CN105829372B - Resin combination, the resin combination is cured made of solidfied material and optics adhesive containing the resin combination - Google Patents

Abstract

A kind of resin combination contains comprising the monomeric unit from conjugated diene compound（a1）And the polymer with polymerizable functional group（A）, include the monomeric unit from farnesene（b1）And the polymer without polymerizable functional group（B）And polymerization initiator（C）, polymer（A）With polymer（B）Mass ratio [（A）/（B）] it is 0.01~100.

Description

Resin combination, by the resin combination cure made of solidfied material and contain the tree The optics adhesive of oil/fat composition

Technical field

The present invention relates to the resin combination containing the polymer comprising the monomeric unit from farnesene, by the resin Solidfied material and the optics adhesive containing the resin combination made of composition solidification.

Background technology

In recent years, along with the electronic equipment, universal such as smart mobile phone, tablet PC with screens such as liquid crystal, with The research of transparent resin material and transparent resin bonding agent that the mode of cover screen uses is prevailing.

For example, having been recorded in patent document 1 comprising having in the molecule（Methyl）Polyisoprene, the list of acryloyl group Function（Methyl）In the composition of acrylate monomer and radical polymerization initiator, further cooperation do not have in the molecule The hardening resin composition obtained from amine compound that is obstructed of secondary amino group.

In addition, having been recorded in patent document 2 containing epoxy resin, curing agent and the epoxy containing specific quantity in the molecule Base and with specific number-average molecular weight epoxidized polybutadiene compositions of thermosetting resin.

It should be noted that, although the polymer of β-farnesene has been recorded in patent document 3,4, but fully research is not real Purposes.

Existing technical literature

Patent document

Patent document 1:No. 5073400 bulletins of Japanese Patent No.

Patent document 2:No. 4098107 bulletins of Japanese Patent No.

Patent document 3:International Publication No. 2010/027463

Patent document 4:International Publication No. 2010/027464.

The content of invention

Problems to be solved by the invention

For the hardening resin composition described in patent document 1,2, from the viewpoint of improving coating, glue There are rooms for improvement in terms of degree, required strong in the electronic equipment with screens such as liquid crystal in addition, about its solidfied material There is also rooms for improvement for degree, flexibility and transparency etc..

The present invention is completed in view of above-mentioned actual conditions, and it is low and can form intensity, softness to provide a kind of viscosity Property and transparent excellent solidfied material resin combination, the resin combination is cured made of solidfied material and contain the tree The optics adhesive of oil/fat composition.

Means for solving the problems

Present inventor has performed further investigations, as a result, it has been found that, contained comprising from conjugated diene with specific ratio Close object monomeric unit and with polymerizable functional group polymer and comprising the monomeric unit from farnesene and not The resin combination of polymer with polymerizable functional group be low viscosity, and can be formed intensity, flexibility, hardness and thoroughly The excellent solidfied material of bright property, so as to complete the present invention.

That is, the present invention is using the following contents as main points.

[ 1 ] resin combination contains comprising the monomeric unit from conjugated diene compound（a1）And has and can gather The polymer of the functional group of conjunction（A）, include the monomeric unit from farnesene（b1）And without polymerizable functional group Polymer（B）And polymerization initiator（C）, polymer（A）With polymer（B）Mass ratio [（A）/（B）] it is 0.01~100.

[ 2 ] solidfied material, being will be obtained from the resin combination solidification described in aforementioned [ 1 ].

[ 3 ] optics adhesive contains the resin combination described in aforementioned [ 1 ].

The effect of invention

Through the invention, it is possible to provide a kind of viscosity is low and can form intensity, flexibility and transparent excellent solidfied material Resin combination, the resin combination is cured made of solidfied material and optics adhesive containing the resin combination.

Specific implementation mode

[ resin combination ]

The resin combination of the present invention contains comprising the monomeric unit from conjugated diene compound（a1）And with can The polymer of the functional group of polymerization（A）, include the monomeric unit from farnesene（b1）And do not have polymerizable functional group Polymer（B）And polymerization initiator（C）, polymer（A）With polymer（B）Mass ratio [（A）/（B）] it is 0.01~100.

< polymer（A）>

Polymer（A）Including from the monomeric unit of conjugated diene compound（a1）, and there is polymerizable functional group.

As monomeric unit（a1）Conjugated diene compound be preferably farnesene and carbon atom number 12 it is below conjugation two Ene compound, as 12 conjugated diene compound below of carbon atom number, for example, butadiene, isoprene, 2,3- can be enumerated Dimethyl butadiene, 2- phenyl butadienes, 1,3-pentadiene, 2- methyl-1s, 3- pentadienes, 1,3- hexadienes, 1,3- Octadiene, 1,3- cyclohexadiene, 2- methyl-1s, 3- octadienes, 1,3,7- sarohornenes, myrcene and chlorobutadiene etc..Its In, more preferable farnesene, isoprene and butadiene.These conjugated diene compounds can be used alone a kind, also can and with 2 kinds More than.

Foregoing sources can be derived from the monomeric unit of α-farnesene in the monomeric unit of farnesene, can also be and Derived from following formula（I）The monomeric unit of β-farnesene of expression preferably derives from β-from the viewpoint of ease of manufacturing The monomeric unit of farnesene.It should be noted that also can and with α-farnesene and β-farnesene.

[changing 1]

As aforementioned polymerizable functional group, for example, can enumerate（Methyl）Acryloyl group, epoxy group, oxetanylmethoxy, second Alkenyl ether groups, alkoxysilyl,（Methyl）Acrylamido, styryl, dimaleoyl imino, lactone group, interior acyl Amido, thioether group, Thietane base, acetonide（acetonide）Base, ghiourea group etc..In these, it is preferably selected from（First Base）It is at least one kind of in acryloyl group, epoxy group, oxetanylmethoxy, vinyl ether group and alkoxysilyl, more preferably （Methyl）Acryloyl group.It should be noted that these functional groups can have substituent group.

In this specification, "（Methyl）Acryloyl group " refers to " acryloyl group or methylacryloyl ".In addition, this specification In, "（Methyl）Acrylic acid " refers to " acrylic or methacrylic acid ".

As the polymer used in the manufacture present invention（A）The 1st method, for example, following methods can be enumerated：By will before Conjugated diene compound and the as needed monomer polymerization other than further existing aforementioned conjugated diene compound are stated, to make The standby unmodified polymer for not having polymerizable functional group, polymerizable functional group is imported to the unmodified polymer.

Specifically, following methods can be enumerated：Make by aforementioned each monomer obtained from active anionic polymerization do not change Property polymer, reacted for carrying out the compound of grafting with maleic anhydride etc., next, with methacrylic acid 2- hydroxyl second There is ester etc. the compound of polymerizable functional group to react.

As the compound for carrying out grafting for foregoing unmodified polymer, for example, maleic anhydride, lemon can be enumerated The unsaturated carboxylic acid anhydrides such as health acid anhydrides, 2,3- dimethyl maleic anhydrides, itaconic anhydride；Maleic acid, fumaric acid, citraconic acid, itaconic acid Equal unsaturated carboxylic acids；The esters of unsaturated carboxylic acids such as maleate, fumarate, citraconate, itaconate；Maleic amide, rich horse The unsaturation carboxylic acid amides such as amide, citraconoyl amine, clothing health amide；Maleimide, fumarimide, citraconimide, clothing health acyl The unsaturated carboxylic acids acid imide such as imines；Maleimide, vinyltrimethoxysilane, γ-methacryloxypropyl three Methoxy silane etc..

In addition, as the aforementioned compound with polymerizable functional group, for example, can enumerate（Methyl）Acrylic acid；Propylene Sour 2- hydroxy methacrylates, 2-hydroxyethyl methacrylate, acrylic acid 2- hydroxy propyl esters, pentaerythritol triacrylate, season penta Tetrol trimethyl acrylic ester, dipentaerythritol monohydroxy acrylate etc.（Methyl）Acrylate；2- hydroxyethylvinyls Ether, N-（2- hydroxyethyls）Acrylamide, N-（2- hydroxyethyls）Methacrylamide, N-（2- hydroxyethyls）Malaysia Acid imide, 4-Vinyl phenol etc..It should be noted that the position that can import polymerizable functional group can be polymer Polymerizable end can also be side chain.In addition, above-mentioned functional group can combine it is one kind or two or more.

As the polymer used in the manufacture present invention（A）The 2nd method, for example, following methods can be enumerated：Passing through profit The work of active anionic polymerization unmodified polymer obtained from is carried out to aforementioned conjugated diene compound with aftermentioned method Property end, make at least one be selected from hydroxyl, carboxyl, carbonyl, thiocarbonyl, etheride base, anhydride group, thiocarboxylic acid base, Aldehyde radical, thioformyl, carboxylate, amide groups, sulfonic group, sulfonate group, phosphate, phosphate-based, amino, imino group, itrile group, Pyridyl group, quinolyl, epoxy group, epithio base, thioether group, isocyanate group, isothiocyanate group, silanol group, alkoxyl silicone The compound of functional group in alkane, silyl halide, halogenation tinbase, alkoxy tinbase and phenyl tinbase etc. carries out addition reaction, connects Get off, it is made to be reacted with the compound with polymerizable functional group.

As for aforementioned conjugated diene compound carry out active anionic polymerization active anionic polymerization initiator, For example, lithium methide, ethyl-lithium, n-BuLi, s-butyl lithium, tert-butyl lithium, hexyl lithium, phenyl lithium, stibene can be enumerated The organo monolithium compounds such as lithium；Two lithium methane, two lithium naphthalenes,-two lithium butane of Isosorbide-5-Nitrae,-two lithium -2- ethyl cyclohexanes of Isosorbide-5-Nitrae, 1, The multi-functional organo-lithium compounds such as 3,5- tri- lithium benzene；Sodium naphthalene, potassium naphthalene etc..In addition, also can and use and organic alkali metal compound It reacts, the compounds such as di isopropenylbenzene, dibenzyl toluene that multifunctional organic alkali metal compound is provided.

In addition, addition reaction, compound at least one aforementioned functional groups are carried out as in reactive terminal, for example, The cyclic ethers such as epoxides, oxetanes can be enumerated；The cyclic amines such as pyrrolidines；Cyclic thioethers such as thiirane etc..

As the polymer used in the manufacture present invention（A）The 3rd method, following methods can be enumerated：Utilize aftermentioned side Method, by conjugated diene compound and the monomer polymerization as needed and other than further existing conjugated diene compound, thus Unmodified polymer is prepared, epoxidation is carried out to the unmodified polymer, then makes the compound for the functional group for having polymerizable Reaction.As for by the epoxidised compound of foregoing unmodified polymer, for example, peracetic acid can be enumerated, benzylhydroperoxide waited Acid.

As the compound with polymerizable functional group in these methods, for example, acrylic acid, metering system can be enumerated The carboxylic acids such as acid.The position that polymerizable functional group can be imported can be the polymerizable end of polymer, can also be side chain.In addition, The aforementioned compound with polymerizable functional group can combine one kind or two or more.

When in order to inhibit when carrying out function dough to foregoing unmodified polymer or preserve polymer-modified, because of deterioration Caused by molecular weight reduction, discoloration and gelation, can be appropriate anti-in unmodified polymer or polymer-modified middle combination Aging agent.Specifically, 2,6- di-tert-butyl-4-methy phenols can be enumerated（BHT）, 2,2 '-di-2-ethylhexylphosphine oxides（4- first Base -6- tert-butyl phenols）, 4,4 '-thiobis（3 methy 6 tert butyl phenol）, 4,4 '-butylidenebis（3- first Base -6- tert-butyl phenols）（AO-40）, bis- [1, the 1- dimethyl -2- [3- of 3,9-（3- tertiary butyl-4-hydroxies- 5- aminomethyl phenyls）Propiono oxygroup] ethyl] -2,4,8,10- tetra- oxaspiro [5.5] hendecanes（AO-80）, 2,4- it is bis- [（Octylthio）Methyl] -6- methylphenols（Irganox 1520L）, 2,4- it is bis- [（Dodecyl sulfenyl）Methyl] -6- Methylphenol（Irganox 1726）, acrylic acid 2- [1-（2- hydroxyl -3,5- di-tert-pentyl-phenyls）Ethyl] -4,6- Di-tert-pentyl-phenyl ester（Sumilizer GS）, acrylic acid 2- tertiary butyls -6-（3- tertiary butyl -2- hydroxy-5-methyl bases Benzyl）- 4- methylbenzene base esters（Sumilizer GM）, 6- tertiary butyl -4- [3-（2,4,8,10- tetra-tert hexichol And [d, f] [miscellaneous English in heptan of 1,3,2] Delnavs（dioxaphosphepin）- 6- base oxygroups）Propyl] -2- methylphenols （Sumilizer GP）, phosphorous acid three（2,4- di-tert-butyl-phenyls）Ester（Irgafos 168）, 3,3 '-two thiobis propionic acid Double stearyls, quinhydrones, p methoxy phenol, N- phenyl-N '-（1,3- dimethylbutyl）P-phenylenediamine（ノクラッ ク6C）, decanedioic acid it is double（2,2,6,6- tetramethyl -4- piperidyls）Ester（LA-77Y）, N, the bis- octade-cylhydroxylamines of N- （Irgastab FS 042）, it is double（4- t-octyl phenyl）Amine（Irganox 5057）Deng.In addition, above-mentioned antiaging agent can be independent Using a kind, can also be used in combination of two or more.

For the additive amount of antiaging agent, relative to unmodified polymer or polymer-modified 100 mass parts, preferably For 0.01~10 mass parts, more preferably 0.1~3 mass parts.

Constitute polymer（A）Monomeric unit can be only by foregoing sources in the monomeric unit of conjugated diene compound（a1）Shape At also can be by foregoing sources in the monomeric unit of conjugated diene compound（a1）With the list other than conjugated diene compound The monomeric unit of body（a2）It is formed.That is, unmodified polymer can be obtained from only polymerizeing aforementioned conjugated diene compound Polymer can also be the copolymer of aforementioned conjugated diene compound and the monomer other than aforementioned conjugated diene compound.

When unmodified polymer is copolymer, the monomer list as monomer of the foregoing sources other than conjugated diene compound Member（a2）, the monomeric unit from aromatic vinyl compound can be enumerated.

As aromatic vinyl compound, for example, can enumerate styrene, α-methylstyrene, 2-methyl styrene, 3- methyl styrenes, 4- methyl styrenes, 4- propylstyrenes, 4- t-butyl styrenes, 4- cyclohexylstyrenes, 4- Dodecylstyrene, 2,4-DMS, 2,4- diisopropyls styrene, 2,4,6- trimethyl styrenes, 2- Ethyl -4- benzylstyrenes, 4-（Phenyl butyl）Styrene, 1- vinyl naphthalenes, 2- vinyl naphthalenes, vinyl anthracene, N, N- diethyl -4- amino-ethyls styrene, vinylpyridine, 4- methoxy styrenes, monochlorostyrene, dichloro-benzenes second Alkene, divinylbenzene etc..Wherein, optimization styrene, α-methylstyrene, 4- methyl styrenes.

When the monomeric unit using the monomer other than conjugated diene compound（a2）When, for deriving from conjugation two The monomeric unit of monomer other than ene compound（a2）Relative to the monomer list from conjugated diene compound in copolymer Member（a1）With the monomeric unit of the monomer other than conjugated diene compound（a2）Total amount ratio for, from reduce set From the viewpoint of the viewpoint of the viscosity of oil/fat composition, the good elongation characteristics for keeping cured film and flexibility, preferably 1~99 Quality %, more preferably 1~80 mass %, further preferably 1~70 mass %, still more preferably it is 1~50 mass %.

The polymer used in the present invention（A）Number-average molecular weight（Mn）Preferably 1,000~1,000,000,2 are more preferably, 000~500,000, be more preferably 8,000~500,000, further preferably 15,000~450,000, still more preferably be 15,000~ 300000, still more preferably it is 20,000~200,000.Polymer（A）Mn in aforementioned range when, the not only softness of solidfied material Property, mechanical strength improve, and resin combination become low viscosity.

It should be noted that the number-average molecular weight in this specification（Mn）Refer to using gel permeation chromatography（GPC）It measures Polystyrene conversion number-average molecular weight.

The polymer used in the present invention（A）38 DEG C at melt viscosity be preferably 0.1~3,000Pa s, more preferably For 0.2~3,000Pa s, more preferably 0.2~2,800Pa s, further preferably 0.3~2,600Pa s.Polymer（A） Melt viscosity in aforementioned range when, may not be present and unevenly, equably resin combination is applied on the face of being applied, because And coating becomes good.

It should be noted that in this specification, the melt viscosity of polymer is to utilize the side described in aftermentioned embodiment The value that method is found out.

The polymer used in the present invention（A）Every 1 strand polymerizable functional group number be preferably 1~150, More preferably 1.5~75, it is more preferably 1.5~30.The number of the polymerizable functional group of every 1 strand is in aforementioned range When interior, polymer can be reduced（A）Viscosity, also, curing rate can be improved, in turn, can contraction when curing be inhibited low.

It should be noted that the number of the polymerizable functional group of every 1 strand can be according to the following formula by polymer（A）'s Number-average molecular weight（Mn）And polymer（A）Functional equivalent（g/eq）It calculates.

（The number of the polymerizable functional group of every 1 strand）=（Mn）/（Functional equivalent）

Functional equivalent is the amount for indicating " molecular weight of the polymer of every 1 functional group ".For example, by polymerizable function Functional equivalent when group is methylacryloyl is known as " methylacryloyl equivalent ", refers to " every 1 methylacryloyl The molecular weight of polymer ".Functional equivalent can be calculated based on the reactivity of modifying agent, it is possible to use infra-red sepectrometry, nuclear-magnetism are total The various analysis machines such as vibration wave spectrometry are found out.

The polymer used in the present invention（A）It can be used alone a kind, can also be used in mixed way monomeric unit, molecular weight and official Can group the respectively different aforementioned polymer of more than two kinds of type（A）.

Polymer in resin combination total amount（A）Content be preferably 1~99 mass %, more preferably 2~98 mass %, Further preferably 5~95 mass %, still more preferably be 10~90 mass %, be still more preferably 15~85 mass %.Tree Polymer in oil/fat composition（A）Content within the above range when, intensity, flexibility and the transparency can be formed and excellent consolidated Compound.

< polymer（B）>

Polymer（B）It is comprising the monomeric unit from farnesene（b1）And it is poly- without polymerizable functional group Close object.As the farnesene, can be used and in polymer above-mentioned（A）The identical farnesene of the middle farnesene illustrated.It constitutes Polymer（B）Monomeric unit can only origin be derived from farnesene monomeric unit（b1）Formed, also can origin derived from farnesene Monomeric unit（b1）With the monomeric unit of the monomer other than farnesene（b2）It is formed.

Monomeric unit as the monomer other than farnesene（b2）, can enumerate from conjugated diene compound and The monomeric unit of aromatic vinyl compound.

As conjugated diene compound, preferably 12 conjugated diene compound below of carbon atom number, as carbon atom number 12 conjugated diene compounds below, for example, butadiene, isoprene, 2,3- dimethyl butadienes, 2- phenyl fourths can be enumerated Diene, 1,3-pentadiene, 2- methyl-1s, 3- pentadienes, 1,3- hexadienes, 1,3- octadienes, 1,3- cyclohexadiene, 2- methyl-1s, 3- octadienes, 1,3,7- sarohornenes, myrcene, chlorobutadiene etc..Wherein, more preferable isoprene, fourth two Alkene.These conjugated diene compounds can be used alone a kind, can also be used in combination of two or more.

As aromatic vinyl compound, for example, can enumerate styrene, α-methylstyrene, 2-methyl styrene, 3- methyl styrenes, 4- methyl styrenes, 4- propylstyrenes, 4- t-butyl styrenes, 4- cyclohexylstyrenes, 4- Dodecylstyrene, 2,4-DMS, 2,4- diisopropyls styrene, 2,4,6- trimethyl styrenes, 2- Ethyl -4- benzylstyrenes, 4-（Phenyl butyl）Styrene, 1- vinyl naphthalenes, 2- vinyl naphthalenes, vinyl anthracene, N, N- diethyl -4- amino-ethyls styrene, vinylpyridine, 4- methoxy styrenes, monochlorostyrene, dichloro-benzenes second Aromatic vinyl compounds such as alkene, divinylbenzene etc..Wherein, optimization styrene, α-methylstyrene, 4- methylbenzene second Alkene.

When the monomeric unit using the monomer other than farnesene（b2）When, for the list other than farnesene The monomeric unit of body（b2）Relative to the monomeric unit from farnesene in copolymer（b1）With other than farnesene Monomer monomeric unit（b2）Total amount ratio for, from reduce resin combination viscosity viewpoint, improve solidification speed The viewpoint of degree and from the viewpoint of keeping good elongation characteristics and the flexibility of cured film, it is preferably 1~99 mass %, more excellent It is selected as 1~80 mass %, further preferably 1~70 mass %, is still more preferably 1~50 mass %.

The polymer used in the present invention（B）Number-average molecular weight（Mn）Preferably 1,000~1,000,000, it is more preferably 1, 000~500,000, be more preferably 1,000~200,000, further preferably 5,000~200,000, still more preferably be 5,000~15 Ten thousand.Polymer（B）Mn in aforementioned range when, not only the flexibility of solidfied material, mechanical strength improve, but also resin combination As low viscosity.

The polymer used in the present invention（B）38 DEG C at melt viscosity be preferably 0.1~3,000Pa s, more preferably For 0.2~3,000Pa s, more preferably 0.2~2,800Pa s, further preferably 0.3~2,600Pa s.Polymer（B） Melt viscosity in aforementioned range when, may not be present and unevenly, equably resin combination is applied on the face of being applied, because And coating becomes good.

The polymer used in the present invention（B）Molecular weight distribution（Mw/Mn）Preferably 1.0~8.0,1.0 are more preferably ~5.0, it is more preferably 1.0~3.0.When Mw/Mn is in aforementioned range, obtained polymer（B）Viscosity deviation become It is small.

The polymer used in the present invention（B）Glass transition temperature according to combination（Microstructure）, derive from The amount of monomer other than the monomer of farnesene and the farnesene further used as needed and change, preferably -90~0 DEG C Range, more preferably -90~-10 DEG C of range.For aforementioned range when, soft solidfied material can be obtained, as this hair In the optics adhesive of one of bright purposes, layer difference following, impact absorbency become good.

The polymer used in the present invention（B）It can be used alone a kind, can also be used in mixed way monomeric unit, molecular weight difference Different aforementioned polymers of more than two kinds（B）.The polymer used in the present invention（B）Using emulsion polymerization or international public affairs Open No. 2010/027463, method described in International Publication No. 2010/027464 etc. manufactures.Wherein, preferred emulsion is poly- Legal or solution polymerization process, further preferred solution polymerization process.

（Emulsion polymerization）

As polymer in order to obtain（B）Emulsion polymerization, well known method can be applied.For example, depositing in emulsifier In the lower farnesene monomer emulsion dispersion by specified amount, emulsion polymerization is carried out using radical polymerization initiator.

As emulsifier, for example, the hard soap or rosinate of 10 or more carbon atom number can be used.As specific Example, can enumerate the sylvite or sodium salt of the aliphatic acid such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid.

As dispersant, usually can be used water, also can be when not damaging polymerization stability in the range of, containing methanol, The water-miscible organic solvents such as ethyl alcohol.

As radical polymerization initiator, for example, persulfate as ammonium persulfate, potassium peroxydisulfate, organic can be enumerated Peroxide, hydrogen peroxide etc..

In order to adjust the molecular weight of polymer, chain-transferring agent also can be used.As chain-transferring agent, for example, uncle ten can be enumerated The thio-alcohols such as dialkyl group mercaptan, n-dodecyl mercaptan；Carbon tetrachloride, thioacetic acid, diterpene, terpineol, γ-terpinenes, α-methylstyrenedimer etc..

Emulsion polymerization temperature can suitably be selected according to the type of the radical polymerization initiator used, it is often preferred that 0 ~100 DEG C, more preferably 0~60 DEG C.Polymerization methods can be any one of continuous polymerization, batch polymerization.Polymerisation can It is terminated by adding polymerization terminator.

As polymerization terminator, for example, can enumerate the amine compounds such as isopropyl hydroxyl amine, diethylhydroxylamine, hydroxylamine, The oxime-based compounds such as quinhydrones, benzoquinones, sodium nitrite etc..

After polymerisation terminates, as needed, antiaging agent can be added.After polymerisation terminates, as needed, from obtaining Latex remove unreacted monomer, next, using salt such as sodium chloride, calcium chloride, potassium chloride as coagulator, as needed, one The acid such as nitric acid, sulfuric acid are added on side, and the pH of coagulation system is adjusted to defined value, on one side solidifies polymer, then separation point Solvent is dissipated, polymer is recycled.Next, after washing, dehydration, it is dried, this makes it possible to obtain polymer.It needs to illustrate It is that, in solidification, as needed, can be mixed with the filling oil for forming emulsified dispersed liquid with latex in advance, with oil-filled polymer Form recycling.

（Solution polymerization process）

As the solution polymerization process of polymer in order to obtain, well known method can be applied.For example, in a solvent, using neat Lattice strangle series catalysts, metallocene series catalysts, the active metal that can carry out anionic polymerisation, according to expectation, in polar compound In the presence of, by farnesene monomer polymerization.

As the active metal of anionic polymerisation can be carried out, for example, the alkali metal such as lithium, sodium, potassium can be enumerated；Beryllium, magnesium, calcium, The alkaline-earth metal such as strontium, barium；Lanthanide rares metalloid such as lanthanum, neodymium etc..Wherein, preferably alkali and alkaline earth metal ions, particularly preferably For alkali metal.In addition, it may be more preferable to use organic alkali metal compound.

As solvent, for example, the aliphatic such as normal butane, pentane, isopentane, n-hexane, normal heptane, isooctane can be enumerated Hydrocarbon；The ester ring type hydrocarbons such as pentamethylene, hexamethylene, methyl cyclopentane；Aromatic hydrocarbons such as benzene,toluene,xylene etc..

As organic alkali metal compound, for example, lithium methide, ethyl-lithium, n-BuLi, s-butyl lithium, tertiary fourth can be enumerated The organo monolithium compounds such as base lithium, hexyl lithium, phenyl lithium, stibene lithium；Two lithium methane, two lithium naphthalenes ,-two lithium fourth of Isosorbide-5-Nitrae The multi-functional organo-lithium compounds such as alkane,-two lithium -2- ethyl cyclohexanes of Isosorbide-5-Nitrae, 1,3,5- tri- lithium benzene；Sodium naphthalene, potassium naphthalene etc.. Wherein, preferably organo-lithium compound, more preferably organo monolithium compounds.The usage amount of organic alkali metal compound can basis The molecular weight of required polymer is suitably determined, relative to the monomer other than farnesene and farnesene used as needed 100 mass parts of total amount, preferably 0.01~7 mass parts.

In addition, the secondary amine such as organic alkali metal compound and dibutylamine, dihexyl amine, dibenzyl amine can also reacted, with The form of organic alkali metal amide uses.

Polar compound is to adjust the microstructure at farnesene position with not making reaction inactivation in anionic polymerisation And use, for example, the ether compounds such as dibutyl ethers, tetrahydrofuran, ethylene glycol Anaesthetie Ether can be enumerated；Tetramethylethylenediamine, The tertiary amines such as Trimethylamine；Alkali metal alcoholates, phosphine compound etc..Polar compound can be with excellent relative to organic alkali metal compound The range for being selected as 0.01~1000 molar equivalent uses.

The temperature of polymerisation is usually -80~150 DEG C, preferably 0~100 DEG C, further preferably 10~90 DEG C Range.Polymerization methods can be any one of batch-type or continous way.

For polymerisation, the alcohol such as methanol, isopropanol can be added and terminate reaction as polymerization terminator.It will obtain Polymerization liquid be injected into the poor solvents such as methanol, so that polymer is precipitated, alternatively, polymerization liquid is washed with water, detach Afterwards, it is dried, thus separates polymer.

In the present invention, aforementioned polymer（A）With aforementioned polymer（B）Mass ratio [（A）/（B）] it is 0.01~100, excellent Be selected as 0.05~100, more preferably 0.1~50, further preferably 0.1~25, be still more preferably 0.1~10.It is aforementioned Mass ratio（A）/（B）When in aforementioned range, viscosity is sufficiently low, the good resin combination of the elongation at break after being cured Object.

In the present invention, preferred polymers（A）And polymer（B）At least one of 38 DEG C at melt viscosity be 0.1 ~3,000Pa s, more preferable polymer（A）And polymer（B）The melt viscosity of the two is the range of 0.1~3,000Pa s.

< polymerization initiators（C）>

Polymerization initiator used in the present invention（C）, the irradiation using ultraviolet light isoreactivity energy-ray can be enumerated The Photoepolymerizationinitiater initiater of equal initiated polymerizations, the thermal polymerization reacted using thermal-initiated polymerization.Wherein, from using short The irradiation of time and by resin solidification and obtained in the case of not making substrate deterioration solidfied material it is such from the viewpoint of, it is excellent It is selected as Photoepolymerizationinitiater initiater, more preferably utilizes the Photoepolymerizationinitiater initiater of ultraviolet irradiation initiated polymerization.It is poly- as light Initiator is closed, for example, cationic system Photoepolymerizationinitiater initiater, free base system polymerization initiator can be enumerated.

As cationic system Photoepolymerizationinitiater initiater, for example, aryl diazonium salt, aromatic iodonium salts, aromatics sulfonium salt, cyclopentadienyl can be enumerated Metal based compound etc..

Cationic system Photoepolymerizationinitiater initiater as aryl diazonium salt, it is known that " P-33（Trade name）"（Co., Ltd. ADEKA systems）Deng.

Cationic system Photoepolymerizationinitiater initiater as aromatic iodonium salts, it is known that " Rhodorsil Photo Initiator 2074（Trade name）"（ロ ー デ ィ ア Co. Ltd. systems）,"イルガキュア250（Trade name）"（BASF Co. Ltd. systems） Deng.

Cationic system Photoepolymerizationinitiater initiater as aromatics sulfonium salt, it is known that " FC-509（Trade name）"（Sumitomo ス リ ー エ System Co. Ltd. system）,"イルガキュア270（Trade name）"（BASF Co. Ltd. systems）Deng.

Cationic system Photoepolymerizationinitiater initiater as metallocene system, it is known that " イ Le ガ キ ュ ア 261（Trade name）"（BASF Co. Ltd. system）Deng.

As free base system Photoepolymerizationinitiater initiater, for example, acetophenone system, benzophenone series, alkyl phenones system, acyl can be enumerated Base phosphine oxide system, benzoin system, ketal system, anthraquinone system, disulfide system, thioxanthones system, thiuram system, fluorine amine system etc..It is wherein excellent Select 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, aminoalkyl benzene can be enumerated Ketone system etc..As the free base system Photoepolymerizationinitiater initiater of hydroxyalkylphenones system, " DAROCUR1173 can be enumerated（Trade name）" （2- hydroxy-2-methyl -1- phenyl-propane -1- ketone）,"イルガキュア184（Trade name）"（1- hydroxy cyclohexylphenyls Base phenyl ketone）,"イルガキュア2959（Trade name）"（1- [ 4-（2- hydroxyl-oxethyls）Phenyl ] -2- hydroxyls - 2- methyl-1s-propane -1- ketone）Deng.

As the free base system Photoepolymerizationinitiater initiater of amino alkylphenone system, " イ Le ガ キ ュ ア 907 can be enumerated（Commodity Name）"（2- methyl-1s-（4- methylsulfanylphenyls）- 2- morpholinyls（morpholino）Propane -1- ketone）,"イルガ キュア369（Trade name）"（2- benzyl -2- dimethylaminos -1-（4- morpholino phenyls）- 1- butanone）Deng.

As the free base system Photoepolymerizationinitiater initiater of acylphosphine oxide system, " LUCIRIN TPO can be enumerated（Trade name）"（2, 4,6- trimethyl benzoyl diphenyl base phosphine oxides）,"イルガキュア819（Trade name）"（It is double（2,4,6- trimethylbenzenes Formoxyl）Phenyl phosphine oxide）（It is BASF Co. Ltd. systems）Deng.

In these, preferably the free base system Photoepolymerizationinitiater initiater of hydroxyalkylphenones system, more preferably 2- hydroxyls- 2- methyl-1s-phenyl-propane -1- ketone.They can be used alone a kind, can also be used in combination of two or more.

Polymerization initiator（C）Content in the total amount of resin combination is preferably 0.1~20 mass %, more preferably 0.5 ~20 mass %, further preferably 1.0~20 mass %, still more preferably it is 1.0~15 mass %, most preferably 1.0~10 Quality %.Polymerization initiator（C）Content in aforementioned range when, be preferred from the aspect of curing rate and mechanics physical property.

< monomers（D）>

For the resin combination of the present invention, in order to further increase the viscosity of the resin combination, treatability and Intensity after solidification can contain monomer as needed（D）.As monomer（D）, preferably having can be with polymer（A）The official of reaction The compound that can be rolled into a ball, for example, can enumerate has in the molecule（Methyl）Acryloyl group, epoxy group, oxetanylmethoxy, vinyl ethers The compound of group, alkoxysilyl.

As specific compound, for example, can enumerate（Methyl）Methyl acrylate,（Methyl）Ethyl acrylate,（Methyl） Propyl acrylate,（Methyl）Butyl acrylate,（Methyl）Propylene acid butyl ethoxylated ester,（Methyl）Propylene acid butyl ethyl ester,（First Base）2-EHA,（Methyl）Lauryl acrylate,（Methyl）Acrylic acid double cyclopentenyl ester （dicyclopentenyl（meth）acrylate）,（Methyl）Acrylic acid double cyclopentenyl oxygroup ethyl ester （dicyclopentenyloxyethyl（meth）acrylate）,（Methyl）Acrylic acid Bicvclopentyl ester （dicyclopentanyl（meth）acrylate）,（Methyl）Acrylic acid Bicvclopentyl oxygroup ethyl ester （dicyclopentanyl oxyethyl（meth）acrylate）,（Methyl）Cyclohexyl acrylate,（Methyl）The different ice of acrylic acid Piece base ester,（Methyl）Acrylic acid 2- hydroxy methacrylates,（Methyl）Acrylic acid 2- hydroxy propyl esters,（Methyl）Acrylic acid phenoxy group hydroxyl Propyl ester,（Methyl）Acrylic acid morpholine ester,（Methyl）Phenoxyethyl acrylate,（Methyl）Acrylic acid N, N- diethylamino second Ester,（Methyl）Acrylic acid N, N- dimethylamino ethyl ester,（Methyl）Glycidyl acrylate, methoxyl group diethylene glycol（First Base）Acrylate, methoxyl group dipropylene glycol（Methyl）Acrylate, Nonylphenoxy polyethylene glycol（Methyl）Acrylate etc. is single Function（Methyl）Acrylate；

1,4-butanediol two（Methyl）Acrylate, 1,6- hexylene glycols two（Methyl）Acrylate, 1,9- nonanediols two （Methyl）Acrylate, dihydroxymethyl tristane two（Methyl）Acrylate, ethylene glycol two（Methyl）Acrylate, glycerine two （Methyl）Acrylate, ethylene-oxide-modified bisphenol-A two（Methyl）Acrylate, triethylene glycol two（Methyl）Acrylate etc. two Function（Methyl）Acrylate；

Trimethylolpropane tris（Methyl）Acrylate, ethylene-oxide-modified trimethylolpropane tris（Methyl）Acrylic acid Ester, two trimethylolpropanes four（Methyl）Acrylate, pentaerythrite three（Methyl）Acrylate, pentaerythrite four（Methyl）Third Olefin(e) acid ester, dipentaerythritol six（Methyl）Acrylate, two trimethylolpropanes four（Methyl）Acrylate etc. is multifunctional（First Base）Acrylate；

3,4- epoxycyclohexyethylSiOi enylmethyls -3 ', 4 '-epoxycyclohexyethylSiOi olefinic carboxylic acid esters, 1,2- epoxy group -4- second Alkenyl hexamethylene, 1,2：Bicyclic [ 3.1.1 ] heptane of 8,9- bicyclic oxygen limonenes, 2,6,6- trimethyl -2,3- epoxy groups Equal epoxides；

3- ethyl -3- hydroxymethyl oxetanes, Isosorbide-5-Nitrae-it is bis-（3- ethyl -3- oxetanylmethoxy methoxyl groups） Methyl ] benzene, 3- ethyls -3-（Phenoxymethyl）Oxetanes, bis- [ 1- ethyls（3- oxetanylmethoxies）Methyl ether, 3- ethyls -3-（2- Ethylhexoxymethyls）The oxetane compounds such as oxetanes；

The vinyl ethers such as 2- hydroxyethyl vinyl ethers, 4- hydroxybutyl vinyl ethers, diethylene glycol monovinyl base ether Compound；

Mercapto methyl trimethoxy silane, glycidyl oxy methyl trimethoxy silane, vinyl methyl trimethoxy silicon Silane compounds such as alkane etc..

Wherein, as monomer（D）, from polymer（A）Compatibility it is good from the viewpoint of, be preferably selected from simple function （Methyl）Acrylate, two functions（Methyl）Acrylate and multifunctional（Methyl）In acrylate it is at least one kind of, more preferably Selected from simple function（Methyl）Acrylate and two functions（Methyl）It is at least one kind of in acrylate.Wherein, particularly preferably（Methyl） Acrylic acid double cyclopentenyl oxygroup ethyl ester, 1,9- nonanediols two（Methyl）Acrylate,（Methyl）Butyl acrylate,（First Base）2-EHA,（Methyl）Acrylic acid double cyclopentenyl ester,（Methyl）Phenoxyethyl acrylate etc..They can It is used alone a kind, can be also used in combination of two or more.

Aforementioned monomer（D）Using radical polymerization initiator, cationic polymerization initiators and anionic polymerization initiator Equal polymerization initiators and aforementioned polymer（A）Polymerizable functional group reactions.For aforementioned monomer（D）Content for, phase For polymer（A）And polymer（B）Total 100 mass parts, preferably 0.01~1,000 mass parts, more preferably 0.1~ 800 mass parts, further preferably 1.0~600 mass parts are still more preferably 1.0~400 mass parts.Monomer（D）Contain When amount is in aforementioned range, viscosity reduces, and operability improves.In addition, when curing the resin combination of the present invention, cured film Fracture strength and tensile elongation improve, thus the excellent solidfied material of flexibility can be obtained.

< is obstructed amine compound（E）>

For the resin combination of the present invention, in order to further increase the resin combination and solidification therefrom Heat resistance, the weatherability of object can contain the amine compound that is obstructed in the molecule as needed（E）.It should be noted that conduct Be obstructed amine compound（E）, it is preferable to use not having the amine compound that is obstructed of secondary amino group in the molecule.By using it is described Intramolecular does not have the amine compound that is obstructed of secondary amino group（E）, the resin combination can be significantly improved and consolidated by what they were obtained The reduction of mechanics physical property of the compound after hankering exposure, the variation of tone.

As such amine compound that is obstructed for not having secondary amino group in the molecule（E）, for example, it is double to enumerate decanedioic acid （1,2,2,6,6- pentamethyl -4- piperidyls）Ester, decanedioic acid are double（2,2,6,6- tetramethyl -4- piperidyls）Ester, 3, 5- is bis-（1,1- dimethyl ethyl）- 4- hydroxy phenyls ] methyl } butylmalonic acid pair（1,2,2,6,6- pentamethyl -4- Piperidyl）Ester, decanedioic acid are double（2,2,6,6- tetramethyl -1-（Octyl oxygroup）- 4- piperidyls）Ester, decanedioic acid methyl 1, 2,2,6,6- pentamethyl -4- piperidines base esters, 1,2,3,4- butane tetracarboxylic acid four（1,2,2,6,6- pentamethyl -4- piperidines Base）Ester, 1,2,2,6,6- pentamethyl -4- piperidines base esters of methacrylic acid etc..

Wherein, preferably decanedioic acid is double（1,2,2,6,6- pentamethyl -4- piperidyls）Ester, decanedioic acid methyl 1,2,2,6, 6- pentamethyl -4- piperidines base ester, 1,2,3,4- butane tetracarboxylic acid four（1,2,2,6,6- pentamethyl -4- piperidyls）Ester Deng.They can be used alone a kind, can also be used in combination of two or more.

The amine compound that is obstructed in the total amount of resin combination（E）Content be preferably 0.01~10 mass %, more preferably For 0.5~7 mass %, further preferably 1~4 mass %.Be obstructed amine compound（E）Content in aforementioned range when, from It is preferred in terms of improving heat resistance and from the aspect of the mechanics physical property of raising solidfied material.

It is poly- in addition to that can contain in the range of not interfering the effect of the present invention for the resin combination of the present invention Close object（A）And polymer（B）Except, also containing will not have obtained from the conjugated diene compound polymerization other than farnesene The conjugated diene polymer of polymerizable functional group.As the conjugated diene compound other than farnesene, can enumerate butadiene, Isoprene, 2,3- dimethyl butadienes, 2- phenyl butadienes, 1,3-pentadiene, 2- methyl-1s, 3- pentadienes, 1, 3- hexadienes, 1,3- octadienes, 1,3- cyclohexadiene, 2- methyl-1s, 3- octadienes, 1,3,7- sarohornenes, spiceleaf Alkene, chlorobutadiene etc..

In addition, for the resin combination of the present invention, in the range of not interfering the effect of the present invention, in addition to polymerization Object（A）And polymer（B）Except, also contain by other than farnesene conjugated diene compound and aromatic vinyl compound be total to Do not have conjugated diene compound-aromatic vinyl compound based copolymer of polymerizable functional group obtained from poly-.As The example of conjugated diene compound can be used and aforementioned same conjugated diene compound.

As aromatic vinyl compound, for example, can enumerate styrene, α-methylstyrene, 2-methyl styrene, 3- methyl styrenes, 4- methyl styrenes, 4- propylstyrenes, 4- t-butyl styrenes, 4- cyclohexylstyrenes, 4- Dodecylstyrene, 2,4-DMS, 2,4- diisopropyls styrene, 2,4,6- trimethyl styrenes, 2- Ethyl -4- benzylstyrenes, 4-（Phenyl butyl）Styrene, 1- vinyl naphthalenes, 2- vinyl naphthalenes, vinyl anthracene, N, N- diethyl -4- amino-ethyls styrene, vinylpyridine, 4- methoxy styrenes, monochlorostyrene, dichloro-benzenes second Alkene, divinylbenzene etc..

In addition to polymer（A）And polymer（B）The aforementioned conjugated diene polymer and conjugated diene contained in addition The content for closing object-aromatic vinyl compound based copolymer is not particularly limited, in resin combination, preferably 50 mass % Below, 30 mass % or less, further preferably 10 mass % or less are more preferably.

The manufacturing method > of < resin combinations

The manufacturing method of resin combination as the present invention, is not particularly limited, for example, can make in the following manner It makes：At room temperature, using blender, kneader（kneader）Etc. common mixing arrangement, by aforementioned polymer（A）, it is aforementioned poly- Close object（B）, polymerization initiator（C）It is mixed with other compositions used as needed.

The melt viscosity > of < resin combinations

Melt viscosity at 38 DEG C of resin combination of the present invention be preferably 15Pa s or less, more preferably 12Pa s with Under, further preferably 10Pa s or less.It, can be on being applied face when the melt viscosity of resin combination is in aforementioned range It is coated with resin combination evenly, is also easy to prevent being mixed into for bubble, therefore, coating becomes good.It should be noted that this theory In bright book, the melt viscosity of resin combination is the value found out using the method described in aftermentioned embodiment.

For the resin combination of the present invention, melt viscosity is low, and curability is excellent, and intensity, softness can be obtained Property and the excellent solidfied material of the transparency therefore can be suitably used for bonding agent, adhesive（Especially optics adhesive）, apply Cover the purposes such as agent, sealing material and ink.

[ solidfied material ]

The solidfied material of the present invention is product obtained from curing the resin combination of the aforementioned present invention, for example, can pass through It to resin combination irradiation energy ray of the invention or is heated, to make aforementioned polymer（A）And polymerization initiator（C） Reaction, is thus cured.

As for carrying out cured energy-ray, preferably ultraviolet light.As ultraviolet source, for example, xenon lamp, low can be enumerated Medium pressure mercury lamp, high-pressure mercury-vapor lamp, metal halide lamp, microwave mode Excimer lamp etc..As the atmosphere of irradiation ultraviolet light, preferably The inert gas atmospheres such as nitrogen, carbon dioxide or the atmosphere for reducing oxygen concentration.

It is preferably 10~200 DEG C to irradiate atmosphere temperature, and UV exposures are preferably 200~10,000mJ/cm²。

[ optics adhesive ]

The optics of the present invention is the optics adhesive of the resin combination containing the aforementioned present invention with adhesive, can be suitable Ground is for electronic equipments such as smart mobile phone, liquid crystal display, organic el display etc..

Aforementioned optical adhesive also can be as needed properly added various in the range of without departing from the purpose of the present invention Additive.As aforementioned additive, inhaled for example, tackifier, plasticizer, pigment, colorant, antiaging agent, ultraviolet light can be enumerated Receive agent etc..

Embodiment

Hereinafter, the present invention is explained in detail by embodiment, but the present invention is not restricted by the embodiments.

Each ingredient used in the present embodiment and comparative example is as described below.

< polymer（A）>

The polymer obtained by aftermentioned Production Example 1,2（A-1）With（A-2）

< polymer（B）>

The polymer obtained by aftermentioned Production Example 3,4（B-1）With（B-2）

< polymerization initiators（C）>

Polymerization initiator（C-1）

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

BASF Co. Ltd. systems, trade name " DAROCUR 1173 "

< monomers（D）>

Methacrylic acid double cyclopentenyl oxygroup ethyl ester

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

< is obstructed amine compound（E）>

Be obstructed amine compound（E-1）

Decanedioic acid is double（1,2,2,6,6- pentamethyl -4- piperidyls）Ester and 1,2,2,6,6- five first of decanedioic acid methyl The mixture of base -4- piperidines base esters

BASF Co. Ltd. systems, trade name " TINUVIN 765 "

< other polymers（X）>

Polymer（X-1）~（X-3）

The polymer obtained by aftermentioned Production Example 5~7（X-1）,（X-2）With（X-3）.

1~7 > of < Production Examples

Production Example 1：Polyisoprene with methylacryloyl in the molecule（A-1）Manufacture

By regarding n-BuLi as initiator in n-hexane to isoprene progress anionic polymerisation, obtains number and divide equally The polyisoprene of son amount 36,000.1.5 mass parts of maleic anhydride are added into 100 mass parts of polyisoprene, at 180 DEG C Lower react within 15 hours, obtaining averagely every 1 molecule as a result, has the polyisoprene of 3 anhydride groups.Next, flat to this Every 1 molecule adds the methacrylic acid 2- hydroxyls of 2.0 mass parts in 100 mass parts of polyisoprene with 3 anhydride groups Ethyl ester, carries out after shading at 120 DEG C reacting for 10 hours, obtains averagely every 1 molecule as a result, with 3 methylacryloyls Modified liquid polyisoprene（Hereinafter also referred to " polymer（A-1）"）.Polymer（A-1）Physical property it is shown in table 1.

Production Example 2：Poly- farnesene with methylacryloyl in the molecule（A-2）Manufacture

In having carried out the autoclave of 5 liters of capacity of nitrogen displacement, it is packed into hexamethylene 1520g and 10.5 matter of s-butyl lithium % cyclohexane solution 7.8g are measured, then heat to 50 DEG C, add β-farnesene 1510g, polymerize within 2 hours.It is poly- by what is obtained It closes solution to be injected into methanol, makes unmodified polymer reprecipitation, be filtered, carry out being dried in vacuo for 10 hours at 80 DEG C, The poly- farnesene of 1200g is obtained as a result,（Unmodified polymer）.

100 mass parts of poly- farnesene being packed into the autoclave for having carried out 1 liter of the capacity of nitrogen displacement, add horse Come 1.5 mass parts of acid anhydrides and BHT（2,6- di-tert-butyl-4-methy phenols, Honshu Chemical Ind's system）1 mass Part, it carries out reacting for 20 hours at 160 DEG C, obtaining averagely every 1 molecule as a result, has the poly- farnesene of 11 anhydride groups.It connects down Come, the 2-hydroxyethyl methacrylate of 2.0 mass parts, shading, at 80 DEG C are added into 100 mass parts of poly- farnesene Lower react within 6 hours, obtaining averagely every 1 molecule has the poly- farnesene of modification liquid of 11 methylacryloyls（Below Referred to as " polymer（A-2）"）.Polymer（A-2）Physical property it is shown in table 1.

Production Example 3：Poly- farnesene（B-1）Manufacture

It is loaded as the hexamethylene 241g of solvent in having carried out nitrogen displacement and dried pressure vessel, as initiation The s-butyl lithium of agent（10.5 mass % cyclohexane solutions）28.3g is warming up to 50 DEG C, then adds β-farnesene 342g, carries out 1 Hour polymerization.The polymerization liquid obtained with methyl alcohol process uses water washing polymerization liquid.By the polymerization liquid after washing It is separated from water, drying in 12 hours is carried out at 70 DEG C, obtains the poly- farnesene of liquid as a result,（Hereinafter also referred to " polymer（B- 1）"）.Polymer（B-1）Physical property it is shown in table 1.

Production Example 4：Poly- farnesene（B-2）Manufacture

It is loaded as the hexamethylene 304g of solvent in having carried out nitrogen displacement and dried pressure vessel, as initiation The s-butyl lithium of agent（10.5 mass % cyclohexane solutions）1.5g after being warming up to 50 DEG C, adds β-farnesene 302g, it is small to carry out 1 Shi Juhe.The polymerization liquid obtained with methyl alcohol process uses water washing polymerization liquid.By after washing polymerization liquid with Water detaches, and drying in 12 hours is carried out at 70 DEG C, obtains the poly- farnesene of liquid as a result,（Hereinafter also referred to " polymer（B- 2）"）.Polymer（B-2）Physical property it is shown in table 1.

Production Example 5：Polyisoprene（X-1）Manufacture

By regarding n-BuLi as initiator in n-hexane to isoprene progress anionic polymerisation, obtains number and divide equally The liquid polyisoprene of son amount 20,000.Polyisoprene（X-1）Physical property it is shown in table 1.

Production Example 6：Polybutadiene（X-2）Manufacture

By regarding n-BuLi as initiator in n-hexane to butadiene progress anionic polymerisation, several equal molecules are obtained The liquid polybutadiene of amount 9,000.Polybutadiene（X-2）Physical property it is shown in table 1.

Production Example 7：Polybutadiene（X-3）Manufacture

By regarding n-BuLi as initiator in n-hexane to butadiene progress anionic polymerisation, several equal molecules are obtained The liquid polybutadiene of amount 44,000.Polybutadiene（X-3）Physical property it is shown in table 1.

[table 1]

< Examples 1 to 9 >

With the polymer that ratio will obtain in each Production Example shown in table 2（A-1）,（A-2）,（B-1）,（B-2）, （X-2）, polymerization initiator（C-1）, monomer（D）With the amine compound that is obstructed（E）It puts into stainless steel 300mL containers, At room temperature, it is mixed 20 minutes using stirring blade, manufactures the resin combination of 200g as a result,.It is evaluated using following methods The resin combination arrived.As a result it is shown in table 2.

1~6 > of < comparative examples

Coordinate the polymer obtained in each Production Example with ratio shown in table 3（A-1）,（A-2）,（X-1）~（X- 3）, polymerization initiator（C-1）And monomer（D）, in addition to this, operate similarly with example 1, manufacture resin combination, carry out Evaluation.As a result it is shown in table 3.

< evaluation methods >

（1）The measurement of number-average molecular weight and molecular weight distribution

Using Tosoh Co. Ltd. system GPC-8020, be adjusted with the concentration of sample/tetrahydrofuran=5mg/10mL, It measures.

Number-average molecular weight（Mn）And molecular weight distribution（Mw/Mn）Utilize GPC（Gel permeation chromatography）With standard polyphenyl second Alkene conversion molecular weight is found out.Measurement device and condition are as follows.

Device：Tosoh Co. Ltd. system GPC devices " GPC8020 "

Splitter：Tosoh Co. Ltd. systems " TSKgelG4000HXL "

Detector：Tosoh Co. Ltd. systems " RI-8020 "

Eluent：Tetrahydrofuran（Wako Pure Chemical Industries, Ltd.'s system）

Elute flow quantity：1.0ml/ minute

Sample concentration：5mg/10ml

Column temperature：40℃.

（2）Melt viscosity, glass transition temperature and functional equivalent

Utilize Brookfield type viscosimeters（BROOKFIELD ENGINEERING LABS. INC. systems）Measure aforementioned system Make the polymer obtained in example（A-1）,（A-2）,（B-1）,（B-2）With（X-1）~（X-3）And each embodiment and Melt viscosity at 38 DEG C of the resin combination obtained in comparative example.

The polymer 10mg obtained in acquisition Production Example 1~7 is measured to aluminium dish using differential scanning calorimetry（DSC）, 10 DEG C/min heating rate under the conditions of, measure differential thermogram（thermogram）, using the value of the summit of DDSC as glass Change transition temperature.

Use Jeol Ltd.'s system¹H-NMR measurement devices（500MHz）, in sample/deuterochloroform=100mg/ It is measured at the concentration of 1mL, cumulative frequency 512 times, 50 DEG C of measuring temperature¹H-NMR wave spectrums.

For measuring polymer（A）Obtained from wave spectrum, origin derived from methylacryloyl double bond peak, with derive from The area ratio at the peak of the double bond of main polymer chain calculates the quality of the polymer relative to 1 equivalent methyl acryloyl group, i.e. function Group's equivalent.

In addition, for the polymerizable functional group number of every 1 strand, by polymer（A）Number-average molecular weight and utilize The functional equivalent that above-mentioned method is found out calculates.

（3）Appearance

The resin combination obtained in embodiment and comparative example is injected into the mold of vertical 70mm, horizontal 70mm, thickness 0.5mm In, with thick 50 μm of PET film covering composition surface, then use UV irradiation units（Use Co., Ltd. ジ ー エ ス ユ ア サ コ ー ポ レ ー シ ョ Application mercury vapor lamps HAK125L-F）, it is set as illumination 45mW/cm², conveyor speed 0.25m/min, 1,000mJ/cm is irradiated in being operated at 1 time²UV.It is repeated 3 times, obtains solidfied material.After solidfied material removes PET film, lead to It crosses visually and is observed, according to following benchmark evaluations transparency.

< evaluation criteria >

5：Water white transparency

4：Although confirming very slight coloring but still transparent

3：It is slightly coloured but still transparent although confirming

2：Although confirming apparent coloring but still transparent

1：It is opaque.

（4）Fracture strength and elongation at break

From above-mentioned（3）In in obtained solidfied material the strip of punching width 6mm, long 70mm sample, utilize イ Application ス ト ロ Fracture strength when Application corporation stretching test machine determination carries out tension test with the tensile speed of 50mm/min and extension at break Rate.

[table 2]

[table 3]

By table 2,3 it is found that the resin combination of Examples 1 to 3 and embodiment 6,7 is due to containing with as polymerizable The polyisoprene of the methylacryloyl of functional group（A-1）With poly- farnesene（B-1 or B-2）, so having with only containing The polyisoprene of methylacryloyl（A-1）Comparative example 4 compare, be low viscosity, in the case where not damaging appearance, Elongation at break improves.In addition, in embodiment 2,3 and 6, compared with comparative example 4, fracture strength is further improved.In addition, strictly according to the facts It applies shown in example 8, even if other conjugated diolefin polymers are used in combination, similarly confirms the fracture of viscosity reduction effect, cured film Elongation improvement.In addition, the comparison by embodiment 9 and comparative example 6 shows even for monomer（D）Content more than tree Oil/fat composition similarly confirms viscosity reduction effect, the elongation at break of cured film and fracture strength improvement.

The resin combination of embodiment 4 and 5 is due to having the metering system as polymerizable functional group containing intramolecular The poly- farnesene of acyl group（A-2）With poly- farnesene（B-1）, so with the poly- farnesene with methylacryloyl is only contained （A-2）Comparative example 5 compare, improve viscosity and elongation at break, fracture strength.

On the other hand, the resin combination of comparative example 1~3 is to the poly- isoamyl two in the molecule with methylacryloyl Alkene（A-1）Middle cooperation polyisoprene（X-1）Or polybutadiene（X-2 or X-3）Obtained from composition, but with cooperation The Examples 1 to 3 of poly- farnesene is compared, and elongation at break reduces.

In addition, showing the poly- method for the molecular weight with equal extent by the comparison of embodiment 1 and comparative example 2 Alkene（B-1）And polybutadiene（X-2）For, when using poly- farnesene, viscosity reduction effect is excellent.

Claims (15)

1. resin combination includes source containing polymer A, polymer B, polymerization initiator C and monomer D, the polymer A In conjugated diene compound monomeric unit a1 and have (methyl) acryloyl group, the polymer B include derive from farnesene Monomeric unit b1 and do not have polymerizable functional group, polymer A and the mass ratio of polymer B, i.e. A/B for 0.01~ 100, add up to 100 mass parts, also monomer D, the monomer D containing 33~600 mass parts relative to polymer A and polymer B It is the compound in the molecule with (methyl) acryloyl group.

2. resin combination according to claim 1, wherein polymerization initiator C containing in the total amount of resin combination Amount is 0.1~20 mass %.

3. resin combination according to claim 1 or 2, wherein also contain and account for 0.01 in the total amount of resin combination The amine compound E that is obstructed of~10 mass %.

4. resin combination according to claim 1 or 2, wherein the 38 of polymer A and at least one party in polymer B Melt viscosity at DEG C is 0.1~3,000Pas.

5. resin combination according to claim 1 or 2, wherein the number-average molecular weight of polymer B is 1,000~100 Ten thousand.

6. resin combination according to claim 1 or 2, wherein the monomeric unit only origin for constituting polymer B is derived from method The monomeric unit b1 compositions of alkene.

7. resin combination according to claim 1 or 2, wherein the monomeric unit for constituting polymer B contains from method The monomeric unit b1 of the alkene and monomeric unit b2 of the monomer other than farnesene.

8. resin combination according to claim 7, wherein monomeric unit b2 is the conjugation two other than farnesene The monomeric unit of ene compound.

9. resin combination according to claim 7, wherein monomeric unit b2 is from aromatic ethenyl compound Monomeric unit.

10. resin combination according to claim 1 or 2, wherein the monomeric unit only origin for constituting polymer A is derived from The monomeric unit a1 compositions of conjugated diene compound.

11. resin combination according to claim 1 or 2, wherein the monomeric unit of composition polymer A, which contains, to be derived from The monomeric unit a1 of the conjugated diene compound and monomeric unit a2 of the monomer other than conjugated diene compound.

12. resin combination according to claim 10, wherein the conjugated diene compound as monomeric unit a1 is choosing From at least one kind of in farnesene, isoprene and butadiene.

13. resin combination according to claim 11, wherein the conjugated diene compound as monomeric unit a1 is choosing From at least one kind of in farnesene, isoprene and butadiene.

14. solidfied material, being will be obtained from the resin combination solidification described in any one of claim 1~13.

15. optics adhesive contains the resin combination described in any one of claim 1~13.