CN104507985B - Photopolymerizable resin composition and photopolymerizable resin containing same - Google Patents
Photopolymerizable resin composition and photopolymerizable resin containing same Download PDFInfo
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- CN104507985B CN104507985B CN201380040732.7A CN201380040732A CN104507985B CN 104507985 B CN104507985 B CN 104507985B CN 201380040732 A CN201380040732 A CN 201380040732A CN 104507985 B CN104507985 B CN 104507985B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- 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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- 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
- C08K5/0008—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 the photopolymerization resin comprising the Photopolymerizable resin composition, in more detail
Ground, is related to a kind of thermal initiator for containing in the monomer of predetermined component and can absorbing the ultraviolet for defining half life temperature
Photopolymerizable resin composition.
Background technology
Existing compositions of thermosetting resin uses organic solvent, but the organic solvent for being used wave in the curing process
Send out, and in terms of there is environment, and ultraviolet curing mode is compared, with curing process length, it is suitable for automatic complex procedures
Problem.Therefore, currently tend to being continually striving to researching and developing and a kind of had for improving existing used compositions of thermosetting resin
Problem ultra-violet solidified resin composition.
But, although the ultraviolet-curing resin composition of Korean Patent Laid the 10-2006-0020098th
Comprising uv curing resin, initiator, ultraviolet response type propylene or vinyl monomer and inorganic powder, but as light being drawn
The mixture for sending out agent and thermal initiator is used as initiator, thus is reacted while luminous energy is absorbed, therefore, ultraviolet
In terms of the photopolymerization of line hardening resin composition, still suffer from being difficult the problem of reaction speed and molecular weight.
The content of the invention
The technical problem to be solved in the present invention
In order to solve the above problems, it is an object of the present invention to provide Photopolymerizable resin composition, which is carrying out photopolymerization
When, excessive reaction heat will not be produced because of the reactivity of monomer, and can reaction speed and molecular weight.
Also, in general, in the case of more using chain-transferring agent, molecular weight can be reduced, therefore, another mesh of the present invention
Be, there is provided it is a kind of by the light that the Photopolymerizable resin composition that can also increase molecular weight with chain-transferring agent is polymerized can be lacked
Polymer resin.
Technical scheme
In order to reach an above-mentioned purpose, the Photopolymerizable resin composition of the present invention, it is characterised in that comprising (methyl) propylene
The temperature of esters of gallic acid monomer, the monomer containing cross-linking functional group and 10 hour half-life is less than 70 DEG C, and can absorb ultraviolet
Thermal initiator.
Also, in order to reach above-mentioned another object, the photopolymerization resin of the present invention, it is characterised in that by (methyl) propylene
The temperature of esters of gallic acid monomer, the monomer containing cross-linking functional group and 10 hour half-life is less than 70 DEG C, and can absorb ultraviolet
Thermal initiator be polymerized.
Beneficial effect
The present invention in Photopolymerizable resin composition comprising the low thermal initiator of half life temperature that can absorb ultraviolet,
So as to react slow (mild), and due to above-mentioned thermal initiator, reaction can be also made when Photopolymerizable resin composition is polymerized
It is relatively low that heat is maintained.
Specific embodiment
Can allow with reference to the following examples for describing in detail and advantages and features of the invention and realize these advantages and features
Method definitely.But, the invention is not limited in it is following want disclosed embodiment, can be with mutually different embodiment party
Formula embodies, and the present embodiment is served only for making the disclosure more complete, contributes to the technical field of the invention
Those of ordinary skill intactly informs the category of invention, and the present invention is defined according to the category of the claimed scope of invention.Say
Identical reference in bright book full text censures identical structural element.
Hereinafter, the present invention is described in detail.
Photopolymerizable resin composition
The present invention provides Photopolymerizable resin composition, it is characterised in that (methyl) acrylic ester monomer, official containing bridging property
Can group monomer and the temperature of 10 hour half-life be less than 70 DEG C, and the thermal initiator of ultraviolet can be absorbed.
The species of above-mentioned (methyl) acrylic ester monomer has no particular limits, and for example, can use (methyl) propylene
Acid alkyl ester.Now, if the hydroxyl included in monomer becomes long long-chain, the cohesiveness of Photopolymerizable resin composition declines,
And be difficult to adjust glass transition temperature (Tg) and caking property, it is therefore preferred that (methyl) acrylic ester monomer should be used,
Which has the alkyl that carbon number is 1 to 14.
As the example of these monomers, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propylene can be enumerated
Sour n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) propylene
Sour Zhongshu butyl ester, (methyl) amyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid-2-ethyl butyl ester,
(methyl) n-octyl, (methyl) Isooctyl acrylate monomer, the different nonyl ester of (methyl) acrylic acid, (methyl) dodecyl acrylate and
(methyl) tetradecyl acrylate, can use one or more above-mentioned mixing in the present invention.
When above-mentioned Photopolymerizable resin composition is formed, the monomer containing cross-linking functional group can be added, in the case, this
Invent the polymer that Photopolymerizable resin composition to be formed can be monomer mixture, the polymer of above-mentioned monomer mixture
Comprising (methyl) acrylic ester monomer and the monomer containing cross-linking functional group.
The above-mentioned monomer containing cross-linking functional group gives a kind of friendship that can be reacted with above-mentioned multi-functional crosslinking agent
Lian Xing functional groups, play a part of to adjust durable reliability and the cohesiveness of Photopolymerizable resin composition.Can use containing crosslinking
The monomer of property functional group for example has the monomer containing hydroxyl, carboxyl group-containing monomer and nitrogen containing monomer.
In the present invention, hydroxyl monomer is preferably used in the above-mentioned monomer containing cross-linking functional group, but is not limited to
This.The example of above-mentioned hydroxyl monomer has (methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) 2-hydroxypropyl acrylate, (methyl) third
Olefin(e) acid -4- hydroxy butyl esters, the own ester of (methyl) acrylic acid -6- hydroxyls, (methyl) acrylic acid -8- hydroxyl monooctyl esters, (methyl) acrylic acid -2- hydroxyls
Glycol ester or (methyl) acrylic acid -2- hydroxyl propylene glycol esters, the example of carboxyl group-containing monomer have (methyl) acrylic acid, 2- (first
Base) acryloxyacetic acid, 3- (methyl) acryloxy propionic, 4- (methyl) acryloxy butyric acid, acrylic acid dimer,
Itaconic acid, maleic acid or maleic anhydride, the example of nitrogen containing monomer have Methacrylamide, NVP or N- second
Thiazolinyl caprolactam, but be not limited thereto.The present invention can use one or more above-mentioned mixing.
Also, the Photopolymerizable resin composition of the present invention is except comprising (methyl) acrylic ester monomer and containing friendship property containing connection
Outside the monomer of functional group, thermal initiator can be also included.It is a feature of the present invention that in order to be stably formed the light such as allyl resin
Polymer resin, using the thermal initiator for limiting half life temperature.Above-mentioned thermal initiator forms freedom as one kind by heat
The material of base, can cause the chain polymerization reaction of (methyl) acrylic ester monomer and the monomer containing cross-linking functional group.Also,
Now, the half-life of thermal initiator refers to that the original amount of initiator is decomposed half and forms the time required during free radical.
Under normal circumstances, when photopolymerization resin is formed as Photopolymerizable resin composition, can use light trigger, it is light-initiated
Agent does not have the half-life, as long as luminous energy can be absorbed, can just be reacted, thus is difficult control reaction heat.Therefore, do not drawn using light
Agent is sent out, but use can absorb the thermal initiator of ultraviolet, and the half life temperature of above-mentioned thermal initiator is defined to into low temperature,
So as to control reaction heat, and relatively low exothermic temperature is maintained, so that the polymerization of the resin combination of the photopolymerization of entirety
Reaction keeps slow.
10 hours half life temperatures of above-mentioned thermal initiator are less than 70 DEG C, preferably less than 60 DEG C, more preferably 50 DEG C
Below.On the other hand, the lower limit of 10 hours half life temperatures of the above-mentioned thermal initiator in the present invention has no particular limits.But
If half life temperature was too low in 10 hours, non-homogeneous curing reaction etc. may be caused when photopolymerization resin is formed, therefore, can be
The above-mentioned half life temperature of appropriate control in the range of more than 30 DEG C.
In the case that the temperature that partly declines of above-mentioned thermal initiator is more than 70 DEG C, when polar monomer is polymerized, base can persistently occur
In the side reaction of double bond, and the side reaction for persistently occurring can cause gel reaction, may cause to be hardly formed the polymerization of monomer.Cause
The half life temperature of thermal initiator is set to less than 70 DEG C by this, is maintained low reaction heat, and is opened under conditions of temperature is relatively low
Begin to consume thermal initiator, and cause and terminate relatively fast, high molecular photopolymerization resin can be formed in the short period of time.
Also, above-mentioned thermal initiator is characterised by, ultraviolet can be absorbed.The thermal initiator of ultraviolet can be absorbed and passed through
Heat is different come the general thermal initiator for forming free radical, can form free radical by ultraviolet radiation absorption.The heat of ultraviolet can be absorbed
Initiator compared with general thermal initiator, the 300～400nm wavelength zones mainly used under the conditions of photopolymerization in a mild condition
Domain can also absorb ultraviolet, therefore compare general thermal initiator and can be used in the photopolymerization under temperate condition.Therefore, though one
As 10 hours half life temperatures of thermal initiator maintain less than 70 DEG C, if maintenance above-mentioned half life temperature can be absorbed ultraviolet
The thermal initiator of line is used in polymerization in photopolymerization mode, can also make the condition of polymerization become various, and due to reaction heat it is relatively low,
On this point of can also carry out polymerization in a mild condition has the advantage that.
Specifically, above-mentioned thermal initiator is characterised by, usually azo compound or peroxide compound, but this
Bright feature is that the thermal initiator of the present invention is the azo compound of the half life temperature with above range.Peroxide
Compound has benzoyl peroxide, dilauroyl peroxide, di-t-butyl peroxide, cumyl hydroperoxide etc., but they
Above 70 DEG C of half life temperature.In contrast, azo compound has a relatively low half life temperature, therefore preferably.
Above-mentioned azo compound can be using selected from 2,2 '-azo double (isobutyronitriles), the double (2,4- bis- of 2,2 '-azo
Methyl valeronitrile), 2,2 '-azo double (4- methoxyl group -2,4- methyl pentane nitriles), azo-bis-iso-dimethyl, 2,2 '-azo two
[2- (2- imidazoline -2- bases) propane] dihydrochloride and double [N- (2- the carboxy ethyls) -2- methyl-prop amidines] hydrates of 2,2 '-azo
One or more of group of composition.10 hour half-life can be constituted using selected from one or more of above-mentioned azo compound
Temperature is less than 70 DEG C of thermal initiator, and by limiting the half-life, can bring above-mentioned effect.
The Photopolymerizable resin composition of the present invention is characterised by, relative to above-mentioned (methyl) acrylic acid of 100 weight portions
The above-mentioned heat of esters monomer, the above-mentioned monomer containing cross-linking functional group comprising 3～30 weight portions and 0.003～1 weight portion is drawn
Send out agent.
Preferably, in copolymer, relative to above-mentioned (methyl) acrylic ester monomer of 100 weight portions, comprising 3～30 weights
The above-mentioned monomer containing cross-linking functional group of amount part, if above-mentioned content is less than 3 weight portions, the initial stage cohesive force of binding agent and stripping
Value from intensity can decline, and if above-mentioned content is more than 30 weight portions, when Photopolymerizable resin composition is polymerized, exist easily
Produce the worry of gel reaction.
And, it is preferable that relative to above-mentioned (methyl) acrylic ester monomer of 100 weight portions, comprising 0.003～1 weight
The above-mentioned thermal initiator of amount part, if above-mentioned content is less than 0.003, has problems in terms of initiation reaction, and if above-mentioned content
More than 1 weight portion, there is the worry that the low macromolecule of molecular weight can be polymerized.
Preferably, in above-mentioned Photopolymerizable resin composition, relative to above-mentioned (methyl) the esters of acrylic acid list of 100 weight portions
Body, the chain-transferring agent (Chain Transfer Agent, hereinafter referred to as " CTA ") also comprising 0.002～1 weight portion are above-mentioned
In the case that CTA is less than 0.002 weight portion, it is difficult to controlling reaction temperature and reaction speed, and in the case of being more than 1 weight portion,
Molecular weight is possible to diminish.
Now, above-mentioned chain-transferring agent can adjust photopolymerization resin to be formed also known as chain-transferring agent according to content
Molecular weight.For being formed the radical polymerization (radical of photopolymerization resin by Photopolymerizable resin composition
Polymerization, in), the active site (active site) for causing addition reaction is referred to as into free radical chain (radical
chain).Now, above-mentioned CTA is easier to make for reaction than free radical chain and the existing monomer for addition, so as to stop life
The growth of the free radical chain in length, makes the active points of CTA, finally plays to other monomers the effect of active site of transmitting, therefore,
CTA can be added in radical polymerization, carry out reaction speed.
But, in the case of using excessive CTA, reaction can be caused to be difficult to down, and the photopolymerization for being generated
The molecular weight of resin is reduced, therefore, it is in the present case, anti-to adjust using the thermal initiator for limiting half life temperature
Speed is answered, even if so as to using less CTA, can also increase the molecular weight of generated photopolymerization resin.
Above-mentioned CTA is mainly using sulfydryl (- SH) as functional group, this is because～SH combinations can compare other Sigmas combining
Can be lower, free radical is turned to therefore, it is possible to easily become.More specifically, above-mentioned CTA can include 2- mercaptoacetate (2-
Mercaptoacetate), n-dodecyl mercaptan (n-dodecyl mercaptan) or 4-4'- thiobis-benzenethiol (4-4'-
Thiobis benzenethiol), and above-mentioned 2- mercaptoacetates (2-mercaptoacetate), n-dodecyl mercaptan (n-
Dodecylmercaptan there is longer carbon number), not with stronger penetrating odor, therefore preferably.Above-mentioned 4-4'- is thio
((4-4'-thiobisbenzenthiol) is different from the monomer for affecting physical property, plays the big of Molecular regulator amount for double benzenethiols
Effect that is little or adjusting the degree of polymerization, therefore, the impact to physical property is less.
Photopolymerization resin
The present invention provides photopolymerization resin, it is characterised in that by (methyl) acrylic ester monomer, containing cross-linking functional group
Monomer and the temperature of 10 hour half-life be less than 70 DEG C, and the thermal initiator of ultraviolet can be absorbed be polymerized.
By the polymerization of above-mentioned Photopolymerizable resin composition, the photopolymerization resins such as acrylic resin can be prepared, therefore,
For the initiation of above-mentioned polymerisation, the thermal initiator that can absorb ultraviolet being limited using half life temperature such that it is able to
Make reaction keep slow, and there is reaction speed faster.
Comprising the thermal initiator that can absorb ultraviolet in the Photopolymerizable resin composition of the present invention, polymerization can be by shining
Penetrate induction can absorb ultraviolet thermal initiator activation ultraviolet or electron beam isoreactivity energy-ray performing.
During applicable ultraviolet radiation modality, for example can be by the irradiation such as high-pressure mercury-vapor lamp, metal halide lamp or black light lamp
Ultraviolet.In ultraviolet curing mode, as long as exposure will not damage Photopolymerizable resin composition it is all as it is physical
Matter, and control, in the degree of abundant solidification, to be particularly restricted, for instance, it is preferred that illumination is 50～1000mW/
cm2, light quantity is 50～1000mJ/cm2。
Specifically, when above-mentioned Photopolymerizable resin composition is polymerized, with less than 50J/cm2Light quantity irradiation ultraviolet radiation feelings
Under condition, due to exposure deficiency needed for the initiation of thermal initiator, and there is the worry that cannot form polymerization, and to be more than
1000mJ/cm2Light quantity irradiation ultraviolet radiation in the case of, due to be polymerized excessive velocities, and exist be difficult to control to react ask
Topic.Therefore, by keeping the ultraviolet irradiation amount of above-mentioned light quantity, can either initiation reaction, in terms of the regulation of reaction speed
With remarkable effect.More specifically, reaction speed is fixed on 30 DEG C, and with 50～1000mJ/cm2Light quantity irradiating purple
Outside line, so as to be polymerized, this can make exothermic temperature during polymerization lower.
It is a feature of the present invention that 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, relatively low exothermic temperature is maintained, the UV with double bond will not occur
The side reaction of (ultraviolet) polar monomer and additional gel reaction etc., thus, when there is polymerisation in photopolymerization resin,
Reaction heat and reaction speed can be adjusted.
There is continuity polymerization in (methyl) acrylic ester monomer, the monomer containing cross-linking functional group and thermal initiator anti-
In the case of answering, meeting heat release, and this exothermic temperature is referred to, can just predict the reactivity and reaction speed of polymerisation.It is above-mentioned
When monomer and thermal initiator aggregate into photopolymerization resin, if exothermic temperature is less than 30 DEG C, presence cannot be polymerized to close set
Target molecular weight high molecular problem, and if exothermic temperature be more than 40 DEG C, then due to the reaction between UV polar monomers,
There is a problem of gel reaction or side reaction.
The above-mentioned molecular weight by the photopolymerization resin for preparing that is polymerized is up to more than 1,000,000.When carrying out UV solidifications in the past,
Due to monomer and the reactivity of light trigger, a large amount of reaction heat are produced, thus it is not easy to Molecular regulator amount.Also, in order to adjust
The initiation of free radical, the molecular weight of the photopolymerization resin generated using more CTA is 500,000～600,000 or so.But the present invention
In the case of, the photopolymer resin composition comprising the thermal initiator for defining the half-life is being aggregated into into photopolymerization resin
When, low reaction heat can be kept, even if minimizing to CTA amounts to be added, can also increase molecular weight.
Therefore, specifically, the molecular weight of above-mentioned photopolymerization resin may be provided in more than 1,200,000, more specifically more than 1,400,000,
The molecular weight of above-mentioned photopolymerization resin is weaker less than the peel strength and durability that in the case of 1,000,000, there is binding agent to ask
Topic.
It is illustrated centered on embodiments of the invention above, but this only illustrates, as long as belonging to the present invention
Art personnel, are just understood that thus, it is possible to carry out various deformation and equal other embodiment.Therefore, the present invention really will
Ask the technical scope of protection be judged by the claimed scope of invention.
<Embodiment and comparative example>
Embodiments of the invention are recorded in the following table 1.More specifically, by (methyl) acrylic acid-2-ethyl caproite
(EHA) as (methyl) acrylic ester monomer, by (methyl) acrylic acid -2- hydroxyl ethyl esters (HEA) as hydroxyl monomer, and will
(methyl) acrylic acid (AA) as carboxyl group-containing monomer, also, prepared comprising can absorb ultraviolet thermal initiator (embodiment 1,
Embodiment 2 and comparative example 3, comparative example 4), the thermal initiator (comparative example 5, comparative example 6) or light trigger of ultraviolet can not be absorbed
The Photopolymerizable resin composition of (comparative example 1, comparative example 2).Now, the content of light trigger, thermal initiator or CTA be relative to
The weight portion of (methyl) acrylic ester monomer of 100 weight portions.
Table 1
<Experimental example>The characteristic of-photopolymerization resin
In order that the Photopolymerizable resin composition of upper table 1 carries out photopolymerization, after irradiating the black fluorescent light of about 5 minutes, survey
Exothermic maximum temperature when fixed reaction is carried out.Hereafter, by 1260 unlimited gel chromatography elite system (Infinity Gel
Permeation Chromatogtaphy (GPC) system) (Agilent Technologies of the U.S., Agilent Technologies
(USA)) determine the molecular weight of the photopolymerization resin being polymerized.
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) |
The measurement result of exothermic temperature and molecular weight during the polymerization of the expression above-described embodiment of upper table 2 and comparative example.Reference
In the case of upper table 2, embodiment 1 and embodiment 2, the light for being limited at less than 70 DEG C of thermal initiator comprising half life temperature gathers
The polymerization result of resin composition defines photopolymerization resin of the molecular weight more than 1,000,000, and exothermic temperature when being polymerized
Also it is maintained at less than 40 DEG C of relatively low level.Specifically, during polymerization, reaction is now reacted by ultraviolet initiation reaction
Temperature maintains 30 DEG C.
In contrast to this, in the case of replacing thermal initiator, the comparative example 1 comprising light trigger and comparative example 2, aggregate into light
During polymer resin, as exothermic temperature is high, cause the regulation reacted to have difficulties, and only stay in and prepare the low light of molecular weight and gather
Resin.Also, in the case of comparative example 3 and comparative example 4, reaction temperature is set to into 30 DEG C, and is caused by ultraviolet radiation absorption
Polymerisation, but due to high thermal initiator that the temperature comprising the half-life is more than 70 DEG C, it is impossible to kept for less than 40 DEG C
Relatively low exothermic temperature, therefore, have difficulties in terms of polymerisation, the light with 500,000 or so molecular weight can only be obtained and gathered
Resin.
In the case of comparative example 5 and comparative example 6, although using the thermal initiator that half life temperature is less than 70 DEG C, but by
In reaction temperature is fixed on 70 DEG C, and by thermal booster reaction, rather than by ultraviolet radiation absorption initiation, therefore, measure
About more than 100 DEG C of exothermic temperature, there occurs high exothermic reaction, as a result, due to the carrying out of gel reaction, cannot between monomer
Polymerization, so that fail to determine molecular weight.Conversely, as described above, hot using declining phase temperature for less than 70 DEG C and ultraviolet can be absorbed
The exothermic temperature determined in the embodiment 1 and embodiment 2 of initiator is less than 40 DEG C, and is entered in the case of no gel reaction
Polymerization between row monomer.
Also, compared with comparative example 1 to comparative example 4, in the case of embodiment 1, embodiment 2, although comprising a small amount of
CTA, but as reaction heat is relatively low, so as to there is no the situation of other side reactions, aggregated into the photopolymerization resin of HMW.
Therefore, the characteristic of the Photopolymerizable resin composition of the present invention comprising the thermal initiator that can absorb ultraviolet for defining the half-life
On, reaction heat and reaction speed can be adjusted, even if when photopolymerization resin is formed using a small amount of CTA, also because relatively low is put
Hot temperature, and the big photopolymerization resin of molecular weight can be prepared by the reaction speed of control.
Claims (7)
1. a kind of Photopolymerizable resin composition, it is characterised in that include：
(methyl) acrylic ester monomer；
Monomer containing cross-linking functional group；And
Thermal initiator, the temperature of its 10 hour half-life is 30～70 DEG C, and can absorb ultraviolet；
The thermal initiator is azo compound；
The azo compound is selected from azo-bis-iso-dimethyl, 2,2 '-azo, two [2- (2- imidazoline -2- bases) third
Alkane] double [N- (2- carboxy ethyls) -2- methyl-prop amidines] hydrate compositions of dihydrochloride and 2,2 '-azo group in one kind with
On；
In the Photopolymerizable resin composition, relative to (methyl) acrylic ester monomer described in 100 weight portions, also include
The chain-transferring agent of 0.002～1 weight portion；
Group of the chain-transferring agent selected from 2- mercaptoacetates, n-dodecyl mercaptan and 4-4'- thiobis-benzenethiols composition
One or more of；
The monomer containing cross-linking functional group is hydroxyl monomer.
2. Photopolymerizable resin composition according to claim 1, it is characterised in that (methyl) acrylic ester monomer
It is selected from (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid isopropyl
Ester, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid Zhongshu butyl ester, (methyl) acrylic acid penta
Ester, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid-2-ethyl butyl ester, (methyl) n-octyl, (methyl)
Isooctyl acrylate monomer, the different nonyl ester of (methyl) acrylic acid, (methyl) dodecyl acrylate and (methyl) tetradecyl acrylate composition
One or more of group.
3. Photopolymerizable resin composition according to claim 1, it is characterised in that in the Photopolymerizable resin composition,
Relative to (methyl) acrylic ester monomer described in 100 weight portions, comprising containing cross-linking functional group described in 3～30 weight portions
Monomer and 0.003～1 weight portion the thermal initiator.
4. a kind of photopolymerization resin, it is characterised in that be polymerized by the Photopolymerizable resin composition described in claim 1.
5. photopolymerization resin according to claim 4, it is characterised in that when carrying out the polymerization, irradiates 50～1000mJ/
cm2The ultraviolet of light quantity.
6. photopolymerization resin according to claim 4, it is characterised in that exothermic temperature when carrying out the polymerization is 30～
40℃。
7. photopolymerization resin according to claim 4, it is characterised in that the molecular weight of the photopolymerization resin is 1,000,000
More than.
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| 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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| CN104507985A CN104507985A (en) | 2015-04-08 |
| CN104507985B true CN104507985B (en) | 2017-03-22 |
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| Country | Link |
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| JP (1) | JP6089217B2 (en) |
| KR (1) | KR20140016557A (en) |
| CN (1) | CN104507985B (en) |
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| WO (1) | WO2014021562A1 (en) |
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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 |
| US11041037B2 (en) * | 2018-10-01 | 2021-06-22 | Solenis Technologies, L.P. | Ultra violet assisted photo initiated free radical polymerization |
| CN111434354B (en) * | 2019-01-14 | 2021-10-08 | 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 |
| JP7400844B2 (en) * | 2020-04-16 | 2023-12-19 | 株式会社レゾナック | Photocurable resin composition and cured product |
| CN112094386B (en) * | 2020-08-25 | 2024-10-11 | 浙江新光饰品股份有限公司 | Ashless photosensitive resin for 3D printing |
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| KR20080106761A (en) * | 2007-06-04 | 2008-12-09 | 주식회사 엘지화학 | Pressure-sensitive adhesives composition for solar cell |
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| CN102603970A (en) * | 2012-01-13 | 2012-07-25 | 重庆大学 | Preparation method of cationic polyacrylamide |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| JP2015522704A (en) | 2015-08-06 |
| WO2014021562A1 (en) | 2014-02-06 |
| TWI618720B (en) | 2018-03-21 |
| JP6089217B2 (en) | 2017-03-08 |
| TW201406790A (en) | 2014-02-16 |
| CN104507985A (en) | 2015-04-08 |
| KR20140016557A (en) | 2014-02-10 |
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