JPWO2014157624A1 - POLYMER, PROCESS FOR PRODUCING THE SAME, AND RESIN COMPOSITION CONTAINING THE POLYMER - Google Patents

Abstract

The polymer which has a polymerizable functional group containing the monomer unit (a1) derived from farnesene as a monomer unit which comprises a polymer. A resin composition comprising a polymer (A) having a polymerizable functional group containing a monomer unit (a1) derived from farnesene as a monomer unit constituting the polymer.

Description

The present invention relates to a polymer containing a monomer unit derived from farnesene and a method for producing the same.
Moreover, this invention relates to the resin composition containing the polymer containing the monomer unit derived from farnesene, the hardened | cured material which hardened this, and the optical adhesive containing this hardened | cured material or the said resin composition.

In recent years, with the widespread use of electronic devices having a screen such as a liquid crystal, such as smartphones and tablet PCs, research on transparent resin materials and transparent resin adhesives used to cover the screen has been actively conducted.
For example, Patent Document 1 discloses a composition comprising polyisoprene having a (meth) acryloyl group in the molecule, a monofunctional (meth) acrylate monomer and a radical polymerization initiator, and further having a secondary amino group in the molecule. A curable resin composition containing a hindered amine compound that does not have is described.
Patent Document 2 describes an epoxy resin, a curing agent, and a thermosetting resin composition containing a specific amount of an epoxy group in the molecule and an epoxidized polybutadiene having a specific number average molecular weight. Yes.
Patent Documents 3 and 4 describe polymers of β-farnesene. However, practical applications have not been sufficiently studied, and β-farnesene having a polymerizable functional group has not been studied. There are no studies on polymers.

Japanese Patent No. 5073400 Japanese Patent No. 4098107 International Publication No. 2010/027463 International Publication No. 2010/027464

  In the curable resin composition described in Patent Documents 1 and 2, although the cured product satisfies characteristics such as strength, flexibility, and transparency required in an electronic device having a screen such as a liquid crystal, There has been room for improvement in properties such as an increase in curing speed, a reduction in viscosity, and a low curing shrinkage.

The present invention has been made in view of the above circumstances, and provides a cured product having a low viscosity, a high curing speed, excellent curing shrinkage, and excellent strength, flexibility, low moisture permeability and transparency. The polymer which can be manufactured, and its manufacturing method are provided.
The present invention also provides a resin composition having a low viscosity, a high curing rate, excellent curing shrinkage, and capable of giving a cured product having excellent strength, flexibility, low moisture permeability and transparency, and curing the resin composition. There are provided a cured product and an optical pressure-sensitive adhesive containing the cured product or the resin composition.

  As a result of intensive studies, the present inventors have found that a polymer having a polymerizable functional group introduced into a polymer having a monomer unit derived from farnesene has strength, flexibility, low moisture permeability and transparency. It was found that a cured product excellent in the properties of the polymer can be obtained, and that the polymer has a low viscosity, a high curing rate, and excellent curing shrinkage, and the first aspect of the present invention has been completed.

  In addition, the present inventors have obtained a cured product in which a polymer having a polymerizable functional group introduced into a polymer having a monomer unit derived from farnesene is excellent in strength, flexibility, low moisture permeability and transparency. Further, it was found that the resin composition containing this polymer has a low viscosity, a high curing speed, and excellent curing shrinkage, and completed the second and fourth embodiments of the present invention.

  Furthermore, the present inventors provide a polymer having a polymerizable functional group containing a monomer unit derived from farnesene and a polymerizable functional group containing a monomer unit derived from a conjugated diene compound having 12 or less carbon atoms. It has been found that a resin composition containing a polymer that does not have a specific ratio has a low viscosity and can give a cured product having excellent strength, flexibility, hardness and transparency. Four aspects were completed.

That is, the gist of the present invention is the following [1] to [9].
[1] A polymer having a polymerizable functional group containing the monomer unit (a1) derived from farnesene as the monomer unit constituting the polymer.
[2] Step (1) for preparing an unmodified polymer containing a farnesene-derived monomer unit (a1) and having no polymerizable functional group, and a function polymerizable to the unmodified polymer The method for producing a polymer according to [1], comprising a step (2) of introducing a group.
[3] A resin composition containing the polymer (A) according to [1].

[4] The polymer (A) according to [1], the monomer (D), and the polymerization initiator (C) are contained, and the mass ratio of the polymer (A) to the monomer (D) [( A) / (D)] is 0.01 to 99, and 0.1 to 20 parts by mass of the polymerization initiator (C) with respect to 100 parts by mass in total of the polymer (A) and the monomer (D). A resin composition to contain.
[5] The polymer (A) according to [1], a polymer (B) containing a monomer unit derived from a conjugated diene compound (b1) having 12 or less carbon atoms and having no polymerizable functional group, and polymerization initiation The resin composition which contains an agent (C) and whose mass ratio [(A) / (B)] of a polymer (A) and a polymer (B) is 0.01-100.

[6] Further, the polymer (F) contains a monomer unit derived from a conjugated diene compound (f1) having 12 or less carbon atoms and has a polymerizable functional group, and the polymer (A) and the polymer (F ) The resin composition according to any one of [3] to [5], wherein the mass ratio [(A) / (F)] is 0.01 to 100.
[7] A cured product obtained by curing the resin composition according to any one of [3] to [6].
[8] An optical pressure-sensitive adhesive containing the cured product according to [7].
[9] An optical pressure-sensitive adhesive containing the resin composition according to any one of [3] to [6].

  According to the first aspect of the present invention, a polymer capable of giving a cured product having a low viscosity, a high curing speed, excellent curing shrinkage, and excellent strength, flexibility, low moisture permeability and transparency, And a manufacturing method thereof.

  In addition, according to the second and fourth aspects of the present invention, it is possible to provide a cured product having a low viscosity, a high curing rate, excellent curing shrinkage, and excellent strength, flexibility, low moisture permeability and transparency. The resin composition which can be provided can be provided. Furthermore, the hardened | cured material which hardened this and the optical adhesive containing this hardened | cured material or the said resin composition can be provided.

  Furthermore, according to the third and fourth aspects of the present invention, a resin composition that can give a cured product having a low viscosity and excellent in strength, flexibility and transparency, a cured product obtained by curing the resin composition, and the cured product. Alternatively, an optical pressure-sensitive adhesive containing the resin composition can be provided.

[I] Polymer (first embodiment of the present invention)
The polymer of the present invention (hereinafter referred to as polymer (A)) includes a monomer unit (a1) derived from farnesene as a monomer unit constituting the polymer and has a polymerizable functional group. .
The farnesene-derived monomer unit (a1) may be an α-farnesene-derived monomer unit, or may be a β-farnesene-derived monomer unit represented by the following formula (I). However, from the viewpoint of ease of production, a monomer unit derived from β-farnesene is preferable. Note that α-farnesene and β-farnesene may be mixed and used.

Examples of the polymerizable functional group include (meth) acryloyl group, epoxy group, oxetanyl group, vinyl ether group, alkoxysilyl group, (meth) acrylamide group, styrene group, maleimide group, lactone group, lactam group, sulfide group. , A thietane group, an acetonide group, and a thiourea group. Among these, at least one selected from a (meth) acryloyl group, an epoxy group, an oxetanyl group, a vinyl ether group, and an alkoxysilyl group is preferable, and a (meth) acryloyl group Groups are more preferred. These functional groups may have a substituent.
In the present specification, “(meth) acryloyl” means “acryloyl or methacryloyl”. In the present specification, “(meth) acryl” means “acryl or methacryl”.

The monomer unit constituting the polymer (A) may be composed only of the farnesene-derived monomer unit (a1) or derived from a monomer other than the farnesene-derived monomer unit (a1) and farnesene. It may consist of the monomer unit (a2). That is, the polymer (A) may be obtained by polymerizing only farnesene, or may be a copolymer of farnesene and a monomer other than farnesene.
When the polymer (A) is a copolymer, examples of the monomer unit (a2) derived from a monomer other than farnesene include a monomer unit derived from a conjugated diene compound and an aromatic vinyl compound. Can do.
The conjugated diene compound is preferably a conjugated diene compound having 12 or less carbon atoms. Examples of the conjugated diene compound having 12 or less carbon atoms include butadiene, isoprene, 2,3-dimethyl-butadiene, 2-phenyl-butadiene, 1,3. -Pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene , Myrcene, chloroprene and the like. Of these, isoprene and butadiene are more preferred. These conjugated diene compounds may be used individually by 1 type, and may use 2 or more types together.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4- Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2- Aromatic vinyl compounds such as vinylnaphthalene, vinylanthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene, and the like can be given. Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferable.

  In the case of using a monomer unit (a2) derived from a monomer other than farnesene, a monomer derived from a monomer other than farnesene in the copolymer (a1) and a monomer other than farnesene The proportion of the monomer unit (a2) derived from a monomer other than farnesene relative to the total of the units (a2) is the viewpoint of reducing the viscosity of the polymer, the viewpoint of improving the curing rate, and the good elongation of the cured product. From the viewpoint of maintaining characteristics and flexibility, 1 to 99% by mass is preferable, 1 to 80% by mass is more preferable, 1 to 70% by mass is further preferable, and 1 to 50% by mass is even more preferable.

The number average molecular weight (Mn) of the polymer (A) of the present invention is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, more preferably 8,000 to 500,000, and 15,000 to 45. Is more preferable, 15,000 to 300,000 is still more preferable, and 20,000 to 200,000 is more preferable. When the Mn of the polymer (A) is within the above range, the flexibility, the mechanical strength and the curing rate are improved, and the polymer has a low viscosity. In addition, in this specification, Mn of a polymer (A) is the value calculated | required by the method described in the Example mentioned later.
In addition, the number average molecular weight (Mn) in this specification is a number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  The melt viscosity at 38 ° C. of the polymer (A) of the present invention is preferably from 0.1 to 3000 Pa · s, more preferably from 0.6 to 3000 Pa · s, more preferably from 0.6 to 2800 Pa · s. 5 to 2600 Pa · s is more preferable, and 1.5 to 800 Pa · s is still more preferable. When the melt viscosity (38 ° C.) of the polymer is within the above range, the polymer can be uniformly applied to the surface to be coated, so that the coating property is improved. In the present specification, the melt viscosity (38 ° C.) of the polymer is a value determined by the method described in Examples described later.

  1.0-8.0 are preferable, as for the molecular weight distribution (Mw / Mn) of the polymer (A) of this invention, 1.0-5.0 are more preferable, and 1.0-3.0 are still more preferable. When Mw / Mn is within the above range, the resulting polymer (A) has less variation in viscosity.

  The glass transition temperature of the polymer (A) of the present invention varies depending on the bonding mode (microstructure), other farnesene-derived monomers, and the amount of monomers other than farnesene used as necessary. -90-0 degreeC is preferable and -90--10 degreeC is more preferable. Within the above range, a flexible cured product can be obtained, and the step following ability and the impact absorbing ability can be improved in an adhesive used for a laminated structure such as a liquid crystal screen.

1-150 are preferable, as for the number of the polymerizable functional groups per molecular chain of the polymer (A) of this invention, 1.5-75 are more preferable, and 1.5-30 are still more preferable. When the number of polymerizable functional groups per molecular chain is within the above range, the viscosity of the polymer (A) can be reduced, the curing rate can be improved, and further curing can be achieved. Shrinkage can be kept low.
The number of polymerizable functional groups per molecular chain is expressed by the following formula from the number average molecular weight (Mn) of the polymer (A) and the functional group equivalent (g / eq) of the polymer (A). Calculated.
(Number of polymerizable functional groups per molecular chain) = (Mn) / (functional group equivalent)
The functional group equivalent is “molecular weight of polymer per functional group”. For example, the functional group equivalent when the polymerizable functional group is a methacryloyl group is referred to as “methacryloyl equivalent”, which means “molecular weight of polymer per methacryloyl group”. The functional group equivalent can be calculated based on the reaction rate of the modifier, or can be determined using various analytical instruments such as infrared spectroscopy and nuclear magnetic resonance spectroscopy.
The polymer (A) used in the present invention may be used alone or in combination of two or more kinds of the polymers (A) having different monomer units, molecular weights and functional groups. Also good.

  Ratio of common logarithm of melt viscosity (Pa · s) at 38 ° C. and number average molecular weight (Mn) of polymer (A) of the present invention [ordinary logarithm of melt viscosity at 38 ° C./number average molecular weight (Mn) ] Is preferably 0.000060 or less, preferably 0.000055 or less, and more preferably 0.000050 or less. When the ratio of the common logarithm value of the melt viscosity at 38 ° C. and the number average molecular weight is within the above range, it becomes possible to uniformly apply the polymer to the surface to be coated. Will be better.

<Method for producing polymer (A)>
As a method for producing the polymer (A) of the present invention, a step of preparing an unmodified polymer having no polymerizable functional group by polymerizing farnesene and, if necessary, monomers other than farnesene (1) And a step (2) of introducing a polymerizable functional group into the unmodified polymer.
The step (1) for preparing the unmodified polymer will be described later, and here, the step (2) for mainly introducing a polymerizable functional group into the unmodified polymer will be described. As a first method for producing the polymer of the present invention, an unmodified polymer is prepared by polymerizing farnesene and, if necessary, monomers other than farnesene, and maleic anhydride is added to the unmodified polymer. A method of reacting a compound for grafting such as 2-hydroxyethyl methacrylate and then reacting a compound having a polymerizable functional group such as 2-hydroxyethyl methacrylate is preferable.

Examples of the compound for grafting the unmodified polymer include unsaturated carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, itaconic anhydride; maleic acid, fumaric acid Unsaturated carboxylic acid such as acid, citraconic acid and itaconic acid; unsaturated carboxylic acid ester such as maleic acid ester, fumaric acid ester, citraconic acid ester and itaconic acid ester; maleic acid amide, fumaric acid amide, citraconic acid amide and itaconic acid Unsaturated carboxylic acid amides such as acid amides; unsaturated carboxylic acid imides such as maleic acid imides, fumaric acid imides, citraconic acid imides, itaconic acid imides; maleimides, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc. Can be mentioned.
Examples of the compound having a polymerizable functional group include (meth) acrylic acid; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, (Meth) acrylates such as dipentaerythritol monohydroxyacrylate; 2-hydroxyethyl vinyl ether, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, N- (2-hydroxyethyl) maleimide, 4-ethenylphenol and the like can be mentioned. The position at which the polymerizable functional group is introduced may be the polymerization terminal or the side chain of the polymer. Moreover, the said functional group may combine 1 type (s) or 2 or more types.

  As a second method for producing the polymer of the present invention, for example, a hydroxyl group, a carboxyl group, and a hydroxyl group are added to the unmodified polymer by an addition reaction with the living end of the unmodified polymer obtained by living anionic polymerization of farnesene. Carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphorus Acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silanol group, alkoxysilane, silicon halide group, tin halide group Functional group selected from alkoxytin group and phenyltin group Kutomo one having atomic group, to synthesize a modified polymer is at least one bond, then include a method of reacting a compound having a polymerizable functional group such as acrylic acid.

Examples of the living anion polymerization initiator for living anionic polymerization of farnesene include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium. Organic monolithium compounds; polyfunctional organolithium compounds such as dilithiomethane, dilithionaphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene; sodium naphthalene, potassium And naphthalene. A compound such as diisopropenylbenzene or dibenzyltoluene that reacts with an organic alkali metal reagent to give a polyfunctional organic alkali metal reagent may be used in combination.
Examples of the compound for introducing an atomic group having at least one functional group at the living terminal include cyclic ethers such as epoxide and oxetane; cyclic amines such as pyrrolidine; cyclic sulfides such as ethylene sulfide. In addition, the said functional group may combine 1 type (s) or 2 or more types.

  As a third method for producing the polymer of the present invention, an unmodified polymer was prepared by polymerizing farnesene and, if necessary, monomers other than farnesene, and this unmodified polymer was epoxidized. Thereafter, a method of reacting the above-described compound having a polymerizable functional group may be mentioned.

Examples of the compound for epoxidizing the unmodified polymer include peracids such as peracetic acid and perbenzoic acid.
Examples of the compound having a polymerizable functional group include carboxylic acids such as acrylic acid and methacrylic acid. The position at which the polymerizable functional group is introduced may be the polymerization terminal or the side chain of the polymer. Moreover, the said functional group may combine 1 type (s) or 2 or more types.

When functionalizing the unmodified polymer or storing the modified polymer, an antiaging agent suitable for the unmodified polymer or the modified polymer is used for the purpose of suppressing molecular weight reduction, discoloration and gelation due to deterioration. You may combine. Specifically, 2,6-di-t-butyl-4-methylphenol (BHT), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 4,4′-thiobis (3-methyl) -6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) (AO-40), 3,9-bis [1,1-dimethyl-2- [3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (AO-80), 2,4-bis [( Octylthio) methyl] -6-methylphenol (Irganox 1520L), 2,4-bis [(dodecylthio) methyl] -6-methylphenol (Irganox 1726), 2- [1- (2-hydroxy-3,5-di) t-pentylphenyl) ethyl] -4,6-di-pentylphenyl acrylate (Sumilizer GS), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4- Methylphenyl acrylate (Sumilizer GM), 6-t-butyl-4- [3- (2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphine -6-yloxy) propyl] -2-methylphenol (Sumilizer GP), tris (2,4-di-t-butylphenyl) phosphite (Irgafos 168), dioctadecyl 3,3'-dithiobispropionate, Hydroquinone, p-methoxyphenol, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (NOCRACK 6C), bis 2,2,6,6-tetramethyl-4-piperidyl) sebacate (LA-77Y), N, N-dioctadecylhydroxylamine (Irgastab FS 042), bis (4-t-octylphenyl) amine (Irganox 5057) Etc. Moreover, the said anti-aging agent may use together 1 type, or 2 or more types.
0.01-10 mass parts is preferable with respect to 100 mass parts of unmodified polymers or modified polymers, and, as for the addition amount of an anti-aging agent, 0.1-3 mass parts is more preferable.

  Next, the step (1) for preparing the unmodified polymer will be described. The unmodified polymer which is a raw material of the polymer (A) of the present invention can be produced by an emulsion polymerization method or a method described in International Publication No. 2010/027463 and International Publication No. 2010/027464. Among these, an emulsion polymerization method or a solution polymerization method is preferable, and a solution polymerization method is more preferable.

As an emulsion polymerization method for obtaining an unmodified polymer, a known method can be applied. For example, a predetermined amount of farnesene is emulsified and dispersed in the presence of an emulsifier, and emulsion polymerization is performed using a radical polymerization initiator.
As the emulsifier, for example, a long chain fatty acid salt or rosin acid salt having 10 or more carbon atoms is used. Specific examples include potassium salts or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
As the dispersant, water is usually used, and it may contain a water-soluble organic solvent such as methanol and ethanol as long as the stability during polymerization is not inhibited.
Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, and hydrogen peroxide.
A chain transfer agent can also be used to adjust the molecular weight of the unmodified polymer. Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, γ-terpinene, α-methylstyrene dimer, and the like.
The emulsion polymerization temperature can be appropriately selected depending on the type of the radical polymerization initiator to be used, but is usually preferably 0 to 100 ° C, more preferably 0 to 60 ° C. The polymerization mode may be either continuous polymerization or batch polymerization. The polymerization reaction can be stopped by adding a polymerization terminator.
Examples of the polymerization terminator include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine, and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.
After termination of the polymerization reaction, an antioxidant may be added as necessary. After the polymerization reaction is stopped, unreacted monomers are removed from the obtained latex as necessary, and then a salt such as sodium chloride, calcium chloride, potassium chloride is used as a coagulant, and nitric acid, sulfuric acid, etc. The unmodified polymer is coagulated while adjusting the pH of the coagulation system to a predetermined value by adding an acid, and then the unmodified polymer is recovered by separating the dispersion solvent. Next, after washing with water and dehydration, drying is performed to obtain an unmodified polymer. In addition, during the coagulation, if necessary, latex and an extending oil that has been made into an emulsified dispersion may be mixed and recovered as an oil-modified unmodified polymer.

As a solution polymerization method for obtaining an unmodified polymer, a known method can be applied. For example, the monomer is polymerized in the presence of a polar compound as desired using a Ziegler catalyst, a metallocene catalyst, or an anionically polymerizable active metal in a solvent.
Examples of the anion-polymerizable active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanoid rare earth metals such as lanthanum and neodymium . Of these, alkali metals and alkaline earth metals are preferable, and alkali metals are particularly preferable. Further, among alkali metals, organic alkali metal compounds are more preferably used.
Examples of the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, Aromatic hydrocarbons such as toluene and xylene are exemplified.
Examples of the organic alkali metal compound include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, phenyllithium, stilbenelithium; dilithiomethane, dilithionaphthalene Polyfunctional organolithium compounds such as 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like. Among these, an organic lithium compound is preferable, and an organic monolithium compound is more preferable. The amount of the organic alkali metal compound used is appropriately determined depending on the required molecular weight of the unmodified polymer, but is 0.01 to 7 mass with respect to 100 mass parts of the total amount of monomers other than farnesene and farnesene if necessary. Part is preferred.
The organic alkali metal compound can also be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine, dibenzylamine and the like.
The polar compound is used to adjust the microstructure of the farnesene moiety in anionic polymerization without deactivating the reaction. For example, ether compounds such as dibutyl ether, tetrahydrofuran, ethylene glycol diethyl ether; tetramethylethylenediamine, trimethylamine, etc. Tertiary amines; alkali metal alkoxides, phosphine compounds and the like. The polar compound is preferably used in an amount of 0.01 to 1000 molar equivalents relative to the organic alkali metal compound.

The temperature of the polymerization reaction is usually in the range of −80 to 150 ° C., preferably 0 to 100 ° C., more preferably 10 to 90 ° C. The polymerization mode may be either batch or continuous.
The polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization terminator. The unmodified polymer can be isolated by pouring the obtained polymerization reaction solution into a poor solvent such as methanol to precipitate the unmodified polymer, or washing the polymerization reaction solution with water, separating, and drying.

[II] Resin composition (second embodiment)
The resin composition according to the second aspect of the present invention is a polymer comprising the monomer unit (a1) derived from farnesene as a monomer unit constituting the polymer according to the first aspect of the present invention, that is, a polymer. It is a resin composition containing the polymer (A) having a group.
The polymer (A) in the first aspect of the present invention has a low viscosity, a high curing rate, and an excellent curing shrinkage. The resin composition using the polymer (A) has strength, flexibility, low moisture permeability and A cured product having excellent transparency can be provided.
In the 2nd aspect of this invention, it is preferable to contain the below-mentioned polymerization initiator (C) from a viewpoint which gives the above-mentioned hardened | cured material.

  The resin composition in the second aspect of the present invention includes a polymer (A) having a polymerizable functional group containing a monomer unit (a1) derived from farnesene as a monomer unit constituting the polymer, The monomer (D) and the polymerization initiator (C) are contained, and the mass ratio [(A) / (D)] of the polymer (A) and the monomer (D) is 0.01 to 99. The resin composition containing 0.1 to 20 parts by mass of the polymerization initiator (C) with respect to 100 parts by mass in total of the polymer (A) and the monomer (D) is preferable.

<Polymer (A)>
The polymer (A) used in the second embodiment of the present invention contains a monomer unit (a1) derived from farnesene as a monomer unit constituting the polymer and has a polymerizable functional group. This polymer (A) is the same as the polymer in the first aspect of the present invention, has a low viscosity, a high curing rate, and is excellent in curing shrinkage.

  1-99 mass% is preferable, as for content of the polymer (A) in the resin composition in the 2nd aspect of this invention, 2-98 mass% is more preferable, 5-95 mass% is still more preferable, 90 mass% is still more preferable, and 15-85 mass% is still more preferable. When the content of the polymer (A) in the resin composition is within the above range, a cured product excellent in strength, flexibility, low moisture permeability and transparency can be provided.

<Monomer (D)>
The monomer (D) used in the present invention is not particularly limited as long as it can be polymerized by a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator, but a polymer for obtaining a uniformly cured product. A monomer copolymerizable with the functional group (A) is preferred. Examples of the monomer (D) include compounds having a (meth) acryloyl group, an epoxy group, an oxetanyl group, a vinyl ether group, and an alkoxysilyl group in the molecule.

  Specific compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, butylethoxy (meth) acrylate, butylethyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, lauryl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, cyclohexyl (meth) Acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate Morpholine (meth) acrylate, phenoxyethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, Monofunctional (meth) acrylates such as methoxydipropylene glycol (meth) acrylate and nonylphenoxypolyethylene glycol (meth) acrylate;

1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, ethylene glycol di Bifunctional (meth) acrylates such as (meth) acrylate, glycerin di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, triethylene glycol di (meth) acrylate;
Trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa Polyfunctional (meth) acrylates such as (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate;
3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9-diepoxy limonene, 2,6,6 An epoxy compound such as trimethyl-2,3-epoxybicyclo [3.1.1] heptane;

3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxtanylmethoxy) methyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, bis [1-ethyl (3 -Oxetanyl)] methyl ether, oxetane compounds such as 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane;
Vinyl ether compounds such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether;
Examples of the compound include mercaptomethyltrimethoxysilane, glycidoxymethyltrimethoxysilane, and vinylmethyltrimethoxysilane.
Among these, from the viewpoint of good compatibility with the polymer (A), dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1,9-nonanediol diacrylate, n-butyl acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and phenoxyethyl (meth) acrylate are preferred. These may be used alone or in combination of two or more.

  The mass ratio [(A) / (D)] of the polymer (A) and the monomer (D) is 0.01 to 99, preferably 0.1 to 99, and more preferably 0.2 to 99. Preferably, 0.2-10 is still more preferable, and 0.2-5 is still more preferable. When the mass ratio [(A) / (D)] is within the above range, a cured product excellent in flexibility and low cure shrinkage is obtained reflecting the physical properties of the polymer (A).

<Polymerization initiator (C)>
Examples of the polymerization initiator (C) used in the present invention include a photopolymerization initiator that initiates a polymerization reaction by irradiation with active energy rays such as ultraviolet rays, and a thermal polymerization initiator that initiates a polymerization reaction by heat. From the viewpoint that the resin is cured by irradiation with time and a cured product can be obtained without altering the base material, a photopolymerization initiator is preferable, and a photopolymerization initiator that initiates a polymerization reaction by ultraviolet irradiation is more preferable. preferable. Examples of the photopolymerization initiator include a cationic photopolymerization initiator and a radical polymerization initiator.

Examples of the cationic photopolymerization initiator include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, metallocene compounds, and the like.
As a cationic photopolymerization initiator of an aromatic diazonium salt, “P-33 (trade name)” (manufactured by ADEKA Corporation) and the like are known.
Known examples of cationic photopolymerization initiators of aromatic iodonium salts include “Rhodorsil Photo Initiator 2074 (trade name)” (manufactured by Rhodia Co., Ltd.), “Irgacure 250 (trade name)” (manufactured by BASF Corporation), and the like. Yes.
As the cationic photopolymerization initiator of aromatic sulfonium salt, “FC-509 (trade name)” (manufactured by Sumitomo 3M Limited), “Irgacure 270 (trade name)” (manufactured by BASF Corporation) and the like are known. Yes.

As a metallocene-based cationic photopolymerization initiator, “Irgacure 261 (trade name)” (manufactured by BASF Corporation) and the like are known.
Examples of radical photopolymerization initiators include acetophenone, benzophenone, alkylphenone, acylphosphine oxide, benzoin, ketal, anthraquinone, disulfide, thioxanthone, thiuram, and fluoroamine. It is done. Of these, alkylphenone or acylphosphine oxide radical photopolymerization initiators are preferred.
Examples of the alkylphenone radical photopolymerization initiators include hydroxyalkylphenone and aminoalkylphenone. Hydroxylphenone radical photopolymerization initiators include “DAROCUR1173 (trade name)” (2-hydroxy-2-methyl-1-phenylpropan-1-one), “Irgacure 184 (trade name)” (1 -Hydroxycyclohexyl phenyl ketone), “Irgacure 2959 (trade name)” (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one) and the like. It is done.

Examples of aminoalkylphenone radical photopolymerization initiators include “Irgacure 907 (trade name)” (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one), “Irgacure 369”. (Trade name) ”(2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone) and the like.
Examples of the acylphosphine oxide radical photopolymerization initiator include “LUCIRIN TPO (trade name)” (2,4,6-trimethylbenzoyldiphenylphosphine oxide), “Irgacure 819 (trade name)” (bis (2,4 , 6-trimethylbenzoyl) -phenylphosphine oxide) (all manufactured by BASF Corporation).
Among these, hydroxyalkylphenone-based radical photopolymerization initiators are preferable, and 2-hydroxy-2-methyl-1-phenylpropan-1-one is more preferable. These may be used alone or in combination of two or more.

  Content of a polymerization initiator (C) is 0.1-20 mass parts with respect to a total of 100 mass parts of a polymer (A) and a monomer (D), and 0.5-15 mass parts is Preferably, 1-10 mass parts is more preferable, and 1.5-6 mass parts is still more preferable. When the content of the polymerization initiator (C) is within the above range, it is preferable in terms of curing speed and mechanical properties.

<Hindered amine compound (E)>
The resin composition in the second aspect of the present invention contains a hindered amine compound (E) as necessary in order to further improve the heat resistance and weather resistance of the resin composition and the cured product obtained therefrom. Also good. In addition, as a hindered amine type compound (E), it is preferable to use the hindered amine type compound which does not have a secondary amino group in a molecule | numerator.
By using the hindered amine compound (E) having no secondary amino group in the molecule, the physical properties of the resin composition and the cured product obtained therefrom are deteriorated and the color tone is changed after being exposed to heat. Can be remarkably improved.
Examples of the hindered amine compound (E) having no secondary amino group in the molecule include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] Methyl] butyl malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, methyl 1,2,2,6,6-pentamethyl-4- Piperidyl sebacate, tetrakis 1,2,3,4-butanetetracarboxylate (1,2,2,6,6-pentamethyl-4-piperidinyl), 1,2,2,6,6-pentamethyl-4 Piperidyl methacrylate and the like.
Among these, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 1,2,3 Tetrakis 4-butanetetracarboxylate (1,2,2,6,6-pentamethyl-4-piperidinyl) is preferred. These may be used alone or in combination of two or more.

  The content of the hindered amine compound (E) is preferably 0.01 to 10 parts by mass, and 0.5 to 7 parts by mass with respect to 100 parts by mass in total of the polymer (A) and the monomer (D). Is preferable, and 1-4 parts by mass is more preferable. When the content of the hindered amine compound (E) is within the above range, it is preferable in terms of improving the heat resistance and improving the mechanical properties of the cured product.

<Method for producing resin composition>
The method for producing the resin composition in the second aspect of the present invention is not particularly limited. For example, the polymer (A), the monomer (D), the polymerization initiator (C), and as necessary. It can manufacture by mixing the other components used at room temperature using normal mixing means, such as a stirrer and a kneader.

<Melt viscosity of resin composition>
The resin composition in the second aspect of the present invention has a melt viscosity at 38 ° C. of preferably 15 Pa · s or less, more preferably 12 Pa · s or less, and still more preferably 10 Pa · s or less. When the melt viscosity of the resin composition is within the above range, it is possible to uniformly apply the resin composition to the surface to be coated, and it is easy to prevent air bubbles from being mixed. Become. In the present specification, the melt viscosity of the resin composition is a value determined by the method described in Examples described later.

[Cured product]
The cured product according to the second aspect of the present invention is obtained by curing the resin composition according to the second aspect of the present invention. For example, the resin composition according to the second aspect of the present invention is irradiated with energy rays. Can be cured.
As energy rays for curing, ultraviolet rays are preferable. Examples of the ultraviolet ray source include a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a microwave excimer lamp, and the like. As the atmosphere for irradiating ultraviolet rays, an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere in which the oxygen concentration is lowered is preferable.
The irradiation atmosphere temperature is preferably 10 to 200 ° C., and the UV irradiation amount is preferably 200 to 10,000 mJ / cm ² .

[Optical pressure sensitive adhesive]
The optical pressure-sensitive adhesive according to the second aspect of the present invention contains the cured product or resin composition according to the second aspect of the present invention, and is suitable for electronic devices such as smartphones, liquid crystal displays, and organic EL displays. Can be used.

  Various additives can be appropriately added to the optical pressure-sensitive adhesive as necessary without departing from the object of the present invention. Examples of the additive include a tackifier, a plasticizer, a pigment, a colorant, an anti-aging agent, and an ultraviolet absorber.

[III] Resin composition (third embodiment)
The resin composition according to the third aspect of the present invention is a polymer comprising the monomer unit (a1) derived from farnesene as the monomer unit constituting the polymer of the first aspect of the present invention, that is, the polymer. A polymer (A) having a group, a polymer (B) containing a monomer unit (b1) derived from a conjugated diene compound having 12 or less carbon atoms and having no polymerizable functional group, and a polymerization initiator (C) And the mass ratio [(A) / (B)] of the polymer (A) and the polymer (B) is 0.01 to 100.

<Polymer (A)>
The polymer (A) used in the third aspect of the present invention includes a monomer unit (a1) derived from farnesene as a monomer unit constituting the polymer and has a polymerizable functional group. This polymer (A) is the same as the polymer in the first aspect of the present invention, has a low viscosity, a high curing rate, and is excellent in curing shrinkage.

  1-99 mass% is preferable, as for content of the polymer (A) in the resin composition in the 3rd aspect of this invention, 2-98 mass% is more preferable, 5-95 mass% is still more preferable, 90 mass% is still more preferable, and 15-85 mass% is still more preferable. When the content of the polymer (A) in the resin composition is within the above range, a cured product excellent in strength, flexibility, low moisture permeability and transparency can be provided.

<Polymer (B)>
The polymer (B) contains a monomer unit (b1) derived from a conjugated diene compound having 12 or less carbon atoms and does not have a polymerizable functional group.
Examples of the conjugated diene compound having 12 or less carbon atoms as the monomer unit (b1) include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3- Examples include pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, and chloroprene.
Of these, isoprene and butadiene are more preferred. These conjugated diene compounds may be used individually by 1 type, and may use 2 or more types together.

  The monomer unit constituting the polymer (B) may consist only of the monomer unit (b1) derived from the conjugated diene compound, and the monomer unit (b1) and conjugated diene derived from the conjugated diene compound. It may consist of a monomer unit (b2) derived from a monomer other than the compound. That is, the polymer (B) may be obtained by polymerizing only the conjugated diene compound or may be a copolymer of the conjugated diene compound and a monomer other than the conjugated diene compound.

Examples of the monomer unit (b2) derived from a monomer other than the conjugated diene compound include monomer units derived from an aromatic vinyl compound.
Examples of the aromatic vinyl compound as the monomer unit (b2) include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, and 4-t-butylstyrene. 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene Aromatic vinyl compounds such as 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzene. Can be mentioned. Among these, styrene, α-methylstyrene and 4-methylstyrene are preferable.

  In the case of using the monomer unit (b2) derived from a monomer other than the conjugated diene, the monomer unit (b1) derived from the conjugated diene and the monomer derived from a monomer other than the conjugated diene in the copolymer. The ratio of the monomer unit (b2) derived from the monomer other than the conjugated diene to the total of the monomer units (b2) is a viewpoint of lowering the viscosity of the resin composition, good elongation characteristics and flexibility of the cured product. 1 to 99% by mass is preferable, 1 to 80% by mass is more preferable, 1 to 70% by mass is further preferable, and 1 to 50% by mass is even more preferable.

  The number average molecular weight (Mn) of the polymer (B) used in the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 180,000, still more preferably 3,000 to 160,000, and 4,000. ˜140,000 is more preferred, and 5,000 to 120,000 is even more preferred. When the Mn of the polymer (B) is within the above range, the flexibility and mechanical strength of the cured product are improved, and the resin composition has a low viscosity.

  The melt viscosity at 38 ° C. of the polymer (B) used in the present invention is preferably 0.1 to 3,000 Pa · s, more preferably 0.3 to 3,000 Pa · s, and 0.3 to 2,800 Pa · s. s is further preferable, 0.5 to 2,600 Pa · s is further more preferable, and 0.5 to 800 Pa · s is further more preferable. When the melt viscosity of the polymer (B) is within the above range, the resin composition can be uniformly applied to the surface to be coated without unevenness, so that the coating property is improved.

The polymer (B) can be obtained by living anion polymerization of a conjugated diene compound and, if necessary, a monomer other than the conjugated diene compound. Living anionic polymerization initiators for living anion polymerization of conjugated diene compounds include, for example, methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexyl lithium, phenyl lithium, stilbene lithium and the like. Organic monolithium compounds; polyfunctional organolithium compounds such as dilithiomethane, dilithionaphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene; sodium naphthalene, potassium And naphthalene. Moreover, you may use together compounds, such as diisopropenyl benzene and dibenzyl toluene which react with an organic alkali metal compound and give a polyfunctional organic alkali metal compound.
Although the polymer (B) used for this invention may be used individually by 1 type, you may use together 2 or more types of said polymers (B) from which a monomer unit and molecular weight each differ.

In the present invention, the mass ratio [(A) / (B)] of the polymer (A) and the polymer (B) is 0.01 to 100, preferably 0.05 to 100, more preferably. It is 0.1-50, More preferably, it is 0.1-25, More preferably, it is 0.1-10. When the mass ratio [(A) / (B)] is within the above range, a resin composition having a sufficiently low viscosity and a good elongation at break after curing can be obtained.
In the present invention, at least one of the polymer (A) and the polymer (B) preferably has a melt viscosity at 38 ° C. of 0.1 to 3,000 Pa · s, but the polymer (A) and the polymer It is more preferable that the melt viscosity of both (B) is in the range of 0.1 to 3,000 Pa · s.

<Polymerization initiator (C)>
As a polymerization initiator (C) used by this invention, the polymerization initiator (C) quoted in the 2nd aspect of this invention can be used conveniently.
The content of the polymerization initiator (C) in the resin composition in the third aspect of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass in the total amount of the resin composition. 1.0-20 mass% is still more preferable, 1.0-15 mass% is still more preferable, 1.0-10 mass% is the most preferable. When the content of the polymerization initiator (C) is within the above range, it is preferable in terms of curing speed and mechanical properties.

<Monomer (D)>
The resin composition in the third aspect of the present invention may contain a monomer (D) as necessary in order to further improve the viscosity, handleability and strength after curing of the resin composition.
The monomer (D) preferably has a functional group capable of reacting with the polymer (A). For example, the monomer (D) has a (meth) acryloyl group, an epoxy group, an oxetanyl group, a vinyl ether group, or an alkoxysilyl group in the molecule. Compounds.

As a specific compound, the monomer (D) mentioned in the second aspect of the present invention can be preferably used.
Among the above-mentioned monomers (D), the monomer (D) includes a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, and a polyfunctional monomer from the viewpoint of good compatibility with the polymer (A). It is preferably at least one selected from functional (meth) acrylates, and more preferably at least one selected from monofunctional (meth) acrylates and bifunctional (meth) acrylates.
Among them, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, 1,9-nonanediol di (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like are particularly preferable. These may be used alone or in combination of two or more.

  The monomer (D) can react with the polymerizable functional group of the polymer (A) with a polymerization initiator such as a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator. The content of the monomer (D) is preferably 0.01 to 1,000 parts by mass, preferably 0.1 to 800 parts by mass with respect to 100 parts by mass in total of the polymer (A) and the polymer (B). Is more preferable, 1.0-600 mass parts is still more preferable, and 1.0-400 mass parts is still more preferable. When the content of the monomer (D) is within the above range, the viscosity is lowered and handling properties are improved. Moreover, since the breaking strength and tensile elongation of the cured product are improved when the resin composition in the third aspect of the present invention is cured, a cured product having excellent flexibility can be obtained.

<Hindered amine compound (E)>
The resin composition in the third aspect of the present invention contains a hindered amine compound (E) as necessary in order to further improve the heat resistance and weather resistance of the resin composition and the cured product obtained therefrom. Also good. In addition, as a hindered amine type compound (E), it is preferable to use the hindered amine type compound which does not have a secondary amino group in a molecule | numerator. By using the hindered amine compound (E) having no secondary amino group in the molecule, the physical properties of the resin composition and the cured product obtained therefrom are deteriorated and the color tone is changed after being exposed to heat. Can be remarkably improved.
As specific compounds, the hindered amine compounds (E) mentioned in the second embodiment of the present invention can be suitably used.

  The content of the hindered amine compound (E) in the resin composition in the third aspect of the present invention is preferably 0.01 to 10% by mass, more preferably 0.5 to 7% by mass in the total amount of the resin composition. 1 to 4% by mass is more preferable. When the content of the hindered amine compound (E) is within the above range, it is preferable in terms of improving the heat resistance and improving the mechanical properties of the cured product.

  The resin composition according to the third aspect of the present invention can be polymerized by polymerizing a conjugated diene other than farnesene, in addition to the polymer (A) and the polymer (B), within a range not inhibiting the effects of the present invention. You may contain the modified conjugated diene type polymer which has a functional group. Conjugated dienes other than farnesene include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3- Examples include octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, and chloroprene.

In addition, the resin composition according to the third aspect of the present invention contains, in addition to the polymer (A) and the polymer (B), a conjugated diene other than farnesene and an aromatic vinyl compound, as long as the effects of the present invention are not impaired. A modified conjugated diene-aromatic vinyl compound copolymer having a polymerizable functional group obtained by copolymerization may be contained. Examples of the conjugated diene are the same as those described above.
Examples of the aromatic vinyl compound include styrene, α-methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 4-propyl styrene, 4-t-butyl styrene, 4-cyclohexyl styrene, 4-dodecyl. Styrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2-vinyl Naphthalene, vinylanthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene and the like can be mentioned.

Examples of the polymerizable functional group include (meth) acryloyl group, epoxy group, oxetanyl group, vinyl ether group, alkoxysilyl group, (meth) acrylamide group, styrene group, maleimide group, lactone group, lactam group, sulfide group, A thietane group, an acetonide group, a thiourea group, etc. are mentioned.
The modified conjugated diene polymer having a polymerizable functional group and the modified conjugated diene-aromatic vinyl compound copolymer having a polymerizable functional group are the polymers in the fourth embodiment of the present invention described later. It is included in the concept of (F). Therefore, these polymers will be described in detail in the polymer (F) in the fourth embodiment.

  The contents of the modified conjugated diene polymer and the modified conjugated diene-aromatic vinyl compound copolymer that may be contained in addition to the polymer (A) and the polymer (B) are not particularly limited. However, the total amount of the resin composition is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 10% by mass or less.

<Method for producing resin composition>
The method for producing the resin composition in the third aspect of the present invention is not particularly limited, and for example, the polymer (A), the polymer (B), the polymerization initiator (C), and used as necessary. The other components to be produced can be produced by mixing them at room temperature using ordinary mixing means such as a stirrer or a kneader.

<Melt viscosity of resin composition>
The resin composition in the third aspect of the present invention has a melt viscosity at 38 ° C. of preferably 15 Pa · s or less, more preferably 12 Pa · s or less, and still more preferably 10 Pa · s or less. When the melt viscosity of the resin composition is within the above range, it is possible to uniformly apply the resin composition to the surface to be coated, and it is easy to prevent air bubbles from being mixed. Become. In the present specification, the melt viscosity of the resin composition is a value determined by the method described in Examples described later.

  The resin composition according to the third aspect of the present invention has a low melt viscosity, excellent curability, and further provides a cured product excellent in strength, flexibility and transparency. Adhesives), coating agents, sealing materials and inks can be suitably used.

[Cured product]
The cured product in the third aspect of the present invention is obtained by curing the resin composition of the present invention in the third aspect. For example, the resin composition in the third aspect of the present invention is irradiated with energy rays. Or it can be hardened by making the said polymer (A) and a polymerization initiator (C) react by adding heat.
As energy rays for curing, ultraviolet rays are preferable. Examples of the ultraviolet light source include a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a microwave excimer lamp. As the atmosphere for irradiating ultraviolet rays, an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere in which the oxygen concentration is lowered is preferable.
The irradiation atmosphere temperature is preferably 10 to 200 ° C., and the UV irradiation amount is preferably 200 to 10,000 mJ / cm ² .

[Optical pressure sensitive adhesive]
The optical pressure-sensitive adhesive according to the third aspect of the present invention contains the cured product or resin composition according to the third aspect of the present invention, and is suitable for electronic devices such as smartphones, liquid crystal displays, and organic EL displays. Can be used.

  Various additives can be appropriately added to the optical pressure-sensitive adhesive as necessary without departing from the object of the present invention. Examples of the additive include a tackifier, a plasticizer, a pigment, a colorant, an anti-aging agent, and an ultraviolet absorber.

[IV] Resin composition (fourth embodiment)
The resin composition according to the fourth aspect of the present invention is the monomer unit (f1) derived from a conjugated diene compound having 12 or less carbon atoms in the resin composition according to the second aspect or the third aspect of the present invention. And a polymer (F) having a polymerizable functional group, and the mass ratio [(A) / (F)] of the polymer (A) and the polymer (F) is 0.01 to 100. It is a resin composition.

<Polymer (F)>
The polymer (F) used for the resin composition in the fourth aspect of the present invention is a polymer having a polymerizable functional group containing a monomer unit (f1) derived from a conjugated diene compound having 12 or less carbon atoms.
The conjugated diene compound having 12 or less carbon atoms as the monomer unit (f1) is butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene. 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, chloroprene, and the like are preferable.

  The monomer unit constituting the polymer (F) may be composed only of the monomer unit (f1) derived from the conjugated diene compound having 12 or less carbon atoms, and the monomer unit derived from the conjugated diene compound ( f1) and a monomer unit (f2) derived from a monomer other than the conjugated diene compound having 12 or less carbon atoms (excluding farnesene). That is, the polymer (F) may be obtained by polymerizing only the conjugated diene compound having 12 or less carbon atoms, and a monomer other than the conjugated diene compound having 12 or less carbon atoms and the conjugated diene compound having 12 or less carbon atoms. And a copolymer thereof.

  Examples of the monomer as the monomer unit (f2) include aromatic vinyl compounds. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4- Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2- Vinyl naphthalene, vinyl anthracene, N, N-diethyl-4-aminoethyl styrene, vinyl pyridine, 4-methoxy styrene, monochlorostyrene, dichlorostyrene, divinylbenzene and the like are preferable.

  In the case of using a monomer unit (f2) derived from a monomer other than a conjugated diene having 12 or less carbon atoms, a monomer unit (f1) derived from a conjugated diene compound having 12 or less carbon atoms in the copolymer, And the ratio of the monomer unit (f2) derived from the monomer other than the conjugated diene having 12 or less carbon atoms to the total of the monomer units (f2) derived from the monomer other than the conjugated diene having 12 or less carbon atoms Is preferably 1 to 99% by mass, more preferably 1 to 80% by mass, and 1 to 70% by mass from the viewpoint of reducing the viscosity of the resin composition and maintaining good elongation characteristics and flexibility of the cured product. More preferably, 1-50 mass% is still more preferable.

  As the polymerizable functional group of the polymer (F), the same functional groups as those exemplified as the polymerizable functional group of the polymer (A) can be used. For example, (meth) acryloyl group, epoxy group, oxetanyl group, vinyl ether group, alkoxysilyl group, (meth) acrylamide group, styrene group, maleimide group, lactone group, lactam group, sulfide group, thietane group, acetonide group, thiourea group, etc. Is mentioned. These functional groups may have a substituent.

  The number average molecular weight (Mn) of the polymer (F) used in the present invention is preferably 1,000 to 200,000, more preferably 5,000 to 200,000, still more preferably 8,000 to 100,000, and 11,000. ~ 60,000 is even more preferred. When the Mn of the polymer (F) is within the above range, the flexibility and mechanical strength of the cured product are improved and the resin composition has a low viscosity.

  The melt viscosity at 38 ° C. of the polymer (F) used in the present invention is preferably 0.1 to 3,000 Pa · s, more preferably 0.3 to 3,000 Pa · s, and 0.3 to 2,800 Pa · s. s is further preferable, 0.5 to 2,600 Pa · s is further more preferable, and 0.5 to 800 Pa · s is further more preferable. When the melt viscosity of the polymer (F) is within the above range, the resin composition can be uniformly applied to the surface to be coated, so that the coating property is improved.

The said polymer (F) can be manufactured by the method similar to the said polymer (A). Specifically, a functional group that can be polymerized by first polymerizing a conjugated diene compound having 12 or less carbon atoms and, if necessary, a monomer other than the conjugated diene compound having 12 or less carbon atoms by an emulsion polymerization method or a solution polymerization method. An unmodified polymer having no groups is produced. Subsequently, it can obtain by introduce | transducing the functional group which can superpose | polymerize with respect to this unmodified polymer.
For example, a method in which a compound for grafting such as maleic anhydride is reacted with the unmodified polymer and then a compound having a polymerizable functional group such as 2-hydroxyethyl methacrylate is reacted. The polymer (F) may be a commercially available product.

  The total content of the polymer (A) and the polymer (F) in the resin composition is preferably 1 to 99% by mass, more preferably 2 to 98% by mass, still more preferably 5 to 95% by mass, 90 mass% is still more preferable, and 15-85 mass% is still more preferable. When the content of the polymer (A) and the polymer (F) in the resin composition is within the above range, a cured product excellent in strength, flexibility, low moisture permeability and transparency can be provided.

  In the present invention, the mass ratio [(A) / (F)] of the polymer (A) and the polymer (F) is 0.01 to 100, preferably 0.05 to 100, more preferably. It is 0.1-50, More preferably, it is 0.1-25, More preferably, it is 0.1-10. When the mass ratio [(A) / (F)] is within the above range, a resin composition having a sufficiently low viscosity and a good elongation at break after curing can be obtained.

  Other configurations in the fourth aspect of the present invention, specifically, the method for producing the resin composition, the viscosity of the resin composition, the cured product, and the optical pressure-sensitive adhesive material are the configurations of the second and third aspects. Is the same.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
[Example of the first aspect of the present invention]
Each component used in the example and comparative example of the first aspect is as follows.
<Polymer (A) having polymerizable functional group>
-Polyfarnesene (A-1) to (A-5) having methacryloyl groups in the molecules obtained in Production Examples 1 to 5 described later

<Other curable resins>
・ Polyisoprene (I-X-1)
Polyisoprene / curable resin having a methacryloyl group in the molecule obtained in Comparative Production Example 1 (IX-2)
Polyfarnesene-urethane acrylate (I-X-3) modified with 2-hydroxyethyl methacrylate, synthesized as described in Example 7 of WO2012 / 018862
Urethane acrylate “DBA2210” manufactured by DuPont Co., Ltd.

<Radical polymerization initiator>
2-hydroxy-2-methyl-1-phenylpropan-1-one manufactured by BASF Corporation, trade name “DAROCUR 1173”

<Anti-aging agent>
2,6-di-t-butyl-4-methylphenol (BHT)
Made by Honshu Chemical Industry Co., Ltd.

<Production Examples 1 to 5, Comparative Production Example 1>
Production Example 1: Polyfarnesene (A-1) having a methacryloyl group in the molecule
Into a 5 liter autoclave with nitrogen substitution, 1520 g of cyclohexane and 7.8 g of 10.5 wt% cyclohexane solution of sec-butyllithium were charged, then heated to 50 ° C., and 1510 g of β-farnesene was added. Then, polymerization was performed for 2 hours. The obtained polymerization solution was poured into methanol to reprecipitate the unmodified polymer, and was filtered off, followed by vacuum drying at 80 ° C. for 10 hours to obtain 1200 g of polyfarnesene (unmodified polymer).
When a part of the unmodified polymer was analyzed by GPC, the number average molecular weight (Mn) in terms of standard polystyrene was 113,300, and the molecular weight distribution (Mw / Mn) was 1.18.
300 g of the unmodified polymer obtained in a 1 liter autoclave subjected to nitrogen substitution was charged, 4.5 g of maleic anhydride and 3.0 g of BHT were added, and reacted at 160 ° C. for 20 hours to form an unmodified polymer. Maleic anhydride was added. Next, 6.3 g of 2-hydroxyethyl methacrylate, 0.15 g of hydroquinone, and 0.9 g of N, N-dimethylbenzylamine were added and reacted at 80 ° C. for 6 hours, and polyfarnesene having a methacryloyl group in the molecule (hereinafter, “ Polymer (A-1) ”may be obtained).

Production Examples 2 and 3: Polyfarnesene having a methacryloyl group in the molecule (A-2), (A-3)
An unmodified polymer was produced in the same manner as in Production Example 1 except that the amounts of β-farnesene, sec-butyllithium and cyclohexane were changed to the amounts shown in Table 1, respectively. Table 1 shows the number average molecular weight and molecular weight distribution of the unmodified polymer.
Subsequently, polyfarnesene (A-2) and (A-3) having a methacryloyl group in the molecule were produced by reacting each unmodified polymer in the same manner as in Example 1 (hereinafter, the methacryloyl group was introduced into the molecule). And polyfarnesene (A-2) having a methacryloyl group in the molecule may be referred to as “polymer (A-2)”.

Production Example 4: Farnesene-isoprene copolymer (A-4) having a methacryloyl group in the molecule
In an autoclave having a capacity of 5 liters subjected to nitrogen substitution, 1500 g of cyclohexane and 38.5 g of 10.5 mass% cyclohexane solution of sec-butyllithium were charged, and then the temperature was raised to 50 ° C., and β-farnesene, isoprene, 1540 g of a mixed monomer (β-farnesene / isoprene = 6/4 (mass ratio)) was added and polymerization was carried out for 2 hours. The obtained polymerization solution was poured into methanol to reprecipitate the unmodified polymer, and then filtered and dried under vacuum at 80 ° C. for 10 hours to obtain 1200 g of farnesene-isoprene copolymer (unmodified polymer). It was.
When a part of the unmodified polymer was analyzed by GPC, the number average molecular weight (Mn) of standard polystyrene conversion was 25,300, and the molecular weight distribution (Mw / Mn) was 1.09.
300 g of the unmodified polymer obtained in a 1 liter autoclave subjected to nitrogen substitution was charged, 4.5 g of maleic anhydride and 3.0 g of BHT were added, and reacted at 160 ° C. for 20 hours to form an unmodified polymer. Maleic anhydride was added. Next, 6.3 g of 2-hydroxyethyl methacrylate, 0.15 g of hydroquinone, and 0.9 g of N, N-dimethylbenzylamine were added and reacted at 80 ° C. for 6 hours, and farnesene-isoprene copolymer having a methacryloyl group in the molecule. A coalescence (hereinafter sometimes referred to as “polymer (A-4)”) was obtained.

Production Example 5: Farnesene-isoprene copolymer (A-5) having a methacryloyl group in the molecule
An unmodified polymer was produced in the same manner as in Production Example 4 except that the amounts of β-farnesene, sec-butyllithium, and cyclohexane were changed to the amounts shown in Table 1, respectively. Table 1 shows the number average molecular weight and molecular weight distribution of the unmodified polymer.
Next, the unmodified polymer is reacted in the same manner as in Example 4 to obtain a farnesene-isoprene copolymer having a methacryloyl group in the molecule (hereinafter sometimes referred to as “polymer (A-5)”). Manufactured.

Comparative Production Example 1: Polyisoprene (I-X-1) having a methacryloyl group in the molecule
Into an autoclave having a capacity of 5 liters subjected to nitrogen substitution, 1420 g of cyclohexane and 70.9 g of 10.5 mass% cyclohexane solution of sec-butyllithium were charged, the temperature was raised to 50 ° C., and 1490 g of isoprene was added, Polymerization was performed for 2 hours. The obtained polymerization solution was poured into methanol to reprecipitate polyisoprene, followed by filtration, and vacuum drying at 80 ° C. for 10 hours to obtain 1200 g of polyisoprene.
When a part of polyisoprene was analyzed by GPC, the number average molecular weight (Mn) in terms of standard polystyrene was 19,400, and the molecular weight distribution (Mw / Mn) was 1.03.
300 g of the polyisoprene obtained in a 1 liter autoclave subjected to nitrogen substitution was charged, 4.5 g of maleic anhydride was added, and the mixture was reacted at 160 ° C. for 20 hours to add maleic anhydride to the polyisoprene. Next, 6.3 g of 2-hydroxyethyl methacrylate, 0.15 g of hydroquinone, and 0.9 g of N, N-dimethylbenzylamine were added and reacted at 80 ° C. for 6 hours, and polyisoprene having a methacryloyl group in the molecule (hereinafter, In some cases, “polyisoprene (I-X-1)” was obtained.

<Examples 1-5, Comparative Examples 1-3>
Example 1
For the polymer (A-1), the number average molecular weight, methacryloyl equivalent, number of functional groups per molecular chain and melt viscosity were measured by the method described later. The results are shown in Table 2.
Moreover, 3 mass parts of radical polymerization initiators were added with respect to 100 mass parts of polymers (A-1), and the curable resin composition was produced.
With respect to the obtained curable resin composition, the curing rate, transparency, curing shrinkage rate, breaking strength, breaking elongation, moisture permeability and hardness were evaluated by the methods described later. The results are shown in Table 2.

Examples 2-5
Various evaluations were performed in the same manner as in Example 1 except that the polymer (A-1) was changed to the polymers (A-2) to (A-5). The results are shown in Table 2.

Comparative Example 1
Various evaluations were performed in the same manner as in Example 1 except that the polymer (A-1) was changed to polyisoprene (I-X-1). The results are shown in Table 2.

Comparative Example 2
Various evaluations were performed in the same manner as in Example 1 except that the polymer (A-1) was changed to the curable resin (I-X-2). The results are shown in Table 2.

Comparative Example 3
Various evaluations were performed in the same manner as in Example 1 except that the polymer (A-1) was changed to urethane acrylate (I-X-3). The results are shown in Table 2.

Evaluation methods in Examples and Comparative Examples of the first aspect are as follows.
(I-1) Measurement of number average molecular weight and molecular weight distribution “GPC-8020” manufactured by Tosoh Corporation was used to adjust and measure the concentration of sample / tetrahydrofuran = 5 mg / 10 mL. In addition, Wako Pure Chemical Industries Ltd. tetrahydrofuran was used as a developing solution.
The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were determined in terms of standard polystyrene equivalent molecular weight by GPC (gel permeation chromatography). The measuring apparatus and conditions are as follows.
・ Device: GPC device “GPC8020” manufactured by Tosoh Corporation
Separation column: “TSKgel G4000HXL” manufactured by Tosoh Corporation
Detector: “RI-8020” manufactured by Tosoh Corporation
・ Eluent: Tetrahydrofuran ・ Eluent flow rate: 1.0 ml / min ・ Sample concentration: 5 mg / 10 ml
-Column temperature: 40 ° C

(I-2) Measurement of methacryloyl equivalent and the number of polymerizable functional groups per molecular chain Using ¹ H-NMR (500 MHz) manufactured by JEOL Ltd., concentration of sample / deuterated chloroform = 100 mg / 1 mL, integration The measurement was performed 512 times at a measurement temperature of 50 ° C. From the area ratio between the peak derived from the double bond of the (meth) acryloyl group and the peak derived from the polymer main chain in the obtained spectrum, the equivalent of the methacryloyl group to the polymer mass was calculated.
Further, the number of polymerizable functional groups per molecular chain was calculated from the number average molecular weight of the polymer and the functional group equivalent to the polymer mass determined by the above method.

(I-3) Method for Measuring Melt Viscosity The melt viscosity (Pa · s) of the polymer at 38 ° C. was measured with a Brookfield viscometer (manufactured by BROOKFIELD ENGINEERING LABS. INC.).
(I-4) Curing speed Each curable resin composition obtained in Examples and Comparative Examples was poured into a mold having a length of 70 mm, a width of 70 mm, and a thickness of 0.5 mm, and the surface of the composition was 50 μm thick. After covering with PET film, using UV irradiation device (manufactured by GS Yuasa Corporation, using HAK125L-F as a mercury lamp), setting illuminance 30mW / cm ² and conveyor speed 2m / min. Was irradiated with 150 mJ / cm ² of UV.
This was repeated 1, 2, 4, 6, 8, and 16 times to obtain 500 mg of cured products having a total UV irradiation amount of 150, 300, 600, 900, 1200, and 2400 mJ / cm ² , respectively. After the PET film was peeled off, the cured product was immersed in toluene at room temperature for 24 hours, the insoluble part was filtered off with a 200 mesh wire net, washed, and then vacuum dried at 80 ° C. for 12 hours. After drying, each sample was weighed, and the polymer gel fraction at each UV irradiation dose was calculated according to the following formula.

Gel fraction (%) = (mass of toluene insoluble part) / (mass of cured product before toluene immersion) × 100

From the data obtained by this test, the UV irradiation amount when the gel fraction reached 80% was estimated and the curing rate was evaluated. In addition, it evaluated according to the following reference | standard based on the UV irradiation amount required to reach | attain the gel fraction of 80%.
<Evaluation criteria>
5: 500mJ / cm ² less than 4: 500mJ / cm ² or more and less than ^{1000mJ / cm 2 3: 1000mJ /} cm 2 or more, 2000 mJ / cm ² less than ^2: 2000mJ / cm 2 or more, 3000 mJ / cm ² less than 1: 3000 mJ / cm ² or more

(I-5) Transparency The curable resin compositions obtained in Examples and Comparative Examples were injected into a mold having a length of 70 mm, a width of 70 mm, and a thickness of 0.5 mm, and the surface of the composition was PET having a thickness of 50 μm. After covering with a film, using a UV irradiation device (manufactured by GS Yuasa Corporation, using HAK125L-F as a mercury lamp), the illuminance is set to 45 mW / cm ² and the conveyor speed is set to 0.25 m / min. The work was irradiated with 1000 mJ / cm ² of UV. This was repeated three times to obtain a cured product. After peeling the PET film from the cured product, the transparency was evaluated by visual observation.
<Evaluation criteria>
5: colorless and transparent 4: very slight coloring is observed, but transparent 3: slightly colored, but transparent 2: clear coloring is observed, but transparent 1: opaque

(I-6) Curing Shrinkage Ratio The density of the cured product obtained in the above (I-5) was measured based on the method described in JIS K 6911, and this was used as the density of the composition after curing. The density of the composition before curing was measured using a specific gravity bottle method described in JIS K0061. After measuring the density before and after curing, the curing shrinkage was determined based on the following formula and evaluated according to the following criteria.
Curing shrinkage (%) = [1- (density of composition before curing) / (density of composition after curing)] × 100
<Evaluation criteria>
5: Curing shrinkage rate is less than 1% 4: Curing shrinkage rate is 1% or more and less than 3% 3: Curing shrinkage rate is 3% or more and less than 5% 2: Curing shrinkage rate is 5% or more and less than 10% 1: Curing shrinkage is 10% or more

(I-7) Breaking strength and breaking elongation A strip-shaped sample having a width of 6 mm and a length of 70 mm was punched from the cured product obtained in (I-5) above, and a tensile test was performed at a pulling rate of 10 mm / min. The breaking strength and elongation at break were measured with a tensile tester manufactured by Instron.

(I-8) Moisture permeability test Using the cured product obtained in (I-5) above, a moisture permeability test was performed based on JIS Z 0208 Condition B, and evaluation was performed according to the following criteria.
<Evaluation criteria>
5: Moisture permeability is less than 25 g / m ² · 24 h 4: Moisture permeability is 25 g / m ² · 24 h or more, less than 50 g / m ² · 24 h 3: Moisture permeability is 50 g / m ² · 24 h or more, 100 g / m ² · Less than 24 h 2: Moisture permeability is 100 g / m ² · 24 h or more, less than 200 g / m ² · 24 h 1: Moisture permeability is 200 g / m ² · 24 h or more

(I-9) Hardness The curable resin compositions obtained in Examples and Comparative Examples were injected into a mold having a length of 70 mm, a width of 35 mm, and a thickness of 2.0 mm, and the surface of the composition was a PET film having a thickness of 50 μm. And then using a UV irradiation device (manufactured by GS Yuasa Corporation, using HAK125L-F as a mercury lamp) with an illuminance of 45 mW / cm ² and a conveyor speed of 0.25 m / min. Were irradiated with 1000 mJ / cm ² of UV. This was repeated three times to obtain a cured product. Three sheets of the cured product having a thickness of 2.0 mm were stacked to obtain a 6.0 mm sample, and the hardness (JIS A) was measured in accordance with JIS K 6253.

From the results shown in Table 2, it can be seen that the polymers (A-3) to (A-5) of the present invention have a lower melt viscosity at the same molecular weight than the polyisoprene (I-X-1).
Further, the polymers (A-1) to (A-5) of the present invention have a faster curing rate than the polyisoprene (I-X-1), and in particular, polymers having a high molecular weight as in Examples 1 and 2. (A-1) and (A-2) are excellent in the curing rate.
Furthermore, the polymers (A-1) to (A-5) of the present invention have good transparency, low curing shrinkage, low moisture permeability, and flexibility, like the polyisoprene (I-X-1). You can see that it has.
In addition, since the curable resin (I-X-2) of Comparative Example 2 gels in the process of producing a polyfarnesene 2-hydroxyethyl methacrylate modified product and becomes insoluble in a solvent, measurement of the number average molecular weight and methacryloyl equivalent is performed. I couldn't.
Comparative Example 3 using urethane acrylate (I-X-3) is excellent in the curing rate as in Examples 1 to 5, but the polymer (A-) of the present invention in terms of shrinkage rate and moisture permeability during curing. 1) to (A-5) were superior.

[Example of the second aspect of the present invention]
Each component used in the Example of the 2nd mode and a comparative example is as follows.
<Polymer (A) having polymerizable functional group>
-Polymers (A-1) to (A-5) used in Examples 1 to 5 of the first aspect
Table 3 shows the number average molecular weight, molecular weight distribution, melt viscosity, methacryloyl equivalent and the number of polymerizable functional groups per molecular chain of the polymers (A-1) to (A-5).

<Polymerization initiator (C) (radical polymerization initiator)>
・ Polymerization initiator (C-1)
2-hydroxy-2-methyl-1-phenylpropan-1-one manufactured by BASF Corporation, trade name “DAROCUR 1173”

<Monomer (D)>
Monomer (D-1): dicyclopentenyloxyethyl methacrylate, manufactured by Hitachi Chemical Co., Ltd., trade name “Fancryl FA-512M”
Monomer (D-2): 1,9-nonanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Biscoat # 260”
Monomer (D-3): n-butyl acrylate manufactured by Tokyo Chemical Industry Co., Ltd., trade name “Butyl Acrylate”

<Hindered amine compound (E)>
・ Hindered amine compounds (E-1)
A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, manufactured by BASF Corporation, trade name "TINUVIN 765"

<Anti-aging agent>
・ 2,6-di-t-butyl-4-methylphenol (BHT) manufactured by Honshu Chemical Industry Co., Ltd.

<Other polymer (II-X)>
Polymer (II-X-1): Urethane acrylate “DBA2210” manufactured by DuPont Co., Ltd.
Polymer (II-X-2): Polyfarnesene modified with 2-hydroxyethyl methacrylate synthesized according to the description in Example 7 of International Publication No. 2012/018862, Polymer (II-X-3): First Unmodified polymer / polymer (II-X-4) taken out after addition of maleic anhydride after polymerization of polyfarnesene in Production Example 3 in the embodiment: After reaction with maleic anhydride in Production Example 3 in the first embodiment , Polymer / polymer (II-X-5) taken out before addition of 2-hydroxyethyl methacrylate: “TEA-1000” (acryloyl group-containing polybutadiene) manufactured by Nippon Soda Co., Ltd.

<Examples 6 to 14>
Polymers (A-1) to (A-5), monomers (D-1) to (D-3), and a polymerization initiator (C-1) in a ratio shown in Table 4 in a stainless steel 300 mL container. The resin composition was prepared by charging and mixing at room temperature using a stirring blade for 20 minutes. The obtained resin composition was evaluated by the following method. The results are shown in Table 4.

<Examples 15 to 23>
Table 5 shows polymers (A-1) to (A-5), monomers (D-1) to (D-3), a polymerization initiator (C-1), and a hindered amine compound (E-1). A resin composition was prepared and evaluated in the same manner as in Example 6 except that it was blended in the ratio shown. The results are shown in Table 5.

<Comparative Examples 4-8>
Except for blending other curable resins (II-X-1) to (II-X-5), monomer (D-1) and polymerization initiator (C-1) in the proportions shown in Table 6. Resin compositions were prepared and evaluated in the same manner as in Example 6. The results are shown in Table 6.

Evaluation methods in Examples and Comparative Examples of the second aspect are as follows.
(II-1) Measurement of number average molecular weight and molecular weight distribution It was measured by the same method as (I-1) of the first embodiment.

(II-2) Measurement of methacryloyl equivalent, and the number of polymerizable functional groups per molecular chain Measured by the same method as (I-2) of the first embodiment.

(II-3) Melt Viscosity For the polymers (A-1) to (A-5) obtained in Production Examples 1 to 5 and the resin compositions obtained in Examples and Comparative Examples, It was measured by the same method as I-3).

(II-4) UV irradiation amount and curing rate The resin compositions obtained in Examples and Comparative Examples were tested by the same method as in (I-4) of the first aspect, and the gel fraction was determined.
From the data obtained by this test, the UV irradiation amount when the gel fraction reached 80% was estimated and evaluated according to the following criteria.
<Evaluation criteria>
○: Less than 1,000 mJ / cm ² Δ: 1,000 mJ / cm ² or more, less than 2,000 mJ / cm ² ×: 2,000 mJ / cm ² or more

(II-5) Appearance (transparency)
A cured product was produced in the same manner as (I-5) in the first aspect. After peeling off the PET film from the obtained cured product, the film was observed with the naked eye, and the transparency was evaluated according to the following criteria.
<Evaluation criteria>
○: Colorless and transparent Δ: Some coloration is observed but transparent ×: Clear coloration or turbidity is observed

(II-6) Curing Shrinkage Ratio About the cured product obtained in the above (II-5), the curing shrinkage ratio was determined by the same method as (I-6) of the first embodiment, and evaluated according to the following criteria.
<Evaluation criteria>
◎: Curing shrinkage rate is less than 3% ○: Curing shrinkage rate is 3% or more and less than 5% Δ: Curing shrinkage rate is 5% or more and less than 10% ×: Curing shrinkage rate is 10% or more

(II-7) Breaking strength and breaking elongation A strip-shaped sample having a width of 6 mm and a length of 70 mm was punched from the cured product obtained in (II-5) above, and a tensile test was performed at a pulling speed of 50 mm / min. The breaking strength and elongation at break were measured with a tensile tester manufactured by Instron.

(II-8) Moisture permeability test About the hardened | cured material obtained in said (II-5), the test was done by the same method as (I-8) of a 1st aspect, and it evaluated according to the following reference | standard.
<Evaluation criteria>
5: Moisture permeability is less than 25 g / m ² · 24 h 4: Moisture permeability is 25 g / m ² · 24 h or more, less than 50 g / m ² · 24 h 3: Moisture permeability is 50 g / m ² · 24 h or more, 100 g / m ² · Less than 24 h 2: Moisture permeability is 100 g / m ² · 24 h or more, less than 200 g / m ² · 24 h 1: Moisture permeability is 200 g / m ² · 24 h or more

(II-9) Hardness The resin compositions obtained in Examples and Comparative Examples were measured by the same method as (I-9) in the first aspect.

(II-10) Heat resistance test (hue stability test)
The cured product obtained by removing the PET film in (II-5) above was allowed to stand in a 25 ° C. atmosphere for 24 hours, and then a strip-shaped test piece having a length of 60 mm × width of 6 mm × thickness of 0.5 mm was produced. Next, the prepared test piece was left in a gear oven at 100 ° C. for 72 hours, 144 hours, and 240 hours, and the hue change in each test piece was visually observed together with the test piece before heat treatment (displayed in 0 hours). And evaluated according to the following criteria. In addition, this test was done about the hardened | cured material obtained from the resin composition of Examples 15-23 and Comparative Examples 4-8.
<Evaluation criteria>
◎: Colorless ○: Pale yellow △: Yellow ×: Brown

(II-11) Heat resistance test (tensile modulus)
The test piece prepared in (II-5) above was allowed to stand at 100 ° C. for 72 hours, 144 hours, and 240 hours, and then a tensile test was performed at a tensile speed of 50 mm / min. It was measured with an Instron tensile tester. A lower tensile elastic modulus is better because it is more flexible, and a smaller change rate after the passage of time is better. In addition, this test was done about the hardened | cured material obtained from the resin composition of Examples 15-23 and Comparative Examples 4-8.

Examples 6 to 10 use polymers (A-1) to (A-5) containing monomer units derived from farnesene, and polymers containing no monomer derived from farnesene (II-X- Compared to Comparative Example 8 using 5), the viscosity is low and the curability is excellent, and the obtained cured product has a high elongation at break and low hardness, and is excellent in flexibility. In addition, the resin compositions according to Examples 11 to 14 using the polymer (A-3) have a lower viscosity than that of Comparative Example 8, but have the same or higher curing rate.
Examples 6 to 14 are excellent in curing shrinkage and moisture permeability compared to Comparative Example 4 in which urethane acrylate (II-X-1) is used instead of the polymer containing the farnesene monomer.
The polymer (II-X-2) used in Comparative Example 5 gelled in the process of producing a polyfarnesene 2-hydroxyethyl methacrylate modified product, and a uniform polymer could not be obtained. As a result, the number average molecular weight and methacryloyl equivalent could not be measured. Moreover, evaluation as another resin composition could not be performed.

  The cured products obtained in the examples were transparent, whereas the cured products obtained in Comparative Examples 6 and 7 were cloudy and were fragile, so various evaluations could not be performed. Since Comparative Examples 6 and 7 use a polymer having no polymerizable functional group, it is considered that the compatibility with other components is poor and the phases are separated in the cured polymer.

  In Examples 15 to 23 in which the hindered amine compound (E) is used in combination, it can be seen that even in a high-temperature environment, the hue stability and the change rate of the tensile elastic modulus are small, and the heat resistance is excellent.

[Example of the third aspect of the present invention]
The components used in the examples and comparative examples of the third aspect are as follows.
<Polymer (A) having polymerizable functional group>
-Polymers (A-1), (A-3) and (A-5) used in Examples 1, 3 and 5 of the first aspect

<Polymer (B)>
-Polymers (B-1) to (B-3) obtained by Production Examples 6 to 8 described later
<Polymerization initiator (C)>
・ Polymerization initiator (C-1)
2-hydroxy-2-methyl-1-phenylpropan-1-one manufactured by BASF Corporation, trade name “DAROCUR 1173”

<Monomer (D)>
・ Acrylic monomer (D-1)
Dicyclopentenyloxyethyl methacrylate, manufactured by Hitachi Chemical Co., Ltd., trade name “Fancryl FA-512M”

<Hindered amine compound (E)>
・ Hindered amine compounds (E-1)
A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, manufactured by BASF Corporation, trade name "TINUVIN 765"

<Production Examples 6 to 8>
Production Example 6: Liquid polybutadiene (B-1)
By subjecting butadiene to anionic polymerization in n-hexane using n-butyllithium as an initiator, a liquid polybutadiene having a number average molecular weight of 9,000 (hereinafter also referred to as “polymer (B-1)”) was synthesized. Table 7 shows the physical properties of the polymer (B-1).
Production Example 7: Liquid polyisoprene (B-2)
Liquid polyisoprene having a number average molecular weight of 9,000 was obtained by anionic polymerization of isoprene in n-hexane using n-butyllithium as an initiator. (Hereinafter, also referred to as “polymer (B-2)”) was synthesized. Table 7 shows the physical properties of the polymer (B-2).

Production Example 8: Liquid polyisoprene (B-3)
Liquid polyisoprene having a number average molecular weight of 20,000 (hereinafter also referred to as “polymer (B-3)”) was synthesized by anionic polymerization of isoprene in n-hexane using n-butyllithium as an initiator. . Table 7 shows the physical properties of the polymer (B-3).

<Examples 24-34>
Polymers (A-1), (A-3) and (A-5), polymers (B-1) to (B-3), a polymerization initiator (C), a monomer (D-1) and The hindered amine compound (E-1) was charged into a stainless steel 300 mL container at the ratios shown in Tables 8 and 9, and mixed at room temperature for 20 minutes using a stirring blade to prepare 200 g of a resin composition. The obtained resin composition was evaluated by the following method. The results are shown in Table 8 and Table 9.

The evaluation method in the Example of the third aspect is as follows.
(III-1) Measurement of number average molecular weight and molecular weight distribution It was measured by the same method as (I-1) of the first embodiment. In Table 7, the first decimal place is rounded off to the nearest whole number.

(III-2) Melt viscosity The polymers obtained in Production Examples 1, 3, 5 to 8 and the resin compositions obtained in Examples were measured by the same method as (I-3) of the first aspect.

(III-3) Glass transition temperature 10 mg of each polymer obtained in Production Examples 1, 3, 5 to 8 was sampled in an aluminum pan and subjected to differential scanning calorimetry (DSC) at a heating rate of 10 ° C./min. A thermogram was measured, and the peak top value of DDSC was taken as the glass transition temperature.

(III-4) Number of polymerizable functional groups per molecular chain For the polymers (A-1), (A-3) and (A-5), the same method as (I-2) of the first aspect is used. It was measured. In Table 7, the first decimal place is rounded off to the nearest whole number.

(III-5) Appearance (transparency)
About the resin composition obtained in the Example, the hardened | cured material was produced by the same method as (I-5) of a 1st aspect. After peeling off the PET film from the obtained cured product, the film was observed with the naked eye, and the transparency was evaluated according to the following criteria.
<Evaluation criteria>
5: colorless and transparent 4: very slight coloring is observed, but transparent 3: slightly colored, but transparent 2: clear coloring is observed, but transparent 1: opaque

(III-6) Breaking strength and breaking elongation About the hardened | cured material obtained in said (III-5), it measured by the same method as (II-7) of a 2nd aspect.

  When Examples 24, 25, 26, 29, and 30 were compared with Example 2 of Example 6, Example 27 and Example 8 of Example 2, and Example 28 and Example 10 of Example 2 were compared, respectively, (A) A resin composition containing a modified liquid polyfarnesene having a methacryloyl group which is a functional group polymerizable in the molecule as a component, and a liquid diene rubber as a component (B) has an appearance and breaking elongation by active energy ray curing. It turns out that the hardened | cured material comparable with a 2nd aspect is given. Furthermore, by including the liquid diene rubber as the component (B), the breaking strength was greatly improved while maintaining the transparency. In addition, the melt viscosity was reduced and handling was improved.

[Example of the fourth aspect of the present invention]
The components used in the examples and comparative examples of the fourth aspect are as follows.
<Polymer (A) having polymerizable functional group>
-Polymers (A-1) and (A-3) used in Examples 1 and 3 of the first aspect

<Polymer (B)>
-Polymers (B-1) and (B-2) obtained by Production Examples 6 and 7 of the third aspect
<Polymerization initiator (C)>
・ Polymerization initiator (C-1)
2-hydroxy-2-methyl-1-phenylpropan-1-one manufactured by BASF Corporation, trade name “DAROCUR 1173”

<Monomer (D)>
・ Acrylic monomer (D-1)
Dicyclopentenyloxyethyl methacrylate, manufactured by Hitachi Chemical Co., Ltd., trade name “Fancryl FA-512M”

<Hindered amine compound (E)>
・ Hindered amine compounds (E-1)
A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, manufactured by BASF Corporation, trade name "TINUVIN 765"

<Polymer (F-1)>
-Polymer (F-1) obtained by Production Example 9 below
Production Example 9: Modified liquid polyisoprene (F-1) having a methacryloyl group in the molecule
Isoprene was anionically polymerized in n-hexane using n-butyllithium as an initiator to obtain polyisoprene having a number average molecular weight of 36,000.
Next, a modified liquid polyisoprene having a methacryloyl group in the molecule (hereinafter, also referred to as “polymer (F-1)”) is obtained by reacting the unmodified polymer in the same manner as in Production Example 1 of the first aspect. Synthesized. About the polymer (F-1), the physical property was evaluated similarly to (III-1)-(III-6) in a 3rd aspect. The results are shown in Table 10.

<Examples 35 to 38>
Polymer (A-1) or (A-3), Polymer (F), Polymer (B-1) or (B-2), Polymerization initiator (C-1), Monomer (D-1 ) And the hindered amine compound (E-1) in a ratio shown in Table 11 into a stainless steel 300 mL container, and mixed at room temperature for 20 minutes using a stirring blade to prepare 200 g of a resin composition. . The obtained resin composition was evaluated by the following method. The results are shown in Table 11.

The evaluation method in the Example of the fourth aspect is as follows.
(IV-1) Melt viscosity About the resin composition obtained in the Example, it measured by the same method as (I-3) of a 1st aspect.

(IV-2) Appearance (transparency)
About the resin composition obtained in the Example, the hardened | cured material was produced by the same method as (I-5) of a 1st aspect. After peeling off the PET film from the obtained cured product, the film was observed with the naked eye, and the transparency was evaluated according to the following criteria.
<Evaluation criteria>
5: colorless and transparent 4: very slight coloring is observed, but transparent 3: slightly colored, but transparent 2: clear coloring is observed, but transparent 1: opaque

(IV-3) Breaking strength and breaking elongation About the hardened | cured material obtained in said (IV-2), it measured by the same method as (II-7) of a 2nd aspect.

  Example 35 and the first aspect Example 3, Example 36 and the second aspect Example 8, Example 37 and the third aspect Example 27, and Example 38 and the third aspect Example 31 are respectively compared. It can be seen that the composition obtained by mixing the polymer (F) in addition to the polymer (A) also gives a cured product comparable to other embodiments by active energy ray curing.

Claims (25)

  The polymer which has a polymerizable functional group containing the monomer unit (a1) derived from farnesene as a monomer unit which comprises a polymer.   The polymerizable functional group is at least one selected from a (meth) acryloyl group, an epoxy group, an oxetanyl group, a vinyl ether group, and an alkoxysilyl group, which may have a substituent. Polymer.   The polymer according to claim 1 or 2, wherein the melt viscosity at 38 ° C is 0.1 to 3000 Pa · s.   The polymer in any one of Claims 1-3 whose number average molecular weights are 1000-1 million.   The polymer in any one of Claims 1-4 in which the monomer unit which comprises a polymer consists only of the monomer unit (a1) derived from farnesene.   The monomer unit constituting the polymer contains a monomer unit (a1) derived from farnesene and a monomer unit (a2) derived from a monomer other than farnesene. The polymer described in 1.   The polymer according to claim 6, wherein the monomer unit (a2) is a monomer unit derived from a conjugated diene compound other than farnesene.   The polymer according to claim 6, wherein the monomer unit (a2) is a monomer unit derived from an aromatic vinyl compound.   The polymer according to claim 8, wherein the aromatic vinyl compound is at least one selected from styrene, α-methylstyrene, and 4-methylstyrene.   The ratio of the common logarithm value of the melt viscosity at 38 ° C and the number average molecular weight (Mn) [the common logarithm value of the melt viscosity at 38 ° C / number average molecular weight (Mn)] is 0.000060 or less. The polymer in any one of.   Step (1) for preparing an unmodified polymer containing a farnesene-derived monomer unit (a1) and having no polymerizable functional group, and introducing a polymerizable functional group into the unmodified polymer The manufacturing method of the polymer in any one of Claims 1-10 which has a process (2) to do.   The production of the polymer according to claim 11, wherein the step (2) is a step of reacting a compound having a polymerizable functional group after reacting with a compound for grafting on the unmodified polymer. Method.   The resin composition containing the polymer (A) in any one of Claims 1-10.   Furthermore, the resin composition of Claim 13 containing a polymerization initiator (C).   A polymer (A) according to any one of claims 1 to 10, a monomer (D) and a polymerization initiator (C), and a mass ratio of the polymer (A) and the monomer (D). [(A) / (D)] is 0.01 to 99, and the polymerization initiator (C) is 0.1 to 20 with respect to 100 parts by mass in total of the polymer (A) and the monomer (D). A resin composition containing part by mass.   Furthermore, the resin composition of Claim 15 which contains 0.01-10 mass parts of hindered amine type compounds (E) with respect to a total of 100 mass parts of a polymer (A) and a monomer (D).   The polymer (A) according to any one of claims 1 to 10, a polymer (B) containing a monomer unit derived from a conjugated diene compound (b1) having 12 or less carbon atoms and having no polymerizable functional group, and A resin composition containing a polymerization initiator (C) and having a mass ratio [(A) / (B)] of a polymer (A) and a polymer (B) of 0.01 to 100.   The resin composition of Claim 17 whose content of a polymerization initiator (C) is 0.1-20 mass% in the whole quantity of a resin composition.   The resin composition according to claim 17 or 18, wherein the conjugated diene compound (b1) having 12 or less carbon atoms is at least one selected from isoprene and butadiene.   Furthermore, 0.01-1,000 mass parts of monomers (D) are contained with respect to a total of 100 mass parts of a polymer (A) and a polymer (B), In any one of Claims 17-19 The resin composition as described.   Furthermore, the resin composition in any one of Claims 17-20 which contains 0.01-10 mass% of hindered amine type compounds (E) in the whole quantity of a resin composition.   Furthermore, it contains a polymer (F) containing a monomer unit derived from a conjugated diene compound (f1) having 12 or less carbon atoms and having a polymerizable functional group, and comprises a polymer (A) and a polymer (F). The resin composition according to any one of claims 13 to 21, wherein the mass ratio [(A) / (F)] is 0.01 to 100.   Hardened | cured material which hardened the resin composition in any one of Claims 13-22.   An optical pressure-sensitive adhesive containing the cured product according to claim 23.   The optical adhesive containing the resin composition in any one of Claims 13-22.