CN1867593A - Polymer having oxetanyl group and cation-curable resin composition containing the same - Google Patents
Polymer having oxetanyl group and cation-curable resin composition containing the same Download PDFInfo
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- CN1867593A CN1867593A CN 200480030208 CN200480030208A CN1867593A CN 1867593 A CN1867593 A CN 1867593A CN 200480030208 CN200480030208 CN 200480030208 CN 200480030208 A CN200480030208 A CN 200480030208A CN 1867593 A CN1867593 A CN 1867593A
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Abstract
To provide a cationically polymerizable polymer with which the viscosity of a composition can be regulated in a wide region of from several tens of mPa.s to several tens of Pa.s; and to provide a composition containing the polymer. The composition has excellent curability and gives a cured article which has satisfactory adhesion and excellent flexibility, is soft, and has excellent recovery from deformation at room temperature although it has a low modulus. [MEANS FOR SOLVING PROBLEMS] The polymer is one obtained from: at least one member selected from the group consisting of a maleic-modified polybutadiene, maleic-modified polyisoprene, hydroxylated polybutadiene, hydroxylated polyisoprene, hydroxylated ethylene/butylene copolymer, hydroxylated hydrogenated polybutadiene, and hydroxylated hydrogenated polyisoprene; and a compound of the formula (1). (In the formula (1), R<1> represents hydrogen or optionally branched C1-6 alkyl).
Description
Technical field
The present invention relates to taking place in the solidification compound of cationoid polymerisation, as the cationically polymerizable polymkeric substance of its formula material and the resin combination that contains this polymkeric substance by irradiation and/or heating as ultraviolet ray and electron rays isoreactivity energy line.In addition, the present invention relates to the good cation-curable resin composition of solidified nature, its can make flexible good, at room temperature be the also good cured article of Restoration after low elastic modulus and the change of shape.
Background technology
Major part in irradiation by the active energy ray as ultraviolet ray and electron rays etc. or the curable resin composition that cationoid polymerisation takes place in heating is a Resins, epoxy.Resins, epoxy is good at aspects such as thermotolerance, cementability and resistances to chemical reagents usually, but its great majority are thermohardening types of the two-pack that produced by the addition reaction of amine or acid anhydrides etc.Widely-used unlike Resins, epoxy by the curing system that cationoid polymerisation produces.But the cationic curing system is not owing to having amine or ester isopolarity base, so be favourable aspect the water-intake rate that reduces cured article.In addition, the cationic curing system can form the heat-curing resin of single component by using the hot cationic polymerization initiators of potentiality.In addition, be mixed with the epoxy resin of light cationic polymerization initiators and the light cation-curable resin composition of trimethylene oxide class, in recent years because following reason and more noticeable.Promptly owing to compare with having accounted for light-cured resin most (methyl) esters of acrylic acid, epoxy compounds and oxetane compound have that shrinking percentage when solidifying is little, good to the adaptation of body material, water-intake rate is low and its polymerization can be by advantages such as airborne oxygen hinder.Since such reason, cation-curable resin composition, and especially the light cation-curable resin composition is more noticeable.But, if with compare then by the curing system of generation such as epoxy group(ing) and amine etc. that price is higher, so be at general purpose material not equal to be more noticeable in the field of the special rerum naturas of needs such as electronic material and optical material.
As one of electronic material and the desired special rerum natura of optical material, though for example be have under room temperature (about 25 ℃) the same with tackiness agent or more more soft than it, the rerum natura that the Restoration after the change of shape is good.In other words, this rerum natura is in dynamic viscoelastic is measured, the rerum natura (being designated hereinafter simply as low elastic modulus and low tan δ) that storage Young's modulus (G ') is low and tan δ is also low., in the former epoxies cation-curable resin composition,, do not finding good material aspect such rerum natura except silicone.And the resinoid cured article of silicone is bonding owing to being difficult to other material usually, so its purposes is restricted.
But when usually requiring to have the flexibility of same degree with so-called flexible resin(a), known have an epoxy resin composition that has used epoxidized polybutadiene.In addition, as having the flexible Resins, epoxy that further improves than present commercially available epoxidized polybutadiene, the polyhutadiene that has carboxyl endways and (for example, the referring to Patent Document 1) such as addition reactions that have the epoxy compounds of two cyclohexane oxide structures in 1 molecule are arranged.But this compound according to its solidified nature, and is not known the performance that can embody which kind of degree yet aspect low elastic modulus and low tan δ.
A kind of optical stereo appearance of being made up of epoxy compounds, oxetane compound and light cationic polymerization initiators is disclosed (for example, referring to Patent Document 2) with Photocurable resin composition.Wherein extensive list all cpds or the composition that can consider, but with the present invention in be different materials as the low elastic modulus resin of target compound.
Manufacture method with macromonomer of the group that contains trimethylene oxide endways is disclosed (for example, referring to Patent Document 3), is expressed as the polyisoprene that contains the trimethylene oxide ring at an end as compound.But its rerum natura as the cation-curable resin is also unclear, and Mo Duan structure does not demonstrate the structure among the present invention yet in addition.In addition, because this compound contains a plurality of pairs of keys at intramolecularly, degrade so be easy to be subjected to oxidation.And, the manufacture method of this patent is: obtain by the polymerization terminator that has the trimethylene oxide ring in the reactive terminal addition of the polymkeric substance that is obtained by anionoid polymerization, this method also needs to be suitable for the producing apparatus of this accurate reaction owing to the obstruction that is subjected to micro-moisture in airborne moisture and the reaction soln needs strict dehydration procedure.In addition, owing to anionic polymerization initiators such as butyllithium can be decomposed by airborne moisture, so not easy to operate.
Patent documentation 1: the spy opens (claims) 2001-329045 number
Patent documentation 2: the spy opens flat 10-168165 number (claims)
Patent documentation 3: the spy opens (claims, embodiment) flat 7-309856 number
Summary of the invention
The purpose of this invention is to provide can be with composition viscosity from the number cationically polymerizable polymkeric substance that 10mPas～number 10Pas adjusts significantly.The solidified nature of said composition is good, this cured article be adaptation good, flexible good, soft and at room temperature (for example about 25 ℃) be the low elastic modulus also good material of Restoration after the change of shape simultaneously.In addition, the present invention also provides the composition that contains this polymkeric substance.
In order to solve above-mentioned problem, present inventors are attentively research repeatedly, found that by the following method to solve above-mentioned problem, thereby finished the present invention.
1. polymkeric substance, its be by be selected from maleation polyhutadiene, maleation polyisoprene, contain hydroxyl polyhutadiene, contain hydroxyl polyisoprene, contain hydroxyl ethene-butylene copolymer, contain the hydrogenated butadiene polymer of hydroxyl and contain at least a in the hydrogenated polyisoprene of hydroxyl or more than one material and formula (1) shown in the polymkeric substance that obtains of compound reaction with oxetanyl.
The R of formula (1)
1Expression hydrogen atom or carbonatoms are 1～6 the alkyl that also can have side chain.
2. polymkeric substance, it is the polymkeric substance with oxetanyl that is obtained by the reaction of compound shown in maleation polyhutadiene and/or maleation polyisoprene and the formula (1).
3. polymkeric substance, its be by be selected from polyhutadiene, the polyisoprene that contains hydroxyl, the ethylene-butene copolymer that contains hydroxyl that contain hydroxyl, contain the hydrogenated butadiene polymer of hydroxyl and contain at least a in the hydrogenated polyisoprene of hydroxyl or more than one material and formula (1) shown in the polymkeric substance that obtains of compound reaction with oxetanyl.
4. cation-curable resin composition, it contains the polymkeric substance with oxetanyl of above-mentioned record and carries out the activatory cationic polymerization initiators and/or carry out the activatory cationic polymerization initiators by heating by active energy ray.
5. cation-curable resin composition, its contain above-mentioned record the polymkeric substance with oxetanyl, have the compound of epoxy group(ing) and/or the compound except polymkeric substance and carry out the activatory cationic polymerization initiators and/or carry out the activatory cationic polymerization initiators by heating by active energy ray with oxetanyl with oxetanyl.
6. cured article, it is by to the cation-curable resin composition irradiation active energy ray of above-mentioned record and/or heat and form.
Description of drawings
The stock polymer that Fig. 1 represents embodiment 1 promptly has the hydrogenated butadiene polymer (the system Port リ テ of Mitsubishi Chemical-Le HA) of hydroxyl at two ends
1The H-NMR spectrogram.
Resultant that Fig. 2 represents embodiment 1 promptly has the hydrogenated butadiene polymer of oxetanyl at two ends
1The H-NMR spectrogram.
Stock polymer that Fig. 3 represents embodiment 2 promptly has the ethylene-butene copolymer (KRATON corporate system L-1203) of hydroxyl at an end
1The H-NMR spectrogram.
Resultant that Fig. 4 represents embodiment 2 promptly has the ethylene-butene copolymer of oxetanyl at an end
1The H-NMR spectrogram.
Fig. 5 represents the composition of embodiment 8 and 9 is cured with ultraviolet ray and the dynamic viscoelastic spectrogram (temperature dependency) of the cured article that forms.
Fig. 6 represents the composition of embodiment 12 and 13 is cured with ultraviolet ray and the dynamic viscoelastic spectrogram (temperature dependency) of the cured article that forms.
Fig. 7 represents the composition of embodiment 14 and 16 is cured with ultraviolet ray and the dynamic viscoelastic spectrogram (temperature dependency) of the cured article that forms.
The explanation of symbol
The transverse axis of Fig. 1～4:
1The PPM value of H-NMR spectrogram.
The longitudinal axis of Fig. 1～4:
1Arbitrary value in the H-NMR spectrogram.
The transverse axis of Fig. 5～7: temperature ℃
The right longitudinal axis of Fig. 5～7: the value of tan δ (logarithmic scale).
The left longitudinal axis of Fig. 5～7: the value (Pa, logarithmic scale) of storage Young's modulus (G ').
The heavy line of Fig. 5: the curve of the storage Young's modulus of expression forms the composition of embodiment 8 with ultraviolet being cured cured article (G ').
The fine line of Fig. 5: the curve of the storage Young's modulus of expression forms the composition of embodiment 9 with ultraviolet being cured cured article (G ').
The thick dashed line of Fig. 5: the curve of the tan δ of expression forms the composition of embodiment 8 with ultraviolet being cured cured article.
The fine dotted line of Fig. 5: the curve of the tan δ of expression forms the composition of embodiment 9 with ultraviolet being cured cured article.
The heavy line of Fig. 6: the curve of the storage Young's modulus of expression forms the composition of embodiment 12 with ultraviolet being cured cured article (G ').
The fine line of Fig. 6: the curve of the storage Young's modulus of expression forms the composition of embodiment 13 with ultraviolet being cured cured article (G ').
The thick dashed line of Fig. 6: expression is with the composition of embodiment 12 curve with the tan δ of the ultraviolet cured article that is cured formation.
The fine dotted line of Fig. 6: the curve of the tan δ of expression forms the composition of embodiment 13 with ultraviolet being cured cured article.
The fine line of Fig. 7: the curve of the storage Young's modulus of expression forms the composition of embodiment 14 with ultraviolet being cured cured article (G ').
The heavy line of Fig. 7: the curve of the storage Young's modulus of expression forms the composition of embodiment 16 with ultraviolet being cured cured article (G ').
The fine dotted line of Fig. 7: the curve of the tan δ of expression forms the composition of embodiment 14 with ultraviolet being cured cured article.
The thick dashed line of Fig. 7: the curve of the tan δ of expression forms the composition of embodiment 16 with ultraviolet being cured cured article.
Embodiment
Polymkeric substance with oxetanyl of the present invention is the polymkeric substance that contains the compound with oxetanyl (being called the maleation compound with oxetanyl) that is obtained by the reaction of compound shown in maleation polyhutadiene and/or maleation polyisoprene and the formula (1).
Polymkeric substance with oxetanyl of the present invention, be by be selected from the polyhutadiene, the polyisoprene that contains hydroxyl that contain hydroxyl, contain the hydrogenated butadiene polymer of hydroxyl and contain at least a in the hydrogenated polyisoprene of hydroxyl or more than one material and formula (1) shown in the material that obtains of compound reaction.And, this material be by following formula (2) expression have the compound (being called compound) of oxetanyl at two or more ends by formula (2) expression, this material is included in the polymkeric substance with oxetanyl of the present invention.
In the formula (2), R
1Expression hydrogen atom or carbonatoms are 1～6 the alkyl that also can have side chain, R
2Expression polyhutadiene, polyisoprene, hydrogenated butadiene polymer or hydrogenated polyisoprene are worked as R
2Be when having the polymkeric substance of side chain, also can be at compound keyed jointing shown in the end of side chain and the formula (3).
The R of formula (3)
1Expression hydrogen atom or carbonatoms are 1～6 the alkyl that also can have side chain.
Polymkeric substance with oxetanyl of the present invention, be by be selected from polyhutadiene, the polyisoprene that contains hydroxyl, the ethylene-butene copolymer that contains hydroxyl that contain hydroxyl, contain the hydrogenated butadiene polymer of hydroxyl and contain at least a in the hydrogenated polyisoprene of hydroxyl or more than one material and formula (1) shown in the material that obtains of compound reaction.And this material is by the compound with oxetanyl of following formula (4) expression (being called the compound by formula (4) expression), and this material is included in the polymkeric substance with oxetanyl of the present invention.
In the formula (4), R
1Expression hydrogen atom or carbonatoms are 1～6 the alkyl that also can have side chain, R
2Expression polyhutadiene, polyisoprene, ethylene-butene copolymer, hydrogenated butadiene polymer or hydrogenated polyisoprene.
That is, the polymkeric substance with oxetanyl of the present invention is a maleation compound with oxetanyl, by the compound of formula (2) expression and/or by the compound of formula (4) expression.In addition, when the polymkeric substance with oxetanyl of the present invention is mixture, mix again after also can synthesizing separately respectively.In addition, by the compound of formula (2) expression and the compound of representing by formula (4), also can obtain their mixture by synthetic method.
The resin that is obtained by the composition that contains following polymkeric substance, its good stability, this polymkeric substance are the polymkeric substance with oxetanyl of the present invention that has used the hydrogenation material in synthesis material.Used the polymkeric substance with oxetanyl of the present invention of material of the two keys of existence of polyhutadiene etc. and so in synthesis material, its intermiscibility when making composition is good.
Cation-curable resin composition of the present invention is, contains the polymkeric substance with oxetanyl of the present invention and carries out the activatory cationic polymerization initiators and/or carry out the composition of activatory cationic polymerization initiators by heating by active energy ray.Perhaps, cation-curable resin composition of the present invention is, contains the polymkeric substance with oxetanyl of the present invention, has the compound of epoxy group(ing) and/or the compound with oxetanyl except the polymkeric substance with oxetanyl and carry out the activatory cationic polymerization initiators and/or carry out the composition of activatory cationic polymerization initiators by heating by active energy ray.
Cation-curable resin composition of the present invention is, will be by the compound of formula (2) expression and/or by the compound of formula (4) expression and/or have the maleation compound of oxetanyl and carry out the activatory cationic polymerization initiators and/or carry out the composition that the activatory cationic polymerization initiators mixes by heating by active energy ray.Cation-curable resin composition of the present invention is to carry out the activatory cationic polymerization initiators and/or to carry out the composition that the activatory cationic polymerization initiators mixes by heating by the compound of formula (2) expression with by the compound of formula (4) expression and by active energy ray.In the composition of the present invention, also contain compound in addition to these sometimes, also contain epoxy compounds in addition sometimes with oxetanyl.
The present invention is shone active energy ray and/or is heated the cured article that forms by the cation-curable resin composition to above-mentioned record.
Cation-curable resin composition of the present invention is, contain by the compound of formula (2) expression and by active energy ray and carry out the activatory cationic polymerization initiators and/or carry out the cation-curable resin composition of activatory cationic polymerization initiators by heating, wherein also can also contain compound with epoxy group(ing) and/or except above-mentioned by the compound the compound of formula (2) expression with oxetanyl.
Cation-curable resin composition of the present invention is to carry out the activatory cationic polymerization initiators and/or to carry out the composition that the activatory cationic polymerization initiators mixes by heating by the compound of formula (4) expression with by active energy ray.Cation-curable resin composition of the present invention still also contains compound with epoxy group(ing) and/or the cation-curable resin composition that has the compound of two or more oxetanyls in a molecule sometimes.Or wherein also contain the compound compositions that in a molecule, has an oxetanyl except formula (4) sometimes.
Cation-curable resin composition of the present invention is, will have the maleation compound of oxetanyl and carries out the activatory cationic polymerization initiators and/or carry out the composition that the activatory cationic polymerization initiators mixes by heating by active energy ray.In addition, be to have the maleation compound of oxetanyl and to carry out the activatory cationic polymerization initiators and/or carry out the activatory cationic polymerization initiators and have the compound of epoxy group(ing) and/or the composition that the compound with oxetanyl except the maleation compound with oxetanyl mixes by heating by active energy ray.When paying attention to solidified nature, preferably sneak into epoxy compounds.
On the other hand, in elastic adhesive etc., in the time need suitably adjusting or when the less polyhutadiene of maleation rate or polyisoprene during, also can sneak into the compound that in a molecule, has two or more epoxy group(ing) and/or the compound that in a molecule, has two or more oxetanyls except maleation compound with oxetanyl as raw material to low elastic modulus and obdurability.At this moment, also can sneak in a part the compound that not only contains epoxy group(ing) but also contain oxetanyl.
In the manufacturing by the compound of formula (2) expression, do not need the compound of strict dehydration procedure or difficult operation.Polyhutadiene, polyisoprene, hydrogenated butadiene polymer and/or the hydrogenated polyisoprene that for example can be hydroxyl with two or more ends carry out tosylation or methylsulfonylization, and the compound shown in itself and the formula (1) is reacted to obtain the compound by formula (2) expression.
In the manufacture method by the compound of formula (4) expression, do not need the compound of strict dehydration procedure and difficult operation.For example ethylene-butene copolymer, polyhutadiene, polyisoprene, hydrogenated butadiene polymer and/or the hydrogenated polyisoprene that can be hydroxyl with an end carries out tosylation or methylsulfonylization, and the compound shown in itself and the formula (1) is reacted to obtain the compound by formula (4) expression.Other example is that the part of the hydroxyl of two ends are hydroxyls polyhutadiene, polyisoprene, hydrogenated butadiene polymer and/or hydrogenated polyisoprene is carried out tosylation or methylsulfonylization; the method that compound shown in itself and the formula (1) is reacted; in the method, also contain compound in the resultant sometimes with two or more oxetanyls.
Maleation compound with oxetanyl
As employed maleation polyhutadiene and maleation polyisoprene in the maleation compound with oxetanyl of the present invention synthetic, can use various materials.No matter it be by radical polymerization or can by anionoid polymerization.The molecular weight of these materials has no particular limits, but be preferably 500～100000 in viscosity-average molecular weight, and more preferably 1000～80000, be preferably 5000～40000 especially.If this molecular weight is lower than 500, then cured article is difficult to obtain the cation-curable resin composition of low elastic modulus sometimes.In addition when molecular weight greater than 100000 the time since with the intermiscibility variation of other monomer or polymerization starter, so not preferred.The number of the acid anhydrides of promptly introducing in each Molecularly Imprinted Polymer for the maleation rate is preferably each molecule and on average introduces one or more, and more preferably average out to is 2～10,2～5 of preferred especially average out to.When one of maleation rate average out to or when following, then non-reacted polymer build-up, or be easy to cause from cured article and ooze out rising with tan δ that solvent resistance is also poor in addition, so not preferred.On the contrary, when if the maleation rate surpasses average 10, in order to realize needing to reduce markup percentage by the compound of formula (1) expression as the low elastic modulus of feature of the present invention, this moment residual otiose acid anhydrides, so not preferred from water tolerance and low absorbefacient viewpoint.
As the maleation polyhutadiene that uses among the present invention, can enumerate Japanese Cao Da system NISSO-PB BN-1015, Nippon Oil(Nippon Mitsubishi Oil) chemistry system M-1000-80, bright dipping petroleum chemistry system Poly bd R-45MA etc.As the maleation polyisoprene that uses among the present invention, can enumerate Network ラ レ system LIR-403 etc.
Maleation compound with oxetanyl of the present invention can be easily synthetic by the compound of formula (1) expression by addition in above-mentioned maleation polyhutadiene or maleation polyisoprene.
In the maleation compound with oxetanyl of the present invention by the preferred markup percentage of the compound of formula (1) expression according to the difference of maleation rate and difference, if but estimate with the markup percentage of each Molecularly Imprinted Polymer, 1～20 of then preferred average out to, more preferably average out to is 2～5.When being lower than 1, then non-reacted polymkeric substance increases, and perhaps is easy to cause from cured article ooze out or the rising of tan δ, and solvent resistance is also poor in addition, so not preferred.During on the contrary on average greater than 20, from realizing seeing not preferred as the low elastic modulus aspect of feature of the present invention.In addition, if make Racemic glycidol etc. have epoxy compounds and the maleation polyhutadiene or the addition of maleation polyisoprene of hydroxyl, then the carboxylic acid that is produced by this addition can carry out addition and gelation with the epoxy group(ing) of other polymkeric substance.But, use among the present invention by the compound of formula (1) expression owing to be difficult to carry out addition reaction, so be easy to synthetic maleation compound with oxetanyl with carboxyl.
In addition, the maleation compound with oxetanyl of the present invention, be not only by maleation polyhutadiene or maleation polyisoprene with obtain by the compound addition of formula (1) expression, but also can addition other alcohol.As used here alcohol, suitable is the compound that has a hydroxyl in a part, and if do not have the functional group of obstruction cationoid polymerisations such as amine compound, just can suitably use all cpds.In addition, also can carry out esterification with the carboxylic acid that these alcohol generate after with acid anhydrides and pure addition.
For compound by formula (2) expression
In order to synthesize the two or more ends that used by the compound of formula (2) expression that use in the present composition is polyhutadiene, polyisoprene, hydrogenated butadiene polymer or the hydrogenated polyisoprene of hydroxyl, as long as two or more ends are that hydroxyl is just passable, no matter polymerization process is not particularly limited, be that anionoid polymerization or radical polymerization can.As the compound that obtains by anionoid polymerization, can enumerate the Port リ テ-Le HA etc. of GI-1000, GI-2000, GI-3000 or Mitsubishi Chemical's system of Japanese Cao Da system.The compound that is produced by anionoid polymerization is not owing to there is side chain, so have two hydroxyls.As the compound that obtains by radical polymerization, can enumerate the R-45HT of bright dipping petroleum chemistry system and it be carried out hydrogenant Port リ テ-Le H etc. by Mitsubishi Chemical.The compound that is produced by radical polymerization has side chain, so most compound is the compound with two hydroxyls, but also comprises the compound with two or more hydroxyls.In addition, paying attention under the situation of scale resistance, preferably the compound that these hydrogenation of compounds are formed.Among the present invention, for the polymerization process that synthesizes the compound that is used by the compound of formula (2) expression has no particular limits, but because the hydride that obtains by radical polymerization is solid, poorly soluble to solvent, so from the viewpoint that is easy to make, the preferred especially hydrogenated butadiene polymer that obtains by anionoid polymerization.
For the molecular weight of the synthetic compound that is used by the compound of formula (2) expression has no particular limits, but, be preferably 500～50000, more preferably 1000～10000 according to the molecular-weight average with polystyrene conversion (Mw) of GPC.If molecular weight is lower than 500, then cured article can not obtain the cation-curable resin of low elastic modulus sometimes, so not preferred.In addition when molecular weight greater than 50000 the time since with the intermiscibility variation of other monomer of blended in composition and polymerization starter, so not preferred.
The present invention for example can be obtained by the material (being called tosylation thing or methylsulfonyl thing) that the hydroxyl of above-mentioned raw materials polymkeric substance is carried out tosylation or methylsulfonyl formation by the compound of formula (2) expression.Tosylation thing or methylsulfonyl thing for example can be dissolved in solvent by making stock polymer and tertiary amine or pyridine (only abbreviating tertiary amines later on as), add toluene sulfonyl chloride or methylsulfonyl chloride and the method that heats and obtaining.As use therein tertiary amines, can enumerate triethylamine, Tributylamine, N, N-dimethyl benzylamine, 4-(N, N-dimethyl)-aminopyridine etc., but viewpoint low from hazardous property or that be easy to obtain, the suitable especially triethylamine that uses.As solvent, can enumerate tetrahydrofuran (THF) (THF), 1, ether solvents such as 2-diethoxyethane and dibutyl ether; Aliphatic hydrocarbon kind solvents such as heptane; Aromatic hydrocarbon solvents such as toluene; And chlorine kind solvent such as chloroform etc., but particularly suitable is ether solvent.About the selection of toluene sulfonyl chloride or methylsulfonyl chloride,, be preferably toluene sulfonyl chloride if consider the processing ease degree.The add-on of toluene sulfonyl chloride or methylsulfonyl chloride and tertiary amines, preferably with the hydroxyl of polymkeric substance for wait mole or more than.Be preferably 1.2～1.6 times of moles especially.In addition, preferred tertiary amine analogy toluene sulfonyl chloride etc. is excessive.Temperature of reaction only otherwise follow side reaction or decomposition etc. and can obtain enough speed of response just has no particular limits, and still is preferably the scope of room temperature～150 ℃, more preferably 50 ℃～150 ℃ scope.The shielding gas of reaction system does not need to resemble strict dehydration procedure the anionoid polymerization, though in addition in atmosphere also can, but the preferred rare gas element such as nitrogen that feeds.
Among the present invention, can after above-mentioned tosylation or methylsulfonylization, directly drop into compound by formula (1) expression.But when using excessive toluene sulfonyl chloride or methylsulfonyl chloride with respect to hydroxyl, be preferably temporary transient refining after the method for compound shown in the throw-in type (1) again.Its reason is because sometimes by the tosylate of the compound of formula (1) expression or methanesulfonates meeting with by the compound reaction generation ether compound (for example two (1-ethyl (3-oxetanyl)) methyl ether) of formula (1) expression.Promptly; because the boiling point of these materials is high and separate relatively difficulty with the compound by formula (2) expression as target compound; so in order to improve purity by the compound of formula (2) expression, the preferred method that tosylation thing or methylsulfonyl thing are re-used after refining.
The refining method that can be listed below of tosylation thing or methylsulfonyl thing; promptly at first the solution of reactant is dropped into the tosylation thing or the methylsulfonyl thing is insoluble and toluene sulfonyl chloride or the soluble solvent of methylsulfonyl chloride in; for example carbonatoms is in the ketones solvents such as 1～3 alcohol or acetone, makes the target compound precipitation and the method that reclaims.As the method for further raising purity, this throw out of sening as an envoy to be can enumerate and varsol or THF, 1 such as hexane and heptane are dissolved in, ether solvents such as 2-diethoxyethane and dibutyl ether carry out redeposition purified method repeatedly.Aspect refining, preferred method is: will be by the solution of the varsol of the compound of formula (2) expression, and be that 1～3 alcohol mixes with carbonatoms, make it be separated into two layers, the method for washing again then.In the method, can use a small amount of solvent.Wherein, also can enumerate the method that washes with water according to ordinary method, but owing in the method emulsification takes place sometimes, so especially preferably be 1～3 alcohol, especially wash with methyl alcohol with carbonatoms.At this moment, also can make the mixed solvent of water and methyl alcohol.
Tosylation thing or methylsulfonyl thing can still preferably add basic catalyst by combining last oxetanyl with the compound reaction of being represented by formula (1) when this reacts.In addition, this reaction also can be solvent-free, is dissolved in solvent and carries out but be preferably.As the basic catalyst that is used for this reaction, can enumerate alkali-metal oxyhydroxide or tertiary amine etc., but preferably sodium hydroxide and potassium hydroxide particularly preferably are potassium hydroxide.Here, also can list the method that the compound of being represented by formula (1) with handles such as sodium hydroxide is made as alkoxide in advance, but because industrial not easy to operate, so be preferably the method for using alkali-metal oxyhydroxide.As the solvent in this reaction, can enumerate varsol or THF, 1 such as hexane and heptane, ether solvents such as 2-diethoxyethane and dibutyl ether, but what be fit to is ether solvent, wherein can also suit to use the high material of boiling point especially, for example 1,2-diethoxyethane or dibutyl ether.
By the compound of formula (1) expression add-on with respect to tosylation thing or methylsulfonyl thing; as long as by mole convert be the tosyl group of polymkeric substance or methylsulfonyl wait mole or above just passable; have no particular limits, but be preferably 1.2 times or more than.Have no particular limits for the upper limit, but from yield aspect with respect to reactor volume, be preferably 100 times or below.When excessive use during by the compound of formula (1) expression, sometimes can be separated into two layers as the polymkeric substance of target and the solution that contains by the compound of formula (1) expression, also can will contain by formula (1) thus the layer of the compound of expression reclaims and distills and re-uses.
This temperature of reaction is preferably 60 ℃～150 ℃, is preferably 90～130 ℃ especially.
Produce the viewpoint of decomposing or generating superoxide from suppressing tosylate and methanesulfonates because of water, the shielding gas of this reaction system is preferably nitrogen protection gas.
Reacted refining about this, also can implement according to ordinary method, drops into a large amount of alcohol etc. and make its sedimentary method (redeposition is refining), but just use the few viewpoint of quantity of solvent, preferred especially following method.That is, the excessive compound by formula (1) expression that produces after tosylate precipitation or the two layers of separation is removed, then the method for washing with two coating systems of varsol such as hexane and methyl alcohol.Wherein, because the washing of water sometimes can cause emulsification, so not too suitable.The refined compound of being represented by formula (2) can obtain by this layer is carried out desolventizing owing to be contained in the varsol layer.
Compound by formula (4) expression
Ethylene-butene copolymer, polyhutadiene, polyisoprene, hydrogenated butadiene polymer and hydrogenated polyisoprene that an end by the compound of formula (4) expression that is used for that the synthetic present composition uses is a hydroxyl, so long as it is just passable to have a hydroxyl at an end, polymerization process is not particularly limited.The polyhutadiene of a terminal hydroxyl for example can enumerating the ethylene-butene copolymer that produces by polycoordination and obtain by living anion polymerization or polyisoprene and the material that these hydrogenation of compounds are formed.In addition, when at the polyhutadiene that is hydroxyls by two ends of use in the compound of formula (4) expression synthetic, polyisoprene, hydrogenated butadiene polymer or/and hydrogenated polyisoprene, no matter also polymerization process is not particularly limited, be that living anion polymerization or radical polymerization can.The molecular weight of the material that uses for compound shown in the synthesis type (1) has no particular limits, but according to the molecular-weight average with polystyrene conversion (Mw) of GPC, is preferably 500～50000, and more preferably 1000～10000.If molecular weight is lower than 500, then owing to can not obtain low elasticity cation-curable resin sometimes, thus not preferred, in addition when molecular weight greater than 50000 the time, because with the intermiscibility variation of other monomer of blended in composition or polymerization starter, so not preferred.
The present invention can be with synthetic in the same way by the compound of formula (2) expression by the compound of formula (4) expression.
Under the situation of the polymkeric substance that to use an end be hydroxyl, the add-on of tosylation thing or methylsulfonyl thing is identical with the situation of formula (2), be preferably with hydroxyl etc. mole or more than, 1.2～6 times of moles more preferably.But; when use two ends have hydroxyl such combine the polymkeric substance of a plurality of hydroxyls the time; can sneak into less than the toluene sulfonyl chloride of hydroxyl mole number or methylsulfonyl chloride and carry out tosylation or methylsulfonylization; directly drop into compound then by formula (1) expression; this method is easier, so preferred.
In addition, when use two ends have hydroxyl such in conjunction with the polymkeric substance of a plurality of hydroxyls the time, also can in this polymkeric substance, on average contain and be lower than two oxetanyl, be preferably one.
Above-mentioned tosylation thing or methylsulfonyl thing can still preferably add basic catalyst by combining last oxetanyl with the compound reaction of being represented by formula (1) when this reacts.In addition, this reaction also can be solvent-free, is dissolved in solvent and carries out but be preferably.As the basic catalyst that is used for this reaction, can enumerate alkali-metal oxyhydroxide or tertiary amine etc., but preferably sodium hydroxide and potassium hydroxide particularly preferably are potassium hydroxide.Wherein, also can enumerate the method that the compound of being represented by formula (1) with handles such as sodium hydroxide is made as alkoxide in advance, but because industrial not easy to operate, so be preferably the method for using alkali-metal oxyhydroxide.As the solvent in this reaction, can enumerate varsol or THF, 1 such as hexane and heptane, ether solvents such as 2-diethoxyethane and dibutyl ether, but what be fit to is ether solvent, wherein can also suit to use the high material of boiling point especially, for example 1,2-diethoxyethane or dibutyl ether.
Above-mentioned compound by formula (1) expression is with respect to the add-on of tosylation thing or methylsulfonyl thing; as long as by mole convert be the tosyl group of polymkeric substance or methylsulfonyl wait mole or more than; just have no particular limits, but be preferably 1.2 times or more than.Have no particular limits for the upper limit, but from yield aspect with respect to reactor volume, be preferably 100 times or below.When using excessive compound by formula (1) expression, sometimes can be separated into two layers as the polymkeric substance of target and the solution that contains by the compound of formula (1) expression, also can reclaim and distill, re-use containing layer by the compound of formula (1) expression.
This temperature of reaction is preferably 60 ℃～150 ℃, is preferably 90～130 ℃ especially.
From suppressing to generate the viewpoint of superoxide, the shielding gas of this reaction system is preferably nitrogen protection gas.
This reacted refining can carrying out in the same way with compound by formula (2) expression.Cation-curable resin composition of the present invention
According to the maleation compound with oxetanyl of the present invention, by the compound of formula (2) expression with by the compound of formula (4) expression, because cationically polymerizable is good, so can with its with carry out the activatory cationic polymerization initiators by active energy ray and/or carry out the activatory cationic polymerization initiators by heating and mix, as cation-curable resin composition.From the active energy ray-curable resin that this cation-curable resin composition obtains, can realize the unapproachable rerum natura of material in the past.In addition, from by the compound of formula (2) expression with by the viewpoint of the scale resistance of the storage stability of the compound of formula (4) expression or cured article, the R in the formula
2Preferably ethylene-butene copolymer, hydrogenated butadiene polymer or hydrogenated polyisoprene.
As the cationic polymerization initiators that causes cation-curable resin composition generation cationoid polymerisation of the present invention by the irradiation active energy ray, can enumerate diazonium salt, salt compounded of iodine, sulfonium salt, selenium salt, pyridinium salt, ferrocene salt, phosphonium salt and thiamidine salt (チ オ ピ リ リ ニ ウ system) etc., be preferably salt compounded of iodine and sulfonium salt, more preferably diaryl group iodized salt and dialkyl group phenacyl sulfonium salt, the suitable especially diaryl group iodized salt that uses.
When light cationic polymerization initiators such as salt compounded of iodine and sulfonium salt are used for cation-curable resin composition of the present invention, can enumerate BF as negatively charged ion
4 -, AsF
6 -, SbF
6 -, PF
6 -, and B (C
6F
5)
4 -Deng, be preferably SbF
6 -, PF
6 -, or B (C
6F
5)
4 -, be preferably SbF especially
6 -And B (C
6F
5)
4 -
If enumerate the object lesson of light cationic polymerization initiators, can list two (dodecylphenyl) iodine hexafluoro antimonate (シ リ コ of GE Toshiba-Application corporate system, the principal constituent of UV-9380C), tolyl cumyl iodine four (pentafluorophenyl group) borate (ロ-デ イ ア corporate system, PHOTOINITIATOR2074), two (alkyl (C=10～14) phenyl-iodide) hexafluoro antimonate (with the pure medicine system light of light cationic polymerization initiators WPI-016) etc.
Active energy ray when cation-curable resin composition of the present invention is solidified also can use X line, electron rays, ultraviolet ray and visible light etc., but be preferably ultraviolet ray or visible light, is preferably ultraviolet ray especially.When using ultraviolet ray, its wavelength region is had no particular limits, but be preferably 150～400nm, more preferably 200～380nm.When using ultraviolet ray, can cause cationoid polymerisation expeditiously.
In addition, in cation-curable resin composition of the present invention, as required,, also can and use sensitizing agent in order further to improve the activity of light cationic polymerization initiators.As the sensitizing agent that can use in the present invention, can use for example Network リ ベ ロ disclosed compound in " polymer science progress " (Adv.In Polymer Sci., 62,1 (1984)).Pyrans, perylene, acridine orange, thioxanthone, 2-clopenthixal ketone and benzoflavine etc. are arranged particularly.In addition, also can use the compound that is widely used as the optical free radical polymerization starter, can list benzophenone, 2 particularly, 4-diethyl thioxanthone, 2-isopropyl thioxanthone, 2, thioxanthene ketones such as 4-two clopenthixal ketones; Benzoin ethers such as benzoin methylether, ethoxybenzoin, benzoin iso-propylether; 2,2-dimethoxy-1,2-diphenylethane-benzyl dimethyl ketal classes such as 1-ketone; Alpha-hydroxy alkyl phenyl ketones such as 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone; α-dicarbonyl compounds such as camphorquinone etc.Among the present invention, can suit to use thioxanthene ketone and Alpha-hydroxy alkyl phenyl ketone especially.
The combined amount of light cationic polymerization initiators in cation-curable resin composition of the present invention can suitably be adjusted according to the kind and the irradiation dose of active energy ray.For example under ultraviolet situation, the cation-curable resin composition with respect to amounting to 100 mass parts is preferably 0.1～10 mass parts, more preferably 0.5～5 mass parts, more preferably 1～3 mass parts.When the combined amount of cationic polymerization initiators was also littler than 0.1 mass parts, solidified nature was poor sometimes; Opposite when the time greater than 10 mass parts, exist to make the composition minimizing that really needs in the cured article and reduce the situation of cured article rerum natura and the painted intensive situation that becomes of cured article, so not preferred.
Combined amount when adding sensitizing agent in cation-curable resin composition of the present invention can suitably be adjusted according to the kind and the irradiation dose of active energy ray.For example under ultraviolet situation, the cation-curable resin composition with respect to amounting to 100 mass parts is preferably 5 mass parts or following, more preferably 0.2～2 mass parts.When the combined amount of sensitizing agent during, exist the composition that really needs in the cured article is reduced and to reduce the situation of cured article rerum natura or the painted intensive situation that becomes of cured article greater than 5 mass parts.
When active energy ray was ultraviolet ray or visible light, cation-curable resin composition can be exposed in the air, but the environmental optimization of this moment is that humidity is low, and preferred humidity is 80%R.H. or following, and more preferably humidity is 70%R.H. or following.Wherein, when ultraviolet ray and visible light are set in production line, also can adopt to place, light irradiation device place and carry the method for dry air to reduce the method for humidity with heating unit is installed.
Also compound, the instant heating cationic polymerization initiators that causes cationoid polymerisation by heat-activated can be used for cation-curable resin composition of the present invention.As this compound, can enumerate the combination of various salts such as quaternary ammonium salt, phosphonium salt and sulfonium salt or organoalkoxysilane and aluminium complex etc.As the product that can obtain, can enumerate ア デ カ オ プ ト Application CP-66 and ア デ カ オ プ ト Application CP-77 (is a trade(brand)name, rising sun electrochemical industry (strain) system), サ Application エ イ De SI-60L, サ Application エ イ De SI-80L and サ Application エ イ De SI-100L (all being trade(brand)name, three new chemical industry (strain) system) and CI series (Japanese Cao Da (strain) system) etc.
The blending ratio of hot cationic polymerization initiators in cation-curable resin composition of the present invention, cation-curable resin composition with respect to 100 mass parts, be preferably the scope of 0.01～10 mass parts, more preferably 0.1～5 mass parts, more preferably 0.5～3 mass parts.When this blending ratio is lower than 0.1 mass parts, though sometimes by heat effect with its sensitization, can not carry out the ring-opening reaction of ring-opening polymerization base fully.In addition, even to surpass 10 mass parts it is mixed, owing to promote the polymeric effect more not improve, the rerum natura of cured article descends sometimes in addition, so not preferred.
If be conceived to the light cation-curable resin composition, then with regard to the viewpoint of solidified nature, be preferably contain maleation compound with oxetanyl, by the compound of formula (2) expression and/or by the resin combination of compound, the compound that contains epoxy group(ing) and the light cationic polymerization initiators of formula (4) expression.In the light cationoid polymerisation, oxetane compound is better than the polymerizability of epoxy compounds, but because slower, so, can improve whole solidified nature by in containing the composition of oxetane compound, mixing a spot of epoxy compounds in the reaction of polymerization initial stage.
As the epoxy compounds that is used to improve integrally curing, can utilize all cpds, no matter be multifunctional or multifunctional can.In addition, as the epoxy group(ing) of epoxy compounds, no matter be that intramolecular pair of key is oxidized, or glycidyl ether can.As the intramolecular pair of material that key is oxidized, not only can be the ester ring type epoxy, and can be the oxidized materials of chain molecule such as alkene and polyhutadiene.
Following illustration be used for obtaining have the low elastic modulus same, the Restoration after the change of shape is also good simultaneously cured article under the room temperature (for example about 25 ℃) with tackiness agent preferred mixes routine.One of them example be contain the maleation compound and/or by the compound of formula (2) expression, in a part, have the compound of an oxetanyl and the composition of cationic polymerization initiators.Under the situation of the light-cured resin that contains the light cationic polymerization initiators,, be preferably the compound that in said composition, also contains epoxy group(ing) from the viewpoint of solidified nature.
Another example is to contain by the compound of formula (4) expression, have the compound of two or more cationically polymerizable bases and the composition of cationic polymerization initiators in a part.If will keep good solidified nature, become lowering viscousity simultaneously, then preferably in said composition, also be mixed with the compound that in a part, has an oxetanyl.In addition, under the situation of the light-cured resin that contains the light cationic polymerization initiators,, be preferably the compound that in said composition, also contains epoxy group(ing) from the viewpoint of solidified nature.
In a part, have the compound of an oxetanyl and compare, not only from solidified nature but also also preferred from the viewpoint of security with the compound that in a part, has an epoxy group(ing).Promptly, this be because: most of under a cloud in the molecular weight circlet oxygen compound has mutagenicity, and (Japanese is: change Iso originality), but with regard to oxetane compound, the mutagenicity of 3-ethyl-3-that for example molecular weight is little (2-ethyl hexyl oxy methyl) trimethylene oxide is negative.
Because polymer viscoelastic body normally,, but here, be defined as tan δ during dynamic viscoelastic measured and call solid smaller or equal to 1 material so the differentiation of solid and liquid is difficult to lump together.
The cured article Young's modulus that tan δ is little is low, and the Restoration after the same change of shape is good.
Wherein, so-called room temperature is meant about 25 ℃, owing in fact being often used in the inside of the electronic machine of indoor use, so be roughly 0 ℃～40 ℃ scope.In this temperature range, want to make the Restoration after the low change of shape simultaneously of Young's modulus of cured article good, the preferred glass invert point is-10 ℃ or following, more preferably-25 ℃ or following, is preferably-40 ℃ or following especially.
In addition in the cured article that is obtained by composition of the present invention, by the content and the compounding substances of modulation The compounds of this invention, the dynamic viscoelastic modulus (G ') that can obtain under 25 ℃ is 1 * 10
8Pa or following material perhaps also can obtain 10
7Pa or following material perhaps also can obtain 10
6Pa or following material.
If be conceived to by the compound of formula (2) expression with by the compound of formula (4) expression, then from the viewpoint of the scale resistance of storage stability or cured article, the R in preferred formula (2) and the formula (4)
2Be ethene-butylene copolymer, hydrogenated butadiene polymer or hydrogenated polyisoprene.
Make in the degree that elastic adhesive etc. should be adjusted low elastic modulus under the situation of balance appropriateness of itself and obdurability etc., preferably be blended in the compound that has two or more epoxy group(ing) in a part and/or the compound that in a part, has two or more oxetanyls beyond the polymkeric substance of the present invention.Wherein, also may be combined in a part and not only to contain epoxy group(ing) and but also to contain the compound of oxetanyl.
Can use all cpds as the compound that contains an epoxy group(ing) that is used for cation-curable resin composition of the present invention.If enumerate the example of commercial this compound, can enumerate 1, alpha-olefin epoxide such as 2-epoxy n-Hexadecane, phenylglycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, glycidyl methacrylate etc.
The compound that contains two or more epoxy group(ing) as being used for cation-curable resin composition of the present invention can use all cpds.
If enumerate the example of commercial this compound, can list the Dicyclopentadiene (DCPD) dioxide, titanium dioxide 1, the 8-terpadiene, the 4 vinyl cyclohexene dioxide, (3,4-epoxy group(ing) cyclohexyl methyl-3,4-epoxy-cyclohexane carboxylicesters, two (3,4-epoxy group(ing) cyclohexyl) adipic acid ester, bisphenol A type epoxy resin, the halogenation bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol-S diglycidyl ether, bisphenol f type epoxy resin, o-, m-, p-cresols phenolic resin varnish type epoxy resin, phenol novolak type epoxy resin, 1, the 6-hexanediol diglycidyl ether, the polytetramethylene glycol diglycidylether, trihydroxymethylpropanyltri diglycidyl ether, tetramethylolmethane four glycidyl ethers, the inner loop oxide compound of polyhutadiene, two ends of polyhutadiene are by the compound of glycidyl ether, two key parts of the divinyl of styrene-butadiene copolymer are by epoxidised compound, the part of the polyisoprene of the segmented copolymer of ethylene-butene copolymer and polyisoprene is by epoxidised compound (KRATON corporate system L-207), the vinyl of the ring-opening polymerization polymer of 4 vinyl cyclohexene oxide compound is carried out the compound that epoxidation forms, epoxidized vegetable oil etc.Wherein, the quantity of the epoxy group(ing) in each molecule is had no particular limits, but be preferably 50 or below, be preferably especially 20 or below.When epoxy group(ing) greater than 50 the time, because mixed with little amount can improve Young's modulus, so not preferred.
Has the compound of an oxetanyl as what be used for cation-curable resin composition of the present invention at a part, can list (being the trade(brand)name or the exploitation name of an article in the bracket, the synthetic system in East Asia) 3-ethyl-3-(2-ethyl hexyl oxy methyl) trimethylene oxide (ア ロ Application オ キ セ Application OXT-212 (EHOX)), 3-ethyl-3-(cyclohexyl oxygen ylmethyl) trimethylene oxide (CHOX), 3-ethyl-3-(dodecyloxy methyl) trimethylene oxide (OXR-12), 3-ethyl-3-(octadecane oxygen ylmethyl) trimethylene oxide (OXR-18), 3-ethyl-3-(phenoxymethyl) trimethylene oxide (ア ロ Application オ キ セ Application OXT-211 (POX)), 3-ethyl-3-methylol trimethylene oxide (OXA) etc.
The compound that contains two or more oxetanyls as being used for cation-curable resin composition of the present invention can use various materials.If enumerate the example of this compound, can list (is the trade(brand)name or the exploitation name of an article in the bracket, the synthetic system in East Asia) 1, two { [(3-ethyl-3-oxetanyl) methoxyl group] methyl } benzene (ア ロ Application オ キ セ Application OXT-121 (XDO)) of 4-, two [1-ethyl (3-oxetanyl)] methyl ethers (ア ロ Application オ キ セ Application OXT-221 (DOX)), oxetanyl silsesquioxane (OX-SQ), phenol phenolic varnish trimethylene oxide (PNOX-1009), the etherate (NDMOX) of norbornane dimethanol and 3-ethyl-3-chloromethyl trimethylene oxide (abbreviating OXC later on as), the etherate of TriMethylolPropane(TMP) and OXC (TMPOX), the etherate of quinhydrones and OXC (HQOX), the etherate of Resorcinol and OXC (RSOX), 2, the etherate (2 of 2 '-bis-phenol and OXC, 2 '-BPOX), 4, the etherate of 4 '-bis-phenol and OXC (4,4 '-BPOX), the etherate of Bisphenol F and OXC (BisFOX), the etherate of tristane dimethanol and OXC, alkoxide (OX-SC) that forms by OXA and silane etc.
Wherein, the quantity of the oxetanyl in each molecule is had no particular limits, but be preferably 20 or below, more preferably 5 or below, be preferably especially 3 or below.
With these compositions that mix to form, be preferably and finally be dissolved as homogeneous transparent.When composition mixes, viewpoint from intermiscibility, the material that is suitable for can list KRATON corporate system L-207,1,2-epoxy n-Hexadecane, norbornane dimethanol dioxetane, 3-ethyl-3-(2-ethyl hexyl oxy methyl) trimethylene oxide (EHOX), 3-ethyl-3-(cyclohexyl oxygen ylmethyl) trimethylene oxide (CHOX), 3-ethyl-3-(dodecyloxy methyl) trimethylene oxide (OXR-12) etc.
In composition of the present invention, also can mix fillers such as silica, aluminum oxide, other metal oxide as required.Can give thixotropy etc. thus.In addition, when when the electrically insulating material, the preferred material that mixes, more preferably mineral-type, the material that especially preferably has anion exchange capacity with ion-exchange capacity.As the example of the mineral-type anion ion exchange body that is fit to, can enumerate IXE-500, IXE-530, IXE-550, IXE-700, IXE-800 etc. (all being the synthetic system in East Asia).
In addition, in composition of the present invention, in order to improve the adaptation with inorganic materials, also can the mixed silanes coupler etc. coupler.Silane coupling agent as this example, can enumerate β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane (the chemistry system KBM-303 of SHIN-ETSU HANTOTAI), γ-glycidoxypropyltrime,hoxysilane (the chemistry system KBM-403 of SHIN-ETSU HANTOTAI), γ-glycidoxy propyl-triethoxysilicane (the chemistry system KBE-403 of SHIN-ETSU HANTOTAI), γ-glycidoxy propyl group methyldiethoxysilane (the chemistry system KBM-402 of SHIN-ETSU HANTOTAI), 3-ethyl-3-{[3-(triethoxysilyl) propoxy-] methyl } trimethylene oxide (East Asia synthetic system OXT-610) etc.
In composition of the present invention, when the needs scale resistance, can mix antioxidant.In addition, conduct at this moment is by the compound of formula (2) expression and the compound of being represented by formula (4), especially preferably R
2Be ethylene-butene copolymer, hydrogenated butadiene polymer or hydrogenated polyisoprene.
As the antioxidant that in composition of the present invention, contains, can enumerate phenol antioxidant, sulphur class antioxidant, Phosphorus antioxidant, amine antioxidants, but particularly preferably be phenol antioxidant.
As phenol antioxidant, can enumerate hydroquinone monomethyl ether, 2, the 6-di-tert-butyl hydroxy toluene, 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol), 4,4 '-butylidene is two-and (3 methy 6 tert butyl phenol), triethylene glycol-two-[3-(3 '-tertiary butyl-4-hydroxy-5-aminomethyl phenyl)] propionic ester, [3-(3 for tetramethylolmethane four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] (Ciba Specialty Chemicals corporate system Irganox1010), Octadecane base-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester, 4,4 '-thiobis (3-methyl-6-tert butyl) phenol etc.
Cation-curable resin composition of the present invention can provide from the soft cured article of common so-called flexible resin(a) until the same with tackiness agent or than its softish cured article more.Cation-curable resin composition of the present invention in addition is to have and the low elastic modulus of the tackiness agent same degree Restoration excellent material after the change of shape simultaneously.Therefore, cation-curable resin composition of the present invention is the center with electronic material or optical material, is suitable for use as caking agent, coating agent, sealing compound, sealing agent and insulating material etc.
Especially, the material that forms by active energy line curing in cation-curable resin composition of the present invention is owing to the unapproachable rerum natura of material that can realize in the past, so be particularly suitable for.Wherein, owing to use ultraviolet ray and visible light less expensive and can be with little production line production, so also preferred especially as active energy ray.
Which, can use respectively according to purposes for cation-curable resin composition of the present invention being chosen as active energy line curing system or heat cured system.For example when using or with pressing mold (model) etc., give the purposes aspect of tiny shape, the curing system that ultraviolet curing system that suitable is etc. form by active energy ray as resist.In addition, even coating, silk screen printing, transparent material is bonding etc., from production rate fast and save viewpoint of energy, also be fit to use the curing system that forms by active energy ray.But, can not arrive in the purposes of resin in each other bonding of opaque material or the sealing isoreactivity energy line that contains parts such as metal, what be fit to is heat cured system.But, even in opaque material purposes such as bonding each other, also can utilize distinctive dark reaction in cationic curing, for example behind the light-cured resin irradiates light that is being coated with on the opaque material, bonding other opaque material finishes to solidify by dark reaction and adheres.In addition, after the curing that produces by active energy ray, also can be used in combination the method that is heating and curing.
Embodiment
Embodiment and comparative example have been provided below, to more specifically describe the present invention.But the present invention is not subjected to the restriction of these embodiment and comparative example.In addition, the numerical value in the composite formula table is mass parts.
Hydrogenated butadiene polymer (HAOX) synthetic that has oxetanyl at two ends
＜have a tosylation of the hydrogenated butadiene polymer of hydroxyl at two ends 〉
In the separable flask of 500ML, be added in the hydrogenated butadiene polymer that forms by anionoid polymerization (the system Port リ テ of Mitsubishi Chemical-Le HA) 86.8g (counting 80mmol), tetrahydrofuran (THF) (THF) 142g, triethylamine 24.2g (240mmol) that two ends have hydroxyl with hydroxyl, stirring rod, thermometer and cooling tube are installed, while lead to nitrogen stirring and dissolving in oil bath on the lid of four mouths.After the dissolving,, under 62 ℃, stir and made its reaction in 21 hours to wherein adding toluene sulfonyl chloride 30.5g (160mmol).Reaction is reacted this to thick resultant and is dropped at leisure among the methyl alcohol 950g that stirs under the room temperature after finishing, and restir 30 minutes was placed 1 hour then.After the placement, remove methanol layer, in throw out, add normal hexane 190g then and make its dissolving by decant.It is moved in the separating funnel, remove the methanol layer that is separated into two layers, add methyl alcohol 25g high vibration then and mix, and leave standstill.Afterwards, remove methanol layer.Repeat this operation twice, append normal hexane 48g during still last the washing.The normal hexane layer that will contain resultant moves in the separable flask, desolvates and obtains faint yellow transparent resultant 80g 65 ℃ or following heating up in a steamer while reduce pressure in oil bath.By
1The H-NMR spectrogram can confirm that the hydroxyl of polymkeric substance is by tosylation.
＜to two ends trimethylene oxideization of the hydrogenated butadiene polymer of tosylation 〉
The hydrogenated butadiene polymer 62.0g, n-butyl ether 62.0g, the 3-ethyl-3-hydroxymethyl trimethylene oxide (OXA that in the separable flask of 500ML, add tosylation; the synthetic system in East Asia) 116g, 95% potassium hydroxide 5.9g; stirring rod, thermometer and cooling tube are installed on the lid of four mouths, in oil bath, were made its reaction in 4.5 hours 120 ℃ of following stirrings while lead to nitrogen.After reaction finishes, owing to generate precipitation,, wash this precipitation and this washings is also added in the separating funnel by decant with normal hexane 100g so only liquid is moved in the separating funnel by decant.Because this liquid separation is two layers, so remove the lower floor of containing OXA.Then add methyl alcohol 123g and high vibration and mix, add normal hexane 24g then and mix gently and leave standstill, thereby be separated into two layers, remove sub-cloud.Use methyl alcohol 62g repeated washing three times then, but append the normal hexane of 30～90g scope rapidly and suitably in order to make two layers of separation this moment.The normal hexane layer that will contain resultant moves in the separable flask of 500ML, in 100～120 ℃ oil bath, heat up in a steamer the major part of desolvating while leading to nitrogen, reduced pressure 5 hours in 150 ℃ oil bath in order to remove remaining a spot of solvent then, thereby obtain faint yellow transparent resultant 50g (HAOX).As the Port リ テ-Le HA of raw material and resultant
1The H-NMR spectrogram is shown in respectively among Fig. 1 and Fig. 2.Can confirm that by the NMR spectrogram polymer ends tosyl group is replaced by OXA.In addition, can confirm molecular weight distribution by the GPC that measures resultant, the result is 3876 with the Mw of polystyrene conversion, and Mw/Mn is 1.31.On the other hand, the Mw of stock polymer is 3656, and Mw/Mn is 1.37.
L1203OX's is synthetic
＜have a tosylation of the ethylene-butene copolymer of hydroxyl at an end 〉
In the separable flask of 2L, be added in ethylene-butene copolymer (KRATON Polymers corporate system L-1203) 240g (counting about 60mmol), tetrahydrofuran (THF) (THF) 328g, triethylamine 36.4g that an end has hydroxyl with hydroxyl, stirring rod, thermometer and cooling tube are installed, while lead to nitrogen stirring and dissolving in oil bath on the lid of four mouths.After the dissolving,, under 62 ℃, stir and made its reaction in 27 hours to wherein adding toluene sulfonyl chloride 51.5g (270mmol).Reaction is reacted this to thick resultant and is dropped at leisure among Virahol (IPA) 2.5Kg that stirs under the room temperature after finishing, and then, stirs after 30 minutes and places 1 hour.Remove the IPA layer by decant then, add normal hexane 700g then and make resolution of precipitate.It is moved in the separating funnel of 2L, add after methyl alcohol 120g stirs, add normal hexane 300g again and mix gently and be separated into two layers.After removing the methanol layer of sub-cloud, add methyl alcohol 120g vibration again and mix placement 15 minutes, remove the methanol layer of sub-cloud.With methyl alcohol repeated washing twice again, the normal hexane layer that will contain resultant then moves in the separable flask as mentioned above, desolvates and obtains faint yellow transparent resultant 222g 65 ℃ or following heating up in a steamer while reduce pressure in oil bath.By resultant
1The H-NMR spectrogram can confirm that the hydroxyl of polymkeric substance is by tosylation.
＜the trimethylene oxideization of the ethylene-butene copolymer of tosylation 〉
The ethylene-butene copolymer 204g, n-butyl ether 204g, the 3-ethyl-3-hydroxymethyl trimethylene oxide (OXA that in the separable flask of 2L, add tosylation; the synthetic system in East Asia) 255g, 95% potassium hydroxide 6.5g; stirring rod, thermometer and cooling tube are installed on the lid of four mouths, in oil bath, were made its reaction in 6 hours 120 ℃ of following stirrings while lead to nitrogen.After reaction finishes,,, wash this precipitation, this washings is added in the previous separating funnel by decant with normal hexane 200g so only liquid is moved in the separating funnel by decant owing to generate precipitation.Because the solution separating in the separating funnel is two layers, so remove the lower floor of containing OXA.Then, add methyl alcohol 200g, normal hexane 500g and stir, and then add normal hexane 100g and mix gently and be separated into two layers.Remove this lower floor, use methyl alcohol 200g repeated washing three times again.At this moment, in order to make two layers to separate rapid and clear and suitably append the normal hexane of 100g.The normal hexane layer that will contain resultant moves in the separable flask of 2L, in 100～110 ℃ oil bath, heat up in a steamer the major part of desolvating while leading to nitrogen, reduced pressure 5 hours in 150 ℃ oil bath in order to remove remaining a spot of solvent then, thereby obtain faint yellow transparent resultant 183g.L-1203 and resultant
1The H-NMR spectrogram is shown in respectively among Fig. 3 and Fig. 4.The tosyl group that can confirm polymer ends is thus replaced by OXA.In addition, can confirm molecular weight distribution by the GPC that measures resultant, the result is 5630 with the Mw of polystyrene conversion, and Mw/Mn is 1.04.On the other hand, the Mw of stock polymer is 5510, and Mw/Mn is 1.03.
Embodiment 3
Synthetic (LIOX-1) with maleation compound of oxetanyl
In the separable flask of 500ML, add the Network ラ レ system LIR-403 (viscosity-average molecular weight 25000 of 100g as the maleation polyisoprene, sense radix in each molecule is 3, be about 8mmol in acid anhydrides), 3-ethyl-3-hydroxymethyl trimethylene oxide (OXA, East Asia synthetic (strain) system) 4.65g (40mmol), dimethylbenzene 100g and cover lid, stirring rod, cooling tube and nitrogen ingress pipe are installed, are immersed in the oil bath and stir.At nitrogen flow is to carry out 30 minutes nitrogen replacements under 200ml/ minute, then nitrogen flow is set at 50ml/ minute, on one side be set at 150 ℃ and dimethylbenzene is refluxed bathing temperature, Yi Bian reacted 16 hours.Reactivity is by the peak (1790cm of acid anhydrides in the IR spectrum
-1) absorbancy and as the 2930cm of C-H stretching vibration
-1The peak obtain.Reactivity after 16 hours is 81%.
In this solution, add Irganox1010 (Ciba SpecialtyChemicals corporate system) 0.1g, reduce pressure down at 100 ℃ then and heat up in a steamer removal xylene as antioxidant.Yield is 100%, and residual OXA is 0.3% (according to vapor-phase chromatography).Faint yellow transparent as the polymkeric substance of resultant, the viscosity under 50 ℃ is 153Pas.
Synthetic (LIOX-2) with maleation compound of oxetanyl
In the separable flask of 500ML, add Network ラ レ system LIR-403 (as acid anhydrides is about 7.2mmol), the 3-ethyl-3-hydroxymethyl trimethylene oxide (OXA of 90g as the maleation polyisoprene, East Asia synthetic (strain) system) 4.19g (36mmol), 3-ethyl-3-(2-ethyl hexyl oxy methyl) trimethylene oxide (EHOX, East Asia synthetic (strain) system) 60g and cover lid, stirring rod, cooling tube, nitrogen ingress pipe are installed, are immersed in the oil bath and stir.Under nitrogen flow 200ml/ minute, carry out 30 minutes nitrogen replacements, then nitrogen flow is set at 50ml/ minute, under 165 ℃ of liquid temperature, make its reaction 4 hours, under 140 ℃, make its reaction 4 hours then.Reactivity is obtained with method similarly to Example 1, and the result is 84%.The resultant here is to contain the maleation compound (58%) with oxetanyl, the composition of EHOX (40%), OXA (2%), and outward appearance is faint yellow transparent, and the viscosity under 25 ℃ is 10.9Pas.
Synthesis example 1
Synthesizing of urethane acrylate (PTGUA)
In the separable flask of 500ML, add isophorone diisocyanate (IPDI) 88.8g (0.40mol), dibutyltin dilaurate 0.34g, 2,6-di-tert-butyl-4-methy phenol (BHT) 0.102g, make its reaction while being blown into the polytetramethylene glycol that air drips molecular weight about 1000 (hodogaya chemical industry system PTG1000SN) 203.8g (0.20mol), under 60 ℃, make its reaction 1 hour again.Then, drip 2-hydroxyethylmethacry,ate (HEA) 46.4g (0.40mol), under 80 ℃, make its reaction 1 hour and the acquisition urethane acrylate.
Put down in writing the abbreviation in the composition mixture table below.
HAOX: by the resultant of embodiment 1 acquisition
L1203OX: by the resultant of embodiment 2 acquisitions
LIOX-1: by the resultant of embodiment 3 acquisitions
LIOX-2: by the resultant of embodiment 4 acquisitions
UVR6216:1,2-oxyethyl group n-Hexadecane (ダ ウ ケ ミ カ Le Japan system UVR6216)
EHOX:3-ethyl-3-(2-ethyl hexyl oxy methyl) trimethylene oxide (East Asia synthetic system ア ロ Application オ キ セ Application OXT-212)
L207:KRATON Polymers corporate system L-207 (segmented copolymer of ethylene-butene copolymer and epoxidized polyisoprene, with
1The hydroxyl of H-NMR is that molecular weight that benchmark records is about 6000, and epoxy equivalent (weight) is about 670g/mol, Tg-53 ℃)
POX:3-ethyl-3-(phenoxymethyl) trimethylene oxide (East Asia synthetic system ア ロ Application オ キ セ Application OXT-211)
CHOX:3-ethyl-3-(3-cyclohexyloxy methyl) trimethylene oxide (East Asia synthetic system CHOX)
L1203:KRATON Polymers corporate system L-1203 (have the ethylene-butene copolymer of hydroxyl at an end, with
1The hydroxyl of H-NMR is that molecular weight that benchmark records is about 4000, Tg-63 ℃)
NDMOX: norbornane dimethanol dioxetane (the synthetic system in East Asia, ア ロ Application オ キ セ Application NDMOX (exploitation product))
PGE: phenylglycidyl ether (Na ガ セ ケ system テ Network ス system デ Na コ-Le EX-141)
PTGUA: by synthesis example 1 synthetic urethane acrylate
BADMA: the dimethacrylate of the alcohol that obtains by 4 oxyethane of dihydroxyphenyl propane addition (the chemistry system ラ イ ト エ ス テ of common prosperity society Le BP-4EM)
M120: vinylformic acid 2-ethylhexyl carbitol ester (East Asia synthetic system ア ロ ニ Star Network ス M-120)
EHMA: vinylformic acid 2-ethylhexyl methyl ester
POA: vinylformic acid phenoxy group ethyl ester (the chemistry system ラ イ ト ア of common prosperity society Network リ レ-ト POA)
WPI016: two (alkyl (C=10～14) phenyl-iodide) hexafluoro antimonate (with the pure medicine system cationic polymerization initiators of light WPI-016)
#2074: three cumyl iodine four (pentafluorophenyl group) borates (ロ-デ ィ ア corporate system PHOTOINITIATOR2074)
Dc1173:Ciba Specialty Chemicals corporate system optical free radical polymerization starter Darocur1173 (2-hydroxy-2-methyl-1-phenyl-propane-1-ketone is used as the sensitizing agent of light cationoid polymerisation among the present invention)
Irg184:Ciba Specialty Chemicals corporate system optical free radical polymerization starter Irgacure184 (1-hydroxy-cyclohexyl-phenyl ketone is used as the sensitizing agent of light cationoid polymerisation among the present invention)
WPI003: two (alkyl (C=10～14) phenyl-iodide) hexafluorophosphate (with the pure medicine system cationic polymerization initiators of light WPI-003)
Embodiment 5
Contain mixing and evaluation of physical property thereof by the compound compositions of formula (2) expression
Composition shown in table 1 and the table 2 is mixed according to ordinary method, be modulated into the cation-curable composition, estimate its rerum natura then.
[table 1]
| | | | | Comparative example 1 | |
| | 100 | 90 | 50 | - | - |
| L1203OX | - | - | - | 40 | - |
| UVR6216 | - | 10 | 8 | - | - |
| EHOX | - | - | 42 | 40 | - |
| L207 | - | - | - | 20 | - |
| POX | - | - | - | - | 50 |
| PGE | - | - | - | - | 50 |
| | 2 | 2 | - | - | - |
| #2074 | - | - | 2 | 2 | 2 |
| | 1 | 1 | 1 | 1 | 1 |
[table 2]
| PTGUA | BADMA | M120 | EHMA | POA | Irg184 | |
| Comparative example 2 and 3 | 30 | 20 | 30 | 5 | 15 | 1 |
The viscosity of the composition of record and the dynamic viscoelastic of solidified nature and cured article are measured in his-and-hers watches 1 and the table 2.These evaluation results are shown in Table 3.
＜viscosity 〉
The viscosity (Pas) of each composition under measuring 25 ℃ with eastern machine industry system E type viscometer, these results are recorded in the table 3.
The dynamic viscoelastic of＜cured article is measured: the making of the thick cured article of 1mm and dynamic viscoelastic are measured 〉
On the plate of tetrafluoroethylene system, make the framework of thick 1mm, the embodiment of record in the table 1 and the composition of comparative example are cast in respectively in the framework, use the high pressure mercury vapour lamp irradiation ultraviolet radiation of 60W/cm then.With the intensity under the 365nm is 150mW/cm
2Shone 2 minutes, and confirming after has all solidified the inside, irradiation under the same conditions turns over.With テ ィ-エ-イ Application ス Star Le メ Application ト corporate system RDS-II, the dynamic viscoelastic of the cured article that measure to obtain under vibration number 1Hz is estimated its storage stability (G ') and tan δ.Physics value under in table 3, having put down in writing 25 ℃.
In addition, for the cured article of embodiment 8 and 9, its dynamic viscoelastic spectrogram (temperature dependency) is shown among Fig. 5.
The dynamic viscoelastic of＜solidification process and cured article is measured (measurement temperature: 25 ℃) 〉
With the visco-elasticity of Reologia company (ス ウ エ-デ Application) system photocuring viscoelasticity measurement measurement device after by light-struck solidification process and curing.Promptly, the composition of the comparative example 1 of table 1 record and the comparative example 2 of table 2 record and 3 composition are placed on the quartz plate, and clamp (at interval 0.2mm) from the top with the rotor of diameter 10mm, under 25 ℃ of temperature, under vibration number 1Hz, make its shearing strain on one side, (shore pine ホ ト ニ Network ス system L8222 is adjusted into 50mW/cm from quartz plate irradiated mercury xenon lamp on one side
2(intensity under the 365nm)), measure visco-elasticity.Elastic modulus G ' of cured article (Pa) and tan δ are shown in Table 3.For comparative example 1 and 2, expression is carried out photocuring with resin and the value that finally reaches.For comparative example 3, expression is in order to make G ' about 105Pa, the value when stopping rayed in solidification process.For comparative example 1, by
1H-NMR confirms that monomer is consumed.
The fragility evaluation of＜cured article 〉
For embodiment 6～9 with the thick cured article of 1mm, estimate its fragility in the following manner with the cured article in the photocuring viscoelasticity measurement device for comparative example 1-3.These results are recorded in the table 3.
Zero: even distortion greatly can not broken yet.
△: if distortion will be broken greatly.
*: there is point deformation to break a little and is powder
-: owing to be the middle character of solid and liquid, so be not suitable for explaining with fragility.
＜the solidified nature of filming 〉
Composition for embodiment 6～9 and comparative example 1, being coated with device with scraper on the PET film is that thickness is 20 microns with its coating, is 10m/ minute or the 30m/ minute high pressure mercury vapour lamp (lamp) by the 80W/cm of the high 10cm of lamp with the line speed, the number of pass times when becoming solid up to filming is estimated its solidified nature.This result is recorded in the table 3 and (puts down in writing up to the solidified number of pass times.The record that regards to the result of solidified nature down is identical.)。The environment of this moment is 26 ℃ of temperature, relative humidity 66%.
[table 3]
| Before the curing | Solidified nature | After the curing | ||||
| Viscosity (Pas) | 10m/ minute | 30m/ minute | G’(Pa) | tanδ | | |
| Embodiment | ||||||
| 6 | 83.7 | 2 | 5＜ | 3.3×10 5 | 0.07 | ○ |
| | 15.4 | 1 | 1 | 1.4×10 5 | 0.14 | ○ |
| | 0.169 | 1 | 1 | 3.8×10 4 | 0.20 | ○ |
| | 1.34 | 1 | 1 | 6.7×10 4 | 0.17 | ○ |
| Comparative example 1 | 0.008 | 5＜ | 5＜ | 5.1×10 4 | 2.5 | - |
| Comparative example 2 | 0.185 | - | - | 2.0×10 6 | 0.17 | △ |
| Comparative example 3 | 0.185 | - | - | 1.1×10 5 | 0.01 | × |
For cation-curable resin composition of the present invention, the result of embodiment 6～9 expresses following content.That is, the viscosity before solidifying can be adjusted into relative broad range, solidified nature is good, can provide the also good solid of Restoration after Young's modulus hangs down the while change of shape very much.In addition, cation-curable resin composition of the present invention is compared as the composition of crosslinked composition with the Resins, epoxy L207 of prior art, and thermotolerance is also good.
Contain prescription and evaluation of physical property thereof by the compound compositions of formula (4) expression
Composition shown in the table 4 is mixed according to ordinary method, be modulated into the cation-curable composition, estimate various rerum naturas then.
[table 4]
| Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| L1203OX | 80 | 40 | 40 | 80 | - | - | - |
| L207 | 20 | 20 | 20 | 20 | 20 | - | 20 |
| EHOX | - | 40 | - | - | - | - | 40 |
| CHOX | - | - | 40 | - | - | - | 40 |
| L1203 | - | - | - | - | 80 | - | - |
| POX | - | - | - | - | - | 50 | - |
| PGE | - | - | - | - | - | 50 | - |
| WPI016 | 2 | - | - | 1.5 | 2 | - | - |
| #2074 | - | 1 | 1 | - | - | 2 | 1 |
| | 1 | 1 | 1 | - | 1 | 1 | 1 |
| Dc1173 | - | - | - | 1 | - | - | - |
The viscosity of the composition of record and the dynamic viscoelastic of solidification process and cured article are measured in his-and-hers watches 4 and the table 2.These evaluation results are shown in Table 5.
[table 5]
| Before the curing | After the curing | |||
| Viscosity (Pas) | G’(Pa) | tanδ | Fragility | |
| Embodiment 11 | 43.9 | 9.5×10 4 | 0.15 | ○ |
| Embodiment 12 | 1.34 | 6.7×10 4 | 0.17 | ○ |
| Embodiment 13 | 1.97 | 5.9×10 4 | 0.56 | ○ |
| Embodiment 14 | 43.2 | 9.5×10 4 | 0.15 | ○ |
| Comparative example 2 | 0.19 | 2.0×10 6 | 0.17 | △ |
| Comparative example 3 | 0.19 | 1.1×10 5 | 0.01 | × |
| Comparative example 4 | 58.5 | 4.1×10 3 | 1.4 | - |
| Comparative example 5 | 0.008 | 5.1×10 4 | 2.5 | - |
| Comparative example 6 | 0.091 | 2.1×10 4 | 0.36 | - |
＜the solidified nature of filming 〉
The embodiment 12,13 of record in the table 4 and the composition of comparative example 6 are coated with the device coating with scraper on the PET film be 20 microns of thickness, with line speed 50m/ minute or the 80m/ minute high pressure mercury vapour lamp (lamp) by the 80W/cm of the high 10cm of lamp, the number of pass times when becoming solid up to filming is estimated its solidified nature.The environment of this moment is 26 ℃ of temperature, relative humidity 66%.This results are shown in the table 6.
[table 6]
| 50m/ minute | 80m/ minute | |
| Embodiment 12 | 1 | 1 |
| Embodiment 13 | 1 | 1 |
| Comparative example 6 | 1 | 5＜ |
The making of the cured article that＜1mm is thick and dynamic viscoelastic are measured 〉
Make the framework of thick 1mm on the plate of tetrafluoroethylene system, the embodiment 12 of record and the composition of embodiment 13 are used the high pressure mercury vapour lamp irradiation ultraviolet radiation then in the cast table 4.With the intensity 150m W/cm under the 365nm
2Shone 2 minutes, and confirming after has all solidified the inside, irradiation under the same conditions turns over.With テ ィ-エ-イ Application ス Star Le メ Application ト corporate system RDS-II, under vibration number 1Hz, measure the dynamic viscoelastic of the cured article that is obtained, estimate its storage stability (G ') and tan δ.The temperature dependency of this dynamic viscoelastic spectrogram is shown among Fig. 6.
Embodiment 15
The prescription and the evaluation of physical property thereof that contain maleation compound compositions with oxetanyl
The composition of record in the his-and-hers watches 7 is measured the dynamic viscoelastic of its viscosity and cured article.These evaluation results are shown in Table 7.The composition of record is estimated its solidified nature in the his-and-hers watches 8 in addition, and this result is recorded in the table 8.
Provided the evaluation method of rerum natura below.
[table 7]
| Embodiment 16 | Embodiment 17 | Embodiment 18 | |
| LIOX-1 | 50 | - | - |
| LIOX-2 | - | 70 | 66 |
| EHOX | 50 | 25 | 23 |
| NDMOX | - | - | 6 |
| UVR6216 | - | 5 | 5 |
| L1203OX | - | - | - |
| L207 | - | - | - |
| WPI016 | 1.5 | 1.5 | 1.5 |
| | 1 | 1 | 1 |
| Viscosity (Pas) | 4.10 | 1.78 | 1.70 |
| G’(Pa) | 1.2×10 5 | 1.5×10 4 | 8.7×10 4 |
| tanδ | 0.064 | 0.25 | 0.072 |
＜the solidified nature of filming 〉
On the PET film with table 8 in the composition (embodiment 19～21) of record to be coated with device coating with scraper be 20 microns of thickness, with line speed 50m/ minute or the 80m/ minute high pressure mercury vapour lamp (lamp) by the 160W/cm of the high 10cm of lamp, the number of pass times when becoming solid according to filming was estimated its solidified nature.This result is recorded in the table 8.The environment of this moment is 26 ℃ of temperature, relative humidity 66%.
[table 8]
| Embodiment 19 | Embodiment 20 | Embodiment 21 | |
| LIOX-1 | 50 | 50 | 50 |
| EHOX | 50 | 50 | 45 |
| PGE | - | - | 5 |
| WPI016 | 1.5 | - | - |
| WPI003 | - | 3 | 3 |
| | 1 | 1 | 1 |
| Solidified nature (number of pass times) | 1 | 5 | 2 |
The measurement of the dynamic viscoelastic spectrogram (temperature dependency) of＜cured article 〉
On the plate of tetrafluoroethylene system, make the framework of thick 1mm, the composition of embodiment 14 and embodiment 16 is cast in respectively in the framework, use the high pressure mercury vapour lamp irradiation ultraviolet radiation of 60W/cm then.With the irradiation of the intensity 150mW/cm2 under the 365nm 2 minutes, confirming that after has all solidified the inside irradiation under the same conditions turns over.Under vibration number 1Hz, measure the dynamic viscoelastic spectrogram (temperature dependency) of the cured article that is obtained with Reologia corporate system VAR-100.These visco-elasticity spectrograms are shown among Fig. 7.
In addition, the feel of the cured article of embodiment 14 and embodiment 16 is very soft, and the Restoration after the change of shape is good, even distortion greatly can not destroy yet in addition, is not have brittle material.
Polymkeric substance with oxetanyl of the present invention, because cation-curable is good, so be suitable as the formula material of solidification compound, when especially being suitable for the also good cured article of Restoration after needing flexible good cured article or at room temperature being low elastic modulus and change of shape.In addition, composition of the present invention is suitable as the active energy ray-curable resin of light-cured resin etc.In addition, also can improve the preceding viscosity of curing largely.And this cured article Young's modulus is very low, and thermotolerance is also good simultaneously, does not have fragility in addition.Therefore, be suitable as electronic material or the optical material that needs above-mentioned rerum natura.
In addition, the manufacture method of polymkeric substance of the present invention owing to use the material that is easy to obtain, does not need to be used for the equipment or the operation of strict dehydration, is the comparison limited-production manufacture method that is suitable for as specific electronic material and optical material etc.
Claims (6)
1. polymkeric substance, its be by be selected from maleation polyhutadiene, maleation polyisoprene, contain hydroxyl polyhutadiene, contain hydroxyl polyisoprene, contain hydroxyl ethylene-butene copolymer, contain the hydrogenated butadiene polymer of hydroxyl and contain at least a in the hydrogenated polyisoprene of hydroxyl or more than one material and following formula (1) shown in the polymkeric substance that obtains of compound reaction with oxetanyl
The R of formula (1)
1Expression hydrogen atom or carbonatoms are 1～6 the alkyl that also can have side chain.
2. polymkeric substance, it is the polymkeric substance with oxetanyl that is obtained by the reaction of compound shown in maleation polyhutadiene and/or maleation polyisoprene and the following formula (1).
3. polymkeric substance, its be by be selected from polyhutadiene, the polyisoprene that contains hydroxyl, the ethylene-butene copolymer that contains hydroxyl that contain hydroxyl, contain the hydrogenated butadiene polymer of hydroxyl and contain at least a in the hydrogenated polyisoprene of hydroxyl or more than one material and following formula (1) shown in the polymkeric substance that obtains of compound reaction with oxetanyl.
4. cation-curable resin composition, it contains in each of claim 1～3 respectively the polymkeric substance with oxetanyl of record and carries out the activatory cationic polymerization initiators and/or carry out the activatory cationic polymerization initiators by heating by active energy ray.
5. cation-curable resin composition according to claim 4, it also contains compound with epoxy group(ing) and/or the compound with oxetanyl except the polymkeric substance with oxetanyl.
6. cured article, its be by in claim 4 or 5 respectively the cation-curable resin composition of record irradiation active energy ray and/or heat form.
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| CN110036312A (en) * | 2016-12-28 | 2019-07-19 | 株式会社尼康依视路 | Hard conating, which is formed, uses composition and eyeglass |
| CN113148439A (en) * | 2016-12-28 | 2021-07-23 | 株式会社Lg化学 | Packaging container for cationically polymerizable composition and packaging method using the same |
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| FR2805272B1 (en) * | 2000-02-18 | 2006-08-25 | Rhodia Chimie Sa | SURFACE TREATMENT OF PLASTIC MATERIAL WITH AN ORGANIC COMPOSITION WITH REACTIVE FUNCTIONS POLYMERIZABLE AND / OR RETICULABLE |
| JP2002193965A (en) * | 2000-12-22 | 2002-07-10 | Ube Ind Ltd | Phthalimide derivative having oxetane ring |
| US6743510B2 (en) * | 2001-11-13 | 2004-06-01 | Sumitomo Chemical Company, Limited | Composition comprising a cationic polymerization compound and coating obtained from the same |
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| CN110036312A (en) * | 2016-12-28 | 2019-07-19 | 株式会社尼康依视路 | Hard conating, which is formed, uses composition and eyeglass |
| CN113148439A (en) * | 2016-12-28 | 2021-07-23 | 株式会社Lg化学 | Packaging container for cationically polymerizable composition and packaging method using the same |
| CN110036312B (en) * | 2016-12-28 | 2021-08-06 | 株式会社尼康依视路 | Composition for forming hard coat layer and spectacle lens |
| CN113148439B (en) * | 2016-12-28 | 2022-11-08 | 株式会社Lg化学 | Packaging container for cationically polymerizable composition and packaging method using the same |
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