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

Abstract

A polymer comprising a farnesene-derived monomer unit (a1) as a monomer unit constituting the polymer and having a polymerizable functional group. A resin composition containing a polymer (A) containing a farnesene-derived monomer unit (a1) as a monomer unit constituting the polymer and having a polymerizable functional group.

Description

Polymer, method for producing same, and resin composition containing same

technical field

The present invention relates to a polymer comprising a farnesene-derived monomer unit, and a method for producing the same.

Also, the present invention relates to a resin composition containing a polymer containing a farnesene-derived monomer unit, a cured product obtained by curing the resin composition, and an optical adhesive containing the cured product or the resin composition.

Background technique

In recent years, with the popularization of electronic devices with screens such as liquid crystals, such as smartphones and tablet PCs, research has been actively conducted on transparent resin materials and transparent resin adhesives used to cover screens.

For example, Patent Document 1 describes a curable resin composition containing polyisoprene having a (meth)acryloyl group in the molecule, a monofunctional (meth)acrylate monomer, and a radical In the composition of the polymerization initiator, a hindered amine compound having no secondary amino group in the molecule is further blended.

In addition, Patent Document 2 describes a thermosetting resin composition comprising: an epoxy resin, a curing agent, and an epoxidized polybutylene oxide having a specific number-average molecular weight containing a specific amount of epoxy groups in the molecule. alkene.

It should be noted that polymers of β-farnesene are described in Patent Documents 3 and 4, but their practical use has not been fully studied. In addition, polymers of β-farnesene having polymerizable functional groups have not yet been studied. Research.

prior art literature

patent documents

Patent Document 1: Japanese Patent No. 5073400

Patent Document 2: Japanese Patent No. 4098107

Patent Document 3: International Publication No. 2010/027463

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

Contents of the invention

The problem to be solved by the invention

For the curable resin composition described in Patent Documents 1 and 2, although its cured product satisfies the characteristics such as strength, flexibility and transparency required by electronic devices with screens such as liquid crystals, it is difficult to improve the curing speed and low There is still room for improvement in properties such as increased viscosity and low cure shrinkage.

The present invention is made in view of the above circumstances, and provides a polymer capable of imparting a cured product having low viscosity, fast curing speed, excellent cure shrinkage, strength, flexibility, low moisture permeability, and transparency, and a method for producing the same.

In addition, the present invention provides a resin composition capable of imparting a cured product with low viscosity, fast curing speed, excellent curing shrinkage, and excellent strength, flexibility, low moisture permeability, and transparency, a cured product obtained by curing it, And an adhesive for optics containing the cured product or the aforementioned resin composition.

means of solving problems

As a result of intensive studies by the inventors of the present invention, it was found that a polymer obtained by introducing a polymerizable functional group into a polymer having a monomer unit derived from farnesene can impart strength, flexibility, low moisture permeability, and excellent transparency As a cured product, the viscosity of the polymer is low, the curing speed is fast, and the curing shrinkage is excellent, thereby completing the first aspect of the present invention.

In addition, the inventors of the present invention have found that a polymer obtained by introducing a polymerizable functional group into a polymer having a monomer unit derived from farnesene can provide a cured product having excellent strength, flexibility, low moisture permeability, and transparency, Furthermore, the resin composition containing this polymer has a low viscosity, a fast curing rate, and is excellent in curing shrinkage property, thereby completing the second aspect and the fourth aspect of the present invention.

Furthermore, the inventors of the present invention have found that a polymer containing a monomer unit derived from farnesene and having a polymerizable functional group and a monomer unit derived from a conjugated diene compound having 12 or less carbon atoms are contained in a specific ratio And the resin composition of the polymer which does not have a polymerizable functional group can provide the hardened|cured material which is low in viscosity, and is excellent in strength, flexibility, hardness, and transparency, and has completed the 3rd aspect and 4th aspect of this invention.

That is, the present invention makes the following [1] to [9] the gist.

[1] A polymer comprising a farnesene-derived monomer unit (a1) as a monomer unit constituting the polymer and having a polymerizable functional group.

[2] The method for producing a polymer according to [1], comprising the step (1) of producing an unmodified polymer containing a farnesene-derived monomer unit (a1) and does not have a polymerizable functional group; and the step (2) of introducing a polymerizable functional group to the unmodified polymer.

[3] A resin composition containing the polymer (A) described in [1].

[4] A resin composition comprising the polymer (A), monomer (D) and polymerization initiator (C) described in [1], the mass ratio of the polymer (A) to the monomer (D) [( A)/(D)] is 0.01 to 99, and contains 0.1 to 20 parts by mass of the polymerization initiator (C) with respect to a total of 100 parts by mass of the polymer (A) and the monomer (D).

[5] A resin composition comprising: the polymer (A) described in [1], which contains a monomer unit derived from a conjugated diene compound (b1) having 12 or less carbon atoms and does not have a polymerizable functional group. The mass ratio [(A)/(B)] of the polymer (B), the polymerization initiator (C), and the polymer (A) to the polymer (B) is 0.01-100.

[6] The resin composition according to any one of [3] to [5], further comprising a polymer (F) containing a conjugated bismuth having 12 or less carbon atoms. The monomer unit of the vinyl compound (f1) has a polymerizable functional group, and the mass ratio [(A)/(F)] of the polymer (A) to the polymer (F) is 0.01-100.

[7] A cured product obtained by curing the resin composition described in any one of [3] to [6].

[8] An optical adhesive comprising the cured product described in [7].

[9] An optical adhesive containing the resin composition according to any one of [3] to [6].

The effect of the invention

According to the first aspect of the present invention, it is possible to provide a polymer capable of imparting a cured product having low viscosity, high curing speed, excellent cure shrinkage, strength, flexibility, low moisture permeability, and transparency, and a method for producing the same.

In addition, according to the second aspect and the fourth aspect of the present invention, it is possible to provide a resin combination capable of imparting a cured product having low viscosity, fast curing speed, excellent cure shrinkage, and excellent strength, flexibility, low moisture permeability, and transparency. things. Furthermore, a cured product obtained by curing, and an optical adhesive containing the cured product or the aforementioned resin composition can be provided.

Furthermore, according to the third aspect and the fourth aspect of the present invention, it is possible to provide a resin composition capable of imparting a cured product with low viscosity and excellent strength, flexibility, and transparency, a cured product obtained by curing it, and a resin composition containing the cured product. A cured product or an optical adhesive of the aforementioned resin composition.

Detailed ways

[I] Polymer (first aspect of the present invention)

The polymer of the present invention (hereinafter referred to as polymer (A)) contains a farnesene-derived monomer unit (a1) as a monomer unit constituting the polymer, and has a polymerizable functional group.

The aforementioned farnesene-derived monomer unit (a1) may be a monomer unit derived from α-farnesene, or may be a monomer unit derived from β-farnesene represented by the following formula (I). The monomer unit is preferably a monomer unit derived from β-farnesene from the viewpoint of ease of production. In addition, α-farnesene and β-farnesene may be used in combination.

[chemical 1]

Examples of the aforementioned polymerizable functional groups include (meth)acryloyl groups, epoxy groups, oxetanyl groups, vinyl ether groups, alkoxysilyl groups, (meth)acrylamide groups, styrene groups, group, maleimide group, lactone group, lactam group, sulfide group, thietanyl group, acetonide group, thiourea group, among these, preferably selected from (meth)acryloyl group , an epoxy group, an oxetanyl group, a vinyl ether group, and an alkoxysilyl group, and more preferably a (meth)acryloyl group. In addition, these functional groups may have a substituent.

In this specification, "(meth)acryloyl" means "acryloyl or methacryloyl". In addition, in this specification, "(meth)acrylic" means "acrylic or methacrylic".

The monomer unit constituting the polymer (A) may include only a farnesene-derived monomer unit (a1), or may include a farnesene-derived monomer unit (a1) and a farnesene-derived monomer unit. Monomeric 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, monomer units (a2) derived from monomers other than farnesene include monomer units derived from conjugated diene compounds and aromatic vinyl compounds.

The conjugated diene compound is preferably a conjugated diene compound having 12 or less carbon atoms, and examples of the conjugated diene compound having 12 or less carbon atoms include butadiene, isoprene, 2,3 -Dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octane Diene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, chloroprene, etc. Among these, isoprene and butadiene are more preferable. These conjugated diene compounds may be used alone or in combination of two or more.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4 -tert-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-vinylnaphthalene, vinylanthracene, N,N-di Aromatic vinyl compounds such as ethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene, etc. 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, from the viewpoint of reducing the viscosity of the polymer, increasing the curing speed, and maintaining good elongation characteristics and flexibility of the cured product From the point of view, the monomer unit (a2) derived from a monomer other than farnesene in the copolymer is relative to the monomer unit (a1) derived from farnesene and the monomer unit derived from a monomer other than farnesene. The total ratio of the monomer units (a2) is preferably 1 to 99% by mass, more preferably 1 to 80% by mass, still more preferably 1 to 70% by mass, and still more preferably 1 to 50% by mass.

The number average molecular weight (Mn) of the polymer (A) of the present invention is preferably 10 million to 1 million, more preferably 20 million to 500,000, more preferably 80 million to 500,000, still more preferably 15,000 to 450,000, still more preferably 15,000 to 300,000, more preferably 20,000 to 200,000. When the Mn of the polymer (A) is within the aforementioned range, the flexibility, mechanical strength, and curing speed increase, and the viscosity of the polymer decreases. 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 means the number average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC).

The polymer (A) of the present invention has a melt viscosity at 38°C of preferably 0.1 to 3000 Pa·s, more preferably 0.6 to 3000 Pa·s, more preferably 0.6 to 2800 Pa·s, still more preferably 1.5 to 2600 Pa·s, More preferably, it is 1.5 to 800 Pa·s. When the melt viscosity (38° C.) of the polymer is within the above-mentioned range, there is no unevenness on the surface to be coated, and the polymer can be uniformly coated, so the applicability becomes good. In addition, in this specification, the melt viscosity (38 degreeC) of a polymer is the value calculated|required by the method described in the Example mentioned later.

The molecular weight distribution (Mw/Mn) of the polymer (A) of the present invention is preferably 1.0 to 8.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 3.0. When Mw/Mn is within the aforementioned range, the viscosity variation of the obtained polymer (A) becomes small.

The glass transition temperature of the polymer (A) of the present invention will also vary depending on the bonding method (microstructure), other farnesene-derived monomers, and the amount of monomers other than farnesene further used if necessary. Change, preferably -90~0°C, more preferably -90~-10°C. When it is the said range, a soft hardened|cured material can be obtained, and the adhesive agent used for laminated structures, such as a liquid crystal screen, becomes favorable in step followability and impact absorption.

The number of polymerizable functional groups per molecular chain of the polymer (A) of the present invention is preferably 1-150, more preferably 1.5-75, and even more preferably 1.5-30. 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 increased, and shrinkage during curing can be suppressed low.

The number of polymerizable functional groups per molecular chain is calculated from the number average molecular weight (Mn) of the polymer (A) and the functional group equivalent (g/eq) of the polymer (A) as shown in the following formula.

(Number of polymerizable functional groups per molecular chain)=(Mn)/(functional group equivalent).

The functional group equivalent means "the average molecular weight of a polymer having one functional group". For example, the functional group equivalent when the polymerizable functional group is a methacryloyl group is referred to as "methacryloyl equivalent" and means "molecular weight of a polymer having one methacryloyl group on average". The functional group equivalent can also be calculated based on the reaction rate of the modifier, and can also be obtained 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 polymers (A) each having a different type of monomer unit, molecular weight, and functional group.

The ratio of the common logarithm value of the melt viscosity (Pa·s) at 38°C to the number average molecular weight (Mn) of the polymer (A) of the present invention [common logarithm value of the melt viscosity at 38°C/number average molecular weight (Mn )] is preferably 0.000060 or less, preferably 0.000055 or less, more preferably 0.000050 or less. When the ratio of the common logarithm value of the melt viscosity at 38° C. to the number average molecular weight is within the above range, the polymer can be uniformly coated without unevenness on the surface to be coated, and thus the coatability becomes good.

<Production method of polymer (A)>

Examples of the method for producing the polymer (A) of the present invention include a production method comprising the step (1) of producing an unmodified polymer by polymerizing farnesene and, if necessary, Further polymerizing a monomer other than farnesene without a polymerizable functional group; and a step (2) of introducing a polymerizable functional group to the unmodified polymer.

The step (1) of preparing the unmodified polymer will be described later, and here, the step (2) of introducing a polymerizable functional group to the unmodified polymer will be mainly described. As the first method for producing the polymer of the present invention, a method of preparing an unmodified polymer by polymerizing farnesene and, if necessary, further polymerizing monomers other than farnesene, and combining the unmodified polymer with A compound for grafting such as maleic anhydride is reacted, followed by a reaction with a compound having a polymerizable functional group such as 2-hydroxyethyl methacrylate.

As the compound used for grafting the aforementioned unmodified polymer, unsaturated carboxylic anhydrides such as maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, itaconic anhydride, etc.; Unsaturated carboxylic acids such as toric acid, fumaric acid, citraconic acid, and itaconic acid; unsaturated carboxylic acid esters such as maleic acid, fumaric acid, citraconic acid, and itaconic acid; Unsaturated carboxylic acid amides such as fumaramide, citraconamide, and itaconamide; unsaturated carboxylic acid imides such as maleimide, fumarimide, citraconimide, and itaconamide; Maleimide, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc.

In addition, examples of the compound having the aforementioned polymerizable functional group include (meth)acrylic acid; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, pentaerythritol (Meth)acrylates such as trimethacrylate, dipentaerythritol monohydroxyacrylate; 2-hydroxyethyl vinyl ether, N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl) Methacrylamide, N-(2-hydroxyethyl)maleimide, 4-vinylphenol, etc. It should be noted that the position where the polymerizable functional group is to be introduced may be the polymer terminal of the polymer or a side chain. In addition, the above-mentioned functional groups may be used alone or in combination of two or more.

As the second method for producing the polymer of the present invention, for example, a method in which a living terminal of an unmodified polymer obtained by living anionic polymerization of farnesene is added to form a bond to the unmodified polymer Combine at least one with at least one selected from hydroxyl, carboxyl, carbonyl, thiocarbonyl, acid halide, acid anhydride, thiocarboxylic acid, aldehyde, thioaldehyde, carboxylate, amido, sulfonate Acid group, sulfonate group, phosphoric acid group, phosphate group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothio group cyanate group, silanol group, alkoxysilane, silicon halide group, tin halide group, alkoxytin group and phenyltin group, etc. to synthesize modified polymers, and then make it with Compounds with polymerizable functional groups such as acrylic acid react.

Examples of the living anionic polymerization initiator for the living anionic polymerization of farnesene include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, benzene Lithium, stilbene lithium and other organic monolithium compounds; dilithium methane, dilithium naphthalene, 1,4-dilithium butane, 1,4-dilithium-2-ethylcyclohexane, 1,3 , 5-trilithium benzene and other polyfunctional organolithium compounds; sodium naphthalene, potassium naphthalene, etc. In addition, compounds such as diisopropenylbenzene and dibenzyltoluene that react with an organic alkali metal reagent to impart a polyfunctional organic alkali metal reagent can also be used in combination.

In addition, examples of the compound for introducing an atomic group having at least one functional group into the active terminal include cyclic ethers such as epoxy and oxetane; cyclic amines such as pyrrolidine; and cyclic sulfur compounds such as vinyl sulfide. things etc. In addition, the said functional group may be 1 type or it may combine 2 or more types.

As a third method for producing the polymer of the present invention, a method may be mentioned in which an unmodified polymer is prepared by polymerizing farnesene and, if necessary, further polymerizing a monomer other than farnesene, and the unmodified polymer After epoxidation, it is reacted with a compound having the above-mentioned polymerizable functional group.

Examples of the compound used for epoxidizing the unmodified polymer include peracids such as peracetic acid and perbenzoic acid.

Moreover, as a compound which has the said polymerizable functional group, carboxylic acid, such as acrylic acid and methacrylic acid, is mentioned, for example. It should be noted that the position where the polymerizable functional group is to be introduced may be the polymer terminal of the polymer or a side chain. In addition, the above-mentioned functional groups may be used alone or in combination of two or more.

When functionalizing the above-mentioned unmodified polymer and storing the modified polymer, in order to suppress the decrease in molecular weight, discoloration, and gelation caused by deterioration, it is also possible to combine it with the unmodified polymer or the modified polymer. Appropriate anti-aging agent. Specifically, 2,6-di-tert-butyl-4-methylphenol (BHT), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4, 4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol) (AO-40), 3,9 -bis[1,1-dimethyl-2-[3-(3-tert-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[(10 Dialkylthio)methyl]-6-methylphenol (Irganox 1726), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert Amylphenyl acrylate (Sumilizer GS), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate (Sumilizer GM) , 6-tert-butyl-4-[3-(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphapan-6-yl oxy)propyl]-2-methylphenol (Sumilizer GP), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168), dioctadecyl-3,3'-disulfide Dipropionate, hydroquinone, p-methoxyphenol, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (NOCRAC 6C), bis(2,2, 6,6-tetramethyl-4-piperidinyl) sebacate (LA-77Y), N,N-dioctadecylhydroxylamine (Irgastab FS 042), bis(4-tert-octylphenyl ) amine (Irganox 5057), etc. In addition, the above-mentioned anti-aging agents may be used alone or in combination of two or more.

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

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

As the emulsion polymerization method for obtaining an unmodified polymer, known methods 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 an emulsifier, for example, a long-chain fatty acid salt or rosin salt having 10 or more carbon atoms can be 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.

Water is generally used as a dispersant, and water-soluble organic solvents such as methanol and ethanol may be contained within a range not impairing stability during polymerization.

Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, hydrogen peroxide, and the like.

In order to adjust the molecular weight of the unmodified polymers, it is also possible to use chain transfer agents. Examples of chain transfer agents include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, and γ-terpinene , α-methylstyrene dimer, etc.

The emulsion polymerization temperature can be appropriately selected according to the type of radical polymerization initiator to be used, but usually, it is preferably 0 to 100°C, and more preferably 0 to 60°C. The polymerization method may be either continuous polymerization or batch polymerization. Polymerization can be terminated by adding a polymerization inhibitor.

Examples of the polymerization inhibitor include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine, and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, sodium nitrite, and the like.

After the polymerization reaction is stopped, an anti-aging agent may be added as needed. After the polymerization reaction is terminated, unreacted monomers are removed from the obtained latex as needed, and then salts such as sodium chloride, calcium chloride, and potassium chloride are used as coagulants, and acids such as nitric acid and sulfuric acid are added as needed to convert the coagulation system. After adjusting the pH to a predetermined value and coagulating the unmodified polymer, the dispersion solvent is separated to recover the unmodified polymer. Next, an unmodified polymer can be obtained by drying after water washing and dehydration. It should be noted that, when coagulating, if necessary, the latex may be mixed with spreading oil as an emulsified dispersion in advance, and recovered as an unmodified polymer in the oil.

As a solution polymerization method for obtaining an unmodified polymer, known methods can be applied. For example, a monomer is polymerized in the presence of a polar compound using a Ziegler catalyst, a metallocene catalyst, or an anionically polymerizable active metal in a solvent.

Examples of active metals capable of anionic polymerization include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; and lanthanide rare earth metals such as lanthanum and neodymium. Among them, alkali metals and alkaline earth metals are preferable, and alkali metals are particularly preferable. Furthermore, among alkali metals, organic alkali metal compounds are more preferably used.

Examples of solvents include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; Formula hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, etc.

Examples of organic alkali metal compounds include organic monolithium such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, phenyllithium, and stilbene lithium. Compounds; polyfunctional organolithium compounds such as dilithium methane, dilithium naphthalene, 1,4-dilithium butane, 1,4-dilithium-2-ethylcyclohexane, 1,3,5-trilithium benzene ; Sodium naphthalene, potassium naphthalene, etc. Among them, organic lithium compounds are preferable, and organic monolithium compounds are more preferable. The amount of the organic alkali metal compound used can be appropriately determined according to the molecular weight of the desired unmodified polymer, and is preferably 0.01 parts by mass relative to 100 parts by mass of the total amount of farnesene and, if necessary, monomers other than farnesene. ~7 parts by mass.

Organic alkali metal compounds can also be used as organic alkali metal amides by reacting with secondary amines such as dibutylamine, dihexylamine, and dibenzylamine.

Polar compounds will not deactivate the reaction during anionic polymerization, and are used to adjust the microstructure of the farnesene site. Examples include ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol diethyl ether; tetramethylethylenediamine , trimethylamine and other tertiary amines; alkali metal alkoxides, phosphine compounds, etc. The polar compound is preferably used in an equivalent amount of 0.01 to 1000 moles relative to the organic alkali metal compound.

The temperature of the polymerization reaction is usually -80 to 150°C, preferably 0 to 100°C, more preferably 10 to 90°C. The polymerization method may be either a batch type or a continuous type.

During the polymerization reaction, alcohol such as methanol and isopropanol can be added as a polymerization inhibitor to terminate the reaction. The obtained polymerization reaction liquid is poured into a poor solvent such as methanol to precipitate the unmodified polymer, or the polymerization reaction liquid is washed with water, separated and then dried to isolate the unmodified polymer.

[II] Resin composition (second method)

The resin composition in the second aspect of the present invention contains the polymer of the first aspect of the present invention, that is, contains a farnesene-derived monomer unit (a1) as a monomer unit constituting the polymer and has a polymerizable Functional group polymer (A) resin composition.

The polymer (A) in the first aspect of the present invention has a low viscosity, a fast curing rate, and excellent curing shrinkage, and the resin composition using it can impart a cured product having excellent strength, flexibility, low moisture permeability, and transparency. things.

In the 2nd aspect of this invention, it is preferable to contain the polymerization initiator (C) mentioned later from a viewpoint of providing the said hardened|cured material.

In addition, the resin composition in the second aspect of the present invention is preferably a resin composition containing a monomer unit (a1) derived from farnesene as a monomer unit constituting a polymer and having a Polymer (A), monomer (D) and polymerization initiator (C) of polymerized functional groups, the mass ratio of polymer (A) to monomer (D) [(A)/(D)] is 0.01~99, The polymerization initiator (C) is contained in an amount of 0.1 to 20 parts by mass with respect to a total of 100 parts by mass of the polymer (A) and the monomer (D).

<Polymer (A)>

The polymer (A) used in the second aspect of the present invention contains a farnesene-derived monomer unit (a1) as a monomer unit constituting the polymer and has a polymerizable functional group. This polymer (A) is the same as the polymer in the above-mentioned first aspect of the present invention, and has a low viscosity, a fast curing rate, and excellent cure shrinkage.

The content of the polymer (A) in the resin composition in the second aspect of the present invention is preferably 1 to 99% by mass, more preferably 2 to 98% by mass, still more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, more preferably 15 to 85% by mass. 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 using a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator. In order to obtain a cured product that is uniformly cured, preferably It is a monomer which can polymerize with the functional group of a polymer (A). As a monomer (D), the compound which has a (meth)acryloyl group, an epoxy group, an oxetanyl group, a vinyl ether group, and an alkoxysilyl group in a molecule|numerator, for example is mentioned.

Specific compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, butylethoxy (meth)acrylate , Butyl ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate Enoxyethyl ester, dicyclopentyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, ( 2-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, phenoxyhydroxypropyl (meth)acrylate, morpholino (meth)acrylate, phenoxy (meth)acrylate Ethyl ester, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, methoxydi Monofunctional (meth)acrylates such as ethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate;

1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dimethyloltri Cyclodecane di(meth)acrylate, Ethylene glycol di(meth)acrylate, Glycerin di(meth)acrylate, Ethylene oxide modified bisphenol A di(meth)acrylate, Triethyl Difunctional (meth)acrylates such as diol di(meth)acrylates;

Trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate base) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate and other multifunctional (meth)acrylates;

3,4-Epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate, 1,2-epoxy-4-vinylcyclohexane, 1,2:8 ,9-diepoxylimonene, 2,6,6-trimethyl-2,3-epoxybicyclo[3.1.1]heptane and other epoxy compounds;

3-Ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 3-ethyl- 3-(phenoxymethyl)oxetane, bis[1-ethyl(3-oxetane)]methyl ether, 3-ethyl-3-(2-ethylhexyloxymethyl base) oxetane compounds such as oxetane;

2-Hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and other vinyl ether compounds;

Compounds such as mercaptomethyltrimethoxysilane, glycidoxymethyltrimethoxysilane, and vinylmethyltrimethoxysilane.

Among these, dicyclopentyloxyethyl (meth)acrylate and dicyclopentyloxyethyl (meth)acrylic acid are preferable from the viewpoint of good compatibility with the polymer (A). ester, 1,9-nonanediol diacrylate, n-butyl acrylate, 2-ethylhexyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentene (meth)acrylate esters, phenoxyethyl (meth)acrylate. These may be used individually by 1 type, and may use it in combination of 2 or more types.

The mass ratio [(A)/(D)] of the polymer (A) to the monomer (D) is 0.01 to 99, preferably 0.1 to 99, more preferably 0.2 to 99, further preferably 0.2 to 10, and further Preferably it is 0.2~5. When the mass ratio [(A)/(D)] is within the above range, the physical properties of the polymer (A) are exhibited, and a cured product having excellent flexibility and low cure shrinkage can be obtained.

<Polymerization Initiator (C)>

Examples of the polymerization initiator (C) used in the present invention include photopolymerization initiators that initiate polymerization by irradiation with active energy rays such as ultraviolet rays, and thermal polymerization initiators that initiate polymerization by heat. From the viewpoint of curing by short-time irradiation and obtaining a cured product without deteriorating the substrate, a photopolymerization initiator is preferable, and a photopolymerization initiator that initiates a polymerization reaction by irradiation of ultraviolet rays is more preferable. As a photoinitiator, a cationic photoinitiator and a radical type polymerization initiator are mentioned, for example.

As a cationic photoinitiator, an aromatic diazonium salt, an aromatic iodonium salt, an aromatic sulfonium salt, a metallocene compound etc. are mentioned, for example.

As a cationic photopolymerization initiator of an aromatic diazonium salt, "P-33 (trade name)" (ADEKA Corporation), etc.

As cationic photopolymerization initiators of aromatic iodonium salts, "Rhodorsil Photo Initiator 2074 (trade name)" (manufactured by Rodia Corporation), "IRGACURE 250 (trade name)" (manufactured by BASF Corporation) and the like are known.

As a cationic photopolymerization initiator of an aromatic sulfonium salt, "FC-509 (trade name)" (manufactured by Sumitomo 3M Co., Ltd.), "IRGACURE 270 (trade name)" (manufactured by BASF Corporation), etc. are known.

As a metallocene-based cationic photopolymerization initiator, "IRGACURE 261 (trade name)" (manufactured by BASF Corporation) and the like are known.

Examples of radical-based photopolymerization initiators include acetophenone-based, benzophenone-based, alkylphenone-based, acylphosphine oxide-based, benzoin-based, ketal-based, anthraquinone-based, disulfide-based Phytoxanthone-based, thiuram-based, fluoroamine-based, etc. Among these, alkylphenone-based or acylphosphine oxide-based radical photopolymerization initiators are preferable.

Examples of the alkylphenone-based radical photopolymerization initiator include hydroxyalkylphenone-based, aminoalkylphenone-based, and the like. Examples of hydroxyalkylphenone-based radical photopolymerization initiators include "DAROCUR 1173 (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), etc.

Examples of radical photopolymerization initiators based on aminoalkylphenones include "IRGACURE 907 (trade name)" (2-methyl-1-(4-methylthiophenyl)-2-morpholine propan-1-one), "IRGACURE 369 (trade name)" (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone), etc.

Examples of acylphosphine oxide-based radical photopolymerization initiators include "LUCIRIN TPO (trade name)" (2,4,6-trimethylbenzoyldiphenylphosphine oxide), "IRGACURE 819 (trade name) "(bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) (both manufactured by BASF Corporation), etc.

Among these, a hydroxyalkylphenone-based radical photopolymerization initiator is preferable, and 2-hydroxy-2-methyl-1-phenylpropan-1-one is more preferable. These may be used individually by 1 type, and may use it in combination of 2 or more types.

The content of the polymerization initiator (C) is 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total of the polymer (A) and the monomer (D). More preferably, it is 1.5-6 mass parts. When the content of the polymerization initiator (C) is within the above range, it is preferable from the viewpoint of curing speed and mechanical properties.

<Hindered Amine Compound (E)>

In the resin composition of the second aspect of the present invention, a hindered amine compound (E) may be contained as necessary in order to further improve the heat resistance and weather resistance of the resin composition and a cured product obtained therefrom. In addition, it is preferable to use the hindered amine type compound which does not have a secondary amino group in a molecule|numerator as a hindered amine type compound (E).

By using the hindered amine compound (E) having no secondary amino group in the molecule, it is possible to remarkably improve the decrease in mechanical properties and the change in color tone of the resin composition and cured products obtained therefrom after exposure to heat.

Examples of hindered amine compounds (E) that do not have a secondary amino group in the molecule include bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis( 2,2,6,6-Tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5 -Bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-1-( Octyloxy)-4-piperidinyl) ester, methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate, 1,2,3,4-butane Tetracarboxylic acid tetra(1,2,2,6,6-pentamethyl-4-piperidinyl), 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, etc. .

Among these, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl-1,2,2,6,6-pentamethyl- 4-piperidinyl sebacate, 1,2,3,4-butanetetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl). These may be used individually by 1 type, and may use it in combination of 2 or more types.

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

<Manufacturing method of resin composition>

The method for producing the resin composition according to the second aspect of the present invention is not particularly limited. For example, the polymer (A), the monomer (D), The polymerization initiator (C) and other components used as needed are mixed and manufactured.

<Melt Viscosity of Resin Composition>

The melt viscosity at 38° C. of the resin composition according to the second aspect of the present invention is preferably 15 Pa·s or less, more preferably 12 Pa·s or less, even more preferably 10 Pa·s or less. When the melt viscosity of the resin composition is within the above range, the resin composition can be uniformly coated on the surface to be coated, and the mixing of air bubbles can be easily prevented, so that the coatability becomes good. In addition, in this specification, the melt viscosity of a resin composition is the value calculated|required by the method described in the Example mentioned later.

[cured product]

The cured product of the second aspect of the present invention is obtained by curing the above-mentioned resin composition of the second aspect of the present invention, and can be cured, for example, by irradiating the resin composition of the second aspect of the present invention with energy rays.

As energy rays for curing, ultraviolet rays are preferable. Examples of the ultraviolet light source include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and microwave-based excimer lamps. The atmosphere for irradiating ultraviolet rays is preferably an inert gas atmosphere such as nitrogen or carbon dioxide, or an atmosphere in which the oxygen concentration is reduced.

The irradiation atmosphere temperature is preferably 10 to 200° C., and the UV irradiation amount is preferably 200 to 10,000 mJ/cm ² .

[Adhesives for optics]

The optical adhesive according to the second aspect of the present invention contains the cured product or the resin composition according to the second aspect of the present invention, and can be suitably used in electronic devices such as smartphones, liquid crystal displays, and organic EL displays.

Various additives may be appropriately added to the aforementioned optical adhesive as needed within a range not departing from the object of the present invention. As said additive, a thickener, a plasticizer, a pigment, a coloring agent, an antiaging agent, an ultraviolet absorber, etc. are mentioned, for example.

[III] Resin composition (third mode)

The resin composition of the third aspect of the present invention is a resin composition containing: the polymer of the first aspect of the present invention, that is, a monomer unit derived from farnesene as a monomer unit constituting the polymer ( a1) a polymer (A) having a polymerizable functional 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 polymer The initiator (C), the mass ratio of the polymer (A) to the polymer (B) [(A)/(B)] is 0.01-100.

<Polymer (A)>

The polymer (A) used in the third aspect of the present invention contains a farnesene-derived monomer unit (a1) as a monomer unit constituting the polymer and has a polymerizable functional group. This polymer (A) is the same as the polymer in the above-mentioned first aspect of the present invention, and has a low viscosity, a fast curing rate, and excellent cure shrinkage.

The content of the polymer (A) in the resin composition in the third aspect of the present invention is preferably 1 to 99% by mass, more preferably 2 to 98% by mass, still more preferably 5 to 95% by mass, and still more preferably 10 to 90% by mass, more preferably 15 to 85% by mass. 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 in the monomer unit (b1) include butadiene, isoprene, 2,3-dimethylbutadiene, and 2-phenylbutadiene ene, 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, and chloroprene, etc.

Among these, isoprene and butadiene are more preferred. These conjugated diene compounds may be used alone or in combination of two or more.

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

Examples of the monomer unit (b2) derived from a monomer other than the conjugated diene compound include a monomer unit derived from an aromatic vinyl compound.

Examples of the aromatic vinyl compound belonging to the monomer unit (b2) include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-Propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylbenzene Ethylene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, ethylene Aromatic vinyl such as anthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzene base compounds, etc. Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferable.

In the case of using a monomer unit (b2) derived from a monomer other than a conjugated diene, copolymerization The monomer unit (b2) derived from a monomer other than a conjugated diene in the compound is relative to the monomer unit (b1) derived from a conjugated diene and the unit derived from a monomer other than a conjugated diene The total ratio of the monomer units (b2) is preferably 1 to 99% by mass, more preferably 1 to 80% by mass, still more preferably 1 to 70% by mass, and still more preferably 1 to 50% by mass.

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, still more preferably 4,000 to 140,000, and even more preferably More preferably, it is 5,000 to 120,000. 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 viscosity of the resin composition is reduced.

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, still more preferably 0.3 to 2,800 Pa·s, still more preferably 0.5 to 2,600 Pa·s, more preferably 0.5 to 800 Pa·s. When the melt viscosity of the polymer (B) is within the above range, there is no unevenness with respect to the surface to be coated, and the resin composition can be uniformly coated, so the applicability becomes good.

The aforementioned polymer (B) can be obtained by living anionic polymerization of a conjugated diene compound and, if necessary, monomers other than the conjugated diene compound. Examples of living anionic polymerization initiators for living anionic polymerization of conjugated diene compounds include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, Organic monolithium compounds such as phenyl lithium and stilbene lithium; dilithium methane, dilithium naphthalene, 1,4-dilithium butane, 1,4-dilithium-2-ethylcyclohexane, 1, 3,5-Trilithium benzene and other polyfunctional organolithium compounds; sodium naphthalene, potassium naphthalene, etc. In addition, compounds such as diisopropenylbenzene and dibenzyltoluene that react with the organic alkali metal compound to impart a polyfunctional organic alkali metal compound can also be used in combination.

The polymer (B) used in the present invention may be used alone or in combination of two or more polymers (B) having different monomer units and molecular weights.

In the present invention, the mass ratio [(A)/(B)] of the aforementioned polymer (A) to the aforementioned polymer (B) is 0.01 to 100, preferably 0.05 to 100, more preferably 0.1 to 50, and even more preferably 0.1 to 25, more preferably 0.1 to 10. When the aforementioned mass ratio [(A)/(B)] is within the aforementioned range, a resin composition having sufficiently low viscosity and 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, and the melt viscosity of both the polymer (A) and the polymer (B) The melt viscosity is more preferably in the range of 0.1 to 3,000 Pa·s.

<Polymerization Initiator (C)>

As the polymerization initiator (C) used in the present invention, the polymerization initiators (C) listed in the second aspect of the present invention can be used suitably.

The content of the polymerization initiator (C) in the resin composition of the third aspect of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass, and even more preferably 0.1 to 20% by mass in the total amount of the resin composition. 1.0 to 20% by mass, more preferably 1.0 to 15% by mass, most preferably 1.0 to 10% by mass. When the content of the polymerization initiator (C) is within the above range, it is preferable from the viewpoint of curing speed and mechanical properties.

<Monomer (D)>

In the resin composition of the third aspect of the present invention, in order to further improve the viscosity, handleability, and strength after curing of the resin composition, a monomer (D) may be contained as needed.

The monomer (D) preferably has a functional group capable of reacting with the polymer (A), such as a (meth)acryloyl group, epoxy group, oxetanyl group, vinyl ether, Group, alkoxysilyl compound.

As a specific compound, the monomer (D) mentioned in the 2nd aspect of this invention can be used suitably.

Among the aforementioned monomers (D), the monomer (D) is preferably selected from monofunctional (meth)acrylates, difunctional ( At least one of meth)acrylate and polyfunctional (meth)acrylate, more preferably at least one selected from monofunctional (meth)acrylate and difunctional (meth)acrylate.

Among them, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, 1,9-nonanediol di(meth)acrylate, Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, phenoxy (meth)acrylate ethyl ester etc. These may be used individually by 1 type, and may use it in combination of 2 or more types.

The monomer (D) can react with the polymerizable functional group of the polymer (A) using 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, more preferably 0.1 to 800 parts by mass, and even more preferably 1.0 to 600 parts by mass based on 100 parts by mass of the total of the polymer (A) and the polymer (B). parts, more preferably 1.0 to 400 parts by mass. When the content of the monomer (D) is within the above range, the viscosity is reduced and the handleability is improved. In addition, when the resin composition in the third aspect of the present invention is cured, the breaking strength and tensile elongation of the cured product are improved, so a cured product excellent in flexibility can be obtained.

<Hindered Amine Compound (E)>

In the resin composition of the third aspect of the present invention, in order to further improve the heat resistance and weather resistance of the resin composition and a cured product obtained therefrom, a hindered amine compound (E) may be contained as necessary. In addition, it is preferable to use the hindered amine type compound which does not have a secondary amino group in a molecule|numerator as a hindered amine type compound (E). By using the hindered amine-based compound (E) having no secondary amino group in the molecule, it is possible to remarkably improve the decrease in mechanical properties and the change in color tone of the resin composition and cured products obtained therefrom after exposure to heat.

As a specific compound, the hindered amine compound (E) mentioned in the 2nd aspect of this invention can be used suitably.

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

The resin composition of the third aspect of the present invention may contain, in addition to the polymer (A) and the polymer (B), a conjugated bismuth other than farnesene within the range that does not impair the effects of the present invention. A modified conjugated diene polymer with polymerizable functional groups obtained by olefin polymerization. Examples of conjugated dienes other than farnesene include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, and 1,3-pentadiene , 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene ene, 1,3,7-octatriene, myrcene and chloroprene, etc.

In addition, the resin composition of the third aspect of the present invention may contain, in addition to the polymer (A) and the polymer (B), co-polymers other than farnesene within the range that does not impair the effects of the present invention. Modified conjugated diene-aromatic vinyl compound copolymer with polymerizable functional groups obtained by copolymerizing conjugated diene and aromatic vinyl compound. As examples of the conjugated diene, the same examples as described above can be used.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4 -tert-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-vinylnaphthalene, vinylanthracene, N,N-di Ethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene, etc.

Examples of the aforementioned polymerizable functional groups include (meth)acryloyl groups, epoxy groups, oxetanyl groups, vinyl ether groups, alkoxysilyl groups, (meth)acrylamide groups, styrene groups, group, maleimide group, lactone group, lactam group, sulfide group, thietanyl group, acetonide group, thiourea group, etc.

It should be noted that the aforementioned modified conjugated diene polymer having a polymerizable functional group and the modified conjugated diene-aromatic vinyl compound copolymer having a polymerizable functional group are included in the second aspect of the present invention described later. Four-way polymer (F) concept. Therefore, these polymers are described in detail in the polymer (F) of the fourth aspect.

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

<Manufacturing method of resin composition>

The method for producing the resin composition according to the third aspect of the present invention is not particularly limited. For example, the polymer (A), the polymer (B), The polymerization initiator (C) and other components used as needed are mixed and manufactured.

<Melt Viscosity of Resin Composition>

The melt viscosity at 38° C. of the resin composition according to the third aspect of the present invention is preferably 15 Pa·s or less, more preferably 12 Pa·s or less, even more preferably 10 Pa·s or less. When the melt viscosity of the resin composition is within the above-mentioned range, the resin composition can be uniformly applied to the surface to be coated, and the mixing of air bubbles can be easily prevented, so that the coatability becomes good. In addition, in this specification, the melt viscosity of a resin composition is the value calculated|required by the method described in the Example mentioned later.

The resin composition according to the third aspect of the present invention can obtain a cured product having low melt viscosity and excellent curability, further strength, flexibility and transparency, so it can be suitably used for adhesives, adhesives (especially optical Adhesives), coating agents, sealing materials and inks, etc.

[cured product]

The cured product of the third aspect of the present invention is obtained by curing the resin composition of the present invention according to the third aspect, for example, by irradiating the resin composition of the third aspect of the present invention with energy rays or applying heat to polymerize the resin composition of the third aspect. The reaction between the substance (A) and the polymerization initiator (C) enables curing.

As energy rays for curing, ultraviolet rays are preferable. Examples of the ultraviolet light source include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and microwave-based excimer lamps. The atmosphere for irradiating ultraviolet rays is preferably an inert gas atmosphere such as nitrogen or carbon dioxide, or an atmosphere in which the oxygen concentration is reduced.

The irradiation atmosphere temperature is preferably 10 to 200° C., and the UV irradiation amount is preferably 200 to 10,000 mJ/cm ² .

[Adhesives for optics]

The optical adhesive according to the third aspect of the present invention contains the cured product or the resin composition according to the third aspect of the present invention, and can be suitably used in electronic devices such as smartphones, liquid crystal displays, and organic EL displays.

Various additives may be appropriately added to the aforementioned optical adhesive as needed within a range not departing from the object of the present invention. As said additive, a thickener, a plasticizer, a pigment, a coloring agent, an antiaging agent, an ultraviolet absorber, etc. are mentioned, for example.

[IV] Resin composition (fourth form)

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

<Polymer (F)>

The polymer (F) used in the resin composition of the fourth aspect of the present invention contains a monomer unit (f1) derived from a conjugated diene compound having 12 or less carbon atoms and has a polymerizable functional group.

The conjugated diene compound having 12 or less carbon atoms as the monomer unit (f1) is preferably 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 and chloroprene, etc.

The monomer unit constituting the polymer (F) may contain only the aforementioned monomer unit (f1) derived from a conjugated diene compound having 12 or less carbon atoms, or may include the aforementioned monomer unit derived from a conjugated diene compound (f1) and a monomer unit (f2) derived from a monomer (excluding farnesene) other than a conjugated diene compound having 12 or less carbon atoms. That is, the polymer (F) may be obtained by polymerizing only the conjugated diene compound having 12 or less carbon atoms, or may be a conjugated compound of the conjugated diene compound having 12 or less carbon atoms and the aforementioned conjugated diene compound having 12 or less carbon atoms. Copolymers of monomers other than diene compounds.

As a monomer of a monomer unit (f2), an aromatic vinyl compound is mentioned, for example. As the aromatic vinyl compound, for example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-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-vinylnaphthalene, vinylanthracene, N,N- Diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene, and the like.

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

As the polymerizable functional group that the polymer (F) has, the same functional group as the functional group exemplified as the polymerizable functional group that the polymer (A) has can be used. Examples include (meth)acryloyl, epoxy, oxetanyl, vinyl ether, alkoxysilyl, (meth)acrylamide, styryl, maleinyl Amino group, lactone group, lactam group, sulfide group, thietanyl group, acetonide group, thiourea group, etc. In addition, 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, still more preferably 11,000 to 60,000. 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 viscosity of the resin composition is reduced.

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, still more preferably 0.3 to 2,800 Pa·s, still more preferably 0.5 to 2,600 Pa·s, more preferably 0.5 to 800 Pa·s. When the melt viscosity of the polymer (F) is within the above-mentioned range, the resin composition can be uniformly coated without unevenness on the surface to be coated, so that the coatability becomes good.

The aforementioned polymer (F) can be produced by the same method as the aforementioned polymer (A). Specifically, first, a conjugated diene compound having 12 or less carbon atoms and monomers other than a conjugated diene compound having 12 or less carbon atoms are polymerized by emulsion polymerization or solution polymerization, thereby Unmodified polymers are produced without polymerizable functional groups. Next, it can be obtained by introducing a polymerizable functional group into the unmodified polymer.

For example, the above-mentioned unmodified polymer is reacted with a compound for grafting such as maleic anhydride, and then reacted with a compound having a polymerizable functional group such as 2-hydroxyethyl methacrylate. method. In addition, the said polymer (F) can use a commercial item.

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, still more preferably 10% by mass. ~90% by mass, more preferably 15~85% by mass. 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 aforementioned polymer (A) to the aforementioned polymer (F) is 0.01 to 100, preferably 0.05 to 100, more preferably 0.1 to 50, and even more preferably 0.1 to 25, more preferably 0.1 to 10. When the aforementioned mass ratio [(A)/(F)] is within the aforementioned range, a resin composition having sufficiently low viscosity and 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 adhesive material are the same as those in the aforementioned second and third aspects.

Example

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]

The components used in the examples and comparative examples of the first aspect are as follows.

<Polymer (A) having a polymerizable functional group>

・Polyfarnesenes (A-1) to (A-5) having a methacryloyl group in the molecule obtained in Production Examples 1 to 5 described later.

<Other curable resins>

・Polyisoprene (I-X-1)

Polyisoprene having a methacryloyl group in the molecule obtained from Comparative Production Example 1

・Curable resin (I-X-2)

Polyfarnesene modified with 2-hydroxyethyl methacrylate, synthesized according to Example 7 of International Publication No. 2012/018682

・Urethane acrylate (I-X-3)

Urethane acrylate "DBA2210" manufactured by DuPont Co., Ltd.

<Radical polymerization initiator>

・2-Hydroxy-2-methyl-1-phenylpropan-1-one

BASF Corporation make, brand name "DAROCUR 1173".

<Anti-aging agent>

・2,6-di-tert-butyl-4-methylphenol (BHT)

Made by Honshu Chemical Industry Co., Ltd.

<Manufacturing Examples 1 to 5, Comparative Manufacturing Example 1>

Production Example 1: Polyfarnesene (A-1) having a methacryloyl group in the molecule

1,520 g of cyclohexane and 7.8 g of a 10.5% by mass cyclohexane solution of sec-butyllithium were charged into a 5-liter autoclave replaced with nitrogen, and then the temperature was raised to 50° C., and 1,510 g of β-farnesene was added for 2 hours. polymerization. The resulting polymerization solution was poured into methanol, the unmodified polymer was reprecipitated, filtered, and vacuum-dried 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 standard polystyrene-equivalent number average molecular weight (Mn)=113,300, and the molecular weight distribution (Mw/Mn)=1.18.

300 g of the obtained unmodified polymer was charged into a nitrogen-substituted autoclave with a capacity of 1 liter, 4.5 g of maleic anhydride and 3.0 g of BHT were added, and the reaction was carried out at 160° C. for 20 hours to allow the unmodified polymer to into maleic anhydride. 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 to obtain a compound having formazan in the molecule. Acryloyl polyfarnesene (hereinafter sometimes referred to as "polymer (A-1)").

Production Examples 2 and 3: Polyfarnesene (A-2), (A-3) having a methacryloyl group in the molecule

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 used were changed to the amounts described in Table 1, respectively. Table 1 shows the number average molecular weight and molecular weight distribution of the unmodified polymer.

Next, each unmodified polymer was reacted in the same manner as in Example 1 to produce polyfarnesenes (A-2) and (A-3) having a methacryloyl group in the molecule (hereinafter sometimes referred to as Polyfarnesene (A-2) having a methacryloyl group in its molecule is called "polymer (A-2)", and polyfarnesene (A-3) having a methacryloyl group in its molecule is called "polymer (A-2)". Polymer (A-3)").

Production Example 4: Farnesene-isoprene copolymer (A-4) having a methacryloyl group in the molecule

1,500 g of cyclohexane and 38.5 g of a 10.5% by mass cyclohexane solution of sec-butyllithium were put into a nitrogen-purged autoclave with a capacity of 5 liters, then the temperature was raised to 50°C, and β-farnesene and isoprene were added. 1540 g of mixed monomers (β-farnesene/isoprene=6/4 (mass ratio)) were polymerized for 2 hours. The resulting polymerization solution was poured into methanol, the unmodified polymer was reprecipitated, filtered, and vacuum-dried at 80° C. for 10 hours to obtain 1200 g of a farnesene-isoprene copolymer (unmodified polymer).

When a part of the unmodified polymer was analyzed by GPC, the standard polystyrene-equivalent number average molecular weight (Mn)=25,300, and the molecular weight distribution (Mw/Mn)=1.09.

300 g of the obtained unmodified polymer was charged into a nitrogen-substituted autoclave with a capacity of 1 liter, 4.5 g of maleic anhydride and 3.0 g of BHT were added, and the reaction was carried out at 160° C. for 20 hours to allow the unmodified polymer to into maleic anhydride. 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 to obtain a compound having formazan in the molecule. Acryloyl farnesene-isoprene copolymer (hereinafter, sometimes referred to as "polymer (A-4)").

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 used were changed to those shown in Table 1. Table 1 shows the number average molecular weight and molecular weight distribution of the unmodified polymer.

Next, the unmodified polymer was reacted in the same manner as in Example 4 to produce a farnesene-isoprene copolymer having a methacryloyl group in the molecule (hereinafter, sometimes referred to as "polymer (A) -5)").

Comparative Production Example 1: Polyisoprene (I-X-1) having a methacryloyl group in the molecule

1,420 g of cyclohexane and 70.9 g of a 10.5% by mass cyclohexane solution of sec-butyllithium were charged into a nitrogen-purged autoclave with a capacity of 5 liters, then the temperature was raised to 50°C, 1,490 g of isoprene was added, and polymerization was carried out for 2 hours. . The resulting polymerization solution was poured into methanol, polyisoprene was reprecipitated, filtered, and vacuum-dried at 80° C. for 10 hours to obtain 1200 g of polyisoprene.

When a part of the polyisoprene was analyzed by GPC, the standard polystyrene-equivalent number average molecular weight (Mn)=19,400, and the molecular weight distribution (Mw/Mn)=1.03.

300 g of the obtained polyisoprene was charged into a nitrogen-substituted autoclave with a capacity of 1 liter, 4.5 g of maleic anhydride was added, and reacted at 160° C. for 20 hours to add maleic acid to the polyisoprene. anhydride. 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 to obtain a compound having formazan in the molecule. Acryloyl polyisoprene (hereinafter, sometimes referred to as "polyisoprene (I-X-1)").

[Table 1]

<Examples 1~5, Comparative Examples 1~3>

Example 1

For the polymer (A-1), the number average molecular weight, the methacryloyl equivalent, the number of functional groups per molecular chain, and the melt viscosity were measured by the methods 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 polymer (A-1), and curable resin composition was produced.

About the curable resin composition obtained, the curing rate, transparency, cure shrinkage, breaking strength, breaking elongation, moisture permeability, and hardness were evaluated by the method mentioned later. The results are shown in Table 2.

Example 2~5

Except having changed polymer (A-1) into polymer (A-2)-(A-5), it carried out similarly to Example 1, and performed various evaluation. The results are shown in Table 2.

Comparative example 1

Except having changed the polymer (A-1) into polyisoprene (I-X-1), it carried out similarly to Example 1, and performed various evaluation. The results are shown in Table 2.

Comparative example 2

Except having changed polymer (A-1) into curable resin (I-X-2), it carried out similarly to Example 1, and performed various evaluation. The results are shown in Table 2.

Comparative example 3

Except having changed polymer (A-1) into urethane acrylate (I-X-3), it carried out similarly to Example 1, and performed various evaluation. The results are shown in Table 2.

Evaluation methods in Examples and Comparative Examples of the first embodiment are as follows.

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

Using "GPC-8020" manufactured by Tosoh Corporation, the concentration of sample/tetrahydrofuran=5 mg/10 mL was adjusted and measured. In addition, tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. was used as a developing solution.

The number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were calculated|required from the standard polystyrene equivalent molecular weight by GPC (gel permeation chromatography). The measurement apparatus and conditions are as follows.

・Device : GPC device "GPC8020" manufactured by Tosoh Corporation

・Separation column: "TSKgelG4000HXL" manufactured by Tosoh Corporation

・Detector: "RI-8020" manufactured by Tosoh Corporation

・Eluent : Tetrahydrofuran

・Eluent flow rate: 1.0ml/min

・Sample concentration: 5mg/10ml

・Column temperature: 40℃.

(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., the measurement was performed at a concentration of sample/deuterochloroform=100 mg/1 mL, the number of integrations was 512 times, and the measurement temperature was 50° C. The equivalent of the methacryloyl group to the polymer mass was calculated from the area ratio of the peak derived from the double bond of the (meth)acryloyl group to the peak derived from the polymer main chain in the obtained spectrum.

In addition, the number of polymerizable functional groups per molecular chain is calculated from the number average molecular weight of the polymer and the functional group equivalent to the polymer mass obtained by the above method.

(I-3) Measuring method of melt viscosity

The melt viscosity (Pa·s) at 38° C. of the polymer 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 injected into a mold with a length of 70 mm, a width of 70 mm, and a thickness of 0.5 mm. After covering the surface of the composition with a PET film with a thickness of 50 μm, a UV irradiation device (Co. HAK125L-F (manufactured by Gees Yuasa Co., Ltd., used as a mercury lamp) was set to 30 mW/cm ² of illuminance, 2 m/min of conveyor speed, and irradiated with UV of 150 mJ/cm ² in one operation.

This was repeated 1, 2, 4, 6, 8, and 16 times to obtain 500 mg of cured products whose total UV irradiation amounts were 150, 300, 600, 900, 1200, and 2400 mJ/cm ² . After peeling off the PET film, the cured product was immersed in toluene at room temperature for 24 hours, and the insoluble part was filtered through a 200-mesh metal mesh, washed and vacuum-dried at 80°C for 12 hours. After drying, each sample was weighed, and the gel fraction of the polymer at each UV irradiation amount 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 amount of UV irradiation at which the gel fraction reached 80% was estimated, and the curing speed was evaluated. In addition, based on the UV irradiation dose required until the gel fraction becomes 80%, it evaluated according to the following reference|standard.

<Evaluation criteria>

5: Less than 500mJ/cm ²

4: More than 500mJ/cm ² and less than 1000mJ/cm ²

3: More than 1000mJ/cm ² and less than 2000mJ/cm ²

2: More than 2000mJ/cm ² and less than 3000mJ/cm ²

1: 3000mJ/cm ² or more.

(I-5) Transparency

The curable resin compositions obtained in Examples and Comparative Examples were poured into a mold with a length of 70 mm, a width of 70 mm, and a thickness of 0.5 mm. After covering the surface of the composition with a PET film with a thickness of 50 μm, a UV irradiation device (Ji-Es Co., Ltd.・Manufactured by Yuasa Corporation, HAK125L-F was used as a mercury lamp), the illuminance was set to 45 mW/cm ² , the conveyor speed was 0.25 m/min, and 1000 mJ/cm ² of UV was irradiated in one operation. This was repeated 3 times to obtain a cured product. After the PET film was peeled off from the cured product, transparency was evaluated by visual observation.

<Evaluation criteria>

5: colorless and transparent

4: Only slightly colored but transparent

3: Slight coloring was observed, but transparent

2: Clear coloring was observed, but transparent

1: Opaque.

(I-6) Curing shrinkage

The density of the cured product obtained in (I-5) above was measured based on the method described in JIS K 6911, and this was defined as the density of the cured composition. The density of the composition before curing was measured using the pycnometer method described in JIS K 0061. After measuring the density before and after curing, the curing shrinkage rate was obtained based on the following formula, and evaluated according to the following criteria.

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

<Evaluation criteria>

5: Curing shrinkage is less than 1%

4: Curing shrinkage rate is more than 1% and less than 3%

3: Curing shrinkage rate is more than 3% and less than 5%

2: Curing shrinkage rate is more than 5% and less than 10%

1: The curing shrinkage rate is more than 10%.

(I-7) Breaking strength and breaking elongation

A short strip sample with a width of 6 mm and a length of 70 mm was punched out from the cured product obtained in the above (I-5), and the tensile test was performed at a tensile speed of 10 mm/min using a tensile testing machine manufactured by Instron Corporation. breaking strength and elongation at break.

(I-8) Moisture permeability test

Using the cured product obtained in (I-5) above, based on JIS Z 0208 Condition B The moisture permeability test was carried out, and the evaluation was performed according to the following criteria.

<Evaluation criteria>

5: Moisture permeability is less than 25g/m ²・24h

4: Moisture permeability is above 25g/m2^・24h and less than 50g/m2^・24h

3: Moisture permeability is more than 50g/m2^・24h and less than 100g/m2^・24h

2: Moisture permeability is above 100g/m2^・24h and less than 200g/m2^・24h

1: Moisture permeability is 200g/m2^・24h or more.

(I-9) Hardness

The curable resin compositions obtained in Examples and Comparative Examples were poured into a mold with a length of 70 mm, a width of 35 mm, and a thickness of 2.0 mm. After covering the surface of the composition with a PET film with a thickness of 50 μm, a UV irradiation device (Co., Ltd. HAK125L-F, manufactured by Jesse Yuasa Corporation, was used as a mercury lamp), the illuminance was set to 45 mW/cm ² , the conveyor speed was 0.25 m/min, and 1000 mJ/cm ² of UV was irradiated by one operation. This was repeated 3 times to obtain a cured product. Three obtained cured products having a thickness of 2.0 mm were stacked to form a 6.0 mm sample, and the hardness was measured according to JIS K 6253 (JIS A).

[Table 2]

From the results shown in Table 2, it can be seen that polymers (A-3) to (A-5) of the present invention have lower melt viscosities at the same molecular weight than polyisoprene (I-X-1).

In addition, compared with polyisoprene (I-X-1), the polymers (A-1) to (A-5) of the present invention have faster curing speeds, and especially those with high molecular weights like Examples 1 and 2 Polymers (A-1) and (A-2) were excellent in curing speed.

Furthermore, it was found that the polymers (A-1) to (A-5) of the present invention have good transparency, low cure shrinkage, low moisture permeability, and flexibility similarly to polyisoprene (I-X-1).

It should be noted that the curable resin (I-X-2) of Comparative Example 2 gelled in the process of producing the 2-hydroxyethyl methacrylate modified polyfarnesene and was insoluble in solvents, so it could not be processed. Determination of number average molecular weight and methacryloyl equivalent.

Comparative Example 3 using urethane acrylate (I-X-3) was excellent in curing speed as in Examples 1 to 5, but the polymer of the present invention ( A-1)~(A-5) are more excellent.

[Example of the second aspect of the present invention]

The components used in Examples and Comparative Examples of the second aspect are as follows.

<Polymer (A) having a polymerizable functional group>

・Polymers (A-1) to (A-5) used in Examples 1 to 5 of the first aspect

In addition, 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) are shown in the table 3.

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

・Polymerization initiator (C-1)

2-Hydroxy-2-methyl-1-phenylpropan-1-one

BASF Corporation make, brand name "DAROCUR 1173".

<Monomer (D)>

・Monomer (D-1): Dicyclopentenyloxyethyl methacrylate

Hitachi Chemical Industry Co., Ltd., brand name "Fanclear FA-512M"

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

Made by Osaka Organic Chemical Industry Co., Ltd., brand name "Biscoat #260"

・Monomer (D-3): n-butyl acrylate

Tokyo Kasei Kogyo Co., Ltd., trade name "Butyl Acrylate".

<Hindered Amine Compound (E)>

・Hindered amine compounds (E-1)

Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidinyldecane mixture of diacids

BASF Corporation make, brand name "TINUVIN 765".

<Anti-aging agent>

・2,6-di-tert-butyl-4-methylphenol (BHT) manufactured by Honshu Chemical Industry Co., Ltd.

<Other polymers (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 Example 7 of International Publication No. 2012/018682

・Polymer (II-X-3): In Production Example 3 of the first aspect, the unmodified polymer obtained after polymerizing polyfarnesene and taking out before adding maleic anhydride

・Polymer (II-X-4): In Production Example 3 of the first mode, the polymer was taken out after reacting with maleic anhydride and before adding 2-hydroxyethyl methacrylate

・Polymer (II-X-5): "TEA-1000" (acryloyl group-containing polybutadiene) manufactured by Nippon Soda Co., Ltd.

[table 3]

<Example 6~14>

Put polymers (A-1) to (A-5), monomers (D-1) to (D-3), and polymerization initiator (C-1) in the ratio shown in Table 4 into a stainless steel 300mL container , mixed using a stirring blade at room temperature for 20 minutes, thereby preparing a resin composition. The obtained resin composition was evaluated by the following method. The results are shown in Table 4.

<Example 15~23>

Table 5 Except having mixed the shown ratio, it carried out similarly to Example 6, the resin composition was prepared, and it evaluated. The results are shown in Table 5.

<Comparative example 4~8>

Mix other curable resins (II-X-1)~(II-X-5), monomer (D-1), and polymerization initiator (C-1) in the ratio shown in Table 6, except Except that, it carried out similarly to Example 6, the resin composition was prepared, and it evaluated. The results are shown in Table 6.

The evaluation methods of Examples and Comparative Examples of the second aspect are as follows.

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

It measures by the same method as (I-1) of the 1st aspect.

(II-2) Measurement of methacryloyl equivalent and the number of polymerizable functional groups per molecular chain

It measures by the same method as (I-2) of the 1st aspect.

(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, the same method as (I-3) of the first embodiment was used to measure.

(II-4) UV irradiation amount and curing speed

The resin compositions obtained in Examples and Comparative Examples were tested by the same method as (I-4) of the first aspect, and the gel fraction was obtained.

The amount of UV irradiation at which the gel fraction reached 80% was estimated from the data obtained by this test, and the evaluation was performed according to the following criteria.

<Evaluation criteria>

○: Less than 1,000mJ/cm ²

△: More than 1,000mJ/cm ² and less than 2,000mJ/cm ²

×: 2,000 mJ/cm ² or more.

(II-5) Appearance (transparency)

A cured product was produced by the same method as (I-5) of the first aspect. After peeling off the PET film from the obtained cured product, visual observation was performed, and transparency was evaluated according to the following criteria.

<Evaluation criteria>

○: Colorless and transparent

△: Some coloring was observed, but not transparent

×: Conspicuous coloring or turbidity was observed.

(II-6) Curing shrinkage

About the hardened|cured material obtained in said (II-5), cure shrinkage rate was calculated|required by the method similar to (I-6) of 1st aspect, and it evaluated according to the following reference|standard.

<Evaluation criteria>

◎: Curing shrinkage rate is less than 3%

○: Curing shrinkage rate is more than 3% and less than 5%

△: Curing shrinkage rate is more than 5% and less than 10%

×: The curing shrinkage rate is 10% or more.

(II-7) Breaking strength and breaking elongation

A short strip sample with a width of 6 mm and a length of 70 mm was punched out from the cured product obtained in the above (II-5), and a tensile test was performed at a tensile speed of 50 mm/min using a tensile testing machine manufactured by Instron Corporation. breaking strength and elongation at break.

(II-8) Moisture permeability test

The cured product obtained in the above (II-5) was tested by the same method as in (I-8) of the first aspect, and evaluated in accordance with the following criteria.

<Evaluation criteria>

5: Moisture permeability is less than 25g/m ²・24h

4: Moisture permeability is above 25g/m2^・24h and less than 50g/m2^・24h

3: Moisture permeability is more than 50g/m2^・24h and less than 100g/m2^・24h

2: Moisture permeability is above 100g/m2^・24h and less than 200g/m2^・24h

1: Moisture permeability is 200g/m2^・24h or more.

(II-9) Hardness

About the resin composition obtained by the Example and the comparative example, it measured by the method similar to (I-9) of 1st aspect.

(II-10) Heat resistance test (hue stability test)

The cured product obtained by peeling off the PET film in (II-5) above was left to stand in an atmosphere of 25° C. for 24 hours, and then a strip-shaped test piece of 60 mm in length×6 mm in width×0.5 mm in thickness was prepared. Next, the produced test piece was left to stand in a 100°C thermostat (GEAR OVEN) for 72 hours, 144 hours, and 240 hours, respectively, and it was visually confirmed together with the test piece before heat treatment (marked as 0 hour) The hue change of each test piece was evaluated by the following criteria. In addition, this test was performed with respect to 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 of elasticity)

After the test piece prepared in the above (II-5) was left to stand at 100°C for 72 hours, 144 hours, and 240 hours, a tensile test was performed at a tensile speed of 50mm/min. A testing machine was used to measure the tensile modulus of elasticity at various times. It should be noted that a low tensile elastic modulus is good because it is soft, and a small change ratio with time is good. In addition, this test was performed with respect to the hardened|cured material obtained from the resin composition of Examples 15-23 and Comparative Examples 4-8.

[Table 4]

[table 5]

[Table 6]

*1: Since the polymer could not be obtained, the composition could not be measured.

*2: The gelation rate does not exceed 80%, so the UV irradiation amount at the time of curing cannot be measured.

*3: Unable to measure due to deterioration.

Compared with Comparative Example 8 using a polymer (II-X-5) not containing a farnesene-derived monomer, Examples 6 to 10 used a polymer containing a farnesene-derived monomer unit (A-1) to (A-5) have low viscosity and excellent rapid curing properties, and the resulting cured products have high elongation at break, low hardness, and excellent flexibility. In addition, the resin compositions described in Examples 11 to 14 using the polymer (A-3) had a lower viscosity than the resin composition of Comparative Example 8, and their curing speeds were equal to or higher than that of the resin composition of Comparative Example 8.

Examples 6 to 14 were excellent in cure shrinkage and moisture permeability compared with Comparative Example 4 in which urethane acrylate (II-X-1) was used instead of the polymer containing a farnesene monomer.

It should be noted that the polymer (II-X-2) used in Comparative Example 5 gelled during the production of the 2-hydroxyethyl methacrylate modified polyfarnesene, and a uniform Since the polymer is insoluble in a solvent, the number average molecular weight and the methacryloyl equivalent cannot be measured. In addition, evaluation as another resin composition was not possible.

While the cured products obtained in Examples were transparent, the cured products obtained in Comparative Examples 6 and 7 were cloudy or brittle, so various evaluations could not be performed. Since Comparative Examples 6 and 7 used polymers having no polymerizable functional group, it is considered that the compatibility with other components was poor and phase separation occurred in the cured polymer.

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

[Example of the third aspect of the present invention]

The components used in Examples and Comparative Examples of the third aspect are as follows.

<Polymer (A) having a 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 in Production Examples 6 to 8 described later.

<Polymerization Initiator (C)>

・Polymerization initiator (C-1)

2-Hydroxy-2-methyl-1-phenylpropan-1-one

BASF Corporation make, brand name "DAROCUR 1173".

<Monomer (D)>

・Acrylic monomer (D-1)

Dicyclopentenyloxyethyl methacrylate

The Hitachi Chemical Industry Co., Ltd. product, brand name "fan creil FA-512M".

<Hindered Amine Compound (E)>

・Hindered amine compounds (E-1)

Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidinyldecane mixture of diacids

BASF Corporation make, brand name "TINUVIN 765".

<Manufacturing Examples 6~8>

Production Example 6: Liquid polybutadiene (B-1)

Liquid polybutadiene with a number average molecular weight of 9,000 (hereinafter also referred to as "polymer (B-1)") was synthesized by anionic polymerization of butadiene and n-butyllithium in n-hexane as an initiator. ). 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 and n-butyllithium in n-hexane as an initiator. (Hereinafter, also referred to as "polymer (B-2)"). 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 )”). Table 7 shows the physical properties of the polymer (B-3).

[Table 7]

<Example 24~34>

Polymers (A-1), (A-3) and (A-5), polymers (B-1)~(B-3), polymerization initiator (C), monomer (D-1) and The hindered amine compound (E-1) was put into a stainless steel 300 mL container at the ratio shown in Table 8 and Table 9, and was 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 of the Example of the 3rd aspect is as follows.

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

It measures by the same method as (I-1) of the 1st aspect. In addition, in Table 7, one decimal place is rounded off, and it describes as an integer.

(III-2) Melt viscosity

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

(III-3) Glass transition temperature

10 mg of each polymer obtained in Production Examples 1, 3, 5-8 was collected in an aluminum pan, and the thermogram was measured by differential scanning calorimetry (DSC) at a heating rate of 10°C/min. DDSC The peak top value of is recorded as the glass transition temperature.

(III-4) Average number of polymerizable functional groups per molecular chain

Polymers (A-1), (A-3) and (A-5) were measured by the same method as (I-2) of the first embodiment. In addition, in Table 7, one decimal place is rounded off, and it describes as an integer.

(III-5) Appearance (transparency)

About the resin composition obtained in the Example, the cured product was produced by the method similar to (I-5) of the 1st aspect. After peeling off the PET film from the obtained cured product, visual observation was performed, and transparency was evaluated according to the following criteria.

<Evaluation criteria>

5: colorless and transparent

4: Extremely slightly colored, but transparent

3: Slight coloring was observed, but transparent

2: Clear coloring was observed, but transparent

1: Opaque.

(III-6) Breaking strength and breaking elongation

The cured product obtained in the above (III-5) was measured by the same method as in (II-7) of the second embodiment.

[Table 8]

[Table 9]

When respectively comparing Embodiment 24, 25, 26, 29, 30 with the second embodiment embodiment 6, embodiment 27 and the second embodiment embodiment 8, and embodiment 28 with the second embodiment embodiment 10, it can be seen that: ) component, modified liquid polyfarnesene having methacryloyl group as a polymerizable functional group in the molecule, and a resin composition of liquid diene rubber as component (B) is cured by active energy rays to give appearance, fracture In terms of elongation, it is not inferior to the cured product of the second method. Furthermore, since the liquid diene rubber which is the component (B) is contained, the breaking strength is greatly improved while maintaining transparency. In addition, the melt viscosity is also lowered, and the handleability is improved.

[Example of the fourth aspect of the present invention]

Each component used in the Example and the comparative example of a 4th aspect is as follows.

<Polymer (A) having a polymerizable functional group>

・Polymers (A-1) and (A-3) used in Examples 1 and 3 of the first embodiment.

<Polymer (B)>

・Use the polymers (B-1) and (B-2) obtained in Production Examples 6 and 7 of the third aspect.

<Polymerization Initiator (C)>

・Polymerization initiator (C-1)

2-Hydroxy-2-methyl-1-phenylpropan-1-one

BASF Corporation make, brand name "DAROCUR 1173".

<Monomer (D)>

・Acrylic monomer (D-1)

Dicyclopentenyloxyethyl methacrylate

The Hitachi Chemical Industry Co., Ltd. product, brand name "fan creil FA-512M".

<Hindered Amine Compound (E)>

・Hindered amine compounds (E-1)

Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidinyldecane mixture of diacids

BASF Corporation make, brand name "TINUVIN 765".

<Polymer (F-1)>

・Polymer (F-1) obtained in Production Example 9 below.

Production Example 9: Modified liquid polyisoprene (F-1) having a methacryloyl group in the molecule

Polyisoprene having a number average molecular weight of 36,000 was obtained by anionically polymerizing isoprene and n-butyllithium in n-hexane as an initiator.

Next, the aforementioned unmodified polymer was reacted in the same manner as in Production Example 1 of the first embodiment to synthesize a modified liquid polyisoprene having a methacryloyl group in its molecule (hereinafter also referred to as " Polymer (F-1)"). Regarding the polymer (F-1), physical properties were evaluated in the same manner as in (III-1) to (III-6) in the third embodiment. The results are shown in Table 10.

[Table 10]

<Example 35~38>

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) were put into a stainless steel 300 mL container at the ratio shown in Table 11, 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 methods in the examples of the fourth aspect are as follows.

(IV-1) Melt viscosity

About the resin composition obtained in the Example, it measured by the method similar to (I-3) of 1st aspect.

(IV-2) Appearance (transparency)

About the resin composition obtained in the Example, the hardened|cured material was produced by the method similar to (I-5) of 1st aspect. After peeling off the PET film from the obtained cured product, visual observation was performed, and transparency was evaluated according to the following criteria.

<Evaluation criteria>

5: colorless and transparent

4: Extremely slightly colored, but transparent

3: Slight coloring was observed, but transparent

2: Clear coloring is observed, but transparent

1: Opaque.

(IV-3) Breaking strength and breaking elongation

The cured product obtained in (IV-2) above was measured by the same method as in (II-7) of the second aspect.

[Table 11]

Comparing Example 35 with Example 3 of the first form, Example 36 with Example 8 of the second form, Example 37 with Example 27 of the third form, and Example 38 with Example 31 of the third form, it can be seen that: A composition in which the polymer (F) is blended in addition to the polymer (A) can also be cured by active energy rays to give a cured product that is not inferior to other methods.

Claims (25)

1. A polymer comprising a farnesene-derived monomer unit (a1) as a monomer unit constituting the polymer and having a polymerizable functional group. 2. The polymer according to claim 1, wherein the polymerizable functional group is selected from (meth)acryloyl groups, epoxy groups, oxetanyl groups, vinyl ether groups and alkoxysilyl groups which may have substituents at least one of the bases. 3. The polymer according to claim 1 or 2, which has a melt viscosity at 38° C. of 0.1 to 3000 Pa·s. 4. The polymer according to any one of claims 1 to 3, which has a number average molecular weight of 1,000 to 1,000,000. 5. The polymer according to any one of claims 1 to 4, wherein the monomer units constituting the polymer contain only farnesene-derived monomer units (a1). 6. The polymer according to any one of claims 1 to 4, wherein the monomer unit constituting the polymer contains a monomer unit (a1) derived from farnesene and a monomer unit derived from a monomer other than farnesene Monomer unit (a2). 7. The polymer according to claim 6, wherein the monomer unit (a2) is a monomer unit derived from a conjugated diene compound other than farnesene. 8. The polymer according to claim 6, wherein the monomer unit (a2) is a monomer unit derived from an aromatic vinyl compound. 9. The polymer according to claim 8, wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene, α-methylstyrene and 4-methylstyrene. 10. The polymer according to any one of claims 1 to 9, wherein the ratio of the common logarithm value of the melt viscosity at 38°C to 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. 11. the manufacture method of the polymer described in any one in claim 1～10, it possesses following steps: A step (1) of preparing an unmodified polymer containing a farnesene-derived monomer unit (a1) and having no polymerizable functional group; and a step of introducing a polymerizable functional group to the unmodified polymer (2 ). 12. The method for producing a polymer according to claim 11, wherein step (2) is to react the unmodified polymer with a compound for grafting it and then react with a compound having a polymerizable functional group process. 13. A resin composition containing the polymer (A) according to any one of claims 1 to 10. 14. The resin composition according to claim 13, further comprising a polymerization initiator (C). 15. resin composition, it contains polymer (A), monomer (D) and polymerization initiator (C) described in any one in claim 1～10, polymer (A) and monomer (D) The mass ratio [(A)/(D)] is 0.01 to 99, and 0.1 to 20 parts by mass of the polymerization initiator (C) is contained with respect to a total of 100 parts by mass of the polymer (A) and the monomer (D). 16. The resin composition according to claim 15, further comprising 0.01 to 10 parts by mass of a hindered amine compound (E) with respect to a total of 100 parts by mass of the polymer (A) and the monomer (D). 17. A resin composition comprising the polymer (A) according to any one of claims 1 to 10, comprising a monomer unit derived from a conjugated diene compound (b1) having 12 or less carbon atoms and having no The polymer (B) with polymerizable functional groups and the polymerization initiator (C), the mass ratio [(A)/(B)] of the polymer (A) to the polymer (B) is 0.01-100. 18. The resin composition according to claim 17, wherein the content of the polymerization initiator (C) is 0.1 to 20% by mass in the total amount of the resin composition. 19. 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. 20. The resin composition according to any one of claims 17 to 19, wherein 0.01 to 1,000 parts by mass of a monomer ( D). 21. The resin composition according to any one of claims 17 to 20, further comprising 0.01 to 10% by mass of the hindered amine compound (E) in the total amount of the resin composition. 22. The resin composition according to any one of claims 13 to 21, further comprising a polymer (F), the polymer (F) comprising a conjugated diene compound (f1) derived from a carbon number of 12 or less ) and has a polymerizable functional group, the mass ratio [(A)/(F)] of the polymer (A) to the polymer (F) is 0.01-100. 23. A cured product obtained by curing the resin composition according to any one of claims 13 to 22. 24. An optical adhesive comprising the cured product according to claim 23. 25. An optical adhesive comprising the resin composition according to any one of claims 13 to 22.