CN111205810A - Photo-thermal dual-curing adhesive and preparation method thereof - Google Patents
Photo-thermal dual-curing adhesive and preparation method thereof Download PDFInfo
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- CN111205810A CN111205810A CN202010143100.5A CN202010143100A CN111205810A CN 111205810 A CN111205810 A CN 111205810A CN 202010143100 A CN202010143100 A CN 202010143100A CN 111205810 A CN111205810 A CN 111205810A
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- diisocyanate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
Abstract
The photo-thermal dual-curing adhesive prepared by the invention is composed of the following raw materials in percentage by weight: 20-40% of modified resin with oxetanyl and isocyanate groups on one molecule, 20-40% of polyester polyurethane modified acrylate resin, 20-40% of acrylate monomer, 1-5% of free radical photoinitiator, 1-5% of free radical thermal initiator and 3-10% of latent amine curing agent. The photo-thermal dual-curing adhesive prepared by the invention has the advantages of better storage stability, high bonding strength, better high temperature and high humidity resistance and wide application range.
Description
Technical Field
The invention belongs to the field of photocuring materials, and relates to a photo-thermal dual-curing adhesive and a preparation method thereof, which are suitable for application in the field of electronics.
Background
The photo-curing adhesive has the advantages of high curing speed, environmental friendliness, low energy consumption, no solvent volatilization and the like, so that the photo-curing adhesive is widely researched and is rapidly popularized in various industries. However, the photo-curing adhesive also has its own limitations, the semi-transparent material or the shading part of the assembly absorbs, blocks and reflects ultraviolet light, the initiation efficiency of the photo-initiator is not high, the adhesive is not easy to be cured completely, and the mechanical property of the adhesive layer of the adhesive is greatly reduced.
To overcome the disadvantage of the inability to cure the shadow portion during photopolymerization, researchers have developed dual cure systems that combine photocuring with other curing approaches. In dual cure systems, the crosslinking or polymerization of the system is accomplished by two separate stages having different reaction principles, one of which is through a photocuring reaction and the other of which is through a dark reaction, including thermal, moisture, oxygen, or anaerobic curing reactions, and the like. Thus, the system can be rapidly set or achieve surface dry by photo-curing, and the shadow part or the bottom part is completely cured by dark reaction, so that the system is completely dry.
Disclosure of Invention
In order to solve the problem of poor curing of the ultraviolet curing adhesive in the shadow part in the prior art, the invention provides the adhesive capable of photo-thermal dual curing and the preparation method thereof, so that the ultraviolet curing adhesive can meet the requirement of curing the shadow part.
The technical scheme for solving the technical problems is as follows:
a photo-thermal dual-curing adhesive is composed of the following raw materials in percentage by weight: 20-40% of modified resin with oxetanyl and isocyanate groups on one molecule, 20-40% of polyester polyurethane modified acrylate resin, 20-40% of acrylate monomer, 1-5% of free radical photoinitiator, 1-5% of free radical thermal initiator and 3-10% of latent amine curing agent.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the modified resin having both an oxetanyl group and an isocyanate group in one molecule is a polymer resin obtained by reacting 3-ethyl-3-oxetanemethanol with a diisocyanate, and the structural formula is represented by the following general formula (I):
wherein: r represents a part which does not contain isocyanate in the molecular structure of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) or Hexamethylene Diisocyanate (HDI).
The synthesis method comprises the following steps: 116g of 3-ethyl-3-oxetanemethanol (cas: 3047-32-3), 174g of diisocyanate and 0.01g of dibutyltin dilaurate serving as a catalyst are added into a three-neck flask with a thermometer, the temperature is increased to 65 ℃, the temperature is controlled to be 70-75 ℃, and the reaction lasts for 2-3 hours. And analyzing the NCO group by an infrared spectrometer, and stopping heating reaction when the NCO peak is unchanged to obtain the modified resin simultaneously having the oxetanyl group and the isocyanate group. The reaction formula is as follows:
wherein: r represents a part which does not contain isocyanate in the molecular structure of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) or Hexamethylene Diisocyanate (HDI).
The diisocyanate comprises: toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) or Hexamethylene Diisocyanate (HDI), and the like, and any mixture thereof.
Further, the polyester urethane acrylate resin refers to a polyester urethane acrylate resin synthesized by using polyester diol, diisocyanate and hydroxyl acrylate, wherein the polyester diol comprises: adipic acid polyester diol, polycaprolactone diol, polycarbonate diol and the like, wherein the diisocyanate comprises: toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) or Hexamethylene Diisocyanate (HDI), and the like, and any mixture thereof. The synthesis method of the polyester polyurethane acrylate resin comprises the following steps: firstly, 1 mol of polyester diol, 2 mol of diisocyanate and a catalyst dibutyltin dilaurate (20ppm) are added into a three-neck flask with a thermometer, the temperature is controlled at 70-75 ℃, the reaction is carried out for 2 hours, then 2 mol of hydroxy acrylate as a blocking agent and p-hydroxyanisole (500ppm) as a polymerization inhibitor are added, the reaction is carried out for 2-3 hours at 70-75 ℃, an infrared spectrometer is used for analyzing the content of NCO groups, and the heating reaction is stopped when the peak of NCO is completely disappeared, so that the polyester type polyurethane acrylate resin is obtained. The polyester urethane acrylate resin includes: CN966J75, CN996, CN8888 and the like of Saedoma, 843S and the like of DYMAX, U379, U299 and the like of Yongxing chemical.
Further, the acrylate monomer comprises one or a mixture of any more of tetrahydrofuran acrylate (THFA), Lauryl Acrylate (LA), hydroxyethyl acrylate (HEA), isobornyl acrylate (IBOA), 1.6 hexanediol diacrylate (HDDA), pentaerythritol triacrylate (PETA).
Further, the radical photoinitiator is one or a mixture of any of trade marks 1173 (2-hydroxy-2-methyl-1-phenyl acetone), 184 (1-hydroxycyclohexyl phenyl ketone), 907 (2-methyl-1- (4-methylmercaptophenyl) -2-morpholine-1-one), 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone), 819 (bis (2,4, 6-trimethylbenzoyl) phenylphosphorus oxide), 651(α' -dimethylbenzyl ketal), ITX (isopropyl thioxanthone), BP (benzophenone), OMBB (methyl o-benzoylbenzoate), TPO (2,4, 6-trimethylbenzoyldiphenyl phosphorous oxide).
Further, the free radical thermal initiator is an azo compound and an organic peroxide, wherein the azo compound comprises one or a mixture of any more of 2, 2 ' -azobis (isobutyronitrile), 2, 2 ' -azobis (2, 4-dimethylvaleronitrile), 2, 2 ' -azobis (2-methylbutyronitrile) and the like; the organic peroxide comprises one or a mixture of any more of benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, methyl ethyl ketone peroxide, 1, 1-di (tert-hexylperoxy) cyclohexane and the like.
Further, the latent amine curing agent is an imidazole compound, an amine-epoxy polymer (a reaction product of an amine compound and an epoxy compound) and an amine-isocyanate polymer (a reaction product of an amine compound and an isocyanate compound); the imidazole compound includes 2-heptadecylimidazole, 2-phenyl-4, 5-dimethylol imidazole, 2-undecyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 2-phenyl-4-benzyl-5-hydroxymethyl imidazole, etc.; amine-epoxy polymers include, Amicure PN-23, Amicure PN-40, Amicure PN-50, Amicure PN-H (produced by Aomoto Fine technologies, Inc.); the amine-isocyanate compound includes "Fujicure FXE-1000, Fujicure FXR-1030 (produced by Fuji chemical Co., Ltd.), and the like.
The preparation method of the photo-thermal dual-curing adhesive comprises the following steps: 20-40% of modified resin with oxetanyl and isocyanate groups on one molecule, 20-40% of polyurethane modified acrylate resin, 20-40% of acrylate monomer, 1-5% of free radical photoinitiator, 1-5% of free radical thermal initiator and 3-10% of latent amine curing agent are sequentially added into a stirrer, stirred for 0.5-2 hours at 500-1000 rpm, vacuumized to the vacuum degree of-0.08-0.05 MPa, stirred uniformly, naturally aired to room temperature, and sealed and packaged.
The invention has the beneficial effects that: the photo-thermal dual-curing adhesive prepared by the invention contains three reaction structures of oxetane group, acrylate group and isocyanate group in a formula, and has photo-curing and thermosetting functions by utilizing the thermosetting characteristics of the oxetane group, the isocyanate group and the acrylate group and the photo-curing characteristics of the acrylate group, so that the adhesive in a shadow part can be fully cured by heating, and the strength after curing and the high-temperature high-humidity reliability are higher.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Examples of synthesis of a modified resin having both an oxetanyl group and an isocyanate group in one molecule:
adding 116g of 3-ethyl-3-oxetanemethanol (cas: 3047-32-3), 174g of toluene diisocyanate TDI, and 0.01g of dibutyltin dilaurate serving as a catalyst into a three-neck flask with a thermometer, heating to 65 ℃, controlling the temperature at 70-75 ℃, and reacting for 2-3 h; and analyzing the NCO group by using an infrared spectrometer, and stopping heating reaction when the NCO peak is unchanged to obtain the modified resin simultaneously having the oxetanyl group and the isocyanate group.
Example 1
Accurately weighing 30g of modified resin which simultaneously has oxetanyl and isocyanate groups; sandoma CN996, 30 g; THFA, 30 g; 184, 3g of free radical photoinitiator; the curing agent comprises a free radical thermal initiator BPO (bisphenol A), 2g and a latent amine curing agent PN-407 g; sequentially adding the components into a double-planetary power mixing stirrer, vacuumizing to the vacuum degree of-0.08 MPa, stirring at 500 rpm for 2 hours, uniformly stirring, naturally airing to room temperature to obtain the ultraviolet curing adhesive, and sealing and packaging.
Example 2
Accurately weighing 20g of modified resin which simultaneously has oxetanyl and isocyanate groups and is prepared by the following steps; sandoma CN966J75, 40 g; IBOA, 30 g; 1g of free radical photoinitiator TPO; the curing agent comprises a free radical thermal initiator BPO (bisphenol A), 5g and a latent amine curing agent PN-503 g; sequentially adding the components into a double-planetary power mixing stirrer, vacuumizing to the vacuum degree of-0.05 MPa, stirring at 750 revolutions per minute for 1 hour, uniformly stirring, naturally airing to room temperature to obtain the ultraviolet curing adhesive, and sealing and packaging.
Example 3
Accurately weighing 40g of modified resin which simultaneously has oxetanyl and isocyanate groups and is prepared by the following steps; sandoma CN996, 20 g; LA, 30 g; 184, 5g of free radical photoinitiator; 2g of free radical thermal initiator AIBN, and 10307 g of latent amine curing agent FXR; sequentially adding the components into a double-planetary power mixing stirrer, vacuumizing to the vacuum degree of-0.06 MPa, stirring at 700 rpm for 1.5 hours, uniformly stirring, naturally airing to room temperature to obtain the ultraviolet curing adhesive, and sealing and packaging.
Example 4
Accurately weighing 30g of modified resin which simultaneously has oxetanyl and isocyanate groups; u384, 40g of Yangxing chemistry; HDDA, 20 g; free radical photoinitiator 651, 3 g; 2g of free radical thermal initiator AIBN, and 10007 g of latent amine curing agent FXR; sequentially adding the components into a double-planetary power mixing stirrer, vacuumizing to the vacuum degree of-0.07 MPa, stirring at 800 rpm for 1 hour, uniformly stirring, naturally airing to room temperature to obtain the ultraviolet curing adhesive, and sealing and packaging.
Example 5
Accurately weighing 40g of modified resin which simultaneously has oxetanyl and isocyanate groups and is prepared by the following steps; 843 resin from DYMAX, 20 g; IBOA, 30 g; 184, 5g of free radical photoinitiator; the curing agent comprises a free radical thermal initiator BPO (bisphenol A), 2g and a latent amine curing agent PN-407 g; sequentially adding the components into a double-planetary power mixing stirrer, vacuumizing to the vacuum degree of-0.08 MPa, stirring at 1000 rpm for 0.5 hour, uniformly stirring, naturally airing to room temperature to obtain the ultraviolet curing adhesive, and sealing and packaging.
Comparative example 1
Accurately weighing raw materials, CN966J75 (bifunctional, polyester type) of Saedoma, 52 g; IBOA, 44 g; 20g of mercaptan TMMP; photoinitiator 184, 3 g; photoinitiator TPO, 1 g; a latent amine curing agent PN-40; sequentially adding the components into a double-planetary power mixing stirrer, vacuumizing to the vacuum degree of-0.08 MPa, stirring at 500 rpm for 2 hours, uniformly stirring, naturally airing to room temperature to obtain the ultraviolet curing adhesive, and sealing and packaging.
Comparative example 2
The following raw materials, 6363 (bifunctional, polyether type) from corning, 55 g; THFA, 41 g; mercaptan PETMP, 32 g; photoinitiator 1173, 3 g; photoinitiator TPO, 1 g; latent amine curing agent FXR-10307 g; sequentially adding the components into a double-planetary power mixing stirrer, vacuumizing to the vacuum degree of-0.05 MPa, stirring at 750 revolutions per minute for 1 hour, uniformly stirring, naturally airing to room temperature to obtain the ultraviolet curing adhesive, and sealing and packaging.
The properties of a photo-thermally dual curable adhesive of the present invention were tested by the following tests.
Test examples
And (3) photocuring conditions: the light intensity is 30mW/cm2Illumination time 100 s;
and (3) testing the shear strength: universal tester, substrate: PC and ABS
And (3) viscosity testing: HAKKE viscometer, 25 degree, 20 revolutions
The test results are shown in table 1:
TABLE 1 comparative test results of the performance of samples prepared in examples 1-5 with conventional light-cured adhesives
From the results, compared with the existing common photo-curing adhesive, the photo-thermal dual-curing adhesive has good storage stability and better mechanical property retention rate after high temperature and high humidity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. The photo-thermal dual-curing adhesive is characterized by comprising the following raw materials in percentage by weight: 20-40% of modified resin with oxetanyl and isocyanate groups on one molecule, 20-40% of polyester polyurethane modified acrylate resin, 20-40% of acrylate monomer, 1-5% of free radical photoinitiator, 1-5% of free radical thermal initiator and 3-10% of latent amine curing agent;
the modified resin having both an oxetanyl group and an isocyanate group in one molecule has a structural formula represented by the following general formula (I):
wherein: r represents toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate, and the molecular structure of the toluene diisocyanate, the isophorone diisocyanate, the diphenylmethane diisocyanate or the hexamethylene diisocyanate does not contain isocyanate.
2. The photo-thermal dual-curable adhesive according to claim, wherein the modified resin having both an oxetanyl group and an isocyanate group in one molecule is synthesized by: adding 116g of 3-ethyl-3-oxetanemethanol, 174g of diisocyanate and 0.01g of dibutyltin dilaurate serving as a catalyst into a three-neck flask with a thermometer, heating to 65 ℃, controlling the temperature to be 70-75 ℃, and reacting for 2-3 h; analyzing NCO groups by an infrared spectrometer, and stopping heating reaction when the NCO peak is unchanged to obtain modified resin simultaneously having oxetanyl and isocyanate groups;
the diisocyanate comprises: one or a mixture of any several of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate.
3. The photo-thermal dual-curable adhesive according to claim, wherein the polyester urethane acrylate resin is synthesized by the following steps: firstly, adding 1 mole of polyester diol, 2 moles of diisocyanate and a catalyst dibutyltin dilaurate into a three-necked flask with a thermometer at the dosage of 20ppm, controlling the temperature at 70-75 ℃, reacting for 2 hours, then adding 2 moles of hydroxy acrylate and a polymerization inhibitor p-hydroxyanisole as a blocking agent at the dosage of 500ppm and 70-75 ℃, reacting for 2-3 hours, analyzing the content of NCO groups by using an infrared spectrometer, and stopping heating reaction when the peak of NCO completely disappears to obtain polyester type polyurethane acrylate resin;
the polyester diol comprises: adipic acid-based polyester diol, polycaprolactone diol, and polycarbonate diol, wherein the diisocyanate comprises: one or a mixture of any several of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate.
4. The photo-thermal dual-curable adhesive according to claim, wherein the acrylate monomer comprises one or a mixture of any of tetrahydrofuran acrylate, lauryl acrylate, hydroxyethyl acrylate, isobornyl acrylate, 1, 6 hexanediol diacrylate, pentaerythritol triacrylate, and the free radical photoinitiator is one or a mixture of any of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylmercapto phenyl) -2-morpholine-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinyl phenyl) -1-butanone, bis (2,4, 6-trimethylbenzoyl) phenyl phosphorus oxide, α ' -dimethylbenzyl ketal, isopropyl thioxanthone, benzophenone, methyl o-benzoylbenzoate, 2,4, 6-trimethylbenzoyl diphenyl phosphorus oxide, and the free radical photoinitiator is one or a mixture of any of 2, 2 ' -azobis (isobutyronitrile), 2, 2 ' -azobis (2, 4-dimethylvaleronitrile), 2, 2 ' -dimethylvaleronitrile, 2, 2 ' -dimethylbutyl hydroperoxide), 2, 1-di-tert-butyl hydroperoxide cumene hydroperoxide, and any of tert-butyl hydroperoxide.
5. The photo-thermal dual curable adhesive according to claim, wherein the latent amine curing agent comprises one of 2-heptadecylimidazole, 2-phenyl-4, 5-dimethylol imidazole, 2-undecyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 2-phenyl-4-benzyl-5-hydroxymethyl imidazole, Amicure PN-23, Amicure PN-40, Amicure PN-50, Amicure PN-H, Fujicure FXE-1000, Fujicure FXR-1030, manufactured by Kunstedt.
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| CN112143442A (en) * | 2020-09-29 | 2020-12-29 | 山东凯恩新材料科技有限公司 | Water-resistant high-temperature-resistant mixed acrylate flexible ultraviolet curing adhesive and preparation method thereof |
| CN113493654A (en) * | 2021-06-16 | 2021-10-12 | 烟台德邦科技股份有限公司 | Photo-thermal dual-curing adhesive and preparation method thereof |
| CN113980582A (en) * | 2021-10-08 | 2022-01-28 | 烟台德邦科技股份有限公司 | Light, heat and moisture curable adhesive and preparation method thereof |
| CN113980627A (en) * | 2021-11-08 | 2022-01-28 | 苏州凡络新材料科技有限公司 | Color-changing light-temperature dual-curing adhesive capable of changing color twice and preparation method thereof |
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| CN113980627A (en) * | 2021-11-08 | 2022-01-28 | 苏州凡络新材料科技有限公司 | Color-changing light-temperature dual-curing adhesive capable of changing color twice and preparation method thereof |
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