CN105121482A

CN105121482A - Polymer, method for producing same, and resin composition containing said polymer

Info

Publication number: CN105121482A
Application number: CN201480017895.8A
Authority: CN
Inventors: 元田哲史; 加登大辅; 平田惠
Original assignee: Kuraray Co Ltd; Amyris Inc
Current assignee: Kuraray Co Ltd; Amyris Inc
Priority date: 2013-03-29
Filing date: 2014-03-28
Publication date: 2015-12-02
Also published as: TWI627218B; WO2014157624A1; KR102167198B1; JPWO2014157624A1; KR20150135305A; TW201500440A

Abstract

This polymer has a polymerizable functional group and contains a monomer unit (a1) derived from Farnesene as the monomer using configuring the polymer. This resin composition contains the polymer (A) having a polymerizable functional group and containing a monomer unit (a1) derived from Farnesene as the monomer unit configuring the polymer.

Description

Polymkeric substance and manufacture method thereof and the resin combination containing this polymkeric substance

Technical field

The present invention relates to the polymkeric substance and manufacture method thereof that comprise the monomeric unit being derived from farnesene.

In addition, the present invention relates to the resin combination containing the polymkeric substance comprising the monomeric unit being derived from farnesene, the cured article making it solidify and contain the optics tackiness agent of this cured article or aforementioned resin.

Background technology

In recent years, along with liquid crystal etc. has the universal of electronic machine, such as smart mobile phone or the dull and stereotyped PC etc. of picture, the research of the transparent resin material that the mode carrying out energetically covering picture uses and transparent resin caking agent.

Such as; a kind of curable resin composition is described in patent documentation 1; wherein, comprising in molecule in polyisoprene, (methyl) acrylate monomer of simple function and the composition of radical polymerization initiator with (methyl) acryl the hindered amine based compound coordinating further and not there is in molecule secondary amino group.

In addition, describe a kind of compositions of thermosetting resin in patent documentation 2, it contains: epoxy resin, solidifying agent and the epoxy group(ing) containing specified quantitative in molecule and have the epoxidized polybutadiene of specific number-average molecular weight.

It should be noted that, describe the polymkeric substance of β-farnesene in patent documentation 3,4, but not yet fully study for its practical purposes, in addition, the polymkeric substance for the β-farnesene with polymerizable functional group is also not yet studied.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent No. 5073400 publication

Patent documentation 2: Japanese Patent No. 4098107 publication

Patent documentation 3: No. 2010/027463rd, International Publication

Patent documentation 4: No. 2010/027464th, International Publication.

Summary of the invention

The problem that invention will solve

For the curable resin composition recorded in patent documentation 1,2, although its cured article meets the intensity required by electronic machine, the characteristic such as flexibility and the transparency that liquid crystal etc. has picture, but for raising, the characteristic such as lowering viscousity and low cure shrinkage of curing speed, the leeway be still improved.

The present invention carries out in view of above-mentioned truth, provides and can give that viscosity is low, curing speed is fast and then cure shrinkage is excellent and the polymkeric substance of the cured article that intensity, flexibility, low-moisture permeability and the transparency are excellent and manufacture method thereof.

In addition, the invention provides can give that viscosity is low, curing speed is fast and then cure shrinkage is excellent and the resin combination of the cured article that intensity, flexibility, low-moisture permeability and the transparency are excellent, the cured article making it solidify and the optics tackiness agent containing this cured article or aforementioned resin.

For the means of dealing with problems

The present inventor etc. conduct in-depth research, found that: the polymkeric substance importing polymerizable functional group in the polymkeric substance with the monomeric unit being derived from farnesene can give intensity, flexibility, low-moisture permeability and the transparency excellent cured article, and then, curing speed low as the viscosity of polymkeric substance is fast and then cure shrinkage is excellent, thus complete the 1st aspect of the present invention.

In addition, the discoveries such as the present inventor: the polymkeric substance importing polymerizable functional group in the polymkeric substance with the monomeric unit being derived from farnesene can give intensity, flexibility, low-moisture permeability and the transparency excellent cured article, and then the viscosity of resin combination containing this polymkeric substance is low, curing speed fast and then cure shrinkage excellent, thus complete the 2nd aspect of the present invention, fourth way.

And then, the discoveries such as the present inventor: contain with specific ratio the monomeric unit that comprises and be derived from farnesene and there is the polymkeric substance of polymerizable functional group and comprise the monomeric unit of the conjugated diene compound being derived from carbonatoms less than 12 and the resin combination without the polymkeric substance of polymerizable functional group can give the cured article of low viscosity and then intensity, flexibility, hardness and transparency excellence, thus completing the 3rd aspect of the present invention, fourth way.

That is, the present invention using following [1] ~ [9] as purport.

[1] polymkeric substance, wherein, comprises as the monomeric unit forming polymkeric substance the monomeric unit (a1) being derived from farnesene, and has polymerizable functional group.

The manufacture method of the polymkeric substance [2] Gen Ju [1], it possesses following operation: the operation (1) preparing unmodified polymer, and described unmodified polymer comprises the monomeric unit (a1) that is derived from farnesene and do not have polymerizable functional group; And, this unmodified polymer is imported to the operation (2) of polymerizable functional group.

[3] resin combination, the polymkeric substance (A) that it contains described in [1].

[4] resin combination, it contains described in [1] polymkeric substance (A), monomer (D) and polymerization starter (C), polymkeric substance (A) is 0.01 ~ 99 with the mass ratio [(A)/(D)] of monomer (D), relative to total 100 mass parts of polymkeric substance (A) and monomer (D), the polymerization starter (C) containing 0.1 ~ 20 mass parts.

[5] resin combination, it contains: the polymkeric substance (A) described in [1], comprise the conjugated diene compound (b1) being derived from carbonatoms less than 12 monomeric unit and not there is polymkeric substance (B) and the polymerization starter (C) of polymerizable functional group, polymkeric substance (A) is 0.01 ~ 100 with the mass ratio [(A)/(B)] of polymkeric substance (B).

[6] according to the resin combination according to any one of [3] ~ [5], it is also containing polymkeric substance (F), described polymkeric substance (F) comprises the monomeric unit of the conjugated diene compound (f1) being derived from carbonatoms less than 12 and has polymerizable functional group, and polymkeric substance (A) is 0.01 ~ 100 with the mass ratio [(A)/(F)] of polymkeric substance (F).

[7] cured article, it makes the resin combination according to any one of [3] ~ [6] that solidification occur.

[8] optics tackiness agent, the cured article that it contains described in [7].

[9] optics tackiness agent, it contains [3] ~ [6] according to any one of resin combination.

The effect of invention

According to the 1st aspect of the present invention, can provide and can give that viscosity is low, curing speed is fast and then cure shrinkage is excellent and the polymkeric substance of the cured article of intensity, flexibility, low-moisture permeability and transparency excellence and manufacture method thereof.

In addition, according to the 2nd aspect of the present invention, fourth way, can provide and can give that viscosity is low, curing speed is fast and then cure shrinkage is excellent and the resin combination of the cured article of intensity, flexibility, low-moisture permeability and transparency excellence.And then, the cured article making it solidify and the optics tackiness agent containing this cured article or aforementioned resin can be provided.

And then, according to the 3rd aspect of the present invention, fourth way, can provide and can give the low and resin combination of the cured article of intensity, flexibility and transparency excellence of viscosity, the cured article making it solidify and the optics tackiness agent containing this cured article or aforementioned resin.

Embodiment

[I] polymkeric substance (1st aspect of the present invention)

In polymkeric substance of the present invention (hereinafter referred to as polymkeric substance (A)), comprise as the monomeric unit forming polymkeric substance the monomeric unit (a1) being derived from farnesene, and there is polymerizable functional group.

The aforementioned monomeric unit (a1) being derived from farnesene can for being derived from the monomeric unit of α-farnesene, in addition, also for being derived from the monomeric unit of the β-farnesene shown in following formula (I), from the view point of ease of manufacturing, the monomeric unit of β-farnesene can be preferably derived from.It should be noted that, also can by α-farnesene and β-farnesene used in combination.

[changing 1]

As aforementioned polymerizable functional group; such as (methyl) acryl, epoxy group(ing), oxetanyl, vinyl ether group, alkoxysilyl, (methyl) acrylamido, styryl, dimaleoyl imino, lactone group, lactam group, sulfide base, Thietane base, acetonide base, thioureido can be listed; among these; preferably be selected from least a kind in (methyl) acryl, epoxy group(ing), oxetanyl, vinyl ether group and alkoxysilyl, be more preferably (methyl) acryl.It should be noted that, these functional groups can have substituting group.

In this specification sheets, " (methyl) acryl " refers to " acryl or methacryloyl ".In addition, in this specification sheets, " (methyl) acrylic acid or the like " refers to " acrylic acid or the like or methacrylic ".

The monomeric unit forming polymkeric substance (A) only can comprise the monomeric unit (a1) being derived from farnesene, also can comprise the monomeric unit (a1) being derived from farnesene and the monomeric unit (a2) being derived from the monomer outside farnesene.That is, farnesene can only be polymerized by polymkeric substance (A), also can be the multipolymer of the monomer outside farnesene and farnesene.

When polymkeric substance (A) is for multipolymer, as the monomeric unit (a2) of the monomer be derived from outside farnesene, the monomeric unit being derived from conjugated diene compound and aromatic ethenyl compound can be listed.

As conjugated diene compound, be preferably the conjugated diene compound of carbonatoms less than 12, as the conjugated diene compound of carbonatoms less than 12, such as divinyl, isoprene, 2 can be listed, 3-dimethylbutadiene, 2-phenyl butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1，3-cyclohexadiene, 2-methyl isophthalic acid, 3-octadiene, 1,3,7-sarohornene, myrcene, chloroprene etc.Among these, be more preferably isoprene, divinyl.These conjugated diene compounds can be used alone a kind, also can combinationally use two or more.

As aromatic ethenyl compound, such as vinylbenzene can be listed, alpha-methyl styrene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, 4-propylstyrene, 4-t-butyl styrene, 4-cyclohexylstyrenes, 4-dodecylstyrene, 2, 4-dimethyl styrene, 2, 4-di-isopropyl vinylbenzene, 2, 4, 6-trimethyl styrene, 2-ethyl-4-benzylstyrene, 4-(phenyl butyl) vinylbenzene, 1-vinyl naphthalene, 2-vinyl naphthalene, vinyl anthracene, N, N-diethyl-4-amino-ethyl vinylbenzene, vinyl pyridine, 4-methoxy styrene, monochlorostyrene, dichlorostyrene, the aromatic ethenyl compounds etc. such as Vinylstyrene.Among these, be preferably vinylbenzene, alpha-methyl styrene, 4-vinyl toluene.

When using monomeric unit (a2) of the monomer be derived from outside farnesene, from the viewpoint reducing polymer viscosity, improve the viewpoint of curing speed, and keep the good elongation characteristics of cured article and the viewpoint of flexibility to set out, the monomeric unit (a2) being derived from the monomer outside farnesene in multipolymer is preferably 1 ~ 99 quality % relative to the ratio of total of the monomeric unit (a1) being derived from farnesene and the monomeric unit (a2) that is derived from the monomer outside farnesene, be more preferably 1 ~ 80 quality %, more preferably 1 ~ 70 quality %, further be preferably 1 ~ 50 quality %.

The number-average molecular weight (Mn) of polymkeric substance of the present invention (A) is preferably 1,000 ~ 1,000,000, is more preferably 2, and 000 ~ 500,000, be more preferably 8,000 ~ 500,000, more preferably 15,000 ~ 450,000, be further preferably 15,000 ~ 300,000, be further preferably 20,000 ~ 200,000.When the Mn of polymkeric substance (A) is in aforementioned range, flexibility, mechanical strength and curing speed improve, simultaneously the viscosity of polymkeric substance.It should be noted that, in this specification sheets, the Mn of polymkeric substance (A) is the value that the method utilizing aftermentioned embodiment to record is obtained.

It should be noted that, the number-average molecular weight (Mn) in this specification sheets refers to the number-average molecular weight of the polystyrene conversion utilizing gel permeation chromatography (GPC) to measure.

Melt viscosity at 38 DEG C of polymkeric substance of the present invention (A) is preferably 0.1 ~ 3000Pa s, is more preferably 0.6 ~ 3000Pa s, is more preferably 0.6 ~ 2800Pa s, more preferably 1.5 ~ 2600Pa s, be further preferably 1.5 ~ 800Pa s.When the melt viscosity (38 DEG C) of polymkeric substance is in aforementioned range, there is no inequality relative to applied, can coated polymeric equably, therefore coating becomes good.It should be noted that, in this specification sheets, the melt viscosity (38 DEG C) of polymkeric substance is the value that the method utilizing aftermentioned embodiment to record is obtained.

The molecular weight distribution (Mw/Mn) of polymkeric substance of the present invention (A) is preferably 1.0 ~ 8.0, is more preferably 1.0 ~ 5.0, more preferably 1.0 ~ 3.0.When Mw/Mn is in aforementioned range, the viscosity deviation of resulting polymers (A) diminishes.

The second-order transition temperature of polymkeric substance of the present invention (A) also can because of bonding pattern (microstructure), be derived from other farnesene monomer and use the amount of the monomer outside farnesene further as required and change, be preferably-90 ~ 0 DEG C, be more preferably-90 ~-10 DEG C.During for aforementioned range, can obtain soft cured article, for the caking agent used in the stepped constructions such as liquid crystal panel, difference of height tracing ability, impact absorbency become good.

The quantity of the polymerizable functional group of average 1 molecular chain of polymkeric substance of the present invention (A) is preferably 1 ~ 150, is more preferably 1.5 ~ 75, more preferably 1.5 ~ 30.When the quantity of the polymerizable functional group of average 1 molecular chain is in aforementioned range, the viscosity of polymkeric substance (A) can be reduced, can curing speed be improved simultaneously, can also contraction during solidification be suppressed lower.

It should be noted that, the quantity of the polymerizable functional group of average 1 molecular chain is calculated with the functional equivalent (g/eq) of polymkeric substance (A) by the number-average molecular weight (Mn) of polymkeric substance (A) like that by following formula.

(quantity of the polymerizable functional group of average 1 molecular chain)=(Mn)/(functional equivalent).

Functional equivalent refers to " molecular weight of the polymkeric substance of average 1 functional group ".Such as, functional equivalent when being methacryloyl by polymerizable functional group is called " methacryloyl equivalent ", refers to " molecular weight of the polymkeric substance of average 1 methacryloyl ".Functional equivalent also can calculate based on the reactivity of properties-correcting agent, and the various analytical instrument of infrared spectroscopy, nuclear magnetic resonance spectrometry etc. can also be used to obtain.

The polymkeric substance (A) used in the present invention can be used alone a kind, also can combinationally use different separately two or more aforementioned polymer (A) of kind of monomeric unit, molecular weight and functional group.

The denary logarithm value of the melt viscosity (Pa s) at 38 DEG C of polymkeric substance of the present invention (A) and the ratio [the denary logarithm value/number-average molecular weight (Mn) of the melt viscosity at 38 DEG C] of number-average molecular weight (Mn) are preferably less than 0.000060, be preferably less than 0.000055, be more preferably less than 0.000050.The denary logarithm value of the melt viscosity at 38 DEG C with when the ratio of number-average molecular weight is in aforementioned range, do not have relative to applied inequality, can coated polymeric equably, therefore coating becomes good.

The manufacture method > of < polymkeric substance (A)

As the method manufacturing polymkeric substance of the present invention (A), can list the manufacture method possessing following operation: the operation (1) preparing unmodified polymer, described unmodified polymer is by polymerization farnesene and be polymerized the monomer outside farnesene further as required and do not have polymerizable functional group; And, this unmodified polymer is imported to the operation (2) of polymerizable functional group.

See below for the operation (1) preparing unmodified polymer, be described mainly for the operation (2) this unmodified polymer being imported to polymerizable functional group herein.As the first method manufacturing Inventive polymers, be preferably following method: by polymerization farnesene and as required further polymerization farnesene outside monomer prepare unmodified polymer, this unmodified polymer and maleic anhydride etc. are reacted for the compound carrying out grafting, then, the compound making itself and 2-hydroxyethyl methacrylate etc. have polymerizable functional group reacts.

As the compound for carrying out grafting to foregoing unmodified polymkeric substance, the unsaturated carboxylic acid anhydrides such as such as maleic anhydride, citraconic anhydride, 2,3-dimethyl maleic anhydrides, itaconic anhydride can be listed; The unsaturated carboxylic acids such as toxilic acid, fumaric acid, citraconic acid, methylene-succinic acid; The esters of unsaturated carboxylic acids such as maleic acid ester, fumarate, citraconate, itaconic ester; The unsaturated carboxylic acid acid amides such as maleinamide, fumaramide, citraconoyl amine, clothing health acid amides; The unsaturated carboxylic acid imides such as maleimide, fumarimide, citraconimide, clothing health imide; Maleimide, vinyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane etc.

In addition, as the compound with aforementioned polymerizable functional group, (methyl) vinylformic acid can be listed such as; (methyl) acrylate such as vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, vinylformic acid 2-hydroxy propyl ester, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, Dipentaerythritol monohydroxy acrylate; 2-hydroxyethyl vinylethers, N-(2-hydroxyethyl) acrylamide, N-(2-hydroxyethyl) Methacrylamide, N-(2-hydroxyethyl) maleimide, 4-Vinyl phenol etc.It should be noted that, the position that import polymerizable functional group can be the polymerizable end of polymkeric substance, also can be side chain.In addition, above-mentioned functional group can be a kind or combine two or more.

As the second method manufacturing Inventive polymers, such as following method can be listed: the addition reaction of the reactive terminal of the unmodified polymer obtained by carrying out active anionic polymerization to farnesene, to unmodified polymer bonding at least 1, there is at least 1 and be selected from hydroxyl, carboxyl, carbonyl, thiocarbonyl, etheride base, anhydride group, thiocarboxylic acid base, aldehyde radical, thioformyl, carboxylic acid ester groups, amide group, sulfonic group, sulfonate group, phosphate, phosphate-based, amino, imino-, itrile group, pyridyl, quinolyl, epoxy group(ing), sulfo-epoxy group(ing), sulfide base, isocyanate group, different sulfocyanic acid ester group, silanol group, organoalkoxysilane, silyl halide, halogenation tinbase, the atomic group of the functional group in alkoxyl group tinbase and phenyl tinbase etc. carrys out synthesis modification polymkeric substance, then, the compound making itself and vinylformic acid etc. have polymerizable functional group reacts.

As the active anionic polymerization initiator for carrying out active anionic polymerization to aforementioned farnesene, the organo monolithium compounds such as such as lithium methide, lithium ethide, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, hexyl lithium, phenyl lithium, stilbene lithium can be listed; The multi-functional organolithium compounds such as two lithium methane, two lithium naphthalenes, Isosorbide-5-Nitrae-two lithium butane, Isosorbide-5-Nitrae-two lithium-2-ethylcyclohexane, 1,3,5-tri-lithium benzene; Sodium naphthalene, potassium naphthalene etc.In addition, also can combinationally use and react with organic alkali metal reagent and give the compound such as di isopropenylbenzene, dibenzyl toluene of multifunctional organic alkali metal reagent.

In addition, as importing the compound at least with the atomic group of 1 functional group to reactive terminal, the cyclic ether such as epoxide, trimethylene oxide can be listed; The cyclic amine such as tetramethyleneimine; The cyclical sulfides etc. such as ethene sulfide.It should be noted that, above-mentioned functional group can be a kind or combine two or more.

As the third method manufacturing Inventive polymers, following method can be listed: by polymerization farnesene and as required further polymerization farnesene outside monomer prepare unmodified polymer, after carrying out epoxidation to this unmodified polymer, it is made to react with the compound with above-mentioned polymerizable functional group.

As for carrying out epoxidised compound to foregoing unmodified polymkeric substance, the such as peracid such as peroxyacetic acid, peroxybenzoic acid can be listed.

In addition, as the compound with aforementioned polymerizable functional group, the such as carboxylic acid such as vinylformic acid, methacrylic acid can be listed.It should be noted that, the position that import polymerizable functional group can be the polymerizable end of polymkeric substance, also can be side chain.In addition, above-mentioned functional group can be a kind or combine two or more.

When functionalization carries out to foregoing unmodified polymkeric substance, polymer-modified preservation time, in order to suppress that the molecular weight caused by deterioration reduces, variable color and gelation, also can to unmodified polymer or the suitable anti-aging agent of polymer-modified middle combination.Specifically, 2,6 di tert butyl 4 methyl phenol (BHT) can be listed, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol) (AO-40), 3,9-pair [1,1-dimethyl-2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] ethyl]-2,4,8,10-tetra-oxaspiro [5.5] undecanes (AO-80), two [(pungent sulfenyl) the methyl]-6-methylphenol (Irganox1520L) of 2,4-, two [(dodecylthio) the methyl]-6-methylphenol (Irganox1726) of 2,4-, 2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl acrylate (SumilizerGS), the 2-tertiary butyl-6-(3-the tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate (SumilizerGM), the 6-tertiary butyl-4-[3-(2,4,8,10-tetra-tert dibenzo [d, f] [1,3,2] dioxy phospha seven ring-6-base oxygen base) propyl group]-2-methylphenol (SumilizerGP), tricresyl phosphite (2,4-di-tert-butyl-phenyl) (Irgafos168), two octadecyl-3,3 '-dithio double propionate, quinhydrones, p methoxy phenol, N-phenyl-N '-(1,3-dimethylbutyl)-Ursol D (NOCRAC6C), two (2,2,6,6-tetramethyl--4-piperidyl) sebate (LA-77Y), the two octade-cylhydroxylamine (IrgastabFS042) of N, N-, two (the tertiary octyl phenyl of 4-) amine (Irganox5057) etc.In addition, above-mentioned anti-aging agent can be a kind or combinationally use two or more.

The addition of anti-aging agent is preferably 0.01 ~ 10 mass parts relative to unmodified polymer or polymer-modified 100 mass parts, is more preferably 0.1 ~ 3 mass parts.

Then, be described for the operation (1) preparing unmodified polymer.The method etc. that the raw material of polymkeric substance of the present invention (A) and unmodified polymer can utilize emulsion polymerization or No. 2010/027463rd, International Publication, No. 2010/027464th, International Publication is recorded manufactures.Wherein, emulsion polymerization or solution polymerization process, more preferably solution polymerization process is preferably.

As the emulsion polymerization for obtaining unmodified polymer, known method can be applied.Such as, the farnesene of specified amount is carried out emulsion dispersion under the existence of emulsifying agent, utilize radical polymerization initiator to carry out letex polymerization.

As emulsifying agent, hard soap or the sylvate of such as carbonatoms more than 10 can be used.As concrete example, sylvite or the sodium salt of the lipid acid such as capric acid, lauric acid, tetradecanoic acid, palmitinic acid, oleic acid, stearic acid can be listed.

Usually using water as dispersion agent, in the scope of the stability when not damaging polymerization, the water-miscible organic solvent such as methyl alcohol, ethanol can be comprised.

As radical polymerization initiator, the persulphate of such as ammonium persulphate, Potassium Persulphate and so on, organo-peroxide, hydrogen peroxide etc. can be listed.

In order to adjust the molecular weight of unmodified polymer, also can usage chain transfer agent.As chain-transfer agent, the thio-alcohols such as such as tertiary lauryl mercaptan, n-dodecyl mercaptan can be listed; Tetracol phenixin, Thiovanic acid, diterpene, terpinolene, γ-terpinene, α-methylstyrenedimer etc.

Letex polymerization temperature suitably can be selected according to the kind of used radical polymerization initiator, is usually preferably 0 ~ 100 DEG C, is more preferably 0 ~ 60 DEG C.Polymerization methods can be any one in successive polymerization, batchwise polymerization.Polyreaction stops by adding stopper.

As stopper, quinone based compound, the Sodium Nitrites etc. such as amine compound, quinhydrones, benzoquinones such as such as isopropyl hydroxyl amine, diethylhydroxylamine, oxyamine can be listed.

Polyreaction also can add anti-aging agent after stopping as required.After polyreaction stops, unreacted monomer is removed as required from gained latex, then, using salt such as sodium-chlor, calcium chloride, Repone K as peptizer, add the acid such as nitric acid, sulfuric acid as required and the pH of coagulation system be adjusted to prescribed value, after making unmodified polymer solidify, isolate dispersion solvent simultaneously, thus reclaim unmodified polymer.Then, by carrying out drying after washing and dehydration, unmodified polymer can be obtained.It should be noted that, also can in advance latex be mixed with the extension oil making emulsified dispersed liquid as required when solidifying, reclaim with the form of the unmodified polymer of oil exhibition.

As the solution polymerization process for obtaining unmodified polymer, known method can be applied.Such as use Ziegler series catalysts, metallocene series catalysts in a solvent, the active metal of anionoid polymerization can be carried out, according under the existence being desirably in polar compound, monomer is polymerized.

As the active metal that can carry out anionoid polymerization, the basic metal such as such as lithium, sodium, potassium can be listed; The alkaline-earth metal such as beryllium, magnesium, calcium, strontium, barium; The lanthanide rare such as lanthanum, neodymium metal etc.Wherein, be preferably alkali and alkaline earth metal ions, be particularly preferably basic metal.And then, among basic metal, more preferably use organic alkali metal compound.

As solvent, the aliphatic hydrocarbons such as such as normal butane, Skellysolve A, iso-pentane, normal hexane, normal heptane, octane-iso can be listed; The ester ring type hydrocarbon such as pentamethylene, hexanaphthene, methylcyclopentane; The aromatic hydrocarbonss etc. such as benzene,toluene,xylene.

As organic alkali metal compound, the organo monolithium compounds such as such as lithium methide, lithium ethide, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, hexyl lithium, phenyl lithium, stilbene lithium can be listed; The multi-functional organolithium compounds such as two lithium methane, two lithium naphthalenes, Isosorbide-5-Nitrae-two lithium butane, Isosorbide-5-Nitrae-two lithium-2-ethylcyclohexane, 1,3,5-tri-lithium benzene; Sodium naphthalene, potassium naphthalene etc.Wherein, be preferably organolithium compound, be more preferably organo monolithium compounds.The consumption of organic alkali metal compound suitably can determine according to the molecular weight of required unmodified polymer, relative to total amount 100 mass parts of the monomer outside farnesene and the farnesene that uses as required, is preferably 0.01 ~ 7 mass parts.

Organic alkali metal compound can also react with the secondary amine such as dibutylamine, dihexyl amine, dibenzyl amine and be used as organic alkali metal acid amides.

Polar compound can not make reaction inactivation in anionoid polymerization, for adjusting the microstructure at farnesene position, can list the ether compounds such as such as dibutyl ether, tetrahydrofuran (THF), ethylene glycol diethyl ether; The tertiary amine such as Tetramethyl Ethylene Diamine, Trimethylamine 99; Alkali metal alcoholates, phosphine compound etc.Polar compound preferably uses with the scope of 0.01 ~ 1000 molar equivalent relative to organic alkali metal compound.

The temperature of polyreaction is generally-80 ~ 150 DEG C, be preferably 0 ~ 100 DEG C, the more preferably scope of 10 ~ 90 DEG C.Polymerization methods can be any one in intermittent type or continous way.

In polyreaction, add the alcohol such as methyl alcohol, Virahol as stopper, can termination reaction.Gained polymerization liquid be injected in the poor solvents such as methyl alcohol and unmodified polymer is separated out, or polymerization liquid use water is cleaned, carrying out drying after separation, thus can unmodified polymer be separated.

[II] resin combination (second method)

Resin combination in the 2nd aspect of the present invention is polymkeric substance containing the 1st aspect of the present invention, namely comprises as the monomeric unit forming polymkeric substance the monomeric unit (a1) that is derived from farnesene and have the resin combination of the polymkeric substance (A) of polymerizable functional group.

The viscosity of the polymkeric substance (A) in the 1st aspect of the present invention is low, curing speed fast and then cure shrinkage is excellent, and the resin combination employing it can give the cured article of intensity, flexibility, low-moisture permeability and transparency excellence.

In the 2nd aspect of the present invention, from the view point of the said curing thing of imparting, preferably containing aftermentioned polymerization starter (C).

In addition, as the resin combination in the 2nd aspect of the present invention, be preferably following resin combination, it contains: comprise the monomeric unit (a1) that is derived from farnesene as the monomeric unit forming polymkeric substance and have the polymkeric substance (A) of polymerizable functional group, monomer (D) and polymerization starter (C), polymkeric substance (A) is 0.01 ~ 99 with the mass ratio [(A)/(D)] of monomer (D), relative to total 100 mass parts of polymkeric substance (A) and monomer (D), the polymerization starter (C) containing 0.1 ~ 20 mass parts.

< polymkeric substance (A) >

In the polymkeric substance (A) that the 2nd aspect of the present invention uses, comprise the monomeric unit (a1) that is derived from farnesene as the monomeric unit forming polymkeric substance and there is polymerizable functional group.This polymkeric substance (A) is same with the polymer phase in the aforementioned 1st aspect of the present invention, and viscosity is low, curing speed is fast and then cure shrinkage excellent.

The content of the polymkeric substance (A) in the resin combination in the 2nd aspect of the present invention is preferably 1 ~ 99 quality %, is more preferably 2 ~ 98 quality %, more preferably 5 ~ 95 quality %, be further preferably 10 ~ 90 quality %, be further preferably 15 ~ 85 quality %.When the content of the polymkeric substance (A) in resin combination is in above-mentioned scope, the cured article of intensity, flexibility, low-moisture permeability and transparency excellence can be given.

< monomer (D) >

As the monomer used in the present invention (D), as long as radical polymerization initiator, cationic polymerization initiators and anionic polymerization initiator can be utilized to be polymerized, just be not particularly limited, in order to obtain uniform curing cured article, preferably can carry out with the functional group of polymkeric substance (A) monomer that is polymerized.As monomer (D), the compound such as in molecule with (methyl) acryl, epoxy group(ing), oxetanyl, vinyl ether group, alkoxysilyl can be listed.

As concrete compound, (methyl) methyl acrylate can be listed, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid butyl ethoxy ester, (methyl) vinylformic acid butyl ethyl ester, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid bicyclopentane ester, (methyl) vinylformic acid bicyclopentane oxygen base ethyl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid phenoxy group hydroxy propyl ester, (methyl) vinylformic acid morpholine ester, (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N, N-dimethyl aminoethyl (methyl) acrylate, (methyl) glycidyl acrylate, methoxyl group Diethylene Glycol (methyl) acrylate, methoxyl group dipropylene glycol (methyl) acrylate, simple function (methyl) acrylate such as Nonylphenoxy polyoxyethylene glycol (methyl) acrylate,

1,4-butyleneglycol two (methyl) acrylate, 1, two senses (methyl) acrylate such as 6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, glycerine two (methyl) acrylate, ethylene-oxide-modified dihydroxyphenyl propane two (methyl) acrylate, triethylene glycol two (methyl) acrylate;

Multifunctional (methyl) acrylate such as trimethylolpropane tris (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate;

3,4-epoxy hexane ylmethyl-3 ', the epoxy compoundss such as 4 '-epoxycyclohexyethylSiOi olefinic carboxylic acid ester, 1,2-epoxy group(ing)-4-vinyl cyclohexane, 1,2:8,9-bicyclic oxygen limonene, 2,6,6-trimethylammonium-2,3-epoxy group(ing) dicyclo [3.1.1] heptane;

3-ethyl-3-hydroxymethyl-oxetane, Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 3-ethyl-3-(phenoxymethyl) trimethylene oxide, two [1-ethyl (3-trimethylene oxide)] methyl ether, 3-ethyl-3-(2-Ethylhexoxymethyl) oxetane compound such as trimethylene oxide;

The vinyl ether compounds such as 2-hydroxyethyl vinylethers, 4-hydroxy butyl vinyl ether, diethylene glycol monovinyl base ether;

The compounds such as mercapto methyl Trimethoxy silane, glycidyl oxy methyl Trimethoxy silane, vinyl methyl Trimethoxy silane.

Among these, from the view point of good with the consistency of polymkeric substance (A), be preferably bicyclopentane oxygen base ethyl (methyl) acrylate, dicyclopentenyl oxygen base ethyl (methyl) acrylate, 1,9-nonanediol diacrylate, n-butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid bicyclopentane ester, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) acrylate.They can be used alone a kind, also can combinationally use two or more.

The mass ratio [(A)/(D)] of polymkeric substance (A) and monomer (D) is 0.01 ~ 99, be preferably 0.1 ~ 99, be more preferably 0.2 ~ 99, more preferably 0.2 ~ 10, be further preferably 0.2 ~ 5.When mass ratio [(A)/(D)] is in aforementioned range, the physical property of polymkeric substance (A) can be shown, the cured article of the low cure shrinkage excellence of flexibility can be obtained.

< polymerization starter (C) >

As the polymerization starter used in the present invention (C), the irradiation utilizing ultraviolet isoreactivity energy-ray etc. and the Photoepolymerizationinitiater initiater of initiated polymerization can be listed, utilize heat and the thermal polymerization of initiated polymerization, to solidify because of the irradiation of short period of time from the view point of resin and can cured article be obtained and not make substrate deterioration, be preferably Photoepolymerizationinitiater initiater, be more preferably the Photoepolymerizationinitiater initiater utilizing ultraviolet irradiation and initiated polymerization.As Photoepolymerizationinitiater initiater, such as positively charged ion system Photoepolymerizationinitiater initiater, free base system polymerization starter can be listed.

As positively charged ion system Photoepolymerizationinitiater initiater, such as aromatic diazonium salt, aromatic iodonium salts, aromatic series sulfonium salt, metallocene based compound etc. can be listed.

As the positively charged ion system Photoepolymerizationinitiater initiater of aromatic diazonium salt, there will be a known " P-33(trade(brand)name) " (ADEKACorporation system) etc.

As the positively charged ion system Photoepolymerizationinitiater initiater of aromatic iodonium salts, there will be a known " RhodorsilPhotoInitiator2074(trade(brand)name) " (Rodia Inc.), " IRGACURE250(trade(brand)name) " (BASF Co., Ltd. system) etc.

As the positively charged ion system Photoepolymerizationinitiater initiater of aromatic series sulfonium salt, there will be a known " FC-509(trade(brand)name) " (Sumitomo 3M Inc.), " IRGACURE270(trade(brand)name) " (BASF Co., Ltd. system) etc.

As the positively charged ion system Photoepolymerizationinitiater initiater of metallocene system, there will be a known " IRGACURE261(trade(brand)name) " (BASF Co., Ltd. system) etc.

As free base system Photoepolymerizationinitiater initiater, such as methyl phenyl ketone system, benzophenone series, alkyl phenones system, acylphosphine oxide system, bitter almond oil camphor system, ketal system, anthraquinone system, curing system, thioxanthone system, thiuram system, fluorine amine system etc. can be listed.Among these, be preferably the free base system Photoepolymerizationinitiater initiater of alkyl phenones system or acylphosphine oxide system.

As the free base system Photoepolymerizationinitiater initiater of alkyl phenones system, hydroxyalkylphenones system, amino alkylphenone system etc. can be listed.As the free base system Photoepolymerizationinitiater initiater of hydroxyalkylphenones system, can list " DAROCUR1173(trade(brand)name) " (2-hydroxy-2-methyl-1-phenyl-propane-1-ketone), " IRGACURE184(trade(brand)name) " (1-hydroxycyclohexylphenylketone), " IRGACURE2959(trade(brand)name) " (1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone) etc.

As the free base system Photoepolymerizationinitiater initiater of amino alkylphenone system, can list " IRGACURE907(trade(brand)name) " (2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino propane-1-ketone), " IRGACURE369(trade(brand)name) " (2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-1-butanone) etc.

As the free base system Photoepolymerizationinitiater initiater of acylphosphine oxide system; can list " LUCIRINTPO(trade(brand)name) " (2; 4; 6-trimethyl benzoyl diphenyl base phosphine oxide), " IRGACURE819(trade(brand)name) " (two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide) (being BASF Co., Ltd. system) etc.

Among these, be preferably the free base system Photoepolymerizationinitiater initiater of hydroxyalkylphenones system, be more preferably 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone.They can be used alone a kind, also can combinationally use two or more.

The content of polymerization starter (C) is 0.1 ~ 20 mass parts relative to total 100 mass parts of polymkeric substance (A) and monomer (D), is preferably 0.5 ~ 15 mass parts, is more preferably 1 ~ 10 mass parts, more preferably 1.5 ~ 6 mass parts.When the content of polymerization starter (C) is in aforementioned range, be preferred from the viewpoint of curing speed and mechanics physical property.

< hindered amine based compound (E) >

In the resin combination of the 2nd aspect of the present invention, in order to improve thermotolerance, the weathering resistance of this resin combination and cured article therefrom further, also hindered amine based compound (E) can be contained as required.It should be noted that, as hindered amine based compound (E), be preferably used in the hindered amine based compound in molecule without secondary amino group.

By using the described hindered amine based compound (E) in molecule without secondary amino group, this resin combination and the reduction of mechanics physical property of cured article after being exposed to heat obtained by them, the change of tone can be improved significantly.

As the hindered amine based compound (E) in molecule without secondary amino group, such as two (1 can be listed, 2, 2, 6, 6-pentamethyl--4-piperidyl) sebate, two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) [[3, 5-two (1, 1-dimethyl ethyl)-4-hydroxy phenyl] methyl] butyl malonic acid ester, sebacic acid two (2, 2, 6, 6-tetramethyl--1-(octyloxy)-4-piperidyl) ester, methyl isophthalic acid, 2, 2, 6, 6-pentamethyl--4-piperidinyl sebacate, 1, 2, 3, 4-BTCA four (1, 2, 2, 6, 6-pentamethyl--4-piperidyl), 1, 2, 2, 6, 6-pentamethyl--4-piperidino methyl acrylate etc.

Among these, be preferably two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, methyl isophthalic acid, 2,2,6,6-pentamethyl--4-piperidinyl sebacate, 1,2,3,4-BTCA four (1,2,2,6,6-pentamethyl--4-piperidyl).They can be used alone a kind, also can combinationally use two or more.

The content of hindered amine based compound (E) is preferably 0.01 ~ 10 mass parts relative to total 100 mass parts of polymkeric substance (A) and monomer (D), is preferably 0.5 ~ 7 mass parts, is more preferably 1 ~ 4 mass parts.When the content of hindered amine based compound (E) is in aforementioned range, be preferred from the viewpoint of the mechanics physical property of the viewpoint and raising cured article that improve thermotolerance.

The manufacture method > of < resin combination

As the manufacture method of the resin combination of the 2nd aspect of the present invention, be not particularly limited, such as, can manufacture by room temperature using the common mixing means such as stirrer, kneader to mix aforementioned polymer (A), aforementioned monomer (D), polymerization starter (C) and other composition of using as required.

The melt viscosity > of < resin combination

Melt viscosity at 38 DEG C of the resin combination of the 2nd aspect of the present invention is preferably below 15Pa s, is more preferably below 12Pa s, more preferably below 10Pa s.When the melt viscosity of resin combination is in aforementioned range, can on applied coating resin composition equably, also easily prevent being mixed into of bubble, therefore coating becomes good.It should be noted that, in this manual, the melt viscosity of resin combination is the value that the method utilizing aftermentioned embodiment to record is obtained.

[cured article]

The cured article of the 2nd aspect of the present invention makes the resin composition of the aforementioned 2nd aspect of the present invention obtain, and such as, by the resin combination irradiation energy ray to the 2nd aspect of the present invention, it can be made to solidify.

As the energy-ray for making it solidify, be preferably ultraviolet.As ultraviolet source, such as xenon lamp, low pressure mercury lamp, high voltage mercury lamp, metal halide lamp, microwave mode Excimer lamp etc. can be listed.As the atmosphere of irradiation ultraviolet radiation, be preferably not reactive gas atmosphere or the atmosphere that oxygen concentration is reduced such as nitrogen, carbonic acid gas.

Irradiate atmosphere temperature and be preferably 10 ~ 200 DEG C, UV irradiation dose is preferably 200 ~ 10,000mJ/cm ².

[optics tackiness agent]

The optics tackiness agent of the 2nd aspect of the present invention contains cured article or the resin combination of the aforementioned 2nd aspect of the present invention, can compatibly for electronic machines etc. such as smart mobile phone, liquid-crystal display, OLED display.

Aforementioned optical tackiness agent also can suitably add various additive as required in the scope not departing from the object of the invention.As aforementioned additive, such as tackifier, softening agent, pigment, tinting material, anti-aging agent, UV light absorber etc. can be listed.

[III] resin combination (Third Way)

The resin combination of the 3rd aspect of the present invention is following resin combination, it contains: the polymkeric substance of the 1st aspect of the present invention, namely as form polymkeric substance monomeric unit and comprise the monomeric unit (a1) that is derived from farnesene and have polymerizable functional group polymkeric substance (A), comprise the conjugated diene compound being derived from carbonatoms less than 12 monomeric unit (b1) and not there is polymkeric substance (B) and the polymerization starter (C) of polymerizable functional group, polymkeric substance (A) is 0.01 ~ 100 with the mass ratio [(A)/(B)] of polymkeric substance (B).

< polymkeric substance (A) >

In the polymkeric substance (A) that the 3rd aspect of the present invention uses, comprise the monomeric unit (a1) that is derived from farnesene as the monomeric unit forming polymkeric substance and there is polymerizable functional group.This polymkeric substance (A) is same with the polymer phase in the aforementioned 1st aspect of the present invention, and viscosity is low, curing speed is fast and then cure shrinkage excellent.

The content of the polymkeric substance (A) in the resin combination in the 3rd aspect of the present invention is preferably 1 ~ 99 quality %, is more preferably 2 ~ 98 quality %, more preferably 5 ~ 95 quality %, be further preferably 10 ~ 90 quality %, be further preferably 15 ~ 85 quality %.When the content of the polymkeric substance (A) in resin combination is in above-mentioned scope, the cured article of intensity, flexibility, low-moisture permeability and transparency excellence can be given.

< polymkeric substance (B) >

Polymkeric substance (B) comprises the monomeric unit (b1) of the conjugated diene compound being derived from carbonatoms less than 12 and does not have polymerizable functional group.

As the conjugated diene compound of the carbonatoms less than 12 of monomeric unit (b1), such as divinyl, isoprene, 2 can be listed, 3-dimethylbutadiene, 2-phenyl butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1，3-cyclohexadiene, 2-methyl isophthalic acid, 3-octadiene, 1,3,7-sarohornene, myrcene and chloroprene etc.

Among these, be more preferably isoprene and divinyl.These conjugated diene compounds can be used alone a kind, also can combinationally use two or more.

The monomeric unit forming polymkeric substance (B) only can comprise the aforementioned monomeric unit (b1) being derived from conjugated diene compound, also can comprise and is aforementionedly derived from the monomeric unit (b1) of conjugated diene compound and is derived from the monomeric unit (b2) of the monomer outside conjugated diene compound.That is, aforementioned conjugated diene compound can only be polymerized by polymkeric substance (B), also can be the multipolymer of the monomer outside aforementioned conjugated diene compound and aforementioned conjugated diene compound.

As the aforementioned monomeric unit (b2) being derived from monomer outside conjugated diene compound, the monomeric unit being derived from aromatic ethenyl compound can be listed.

As the aromatic ethenyl compound belonging to monomeric unit (b2), such as vinylbenzene can be listed, alpha-methyl styrene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, 4-propylstyrene, 4-t-butyl styrene, 4-cyclohexylstyrenes, 4-dodecylstyrene, 2, 4-dimethyl styrene, 2, 4-di-isopropyl vinylbenzene, 2, 4, 6-trimethyl styrene, 2-ethyl-4-benzylstyrene, 4-(phenyl butyl) vinylbenzene, 1-vinyl naphthalene, 2-vinyl naphthalene, vinyl anthracene, N, N-diethyl-4-amino-ethyl vinylbenzene, vinyl pyridine, 4-methoxy styrene, monochlorostyrene, dichlorostyrene, and the aromatic ethenyl compound etc. such as Vinylstyrene.Among these, be preferably vinylbenzene, alpha-methyl styrene and 4-vinyl toluene.

When using monomeric unit (b2) of the monomer be derived from outside conjugated diolefine, from the view point of reduce resin combination viscosity viewpoint, keep the good elongation characteristics of cured article and flexibility, the monomeric unit (b2) being derived from the monomer outside conjugated diolefine in multipolymer is preferably 1 ~ 99 quality % relative to the monomeric unit (b1) being derived from conjugated diolefine and the ratio of total of the monomeric unit (b2) being derived from the monomer outside conjugated diolefine, is more preferably 1 ~ 80 quality %, more preferably 1 ~ 70 quality %, be further preferably 1 ~ 50 quality %.

The number-average molecular weight (Mn) of polymkeric substance used in the present invention (B) is preferably 1,000 ~ 200,000, is more preferably 2,000 ~ 180,000, more preferably 3, and 000 ~ 160,000, be further preferably 4,000 ~ 140,000, be further preferably 5,000 ~ 120,000.When the Mn of polymkeric substance (B) is in aforementioned range, flexibility, the mechanical strength of cured article improve, the viscosity of resin combination simultaneously.

Melt viscosity at 38 DEG C of polymkeric substance used in the present invention (B) is preferably 0.1 ~ 3,000Pa s, be more preferably 0.3 ~ 3,000Pa s, more preferably 0.3 ~ 2,800Pa s, be further preferably 0.5 ~ 2,600Pa s, be further preferably 0.5 ~ 800Pa s.When the melt viscosity of polymkeric substance (B) is in aforementioned range, there is no inequality relative to applied, can coating resin composition equably, therefore coating becomes good.

Aforementioned polymer (B) can by carrying out active anionic polymerization to obtain to the monomer outside conjugated diene compound and conjugated diene compound as required.As the active anionic polymerization initiator for carrying out active anionic polymerization to conjugated diene compound, the organo monolithium compounds such as such as lithium methide, lithium ethide, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, hexyl lithium, phenyl lithium, stilbene lithium can be listed; The multi-functional organolithium compounds such as two lithium methane, two lithium naphthalenes, Isosorbide-5-Nitrae-two lithium butane, Isosorbide-5-Nitrae-two lithium-2-ethylcyclohexane, 1,3,5-tri-lithium benzene; Sodium naphthalene, potassium naphthalene etc.In addition, also can combinationally use and can react with organic alkali metal compound and give the compound such as di isopropenylbenzene, dibenzyl toluene of multifunctional organic alkali metal compound.

Polymkeric substance used in the present invention (B) can be used alone a kind, also can combinationally use monomeric unit, molecular weight distinguishes different two or more aforementioned polymer (B).

In the present invention, the mass ratio [(A)/(B)] of aforementioned polymer (A) and aforementioned polymer (B) is 0.01 ~ 100, be preferably 0.05 ~ 100, be more preferably 0.1 ~ 50, more preferably 0.1 ~ 25, be further preferably 0.1 ~ 10.When aforementioned mass ratio [(A)/(B)] is in aforementioned range, can obtain that viscosity is fully low, the good resin combination of elongation at break after solidification.

In the present invention, the melt viscosity at 38 DEG C of at least one in polymkeric substance (A) and polymkeric substance (B) is preferably 0.1 ~ 3,000Pa s, and polymkeric substance (A) and polymkeric substance (B) both melt viscosities are more preferably the scope of 0.1 ~ 3,000Pa s.

< polymerization starter (C) >

As polymerization starter used in the present invention (C), the polymerization starter (C) listed in the 2nd aspect of the present invention compatibly can be used in.

About the content of the polymerization starter (C) in the resin combination of the 3rd aspect of the present invention, in the total amount of resin combination, be preferably 0.1 ~ 20 quality %, be more preferably 0.5 ~ 20 quality %, more preferably 1.0 ~ 20 quality %, be further preferably 1.0 ~ 15 quality %, most preferably be 1.0 ~ 10 quality %.When the content of polymerization starter (C) is in aforementioned range, be preferred from the viewpoint of curing speed and mechanics physical property.

< monomer (D) >

In the resin combination of the 3rd aspect of the present invention, in order to improve the intensity after the viscosity of this resin combination, treatability and solidification further, also monomer (D) can be contained as required.

As monomer (D), preferably there is the functional group that can react with polymkeric substance (A), the compound such as in molecule with (methyl) acryl, epoxy group(ing), oxetanyl, vinyl ether group, alkoxysilyl can be listed.

As concrete compound, the monomer (D) listed in the 2nd aspect of the present invention compatibly can be used.

Among aforementioned monomer (D), as monomer (D), good from the view point of the consistency of itself and polymkeric substance (A), preferably be selected from least a kind in simple function (methyl) acrylate, two senses (methyl) acrylate and multifunctional (methyl) acrylate, be more preferably at least a kind that is selected from simple function (methyl) acrylate and two senses (methyl) acrylate.

Wherein, be particularly preferably dicyclopentenyl oxygen base ethyl (methyl) acrylate, bicyclopentane oxygen base ethyl (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid bicyclopentane ester, (methyl) acrylate etc.They can be used alone a kind, also can combinationally use two or more.

Aforementioned monomer (D) can utilize the polymerization starters such as radical polymerization initiator, cationic polymerization initiators and anionic polymerization initiator and react with the polymerizable functional group of aforementioned polymer (A).The content of aforementioned monomer (D) is preferably 0.01 ~ 1 relative to total 100 mass parts of polymkeric substance (A) and polymkeric substance (B), 000 mass parts, be more preferably 0.1 ~ 800 mass parts, more preferably 1.0 ~ 600 mass parts, be further preferably 1.0 ~ 400 mass parts.When the content of monomer (D) is in aforementioned range, viscosity reduces, operability improves.In addition, when making the resin composition in the 3rd aspect of the present invention, the breaking tenacity of cured article and tensile elongation improve, therefore, it is possible to obtain the cured article of flexibility excellence.

< hindered amine based compound (E) >

In the resin combination of the 3rd aspect of the present invention, in order to improve thermotolerance, the weathering resistance of this resin combination and cured article therefrom further, also hindered amine based compound (E) can be contained as required.It should be noted that, as hindered amine based compound (E), be preferably used in the hindered amine based compound in molecule without secondary amino group.By using the described hindered amine based compound (E) in molecule without secondary amino group, that can improve this resin combination and the cured article that obtained by them significantly is exposed to the reduction of mechanics physical property after heat, the change of tone.

As concrete compound, the hindered amine based compound (E) listed in the 2nd aspect of the present invention compatibly can be used in.

About the content of the hindered amine based compound (E) in the resin combination of the 3rd aspect of the present invention, in the total amount of resin combination, be preferably 0.01 ~ 10 quality %, be more preferably 0.5 ~ 7 quality %, more preferably 1 ~ 4 quality %.When the content of hindered amine based compound (E) is in aforementioned range, be preferred from the viewpoint of the mechanics physical property of the viewpoint and raising cured article that improve thermotolerance.

In the resin combination of the 3rd aspect of the present invention, in the scope not damaging effect of the present invention, except polymkeric substance (A) and polymkeric substance (B), can also containing the modified conjugated diene polymer with polymerizable functional group that the polymerization of conjugated dienes outside farnesene is obtained.As the conjugated diolefine outside farnesene, divinyl, isoprene, 2 can be listed, 3-dimethylbutadiene, 2-phenyl butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1，3-cyclohexadiene, 2-methyl isophthalic acid, 3-octadiene, 1,3,7-sarohornene, myrcene and chloroprene etc.

In addition, in the resin combination of the 3rd aspect of the present invention, in the scope not damaging effect of the present invention, except polymkeric substance (A) and polymkeric substance (B), can also containing the modified conjugated diene with polymerizable functional group-aromatic ethenyl compound based copolymer that the conjugated diolefine outside farnesene and aromatic ethenyl compound copolymerization are obtained.As the example of conjugated diolefine, example as hereinbefore can be used.

As aromatic ethenyl compound, such as vinylbenzene can be listed, alpha-methyl styrene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, 4-propylstyrene, 4-t-butyl styrene, 4-cyclohexylstyrenes, 4-dodecylstyrene, 2, 4-dimethyl styrene, 2, 4-di-isopropyl vinylbenzene, 2, 4, 6-trimethyl styrene, 2-ethyl-4-benzylstyrene, 4-(phenyl butyl) vinylbenzene, 1-vinyl naphthalene, 2-vinyl naphthalene, vinyl anthracene, N, N-diethyl-4-amino-ethyl vinylbenzene, vinyl pyridine, 4-methoxy styrene, monochlorostyrene, dichlorostyrene, Vinylstyrene etc.

As aforementioned polymerizable functional group, (methyl) acryl, epoxy group(ing), oxetanyl, vinyl ether group, alkoxysilyl, (methyl) acrylamido, styryl, dimaleoyl imino, lactone group, lactam group, sulfide base, Thietane base, acetonide base, thioureido etc. can be listed such as.

It should be noted that, the aforementioned modified conjugated diene polymer with polymerizable functional group and the modified conjugated diene-aromatic ethenyl compound based copolymer with polymerizable functional group are included in the concept of polymkeric substance (F) of the aftermentioned 4th aspect of the present invention.Therefore, about these polymkeric substance, explain in the polymkeric substance (F) of fourth way.

The aforementioned modified conjugated diene polymer that also can contain except polymkeric substance (A) and polymkeric substance (B) and the content of modified conjugated diene-aromatic ethenyl compound based copolymer are not particularly limited, below 50 quality % are preferably in the total amount of resin combination, be more preferably below 30 quality %, more preferably below 10 quality %.

The manufacture method > of < resin combination

As the manufacture method of the resin combination of the 3rd aspect of the present invention, be not particularly limited, such as, can manufacture by room temperature using the common mixing means such as stirrer, kneader to mix aforementioned polymer (A), aforementioned polymer (B), polymerization starter (C) and other composition of using as required.

The melt viscosity > of < resin combination

Melt viscosity at 38 DEG C of the resin combination of the 3rd aspect of the present invention is preferably below 15Pa s, is more preferably below 12Pa s, more preferably below 10Pa s.When the melt viscosity of resin combination is in aforementioned range, can to applied face coating resin composition equably, also easily prevent being mixed into of bubble, therefore coating becomes good.It should be noted that, in this manual, the melt viscosity of resin combination is the value that the method utilizing aftermentioned embodiment to record is obtained.

The resin combination of the 3rd aspect of the present invention can obtain that melt viscosity is low, the cured article of solidified nature and then intensity, flexibility and transparency excellence, therefore can compatibly for the purposes of caking agent, tackiness agent (especially optics tackiness agent), coating agent, sealing material and ink etc.

[cured article]

The cured article of the 3rd aspect of the present invention makes the resin composition of the present invention of aforementioned Third Way obtain, such as, by to the resin combination irradiation energy ray of the 3rd aspect of the present invention or apply heat, aforementioned polymer (A) and polymerization starter (C) are reacted, it can be made thus to solidify.

[optics tackiness agent]

The optics tackiness agent of the 3rd aspect of the present invention contains cured article or the resin combination of the aforementioned 3rd aspect of the present invention, can compatibly for electronic machines etc. such as smart mobile phone, liquid-crystal display, OLED display.

[IV] resin combination (fourth way)

The resin combination of the 4th aspect of the present invention is following resin combination, it contains polymkeric substance (F) further in the resin combination of the 2nd aspect of the present invention or the resin combination of Third Way, described polymkeric substance (F) comprises the monomeric unit (f1) of the conjugated diene compound being derived from carbonatoms less than 12 and has polymerizable functional group, and polymkeric substance (A) is 0.01 ~ 100 with the mass ratio [(A)/(F)] of polymkeric substance (F).

< polymkeric substance (F) >

The polymkeric substance (F) that the resin combination of the 4th aspect of the present invention uses be comprise the conjugated diene compound being derived from carbonatoms less than 12 monomeric unit (f1) and there is the polymkeric substance of polymerizable functional group.

Conjugated diene compound as the carbonatoms less than 12 of monomeric unit (f1) is preferably divinyl, isoprene, 2,3-dimethylbutadiene, 2-phenyl butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl isophthalic acid, 3-octadiene, 1,3,7-sarohornene, myrcene and chloroprene etc.

The monomeric unit forming polymkeric substance (F) only can comprise the aforementioned monomeric unit (f1) being derived from the conjugated diene compound of carbonatoms less than 12, also can comprise the monomeric unit (f2) of the monomer (wherein not comprising farnesene) outside the aforementioned monomeric unit (f1) being derived from conjugated diene compound and the conjugated diene compound being derived from carbonatoms less than 12.Namely, the conjugated diene compound of aforementioned carbonatoms less than 12 can only be polymerized by polymkeric substance (F), also can be the multipolymer of the monomer outside the conjugated diene compound of aforementioned carbonatoms less than 12 and the conjugated diene compound of aforementioned carbonatoms less than 12.

Monomer as monomeric unit (f2) can list such as aromatic ethenyl compound.As described aromatic ethenyl compound, such as be preferably vinylbenzene, alpha-methyl styrene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, 4-propylstyrene, 4-t-butyl styrene, 4-cyclohexylstyrenes, 4-dodecylstyrene, 2, 4-dimethyl styrene, 2, 4-di-isopropyl vinylbenzene, 2, 4, 6-trimethyl styrene, 2-ethyl-4-benzylstyrene, 4-(phenyl butyl) vinylbenzene, 1-vinyl naphthalene, 2-vinyl naphthalene, vinyl anthracene, N, N-diethyl-4-amino-ethyl vinylbenzene, vinyl pyridine, 4-methoxy styrene, monochlorostyrene, dichlorostyrene, Vinylstyrene etc.

When using monomeric unit (f2) of the monomer outside the conjugated diolefine being derived from carbonatoms less than 12, from the viewpoint of the viscosity of reduction resin combination, the good elongation characteristics of cured article and the viewpoint of flexibility is kept to set out, the monomeric unit (f2) of the monomer outside the conjugated diolefine being derived from carbonatoms less than 12 in multipolymer relative to be derived from carbonatoms less than 12 conjugated diene compound monomeric unit (f1) and be derived from carbonatoms less than 12 conjugated diolefine outside the ratio of total of monomeric unit (f2) of monomer be preferably 1 ~ 99 quality %, be more preferably 1 ~ 80 quality %, more preferably 1 ~ 70 quality %, further be preferably 1 ~ 50 quality %.

As the polymerizable functional group that aforementioned polymer (F) has, the functional group that the functional group that exemplifies with the polymerizable functional group had as polymkeric substance (A) is identical can be used.Such as (methyl) acryl, epoxy group(ing), oxetanyl, vinyl ether group, alkoxysilyl, (methyl) acrylamido, styryl, dimaleoyl imino, lactone group, lactam group, sulfide base, Thietane base, acetonide base, thioureido etc. can be listed.It should be noted that, these functional groups can have substituting group.

The number-average molecular weight (Mn) of polymkeric substance used in the present invention (F) is preferably 1,000 ~ 200,000, is more preferably 5,000 ~ 200,000, more preferably 8, and 000 ~ 100,000, be further preferably 11,000 ~ 60,000.When the Mn of polymkeric substance (F) is in aforementioned range, flexibility, the mechanical strength of cured article improve, the viscosity of resin combination simultaneously.

Melt viscosity at 38 DEG C of polymkeric substance used in the present invention (F) is preferably 0.1 ~ 3,000Pa s, be more preferably 0.3 ~ 3,000Pa s, more preferably 0.3 ~ 2,800Pa s, be further preferably 0.5 ~ 2,600Pa s, be further preferably 0.5 ~ 800Pa s.When the melt viscosity of polymkeric substance (F) is in aforementioned range, do not have inequality relative to applied, can coat resin combination equably, therefore coating becomes good.

Aforementioned polymer (F) can utilize the method identical with aforementioned polymer (A) to manufacture.Specifically, first by utilizing emulsion polymerization or solution polymerization process to be polymerized the monomer outside the conjugated diene compound of the conjugated diene compound of carbonatoms less than 12 and carbonatoms as required less than 12, thus the unmodified polymer without polymerizable functional group is manufactured.Then, by importing polymerizable functional group to this unmodified polymer, thus can obtain.

Include, for example out: foregoing unmodified polymkeric substance and maleic anhydride etc. are reacted for the compound of grafting, then, the method that the compound making itself and 2-hydroxyethyl methacrylate etc. have polymerizable functional group reacts.It should be noted that, aforementioned polymer (F) can use commercially available product.

Polymkeric substance (A) in resin combination and the total content of polymkeric substance (F) are preferably 1 ~ 99 quality %, are more preferably 2 ~ 98 quality %, more preferably 5 ~ 95 quality %, be further preferably 10 ~ 90 quality %, be further preferably 15 ~ 85 quality %.When polymkeric substance (A) in resin combination and the content of polymkeric substance (F) are in above-mentioned scope, the cured article of intensity, flexibility, low-moisture permeability and transparency excellence can be given.

In the present invention, the mass ratio [(A)/(F)] of aforementioned polymer (A) and aforementioned polymer (F) is 0.01 ~ 100, be preferably 0.05 ~ 100, be more preferably 0.1 ~ 50, more preferably 0.1 ~ 25, be further preferably 0.1 ~ 10.When aforementioned mass ratio [(A)/(F)] is in aforementioned range, can obtain that viscosity is fully low, the good resin combination of elongation at break after solidification.

The manufacture method of other formation, specifically resin combination in the 4th aspect of the present invention, the viscosity of resin combination, cured article and optics jointing material etc. are identical with the formation of aforementioned second method, Third Way.

Embodiment

Below, utilize embodiment to describe the present invention in detail, but the present invention is not limited to these embodiments.

[embodiment of the 1st aspect of the present invention]

The each composition used in the embodiment of first method and comparative example is as follows.

< has polymkeric substance (A) > of polymerizable functional group

There is in the molecule obtained by aftermentioned Production Example 1 ~ 5 poly-farnesene (A-1) ~ (A-5) of methacryloyl.

Other curable resin of < >

Polyisoprene (I-X-1)

By comparing the polyisoprene in molecule that Production Example 1 obtains with methacryloyl

Curable resin (I-X-2)

That synthesize according to the record of the embodiment 7 of No. 2012/018682nd, International Publication, carried out modification with 2-hydroxyethyl methacrylate poly-farnesene

Urethane acrylate (I-X-3)

The urethane acrylate " DBA2210 " that デュポン Co., Ltd. manufactures.

< radical polymerization initiator >

2-hydroxy-2-methyl-1-phenyl-propane-1-ketone

BASF Co., Ltd. system, trade(brand)name " DAROCUR1173 ".

< anti-aging agent >

2,6 di tert butyl 4 methyl phenol (BHT)

Honshu Chemical Ind's system.

< Production Example 1 ~ 5, compare Production Example 1>

Production Example 1: the poly-farnesene (A-1) in molecule with methacryloyl

Drop into hexanaphthene 1520g and s-butyl lithium 10.5 quality % cyclohexane solution 7.8g in the autoclave of capacity 5 liters having carried out nitrogen replacement after, be warming up to 50 DEG C, add β-farnesene 1510g, carry out polymerization in 2 hours.Gained polymeric solution is injected in methyl alcohol, makes unmodified polymer redeposition and filter, with 80 DEG C of vacuum-dryings 10 hours, thus obtain 1200g and gather farnesene (unmodified polymer).

When utilizing the part of GPC to unmodified polymer to analyze, the number-average molecular weight (Mn)=113 that polystyrene standard converts, 300, molecular weight distribution (Mw/Mn)=1.18.

To carried out nitrogen replacement capacity 1 liter autoclave in drop into gained unmodified polymer 300g, add maleic anhydride 4.5g and BHT3.0g, make it react 20 hours with 160 DEG C, thus make unmodified polymer addition have maleic anhydride.Then; add 2-hydroxyethyl methacrylate 6.3g, Resorcinol 0.15g, N; N-dimethyl benzyl amine 0.9g, makes it react 6 hours with 80 DEG C, thus obtains the poly-farnesene (hereinafter sometimes referred to " polymkeric substance (A-1) ") in molecule with methacryloyl.

Production Example 2,3: there is the poly-farnesene (A-2) of methacryloyl, (A-3) in molecule

Except the consumption of β-farnesene, s-butyl lithium, hexanaphthene being changed to respectively amount that table 1 records, manufacture unmodified polymer in the same manner as Production Example 1.The number-average molecular weight of unmodified polymer and molecular weight distribution are shown in table 1.

Then; for each unmodified polymer; react similarly to Example 1; thus be manufactured in molecule the poly-farnesene (A-2) and (A-3) (following, sometimes the poly-farnesene (A-2) in molecule with methacryloyl to be called " polymkeric substance (A-2) ", to be called " polymkeric substance (A-3) " by the poly-farnesene (A-3) in molecule with methacryloyl) with methacryloyl.

Production Example 4: the farnesene-isoprene copolymer (A-4) in molecule with methacryloyl

Drop into hexanaphthene 1500g and s-butyl lithium 10.5 quality % cyclohexane solution 38.5g in the autoclave of capacity 5 liters having carried out nitrogen replacement after, be warming up to 50 DEG C, add the mix monomer (β-farnesene/isoprene=6/4(mass ratio) of β-farnesene and isoprene) 1540g, carries out polymerization in 2 hours.Gained polymeric solution is injected in methyl alcohol, makes unmodified polymer redeposition and filter, with 80 DEG C of vacuum-dryings 10 hours, thus obtain 1200g farnesene-isoprene copolymer (unmodified polymer).

When utilizing the part of GPC to unmodified polymer to analyze, the number-average molecular weight (Mn)=25 that polystyrene standard converts, 300, molecular weight distribution (Mw/Mn)=1.09.

To carried out nitrogen replacement capacity 1 liter autoclave in drop into gained unmodified polymer 300g, add maleic anhydride 4.5g and BHT3.0g, make it react 20 hours with 160 DEG C, thus make unmodified polymer addition have maleic anhydride.Then; add 2-hydroxyethyl methacrylate 6.3g, Resorcinol 0.15g, N; N-dimethyl benzyl amine 0.9g; it is made to react 6 hours with 80 DEG C; thus obtain the farnesene-isoprene copolymer (following, to be sometimes referred to as " polymkeric substance (A-4) ") in molecule with methacryloyl.

Production Example 5: the farnesene-isoprene copolymer (A-5) in molecule with methacryloyl

Except the consumption of β-farnesene, s-butyl lithium, hexanaphthene being changed to respectively amount that table 1 records, manufacture unmodified polymer in the same manner as Production Example 4.The number-average molecular weight of unmodified polymer and molecular weight distribution are shown in table 1.

Then, for unmodified polymer, react similarly to Example 4, thus be manufactured in molecule the farnesene-isoprene copolymer (following, to be sometimes referred to as " polymkeric substance (A-5) ") with methacryloyl.

Relatively Production Example 1: the polyisoprene (I-X-1) in molecule with methacryloyl

Drop into hexanaphthene 1420g and s-butyl lithium 10.5 quality % cyclohexane solution 70.9g in the autoclave of capacity 5 liters having carried out nitrogen replacement after, be warming up to 50 DEG C, add isoprene 1490g, carry out polymerization in 2 hours.Gained polymeric solution is injected in methyl alcohol, makes polyisoprene redeposition and filter, with 80 DEG C of vacuum-dryings 10 hours, thus obtain 1200g polyisoprene.

When utilizing the part of GPC to polyisoprene to analyze, the number-average molecular weight (Mn)=19 that polystyrene standard converts, 400, molecular weight distribution (Mw/Mn)=1.03.

To carried out nitrogen replacement capacity 1 liter autoclave in drop into gained polyisoprene 300g, add maleic anhydride 4.5g, make it react 20 hours with 160 DEG C, thus make polyisoprene addition have maleic anhydride.Then; add 2-hydroxyethyl methacrylate 6.3g, Resorcinol 0.15g, N, N-dimethyl benzyl amine 0.9g, makes it react 6 hours with 80 DEG C; thus obtain the polyisoprene (following, to be sometimes referred to as " polyisoprene (I-X-1) ") in molecule with methacryloyl.

[table 1]

< embodiment 1 ~ 5, comparative example 1 ~ 3>

Embodiment 1

For polymkeric substance (A-1), aftermentioned method is utilized to carry out number-average molecular weight, methacryloyl equivalent, the average functional group number of 1 molecular chain and the mensuration of melt viscosity.Show the result in table 2.

In addition, relative to polymkeric substance (A-1) 100 mass parts, add radical polymerization initiator 3 mass parts, thus make curable resin composition.

For gained curable resin composition, utilize aftermentioned method evaluation curing speed, the transparency, cure shrinkage, breaking tenacity, elongation at break, water vapour permeability and hardness.Show the result in table 2.

Embodiment 2 ~ 5

Polymkeric substance (A-1) is changed to polymkeric substance (A-2) ~ (A-5) respectively, in addition, operates similarly to Example 1, carry out various evaluation.Show the result in table 2.

Comparative example 1

Polymkeric substance (A-1) is changed to polyisoprene (I-X-1), in addition, operates similarly to Example 1, carry out various evaluation.Show the result in table 2.

Comparative example 2

Polymkeric substance (A-1) is changed to curable resin (I-X-2), in addition, operates similarly to Example 1, carry out various evaluation.Show the result in table 2.

Comparative example 3

Polymkeric substance (A-1) is changed to urethane acrylate (I-X-3), in addition, operates similarly to Example 1, carry out various evaluation.Show the result in table 2.

Evaluation method in the embodiment of first method and comparative example is as follows.

(I-1) mensuration of number-average molecular weight and molecular weight distribution

" GPC-8020 " that use TOSOH Co., Ltd to manufacture, carries out adjusting and measuring with the concentration of sample/tetrahydrofuran (THF)=5mg/10mL.It should be noted that, as developing solution, employ the tetrahydrofuran (THF) that Wako Pure Chemical Industries, Ltd. manufactures.

Number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) utilize GPC(gel permeation chromatography) obtained by polystyrene standard conversion molecular weight.Determinator and condition as follows.

Device: the GPC device " GPC8020 " that TOSOH Co., Ltd manufactures

Separator column: " TSKgelG4000HXL " that TOSOH Co., Ltd manufactures

Detector: " RI-8020 " that TOSOH Co., Ltd manufactures

Elutriant: tetrahydrofuran (THF)

Elutriant flow: 1.0ml/ minute

Sample concentration: 5mg/10ml

Column temperature: 40 DEG C.

(I-2) mensuration of methacryloyl equivalent and the polymerizable functional group number of average 1 molecular chain

Jeol Ltd. is used to manufacture ¹h-NMR(500MHz), the concentration of sample/deuterochloroform=100mg/1mL, integrating number of times 512 times, measure temperature 50 C under measure.The equivalent of methacryloyl relative to polymer quality is calculated by the peak being derived from the double bond of (methyl) acryl in gained spectrogram and the area ratio at the peak being derived from main polymer chain.

In addition, for the polymerizable functional group number of average 1 molecular chain, calculated with the functional equivalent relative to polymer quality utilizing aforesaid method to obtain by the number-average molecular weight of polymkeric substance.

(I-3) measuring method of melt viscosity

Melt viscosity (Pa s) at utilizing BROOKFIELD type viscometer (BROOKFIELDENGINEERINGLABS.INC. system) to measure 38 DEG C of polymkeric substance.

(I-4) curing speed

The each curable resin composition obtained in embodiment and comparative example is injected in the mould of vertical 70mm, horizontal 70mm, thickness 0.5mm, after the PET film of composition surface thickness 50 μm is covered, use UV irradiating unit (Co., Ltd. ジーエスユアサコーポレーショ Application system, use HAK125L-F as mercury lamp), be set as illumination 30mW/cm ², line speed 2m/min, utilize 1 operation to irradiate 150mJ/cm ²uV.

Repeated 1,2,4,6,8,16 time, the total obtaining UV irradiation dose be respectively 150,300,600,900,1200,2400mJ/cm ²the each 500mg of cured article.For cured article, peel off after PET film, with room temperature immersion 24 hours in toluene, by the insoluble part of wire netting leaching of 200mesh, with 80 DEG C of vacuum-dryings 12 hours after cleaning.After drying, weigh each sample, thus calculate the gel fraction of the polymkeric substance under each UV irradiation dose according to the following formula.

Gel fraction (%)=(quality of toluene insoluble part)/(quality of the cured article before toluene dipping) × 100.

UV irradiation dose when gel fraction reaches 80% is extrapolated, evaluate cure speed by the data utilizing this test to obtain.It should be noted that, reach UV irradiation dose required till 80% based on gel fraction, evaluate according to following benchmark.

< metewand >

5: less than 500mJ/cm ²

4:500mJ/cm ²above, less than 1000mJ/cm ²

3:1000mJ/cm ²above, less than 2000mJ/cm ²

2:2000mJ/cm ²above, less than 3000mJ/cm ²

1:3000mJ/cm ²above.

(I-5) transparency

The curable resin composition obtained in embodiment and comparative example is injected in the mould of vertical 70mm, horizontal 70mm, thickness 0.5mm, after composition surface is covered by the PET film of thickness 50 μm, use UV irradiating unit (Co., Ltd. ジーエスユアサコーポレーショ Application system, use HAK125L-F as mercury lamp), be set as illumination 45mW/cm ², line speed 0.25m/min, utilize 1 operation to irradiate 1000mJ/cm ²uV.Repeated 3 times and obtained cured article.Peel off after PET film from cured article, the transparency is evaluated in visual observation.

< metewand >

5: water white transparency

4: observe only slightly painted, but be transparent

3: observe slightly painted, but be transparent

2: observe obviously painted, but be transparent

1: opaque.

(I-6) cure shrinkage

Method based on JISK6911 record measures the density of the cured article obtained in above-mentioned (I-5), it can be used as the density of the composition after solidification.The pycnometric method that the density of the composition before solidification uses JISK0061 to record measures.After measuring the density before and after solidification, obtain cure shrinkage based on following formula, evaluate according to following benchmark.

Cure shrinkage (%)=[density of the composition before 1-(solidification)/(density of the composition after solidification)] × 100.

< metewand >

5: cure shrinkage is less than 1%

4: cure shrinkage is more than 1%, less than 3%

3: cure shrinkage is more than 3%, less than 5%

2: cure shrinkage is more than 5%, less than 10%

1: cure shrinkage is more than 10%.

(I-7) breaking tenacity and elongation at break

The short strip shape sample of wide 6mm, long 70mm is punched out, breaking tenacity, elongation at break when the stretching test machine determination utilizing イ Application ストロ Application company to manufacture carries out tension test with the draw speed of 10mm/min by the cured article obtained in above-mentioned (I-5).

(I-8) water vapour permeability test

Use the cured article obtained in above-mentioned (I-5), carry out water vapour permeability test based on JISZ0208 condition B, evaluate according to following benchmark.

< metewand >

5: Water Vapour Permeability is less than 25g/m ²24h

4: Water Vapour Permeability is 25g/m ²more than 24h, less than 50g/m ²24h

3: Water Vapour Permeability is 50g/m ²more than 24h, less than 100g/m ²24h

2: Water Vapour Permeability is 100g/m ²more than 24h, less than 200g/m ²24h

1: Water Vapour Permeability is 200g/m ²more than 24h.

(I-9) hardness

The curable resin composition obtained in embodiment and comparative example is injected in the mould of vertical 70mm, horizontal 35mm, thickness 2.0mm, after the PET film of composition surface thickness 50 μm is covered, use UV irradiating unit (Co., Ltd. ジーエスユアサコーポレーショ Application system, use HAK125L-F as mercury lamp), be set as illumination 45mW/cm ², line speed 0.25m/min, utilize 1 operation to irradiate 1000mJ/cm ²uV.Repeated 3 times and obtained cured article.Be overlapping 3 samples being used as 6.0mm of the cured article of 2.0mm by gained thickness, measure hardness (JISA) according to JISK6253.

[table 2]

As the results shown in Table 2: compared with polyisoprene (I-X-1), the melt viscosity under the same molecular amount of polymkeric substance of the present invention (A-3) ~ (A-5) is low.

In addition, compared with polyisoprene (I-X-1), the curing speed of polymkeric substance of the present invention (A-1) ~ (A-5) soon, especially as embodiment 1,2 the curing speed of the high polymkeric substance (A-1) of molecular weight and (A-2) excellent.

And then known: polymkeric substance of the present invention (A-1) ~ (A-5) has the good transparency, low cure shrinkage, low-moisture permeability, flexibility in the same manner as polyisoprene (I-X-1).

It should be noted that, there is gelation in the curable resin (I-X-2) of comparative example 2, be insoluble to solvent, therefore cannot carry out the mensuration of number-average molecular weight, methacryloyl equivalent in the process of 2-hydroxyethyl methacrylate modification body manufacturing poly-farnesene.

The comparative example 3 employing urethane acrylate (I-X-3) curing speed in the same manner as embodiment 1 ~ 5 is excellent, but from the viewpoint of shrinking percentage during solidification, water vapour permeability, polymkeric substance of the present invention (A-1) ~ (A-5) is more excellent.

[embodiment of the 2nd aspect of the present invention]

The each composition used in the embodiment of second method and comparative example is as follows.

< has polymkeric substance (A) > of polymerizable functional group

Polymkeric substance (A-1) ~ (A-5) used in the embodiment 1 ~ 5 of first method

It should be noted that, the quantity of the polymerizable functional group of the number-average molecular weight of polymkeric substance (A-1) ~ (A-5), molecular weight distribution, melt viscosity, methacryloyl equivalent and average 1 molecular chain is shown in table 3.

< polymerization starter (C) (radical polymerization initiator) >

Polymerization starter (C-1)

2-hydroxy-2-methyl-1-phenyl-propane-1-ketone

BASF Co., Ltd. system, trade(brand)name " DAROCUR1173 ".

< monomer (D) >

Monomer (D-1): dicyclopentenyl oxygen base ethylmethyl acrylate

Hitachi Chemical Co., Ltd.'s system, trade(brand)name " Off ァ Application Network リ Le FA-512M "

Monomer (D-2): 1,9-nonanediol diacrylate

Osaka Organic Chemical Industry Co., Ltd.'s system, trade(brand)name " PVC スコート #260 "

Monomer (D-3): n-butyl acrylate

East capital changes into Industrial Co., Ltd's system, trade(brand)name " ButylAcrylate ".

< hindered amine based compound (E) >

Hindered amine based compound (E-1)

Two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate and methyl isophthalic acid, the mixture of 2,2,6,6-pentamethyl--4-piperidinyl sebacate

BASF Co., Ltd. system, trade(brand)name " TINUVIN765 ".

< anti-aging agent >

2,6 di tert butyl 4 methyl phenol (BHT) Honshu Chemical Ind system.

Other polymkeric substance of < (II-X) >

Polymkeric substance (II-X-1): the urethane acrylate " DBA2210 " that デュポン Co., Ltd. manufactures

Polymkeric substance (II-X-2): that synthesize according to the record of the embodiment 7 of No. 2012/018682nd, International Publication, carried out modification with 2-hydroxyethyl methacrylate poly-farnesene

Polymkeric substance (II-X-3): in the Production Example 3 of first method, after farnesene polymerization will be gathered, the unmodified polymer taken out before adding maleic anhydride

Polymkeric substance (II-X-4): in the Production Example 3 of first method, after reacting with maleic anhydride, the polymkeric substance taken out before adding 2-hydroxyethyl methacrylate

Polymkeric substance (II-X-5): " TEA-1000 " (polyhutadiene containing acryl) that Tso Tat Co., Ltd., Japan manufactures.

[table 3]

< embodiment 6 ~ 14>

Polymkeric substance (A-1) ~ (A-5), monomer (D-1) ~ (D-3), polymerization starter (C-1) are fed in stainless steel 300mL container with the ratio shown in table 4, at room temperature use agitating vane to mix 20 minutes, thus prepare resin combination.Utilize following method to evaluate gained resin combination.Show the result in table 4.

< embodiment 15 ~ 23>

Polymkeric substance (A-1) ~ (A-5), monomer (D-1) ~ (D-3), polymerization starter (C-1), hindered amine based compound (E-1) are coordinated with the ratio shown in table 5, in addition, resin combination is prepared in operation similarly to Example 6, evaluates.Show the result in table 5.

< comparative example 4 ~ 8>

Other curable resin (II-X-1) ~ (II-X-5), monomer (D-1), polymerization starter (C-1) are coordinated with the ratio shown in table 6, in addition, resin combination is prepared in operation similarly to Example 6, evaluates.Show the result in table 6.

The embodiment of second method and the evaluation method of comparative example as follows.

(II-1) mensuration of number-average molecular weight and molecular weight distribution

The method identical with (I-1) of first method is utilized to measure.

(II-2) mensuration of methacryloyl equivalent and the polymerizable functional group number of average 1 molecular chain

The method identical with (I-2) of first method is utilized to measure.

(II-3) melt viscosity

For the resin combination obtained in the polymkeric substance obtained in Production Example 1 ~ 5 (A-1) ~ (A-5) and embodiment and comparative example, the method identical with (I-3) of first method is utilized to measure.

(II-4) UV irradiation dose and curing speed

About the resin combination obtained in embodiment and comparative example, utilize the method identical with (I-4) of first method to test, obtain gel fraction.

Extrapolate UV irradiation dose when gel fraction reaches 80% by the data utilizing this test to obtain, evaluate according to following benchmark.

< metewand >

Zero: less than 1,000mJ/cm ²

△: 1,000mJ/cm ²above, less than 2,000mJ/cm ²

×: 2,000mJ/cm ²above.

(II-5) outward appearance (transparency)

The method identical with (I-5) of first method is utilized to make cured article.After gained cured article peels off PET film, carry out visual observation, evaluate the transparency according to following benchmark.

< metewand >

Zero: water white transparency

△: observe some painted, but not transparent

×: visible significantly painted or muddy.

(II-6) cure shrinkage

For the cured article obtained in above-mentioned (II-5), utilize the method identical with (I-6) of first method to obtain cure shrinkage, evaluate according to following benchmark.

< metewand >

◎: cure shrinkage is less than 3%

Zero: cure shrinkage is more than 3%, less than 5%

△: cure shrinkage is more than 5%, less than 10%

×: cure shrinkage is more than 10%.

(II-7) breaking tenacity and elongation at break

The short strip shape sample of wide 6mm, long 70mm is punched out, the breaking tenacity when stretching test machine determination utilizing イ Application ストロ Application company to manufacture carries out tension test with the draw speed of 50mm/min and elongation at break by the cured article obtained in above-mentioned (II-5).

(II-8) water vapour permeability test

For the cured article obtained in above-mentioned (II-5), utilize the method identical with (I-8) of first method to test, evaluate according to following benchmark.

< metewand >

5: Water Vapour Permeability is less than 25g/m ²24h

4: Water Vapour Permeability is 25g/m ²more than 24h, less than 50g/m ²24h

3: Water Vapour Permeability is 50g/m ²more than 24h, less than 100g/m ²24h

2: Water Vapour Permeability is 100g/m ²more than 24h, less than 200g/m ²24h

1: Water Vapour Permeability is 200g/m ²more than 24h.

(II-9) hardness

For the resin combination obtained in embodiment and comparative example, the method identical with (I-9) of first method is utilized to measure.

(II-10) thermal test (form and aspect stability test)

After the cured article obtained peeling off PET film in above-mentioned (II-5) places 24 hours under 25 DEG C of atmosphere, make the short strip shape test film of vertical 60mm × horizontal 6mm × thickness 0.5mm.Then, made test film is left standstill 72 hours, 144 hours, 240 hours respectively in the thermostat container (GEAROVEN) of 100 DEG C, by its visual foxy confirming each test film together with the test film (being labeled as 0 hour) before thermal treatment, following benchmark is utilized to evaluate.It should be noted that, the cured article that this test obtains for the resin combination by embodiment 15 ~ 23 and comparative example 4 ~ 8 carries out.

< metewand >

◎: colourless

Zero: faint yellow

△: yellow

×: brown.

(II-11) thermal test (modulus in tension)

After the test film made in above-mentioned (II-5) is left standstill 72 hours, 144 hours, 240 hours respectively at 100 DEG C, carry out tension test with the draw speed of 50mm/min, utilize tensile testing machine that イ Application ストロ Application company manufactures to measure the modulus in tension under each time.It should be noted that, modulus in tension is low then soft, therefore well, along with the little through changing ratio later of time is good.It should be noted that, the cured article that this test obtains for the resin combination by embodiment 15 ~ 23 and comparative example 4 ~ 8 carries out.

[table 4]

[table 5]

[table 6]

* 1: cannot polymkeric substance be obtained, therefore cannot measure composition.

* 2: gel rate, more than 80%, therefore cannot measure UV irradiation dose during solidification.

* 3: cannot measure due to deterioration.

With employ not containing be derived from farnesene monomer polymkeric substance (II-X-5) comparative example 8 compared with, embodiment 6 ~ 10 employ comprise the monomeric unit being derived from farnesene polymkeric substance (A-1) ~ (A-5) for low viscosity and quick solidification is excellent, and the elongation at break of gained cured article is high, hardness is low, flexibility is excellent.In addition, employ the resin combination described in embodiment 11 ~ 14 of polymkeric substance (A-3) compared with the resin combination of comparative example 8, viscosity is low, curing speed be equal or equal more than.

Embodiment 6 ~ 14 and employ urethane acrylate (II-X-1) and replace the polymkeric substance comprising farnesene monomer comparative example 4 compared with, cure shrinkage and excellent moisture permeability.

It should be noted that, gelation is there is in the polymkeric substance (II-X-2) used in comparative example 5 in the process of 2-hydroxyethyl methacrylate modification body manufacturing poly-farnesene, uniform polymkeric substance cannot be obtained, insoluble in a solvent, therefore cannot carry out the mensuration of number-average molecular weight, methacryloyl equivalent.In addition, the evaluation as other resin combination also cannot be carried out.

The cured article obtained in embodiment is transparent, and on the other hand, the cured article obtained in comparative example 6,7 produces gonorrhoea, or more crisp, therefore cannot carry out various evaluation.Comparative example 6,7 employs the polymkeric substance without polymerizable functional group, therefore can think with the poor compatibility of other composition, polymkeric substance after hardening in there occurs and be separated.

Known: to have combinationally used in the embodiment 15 ~ 23 of hindered amine based compound (E), even if the velocity of variation of form and aspect stability, modulus in tension is also less in high temperature environments, excellent heat resistance.

[embodiment of the 3rd aspect of the present invention]

The each composition used in the embodiment of Third Way and comparative example is as follows.

< has polymkeric substance (A) > of polymerizable functional group

The polymkeric substance (A-1) used in the embodiment 1,3 and 5 of first method, (A-3) and (A-5).

< polymkeric substance (B) >

Polymkeric substance (B-1) ~ (B-3) obtained by aftermentioned Production Example 6 ~ 8.

< polymerization starter (C) >

Polymerization starter (C-1)

2-hydroxy-2-methyl-1-phenyl-propane-1-ketone

BASF Co., Ltd. system, trade(brand)name " DAROCUR1173 ".

< monomer (D) >

Acrylic monomer (D-1)

Dicyclopentenyl oxygen base ethylmethyl acrylate

Hitachi Chemical Co., Ltd.'s system, trade(brand)name " Off ァ Application Network リ Le FA-512M ".

< hindered amine based compound (E) >

Hindered amine based compound (E-1)

BASF Co., Ltd. system, trade(brand)name " TINUVIN765 ".

< Production Example 6 ~ 8>

Production Example 6: aqueous polyhutadiene (B-1)

By making divinyl and n-Butyl Lithium, in as the normal hexane of initiator, anionoid polymerization occur, synthesize the aqueous polyhutadiene (hereinafter also referred to as " polymkeric substance (B-1) ") that number-average molecular weight is 9,000.The physical property of polymkeric substance (B-1) is shown in table 7.

Production Example 7: aqueous polyisoprene (B-2)

By making isoprene and n-Butyl Lithium, in as the normal hexane of initiator, anionoid polymerization occur, thus obtain the aqueous polyisoprene that number-average molecular weight is 9,000.(hereinafter also referred to as " polymkeric substance (B-2) ").The physical property of polymkeric substance (B-2) is shown in table 7.

Production Example 8: aqueous polyisoprene (B-3)

By making isoprene and n-Butyl Lithium, in as the normal hexane of initiator, anionoid polymerization occur, thus obtain the aqueous polyisoprene (hereinafter also referred to as " polymkeric substance (B-3) ") that number-average molecular weight is 20,000.The physical property of polymkeric substance (B-3) is shown in table 7.

[table 7]

< embodiment 24 ~ 34>

Polymkeric substance (A-1), (A-3) and (A-5), polymkeric substance (B-1) ~ (B-3), polymerization starter (C), monomer (D-1) and hindered amine based compound (E-1) are fed in stainless steel 300mL container with the ratio shown in table 8 and table 9, agitating vane is at room temperature used to mix 20 minutes, thus preparation 200g resin combination.Utilize following method to evaluate gained resin combination.Show the result in table 8 and table 9.

The evaluation method of the embodiment of Third Way is as follows.

(III-1) mensuration of number-average molecular weight and molecular weight distribution

The method identical with (I-1) of first method is utilized to measure.It should be noted that, in table 7, one decimal place rounded up and record with integer.

(III-2) melt viscosity

For the resin combination obtained in the polymkeric substance obtained in Production Example 1,3,5 ~ 8 and embodiment, the method identical with (I-3) of first method is utilized to measure.

(III-3) second-order transition temperature

The each polymkeric substance 10mg obtained in Production Example 1,3,5 ~ 8 is taked in aluminium dish, utilizes means of differential scanning calorimetry to measure (DSC) and measure thermogram under the heat-up rate condition of 10 DEG C/min, the summit value of DDSC is denoted as second-order transition temperature.

(III-4) the polymerizable functional group number of average 1 molecular chain

For polymkeric substance (A-1), (A-3) and (A-5), the method identical with (I-2) of first method is utilized to measure.It should be noted that, in table 7, one decimal place rounded up and record with integer.

(III-5) outward appearance (transparency)

For the resin combination obtained in embodiment, the method identical with (I-5) of first method is utilized to make cured article.After gained cured article peels off PET film, carry out visual observation, evaluate the transparency according to following benchmark.

< metewand >

5: water white transparency

4: observe pole slightly painted, but be transparent

3: observe slightly painted, but be transparent

2: observe obviously painted, but be transparent

1: opaque.

(III-6) breaking tenacity and elongation at break

For the cured article obtained in above-mentioned (III-5), the method identical with (II-7) of second method is utilized to measure.

[table 8]

[table 9]

Comparative example 24 respectively, 25, 26, 29, 30 with second method embodiment 6, embodiment 27 and second method embodiment 8, and embodiment 28 is with known during second method embodiment 10: containing as (A) composition, there is in molecule the aqueous poly-farnesene of modification of polymerizable functional group and methacryloyl and give in outward appearance as the resin combination of the aqueous diene series rubber of (B) composition by active energy ray-curable, elongation at break aspect is no less than the cured article of second method.And then owing to containing (B) composition and aqueous diene series rubber, therefore under the condition maintaining the transparency, breaking tenacity is significantly improved.In addition, melt viscosity also reduce, operability improve.

[embodiment of the 4th aspect of the present invention]

The each composition used in the embodiment of fourth way and comparative example is as follows.

< has polymkeric substance (A) > of polymerizable functional group

The polymkeric substance (A-1) used in the embodiment 1 and 3 of first method and (A-3).

< polymkeric substance (B) >

The polymkeric substance (B-1) utilizing the Production Example 6 and 7 of Third Way to obtain and (B-2).

< polymerization starter (C) >

Polymerization starter (C-1)

2-hydroxy-2-methyl-1-phenyl-propane-1-ketone

BASF Co., Ltd. system, trade(brand)name " DAROCUR1173 ".

< monomer (D) >

Acrylic monomer (D-1)

Dicyclopentenyl oxygen base ethylmethyl acrylate

< hindered amine based compound (E) >

Hindered amine based compound (E-1)

BASF Co., Ltd. system, trade(brand)name " TINUVIN765 ".

< polymkeric substance (F-1) >

The polymkeric substance (F-1) obtained by following Production Example 9.

Production Example 9: the aqueous polyisoprene of modification (F-1) in molecule with methacryloyl

Make isoprene and n-Butyl Lithium carry out anionoid polymerization in as the normal hexane of initiator, thus obtain the polyisoprene that number-average molecular weight is 36,000.

Then, for foregoing unmodified polymkeric substance, react in the same manner as the Production Example 1 of first method, thus synthesized the aqueous polyisoprene of the modification in molecule with methacryloyl (hereinafter also referred to as " polymkeric substance (F-1) ").For polymkeric substance (F-1), have rated physical property in the same manner as (III-1) in Third Way ~ (III-6).Show the result in table 10.

[table 10]

< embodiment 35 ~ 38>

Polymkeric substance (A-1) or (A-3), polymkeric substance (F), polymkeric substance (B-1) or (B-2), polymerization starter (C-1), monomer (D-1) and hindered amine based compound (E-1) are fed in stainless steel 300mL container with the ratio shown in table 11, agitating vane is at room temperature used to mix 20 minutes, thus preparation 200g resin combination.Utilize following method to evaluate gained resin combination.Show the result in table 11.

Evaluation method in the embodiment of fourth way is as follows.

(IV-1) melt viscosity

For the resin combination obtained in embodiment, the method identical with (I-3) of first method is utilized to measure.

(IV-2) outward appearance (transparency)

< metewand >

5: water white transparency

4: observe pole slightly painted, but be transparent

3: observe slightly painted, but be transparent

2: observe significantly painted, but be transparent

1: opaque.

(IV-3) breaking tenacity and elongation at break

About the cured article obtained in above-mentioned (IV-2), the method identical with (II-7) of second method is utilized to measure.

[table 11]

Respectively comparative example 35 and first method embodiment 3, embodiment 36 and second method embodiment 8, embodiment 37 and Third Way embodiment 27 and embodiment 38 are with known during Third Way embodiment 31: on the basis of polymkeric substance (A), also coordinated the composition of polymkeric substance (F) also can give cured article no less than alternate manner because of active energy ray-curable.

Claims

1. polymkeric substance, wherein, comprises as the monomeric unit forming polymkeric substance the monomeric unit (a1) being derived from farnesene, and has polymerizable functional group.

2. polymkeric substance according to claim 1, wherein, polymerizable functional group is be selected from least a kind that can have in substituent (methyl) acryl, epoxy group(ing), oxetanylmethoxy, vinyl ether and alkoxysilyl.

3. the polymkeric substance described in claim 1 or 2, its melt viscosity at 38 DEG C is 0.1 ~ 3000Pas.

4. the polymkeric substance according to any one of claim 1 ~ 3, its number-average molecular weight is 1000 ~ 1,000,000.

5. the polymkeric substance according to any one of claim 1 ~ 4, wherein, the monomeric unit forming polymkeric substance only comprises the monomeric unit (a1) being derived from farnesene.

6. the polymkeric substance according to any one of claim 1 ~ 4, wherein, the monomeric unit forming polymkeric substance contains the monomeric unit (a1) being derived from farnesene and the monomeric unit (a2) being derived from the monomer beyond farnesene.

7. polymkeric substance according to claim 6, wherein, monomeric unit (a2) is for being derived from the monomeric unit of the conjugated diene compound beyond farnesene.

8. polymkeric substance according to claim 6, wherein, monomeric unit (a2) is for being derived from the monomeric unit of aromatic ethenyl compound.

9. polymkeric substance according to claim 8, wherein, aromatic ethenyl compound is be selected from least a kind in vinylbenzene, alpha-methyl styrene and 4-vinyl toluene.

10. the polymkeric substance according to any one of claim 1 ~ 9, wherein, the denary logarithm value of melt viscosity at 38 DEG C and the ratio [the denary logarithm value/number-average molecular weight (Mn) of the melt viscosity at 38 DEG C] of number-average molecular weight (Mn) are less than 0.000060.

The manufacture method of the polymkeric substance according to any one of 11. claims 1 ~ 10, it possesses following operation:

Preparation comprises the monomeric unit (a1) that is derived from farnesene and does not have the operation (1) of the unmodified polymer of polymerizable functional group; And, this unmodified polymer is imported to the operation (2) of polymerizable functional group.

The manufacture method of 12. polymkeric substance according to claim 11, wherein, operation (2) is the operation reacted with the compound with polymerizable functional group again after making unmodified polymer and reacting for the compound carrying out grafting to it.

13. resin combinations, it contains the polymkeric substance (A) according to any one of claim 1 ~ 10.

14. resin combinations according to claim 13, it is also containing polymerization starter (C).

15. resin combinations, it contains polymkeric substance (A), monomer (D) and polymerization starter (C) according to any one of claim 1 ~ 10, polymkeric substance (A) is 0.01 ~ 99 with the mass ratio [(A)/(D)] of monomer (D), relative to total 100 mass parts of polymkeric substance (A) and monomer (D), the polymerization starter (C) containing 0.1 ~ 20 mass parts.

16. resin combinations according to claim 15, wherein, relative to total 100 mass parts of polymkeric substance (A) and monomer (D), the hindered amine based compound (E) also containing 0.01 ~ 10 mass parts.

17. resin combinations, it contains polymkeric substance (A) according to any one of claim 1 ~ 10, comprise the monomeric unit of the conjugated diene compound (b1) being derived from carbonatoms less than 12 and do not have polymkeric substance (B) and the polymerization starter (C) of polymerizable functional group, and polymkeric substance (A) is 0.01 ~ 100 with the mass ratio [(A)/(B)] of polymkeric substance (B).

18. resin combinations according to claim 17, wherein, the content of polymerization starter (C) is 0.1 ~ 20 quality % in the total amount of resin combination.

Resin combination described in 19. claims 17 or 18, wherein, the conjugated diene compound (b1) of carbonatoms less than 12 is for being selected from least a kind in isoprene and divinyl.

Resin combination according to any one of 20. claims 17 ~ 19, wherein, relative to total 100 mass parts of polymkeric substance (A) and polymkeric substance (B), the monomer (D) also containing 0.01 ~ 1,000 mass parts.

Resin combination according to any one of 21. claims 17 ~ 20, wherein, the hindered amine based compound (E) also containing 0.01 ~ 10 quality % in the total amount of resin combination.

Resin combination according to any one of 22. claims 13 ~ 21, it is also containing polymkeric substance (F), described polymkeric substance (F) comprises the monomeric unit of the conjugated diene compound (f1) being derived from carbonatoms less than 12 and has polymerizable functional group, and polymkeric substance (A) is 0.01 ~ 100 with the mass ratio [(A)/(F)] of polymkeric substance (F).

23. cured articles, it makes the resin composition according to any one of claim 13 ~ 22 obtain.

24. optics tackiness agents, it contains cured article according to claim 23.

25. optics tackiness agents, it contains the resin combination according to any one of claim 13 ~ 22.