CN104507985A - Photopolymerizable resin composition and photopolymerizable resin containing same - Google Patents
Photopolymerizable resin composition and photopolymerizable resin containing same Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/23—Azo-compounds
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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Abstract
The present invention provides a photopolymerizable resin comprising: a (meth)acrylic ester-based monomer; a cross-linkable functional group-containing monomer; and a thermal initiator capable of absorbing UV rays and having a 10 hour half-life temperature of 70 DEG C or less. In addition, the present invention provides a photopolymerizable resin prepared by polymerizing: a (meth)acrylic ester-based monomer; a cross-linkable functional group-containing monomer; and a thermal initiator capable of absorbing UV rays and having a 10 hour half-life temperature of 70 DEG C or less.
Description
Technical field
The present invention relates to Photopolymerizable resin composition and comprise the photopolymerization resin of this Photopolymerizable resin composition, in more detail, relate to a kind of in the monomer of predetermined component containing absorbing the Photopolymerizable resin composition of the ultraviolet thermal initiator defining half life temperature.
Background technology
With an organic solvent, but the organic solvent used can volatilize existing compositions of thermosetting resin in the curing process, and there is the problem of environment aspect, and compares ultraviolet curing mode, has the problem that curing process is long, be suitable for automatic complex procedures.Therefore, current being tending towards constantly makes great efforts a kind of ultra-violet solidified resin composition for improving the problem that the existing compositions of thermosetting resin used has of research and development.
But, although the ultraviolet-curing resin composition that No. 10-2006-0020098th, Korean Patent Laid comprises uv curing resin, initiator, ultraviolet response type propylene or vinyl monomer and inorganic powder, but due to the mixture of light trigger and thermal initiator is used as initiator, thus react while absorption luminous energy, therefore, in the photopolymerization of ultra-violet solidified resin composition, still there is the problem of very difficult reaction speed and molecular weight.
Summary of the invention
the technical problem to be solved in the present invention
In order to solve the problem, the object of the invention is to, provide Photopolymerizable resin composition, it is when carrying out photopolymerization, can not produce too much reaction heat because of the reactivity of monomer, and can reaction speed and molecular weight.
Further, in general, when many usage chain transfer agent, molecular weight can reduce, and therefore, another object of the present invention is to, and provides a kind of by can less with the photopolymerization resin that the Photopolymerizable resin composition that chain-transfer agent can also increase molecular weight is polymerized.
technical scheme
In order to reach an above-mentioned object, Photopolymerizable resin composition of the present invention, it is characterized in that, comprise (methyl) acrylic ester monomer, be less than 70 DEG C containing the monomer of cross-linking functional group and the temperature of 10 hr half-life and can ultraviolet thermal initiator be absorbed.
And, in order to reach another object above-mentioned, photopolymerization resin of the present invention, is characterized in that, by (methyl) acrylic ester monomer, is less than 70 DEG C and can absorbs ultraviolet thermal initiator to be polymerized containing the monomer of cross-linking functional group and the temperature of 10 hr half-life.
beneficial effect
The present invention comprises in Photopolymerizable resin composition can absorb the low thermal initiator of ultraviolet half life temperature, thus can sluggish (mild), and due to above-mentioned thermal initiator, what reaction heat also can be made to maintain when Photopolymerizable resin composition is polymerized is lower.
Embodiment
With reference to the following examples described in detail can allow advantages and features of the invention and realize these advantages and feature method definitely.But; the present invention is not limited to embodiment disclosed in following wanting; can embody with mutually different embodiments; the present embodiment is only for making disclosure of the present invention more complete; contribute to the category of intactly informing invention to general technical staff of the technical field of the invention, the present invention defines according to the category of the claimed scope of invention.Identical Reference numeral in specification sheets full text censures identical textural element.
Below, the present invention is described in detail.
Photopolymerizable resin composition
The invention provides Photopolymerizable resin composition, it is characterized in that, (methyl) acrylic ester monomer, be less than 70 DEG C containing the monomer of cross-linking functional group and the temperature of 10 hr half-life and can ultraviolet thermal initiator be absorbed.
The kind of above-mentioned (methyl) acrylic ester monomer has no particular limits, and such as, can use (methyl) alkyl acrylate.Now, if the hydroxyl comprised in monomer becomes long long-chain, the cohesive force of Photopolymerizable resin composition declines, and be difficult to regulate second-order transition temperature (Tg) and cohesiveness, therefore, preferably, should use (methyl) acrylic ester monomer, it has the alkyl that carbonatoms is 1 to 14.
As the example of these monomers, (methyl) methyl acrylate can be enumerated, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid Zhongshu butyl ester, (methyl) amyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid-2-ethyl butyl ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) dodecyl acrylate and (methyl) tetradecyl acrylate, one or more above-mentioned mixing can be used in the present invention.
When forming above-mentioned Photopolymerizable resin composition, the monomer containing cross-linking functional group can be added, in the case, the Photopolymerizable resin composition that the present invention will be formed can be the polymkeric substance of monomer mixture, and the polymkeric substance of above-mentioned monomer mixture comprises (methyl) acrylic ester monomer and the monomer containing cross-linking functional group.
The above-mentioned monomer containing cross-linking functional group is given and a kind ofly can be carried out with above-mentioned multi-functional linking agent the cross-linking functional group that reacts, plays and regulates the durable reliability of Photopolymerizable resin composition and the effect of cohesive force.The spendable monomer containing cross-linking functional group such as has containing the monomer of hydroxyl, carboxyl group-containing monomer and nitrogen containing monomer.
In the present invention, in the monomer of the above-mentioned cross-linking functional group of containing, preferably use hydroxyl monomer, but be not limited thereto.The example of above-mentioned hydroxyl monomer has (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxy butyl ester, the own ester of (methyl) vinylformic acid-6-hydroxyl, (methyl) vinylformic acid-8-hydroxyl monooctyl ester, (methyl) vinylformic acid-2-hydroxyl glycol ester or (methyl) vinylformic acid-2-hydroxyl propylene glycol ester, the example of carboxyl group-containing monomer has (methyl) vinylformic acid, 2-(methyl) acryloxyacetic acid, 3-(methyl) acryloxy propionic, 4-(methyl) acryloxy butyric acid, acrylic acid dimer, methylene-succinic acid, toxilic acid or maleic anhydride, the example of nitrogen containing monomer has Methacrylamide, NVP or N-caprolactam, but be not limited thereto.The present invention can use one or more above-mentioned mixing.
Further, Photopolymerizable resin composition of the present invention is except comprising (methyl) acrylic ester monomer and containing except the monomer handed over containing Lian Xing functional group, also can comprising thermal initiator.The invention is characterized in, in order to stably form the photopolymerization resins such as acrylic resin, using the thermal initiator limiting half life temperature.Above-mentioned thermal initiator, as a kind of material being formed free radical by heat, can cause (methyl) acrylic ester monomer and the chain polymerization reaction containing the monomer of cross-linking functional group.Further, now, the time required when the transformation period of thermal initiator refers to that the original amount of initiator is decomposed half and forms free radical.
Under normal circumstances, when forming photopolymerization resin as Photopolymerizable resin composition, can use light trigger, light trigger does not have the transformation period, as long as can absorb luminous energy, just can react, and is thus difficult to control reaction heat.Therefore, do not use light trigger, but use can absorb ultraviolet thermal initiator, and the half life temperature of above-mentioned thermal initiator is defined as low temperature, thus can reaction heat be controlled, and maintain lower exothermic temperature, thus the polyreaction of overall photopolymerisable resin combination is kept slowly.
10 hr half-life temperature of above-mentioned thermal initiator are less than 70 DEG C, are preferably less than 60 DEG C, are more preferably less than 50 DEG C.On the other hand, the lower limit of 10 hr half-life temperature of the above-mentioned thermal initiator in the present invention has no particular limits.If but 10 hr half-life temperature are too low, may non-homogeneous curing reaction etc. be caused when forming photopolymerization resin, therefore, the above-mentioned half life temperature of control that can be suitable in the scope more than 30 DEG C.
When the temperature that partly declines of above-mentioned thermal initiator is more than 70 DEG C, when polar monomer is polymerized, can continue the side reaction based on double bond occurs, and the side reaction continuing to occur can cause gel reaction, the polymerization being difficult to form monomer may be caused.Therefore, the half life temperature of thermal initiator is set to less than 70 DEG C, maintains low reaction heat, and start chargeable heat initiator under the condition that temperature is relatively low, and initiation terminates relatively very fast, can form high molecular photopolymerization resin in the short period of time.
Further, the feature of above-mentioned thermal initiator is, can absorb ultraviolet.Can ultraviolet thermal initiator be absorbed different from the general thermal initiator being formed free radical by heat, form free radical by ultraviolet radiation absorption.Ultraviolet thermal initiator can be absorbed compared with general thermal initiator, under photopolymerization condition in a mild condition, the main 300 ~ 400nm wavelength region may used also can absorb ultraviolet, therefore compare general thermal initiator can be used in mild conditions under photopolymerization.Therefore, even if 10 hr half-life temperature of general thermal initiator maintain less than 70 DEG C, if the ultraviolet thermal initiator that can absorb maintaining above-mentioned half life temperature is used in polymerization in photopolymerization mode, also the condition of polymerization can be made to become various, and due to reaction heat lower, also can carry out that polymerization this point has advantage in a mild condition.
Particularly, the feature of above-mentioned thermal initiator is, is generally azo compound or peroxide compound, but the invention is characterized in, thermal initiator of the present invention is the azo compound of the half life temperature with above-mentioned scope.Peroxide compound has benzoyl peroxide, dilauroyl peroxide, di-t-butyl peroxide, hydrogen phosphide cumene etc., but their half life temperature is all more than 70 DEG C.In contrast, azo compound has relatively low half life temperature, therefore preferably.
Above-mentioned azo compound can use and be selected from by 2,2 '-azo two (isopropyl cyanide), 2,2 '-azo two (2,4-methyl pentane nitrile), 2, two (the 4-methoxyl group-2 of 2 '-azo, 4-methyl pentane nitrile), azo-bis-iso-dimethyl, 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride and 2, more than one in the group of two [N-(2-carboxy ethyl)-2-methyl-prop amidine] hydrate composition of 2 '-azo.Can use be selected from above-mentioned azo compound more than one form the thermal initiator that 10 hr half-life temperature are less than 70 DEG C, and by limiting the transformation period, above-mentioned effect can be brought.
The feature of Photopolymerizable resin composition of the present invention is, relative to above-mentioned (methyl) acrylic ester monomer of 100 weight parts, comprises the above-mentioned containing the monomer of cross-linking functional group and the above-mentioned thermal initiator of 0.003 ~ 1 weight part of 3 ~ 30 weight parts.
Preferably, in multipolymer, relative to above-mentioned (methyl) acrylic ester monomer of 100 weight parts, comprise the above-mentioned monomer containing cross-linking functional group of 3 ~ 30 weight parts, if above-mentioned content is less than 3 weight parts, the initial stage cohesive force of binding agent and the value of stripping strength can decline, and if above-mentioned content is greater than 30 weight parts, when Photopolymerizable resin composition is polymerized, there is the worry producing gel reaction easily.
And, preferably, relative to above-mentioned (methyl) acrylic ester monomer of 100 weight parts, comprise the above-mentioned thermal initiator of 0.003 ~ 1 weight part, if above-mentioned content is less than 0.003, initiation reaction aspect have problems, and if above-mentioned content more than 1 weight part, there is the worry that the low polymer of molecular weight can be polymerized.
Preferably, in above-mentioned Photopolymerizable resin composition, relative to above-mentioned (methyl) acrylic ester monomer of 100 weight parts, also comprise chain-transfer agent (the Chain Transfer Agent of 0.002 ~ 1 weight part, hereinafter referred to as " CTA "), when above-mentioned CTA is less than 0.002 weight part, be difficult to control temperature of reaction and speed of response, and when being greater than 1 weight part, molecular weight likely diminishes.
Now, above-mentioned chain-transfer agent, also known as chain-transfer agent, can regulate the molecular weight of the photopolymerization resin that will be formed according to content.For being formed in the radical polymerization (radicalpolymerization) of photopolymerization resin by Photopolymerizable resin composition, be called free radical chain (radicalchain) by causing the active site of addition reaction (active site).Now, above-mentioned CTA is than free radical chain and the existing monomer for addition is easier reacts, thus the growth of free radical chain in stopping growing, CTA is made to have active site, finally play the effect to other monomer Transport Activities points, therefore, it is possible to add CTA when radical polymerization, carry out reaction speed.
But, when using too much CTA, reaction can be caused to be difficult to go on, and the molecular weight of the photopolymerization resin generated reduces, therefore, in the present case, the thermal initiator limiting half life temperature is used to carry out reaction speed, even if thus use less CTA, also can increase the molecular weight of generated photopolymerization resin.
Above-mentioned CTA mainly using sulfydryl (-SH) as functional group, this is because ~ SH combine can compare other Sigmas combine can be lower, therefore, it is possible to be easily changed to free radical.More specifically, above-mentioned CTA can comprise 2-mercaptoacetate (2-mercaptoacetate), n-dodecyl mercaptan (n-dodecyl mercaptan) or 4-4'-thiobis-benzenethiol (4-4'-thiobis benzenethiol), and above-mentioned 2-mercaptoacetate (2-mercaptoacetate), n-dodecyl mercaptan (n-dodecylmercaptan) have longer carbon number, not there is stronger irritating smell, therefore preferably.((4-4'-thiobisbenzenthiol) is different from the monomer affecting physical properties, plays the size of Molecular regulator amount or the effect of adjusting degree of polymerization, therefore, less on the impact of physical properties for above-mentioned 4-4'-thiobis-benzenethiol.
Photopolymerization resin
The invention provides photopolymerization resin, it is characterized in that, by (methyl) acrylic ester monomer, be less than 70 DEG C and ultraviolet thermal initiator can be absorbed to be polymerized containing the monomer of cross-linking functional group and the temperature of 10 hr half-life.
By the polymerization of above-mentioned Photopolymerizable resin composition, the photopolymerization resins such as acrylic resin can be prepared, therefore, in the initiation of above-mentioned polyreaction, what use half life temperature was limited can absorb ultraviolet thermal initiator, thus reaction can be made to keep slowly, and there is speed of response faster.
Comprise in Photopolymerizable resin composition of the present invention and can absorb ultraviolet thermal initiator, polymerization process can absorb the ultraviolet of ultraviolet thermal initiator sensitization by radiation-induced or electron beam isoreactivity energy-ray performs.
When being suitable for uviolizing mode, such as, by irradiation ultraviolet radiations such as high pressure mercury vapour lamp, metal halide lamp or black lamps.In ultraviolet curing mode, as long as irradiation dose can not damage Photopolymerizable resin composition all as physical properties, and control the degree in fully solidification, would not be subject to special restriction, such as, preferably, illumination is 50 ~ 1000mW/cm
2, light quantity is 50 ~ 1000mJ/cm
2.
Particularly, when above-mentioned Photopolymerizable resin composition polymerization, to be less than 50J/cm
2light quantity irradiation ultraviolet radiation when, due to thermal initiator initiation needed for irradiation dose not enough, and there is the worry that cannot form polymerization, and to be greater than 1000mJ/cm
2light quantity irradiation ultraviolet radiation when, due to polymerization excessive velocities, and exist be difficult to control reaction problem.Therefore, by keeping the ultraviolet irradiation amount of above-mentioned light quantity, can either initiation reaction, also there is remarkable effect in the adjustment of speed of response.More specifically, speed of response is fixed on 30 DEG C, and with 50 ~ 1000mJ/cm
2light quantity carry out irradiation ultraviolet radiation, thus be polymerized, this can make exothermic temperature during polymerization lower.
The invention is characterized in, when being polymerized by above-mentioned Photopolymerizable resin composition and forming Photopolymerizable resin composition, exothermic temperature is 30 ~ 40 DEG C.When carrying out above-mentioned polymerization, maintain relatively low exothermic temperature, the side reaction of UV (ultraviolet) polar monomer of double bond and additional gel reaction etc. can not be had, thus, when photopolymerization resin polymerization reaction take place, reaction heat and speed of response can be regulated.
When (methyl) acrylic ester monomer, containing the monomer of cross-linking functional group and thermal initiator generation continuity polyreaction, can heat release, and with reference to this exothermic temperature, just can predict reactivity and the speed of response of polyreaction.When above-mentioned monomer and thermal initiator aggregate into photopolymerization resin, if exothermic temperature is less than 30 DEG C, then there is the high molecular problem of the target molecular weight that cannot be polymerized to set by conjunction, if and exothermic temperature is greater than 40 DEG C, then due to the reaction between UV polar monomer, can there is the problem of gel reaction or side reaction in existence.
The molecular weight of the above-mentioned photopolymerization resin by polymerization preparation can reach more than 1,000,000.When carrying out UV solidification in the past, due to the reactivity of monomer and light trigger, produce a large amount of reaction heat, therefore, be not easy Molecular regulator amount.Further, in order to regulate the initiation of free radical, the molecular weight of the photopolymerization resin using more CTA to generate is 500,000 ~ about 600,000.But in situation of the present invention, when the photopolymer resin composition comprising the thermal initiator defining the transformation period is aggregated into photopolymerization resin, low reaction heat can be kept, even if minimize the CTA amount that will add, also can increase molecular weight.
Therefore, particularly, the molecular weight of above-mentioned photopolymerization resin can be located at more than 1,200,000, is more specifically more than 1,400,000, when the molecular weight of above-mentioned photopolymerization resin is less than 1,000,000, there is the stripping strength of binding agent and the more weak problem of weather resistance.
Be illustrated centered by embodiments of the invention above, but this is only illustrate, as long as those skilled in the art of the invention, can carry out various deformation and other equal embodiments thus with regard to understanding.Therefore, the technical scope that the present invention is really claimed should by inventing claimed scope to judge.
< embodiment and comparative example >
Embodiments of the invention are recorded in the following table 1.More specifically, by (methyl) ethyl acrylate (EHA) as (methyl) acrylic ester monomer, by (methyl) vinylformic acid-2-hydroxyl ethyl ester (HEA) as hydroxyl monomer, and by (methyl) vinylformic acid (AA) as carboxyl group-containing monomer, and, prepare to comprise and can absorb ultraviolet thermal initiator (embodiment 1, embodiment 2 and comparative example 3, comparative example 4), ultraviolet thermal initiator (comparative example 5 can not be absorbed, comparative example 6) or light trigger (comparative example 1, comparative example 2) Photopolymerizable resin composition.Now, the content of light trigger, thermal initiator or CTA is relative to the weight part of 100 weight parts (methyl) acrylic ester monomer.
Table 1
The characteristic of < experimental example >-photopolymerization resin
In order to make the Photopolymerizable resin composition of upper table 1 carry out photopolymerization, after irradiating the black fluorescent light of about 5 minutes, exothermic maximum temperature when assaying reaction carries out.After this, the molecular weight of the photopolymerization resin be polymerized is measured by 1260 unlimited gel chromatography elite systems (InfinityGel Permeation Chromatogtaphy (GPC) system) (Agilent Technologies of the U.S., AgilentTechnologies (USA)).
Table 2
| Exothermic maximum temperature (DEG C) during polymerization | Molecular weight | |
| Embodiment 1 | 35 | 1000000 |
| Embodiment 2 | 40 | 1500000 |
| Comparative example 1 | 55 | 600000 |
| Comparative example 2 | 75 | 500000 |
| Comparative example 3 | 60 | 650000 |
| Comparative example 4 | 70 | 550000 |
| Comparative example 5 | 100 | -(cannot be polymerized) |
| Comparative example 6 | 100 | -(cannot be polymerized) |
Exothermic temperature when upper table 2 represents the polymerization of above-described embodiment and comparative example and the measurement result of molecular weight.With reference to upper table 2, embodiment 1 and embodiment 2 when, comprise the polymerization result that half life temperature is limited at the Photopolymerizable resin composition of the thermal initiator of less than 70 DEG C and define the photopolymerization resin of molecular weight more than 1,000,000, and exothermic temperature during polymerization also remains on the lower level of less than 40 DEG C.Particularly, during polymerization, react by ultraviolet initiation reaction, the temperature of now reacting maintains 30 DEG C.
In contrast to this, replace thermal initiator, comprise light trigger comparative example 1 and comparative example 2 when, when aggregating into photopolymerization resin, because exothermic temperature is high, cause the adjustment of reacting to have difficulties, and only stay in and prepare the low photopolymerization resin of molecular weight.And, comparative example 3 and comparative example 4 when, temperature of reaction is set to 30 DEG C, and caused polyreaction by ultraviolet radiation absorption, but due to the high thermal initiator that the temperature comprising the transformation period is more than 70 DEG C, the lower exothermic temperature of less than 40 DEG C cannot be kept, therefore, have difficulties in polyreaction, the photopolymerization resin of the molecular weight with about 500,000 can only be obtained.
Comparative example 5 and comparative example 6 when, although use half life temperature is the thermal initiator of less than 70 DEG C, due to temperature of reaction is fixed on 70 DEG C, and pass through thermal booster reaction, instead of caused by ultraviolet radiation absorption, therefore, the exothermic temperature of mensuration is about more than 100 DEG C, there occurs high thermopositive reaction, result, due to the carrying out of gel reaction, cannot be polymerized between monomer, thus fail determining molecular weight.On the contrary, as mentioned above, use the phase temperature that declines to be less than 70 DEG C and the exothermic temperature that can absorb mensuration in the embodiment 1 of ultraviolet thermal initiator and embodiment 2 is less than 40 DEG C, and carry out the polymerization between monomer when there is no gel reaction.
Further, compared with comparative example 1 to comparative example 4, embodiment 1, embodiment 2 when, although comprise a small amount of CTA, because reaction heat is lower, thus there is no the situation of other side reactions, aggregating into the photopolymerization resin of high molecular.Therefore, comprise and define the absorbing in the characteristic of Photopolymerizable resin composition of the present invention of ultraviolet thermal initiator of transformation period, reaction heat and speed of response can be regulated, even if use a small amount of CTA when forming photopolymerization resin, also because of lower exothermic temperature, and by the speed of response controlled, the photopolymerization resin that molecular weight is large can be prepared.
Claims (12)
1. a Photopolymerizable resin composition, is characterized in that, comprises:
(methyl) acrylic ester monomer;
Containing the monomer of cross-linking functional group; And
Thermal initiator, the temperature of its 10 hr half-life is less than 70 DEG C, and can absorb ultraviolet.
2. Photopolymerizable resin composition according to claim 1, it is characterized in that, described (methyl) acrylic ester monomer is for being selected from by (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid Zhongshu butyl ester, (methyl) amyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid-2-ethyl butyl ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) dodecyl acrylate and (methyl) tetradecyl acrylate composition group in more than one.
3. Photopolymerizable resin composition according to claim 1, is characterized in that, the described monomer containing cross-linking functional group be selected from the group that is made up of hydroxyl monomer, carboxyl group-containing monomer and nitrogen containing monomer more than one.
4. Photopolymerizable resin composition according to claim 1, is characterized in that, described thermal initiator is azo compound.
5. Photopolymerizable resin composition according to claim 4, it is characterized in that, described azo compound is selected from by 2,2 '-azo two (isopropyl cyanide), 2,2 '-azo two (2,4-methyl pentane nitrile), 2, two (the 4-methoxyl group-2 of 2 '-azo, 4-methyl pentane nitrile), azo-bis-iso-dimethyl, 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride and 2, more than one in the group of two [N-(2-carboxy ethyl)-2-methyl-prop amidine] hydrate composition of 2 '-azo.
6. Photopolymerizable resin composition according to claim 1, it is characterized in that, in described Photopolymerizable resin composition, relative to (methyl) acrylic ester monomer described in 100 weight parts, comprise the described containing the monomer of cross-linking functional group and the described thermal initiator of 0.003 ~ 1 weight part of 3 ~ 30 weight parts.
7. Photopolymerizable resin composition according to claim 1, is characterized in that, in described Photopolymerizable resin composition, relative to (methyl) acrylic ester monomer described in 100 weight parts, also comprises the chain-transfer agent of 0.002 ~ 1 weight part.
8. Photopolymerizable resin composition according to claim 7, is characterized in that, described chain-transfer agent be selected from the group be made up of 2-mercaptoacetate, n-dodecyl mercaptan and 4-4'-thiobis-benzenethiol more than one.
9. a photopolymerization resin, is characterized in that, is polymerized by Photopolymerizable resin composition according to claim 1.
10. photopolymerization resin according to claim 9, is characterized in that, when carrying out described polymerization, irradiates 50 ~ 1000mJ/cm
2the ultraviolet of light quantity.
11. photopolymerization resins according to claim 9, is characterized in that, exothermic temperature when carrying out described polymerization is 30 ~ 40 DEG C.
12. photopolymerization resins according to claim 9, is characterized in that, the molecular weight of described photopolymerization resin is more than 1,000,000.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2012-0083267 | 2012-07-30 | ||
| KR1020120083267A KR20140016557A (en) | 2012-07-30 | 2012-07-30 | Photopolymerization resin composition and photopolymerization resin including the same |
| PCT/KR2013/006129 WO2014021562A1 (en) | 2012-07-30 | 2013-07-10 | Photopolymerizable resin composition and photopolymerizable resin containing same |
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| JP (1) | JP6089217B2 (en) |
| KR (1) | KR20140016557A (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111434354A (en) * | 2019-01-14 | 2020-07-21 | 西安电子科技大学 | Temperature-sensitive nano-drug preparation for in-depth delivery of tumor drugs and preparation method and application thereof |
| CN112094386A (en) * | 2020-08-25 | 2020-12-18 | 浙江新光饰品股份有限公司 | Photosensitive resin for ashless 3D printing |
| CN113015752A (en) * | 2018-10-01 | 2021-06-22 | 索理思科技公司 | Ultraviolet assisted photoinitiated free radical polymerization |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102132074B1 (en) * | 2018-07-13 | 2020-07-09 | 존스미디어 주식회사 | UV coating composition with increased transmittance rate and method for manufacturing the same |
| JP7400844B2 (en) | 2020-04-16 | 2023-12-19 | 株式会社レゾナック | Photocurable resin composition and cured product |
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| JPH055014A (en) * | 1991-06-26 | 1993-01-14 | Sekisui Chem Co Ltd | Photopolymerizable composition and method for polymerizing and cross-linking the same |
| CA2217126A1 (en) * | 1996-10-08 | 1998-04-08 | Rohm And Haas Company | Acrylic flexible light pipe of improved thermal stability |
| JP5135494B2 (en) * | 1999-12-22 | 2013-02-06 | 綜研化学株式会社 | Acrylic adhesive tape and method for producing the same |
| JP2001335603A (en) * | 2000-05-26 | 2001-12-04 | Toagosei Co Ltd | Method for producing water-soluble polymer |
| WO2005042612A1 (en) * | 2003-11-04 | 2005-05-12 | Soken Chemical & Engineering Co., Ltd. | Polymerizable composition and (meth)acrylic thermally conductive sheet |
| KR100855634B1 (en) * | 2006-12-28 | 2008-09-01 | 엘지엠엠에이 주식회사 | Acrylate syrup and manufacturing method thereof |
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| KR20080106761A (en) * | 2007-06-04 | 2008-12-09 | 주식회사 엘지화학 | Pressure-sensitive adhesives composition for solar cell |
| CN101935374A (en) * | 2010-09-29 | 2011-01-05 | 山东瑞丰高分子材料股份有限公司 | Method for producing acrylate polymer by using high-activity low-temperature starting type initiating agent |
| CN102603970A (en) * | 2012-01-13 | 2012-07-25 | 重庆大学 | Preparation method of cationic polyacrylamide |
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| CN113015752A (en) * | 2018-10-01 | 2021-06-22 | 索理思科技公司 | Ultraviolet assisted photoinitiated free radical polymerization |
| CN113015752B (en) * | 2018-10-01 | 2023-10-24 | 索理思科技公司 | Ultraviolet assisted photo-initiated free radical polymerization |
| CN111434354A (en) * | 2019-01-14 | 2020-07-21 | 西安电子科技大学 | Temperature-sensitive nano-drug preparation for in-depth delivery of tumor drugs and preparation method and application thereof |
| CN112094386A (en) * | 2020-08-25 | 2020-12-18 | 浙江新光饰品股份有限公司 | Photosensitive resin for ashless 3D printing |
Also Published As
| Publication number | Publication date |
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| JP2015522704A (en) | 2015-08-06 |
| TW201406790A (en) | 2014-02-16 |
| KR20140016557A (en) | 2014-02-10 |
| WO2014021562A1 (en) | 2014-02-06 |
| TWI618720B (en) | 2018-03-21 |
| CN104507985B (en) | 2017-03-22 |
| JP6089217B2 (en) | 2017-03-08 |
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