CN103562273A - Curable composition and adhesive for optics - Google Patents
Curable composition and adhesive for optics Download PDFInfo
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- CN103562273A CN103562273A CN201280020326.XA CN201280020326A CN103562273A CN 103562273 A CN103562273 A CN 103562273A CN 201280020326 A CN201280020326 A CN 201280020326A CN 103562273 A CN103562273 A CN 103562273A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/06—Polythioethers from cyclic thioethers
- C08G75/08—Polythioethers from cyclic thioethers from thiiranes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
- C09J181/02—Polythioethers; Polythioether-ethers
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Abstract
Provided are a curable composition and the like that have a high refractive index and possess the properties required of an adhesive for optics in that they are photocurable, low-shrinking, and colorless and transparent and have a workable viscosity. The invention provides a curable composition comprising a polythiol oligomer obtained by reacting a polythiol and sulfur (component A) and a polyene compound (component B), and a curable composition comprising a polythiol oligomer obtained by reacting a polythiol and sulfur (component A), an episulfide compound (component C) and a photobase generator (component D).
Description
Technical field
The suitable solidification compound of caking agent for optics using while the present invention relates to as making composite optic element.
Background technology
The caking agent when acrylic compound etc. of usining is widely used as making optical element as the Photocurable composition of main component.For caking agent, adaptation, light solidified, physical strength, weather resistance and optical characteristics are fundamental property, but in recent years along with the multifunction of optical element, specific refractory power becomes important performance.Particularly the high refractive index of caking agent is because the degree of freedom expansion of optical design is expected high.As use, there is the purposes example of the caking agent of high refractive index, the example of for example composite optic element, can list achromatic lens (achromat lens) that the bonding by two lens forms, the compound prism that mixes the formation complicated shapes such as (hybrid) type non-spherical lens, colour splitting prism forming by glass and resin etc.For the caking agent using in these purposes, not only require high specific refractory power, certainly also require adaptation, light solidified, water white transparency, thermotolerance, be suitable for these performances of viscosity of operation.
As the compound with high refractive index, found the episulfide (patent documentation 1～4) that contains sulphur atom with high density in many molecular structures.For example the specific refractory power of the cured article of two (2,3-epithio propyl group) thioethers is 1.70.This episulfide, because viscosity is low, can easily inject mould, is therefore suitable for the making of the formed bodys such as glasses lens.But, to suppose while using as caking agent, caking agent sagging or mobile when viscosity is too low is offset by convered structure and has problems aspect workability when bonding.In addition, episulfide, because the curing contraction of following is large, becomes the reason that adaptation reduces while therefore using as caking agent conventionally.
In addition; as multifunctional (methyl) acrylic compound with high refractive index; known 9; two (4-(the 2-acryloyl-oxy base oxethyl) phenyl) fluorenes (hereinafter referred to as A-BPEF) (specific refractory power of cured article is 1.62) of 9-, 4,4 '-bis-(methacryloyl sulfenyl) diphenylsulfide (hereinafter referred to as MPSMA) (specific refractory power of cured article is 1.69) etc.But these compounds, owing to being solid under normal temperature, are difficult to independent use.
In addition, the curing contraction of following of multifunctional (methyl) acrylic compound is large conventionally, becomes the reason that adaptation reduces while using as caking agent.
Known on the other hand, the alefinically unsaturated compounds such as (methyl) acrylic compound and mercaptan compound combine alkene-composition of mercaptans, because mercaptan compound contains the sulphur atom that atomic refraction is high, therefore can obtain the cured article that specific refractory power is high.But the addition polymerization that thiol group closes group with ethylenic unsaturated bond is owing to comparing with chain polymerization, cross-linking set is few, exists in addition the thioether bond generate that the tendency of soft cured article is provided, and therefore resulting cured article is deposited at high temperature easily softening problem.In order to obtain sufficient thermotolerance, need to select polyfunctional alefinically unsaturated compounds and mercaptan compound.
In patent documentation 5, recorded the alkene-composition of mercaptans being formed by the difunctionality mercaptan compound that contains Isosorbide-5-Nitrae-dithian ring and isocyanuric acid triallyl ester or cyanuric acid alkatriene propyl diester.But, for the not special record of specific refractory power of cured article.In addition, owing to using dual functional mercaptan compound, cured article at high temperature easily softens (with reference to comparative example).
In patent documentation 6, recorded the alkene-composition of mercaptans being formed by A-BPEF, alefinically unsaturated compounds and mercaptan compound.Known according to embodiment, the specific refractory power of cured article is at the most in 1.58～1.61 scope.
In patent documentation 7, recorded the alkene-composition of mercaptans being formed by MPSMA, vinyl monomer and polythiol.Known according to embodiment, the specific refractory power of cured article is at most 1.649.But MPSMA is easily colored as yellow, be solid in addition, therefore the meltage in composition is limited.
In addition, in patent documentation 8, recorded the resin combination being formed by the sulfocompound that there is the resinous principle of fluorenes ring and MPSMA etc. and have diphenylsulfide skeleton.Exemplified with the resin with specific refractory power 1.724.But the resin combination in this invention is essentially polyester and the mixing thermoplastic resin forming of sulfocompound with fluorenes ring, not solidification compound, can not give light solidified certainly.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 9-71580 communique
Patent documentation 2: Japanese kokai publication hei 9-110979 communique
Patent documentation 3: Japanese kokai publication hei 9-255781 communique
Patent documentation 4: TOHKEMY 2001-163874 communique
Patent documentation 5: TOHKEMY 2000-154251 communique
Patent documentation 6: TOHKEMY 2010-254732 communique
Patent documentation 7: Japanese kokai publication hei 03-021638 communique
Patent documentation 8: TOHKEMY 2005-187661 communique
Summary of the invention
the problem that invention will solve
Therefore, the object of the invention is to, provide and there is high specific refractory power, and also have light solidified, low-shrinkage, water white transparency concurrently, be suitable for the solidification compound of these performances that require with caking agent as optics of viscosity of operation.
for the scheme of dealing with problems
The inventor etc. have carried out in depth research in order to address the above problem, found that, contain polythiol oligopolymer (A composition) that polythiol and reaction of Salmon-Saxl obtain and the solidification compound of polyenic compounds (B composition), further high refractive index, and also have the necessary performance with caking agent as optics concurrently, thereby completed the present invention.
In addition, the discoveries such as the inventor, the solidification compound that contains polythiol oligopolymer (A composition), episulfide (C composition) and Photobase generator (D composition) that polythiol and reaction of Salmon-Saxl obtain, as caking agent, there is the viscosity that is suitable for workability, and it is little to solidify the contraction of following, and as optics caking agent, is therefore suitable.And then find, when polythiol and reaction of Salmon-Saxl, preferably use basic catalyst, while using hindered amine as this catalyzer, can obtain the solidification compound of excellent storage stability (sufficient reacting of episulfide is slow).Discovery based on above, has completed the present invention.
the effect of invention
According to the present invention, can provide and there is high specific refractory power, and also have light solidified, low-shrinkage, water white transparency concurrently, be suitable for operation viscosity these as optics the solidification compounds by the performance of caking agent.
Embodiment
The first solidification compound of the present invention contains polythiol oligopolymer (A composition) and the polyenic compounds (B composition) that polythiol and reaction of Salmon-Saxl obtain and forms.
First the manufacture method of polythiol oligopolymer (A composition) is described.
The polythiol that becomes the raw material of polythiol oligopolymer refers to the compounds in a part with two above thiol groups, can be any one in straight chain shape, a chain, ring-type.When particularly pursuing the high refractive indexization of solidification compound and being suitable for the viscosity of workability, be preferably the compound shown in following general formula (1)～(3).
(in formula (1), p1 and p2 represent 0～1 integer, X independently of one another
1～X
8represent independently of one another hydrogen atom or methyl mercaptan base.)
(in formula (2), q represents 0～3 integer, R
1represent the alkylidene group that simple key or carbonatoms are 1～3.)
(in formula (3), r represents 0～3 integer, R
2represent the alkylidene group that carbonatoms is 1～3.)
Example as the compound shown in general formula (1), can list 1, 5-dimercapto-3-thia pentane, 2-mercapto methyl-1, 5-dimercapto-3-thia pentane, 2, two (mercapto methyl)-1 of 4-, 5-dimercapto-3-thia pentane, 4-mercapto methyl-1, 8-dimercapto-3, 6-dithia octane, 4, two (mercapto methyl)-1 of 8-, 11-dimercapto-3, 6, 9-tri-thia undecanes, 4, two (mercapto methyl)-1 of 7-, 11-dimercapto-3, 6, 9-tri-thia undecanes, 5, two (mercapto methyl)-1 of 7-, 11-dimercapto-3, 6, 9-tri-thia undecanes etc., example as compound shown in general formula (2), can list 2, 5-dimercapto-1, 4-dithian, 2, 5-dimercapto methyl-1, 4-dithian, 2, 5-dimercapto ethyl-1, 4-dithian etc., example as compound shown in general formula (3), can list xylylene two mercaptan etc.Poly-thiol compound as beyond compound shown in general formula (1)～(3), can list ethylene glycol bis (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester), tetramethylolmethane four (3-mercaptopropionic acid ester), phenylene dimercaptan, benzylidene two mercaptan etc.
For becoming the sulphur of raw material of polythiol oligopolymer, sulphur forms many allotropic substances, but is preferably the S8 sulphur of the ring-type of conventionally knowing.Sulphur can be any form, for example, can be lenticular, colloidal, powder or sublimed sulphur.
According to Jounal of Organic Chemistry, 32 volumes, 3833～3836 pages (1967) are known, about reacting of polythiol and sulphur, for example, in the situation that product is dipolymer, mainly according to following reaction formula (6) and (7), carry out.
(in formula, R represents organic group, and n represents more than 1 integer).
About the consumption of sulphur, with respect to 1 molar sulphur alcohol radical, preferably sulphur atom is in the scope of 0.2～0.95 mole, more preferably in the scope of 0.2～0.5 mole.During 0.2 mole of the use quantity not sufficient of sulphur, the transformation efficiency of polythiol is too low and impracticable, while surpassing 0.95 mole, when generating the excessive polythiol oligopolymer of the preferred molecular weight of raw material as optical material, the easy sulphur of remained unreacted, so not preferred.
Polythiol reacts by heating to carry out under the existence of basic catalyst or not with sulphur, is preferably the method for using basic catalyst.As the kind of basic catalyst, can list amine, ammonium salt, Lin, phosphonium salt etc.About the consumption of basic catalyst, 100 moles of the thiol groups containing in the polythiol with respect to raw material, preferably in the scope of 0.005～5 mole, more preferably in the scope of 0.05～0.5 mole.
For the order of addition of each raw material, can be to adding catalyzer in the mixing solutions of polythiol and sulphur or to adding sulphur in the mixing solutions of polythiol and catalyzer or to the mixing solutions that adds polythiol and catalyzer in the mixing solutions of polythiol and sulphur.In order reacting balance to be carried out, can be divided into repeatedly to add catalyzer, sulphur.
Polythiol can carry out with reacting of sulphur under the existence of polyenic compounds (B composition).Polythiol reacts due to the generation that is attended by hydrogen sulfide with sulphur, preferably under exhaust, decompression under react.Can use solvent as required.While using solvent, need distillation to remove the rear operation of solvent.Temperature of reaction is not particularly limited, but preferably in the scope of 0～100 ℃, Yi Bian also on one side observing response carry out the situation temperature that raises lentamente.Reaction times owing to depending on the various conditions such as ratio, temperature of reaction of kind, polythiol and the sulphur of raw material, can not generally stipulate, reacts the straight not sulphur of remained unreacted.
Then the first solidification compound of the present invention is described.
The first solidification compound of the present invention contains aforementioned polythiol oligopolymer (A composition) and polyenic compounds (B composition) form.
Polyenic compounds (B composition) refer in a part has the compound that two above ethylenic unsaturated bonds close group, as ethylenic unsaturated bond, closes group, can list acryl, methacryloyl, vinyl, allyl group etc.While particularly pursuing the high refractive index of solidification compound, be preferably the compound in molecule with aromatic nucleus, heterocycle, as the example of this compound, can list the compound shown in the compound shown in isocyanuric acid triallyl ester, cyanuric acid alkatriene propyl diester, diallyl phthalate, properties of diallyl isophathalate, diallyl terephthalate, trimellitic acid triallyl ester, Pyromellitic Acid tetraallyl ester, general formula (4), general formula (5) etc.
(in formula (4), X represents sulphur atom or alkylsulfonyl, and Z represents (methyl) acryl, vinyl or allyl group.)
(in formula (5), m and n represent that the total of m and n meets 0～4 integer, R
3represent the alkylidene group that carbonatoms is 1～5, R
4represent hydrogen atom or methyl, R
5represent hydrogen atom or methyl.)
Example as compound shown in general formula (4); can list 4; 4 '-bis-(methacryloyl sulfenyl) diphenylsulfide, 4; 4 '-bis-(methacryloyl sulfenyl) sulfobenzide etc.; as compound shown in general formula (5); can list two (4-(2-acryloyl-oxy base oxethyl) phenyl) fluorenes of 9,9-etc.
For the content of the polythiol oligopolymer in the first solidification compound, with respect to 100 weight part solidification compounds, preferably in the scope in 10～80 weight parts, further in the preferred scope in 20～70 weight parts.Polythiol oligopolymer when quantity not sufficient 10 weight part, the effect of high viscosity, low contraction diminishes, the toughness drop of cured article while surpassing 80 weight part, so not preferred.
In solidification compound of the present invention, can add as required stopper, antioxidant, photostabilizer (HALS), UV light absorber, silane coupling agent, releasing agent, pigment, dyestuff etc.
Solidification compound of the present invention is cured by irradiating ultraviolet light, visible ray isoreactivity light under the existence at free base system Photoepolymerizationinitiater initiater.Free base system Photoepolymerizationinitiater initiater is not particularly limited as long as generate active free free radical by photodissociation.Concrete example as this compound; can list 2; 2-methoxyl group-1; 2-diphenylethane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, two (2; 4; 6-trimethylbenzoyl)-phenyl phosphine oxide, 2,4,6-trimethylbenzoyl-phenylbenzene-phosphine oxide etc.Free base system Photoepolymerizationinitiater initiater can separately or mix two or more use.Its content is not particularly limited, but with respect to 100 weight part solidification compounds, preferably in the scope in 0.1～10 weight part, more preferably in the scope in 0.5～5 weight part.
About the viscosity of solidification compound, while supposing to use as caking agent, when viscosity is too low, caking agent sagging or flow is offset by convered structure and not preferred when bonding.In addition, when viscosity is too high, be difficult to carry out discharge, the coating of caking agent, or bonding time enters bubble, so not preferred.The viscosity that is suitable for workability in the first solidification compound is owing to depending on the use-pattern of the caking agent of coating process, adhesive method and so on, can not generally stipulate, but preferably in the scope in 500～20000mPas, more preferably in the scope in 1000～10000mPas.
The second solidification compound of the present invention contains polythiol oligopolymer (A composition), episulfide (C composition) and the Photobase generator (D composition) that polythiol and reaction of Salmon-Saxl obtain and forms.
First, the manufacture method for the polythiol oligopolymer in the second solidification compound (A composition), roughly as described in the explanation for above-mentioned the first solidification compound.Below by with the first solidification compound in the difference of manufacture method of polythiol oligopolymer (A composition) centered by, the manufacture method of the polythiol oligopolymer in the second solidification compound (A composition) is described.
In the second solidification compound, polythiol reacts by heating to carry out under the existence of basic catalyst or not with sulphur, but is preferably the method for using basic catalyst.Particularly, as basic catalyst, be preferably hindered amine.Hindered amine refers in amino both sides has substituent amine.Hindered amine is due to substituent steric hindrance, and during as the polymerizing catalyst of episulfide a little less than activity.Its result, polythiol oligopolymer and episulfide merge the curing composition forming and fully stablize (polymerization of episulfide is fully slow), can prolonged preservation.As hindered amine, be preferably and have 2, 2, 6, the compound of 6-tetramethyl piperidine skeleton, particularly, can list 2, 2, 6, 6-tetramethyl piperidine, 1, 2, 2, 6, 6-pentamethyl-piperidines, 4-hydroxyl-2, 2, 6, 6-tetramethyl piperidine, 4-hydroxyl-1, 2, 2, 6, 6-pentamethyl-piperidines, vinylformic acid 2, 2, 6, 6-tetramethyl--4-piperidyl ester, methacrylic acid 2, 2, 6, 6-tetramethyl--4-piperidyl ester, vinylformic acid 1, 2, 2, 6, 6-pentamethyl--4-piperidyl ester, methacrylic acid 1, 2, 2, 6, 6-pentamethyl--4-piperidyl ester, sebacic acid two (2, 2, 6, 6-tetramethyl--4-piperidyl ester), sebacic acid two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl ester) etc.About the consumption of basic catalyst, 100 moles of the thiol groups containing in the polythiol with respect to raw material, preferably in the scope of 0.005～5 mole, more preferably in the scope of 0.05～0.5 mole.
Polythiol can carry out with reacting also of sulphur under the existence of episulfide (C composition).If but do not select suitable basic catalyst, likely carry out the polymerization of episulfide and cause gelation.Therefore, while using basic catalyst, because above-mentioned reason is preferably hindered amine.
Then the second solidification compound of the present invention is described.
The second solidification compound of the present invention contains aforementioned polythiol oligopolymer (A composition), episulfide (C composition) and Photobase generator (D composition) and forms.
Episulfide (C composition) refers to the compound in a part with an above episulfide group.While particularly pursuing the high refractive index of solidification compound, be preferably the compound shown in following general formula (8).
(in formula (8), m is 0～6 integer, and n is 0～4 integer, R
3and R
4that hydrogen atom or carbonatoms are 1～10 alkyl independently of one another, R
5, R
6that carbonatoms is 1～10 alkylidene group independently of one another.)
As the example of the episulfide shown in general formula (8), can list two (2,3-epithio propyl group) thioethers etc.
General formula (8) although shown in episulfide to solidify the contraction follow large, by with the copolymerization of polythiol oligopolymer, can suppress the curing contraction of following.In addition, general formula (8) although shown in the general viscosity of episulfide low, by mixing with polythiol oligopolymer, adjust to the viscosity of workability excellence.
In the second solidification compound, about the viscosity of solidification compound, in the situation of supposing to use as caking agent, when viscosity is too low, caking agent sagging or flow, substrate skew when bonding and not preferred.In addition, when viscosity is too high, be difficult to carry out discharge, the coating of caking agent, or bonding time enters bubble, so not preferred.The viscosity that is suitable for workability in the second solidification compound is owing to depending on the use-pattern of the caking agent of coating process, adhesive method and so on, can not generally stipulate, but preferably in the scope in 100～50000mPas, more preferably in the scope in 500～10000mPas.
For the content of the polythiol oligopolymer in the second solidification compound, with respect to 100 weight part solidification compounds, preferably in the scope in 10～70 weight parts, further in the preferred scope in 20～50 weight parts.Polythiol oligopolymer when quantity not sufficient 10 weight part, the effect of high viscosity, low contraction diminishes, the toughness drop of cured article while surpassing 70 weight part, so not preferred.
Photobase generator (D composition) refers to by active ray the compound of photodissociation, generation alkali.Particularly the polymerization of episulfide, owing to promoting by amidines such as DBN (diazabicyclo-nonene), DBU (diazabicycloundecene), is therefore preferably the Photobase generator that produces these alkali.Particularly, can list 1 of being replaced by arylalkyl of recording in amidine (amidinium) ketone (left side of following formula (9)), Japanese Unexamined Patent Application Publication 2005-511536 of formation four aromatic yl acid salts of recording in Japanese Unexamined Patent Application Publication 2001-513765,3-diamines (left side of following formula (10)) etc.They can separately or mix two or more use.For the addition of Photobase generator, with respect to 100 weight part solidification compounds, preferably in the scope in 0.01～10 weight part, more preferably in the scope in 0.1～5 weight part.
In addition, except Photobase generator, also can contain photosensitizers.By adding photosensitizers, the photodissociation of Photobase generator is accelerated, and can shorten the set time of Photocurable composition.As the concrete example of photosensitizers, can list benzophenone, thioxanthene ketone, Anthraquinones, camphor quinones, dibenzoyl class, tetramethyldiaminobenzophenone class, anthracene class.They can separately or mix two or more use.About the addition of photosensitizers, with respect to 100 weight part solidification compounds, preferably in the scope in 0.01～10 weight part, more preferably in the scope in 0.1～5 weight part.
In aforementioned solidification compound, can add stopper, polymerization retarder, antioxidant, UV light absorber, silane coupling agent, releasing agent, pigment, dyestuff etc. as required.In addition, can filter as required, deaeration etc.
Embodiment
By the following examples the present invention is specifically described, but the present invention is not limited by them.It should be noted that, the cure shrinkage in embodiment is calculated by the specific refractory power before and after solidifying according to following calculating formula.
X=(1-d1/d2)×100[%]
R=(n
2-1)/(n
2+2)×M/d
Before and after solidifying, R/M is constant, therefore known by above two formulas,
X=[1-{(n1
2-1)/(n1
2+2)}/{(n2
2-1)/(n2
2+2)}]×100[%]
(in formula, X represents that cure shrinkage, d represent that proportion, R after proportion, d2 before proportion, d1 represent to solidify represents to solidify represents that molar refraction, n represent that specific refractory power, M after specific refractory power, n2 before specific refractory power, n1 represent to solidify represents to solidify represent molecular weight.)
In addition, the viscosity of solidification compound is used circular cone/plate viscometer DV-II+ (Brookfield company system) to measure at 25 ℃ of temperature.The specific refractory power of solidification compound and cured article (cured film) is used Abbérefractometer NAR-3T (ATAGO CO., LTD system) to measure.The transmitance of cured article is used spectrophotometer U-3500 (Hitachi High-Technologies Corporation system), at the thickness 0.25mm of cured article, measure under the condition of wavelength 400nm.
Below first for the embodiment of the first solidification compound, describe.
Embodiment 1
In 300ml flask, get 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane 65g, dicyclohexyl methylamine 0.05g, fully stir.Under room temperature, divide lentamente and drip for several times sulphur powder 4.7g.While adding sulphur powder, solution becomes yellow, produces gas.After the generation of gas becomes slowly, in the time of to liquid level circulation nitrogen, temperature is elevated to 60 ℃, continues to stir 3 hours.Carrying out along with reaction, produces gas hardly, and solution becomes colorless transparent.According to above step, make polythiol oligopolymer.
After polythiol oligopolymer is cooled to room temperature, add 35g isocyanuric acid triallyl ester, be stirred to evenly.According to above step, make the first solidification compound.
With respect to 100 weight part the first solidification compounds, add 3 weight part 1-hydroxyl-cyclohexyl-phenyl ketones, be stirred to evenly, and carry out vacuum deaerator.Used and passed through two sheet glass clampings that the demoulding is processed, from the distance of 30cm, irradiated from after the light of metal halide lamp (120W/cm) 3 minutes, the film having solidified is peeled off by sheet glass.According to above step, make the cured film of thickness 0.25mm.The physical property of solidification compound and cured film (cured article) is as shown in table 1.
Embodiment 2～5
The kind of polythiol, sulphur and polyenic compounds and addition are changed into the content shown in table 1, in addition carry out similarly to Example 1 the making of the first solidification compound and cured article.The physical property of the first solidification compound and cured article is as shown in table 1.
Comparative example 1
In 300ml flask, get 2,5-dimercapto methyl-Isosorbide-5-Nitrae-dithian 55g and isocyanuric acid triallyl ester 45g, be stirred to evenly.According to above step, make solidification compound.
The making of cured film is carried out similarly to Example 1.The physical property of solidification compound and cured article is as shown in table 2.It should be noted that, for the value of comparing poor performance with embodiment, draw and roll off the production line.
Comparative example 2～4
The kind of mercaptan compound, alefinically unsaturated compounds and addition are changed into the content shown in table 2, in addition with the similarly making of being cured property composition and cured article of comparative example 1.The physical property of solidification compound and cured article is as shown in table 2.It should be noted that, for the value of comparing poor performance with embodiment, draw underscore.
[table 1]
Table 1
[table 2]
Table 2
Supplementary notes
Comparative example 3: because MPSMA (b-2) can not dissolve completely, therefore can not measure.
The explanation of abridging in table
(a-1) 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane
(a-2) 2,5-dimercapto methyl-Isosorbide-5-Nitrae-dithian
(a-3) xylylene two mercaptan between
(a-4) 1,5-dimercapto-3-thia pentane
(b-1) isocyanuric acid triallyl ester
(b-2) 4,4 '-bis-(methacryloyl sulfenyl) diphenylsulfide
(b-3) trimellitic acid triallyl ester
(b-4) 2, two (4-(acryloxy diethoxy) phenyl) propane of 2-
Below then the embodiment of the second solidification compound is described.
Embodiment 6
In 300ml flask, get 2,5-dimercapto methyl-Isosorbide-5-Nitrae-dithian 40g, Tributylamine 0.05g, fully stir.Under room temperature, divide lentamente and drip for several times sulphur powder 6.0g.While adding sulphur powder, solution becomes yellow, produces gas.After the generation of gas becomes slowly, in the time of to liquid level circulation nitrogen, temperature is elevated to 60 ℃, continues to stir 3 hours.Carrying out along with reaction, produces gas hardly, and solution becomes colorless transparent.According to above step, make polythiol oligopolymer.
In this polythiol oligopolymer (A composition), add two (2,3-epithio propyl group) thioether 60g (C composition), following structural formula (11)
Shown Photobase generator 0.2g (D composition) and as 4-benzoyl-4 '-dimethyl diphenyl sulfide 1g of sensitizer, is stirred to evenly.According to above step, make the second solidification compound.The viscosity of solidification compound is 900mPas (20 ℃).In addition, preserve 1 week the gelation of result solidification compound at 5 ℃.
By two sheet glass clampings having passed through the demoulding and process for solidification compound, from the distance of 30cm, irradiate from after the light of metal halide lamp (120W/cm) 3 minutes, the film having solidified is peeled off by sheet glass.According to above step, make the cured film of thickness 0.25mm.
The physical property of the second solidification compound and cured film is as shown in table 3.
Embodiment 7
In 300ml flask, get 2,5-dimercapto methyl-Isosorbide-5-Nitrae-dithian 40g, two (2,3-epithio propyl group) thioether 60g, methacrylic acid 1,2,2,6,6-pentamethyl--4-piperidyl ester 0.1g, fully stirs.Under room temperature, divide lentamente and drip for several times sulphur powder 6.0g.While adding sulphur powder, solution becomes yellow, produces gas.After the generation of gas becomes slowly, in the time of to liquid level circulation nitrogen, temperature is elevated to 60 ℃, continues to stir 3 hours.Carrying out along with reaction, produces gas hardly, and solution becomes colorless transparent.After being cooled to room temperature, adding the Photobase generator 0.2g shown in aforementioned structural formula (11) (D composition) and as 4-benzoyl-4 '-dimethyl diphenyl sulfide 1g of sensitizer, be stirred to evenly.According to above step, make solidification compound.The viscosity of solidification compound is 1000mPas (20 ℃).The viscosity of preserving after 1 week at 5 ℃ in addition, is 1100mPas (20 ℃).
Make similarly to Example 6 cured article.The physical property of the second solidification compound and cured film is as shown in table 3.
Embodiment 8～14
The kind of polythiol, sulphur and episulfide and addition are changed into the content shown in table 3 and table 4, in addition carry out similarly to Example 7 the making of the second solidification compound and cured article.The physical property of the second solidification compound and cured article as shown in Table 3 and Table 4.
Comparative example 5
Add the Photobase generator 0.2g (D composition) shown in two (2,3-epithio propyl group) thioether 100g, aforementioned structural formula (9) and as 4-benzoyl-4 '-dimethyl diphenyl sulfide 1g of sensitizer, be stirred to evenly.According to above step, make solidification compound.
Make similarly to Example 6 cured article.The physical property of solidification compound and cured article is as shown in table 5.It should be noted that, for the physical property poorer than embodiment, draw underscore.
Comparative example 6
Add 2; 5-dimercapto methyl-1; Photobase generator 0.2g (D composition) shown in 4-dithian 20g, two (2,3-epithio propyl group) thioether 80g, aforementioned structural formula (9) and as 4-benzoyl-4 '-dimethyl diphenyl sulfide 1g of sensitizer, is stirred to evenly.According to above step, make solidification compound.
Make similarly to Example 6 cured article.The physical property of solidification compound and cured article is as shown in table 5.It should be noted that, for the physical property poorer than embodiment, draw underscore.
[table 3]
Table 3
[table 4]
Table 4
[table 5]
Table 5
The explanation of abridging in table
(a '-1) 2,5-dimercapto methyl-Isosorbide-5-Nitrae-dithian
Xylylene two mercaptan between (a '-2)
(a '-3) 1,5-dimercapto-3-thia pentane
(b '-1) Tributylamine
(b '-2) methacrylic acid 1,2,2,6,6-pentamethyl--4-piperidyl ester
(c-1) two (2,3-epithio propyl group) thioether
Claims (9)
1. a solidification compound, it contains polythiol oligopolymer (A composition) and polyenic compounds (B composition) that polythiol and reaction of Salmon-Saxl obtain, or,
Contain polythiol oligopolymer (A composition), episulfide (C composition) and Photobase generator (D composition) that polythiol and reaction of Salmon-Saxl obtain.
2. solidification compound according to claim 1, wherein, polythiol is free more than one in the group of following general formula (1), following general formula (2) and following general formula (3) composition of choosing,
In formula (1), p1 and p2 represent 0～1 integer, X independently of one another
1～X
8represent independently of one another hydrogen atom or methyl mercaptan base,
In formula (2), q represents 0～3 integer, R
1represent the alkylidene group that simple key or carbonatoms are 1～3,
In formula (3), r represents 0～3 integer, R
2represent the alkylidene group that carbonatoms is 1～3.
3. solidification compound according to claim 1 and 2, wherein, the polythiol during about polythiol and reaction of Salmon-Saxl and the ratio of sulphur, with respect to 1 molar sulphur alcohol radical, sulphur atom is in the scope of 0.2～0.95 mole.
4. according to the solidification compound described in any one in claim 1～3, wherein, polyenic compounds (B composition) are more than one in the group of selecting compound shown in the compound shown in free isocyanuric acid triallyl ester, cyanuric acid alkatriene propyl diester, diallyl phthalate, properties of diallyl isophathalate, diallyl terephthalate, trimellitic acid triallyl ester, Pyromellitic Acid tetraallyl ester, general formula (4), general formula (5) and forming
In formula (4), X represents sulphur atom or alkylsulfonyl, and Z represents (methyl) acryl, vinyl or allyl group,
In formula (5), m and n represent that the total of m and n meets 0～4 integer, R
3represent the alkylidene group that carbonatoms is 1～5, R
4represent hydrogen atom or methyl, R
5represent hydrogen atom or methyl.
5. according to the solidification compound described in any one in claim 1～4, it is characterized in that, when polythiol and reaction of Salmon-Saxl, use hindered amine as catalysts.
6. solidification compound according to claim 5, wherein, hindered amine is for having the compound of 2,2,6,6-tetramethyl piperidine skeleton.
7. according to the solidification compound described in any one in claim 1～6, wherein, episulfide (C composition) is the compound shown in following general formula (8),
In formula (8), m is 0～6 integer, and n is 0～4 integer, R
3and R
4that hydrogen atom or carbonatoms are 1～10 alkyl independently of one another, R
5, R
6that carbonatoms is 1～10 alkylidene group independently of one another.
8. solidification compound according to claim 7, wherein, the compound shown in general formula (8) is two (2,3-epithio propyl group) thioethers.
9. an optics caking agent, it contains the solidification compound described in any one in claim 1～8.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-101440 | 2011-04-28 | ||
| JP2011101440A JP5834474B2 (en) | 2011-04-28 | 2011-04-28 | Curable composition and optical adhesive |
| JP2011-103643 | 2011-05-06 | ||
| JP2011103643A JP5742443B2 (en) | 2011-05-06 | 2011-05-06 | Curable composition and optical adhesive |
| PCT/JP2012/060899 WO2012147708A1 (en) | 2011-04-28 | 2012-04-24 | Curable composition and adhesive for optics |
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| CN103562273A true CN103562273A (en) | 2014-02-05 |
| CN103562273B CN103562273B (en) | 2016-03-02 |
| CN103562273B9 CN103562273B9 (en) | 2016-06-01 |
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| CN110430858A (en) * | 2017-03-03 | 2019-11-08 | 登士柏希罗纳有限公司 | The composition and method of the increasable dental composite of viscosity |
| CN110951403A (en) * | 2019-12-02 | 2020-04-03 | 山东益丰生化环保股份有限公司 | UV adhesive with high refractive index and preparation method thereof |
| CN112840004A (en) * | 2018-10-17 | 2021-05-25 | 纳美仕有限公司 | Resin composition |
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| CN110430858B (en) * | 2017-03-03 | 2023-01-24 | 登士柏希罗纳有限公司 | Compositions and methods for dental composites with increased viscosity |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103562273B (en) | 2016-03-02 |
| TW201311847A (en) | 2013-03-16 |
| TWI521035B (en) | 2016-02-11 |
| WO2012147708A1 (en) | 2012-11-01 |
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