CN105022229A - Photocurable composition - Google Patents
Photocurable composition Download PDFInfo
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- CN105022229A CN105022229A CN201510178071.5A CN201510178071A CN105022229A CN 105022229 A CN105022229 A CN 105022229A CN 201510178071 A CN201510178071 A CN 201510178071A CN 105022229 A CN105022229 A CN 105022229A
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Abstract
The invention provides a photocurable composition. In the prior art, it is difficult to maintain the bonding force even after humidity resistance test and thermal circulation test on the basis of ensuring that existing adhesion of light-curable composition for hard adhesive material. The photocurable composition of the present invention comprises (A)-(D) component, but does not include other than the component (B) a (meth) acrylate monomer having a (meth) acrylate groups, with respect to 100 parts by mass of component (A) and comprising 100 to 300 parts by mass of the (B) component. Component (A) is a styrene polymer and block copolymers of ethylene/butene polymer; (B) component is an acrylate monomer having a hydrocarbon group and (meth) acrylic acid ester group-containing (meth); (C) component is a compound having two or more thiol groups; (D) component is a photoinitiator.
Description
Technical field
The present invention relates to a kind of Photocurable composition being suitable for the opticses such as cemented lens.
Background technology
In patent documentation 1, disclose a kind of Photocurable composition using thermoplastic elastomer, acrylate monomer and light trigger as essential component.Particularly, it is characterized in that: to the material being difficult to bond, there is bounding force.But the invention of patent documentation 1 is due to residual tack easy on surface, and in the bonding of optics, dust etc. are easily attached to solidfied material surface, therefore cause the increase of fraction defective, is difficult to carry out process management.In addition, because Photocurable composition is pith in the electronic device, so need, to fail-tests such as humidity test (such as under the environment of 85 DEG C × 85%RH 500 hours) or thermal cycling tests (such as using-40 DEG C × 30 minutes and 80 DEG C × 30 minutes as a circulation, 500 circulations), there is patience.Patience specifically refers to that the pilot projects such as bounding force are stablized.Particularly, owing to mostly using the combination being difficult to engineering plastics or this material and the metal bonded in the opticses such as lens, therefore be difficult to realize the stabilization (following, by acrylate-based and methacrylate based to be called (methyl) in the lump acrylate-based) of bounding force.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-307082 publication
Summary of the invention
Invent problem to be solved
Due to existing Photocurable composition be difficult to make solidfied material to maintain flexibility while, improve surface cure, so not enough to the consideration of manufacturing environment aspect.In addition, even if will to guarantee the bounding force being difficult to jointing material and also to maintain its bounding force after the fail-test such as humidity test or thermal cycling test be very difficult.
Therefore, the present invention completes in view of above-mentioned problem, its object is to: even if provide a kind of material to being difficult to bond also can play the Photocurable composition of enough bounding forces.
Another object of the present invention is to: even if provide a kind of Photocurable composition that also can maintain bounding force after humidity test and/or thermal cycling test.
Another object of the present invention is: provide the application of Photocurable composition as above in bonding agent used for optical part.
For solving the method for problem
Even if the present inventor is in order to solve that above-mentioned problem conducts in-depth research as a result, complete the Photocurable composition that also can maintain bounding force after fail-test.
Following explanation main idea of the present invention.First embodiment of the present invention relates to a kind of Photocurable composition, described Photocurable composition comprises (A) ~ (D) composition, but do not comprise, beyond (B) composition, there is one (methyl) acrylate-based (methyl) acrylate monomer, relative to 100 mass parts (A) composition and comprise (B) compositions of 100 ~ 300 mass parts.
(A) composition is the segmented copolymer of styrene polymer and ethylene/butylene polymkeric substance;
(B) composition has alkyl and one (methyl) acrylate-based (methyl) acrylate monomer;
(C) composition is the compound with two or more mercapto;
(D) composition is light trigger.
Second embodiment of the present invention relates to the Photocurable composition described in the first embodiment, and wherein, the storage modulus of described Photocurable composition at-20 DEG C is 5.0 × 10
8below Pa, the glass transition temperature of loss modulus is below-30 DEG C.
3rd embodiment of the present invention relates to the Photocurable composition described in the first or second embodiment, wherein, relative to (A) composition of 100 mass parts, adds (C) composition of 0.1 ~ 10 mass parts.
4th embodiment of the present invention relates to the Photocurable composition according to any one of the first ~ three embodiment, and wherein, (A) composition comprises: the segmented copolymer of maleic anhydride modified styrene polymer and ethylene/butylene polymkeric substance.
5th embodiment of the present invention relates to the Photocurable composition according to any one of the first ~ four embodiment, wherein, (B) composition comprises: have chain alkyl and one (methyl) acrylate-based (methyl) acrylate monomer and have cyclic hydrocarbon group and one (methyl) acrylate-based (methyl) acrylate monomer.
6th embodiment of the present invention relates to the Photocurable composition according to any one of the first ~ five embodiment, wherein, described Photocurable composition also comprises: have (methyl) acrylate monomer that two or more (methyl) is acrylate-based.
7th embodiment of the present invention is, the application of Photocurable composition in bonding agent used for optical part according to any one of the first ~ six embodiment.
Invention effect
The present invention relates to the Photocurable composition that a kind of formation has flexibility, surface cure and the fusible solidfied material being suitable for optics, even if described Photocurable composition also has stable cohesive for the material being difficult to bond used in the purposes requiring the optics reducing stress, although solidfied material is soft but does not have viscosity on solidfied material surface, due to its soft property so also can guarantee there is stable cohesive after fail-test simultaneously.
Embodiment
Photocurable composition of the present invention comprises following (A) ~ (D) composition.Here, described Photocurable composition does not comprise and has one (methyl) acrylate-based (methyl) acrylate monomer beyond (B) composition, relative to 100 mass parts (A) composition and comprise (B) compositions of 100 ~ 300 mass parts:
(A) composition is the segmented copolymer of styrene polymer and ethylene/butylene polymkeric substance;
(B) composition has alkyl and one (methyl) acrylate-based (methyl) acrylate monomer;
(C) composition is the compound with two or more mercapto; And
(D) composition is light trigger.
Next, details of the present invention is described.
As (A) composition that can use in the present invention, it is the segmented copolymer of styrene polymer and ethylene/butylene polymkeric substance.Here, segmented copolymer refers to, makes different types of polymkeric substance carry out copolymerization each other and the polymkeric substance obtained, according to its structure, there will be a known straight chain A-B block type or linear A-B-A block type.The constitutional isomer of butylene (butene) is referred to as butylene (butylene), and " ethylene/butylene polymkeric substance " is the polymkeric substance of instigating ethene and butylene to carry out copolymerization and obtain.Here, being also not particularly limited the structure of ethylene/butylene polymkeric substance, can be any one in random copolymers, alternating copolymer, periodic copolymer, segmented copolymer.(A) therefore composition has flexibility owing to not comprising unsaturated link, even if also can stably maintain this characteristic after fail-test.
Particularly, preferably (A) composition comprises the segmented copolymer of maleic anhydride modified styrene polymer and ethylene/butylene polymkeric substance, and more preferably (A) composition is made up of styrene polymer and the segmented copolymer of ethylene/butylene copolymers and the segmented copolymer of maleic anhydride modified styrene polymer and ethylene/butylene polymkeric substance.Here, maleic anhydride modifiedly to refer to, comprise a part of maleic anhydride at the interior segmented copolymer carrying out being polymerized.
When (A) composition comprises the segmented copolymer of the segmented copolymer of styrene polymer and ethylene/butylene copolymers and maleic anhydride modified styrene polymer and ethylene/butylene polymkeric substance, although to the segmented copolymer of styrene polymer and ethylene/butylene copolymers, be not particularly limited with the mixing ratio of the segmented copolymer of maleic anhydride modified styrene polymer and ethylene/butylene polymkeric substance, but the segmented copolymer of styrene polymer and ethylene/butylene copolymers, 10:90 ~ 90:10 is preferably with the mixing ratio (mass ratio) of the segmented copolymer of maleic anhydride modified styrene polymer and ethylene/butylene polymkeric substance, be more preferably 20:80 ~ 80:20, be particularly preferably 30:70 ~ 80:20.
Weight-average molecular weight as the styrene polymer of (A) composition and the segmented copolymer of ethylene/butylene copolymers is not particularly limited, suitably can selects according to desired characteristic.In addition, be not particularly limited as modification degree during (A) composition using the segmented copolymer of maleic anhydride modified styrene polymer and ethylene/butylene polymkeric substance, but be preferably 10 ~ 40% relative to from cinnamic all structural units, be more preferably 20 ~ 40%.In addition, the weight-average molecular weight of the segmented copolymer of maleic anhydride modified styrene polymer and ethylene/butylene polymkeric substance is also not particularly limited, suitably can selects according to desired characteristic.
As the object lesson of (A) composition, G1650, G1651, G1652, G1654X, G1657, G1726, FG1901X, FG1924X etc. that Kraton Polymers Japan Co., Ltd. manufactures can be enumerated, but be not limited in this.
As (B) composition that can use in the present invention, that there is alkyl and one (methyl) acrylate-based (methyl) acrylate monomer (following, (methyl) acrylate monomer that will have (methyl) acrylate-based is called simple function (methyl) acrylate monomer).In this manual, " (methyl) acrylic acid ((meth) acrylic) " or " (methyl) acrylate ((meth) acrylate) " is the general designation of acrylate and methacrylate.(methyl) acrylate etc. comprises the compound of (methyl) etc. too, is have the compound of " methyl " in title and do not have the general designation of compound of " methyl ".Namely, " (methyl) acrylate " refers to " acrylate and/or methacrylate ".
Particularly, preferably (methyl) acrylate monomer with chain alkyl is mixed with (methyl) acrylate monomer with cyclic hydrocarbon group.Namely, preferably (B) composition comprises: have chain alkyl and one (methyl) acrylate-based (methyl) acrylate monomer and have cyclic hydrocarbon group and one (methyl) acrylate-based (methyl) acrylate monomer, more preferably (B) composition is by having chain alkyl and one (methyl) acrylate-based (methyl) acrylate monomer and having cyclic hydrocarbon group and one (methyl) acrylate-based (methyl) acrylate monomer forms.Above-mentioned alkyl does not comprise ether as reducing the dissolubility of (A) composition or ester group isopolarity group, and refers to the group be only made up of carbon atom and hydrogen atom.By adding (methyl) acrylate monomer with cyclic hydrocarbon group, the raising of bounding force can be realized.Here, do not comprise, beyond (B) composition, there is one (methyl) acrylate-based (methyl) acrylate monomer.Like this when not comprising acrylate-based (methyl) acrylate monomer of having beyond (B) composition one (methyl), surface cure is good, and the bounding force after fail-test is stablized.
When (B) composition comprise there is chain alkyl and one (methyl) acrylate-based (methyl) acrylate monomer and there is cyclic hydrocarbon group and one (methyl) acrylate-based (methyl) acrylate monomer, to having chain alkyl and one (methyl) acrylate-based (methyl) acrylate monomer, be not particularly limited with the mixing ratio with cyclic hydrocarbon group and one (methyl) acrylate-based (methyl) acrylate monomer, but there is chain alkyl and one (methyl) acrylate-based (methyl) acrylate monomer, 1 ~ 20:1 is preferably with the mixing ratio (mass ratio) with cyclic hydrocarbon group and one (methyl) acrylate-based (methyl) acrylate monomer, be more preferably 1.5 ~ 15:1, be particularly preferably and be greater than 2 and be less than or equal to 11:1.
As the object lesson of (methyl) acrylate monomer with chain alkyl, can enumerate: (methyl) isoamyl acrylate, (methyl) dodecylacrylate, the different myristin of (methyl) acrylic acid, (methyl) octadecyl acrylate, (methyl) acrylic acid isooctadecane base ester, (methyl) Isooctyl acrylate monomer, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate etc., but be not limited in these.Wherein, preferably (methyl) dodecylacrylate, (methyl) acrylic acid isooctadecane base ester, (methyl) Isooctyl acrylate monomer, more preferably dodecylacrylate, acrylic acid isooctadecane base ester, Isooctyl acrylate monomer, particularly preferably at least comprise Isooctyl acrylate monomer as (B) composition.
As the object lesson of (methyl) acrylate monomer with cyclic hydrocarbon group, (methyl) isobornyl acrylate, (methyl) acrylic acid two ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid adamantane esters etc. can be enumerated, but be not limited in these.Wherein, preferably (methyl) isobornyl acrylate, more preferably isobornyl acrylate.
As the concrete commodity of (B) composition, can enumerate: lightacrylate IAA, L-A, IM-A, S-A, IB-XA etc. that Kyoeisha Chemical Co., Ltd. manufactures; Or AIB, TBA, IOAA, LA, STA, IBXA, V#155 etc. that Osaka Organic Chemical Industry Co., Ltd. manufactures; The S-1800A etc. that chemical industry Co., Ltd. of Huo Xinzhong village manufactures, but be not limited in these.
Relative to (A) composition of 100 mass parts, comprise (B) composition of 100 ~ 300 mass parts, preferably comprise (B) composition of 200 ~ 300 mass parts, more preferably comprise (B) composition of 210 ~ 290 mass parts.If (B) composition is more than 100 mass parts, then (A) composition can be made fully to dissolve, can viscosity be reduced simultaneously.On the other hand, if (B) composition is below 300 mass parts, although reason is not yet clear and definite, the outward appearance of composite inhibiting gonorrhoea can be presented.
In Photocurable composition of the present invention, only comprise as simple function (methyl) acrylate monomer and there is alkyl and one (methyl) acrylate-based (methyl) acrylate monomer, but except simple function (methyl) acrylate monomer, can also be used in molecule and there is the acrylate-based compound of two or more (methyl) (following, this compound to be called multifunctional (methyl) acrylate monomer).Namely, according to an embodiment of the invention, Photocurable composition of the present invention also comprises: have (methyl) acrylate monomer that two or more (methyl) is acrylate-based.From the viewpoint of more stably showing bounding force, relative to (A) composition of 100 mass parts, preferably comprise multifunctional (methyl) acrylate monomer of below 30 mass parts, be more preferably 5 ~ 30 mass parts, be particularly preferably 10 ~ 25 mass parts.In addition, if multifunctional (methyl) acrylate monomer is below 30 mass parts, then can not produces harmful effect to itself and the compatibility of (A) composition, the precipitation of gonorrhoea or (A) composition can be suppressed.
As the example of multifunctional (methyl) acrylate monomer when comprising multifunctional (methyl) acrylate monomer at composition of the present invention, can enumerate: trimethylolpropane tris (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, three (methyl) glycerol acrylate, three (methyl) acrylate, pentaerythritol, four (methyl) acrylate, pentaerythritol, four (methyl) acrylic acid dipentaerythritol ester, five (methyl) acrylic acid dipentaerythritol ester, poly-(methyl) acrylic acid dipentaerythritol ester, dihydroxymethyl tristane two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,10-decanediol two (methyl) acrylate, 2-normal-butyl-2-ethyl-1,3-PD two (methyl) acrylate, 3-methyl isophthalic acid, 5-Diacrylate etc., but be not limited in these.Wherein, preferred trimethylolpropane tris (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, 2-normal-butyl-2-ethyl-1, ammediol two (methyl) acrylate, more preferably trimethylolpropane triacrylate, dihydroxymethyl tristane diacrylate, 2-normal-butyl-2-ethyl-1, ammediol diacrylate, particularly preferably at least comprises dihydroxymethyl tristane diacrylate.As concrete commodity, can enumerate: A-TMPT, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, AD-TMP, A-TMMT, A-DPH that chemical industry Co., Ltd. of Xin Zhong village manufactures; Light acrylate DCP-A, light acrylate BEPG-A, light acrylate 1.6HX-A, light acrylate 1.9ND-A, light acrylate MPD-A, light acrylate TMP-A, lightacrylate PE-3A etc. that Kyoeisha Chemical Co., Ltd. manufactures, but be not limited in these.
The total amount of these compositions when comprising simple function (methyl) acrylate monomer and multifunctional (methyl) acrylate monomer to Photocurable composition of the present invention is not particularly limited, as long as contain simple function (methyl) acrylate monomer and multifunctional (methyl) acrylate monomer with above-mentioned amount.Relative to (A) composition of 100 mass parts, the total amount preferably comprising simple function (methyl) acrylate monomer and multifunctional (methyl) acrylate monomer is 130 ~ 330 mass parts, more preferably comprises 200 ~ 300 mass parts.
As (C) composition that can use in the present invention, be the compound with two or more mercapto, particularly there is the compound of 2 ~ 6 mercaptos in the molecule.By add (C) composition, Photocurable composition solidfied material on the surface viscosity can disappear.
As concrete mercaptan compound, can enumerate: three-[(3-mercaptopropionic acid base)-ethyl]-isocyanuric acid ester, pentaerythrite four (3-mercaptopropionic acid ester), dipentaerythritol six (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester), trimethylolpropane tris mercaptoacetate, pentaerythrite four mercaptoacetates etc., but be not limited in these.As concrete commodity, can enumerate: TEMPIC, PEMP, PEMP-20P, DPMP, TMMP that SC organic chemistry Co., Ltd. manufactures; TMTP, PETP, TMTG, PETG etc. that shallow lake KCC manufactures, but be not limited in these.
Relative to (methyl) acrylate monomer 100 mass parts containing (B) composition, (C) composition of preferred interpolation 0.1 ~ 10 mass parts, more preferably add (C) composition of 0.1 ~ 5 mass parts, particularly preferably add (C) composition of 1 ~ 5 mass parts.If (C) composition is more than 0.1 mass parts, surface cure can improve, and viscosity disappears; If (C) composition is below 10 mass parts, can not produce uneven in the solidification of Photocurable composition.
Be light trigger as (D) composition that can use in the present invention, when having irradiated ultraviolet or visible ray homenergic ray to make (methyl) acrylate monomer solidifications such as (B) composition, light trigger has decomposed.Being particularly preferably, producing the light trigger of free radical species when having irradiated energy-ray.
As the object lesson of (D) composition, can enumerate: acetophenone, propiophenone, benzophenone, xanthene alcohol (xanthol), fluorenes, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methyl acetophenone, 4-methyl acetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 2,2-diethoxy acetophenone, to diacetyl benzene, 3-methoxy benzophenone, 2,4,6-tri-methyl benzophenone, polymerization (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone), 4-allyl benzene ethyl ketone, camphorquinone, TMDPO, 4-methyl benzophenone, the chloro-4 '-benzyl benzophenone of 4-, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 3-chlorine xanthone, 3,9-dichloro xanthone, 3-chloro-8-nonyl xanthone, benzoyl, benzoyl methyl ether, benzoin butyl ether, two (4-dimethylaminophenyl) ketone, benzyl methoxyl ketal, CTX, o-toluic acid ester, benzil dimethyl ketal, methyl benzoylformate etc., but be not limited in these.
Relative to (methyl) acrylate monomer 100 mass parts containing (B) composition, (D) composition of preferred interpolation 0.1 ~ 20 mass parts, more preferably (D) composition of 0.1 ~ 10 mass parts is added, further preferably add (D) composition of 1 ~ 10 mass parts, particularly preferably add (D) composition of 1 ~ 8 mass parts.If (D) composition is more than 0.1 mass parts, then surface cure improves, and viscosity disappears; If (D) composition is less than 10 mass parts, then can maintain the storage stability of Photocurable composition.
In the present invention, the filling agent such as inorganic filler or organic filler can suitably be added.By adding filling agent, viscosity, thixotropy can not only be regulated, but also curability, obdurability can be regulated.As inorganic filler, aluminium oxide, silicon dioxide, amorphous silica etc. can be enumerated, but be not limited in these.On the other hand, as organic filler, styrene filling agent, rubber filler, hud typed acrylate filling agent etc. can be enumerated, but be not limited in these.As specific product, can enumerate: the R972 as Aerosil series (dimethyldichlorosilane process), R976 (dimethyldichlorosilane process), RY200 (dimethyl silicone process), RX200 (hexamethyldisilazane process), R800 (octyl group silane treatment) etc. that the AO-802 that Admatechs Company Limited manufactures, Japanese AEROSIL Co., Ltd. manufacture, but be not limited in these.
When Photocurable composition of the present invention comprises filling agent, the combined amount of filling agent only otherwise hinder effect of the present invention and effect desired by playing just is not particularly limited, relative to (A) composition of 100 mass parts, the filling agent of preferred interpolation 0.1 ~ 15 mass parts, more preferably adds the filling agent of 1 ~ 10 mass parts.
In order to its characteristic being adjusted to the degree of the physical property not damaging proterties of the present invention or solidfied material, the adjuvants such as free radical thermal curing agents, emulsion, silane coupling agent, titanium class coupling agent, levelling agent, polymerization inhibitor, antiaging agent, plastifier, thixotropy conferring agents, solvent can be mixed.In addition, when Photocurable composition of the present invention comprises adjuvant as above, the combined amount of adjuvant is not particularly limited, can adopts and known identical amount.
Photocurable composition of the present invention is polymerized rapidly by the irradiation of ultraviolet or visible ray isoreactivity energy-ray, to bond clung body.Even if Photocurable composition of the present invention is difficult to the material bonded for polyphenylene sulfide, cyclic olefin polymer etc., also enough bounding forces can be played.In addition, even if Photocurable composition of the present invention also can play enough cohesive/stationarity for the clung body that material is different.Specifically, the storage modulus of this Photocurable composition at-20 DEG C (E ') is preferably 10.0 × 10
8below Pa, is more preferably 5.0 × 10
8below Pa, is particularly preferably 4.0 × 10
8below Pa.In addition, and the glass transition temperature (maximal value (glass transition temperature) of loss modulus) of the loss modulus of this Photocurable composition (E ") be preferably less than-30 DEG C, be more preferably less than-40 DEG C.Further, the tensile shear bond strength (shear resistance) of this Photocurable composition is preferably more than 1.0MPa, is more preferably more than 2.0MPa.In addition, above-mentioned " storage modulus at-20 DEG C (E ') ", the glass transition temperature (maximal value (glass transition temperature) of loss modulus) of the loss modulus " (E ") " and " tensile shear bond strength (shear resistance) " refer to, the value measured by following embodiment.
Further, even if Photocurable composition of the present invention also can maintain bounding force after humidity test and/or thermal cycling test.Specifically, the rate of change of the tensile shear bond strength (shear resistance) after humidity test is preferably-50 ~ 100%.Equally, the rate of change of the tensile shear bond strength (shear resistance) after thermal cycling test is preferably-50 ~ 100%.In addition, above-mentioned " rate of change of the tensile shear bond strength (shear resistance) after humidity test " and " rate of change of the tensile shear bond strength (shear resistance) after thermal cycling test " refer to, carry out the value measured in the following embodiments.
Therefore, Photocurable composition of the present invention can be suitable as bonding agent used for optical part.Namely, another embodiment of the present invention can provide the application of Photocurable composition in bonding agent used for optical part.Photocurable composition of the present invention (bonding agent used for optical part), to taking superengineering plastics etc. as the effectively fixing of raw-material electronic material or optics base or supporter etc.Particularly, Photocurable composition of the present invention (bonding agent used for optical part) even if can carry out bonding and be suitable for also needing the opticses such as the lens of stable bounding force after fail-test (such as moisture-proof or thermal cycling test) on less bond area.
[embodiment]
Next enumerate embodiment, illustrate in greater detail the present invention, but the present invention is not limited in these embodiments (following, by Photocurable composition simply referred to as " composition ").
In the following embodiments, unless otherwise specified, then carry out under operating in room temperature (25 DEG C).In addition, unless otherwise specified, then " % " and " part " refers to " quality % " and " mass parts " respectively.
In order to modulation group compound, prepare following compositions.
(A) composition: the segmented copolymer of styrene polymer and ethylene/butylene polymkeric substance
There is the segmented copolymer (manufacture of G1726KratonPolymers Japan Co., Ltd.) of the skeleton of styrene-ethylene/butylene-styrene
The segmented copolymer (FG1901X Kraton Polymers Japan Co., Ltd. manufactures) of maleic anhydride modified styrene polymer and ethylene/butylene polymkeric substance
(B) composition: there is alkyl and one (methyl) acrylate-based (methyl) acrylate monomer
Isobornyl acrylate (manufacture of light acrylate IB-XA Kyoeisha Chemical Co., Ltd.)
Isooctyl acrylate monomer (manufacture of IOAA Osaka Organic Chemical Industry Co., Ltd.)
Dodecylacrylate (manufacture of light acrylate L-A Kyoeisha Chemical Co., Ltd.)
Acrylic acid isooctadecane base ester (manufacture of chemical industry Co., Ltd. of S-1800A Xin Zhong village)
(B ') composition: (methyl) acrylate monomer beyond (B) composition
Methoxyl dipropylene glycol acrylate (manufacture of light acrylate DPM-A Kyoeisha Chemical Co., Ltd.)
Multifunctional (methyl) acrylate monomer
Trimethylolpropane triacrylate (manufacture of chemical industry Co., Ltd. of A-TMPT Xin Zhong village)
Dihydroxymethyl tristane diacrylate (manufacture of light acrylate DCP-A Kyoeisha Chemical Co., Ltd.)
2-butyl-2-ethyl-1,3-PD diacrylate (manufacture of light acrylate BEPG-A Kyoeisha Chemical Co., Ltd.)
(C) composition: the compound with two or more mercapto
Pentaerythrite four (3-mercaptopropionic acid ester) (manufacture of PEMP-20P SC organic chemistry Co., Ltd.)
(D) composition: light trigger
1-hydroxycyclohexylphenylketone (manufacture of IRGACURE 184BASF company) 1-hydroxycyclohexyl phenyl ketone
Filling agent
The amorphous silica after surface treatment (AEROSIL Co., Ltd. of AEROSIL R976 Japan manufactures) has been carried out with dimethyldichlorosilane
[embodiment 1 ~ 6, comparative example 1]
Carry out the modulation of the Photocurable composition of embodiment 1 ~ 6 and comparative example 1.Take (A) composition, (B) composition and other (methyl) acrylate monomer and drop in stirred tank, stirring with stirrer and make it even in 30 minutes.Afterwards, then take (C) composition and dropped in stirred tank, then stirring 30 minutes.Finally, take (D) composition and dropped in stirred tank, the vacuum deaerator carried out 30 minutes stirs.Detailed modulation voltage is all according to following table 1, and numerical value all marks by mass parts.In addition, in following table 1, the total that will only be (B) composition is denoted as " total of (B) composition ", the total of (B) composition, (B ') composition and other (methyl) acrylate monomers is denoted as " total of total (methyl) acrylate monomer ", is denoted as using the total of all (methyl) acrylate monomers as the addition of (C) composition during 100 mass parts " (C) composition relative to total (methyl) acrylate monomer of 100 mass parts ".
[table 1]
Table 1
For the Photocurable composition of embodiment 1 ~ 6, comparative example 1, carry out outward appearance confirmation, viscosimetric analysis by the following method, surface cure confirms, thick film curability confirms, Determination of Hardness (Shore A), be the results are summarized in following table 2.
[outward appearance confirmation]
Each composition is loaded in glass container, confirms that glass container is " transparent " or " gonorrhoea ", using its result as " outward appearance " by visual.From the viewpoint of thick film curability, preferred glass container is " transparent ".
[viscosimetric analysis]
Gather the composition of 1cc respectively, be discharged in mensuration cup.Under the following conditions, EHD type viscosity meter (Toki Sangyo Co., Ltd.'s manufacture) is used to carry out viscosimetric analysis.Using its result as " initial viscosity (Pas) ".From the viewpoint of operability, preferred initial viscosity is at below 50Pas.
Condition determination
Cone rotor (cone rotor): 3 ° × R14
Rotational speed: 10rpm
Minute: 3 minutes
Measure temperature: 25 DEG C (utilizing calibration cell to carry out control temperature)
[surface cure confirmation]
Each composition being put into glass container until reach the degree of depth of 2mm, in this condition by using the belt conveying type ultraviolet radiation device of high-pressure mercury-vapor lamp, having irradiated 30kJ/m
2accumulative light quantity, make laminar solidfied material.According to following metewand, utilize finger to touch and confirm, and as " surface cure ".In order to prevent the attachment of dust etc., surface cure is preferably "○".
Zero: there is no latent prints on solidfied material surface
×: there is fingerprint (toughness) at solidfied material remained on surface
[confirmation of thick film curability]
Each composition being put into glass container until reach the degree of depth of 6mm, in this condition by using the belt conveying type ultraviolet radiation device of high-pressure mercury-vapor lamp, having irradiated 30kJ/m
2accumulative light quantity, make laminar solidfied material.Wipe uncured thing, utilize vernier caliper to measure thickness, using this numerical value as " thick film curability (mm) ".In order to make the solid state of solidfied material even, preferred thick film curability is more than 2mm.
[Determination of Hardness (Shore A)]
Under the state that the thickness of each composition is set as 2mm, irradiate 30kJ/m by using the belt conveying type ultraviolet radiation device of high-pressure mercury-vapor lamp
2accumulated light, make laminar solidfied material.Repeatedly carry out aforesaid operations and amount to 3 times, this solidfied material is overlapped into three layers, thus make the laminar solidfied material (sample) of 6mm.While make the pressurized plane of A type hardness tester meter and laminar solidfied material keeping parallelism, in the power of 10N promptly press A type hardness tester pressurized plane and without impact, and make pressurized plane and sample (laminar solidfied material) closely sealed.Maximal value is read, using maximal value as " hardness (not having unit) " when measuring.Details is according to JIS K6253:2012.If hardness is below A60, then can follow the temperature variation of environment.
[table 2]
Table 2
In the Photocurable composition of embodiment 1 ~ 6 and comparative example 1, comparative example 1 presents gonorrhoea in appearance.Although its reason is not yet clear and definite, but infer that its reason is: in comparative example 1, relative to 100 mass parts (A) composition and comprise (B) composition that is more more than scope of the present invention, 334 mass parts, therefore the addition of (B) composition is too much.If in contrast, as embodiment 6, relative to (A) composition of 100 mass parts, (B) composition is below 300 mass parts, then the outward appearance of composition can be made to present transparent.
[embodiment 7, comparative example 2 ~ 4]
In order to verify further, according to following table 3, modulate the Photocurable composition of embodiment 7 and comparative example 2 ~ 4.Numerical value all marks with mass parts.Take (A) composition, (B) composition (in comparative example 3,4 be (B ') composition and (B ') composition) and other (methyl) acrylate monomers drop in stirred tank, stir with stirrer and make it even in 30 minutes.Afterwards, then take (C) composition and dropped in stirred tank, then stirring 30 minutes.Finally, take (D) composition and dropped in stirred tank, the vacuum deaerator carried out 30 minutes stirs.In addition, in following table 3, the total that will only be (B) composition is denoted as " total of (B) composition ", the total of (B) composition, (B ') composition and other (methyl) acrylate monomers is denoted as " total of total (methyl) acrylate monomer ", is denoted as using the total of all (methyl) acrylate monomers as the addition of (C) composition during 100 mass parts " (C) composition relative to total (methyl) acrylate monomer of 100 mass parts ".
[table 3]
Table 3
For the Photocurable composition of embodiment 7, comparative example 2 ~ 4, by the following method, carry out DMA (dynamic viscoelastic) mensuration, tensile shear bond strength mensuration, be the results are summarized in following table 4.In addition to the foregoing, for the Photocurable composition of embodiment 7, comparative example 2 ~ 4, also carry out the operation identical with above-mentioned " surface cure confirms ", namely carry out surface cure confirmation, and be the results are summarized in following table 4.
[DMA (dynamic viscoelastic) mensuration]
The thickness of each composition is set as 1mm, irradiates 30kJ/m
2accumulative light quantity, thus make laminar solidfied material.Being struck out width is 10mm, has made test film.This test film is arranged on DMA device ((strain) Hitachi High-Tech Science DMS6100), carries out the mensuration of DMA (dynamic viscoelastic) the temperature ranges of-40 ~ 100 DEG C.Confirm the storage modulus at-20 DEG C, the maximal value (glass transition temperature) of loss modulus, the maximal value (glass transition temperature) of tan δ, be expressed as " E ' (× 10
8pa) ", " E " (DEG C) ", " tan δ (DEG C) ".In addition, when test film cannot be made, be denoted as " cannot measure ".When bonding the clung body of unlike material, in order to follow the difference of the coefficient of thermal expansion of clung body in high temperature environments, the storage modulus in preferred E ' is 5.0 × 10
8below Pa, E " below-30 DEG C.
[tensile shear bond strength mensuration]
For the combination with following clung body (1) ~ (3), determine tensile shear bond strength.The shape of clung body is long 100mm × wide 25mm × thick 1mm, and each composition that the bond area of wide 25mm × long 10mm is fitted, wipes the part of spilling, fix the end of clung body afterwards with clip.Then, use ultraviolet irradiation machine, irradiate 30kJ/m
2accumulative light quantity and composition is solidified, thus make test film.Test film is fixed on cupping machine ((strain) TSE AC-1KN), stretch along draw direction with the speed of 50mm/ minute, and measure maximum intensity (N), calculated by bond area, and as " shear resistance (MPa) ".Be preferably, if " shear resistance " is more than 1.0MPa, then can fix clung body fully.
Clung body (1): polyphenylene sulfide and cyclic olefin polymer
Clung body (2): cyclic olefin polymer and cyclic olefin polymer
Clung body (3): zinc alloy for die casting and cyclic olefin polymer
Cyclic olefin polymer (ZEON Co., Ltd. of ZEONEX 480R Japan manufactures)
Polyphenylene sulfide (manufacture of SUSTEEL PPS GS-40TOSOH Co., Ltd.)
Zinc alloy for die casting: ZDC2
Below, the measurement result of clung body (1) ~ (3) is called shear resistance 1 ~ 3.
[table 4]
Table 4
Result from above-mentioned table 4: composition of the present invention all shows enough performances in the maximal value (glass transition temperature) of surface cure, storage modulus, loss modulus and tensile shear bond strength.In contrast, the surface cure not comprising the composition of the comparative example 2,4 of (C) composition is poor.In addition, although infer the E of the composition of comparative example 3 and 4 " below-30 DEG C, solidfied material is excessively soft, cannot make test film.In addition, the surface cure of the composition of comparative example 3 is also "×".Infer that its reason is: containing (B ') composition.In addition, in the composition of embodiment 7 and comparative example 2 ~ 4, the initial measured value of shear resistance 1 ~ 3 is the numerical value of more than 1.0MPa.
[embodiment 8 ~ 11]
In order to verify further, according to following table 5, modulate the Photocurable composition of embodiment 8 ~ 11.Numerical value all marks with mass parts.Take (A) composition, (B) composition and other (methyl) acrylate monomers and drop in stirred tank, stirring with stirrer and make it even in 30 minutes.Afterwards, then take (C) composition and dropped in stirred tank, then stirring 30 minutes.Finally, take (D) composition and dropped in stirred tank, the vacuum deaerator carried out 30 minutes stirs.In addition, in following table 5, the total that will only be (B) composition is denoted as " total of (B) composition ", the total of (B) composition, (B ') composition and other (methyl) acrylate monomers is denoted as " total of total (methyl) acrylate monomer ", is denoted as using the total of all (methyl) acrylate monomers as the addition of (C) composition during 100 mass parts " (C) composition relative to total (methyl) acrylate monomer of 100 mass parts ".
And, for the Photocurable composition of embodiment 1 ~ 6,8 ~ 11, carry out the operation identical with the method described in above-mentioned [embodiment 7, comparative example 2 ~ 4], carry out DMA (dynamic viscoelastic) mensuration, tensile shear bond strength mensuration, be the results are summarized in table 6.In addition to the foregoing, for the Photocurable composition of embodiment 1 ~ 6,8 ~ 11, also carry out the operation identical with above-mentioned [surface cure confirms], namely carry out surface cure confirmation, and be the results are summarized in following table 6.
[table 5]
Table 5
[table 6]
Table 6
About the composition of most embodiment 1 ~ 6 and embodiment 8 ~ 11, the result measured from DMA: E ' is 5.0 × 10
8below Pa, E " below-30 DEG C.In addition, about shear resistance 1 ~ 3, the known intensity having shown more than 1.0MPa.
In order to verify further, for the Photocurable composition of the embodiment 7 ~ 10 recorded in table 3 and table 5, carry out following humidity test and thermal cycling test, confirming the change of tensile shear bond strength.Here, the initial value that tensile shear bond strength measures employs the numerical value of table 4 and table 6.Be the results are summarized in table 7.
[humidity test]
With the method identical with the test film method for making in described [tensile shear bond strength measures], make test film.Under the environment of 85 DEG C × 85%RH, test film is placed 500 hours, carry out humidity test.Test film is taken out after humidity test terminates, after the temperature of test film reaches room temperature (25 DEG C), carry out the operation identical with the method described in above-mentioned [tensile shear bond strength measures], determine " shear resistance (MPa) ".In addition, using the change from initial shear strength as " rate of change (%) ".About shear resistance 1 ~ 3, preferably " rate of change " is positioned at the scope of-50 ~ 100%.
[thermal cycling test]
With the method identical with the test film method for making in described [tensile shear bond strength measures], make test film.Using-40 DEG C × 30 minutes and 80 DEG C × 30 minutes as a circulation, place test film and reach 500 circulations, carry out thermal cycling test.Test film is taken out after thermal cycling test terminates, after the temperature of test film reaches room temperature (25 DEG C), carry out the operation identical with the method described in above-mentioned [tensile shear bond strength measures], determine " shear resistance (MPa) ".In addition, using the change from initial shear strength as " rate of change (%) ".About shear resistance 1 ~ 3, preferably " rate of change " is positioned at the scope of-50 ~ 100%.
[table 7]
Table 7
Humidity test
Thermal cycling test
Result from above-mentioned table 7: about the embodiment 7 ~ 10 employing (B) composition, the rate of change of shear resistance just becomes substantially, even if become negative, is also not less than-50%.On the other hand, in the comparative example 3 containing (B ') composition, the rate of change of shear resistance becomes negative, and its rate of change is lower than-50% simultaneously.
Practicality in industry
In recent years, the engineering plastics such as polyphenylene sulfide, cyclic olefin polymer that formed precision is good can be used in the every field headed by electrical/electronic field, but this material is the material being difficult to bond.Therefore, a kind of bonding agent that can bond this material is needed.Particularly in the opticses such as lens, need bond this material and metal under the state that bond area is little and also have stable bounding force after fail-test, the present invention can provide a kind of bonding agent that can meet this requirement.
Claims (7)
1. a Photocurable composition, described Photocurable composition comprises (A) ~ (D) composition, but do not comprise, beyond (B) composition, there is one (methyl) acrylate-based (methyl) acrylate monomer, relative to 100 mass parts (A) composition and comprise (B) compositions of 100 ~ 300 mass parts
(A) composition is the segmented copolymer of styrene polymer and ethylene/butylene polymkeric substance;
(B) composition has alkyl and one (methyl) acrylate-based (methyl) acrylate monomer;
(C) composition is the compound with two or more mercapto;
(D) composition is light trigger.
2. Photocurable composition according to claim 1, wherein, the storage modulus of described Photocurable composition at-20 DEG C is 5.0 × 10
8below Pa, the glass transition temperature of loss modulus is below-30 DEG C.
3. Photocurable composition according to claim 1 and 2, wherein, relative to (A) composition of 100 mass parts, comprises described (C) composition of 0.1 ~ 10 mass parts.
4. the Photocurable composition according to any one of claims 1 to 3, wherein, described (A) composition comprises: the segmented copolymer of maleic anhydride modified styrene polymer and ethylene/butylene polymkeric substance.
5. the Photocurable composition according to any one of Claims 1 to 4, wherein, described (B) composition comprises: have chain alkyl and one (methyl) acrylate-based (methyl) acrylate monomer and have cyclic hydrocarbon group and one (methyl) acrylate-based (methyl) acrylate monomer.
6. the Photocurable composition according to any one of Claims 1 to 5, wherein, described Photocurable composition also comprises: have (methyl) acrylate monomer that two or more (methyl) is acrylate-based.
7. the application of the Photocurable composition according to any one of claim 1 ~ 6 in bonding agent used for optical part.
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| JP2014083289A JP6368984B2 (en) | 2014-04-15 | 2014-04-15 | Photocurable composition |
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| WO2024117226A1 (en) * | 2022-12-01 | 2024-06-06 | 積水化学工業株式会社 | Ultraviolet-curable adhesive composition and method for producing laminate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056087A (en) * | 2005-08-23 | 2007-03-08 | Three Bond Co Ltd | Photocurable moistureproof coating agent composition |
| CN102471424A (en) * | 2009-07-21 | 2012-05-23 | 太阳控股株式会社 | Photocurable resin composition |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3664262B2 (en) * | 1993-04-28 | 2005-06-22 | 日本ゼオン株式会社 | Ultraviolet curable composition, adhesion method using the same, and adhesive |
| JP3658541B2 (en) * | 2001-02-05 | 2005-06-08 | ニチバン株式会社 | Photocurable oil surface adhesive composition |
| JP4645797B2 (en) * | 2004-04-23 | 2011-03-09 | 株式会社スリーボンド | Photo-curable resin composition for difficult-to-adhere materials |
| JP4386269B2 (en) * | 2004-05-28 | 2009-12-16 | 電気化学工業株式会社 | Curable resin composition and sheet |
| JP2009209256A (en) * | 2008-03-04 | 2009-09-17 | Showa Denko Kk | Curable composition containing urethane compound, and cured product thereof |
| JP2009277762A (en) * | 2008-05-13 | 2009-11-26 | Mitsubishi Gas Chem Co Inc | Light transmission electromagnetic wave shielding laminate exhibiting excellent bendability, and its production method |
| JPWO2009154138A1 (en) * | 2008-06-18 | 2011-12-01 | 株式会社ブリヂストン | Adhesive composition and display panel manufacturing method using the same |
| JP2010126697A (en) * | 2008-11-28 | 2010-06-10 | Three M Innovative Properties Co | Pressure-sensitive adhesive composition and pressure-sensitive adhesive tape |
| JPWO2013080737A1 (en) * | 2011-11-29 | 2015-04-27 | 新田ゼラチン株式会社 | Photo-curable sealing material, sealing method, sealing material and casing using the same |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056087A (en) * | 2005-08-23 | 2007-03-08 | Three Bond Co Ltd | Photocurable moistureproof coating agent composition |
| CN102471424A (en) * | 2009-07-21 | 2012-05-23 | 太阳控股株式会社 | Photocurable resin composition |
Non-Patent Citations (3)
| Title |
|---|
| 邓舜扬: "《化学配方与工艺手册》", 31 January 2003 * |
| 马建标: "《功能高分子材料》", 31 July 2000 * |
| 高晶，秦国林: "《UV上光工艺及技术200问》", 31 January 2012 * |
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| KR102285973B1 (en) | 2021-08-04 |
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| KR20150118903A (en) | 2015-10-23 |
| PH12015000107B1 (en) | 2017-01-30 |
| JP6368984B2 (en) | 2018-08-08 |
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