CN115595111B - Oil acid resistant UV-moisture dual-curing adhesive - Google Patents
Oil acid resistant UV-moisture dual-curing adhesive Download PDFInfo
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- CN115595111B CN115595111B CN202211336181.6A CN202211336181A CN115595111B CN 115595111 B CN115595111 B CN 115595111B CN 202211336181 A CN202211336181 A CN 202211336181A CN 115595111 B CN115595111 B CN 115595111B
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/67—Unsaturated compounds having active hydrogen
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- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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Abstract
The invention relates to an oil acid resistant UV-moisture dual-curing adhesive, which is prepared by optimizing and screening the components and the dosage proportion of the components. The invention screens the raw materials, adopts the raw materials with low volatility and low odor and small skin irritation, and is suitable for being used as the adhesive of the electronic components which are in long-term contact with the skin of a human body. The invention achieves excellent anti-oleic acid effect through the combined action of a plurality of factors, has no excessive loss of toughness of the adhesive and has good anti-falling performance.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to an oil acid resistant UV-moisture dual-curing adhesive.
Background
Compared with the common adhesive, the adhesive for electronic components needs to be cured rapidly to meet the production speed requirement of a production line, and generally uses a UV curing technology. However, because the electronic components often have special-shaped parts, because of the complicated three-dimensional structure and thickness, there is a non-illumination area which cannot be reached by UV irradiation, the required strength is difficult to reach by a single UV irradiation curing mode, at present, the dual curing of UV and moisture is mostly adopted, at first, a certain initial adhesion strength is reached by UV irradiation, and in the air, secondary curing is carried out by means of moisture in the air, so that the bonding strength is increased.
Along with popularization and diversification of electronic products, people cannot leave various electronic consumer products in daily life, many electronic consumer products are contacted with human bodies for a long time and used for a long time, and grease and sweat generated by the human bodies in the process can lead the structures and sealing elements of the electronic products to form corrosion and erosion and even generate local electrochemical reaction, so that the bonding and sealing failure of the structures of the electronic products are caused in a short time, and the service life of the electronic products is influenced. Taking the currently most popular TWS (True Wireless Stereo, truly infinite stereo) earphone as an example, the earphone is worn in the auditory canal and is contacted with the auditory canal of a human body for a long time, and the influence of the secretion of the auditory canal and the grease of the human body on the structure and the sealing of the earphone cannot be ignored. Numerous manufacturers of TWS headphones have now recognized this problem and set clear oil acid soaking and aging requirements for glues, whereas traditional UV and UV moisture acrylic glues do not perform as well in terms of oil acid resistance.
For the adhesive for electronic components, besides the adhesive strength, the cured adhesive needs to have certain toughness to achieve good anti-falling performance, especially for some precisely assembled electronic components, such as TWS headphones, the falling of the adhesive may cause internal damage to affect the quality of the headphones, so that the adhesive needs to have excellent adhesive strength and sufficient toughness to improve the anti-falling performance. In the prior art, in order to accelerate the curing speed and strengthen the bonding strength and hardness, polyurethane acrylic ester raw materials with polyfunctional degree are generally adopted, and the curing speed and the bonding strength are improved, but relatively, the toughness is insufficient and the adhesive is not drop-resistant, which is a fatal defect for adhesives for electronic components, particularly TWS earphone adhesives
In addition, bluetooth headset is in the in-service use in-process, and long-term with human ear canal contact, and the skin of ear canal belongs to half inside skin, and is sensitive to the allergen, if TWS has the allergen to volatilize or leak out in the use, very easily arouse human ear canal allergy, appear red swelling, pain, serious can produce symptoms such as whole body anaphylactic reaction. Because the adhesive is also required to have low sensitization for such electronic products that need to be in contact with human skin for a long time, such as watches, health bracelets, cell phones, etc. In adhesives, unreacted monomers, reactive diluents, photoinitiators are potential allergens and it is desirable to eliminate as much as possible the risk of allergy.
The inventor discloses a UV moisture dual-curing adhesive for electronic components in the prior patent CN202211242943.6, which adopts specific acrylate monomers compounded by polyfunctional groups and monofunctional groups, isocyanate trimer and diisocyanate to prepare polyurethane acrylate A and polyurethane acrylate B respectively, and then the polyurethane acrylate A and polyurethane acrylate B are prepared with reactive diluent, photoinitiator and modified photoinitiator prepared from isophorone diisocyanate to prepare the adhesive capable of being cured quickly. However, the adhesive of the patent is not excellent enough in oleic acid resistance after feedback, and the adhesive strength is rapidly reduced under the soaking of oleic acid.
Patent CN112795350a discloses an oil-acid-resistant reactive polyurethane hot melt adhesive, in which the polyol adopts a special polyol structure of polycarbonate diol, polyester diol and polyether diol with special chain-breaking structure, so that the polarity and crosslinking density of the system are improved, and the corrosion to oleic acid can be resisted. On the one hand, the hot melt adhesive needs to be dispensed at a high temperature (120-150 ℃) and has high dispensing equipment requirement, and the adhesive needs to be attached to the outside for a long time (30-120 min) under the pressure of more than 0.1MPa after the adhesive is applied, so that the hot melt adhesive has proper initial adhesive strength. Is not suitable for the requirement of rapid curing of modern electronic devices. In addition, the method of the patent increases the crosslinking density in order to resist the erosion of oleic acid, and when the bonding strength and oleic acid resistance are achieved, part of toughness is inevitably lost, so that the anti-dropping performance of the adhesive is adversely affected. This is a fatal defect for high-precision electronic component adhesives like TWS headphones.
Therefore, it is important to develop an adhesive which is suitable for electronic components, particularly for precision electronic components such as TWS headphones, and has the advantages of low sensitization, good drop resistance, high bonding strength, good weather resistance and excellent comprehensive properties.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to obtain a precise electronic component adhesive (such as an adhesive specially suitable for TWS earphones and the like) which is in contact with human skin for a long time, can meet the requirements of the electronic component adhesive on bonding strength and toughness, has low sensitization and meets the requirements of oil acid aging resistance. In order to achieve the above object, the present invention provides the following technical solutions:
an oil acid resistant UV-moisture dual-curing adhesive comprises the following raw materials in parts by mass: 20-30 parts of polyurethane acrylic ester A,12-15 parts of polyurethane acrylic ester B,8-11 parts of reactive diluent, 1.1-1.4 parts of modified photoinitiator, 1-3 parts of thixotropic agent and 2-5 parts of silane coupling agent; the polyurethane acrylic ester A comprises the following preparation raw materials in parts by mass: 42-50 parts of isocyanate trimer, 10-15 parts of hydroxyl-containing acrylic ester, 13-18 parts of macromolecular dihydric alcohol and 7-10 parts of polysiloxane with side chains containing alkenyl terminal hydroxyl groups; the hydroxyl-containing acrylic ester comprises sorbitol (methyl) acrylate
The polyurethane acrylic ester B comprises the following preparation raw materials in parts by mass: 38-45 parts of diisocyanate, 11-15 parts of macromolecular dihydric alcohol, 8-12 parts of polysiloxane with side chains containing alkenyl terminal hydroxyl groups and 6-8 parts of acrylate with hydroxyl groups; the modified photoinitiator is a product obtained by reacting a hydroxyl-containing photoinitiator with isophorone diisocyanate.
Among the hydroxyl acrylic acid esters as the raw material of the hydroxyl acrylic acid ester A, sorbitol (meth) acrylate accounts for 2-5% of the total mass of the hydroxyl acrylic acid ester, preferably, sorbitol (meth) acrylate accounts for 3.8-4.8% of the total mass of the hydroxyl acrylic acid ester.
The inventor uses a small amount of polyhydroxy (methyl) acrylic acid sorbitol ester to achieve the purpose of increasing the crosslinking of polyurethane acrylic acid ester A, and meanwhile, the final toughness and other mechanical strength of the adhesive are not affected, and the oleic acid resistance and the grease resistance of the adhesive are obviously improved. After being soaked by oleic acid, the adhesive strength retention rate is very high. The content of polyhydroxy (methyl) acrylic ester in the hydroxy acrylic ester cannot be too high or too low, the toughness is affected by too high, and the anti-falling performance is reduced by the adhesive lacking the toughness; the content is too low to effectively play a role in oleic acid resistance.
The modified photoinitiator is a product obtained by reacting a hydroxyl-containing photoinitiator with isophorone diisocyanate (IPDI), the molar ratio of the hydroxyl-containing photoinitiator to the isophorone diisocyanate is 1:1-1.2, and the hydroxyl-containing photoinitiator is at least one selected from 2-hydroxy-2-methyl-1-phenyl-1-acetone (UV-1173) and hydroxycyclohexane benzophenone (UV-184).
The modified photoinitiator is prepared by a preparation method comprising the following steps: mixing IPDI and a photoinitiator containing hydroxyl, reacting for 1-2h under the protection of inert atmosphere at 30-40 ℃ in the dark, continuously heating to 40-60 ℃, reacting for 0.5-1h, cooling, and preserving in the dark to obtain the modified photoinitiator. Further, the photoinitiator contains a polymerization inhibitor in an amount of 100-500ppm.
The invention utilizes two isocyanate activities on isophorone diisocyanate to react with a photoinitiator containing hydroxyl to obtain a modified photoinitiator with one end containing NCO functional groups and the other end being a photoinitiation active group. The photo initiator in the adhesive can initiate double bond polymerization under UV irradiation, but the residual photo initiator becomes a potential allergen because of the complex structure of electronic components, the fast curing speed and the short illumination time, and the glue point can not ensure 100% of the received illumination. The invention creatively reacts the hydroxyl-containing photoinitiator with the IPDI to obtain the modified photoinitiator, and the activity of the photoinitiator and one NCO group are reserved after the reaction. In moisture curing, residual NCO groups can continue to participate in the moisture curing reaction, which can completely eliminate the potential risk of sensitization caused by small molecule photoinitiators that may remain. And the modified photoinitiator of the present invention does not reduce the speed and initial tack of UV radiation curing.
The reactive diluent is selected from isobornyl methacrylate (IBOMA) and/or dicyclopentadienyl ethoxylated methacrylate (dcmea); preferably, the mass ratio of the isobornyl methacrylate to the dicyclopentenyl ethoxylated methacrylate is 1-2: 1-2. Isobornyl methacrylate and dicyclopentenyl ethoxylated methacrylate have low odor, low volatility and low sensitization; meanwhile, the Tg of the two reactive diluents is relatively high, the Tg of the isobornyl methacrylate is about 96 ℃, and the Tg of the dicyclopentanyl alkenyl ethoxylated methacrylate is about 120 ℃, so that the Tg of the finally obtained solidified colloid is above 70 ℃, and the colloid has excellent oil and grease resistance under the aging condition of 65 ℃ and 90RH percent.
The thixotropic agent is selected from fumed silica having a specific surface area (BET) of 100-130m 2 /g; the double bond-containing silane coupling agent is at least one selected from vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri (beta-methoxyethoxy) silane and gamma-methacryloxypropyl trimethoxy silane. The double bond-containing silane coupling agent can participate in the UV curing reaction, and the contained siloxane group can also participate in the moisture curing reaction even under the condition of moisture, so that the adhesive strength is further enhanced together with the cooperation of the isocyanate functional group.
In the preparation of the polyurethane acrylate, the hydroxyl-containing acrylate is selected from mono-functional acrylate and/or multi-functional acrylate, wherein the mono-functional acrylate is selected from hydroxyalkyl (meth) acrylate, and particularly at least one of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; the polyfunctional acrylate is at least one selected from the group consisting of trimethylolpropane diacrylate, monoglyceride methacrylate, glycerol dimethacrylate, pentaerythritol triacrylate and sorbitol (meth) acrylate.
Preferably, in the preparation raw materials of the polyurethane acrylic ester A, the hydroxyl-containing acrylic ester is hydroxyalkyl (methyl) acrylate, pentaerythritol triacrylate and sorbitol (methyl) acrylate according to the mass ratio of 4-6:1-1.5: 0.2-0.3; in the preparation raw materials of the polyurethane acrylic ester B, the hydroxyl-containing acrylic ester is hydroxyethyl (methyl) acrylate, and pentaerythritol triacrylate is prepared according to the mass ratio of 4-6: 1-1.5. The inventor discovers that in the preparation of polyurethane acrylic ester A, the three hydroxyl-containing acrylic esters are compounded according to a certain proportion, so that the three hydroxyl-containing acrylic esters can have synergistic effect, and the comprehensive performance of the adhesive is excellent. Wherein, pentaerythritol triacrylate contains three double bonds, which is beneficial to accelerating the curing speed and the initial adhesion strength during UV curing; the (methyl) acrylic acid sorbitol ester contains 5 hydroxyl groups, and in the preparation process of polyurethane acrylic acid ester, a small amount of (methyl) acrylic acid sorbitol ester can obviously increase the crosslinking degree, and the toughness of the adhesive is not affected, so that the polyurethane acrylic acid sorbitol ester has the advantages of high curing speed and high curing efficiency; and reduces the use of reactive monomers and reduces the risk of sensitising sources. The polyurethane acrylic ester B is used as a soft segment of the adhesive, and the cross-linking density is not required to be too high, so that the use of polyfunctional acrylic ester can be reduced.
Further, the NCO content of the polyurethane acrylate A and/or the polyurethane acrylate B is 5-8%. The NCO content is high, the moisture curing ratio is large, the crosslinking density of the whole colloid is improved, the acid erosion resistance and the oleic acid permeation resistance of the colloid are further improved, and the influence of the oleic acid on the bonding strength is reduced.
The isocyanate trimer is selected from at least one of HDI trimer and IPDI trimer; the diisocyanate is at least one selected from isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and 2, 4-toluene diisocyanate.
The macromolecular dihydric alcohol is at least one selected from polyether dihydric alcohol, polyester dihydric alcohol and polycarbonate dihydric alcohol, and the number average molecular weight of the macromolecular dihydric alcohol is 2000-4000mol/g; the hydroxyl-terminated polysiloxane alkenyl with double bonds in the side chains has the content of 0.05-0.08mmol/g and the viscosity of 500-1000 mPa.s.
The invention adopts macromolecular dihydric alcohol and hydroxyl-terminated polysiloxane as chain extender to increase the molecular weight of polyurethane acrylic ester, and the side chain of the hydroxyl-terminated polysiloxane contains a certain amount of double bonds, so that the polyurethane acrylic ester can participate in UV curing reaction, the initial adhesion is improved, the crosslinking density is improved, the bonding strength is further improved, the toughness is also improved, and the anti-drop performance of the adhesive applied to electronic components is improved. The hydroxyl-terminated polysiloxane with double bonds in the side chains has the alkenyl content of 0.05-0.08mmol/g, and the alkenyl content is too low to effectively add siloxane groups into the structure of the island polyurethane acrylate through UV curing reaction, so that the effect cannot be fully exerted; the alkenyl content is too high to participate in the UV reaction to a large extent, and the formed crosslinking density is too high, which is unfavorable for improving the toughness.
Further, the preparation method of the polyurethane acrylic ester A comprises the following steps: adding isocyanate trimer, catalyst and polymerization inhibitor under inert atmosphere, slowly adding hydroxyl-containing acrylic ester, reacting at 30-40 deg.C for 3-5 hr, and cooling to obtain prepolymer; adding macromolecular dihydric alcohol, polysiloxane with side chain containing alkenyl hydroxyl, and reactive diluent, reacting at 65-75deg.C for 2-3 hr until NCO content is below 3%, and cooling to obtain polyurethane acrylate A.
The preparation method of the polyurethane acrylic ester B comprises the following steps: under inert atmosphere, diisocyanate, macromolecular dihydric alcohol, polysiloxane with alkenyl end hydroxyl in side chain and catalyst are added, the temperature is raised to 30-40 ℃, the reaction is carried out for 3-5h, the temperature is raised to 65-75 ℃, the reaction is continued for 1-2h, the temperature is reduced to 50-60 ℃, hydroxyl-containing acrylic ester and polymerization inhibitor are added, the temperature is raised to 65-75 ℃, the reaction is continued for 2-3h, the NCO content is lower than 3%, and the polyurethane acrylic ester B is obtained after the temperature is reduced.
Further, the macromolecular dihydric alcohol needs to be dehydrated before being used, and the specific method is that the macromolecular dihydric alcohol is stirred for 0.5 to 1 hour at 100 to 120 ℃ under the vacuum degree of 0.01 to 0.1 MPa.
In the preparation process of polyurethane acrylic ester, polymerization inhibitor and catalyst are added, the polymerization inhibitor is used for preventing double bond from reacting, the catalyst is used for catalyzing the reaction between isocyanate and hydroxyl, and the type and the amount of the catalyst are well known in the art. For example, the catalyst is an organotin catalyst, and is specifically selected from at least one of dibutyltin dilaurate and stannous octoate; the addition amount of the organotin catalyst is 50-100ppm of isocyanate compound; the polymerization inhibitor is at least one selected from p-benzoquinone, hydroquinone and p-hydroxyanisole, and the dosage is 80-130ppm of hydroxyl-containing acrylic ester.
In the invention, polyurethane acrylic ester A is prepared by reacting isocyanate trimer with hydroxyl-containing acrylic ester to end-cap acrylic ester, and then reacting with macromolecular dihydric alcohol to chain extend; the polyurethane acrylic ester B is prepared by chain extension of diisocyanate and macromolecular dihydric alcohol and then reaction with acrylic ester with hydroxyl to obtain acrylic ester-terminated polyurethane acrylic ester. The polyurethane acrylic ester A is prepared by adopting a pre-end capping method, the isocyanate trimer is polyisocyanate with 6 functionality, the reactivity of two NCO groups is different, NCO with high activity is reacted with hydroxyl-containing acrylic ester, the rest NCO groups can continue to react with macromolecular dihydric alcohol and hydroxyl on polysiloxane with alkenyl end hydroxyl on a side chain, and the obtained polyurethane acrylic ester has uniform molecular weight distribution and stable property. The polyurethane acrylic ester B is prepared by adopting a post-blocking method, namely diisocyanate is firstly reacted with long-chain dihydric alcohol to be chain-extended, and then the diisocyanate is reacted with hydroxyl-containing acrylic ester to be blocked, so that the polyurethane acrylic ester with larger molecular weight can be obtained. The invention adopts two different polyurethane acrylic esters which respectively play roles, the polyurethane acrylic ester A has large crosslinking density after solidification in the adhesive, and the polyurethane acrylic ester A is used as a hard segment of the adhesive to provide good hardness and bonding strength; the polyurethane acrylic ester B is used as a soft section of the adhesive, and can fully maintain excellent flexibility and toughness when maintaining excellent adhesive strength, so that the anti-dropping performance of electronic components is improved.
The invention also provides a preparation method of the UV moisture dual-cured adhesive, which comprises the following steps: accurately weighing the reactive diluent and the modified photoinitiator, performing vacuum dispersion by using a vacuum centrifugal high-speed dispersing machine to dissolve the modified photoinitiator completely, adding a water removing agent, stirring and dispersing for 3-5min, sealing and standing for 3-5h, adding polyurethane acrylate A and polyurethane acrylate B, stirring and dispersing for 3-5min, adding a silane coupling agent, finally adding a thixotropic agent, stirring and dispersing for 3-5min, performing vacuum dispersion for 3-5min, sampling and testing the performance of the glue, sub-packaging after the glue is qualified, performing high-speed centrifugal defoaming, and performing vacuum plastic packaging.
Compared with the prior art, the invention has the following technical advantages:
1. aiming at the lack of an adhesive suitable for precise electronic components (such as TWS earphone) which are frequently contacted with human skin in the current market, the invention prepares the adhesive with high curing speed, good bonding strength, good weather resistance and excellent combination property of oil and acid resistance through optimizing and screening the components and the proportion.
2. The raw materials are screened, so that the raw materials with low volatility, low smell and small skin irritation are found, the adhesive obtained by the invention has low sensitization and small skin irritation, and the adhesive is suitable for being used as an adhesive for electronic components which are in long-term contact with human skin, such as TWS (time varying surface) headphones and the like.
3. The adhesive with high crosslinking degree is formed into a compact three-dimensional network structure by adopting the raw materials with multi-functionality, so that small molecules such as oleic acid, sebum and the like are difficult to invade the inside of the colloid to cause dissolution and damage. The monomer with rich ester groups is adopted to enter the polymer, so that the polarity is improved, and the oil resistance of the adhesive is further improved; the invention also adopts an active diluent with higher Tg, and controls the Tg of the colloid to be near 70 ℃, so that the colloid has excellent acid and sebum resistant performance under the aging condition of 60 ℃. The invention achieves excellent anti-oleic acid effect through the combined action of a plurality of factors, and has no excessive loss of toughness of the adhesive.
Detailed Description
The present application is further illustrated by the following examples.
The chemicals used in the examples of the present invention are commercially available.
The polysiloxane with the side chain containing alkenyl terminal hydroxyl groups is purchased from the blue star fire organic silicon.
Polycarbonate diol (PCDL, hydroxyl number 110mg KOH/g, molecular weight 2000), purchased from Paston (Perston).
Thixotropic fumed silica TS720 available from Shanghai Seiyaku chemical Co., ltd, has a specific surface area of about 110m 2 /g。
Unless otherwise specified, "parts" are parts by mass and "%" are percentages by mass in the examples of the present invention.
Preparation example 1 Synthesis of modified macromolecular photoinitiator
Into a four-necked glass flask, 50 parts of IPDI (NCO content: 37.6%) was charged, 36.5 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator 1173) premixed with 200ppm of MEHQ was added dropwise, nitrogen was sealed and the reaction temperature was controlled at 40℃and the reaction time was 1.5 hours while taking care of avoiding glare; and continuously heating to 70 ℃ for reaction for 1 hour, sampling and testing the NCO content to be 11.6%, and cooling for standby.
Preparation example 2
(S1) under the nitrogen atmosphere, 42 parts of HDI trimer, catalyst dibutyltin dilaurate (60 ppm of HDI trimer) and polymerization inhibitor hydroquinone (the dosage is 100ppm of hydroxyl-containing acrylate) are added, 10 parts of hydroxyl-containing acrylate (a mixture of hydroxyethyl acrylate, pentaerythritol triacrylate and sorbitol acrylate according to the mass ratio of 4:1:0.2) are slowly added, the mixture is reacted for 3 hours at 43 ℃, and the prepolymer is obtained for standby after cooling;
(S2) 13 parts of polycarbonate diol are dehydrated for 1h at 110 ℃ under vacuum, cooled to 65 ℃, the prepolymer obtained in the step (S1) and 7 parts of polysiloxane with alkenyl end hydroxyl groups (with alkenyl content of 0.05 mmol/g) with side chains are added, the temperature is increased to 72 ℃ under nitrogen, the reaction is carried out for 3h, the NCO content of a sample test product is 6.6%, and the temperature is reduced to room temperature, so that polyurethane acrylate A, which is called polyurethane acrylate A1 in the following, is obtained.
Preparation example 3
(S1) 11 parts of carbonate diol are dehydrated for 1h at 110 ℃ under vacuum, cooled to 65 ℃, 45 parts of 2, 4-toluene diisocyanate and 8 parts of polysiloxane with alkenyl end hydroxyl groups on side chains (the alkenyl content is 0.08 mmol/g), a catalyst of dibutyltin dilaurate (80 ppm of 2, 4-toluene diisocyanate) is reacted for 1.5h at a reaction temperature of 40 ℃ under nitrogen atmosphere, the temperature is raised to 72 ℃, the reaction is carried out for 1h, the temperature is cooled to 40 ℃,6 parts of hydroxyl-containing acrylic ester (a mixture of hydroxyethyl acrylate and pentaerythritol triacrylate according to a mass ratio of 4:1) and a polymerization inhibitor of hydroquinone (the dosage is 100ppm of hydroxyl-containing acrylic ester) are added, the temperature is raised to 72 ℃, the reaction is carried out for 3h, the NCO content of a sampling test product is 5.3%, and the temperature is lowered to room temperature, thus obtaining polyurethane acrylic ester B1.
Preparation example 4
The other conditions were the same as in preparation example 2 except that the hydroxyl-containing acrylate was hydroxyethyl acrylate, and pentaerythritol triacrylate and sorbitol acrylate were used in a mass ratio of 6:1: 0.3. The resulting urethane acrylate was designated A2.
Preparation example 5
The other conditions are the same as in preparation example 3, except that the hydroxyl-containing acrylate is hydroxypropyl acrylate, and pentaerythritol triacrylate is prepared according to a mass ratio of 6: 1. The resulting urethane acrylate was designated B2.
Preparation example 6
The other conditions are the same as in preparation example 2, except that the hydroxyl-containing acrylate is hydroxyethyl acrylate and pentaerythritol triacrylate in a mass ratio of 4: 1. The resulting urethane acrylate was designated A3.
Preparation example 7
The other conditions were the same as in preparation example 3 except that the hydroxyl group-containing acrylate was hydroxypropyl acrylate, and the urethane acrylate obtained was designated as B3.
Preparation example 8
The other conditions were the same as in preparation example 2 except that the alkenyl group content of the side chain hydroxyl terminated polysiloxane was 0.04mmol/g. The resulting urethane acrylate was designated A4.
Preparation example 9
The other conditions were the same as in preparation example 3 except that the alkenyl group content of the side chain hydroxyl terminated polysiloxane was 0.10mmol/g. The resulting urethane acrylate was designated B4.
Preparation example 10
The other conditions were the same as in preparation example 2 except that hydroxyethyl acrylate, pentaerythritol triacrylate and sorbitol acrylate were used in a mass ratio of 4:1:0.3, the resulting urethane acrylate being designated A5.
PREPARATION EXAMPLE 11
The other conditions were the same as in preparation example 2 except that hydroxyethyl acrylate, pentaerythritol triacrylate and sorbitol acrylate were used in a mass ratio of 4:1:0.1, the resulting urethane acrylate being designated A6.
Example 1
2.1 parts of thixotropic agent fumed silica TS720 is placed in an oven to be baked for 24 hours at 120 ℃ for standby; adding 1.4 parts of the modified photoinitiator prepared in preparation example 1 into 11 parts of reactive diluent (mixture of isobornyl methacrylate and dicyclopentadienyl ethoxylated methacrylate according to the mass ratio of 1:1), dispersing in vacuum by using a vacuum centrifugal high-speed dispersing machine for 5min until the modified photoinitiator is completely dissolved, adding 1.2 parts of water scavenger TI, continuing dispersing for 3min, sealing and standing for 5h, adding 20 parts of polyurethane acrylate A1 prepared in preparation example 2, 15 parts of polyurethane acrylate B1 prepared in preparation example 3, 3.3 parts of vinyltrimethoxysilane, dispersing in vacuum for 5min, finally adding the thixotropic agent fumed silica for standby, dispersing in vacuum, centrifuging and defoaming, and vacuum-molding to obtain adhesive 1, wherein the appearance is transparent viscous liquid, and the viscosity is 8600mPa.s/25 ℃ through testing.
Example 2
Other conditions and operations are the same as in example 1, except that urethane acrylate A1 is replaced with an equal mass of urethane acrylate A2, and that the reactive diluent is used in an amount of 8 parts isobornyl methacrylate and dicyclopentenyl ethoxylated methacrylate in a mass ratio of 2: 1.
Example 3
Other conditions and operations were the same as in example 1, except that urethane acrylate B1 was replaced with an equal mass of urethane acrylate B2. And the consumption of the reactive diluent is 9 parts of isobornyl methacrylate and dicyclopentadienyl ethoxylated methacrylate according to the mass ratio of 1: 2.
Example 4
Other conditions and operations were the same as in example 1, except that urethane acrylate B1 was replaced with an equal mass of urethane acrylate B3.
Example 5
Other conditions and operations were the same as in example 1, except that urethane acrylate A1 was replaced with an equal mass of urethane acrylate A4.
Example 6
Other conditions and operations were the same as in example 1, except that urethane acrylate B1 was replaced with an equal mass of urethane acrylate B4.
Example 7
Other conditions and operations were the same as in example 1 except that the silane coupling agent was replaced with 5 parts of vinyltriethoxysilane from 3.3 parts of vinyltrimethoxysilane.
Example 8
Other conditions and operations were the same as in example 1 except that 11 parts of reactive diluent was isobornyl methacrylate.
Example 9
Other conditions and procedures were the same as in example 1 except that 11 parts of reactive diluent was dicyclopentadienyl ethoxylated methacrylate.
Example 10
Other conditions and operations were the same as in example 1, except that urethane acrylate A1 was replaced with an equal mass of urethane acrylate A5.
Example 11
Other conditions and operations were the same as in example 1, except that urethane acrylate A1 was replaced with an equal mass of urethane acrylate A6.
Comparative example 1
Other conditions and operations were the same as in example 1 except that 1.4 parts of the modified photoinitiator prepared in preparation example 1 was replaced with 1 part of photoinitiator 1173.
Comparative example 2
Other conditions and operations were the same as in example 1 except that the silane coupling agent was not added.
Comparative example 3
Other conditions and operations were the same as in example 1, except that urethane acrylate A1 was replaced with an equal mass of urethane acrylate A3.
Application example 1
The crosslinking agents obtained in the above examples and comparative examples were subjected to performance test, and the results are shown in Table 1 below:
the dispensing process adopts a Nordson ASYMTEK pneumatic dispensing machine, the length of a glue line is 25mm, the width of the glue line is 2.5mm, and the height of the glue line is 0.15mm. The curing is to carry out UV curing and then moisture curing;the method specifically comprises the following steps: the UV curing process adopts an NJUV-F300S/2F light curing machine/LED area light source, and the UV curing conditions are as follows: LED ultraviolet lamp with wavelength of 365nm and irradiation light intensity of 1000mj/cm 2 The irradiation time is 5s; moisture curing was carried out in a constant temperature and humidity cabinet at 25.+ -. 1 ℃ and humidity of 50RH% for 7 days.
Adhesive strengthExpressed in terms of shear strength (PC/PC), adhesive toughness expressed in terms of elongation at break,shear Strength and breaking Elongation at breakAll are tested by microcomputer controlled electronic universal tester. The initial tack strength, expressed as the shear strength tested after 2 hours of standing after UV curing, was the bond strength after uv+moisture curing at bond strength.
In order to verify the reliability of the adhesive provided by the invention, the aging resistance and hydrolysis resistance of the adhesive are also tested:
ageing resistance experiment 1: and placing the adhesive double 85 (85 ℃ and 85 RH%) subjected to UV+moisture dual curing in a constant temperature and humidity box for 168 hours (one week), taking out, drying, and retesting the adhesive bonding strength.
Ageing resistance experiment 2: and (3) re-testing the bonding strength of the adhesive after the UV and moisture dual curing at high temperature and low cycle for 168 hours after-40 ℃/12 hours and 120 ℃/12 hours.
Sensitization testSkin sensitization experiments were performed according to ISO10993-10:2002, with no sensitization response for scale 0 and mild to severe sensitization for scale 1-3, respectively.
Number of falling times: and (3) freely falling the cured test piece (PC/PC) from the height of 1 meter to the marble ground, repeatedly falling until the bonding fails, recording the falling times when the bonding fails, carrying out experiments on each sample for 3 times, and taking an average value.
TABLE 1
Application example 2
In order to verify the oil and acid resistance of the adhesive obtained in the examples of the present invention, the following tests were also performed, 3 samples were tested for each test, and the average value was taken, and the results are shown in table 2 below:
1，weight gain test by oleic acid immersion：
The cured adhesive (UV+moisture for 7 days, the same conditions as in application example 1) was cut into blocks of about 15mm. Times.15 mm. Times.5 mm, weighed and designated M 1 Soaking in 60deg.C oleic acid for 7 days, taking out, wiping off surface oleic acid, weighing, and recording as M 2 The weight gain A is calculated according to formula (I).
A＝M 2 -M 1 /M 1 ×100％ (I)
2，Influence of oleic acid on bond Strength：
The cured adhesive (UV+moisture for 7 days, the same conditions as in application example 1) was immersed in oleic acid at 60℃for 7 days, and then taken out, and the adhesive strength was measured to calculate the adhesive strength retention rate.
TABLE 2
| Adhesive agent | Weight gain rate | Retention of adhesive strength |
| Example 1 | 0.48％ | 98.3％ |
| Example 2 | 0.53％ | 97.6％ |
| Example 3 | 0.51％ | 97.4％ |
| Example 4 | 0.57％ | 96.9％ |
| Example 7 | 0.46％ | 98.5％ |
| Example 8 | 0.57％ | 97.0％ |
| Example 9 | 0.46％ | 98.2％ |
| Example 10 | 0.47％ | 98.2％ |
| Example 11 | 0.69％ | 95.7％ |
| Comparative example 3 | 1.12％ | 92.6％ |
The UV-moisture dual-curing adhesive prepared by the invention has excellent acid and acid resistance and oil resistance, and can meet the requirement of adhesive of precise electronic components which are contacted with skin for a long time and secrete oil, such as TWS Bluetooth earphone.
Claims (8)
1. An oil acid resistant UV-moisture dual-curing adhesive is characterized by comprising the following raw materials in parts by mass: 20-30 parts of polyurethane acrylic ester A,12-15 parts of polyurethane acrylic ester B,8-11 parts of reactive diluent, 1.1-1.4 parts of modified photoinitiator, 1-3 parts of thixotropic agent and 2-5 parts of double bond-containing silane coupling agent; the polyurethane acrylic ester A comprises the following preparation raw materials in parts by mass: 42-50 parts of isocyanate trimer, 10-15 parts of hydroxyl-containing acrylic ester I,13-18 parts of macromolecular dihydric alcohol and 7-10 parts of polysiloxane with side chains containing alkenyl terminal hydroxyl groups; in the raw materials of the polyurethane acrylic ester A, hydroxyl-containing acrylic ester I is hydroxyalkyl (methyl) acrylate, pentaerythritol triacrylate and sorbitol (methyl) acrylate according to the mass ratio of 4-6:1-1.5: 0.2-0.3;
the polyurethane acrylic ester B comprises the following preparation raw materials in parts by mass: 38-45 parts of diisocyanate, 11-15 parts of macromolecular dihydric alcohol, 8-12 parts of polysiloxane with side chains containing alkenyl terminal hydroxyl groups and 6-8 parts of acrylate II containing hydroxyl groups; the modified photoinitiator is a product obtained by reacting a hydroxyl-containing photoinitiator with isophorone diisocyanate, the molar ratio of the hydroxyl-containing photoinitiator to isophorone diisocyanate is 1:1-1.2, and the hydroxyl-containing photoinitiator is at least one selected from 2-hydroxy-2-methyl-1-phenyl-1-acetone and hydroxycyclohexane benzophenone; the hydroxyl-containing acrylic ester II is hydroxyethyl (methyl) acrylate, and pentaerythritol triacrylate is prepared from the following components in percentage by mass: 1-1.5;
the preparation method of the polyurethane acrylic ester A comprises the following steps: adding isocyanate trimer, catalyst and polymerization inhibitor under inert atmosphere, slowly adding hydroxyl-containing acrylic ester I, reacting at 30-40 ℃ for 3-5h, and cooling to obtain prepolymer; adding macromolecular dihydric alcohol, polysiloxane with side chain containing alkenyl terminal hydroxyl and reactive diluent, continuing to react for 2-3h at 65-75 ℃ until NCO content is below 3%, and cooling to obtain polyurethane acrylate A;
the preparation method of the polyurethane acrylic ester B comprises the following steps: under inert atmosphere, diisocyanate, macromolecular dihydric alcohol, polysiloxane with alkenyl end hydroxyl in side chain and catalyst are added, the temperature is raised to 30-40 ℃, the reaction is carried out for 3-5h, the temperature is raised to 65-75 ℃, the reaction is continued for 1-2h, the temperature is reduced to 50-60 ℃, hydroxyl-containing acrylic ester II and polymerization inhibitor are added, the temperature is raised to 65-75 ℃, the reaction is continued for 2-3h, the NCO content is lower than 3%, and the polyurethane acrylic ester B is obtained after the temperature is reduced.
2. The oleic acid-resistant UV-moisture dual-curing adhesive according to claim 1, wherein the sorbitol ester (meth) acrylate accounts for 3.8-5% of the total mass of the hydroxyl-containing acrylate in the hydroxyl-containing acrylate I as the raw material of the polyurethane acrylate A.
3. The oleic acid resistant UV-moisture dual cure adhesive of claim 1 wherein the modified photoinitiator is prepared by a preparation process comprising the steps of: mixing IPDI and a photoinitiator containing hydroxyl, reacting for 1-2h under the protection of inert atmosphere at 30-40 ℃ in the dark, continuously heating to 40-60 ℃, reacting for 0.5-1h, cooling, and preserving in the dark to obtain the modified photoinitiator.
4. The oleic acid resistant UV-moisture dual cure adhesive of claim 1, wherein the reactive diluent is selected from isobornyl methacrylate and/or dicyclopentenyl ethoxylated methacrylate.
5. The oleic acid-resistant UV-moisture dual-curing adhesive according to claim 1, wherein the reactive diluent is isobornyl methacrylate and dicyclopentadienyl ethoxylated methacrylate in a mass ratio of 1-2: 1-2.
6. The oleic acid resistant UV-moisture dual cure adhesive of claim 1 wherein the thixotropic agent is selected from fumed silica having a specific surface area of 100 to 130m 2 /g; the double bond-containing silane coupling agent is at least one selected from vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri (beta-methoxyethoxy) silane and gamma-methacryloxypropyl trimethoxy silane.
7. The oleic acid resistant UV-moisture dual cure adhesive of claim 1 wherein the isocyanate trimer is selected from at least one of HDI trimer, IPDI trimer; the diisocyanate is at least one selected from isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and 2, 4-toluene diisocyanate.
8. The oleic acid-resistant UV-moisture dual-cure adhesive of claim 1, wherein the macrodiol is at least one selected from the group consisting of polyether diol, polyester diol, polycarbonate diol, and the macrodiol has a number average molecular weight of 2000-4000g/mol; the side chain contains alkenyl hydroxyl-terminated polysiloxane with alkenyl content of 0.05-0.08mmol/g and viscosity of 500-1000 mPa.s.
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