CN105400472A - Space-time separated preparation method for UV adhesive - Google Patents
Space-time separated preparation method for UV adhesive Download PDFInfo
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- CN105400472A CN105400472A CN201510921307.XA CN201510921307A CN105400472A CN 105400472 A CN105400472 A CN 105400472A CN 201510921307 A CN201510921307 A CN 201510921307A CN 105400472 A CN105400472 A CN 105400472A
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Abstract
The invention provides a space-time separated preparation method for a UV adhesive, which belongs to the technical field of ultraviolet light-cured rapid prototyping methods. The space-time separated preparation method comprises the following steps: (1) uniformly mixing oligomer and a cationic photoinitiator according to a certain ratio and carrying out stirring under ultraviolet irradiation to realize photolysis of the cationic photoinitiator, thereby obtaining uniform liquid A; (2) mixing epoxy resin, an active diluent and an auxiliary agent so as to obtain uniform liquid B; and (3) uniformly mixing the liquid A and the liquid B and then applying the adhesive, wherein the uniform liquid A accounts for 0.1 to 50% of the mass of the mixed liquid. According to the invention, complete space-time separation is realized in the process of illumination and the process of curing molding, ultraviolet irradiation is not needed in the process of curing molding, and unrestricted extension and curing in a lightproof area can be realized; the advantage of rapid curing at low temperature and normal temperature of light-curing technology is retained; and due to space-time separation of the process of illumination and the process of curing molding, the UV adhesive is applicable to adhesive application and curing at extreme conditions like a field condition.
Description
Technical field
The present invention relates to field of polymer composite material, be specifically related to a kind of method utilizing space-time to be separated and prepare UV sizing agent and Application Areas thereof.
Background technology
Due to the agent of ultraviolet light polymerization gluing there is fast setting, some distinguishing features such as consistency is good, intensity is high, environmental protection, be therefore widely used in the fields such as optical field, electronic apparatus, optical digital disk.The solidification of current ultraviolet light polymerization gluing agent is confined to the position of illumination, UV-irradiation less than position be difficult to effectively solidify and curing depth has deficiency, and have in the special applications of some special dimensions UV-irradiation less than place also need effectively to solidify, as bonding for opaque glass plate, wooden boards bonds, sheet metal bonding etc., particularly the agent of ultraviolet light polymerization gluing is used for matrix material adhesive technology field, activation energy required for UV-curing technology is low, can in low-temperature curing, therefore can avoid producing thermal stresses, and UV-curing technology equipment is simple, energy-conserving and environment-protective, be more suitable for outfield to repair, but due to UV-irradiation less than position be difficult to effectively solidify and curing depth has deficiency, need reinforcing aids light transmission good simultaneously, therefore can only repair the damage of composite layer, limit the application of ultraviolet light polymerization gluing agent in composite repair field.
The present invention breaches the restriction of photocuring technology, During Illumination with curing molding process implementation completely space-time be separated, in curing molding process, do not need UV-irradiation, can the unconfined extension solidification in light tight region; Also retains simultaneously photocuring technology can under low temperature normal temperature condition quick-setting advantage; Simultaneously because During Illumination is separated with the space-time of curing molding process, extreme case applying glue and the solidifications such as field can be adapted to.
Summary of the invention
The present invention is directed to the deficiency of above-mentioned prior art, provide the UV sizing agent that a kind of space-time is separated.
Another object of the present invention is to provide a kind of space-time partition method and prepares UV sizing agent and Application Areas thereof.
The present invention mainly solves existing UV-curing technology, Problems existing, namely UV-irradiation less than position be difficult to effectively solidify and curing depth has deficiency, need the defects such as auxiliary agent light transmission is good simultaneously.
For achieving the above object, the present invention adopts following technical scheme.
The preparation method of the composite repair glue that space-time is separated, comprises the steps:
(1) oligopolymer and cation light initiator are mixed by a certain percentage, stir under UV-irradiation, make cation light initiator photodissociation, obtain uniform liquid A;
(2) by epoxy resin, reactive thinner mixes by a certain percentage with auxiliary agent, obtains uniform liquid B;
(3) liquid A is mixed after dryer sizing by a certain percentage with liquid B;
In the step (1) of above-mentioned preparation method, (2), (3), preferred dry environment, the solidification effect preparing the ultra-violet curing glue extending solidification is thus better.
Resin in the step (1) of above-mentioned preparation method is polyether polyols alcohols, polyglycol ethers, polyoxyethylene glycol, or polyoxy glycerol.
The cation light initiator described in step (1) of above-mentioned preparation method comprises salt compounded of iodine, one or more in sulfosalt and iron arene.
Resin in the step (2) of above-mentioned preparation method comprises epoxy resin, one or more in vinyl ether and oxygen helerocyclics; Epoxy resin is bisphenol A epoxide resin, or bisphenol F epoxy resin, or novolac epoxy, or diepoxide polyolefin compound, or naphthalene system epoxy resin, or aliphatic epoxy resin, or cycloaliphatic epoxy resin.
Reactive thinner in the step (2) of above-mentioned preparation method is epoxy monomer, vinyl ether monomers or oxygen heterocyclic monomer.
Auxiliary agent described in the step (2) of above-mentioned preparation method can according to different its kinds of Application Areas choose reasonable and consumption thereof.
Described in the step (1) of above-mentioned preparation method, cation light initiator accounts for the massfraction of liquid A is 0.5%-80%.
The massfraction that in the step (3) of above-mentioned preparation method, liquid A accounts for is 0.1%-50%.
The light polymerization process that the present invention relates to is cationic photopolymerization, has after fixing behavior, can by carrying out post curing treatment to the repair sheets after curing molding, to improve its performance.
Technological principle of the present invention is: cationoid polymerisation is a kind of living polymerisation process, the cation group generated after cation light initiator photodissociation is a kind of active group, its activity stable existence and unattenuated in theory always, in actual production, the property retention alive of cation group more than 1 year; Therefore by after cation light initiator photodissociation, the activity of the cation group of generation can keep for a long time; But add cation photocuring resin by after cation light initiator photodissociation, be separated with the space-time of curing molding to realize illumination, following three problems will be there are: (1), be unfavorable for standing storage; Be easy to make moist after light trigger photodissociation, cause the activity of cation light initiator to reduce, even can not cause cation photocuring resin and react.(2), system is too short for inductive phase; After cation light initiator photodissociation, the activity of active group is high, fast with resin reaction speed, generates a gel group instantaneously, and the initiator after photodissociation is wrapped in gel group, can not react with light-cured resin; (3), cation light initiator is not good in the solvability of cation photocuring resin system, mixes required time longer.
The present invention successfully solves above problem, achieves illumination and is separated with the space-time of curing molding.
Cation light initiator mixes with not volatile oligopolymer such as polyether polyols alcohols by the present invention, makes its photodissociation (obtaining photoinitiator system PI) with the form stirring illumination; The oligopolymer such as the active group generated after photodissociation disperses in a liquid uniformly, polyether polyols alcohols serve as chain-transfer agent in system, make the activity stable existence always of the cation group of generation; Solve the problem being unfavorable for standing storage.
After the not volatile oligopolymer such as cation light initiator and polyether polyols alcohols mix, overallly to improve with the solvability of cation photocuring resin, easier short mix is even, solves its deliquescent problem.
Active group has evenly spread in the oligopolymer such as polyether polyols alcohols, reduce the concentration of active group, thus photoinitiator system PI is with light-cured resin mixing process, there is longer inductive phase, gel group can not be there is instantaneously, speed of response and the inductive phase of whole system can be controlled by hierarchy of control temperature simultaneously, complete mixing of liquid A and liquid B in stage inductive phase, the bubble that may exist in eliminating system, and Process of Applying Glue; By the temperature of change system, inductive phase can be terminated by methods such as UV-irradiation; After terminating inductive phase, whole system will rapid reaction, curing molding.Meanwhile, containing hydroxyl in the oligopolymer such as polyether polyols alcohols, finally can be combined with epoxide group, therefore in whole process, not have solvent evaporates; After terminating inductive phase, its speed of response is similar to the speed of Stereolithography, finally obtains excellent adhesive property.
Filled a prescription by choose reasonable, can the most obvious temperature of length change inductive phase be controlled at 5 DEG C-30 DEG C, different formulas can be adopted according to different construction conditions or select different glue applying methods.
UV sizing agent prepared by space-time partition method of the present invention compared with the prior art have real go out substantive distinguishing features and marked improvement:
1. be separated with the space-time of curing molding owing to achieving illumination, do not need in the curing process to want illumination, so there is no the restriction of curing depth.
2. simple and easy, the environmental protection of Preparation equipment, technique, fast setting, applied widely.
Embodiment
Be described further technical scheme of the present invention below by preferred embodiment, following examples contribute to those skilled in the art and understand the present invention further, but should not be understood as limiting the scope of the invention.It should be pointed out that to one skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong within protection scope of the present invention.
Embodiment 1:
Be add triaryl hexafluoro-antimonic acid sulfosalt that massfraction is 5% (massfraction is the massfraction accounting for liquid A) in the polyoxyethylene glycol of 200 and mix to molecular weight, getting the sample that 20g mixes adds in the beaker of 50ml, stirs and uses mercury lamp with 100mw/cm
2light intensity irradiate 20min.Obtain uniform liquid A (called after PI), be poured in bottle stand-by.By trimethylene oxide with E-52 in mass ratio for 3:7 mixes.In the liquid mixed, add the chopped carbon fiber that massfraction is 2% (massfraction is the massfraction accounting for liquid B), obtain uniform liquid B after mixing stand-by.In liquid B, add massfraction during use is that the liquid A of 5% (massfraction is the massfraction accounting for mixing liquid) mixes.
Embodiment 2:
Be add triaryl phosphofluoric acid sulfosalt that massfraction ratio is 10% (massfraction is the massfraction accounting for liquid A) in the polyoxyethylene glycol of 400 and mix to molecular weight, getting the sample that 20g mixes adds in the beaker of 50ml, stirs and uses mercury lamp with 100mw/cm
2light intensity irradiate 20min.Obtain uniform liquid (called after PI), be poured in bottle stand-by.Mixed by the mass ratio of 2:8 with E51 by trimethylene oxide, adding massfraction is 1% (massfraction is the massfraction accounting for liquid B) short glass fiber, obtains uniform liquid B stand-by after mixing.In liquid B, add massfraction during use is that the liquid A of 20% (massfraction is the massfraction accounting for mixing liquid) mixes.Embodiment 3:
Be add diaryl phosphofluoric acid salt compounded of iodine that massfraction ratio is 40% (massfraction is the massfraction accounting for liquid A) in the polyoxyethylene glycol of 400 and mix to molecular weight, getting the sample that 20g mixes adds in the beaker of 50ml, stirs and uses mercury lamp with 100mw/cm
2light intensity irradiate 20min.Obtain uniform liquid A (called after PI), be poured in bottle stand-by.Epoxy monomer is mixed by the mass ratio of 3:7 with E51, obtains uniform liquid B stand-by.In liquid B, add massfraction during use is that the liquid A of 30% (massfraction is the massfraction accounting for mixing liquid) mixes.
Embodiment 4:
Be add diaryl phosphofluoric acid salt compounded of iodine that massfraction ratio is 40% (massfraction is the massfraction accounting for liquid A) in the polyoxy glycerol of 400 and mix to molecular weight, getting the sample that 20g mixes adds in the beaker of 50ml, stirs and uses mercury lamp with 100mw/cm
2light intensity irradiate 20min.Obtain uniform liquid A (called after PI), be poured in bottle stand-by.By trimethylene oxide, epoxy monomer mixes by the mass ratio of 1:2:7 with F-44, adds the short carbon fiber that massfraction is 5% (massfraction is the massfraction accounting for liquid B), obtains uniform liquid B stand-by after mixing.In liquid B, add massfraction during use is that the liquid A of 10% (massfraction is the massfraction accounting for mixing liquid) mixes.
Table 1:
| Embodiment is numbered | Curing speed | Curing depth | Tensile shear strength |
| 1 | 13min | 15cm solidifies completely | 26MPa |
| 2 | 15min | 15cm solidifies completely | 22MPa |
| 3 | 3min | 15cm solidifies completely | 21MPa |
| 4 | 6min | 15cm solidifies completely | 32MPa |
Note: curing depth: ready-made groove before being filled uniformly by ready-made ultraviolet cured adhesive, then carries out applying glue.
Finally should be noted that: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit; Although with reference to embodiment to invention has been detailed description, those of ordinary skill in the field are to be understood that: still can modify to the specific embodiment of the present invention or carry out equivalent replacement to portion of techniques feature; And not departing from the spirit of technical solution of the present invention, it all should be encompassed in the middle of the technical scheme scope of request of the present invention protection.
Claims (8)
1. a preparation method for the UV sizing agent of space-time separation, comprises the steps:
(1) oligopolymer and cation light initiator are mixed by a certain percentage, stir under UV-irradiation, make cation light initiator photodissociation, obtain uniform liquid A; The massfraction that described cation light initiator accounts for liquid A is 0.5wt%-80wt%;
(2) epoxy resin, reactive thinner are mixed with auxiliary agent, obtain uniform liquid B;
(3) liquid A is mixed after dryer sizing with liquid B; The massfraction that liquid A accounts for mixing liquid is 0.1wt%-50wt%.
2. preparation method according to claim 1, is characterized in that, the oligopolymer in step (1) comprises polyether polyols alcohols, polyglycol ethers, polyoxyethylene glycol, or polyoxy glycerol.
3. preparation method according to claim 1, is characterized in that, the cation light initiator described in step (1) comprises salt compounded of iodine, one or more in sulfosalt and iron arene.
4. preparation method according to claim 1, is characterized in that, the resin in step (2) comprises epoxy resin, one or more in vinyl ether and oxygen helerocyclics.
5. preparation method according to claim 1, is characterized in that, epoxy resin is bisphenol A epoxide resin, or bisphenol F epoxy resin, or novolac epoxy, or diepoxide polyolefin compound, or naphthalene system epoxy resin, or aliphatic epoxy resin, or cycloaliphatic epoxy resin.
6. preparation method according to claim 1, is characterized in that, the reactive thinner in step (2) is epoxy monomer, vinyl ether monomers or oxygen heterocyclic monomer.
7. application rights requires the matrix material prepared by preparation method described in 1-6 any one.
8. the application of the matrix material prepared by the preparation method according to claim 1-6 any one.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909643A (en) * | 2020-07-08 | 2020-11-10 | 江苏矽时代材料科技有限公司 | Time-delay photocuring epoxy resin composition and application thereof |
| CN114507479A (en) * | 2020-11-16 | 2022-05-17 | 常州强力先端电子材料有限公司 | Photocurable composition, adhesive, preparation method of adhesive and bonding method of base material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376070B1 (en) * | 1996-07-15 | 2002-04-23 | Sekisui Kagaku Kogyo Kabushiki Kaisha | Sheet-form, curable pressure-sensitive adhesive |
| CN103360977A (en) * | 2006-04-26 | 2013-10-23 | 日立化成株式会社 | Adhesive tape and solar cell module using the same |
-
2015
- 2015-12-12 CN CN201510921307.XA patent/CN105400472B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376070B1 (en) * | 1996-07-15 | 2002-04-23 | Sekisui Kagaku Kogyo Kabushiki Kaisha | Sheet-form, curable pressure-sensitive adhesive |
| CN103360977A (en) * | 2006-04-26 | 2013-10-23 | 日立化成株式会社 | Adhesive tape and solar cell module using the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909643A (en) * | 2020-07-08 | 2020-11-10 | 江苏矽时代材料科技有限公司 | Time-delay photocuring epoxy resin composition and application thereof |
| CN111909643B (en) * | 2020-07-08 | 2022-05-03 | 江苏矽时代材料科技有限公司 | Time-delay photocuring epoxy resin composition and application thereof |
| CN114507479A (en) * | 2020-11-16 | 2022-05-17 | 常州强力先端电子材料有限公司 | Photocurable composition, adhesive, preparation method of adhesive and bonding method of base material |
| WO2022100752A1 (en) * | 2020-11-16 | 2022-05-19 | 常州强力先端电子材料有限公司 | Photocurable composition, binder and preparation method therefor, and bonding method for substrate |
| CN114507479B (en) * | 2020-11-16 | 2023-12-15 | 常州强力先端电子材料有限公司 | Photocurable composition, binder, preparation method of binder and bonding method of substrate |
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