile rubber and/or vinyl-terminated nitrile rubber.
6. The toughened photocurable adhesive according to any one of claims 1-5, wherein the epoxy acrylic resin is selected from any one of or a combination of at least two of bisphenol A epoxy acrylate, acid-modified epoxy acrylate or amine-modified epoxy acrylate, preferably acid-modified epoxy acrylate and/or amine-modified epoxy acrylate.
7. The toughened photocurable adhesive according to any one of claims 1-6, wherein the mass percentage of the auxiliary agent is 0.1-1%, preferably 0.3-0.8%, based on 100% by mass of the first component;
preferably, the auxiliary agent is a silane coupling agent;
preferably, the silane coupling agent comprises any one or a combination of at least two of gamma-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltriethoxysilane, or vinyltrimethoxysilane;
preferably, the photoinitiator is selected from any one or a combination of at least two of 1173, 184, BP, TPO, 819, ITX or EDB, preferably the photoinitiator ITX.
Preferably, the isocyanate-based curing agent includes any one of or a combination of at least two of TDI, HDI, IPDI, HDI trimer or HDI biuret.
8. The method for preparing the toughened photocurable adhesive according to any of claims 1-7, wherein the method for preparing comprises:
a first component preparation comprising: sequentially adding epoxy acrylic resin, hydroxyl acrylic resin, reactive nitrile rubber and an acrylate monomer into a mixer, starting vacuum, stirring, and controlling the temperature to be less than or equal to 60 ℃ in the stirring process; then stopping stirring and cooling, adding a photoinitiator and an auxiliary agent under the irradiation of a light source with the wavelength of more than 500nm, and stirring to obtain a first component;
a second component preparation comprising: and defoaming the isocyanate curing agent to obtain a second component.
9. Use of the toughened photocurable adhesive according to any one of claims 1-7, which comprises: mixing the first component and the second component, coating the mixture on a substrate, and performing radiation curing under the illumination of a mercury lamp;
preferably, the substrate comprises glass or plastic.
10. Use of the toughened photocurable adhesive according to any one of claims 1-7 in the field of potting, structural bonding or thick coating.
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| CN117511494A (en) * | 2024-01-08 | 2024-02-06 | 山东德亿佳胶业有限公司 | High-transparency shadowless adhesive and preparation method thereof |
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| JP2016102215A (en) * | 2015-12-18 | 2016-06-02 | 大日本印刷株式会社 | Adhesive composition and adhesive film using the same |
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| CN117511494A (en) * | 2024-01-08 | 2024-02-06 | 山东德亿佳胶业有限公司 | High-transparency shadowless adhesive and preparation method thereof |
| CN117511494B (en) * | 2024-01-08 | 2024-03-22 | 山东德亿佳胶业有限公司 | High-transparency shadowless adhesive and preparation method thereof |
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