CN114369439B - Toughening type photo-curable adhesive, and preparation method and application thereof - Google Patents
Toughening type photo-curable adhesive, and preparation method and application thereof Download PDFInfo
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- CN114369439B CN114369439B CN202111434594.3A CN202111434594A CN114369439B CN 114369439 B CN114369439 B CN 114369439B CN 202111434594 A CN202111434594 A CN 202111434594A CN 114369439 B CN114369439 B CN 114369439B
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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 photo-curable adhesive, 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, acrylate monomer, reactive nitrile rubber, photoinitiator and auxiliary agent; the raw materials in the first component are mixed according to a specific proportion, the second component contains isocyanate curing agents, and the adhesive obtained by mixing the two specific components can realize normal-temperature UV rapid curing, has good deep curing effect, good durability and cracking resistance, and has excellent high-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 toughening type photo-curable adhesive, a preparation method and application thereof.
Background
The glued connection is widely applied because of the advantages of light weight, uniform stress distribution, no damage to the continuity of the glued piece, and the like; epoxy resin adhesives are commonly used adhesives, which are curing systems prepared from epoxy resin and curing agent in a certain proportion.
The molecular structure of the epoxy resin is characterized in that the molecular chain contains active epoxy groups, and the epoxy groups can be positioned at the tail end and the middle of the molecular chain. Because the molecular structure contains active epoxy groups, the epoxy groups can be subjected to crosslinking reaction with a curing agent to form insoluble high polymer with a reticular structure, so that the bonding effect is achieved; the traditional epoxy resin adhesive generally adopts a heat curing mode, when the epoxy resin adhesive is applied to the bonding of electronic components, the components are easy to damage by heating, the packaging efficiency is affected, the primary curing speed is low, and the production efficiency is low.
The photocuring mode can avoid thermal damage to components and base materials in the gluing process, but is greatly influenced by the composition of an adhesive system, and the problems of insufficient deep curing and incapability of curing a shadow area exist; in addition, the photo-cured product of the epoxy resin has the problems of high brittleness, impact resistance, vibration resistance and easy cracking; when the adhesive is applied to the bonding process of electronic components and substrates, the problems can leave great hidden danger for the durability of the bonding parts of the components and the substrates.
Therefore, it is still of great importance to develop an adhesive which has excellent durability and cracking resistance and can realize light curing at normal temperature, deep curing and good curing effect in shadow areas.
Disclosure of Invention
The invention aims to provide a toughening type photocurable 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, acrylate monomer, reactive nitrile rubber, photoinitiator and auxiliary agent; the raw materials in the first component are mixed according to a specific proportion, the second component contains isocyanate curing agents, and the adhesive obtained by mixing the two specific components can realize normal-temperature UV rapid curing, has good deep curing effect, good durability and cracking resistance, and has excellent high-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 aim of the invention, 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;
wherein, based on the mass of the first component as 100%, the raw materials of the first component are as follows:
the second component comprises an isocyanate-based curing agent.
The toughening type photocurable adhesive of the present invention comprises two components, wherein the mass percentage of the epoxy acrylic resin in the raw material of the first component is 20 to 60wt%, such as 22wt%, 25wt%, 28wt%, 30wt%, 32wt%, 35wt%, 38wt%, 40wt%, 42wt%, 45wt%, 48wt%, 50wt%, 52wt%, 55wt%, 58wt%, etc., the mass percentage of the hydroxyl acrylic resin is 20 to 60wt%, such as 22wt%, 25wt%, 28wt%, 30wt%, 32wt%, 35wt%, 38wt%, 40wt%, 42wt%, 45wt%, 48wt%, 50wt%, 52wt%, 55wt%, 58wt%, etc., the mass percentage of the acrylate monomer is 10 to 20wt%, such as 12wt%, 14wt%, 15wt%, 16wt%, or 18wt%, the mass percentage of the reactive nitrile rubber is 6 to 30wt%, such as 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 22wt%, 25wt%, 40wt%, 42wt%, 45wt%, 0.0.0.0 wt%, 0.1wt%, 2wt%, 0.1wt% of the light initiator is 0.0.5 wt%, or 0.0.1 wt%, or 0.0 wt%, based on the mass% of the first component being 100 wt%, the mass% of the first component, the raw material is 20 wt.
The traditional epoxy resin adhesive has the defects of long primary curing time, insufficient light curing depth, incapability of curing in shadow areas, high brittleness, no impact resistance and vibration resistance of a cured product, easiness in cracking and great hidden trouble on the durability of bonding parts; in order to overcome the technical problems, the invention develops the adhesive which has the advantages of high normal temperature photo-curing rate, good deep curing effect, good shadow area curing, excellent durability and cracking resistance, and the obtained adhesive has excellent high-low temperature cycle impact performance; the epoxy acrylic resin, the hydroxyl acrylic resin, the acrylic ester monomer, the reactive nitrile rubber, the photoinitiator and the auxiliary agent are adopted in the first component of the adhesive, and the components are matched according to a specific proportion, so that the obtained adhesive has rapid photocuring performance at normal temperature, the required curing energy is low, and the hydroxyl acrylic resin and the monomer in the first component are matched with the isocyanate curing agent in the second component, so that 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 is mutually cooperated with the components, so that good photo-curing effect is ensured, namely, the normal-temperature UV light rapid curing, good photo-curing depth and shadow area curing are realized, meanwhile, the durability and cracking resistance of a bonding part in the using process of the adhesive are further improved, and the high-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 and the isocyanate curing agent in the second component in the adhesive are matched, so that the rapid curing at normal temperature can be realized, and the deep curing and the curing effect of a shadow area 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, cracking resistance and high-low cycle impact resistance of the adhesive are further improved while the photocuring effect is ensured.
The speed of photocuring of the adhesive can reach 3s for 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 shearing strength of the cured adhesive to glass is more than 13MPa.
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., further preferably 1 (0.5 to 0.6).
In the adhesive, the proportion of the first component and the second component meets the range, which is favorable for realizing rapid curing at normal temperature and can ensure the curing depth and the curing effect of a shadow area; 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 to 0.65); within this range, the curing effect is better, and the durability, cracking resistance and high and low temperature impact resistance are better.
Preferably, the hydroxy acrylic resin is selected from any one or a combination of at least two of solid thermoplastic hydroxy acrylate, hydroxy urethane acrylate or hydroxy polyester acrylate, preferably hydroxy urethane acrylate.
The hydroxyl acrylic resin adopted in the adhesive is not only beneficial to realizing normal-temperature photo-curing and ensuring the curing depth, but also has important significance for improving the durability, cracking resistance and high-low temperature impact resistance of the adhesive; the hydroxyl acrylic resin is preferably selected from the three types, and the durability, cracking resistance and high and low temperature impact resistance of the corresponding bonding part are optimal. The hydroxyl-containing polyurethane acrylate is further preferable, 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 matching with other components in the adhesive, thereby ensuring the requirement of the durability of the bonding part.
The bi-component adhesive composition provided by the invention has good flexibility and impact resistance under the conditions of normal temperature and low temperature. After 10 times of circulation at the high and low temperature of between 40 ℃ below zero and 80 ℃, no cracking phenomenon occurs, 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 type hydroxy acrylate is solid hydroxy acrylate with better miscibility with light-cured monomer and resin, preferably ester soluble solid hydroxy acrylate, and more preferably at least one of Mantis AC160, AC162, AC169, japanese Mitsubishi BR113 or BR 106.
Preferably, the hydroxyl-containing polyurethane acrylate is a UV polyurethane resin containing hydroxyl and acrylate structures at the same time, and is preferably any one or a combination of at least two of Lan Kelu L-8468, L-6906 and Bayer dual-curing UV resin LS 2396.
Preferably, the hydroxyl-containing polyester acrylate is a modified UV polyester resin, preferably Lan Kelu L-8460 and/or tripod AD7001.
Preferably, the acrylate monomer is a hydroxyacrylate.
The acrylate monomer in the adhesive is preferably hydroxy acrylate, and is matched with the hydroxy acrylic resin and the isocyanate curing agent in the second component, so that the adhesive has important significance for improving the normal-temperature photo-curing 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 hydroxy acrylate includes any one or a combination of at least two of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, trimethylolpropane diacrylate or pentaerythritol triacrylate, and the combination includes, as an example, 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, etc.
Preferably, the reactive nitrile rubber comprises any one or a combination of at least two of carboxyl terminated nitrile rubber (CTBN), amino terminated nitrile rubber (ATBN), epoxy terminated nitrile rubber (ETBN) or vinyl terminated nitrile rubber (VTBN); the combination illustratively includes a combination of a carboxyl terminated nitrile rubber and an amino terminated nitrile rubber, a combination of an epoxy terminated nitrile rubber and a vinyl terminated nitrile rubber, and the like; preferably a carboxyl terminated nitrile rubber and/or a vinyl terminated nitrile rubber.
The reaction type nitrile rubber in the invention preferably adopts the components, and has important significance for realizing excellent durability, cracking resistance and high-low temperature cycle impact resistance of the adhesive; the adhesive is matched with other components in the adhesive, so that excellent normal-temperature photo-curing performance can be realized, the curing depth effect is good, and the obtained adhesive is good in durability, cracking resistance and high-low temperature cycle impact resistance; and further preferred are carboxyl terminated nitrile rubbers and/or vinyl terminated nitrile rubbers.
Preferably, the epoxy acrylic resin is selected from any one 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, etc.; acid-modified epoxy acrylates and/or amine-modified epoxy acrylates are preferred.
In the adhesive, the epoxy acrylic resin is matched with other components, so that the normal-temperature photo-curing effect, the curing depth and the shadow area curing effect are better, the durability, the cracking resistance and the high-low temperature cycle impact resistance of the adhesive are better, and the acid modified epoxy acrylate and/or the amine modified epoxy acrylate are further preferable.
Preferably, the acid modified epoxy acrylate is any one or a combination of at least two of succinic acid modified epoxy acrylate, glutaric acid modified epoxy acrylate and adipic acid modified epoxy acrylate.
Preferably, the amine modified epoxy acrylate is fatty amine modified epoxy acrylate, preferably any one or a combination of at least two of keda 4100, zhongshan thousand leaf UV1101 and boxing B151.
Preferably, 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% or 0.9% by mass, based on 100% by mass of the first component, and preferably 0.3 to 0.8%.
Preferably, the auxiliary agent is a silane coupling agent.
The adhesive of the invention is added with a silane coupling agent as an auxiliary agent, and the silane coupling agent can generate certain binding force with polar substances and nonpolar substances at the same time, and is characterized in that the molecules are provided with polar and nonpolar parts at the same time, and a molecular bridge can be erected between interfaces of inorganic substances and organic substances by using the silane coupling agent, so that two materials with completely different properties are connected together, thereby effectively improving the bonding strength of an interface layer.
Preferably, the silane coupling agent comprises any one or a combination of at least two of gamma-aminopropyl triethoxysilane (KH-550), gamma-methacryloxypropyl trimethoxysilane HDI (KH-570), gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane (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 photoinitiator ITX.
Preferably, the isocyanate-based curing agent comprises any one or a combination of at least two of TDI, HDI, IPDI, HDI trimer or HDI biuret.
The second component in the adhesive adopts the isocyanate curing agent, and the isocyanate curing agent has the functions of the resin containing hydroxyl groups in the first component, the monomer and the like, can realize normal-temperature curing, has good curing effect in a curing depth and shadow area, has good toughness, and meets the requirements of durability, cracking resistance and high-low temperature impact resistance.
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, hydroxy acrylic resin, reactive nitrile rubber and acrylate monomer into a mixer, starting vacuum, stirring, and controlling the temperature in the stirring process to be less than or equal to 60 ℃; then stopping stirring and cooling, adding the photoinitiator and the 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 is prepared comprising: and (3) 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 are mixed and then coated on a substrate, and radiation-cured under mercury lamp illumination.
Preferably, the substrate comprises glass or plastic.
In a fourth aspect, the present invention provides the use of a toughened photo-curable adhesive according to the first aspect for potting, structural bonding or thick coating applications.
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, so that the adhesive can be rapidly cured by light at normal temperature, and the depth curing can reach more than 20 mm;
(2) The adhesive has good high-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 scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a toughening type light-curable adhesive, which comprises a first component and a second component in a mass ratio of 1:0.5;
wherein, based on the mass of the first component as 100%, the raw materials of the first component are as follows:
the second component is TDI;
among the above components: bisphenol A epoxy acrylate is Boxing B-100M;
the hydroxyl-containing polyurethane acrylate is Lan Kelu L-8468;
carboxyl terminated nitrile rubber (CTBN) is a company of the dow chemical company;
2-isopropyl thioxanthone ITX is selected from Tianjin Jiuzu New Material Co., ltd;
KH-550 is selected from Nanjing full-chemical industry Co., ltd;
TDI is selected from Cangzhou university, inc.
The preparation method of the adhesive comprises the following steps:
preparing a first component: comprising the following steps: sequentially adding bisphenol A epoxy acrylate, hydroxyl-containing polyurethane acrylate, carboxyl-terminated nitrile rubber (CTBN) and hydroxyethyl acrylate into a double planetary vacuum mixer, starting vacuum, stirring at high speed for 80min, and controlling the temperature to be not more than 60 ℃; stopping stirring until the temperature of the glue solution is reduced to 20-25 ℃, turning off an illumination fluorescent lamp and a device window observation lamp, turning on a long-wavelength light source with the wavelength of more than 500nm, adding 2-isopropylthioxanthone ITX and KH-550, stirring for 80min in vacuum, controlling the temperature to 20-25 ℃, and stirring uniformly to obtain a first component;
and (3) preparing a second component: and (3) defoaming the isocyanate curing agent, and then canning the defoamed isocyanate curing agent into a dry anhydrous container.
Example 2
This example differs from example 1 in that the raw materials of the first component are:
wherein the succinic acid modified epoxy acrylate is selected from the new material science and technology limited company of Boxing, guangzhou; the solid thermoplastic hydroxyacrylate is selected from the group consisting of Mantaisi AC160, germany; the photoinitiator ITX is selected from Tianjin Sunday New Material Co.Ltd; KH-560 is selected from Nanjing full-chemical industry Co., ltd.
Example 3
This example differs from example 1 in that the raw materials of the first component are:
wherein the amine modified epoxy acrylate is selected from Keta 4100, the hydroxyl-containing polyester acrylate is selected from Lan Kelu L-8460, the hydroxyethyl methacrylate is selected from Jiangsu Yuchang chemical industry Co., ltd, the epoxy terminated nitrile rubber is selected from Beijing Dewote chemical CHX100, the 2-isopropyl thioxanthone ITX and the A-151 are selected from Tianjin Jiuzu New material Co., ltd.
Example 4
This example differs from example 1 in that the mass of hydroxyl-containing urethane acrylate is replaced by a solid thermoplastic type hydroxyl acrylate, and other parameters and conditions are exactly the same as in example 1.
Wherein the solid thermoplastic hydroxyacrylate is selected from the group consisting of Mantaisi AC160, germany.
Example 5
This example differs from example 1 in that the equivalent mass of photoinitiator ITX is replaced by photoinitiator EDB, and other parameters and conditions are exactly the same as in example 1.
Wherein the photoinitiator EDB is selected from Tianjin Jiuzu New material Co.
Example 6
This example differs from example 1 in that the mass of hydroxyethyl acrylate is replaced by pentaerythritol triacrylate, and other parameters and conditions are exactly the same as in example 1.
Among them, pentaerythritol triacrylate is selected from Changxing chemical industry Co., ltd.
Example 7
This example differs from example 1 in that the mass of the carboxyl terminated nitrile rubber (CTBN) is replaced by the amino terminated nitrile rubber (ATBN), and other parameters and conditions are exactly the same as in example 1.
Wherein the amino terminated nitrile rubber (ATBN) is selected from BFGoodrich.
Example 8
This example differs from example 1 in that KH-550 is replaced by bisphenol A epoxy acrylate, i.e. the adhesive contains no auxiliary agent, and other parameters and conditions are exactly the same as in example 1.
Example 9
This example differs from example 1 in that the equimolar amount of TDI in the second component is replaced by HDI, and other parameters and conditions are exactly the same as in example 1.
Wherein the HDI is selected from Wanhua chemical group Co.
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 hydroxyl groups, and other parameters and conditions are exactly the same as in example 1.
Example 11
This comparative example differs from example 1 in that the mass of hydroxyethyl acrylate is replaced by hydroxypropyl acrylate, and other parameters and conditions are exactly the same as in example 1.
Wherein the hydroxypropyl acrylate is selected from Jiangsu Yuchang chemical Co., ltd.
Comparative example 1
This comparative example differs from example 1 in that the equivalent mass of hydroxyl-containing urethane acrylate is replaced by bisphenol a epoxy acrylate, i.e., no hydroxyl-containing urethane acrylate is added, and other parameters and conditions are exactly the same as in example 1.
Comparative example 2
This comparative example differs from example 1 in that the equivalent mass of bisphenol A epoxy acrylate is replaced by hydroxyl-containing urethane acrylate, i.e., bisphenol A epoxy acrylate is not added, and other parameters and conditions are exactly the same as in example 1.
Comparative example 3
This comparative example differs from example 1 in that the mass of the carboxyl terminated nitrile rubber (CTBN) is replaced with nano titanium dioxide, and other parameters and conditions are exactly the same as in example 1.
Wherein the nano titanium dioxide is selected from winning.
Performance test:
the UV deep curing effect is tested by the following steps: casting the test sample into a tubular container, and irradiating with mercury lamp to obtain a cured product with a curing energy of 5000MJ/cm 2 After being placed for 12 hours at normal temperature, the curing depth is tested; the test results are shown in table 1; here, normal temperature in the test means 25 ℃;
cracking resistance test: taking each group of adhesives, casting by using a mould, completely curing under the irradiation of a mercury lamp to obtain long-strip-shaped samples with the width multiplied by the thickness multiplied by 10mm multiplied by 2mm, correspondingly manufacturing 4 samples for each group of adhesives, putting into a cold and hot impact tester, taking the high temperature multiplied by 1h at 80 ℃, the low temperature multiplied by 1h at 40 ℃ and the low temperature multiplied by 1h as one cycle, and taking out to observe whether the appearance of the samples has cracking phenomenon or not after 10 continuous cycles.
High and low temperature impact tensile strength test: taking each group of adhesives, casting by using a mould, completely curing 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 into a cold and hot impact tester, taking out and placing into a normal temperature after the adhesives are continuously circulated for 10 times at the high temperature of 80 ℃ multiplied by 1h and the low temperature of-40 ℃ multiplied by 1h, and testing the tensile strength by using a tensile machine after taking out and placing into the normal temperature. The experimental results are expressed as arithmetic mean of tensile strength.
TABLE 1
| Depth of cure thickness, mm | High and low temperature impact tensile strength, MPa | Whether or not cracking after 10 cycles at 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 of the table, the adhesive provided by the invention has the characteristics of good deep curing effect, excellent durability, cracking resistance and high and low temperature impact resistance, and in contrast, the test results in comparative examples 1-3 do not have the characteristics.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (18)
1. A toughened, photocurable adhesive, wherein said adhesive comprises a first component and a second component;
wherein, based on the mass of the first component as 100%, the raw materials of the first component are as follows:
the second component comprises an isocyanate-based curing agent;
the mass ratio of the first component to the second component is 1 (0.1-1), and the acrylic ester monomer is hydroxy acrylic ester;
the hydroxy acrylic resin is selected from any one or a combination of at least two of solid thermoplastic hydroxy acrylic ester, hydroxy polyurethane acrylic ester or hydroxy polyester acrylic ester;
the hydroxy acrylic ester comprises any one or a combination of at least two of hydroxyethyl acrylic ester, hydroxyethyl methacrylate, hydroxybutyl acrylic ester or trimethylolpropane diacrylate;
the epoxy acrylic resin is selected from any one or a combination of at least two of bisphenol A epoxy acrylate, acid modified epoxy acrylate or amine modified epoxy acrylate.
2. The toughened photocurable adhesive as claimed in claim 1, wherein the mass ratio of said first component to said second component is 1 (0.45 to 0.65).
3. The toughened photocurable adhesive as claimed in claim 2, wherein the mass ratio of said first component to said second component is 1 (0.5 to 0.6).
4. The toughened photocurable adhesive as claimed in claim 1 wherein said hydroxy acrylic resin is a hydroxy containing urethane acrylate.
5. The toughened photocurable adhesive as claimed in claim 1 wherein said reactive nitrile rubber comprises any one or a combination of at least two of a carboxyl terminated nitrile rubber, an amino terminated nitrile rubber, an epoxy terminated nitrile rubber or a vinyl terminated nitrile rubber.
6. The toughened photocurable adhesive as claimed in claim 5, wherein said reactive nitrile rubber is a carboxyl terminated nitrile rubber and/or a vinyl terminated nitrile rubber.
7. The toughened photocurable adhesive as claimed in claim 6, wherein said epoxy acrylic resin is an acid modified epoxy acrylate and/or an amine modified epoxy acrylate.
8. The toughening photocurable adhesive according to claim 1, wherein the auxiliary agent is 0.1 to 1% by mass based on 100% by mass of the first component.
9. The toughening photocurable adhesive according to claim 8, wherein the auxiliary agent is 0.3 to 0.8% by mass based on 100% by mass of the first component.
10. The toughened photocurable adhesive as claimed in claim 1, wherein said adjuvant is a silane coupling agent.
11. The toughened photo-curable adhesive as claimed in claim 10 wherein said silane coupling agent comprises any one or a combination of at least two of gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane, vinyltriethoxysilane or vinyltrimethoxysilane.
12. The toughened photocurable adhesive as claimed in claim 1 wherein said photoinitiator is selected from any one or a combination of at least two of 1173, 184, BP, TPO, 819, ITX or EDB.
13. The toughened photocurable adhesive as claimed in claim 12, wherein said photoinitiator is photoinitiator ITX.
14. The toughened photocurable adhesive as claimed in claim 1, wherein said isocyanate-based curing agent comprises any one or a combination of at least two of TDI, HDI, IPDI, HDI trimer or HDI biuret.
15. The method of preparing a toughened photocurable adhesive as recited in claim 1, wherein said method of preparing comprises:
a first component preparation comprising: sequentially adding epoxy acrylic resin, hydroxy acrylic resin, reactive nitrile rubber and acrylate monomer into a mixer, starting vacuum, stirring, and controlling the temperature in the stirring process to be less than or equal to 60 ℃; then stopping stirring and cooling, adding the photoinitiator and the 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 is prepared comprising: and (3) defoaming the isocyanate curing agent to obtain a second component.
16. The method of using a toughened photocurable adhesive as recited in claim 1, said method of using comprising: the first component and the second component are mixed and then coated on a substrate, and radiation-cured under mercury lamp illumination.
17. The method of claim 16, wherein the substrate comprises glass or plastic.
18. Use of the toughened photo-curable adhesive as claimed in claim 1 for potting, structural bonding or thick coating applications.
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| CN111040646A (en) * | 2019-12-27 | 2020-04-21 | 烟台德邦科技有限公司 | Acrylate adhesive of room-temperature fast-curing low-shrinkage hybrid system and preparation method thereof |
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