TWI617589B - Resin composition, hardened product obtained by curing the same, and optical adhesive containing the resin composition - Google Patents

Abstract

A resin composition comprising a polymer (A) having a polymerizable functional group containing a monomer unit (a1) derived from a conjugated diene compound, and a monomer unit (b1) containing a bacteriolide The polymer (B) and the polymerization initiator (C) without polymerizable functional groups, the mass ratio [(A) / (B)] of the polymer (A) to the polymer (B) is 0.01 to 100 .

Description

Resin composition, hardened product obtained by curing the same, and optical adhesive containing the resin composition

The present invention relates to a resin composition containing a polymer derived from a monomer unit derived from bacteriolide, a cured product obtained by curing the polymer, and an optical adhesive containing the resin composition.

In recent years, with the spread of electronic devices with screens such as liquid crystals, such as smartphones and tablet PCs, research into transparent resin materials and transparent resin adhesives used to cover screens is actively underway.

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

Further, Patent Document 2 describes a thermosetting resin composition containing an epoxy resin, a hardener, and an epoxidized polybutadiene having a specific amount of epoxy groups in a molecule and a specific number average molecular weight.

In addition, although Patent Documents 3 and 4 describe a polymer of β-bacteriolide, they have not been sufficiently studied for practical use.

[Prior technical literature] [Patent Literature]

[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

The curable resin composition described in Patent Documents 1 and 2 still has room for improvement in viscosity from the viewpoint of improving the coating property. Further, the cured product is required to have a strength required for an electronic device having a screen such as a liquid crystal. There is still room for improvement in softness and transparency.

The present invention has been made in view of the foregoing circumstances, and provides a resin composition having a low viscosity and capable of imparting a hardened material having excellent strength, flexibility, and transparency, a hardened material obtained by hardening the same, and an optical composition containing the resin composition. With adhesive.

As a result of intensive studies conducted by the present inventors, it was found that a polymer having a polymerizable functional group containing a monomer unit derived from a conjugated diene compound in a specific ratio and a polymer having a polymerizable functional group containing a monomer unit derived from bacteriolide The resin composition of the polymerizable functional group polymer has a low viscosity and a hardened material that can impart strength, flexibility, hardness, and transparency, and completed the present invention.

That is, the present invention has the following gist.

[1] A resin composition containing: derived from a conjugated diene A polymer (A) having a polymerizable functional group in the monomer unit (a1) of the compound, and a polymer (B) having no polymerizable functional group containing the monomer unit (b1) derived from the bacteriolide The mass ratio [(A) / (B)] of the polymerization initiator (C), the polymer (A) to the polymer (B) is 0.01 to 100.

[2] A cured product obtained by forming the resin composition of the above [1].

[3] An optical adhesive comprising the resin composition described in [1] above.

According to the present invention, it is possible to provide a resin composition having a low viscosity and capable of imparting a cured product excellent in strength, flexibility, and transparency, a cured product obtained by curing the cured resin, and an optical adhesive containing the resin composition.

[Form of Implementing Invention]

[Resin composition]

The resin composition of the present invention contains a polymer (A) having a polymerizable functional group containing a monomer unit (a1) derived from a conjugated diene compound, and a monomer unit (b1) containing bacteriolide. The polymer (B) and the polymerization initiator (C) without polymerizable functional groups, the mass ratio [(A) / (B)] of the polymer (A) to the polymer (B) is 0.01 to 100 .

<Polymer (A)>

The polymer (A) contains a monomer unit (a1) derived from a conjugated diene compound and has a polymerizable functional group.

The conjugated diene compound as the monomer unit (a1) is preferably bacterial green Alkenes and conjugated diene compounds having a carbon number of 12 or less. Examples of the conjugated diene compounds having a carbon number of 12 or less include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclo Hexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene and chloroprene. Among them, bacteriolide, isoprene and butadiene are more preferred. These conjugated diene compounds may be used individually by 1 type, and may use 2 or more types together.

The aforementioned bacterioluene-derived monomer unit may be an α-bacteriochloroene-derived monomer unit, and may also be a β-bacterioluene-derived monomer unit represented by the following formula (I). From the standpoint of preference, monomer units derived from β-bacteriolide are preferred. In addition, α-bacteriolide and β-bacteriolide can be used in combination.

Examples of the polymerizable functional group include (meth) acrylfluorenyl, epoxy, oxetanyl, vinyl ether, alkoxysilyl, and (meth) acrylfluorene Amino, styryl, maleimido, lactone, lactam, thioether, thiocarbamate, acetal, thiourea, and the like. Among these, at least one selected from the group consisting of (meth) acrylfluorenyl, epoxy, oxetanyl, vinyl ether, and alkoxysilyl, and more preferably (meth) propylene醯 基. In addition, these functional groups may have a substituent.

In this specification, "(meth) acrylfluorenyl" means "acrylfluorenyl or methacrylfluorenyl". In addition, in this specification, "(meth) acrylic acid" means "acrylic or methacrylic acid."

In the first method for producing the polymer (A) used in the present invention, for example, the polymer may be prepared by polymerizing monomers other than the conjugated diene compound and the conjugated diene compound as necessary to prepare the polymer A method of polymerizing a functional group of an unmodified polymer and introducing a polymerizable functional group to the unmodified polymer.

Specific examples include a reaction of an unmodified polymer obtained by living anionic polymerization of each of the monomers with a compound for grafting a maleic anhydride or the like, followed by 2-hydroxyethyl methacrylate and the like. Method for reacting a compound having a polymerizable functional group.

Examples of the compound for grafting the unmodified polymer include unsaturated anhydrides such as maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, and itaconic anhydride; Unsaturated carboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid; unsaturated carboxylic acid esters such as maleate, fumarate, citraconic acid, and iconate; maleic acid Unsaturated carboxylic acid amines such as amidine, ammonium fumarate, ammonium citrate, and ammonium ikonate; ammonium maleate, ammonium fumarate, ammonium citrate, imanitine Unsaturated carboxylic acid imine such as fumarate and imine; maleimide, imine trimethoxysilane, γ-methacrylic acid methoxypropyltrimethoxysilane, etc.

Examples of the compound having a polymerizable functional group include (meth) acrylic acid; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and pentaerythritol triacrylate. (Meth) acrylates such as acrylate, pentaerythritol trimethacrylate, dipentaerythritol monohydroxy acrylate, etc .; 2-hydroxyethyl vinyl ether, N- (2-hydroxyethyl) acrylamide, N- (2 -Hydroxyethyl) methacrylamide, N- (2- Hydroxyethyl) maleimide, 4-vinylphenol and the like. In addition, the position at which the polymerizable functional group is introduced may be the polymerization terminal of the polymer or the chain side. Moreover, the said functional group may be 1 type, or may be used in combination of 2 or more type.

The second method for producing the polymer (A) used in the present invention includes, for example, having at least one member selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, Thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amido group, sulfonic acid group, sulfonic acid ester group, phosphate group, phosphate group, amine group, imine group, nitro group, pyridyl group , Quinolinyl, epoxy, thioepoxy, thioether, isocyanate, isocyanate, silanol, alkoxysilane, silyl halide, tin halide, alkoxytin and Compounds having a functional group such as a phenyltin group are subjected to an addition reaction to a living end group of an unmodified polymer obtained by living anionic polymerization of the conjugated diene compound by a method described later, and then a polymerizable A method of reacting a functional compound.

Examples of the living anionic polymerization initiator for living anionic polymerization of a conjugated diene compound include methyl lithium, ethyl lithium, n-butyl lithium, second butyl lithium, and third butyl. Organic monolithium compounds such as lithium, hexyl lithium, 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 organic lithium compounds; sodium naphthalene, potassium naphthalene and so on. In addition, a compound such as diisopropenylbenzene or benzyltoluene which reacts with an organic alkali metal compound to give a polyfunctional organic alkali metal compound can be used in combination.

Examples of the compound having at least one of the aforementioned functional groups for the addition reaction of an active end group include cyclic ethers such as epoxides and oxetane; cyclic amines such as pyrrolidine; and epithionine Cyclic sulfides and the like.

The third method for producing the polymer (A) used in the present invention includes polymerizing monomers other than the conjugated diene compound and the conjugated diene compound as necessary by a method to be described later to prepare an unconjugated diene compound. A method of modifying a polymer, and epoxidizing the unmodified polymer, and then reacting a compound having a polymerizable functional group. Examples of the compound for epoxidizing the unmodified polymer include peracids such as peracetic acid and perbenzoic acid.

Examples of the compound having a polymerizable functional group in these methods include carboxylic acids such as acrylic acid and methacrylic acid. The position where the polymerizable functional group is introduced may be the polymerization terminal of the polymer or the chain side. The compound having a polymerizable functional group may be used alone or in combination of two or more.

When functionalizing the aforementioned unmodified polymer or storing the modified polymer, the purpose is to suppress a decrease in molecular weight due to deterioration, discoloration, and gelation, and an appropriate anti-aging agent and unmodified polymer can be used. Or modified polymer combinations. Specific examples include 2,6-di-third-butyl-4-cresol (BHT), 2,2'-methylenebis (4-methyl-6-third-butylbutylphenol) ), 4,4'-thiobis (3-methyl-6-third-butylbutylphenol), 4,4'-butylenebis (3-methyl-6-third-butylbutylphenol) ) (AO-40), 3,9-bis [1,1-dimethyl-2- [3- (3-third-butyl-4-hydroxy-5-methylphenyl) propanyloxy] Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (AO-80), 2,4-bis [(octylthio) methyl] -6-cresol (Irganox 1520L ), 2,4-bis [(dodecylthio) methyl] -6-cresol (Irganox 1726), 2- [1- (2-hydroxy-3,5-di-third-pentylphenyl) Ethyl] -4,6-di-third-pentylphenyl acrylate (Sumilizer GS), 2-third-butyl-6- (3-third-butyl-2-hydroxy-5-methylbenzoyl ) -4-methylphenyl acrylate (Sumilizer GM), 6-Third-butyl-4- [3- (2,4,8,10-Tetra-Third-butyldibenzo [d, f ] [1,3,2] Phosphocycloheptane 6-yloxy) propyl] -2-cresol (Sumilizer GP), Phosphite (2,4-di-third-butylphenyl) (Irgafos 168), di-octadecane 3,3'-dithiobispropionate, 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-di-octadecylhydroxylamine (Irgastab FS 042 ), Bis (4-t-octylphenyl) amine (Irganox 5057), and the like. Moreover, the said anti-aging agent may be used individually by 1 type, and may use 2 or more types together.

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

The monomer unit constituting the polymer (A) may include only the aforementioned monomer unit (a1) derived from a conjugated diene compound, or may include the aforementioned monomer unit (a1) derived from a conjugated diene compound and a conjugated diene compound. A monomer unit (a2) of a monomer other than a diene compound. That is, the unmodified polymer may be obtained by polymerizing only the conjugated diene compound, or may be a copolymer of the conjugated diene compound and a monomer other than the conjugated diene compound.

When the unmodified polymer is a copolymer, the monomer unit (a2) derived from a monomer other than the conjugated diene compound may be a monomer unit derived from an aromatic vinyl compound.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methylphenethyl Ene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropyl Styrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2-vinyl Naphthalene, vinyl anthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene, etc. . Among them, styrene, α-methylstyrene, and 4-methylstyrene are preferred.

In the case where a monomer unit (a2) derived from a monomer other than the conjugated diene compound is used, the monomer unit (a2) derived from a monomer other than the conjugated diene compound in the copolymer is derived from the conjugated diene compound The total ratio of the monomer unit (a1) and the monomer unit (a2) derived from monomers other than the conjugated diene compound is from the viewpoint of reducing the viscosity of the resin composition, from the good stretch characteristics and softness of the cured film From the viewpoint of sex, it is more preferably 1 to 99% by mass, more preferably 1 to 80% by mass, more preferably 1 to 70% by mass, and even more preferably 1 to 50% by mass.

The number average molecular weight (Mn) of the polymer (A) used in the present invention is more preferably from 10 to 1 million, preferably from 2,000 to 500,000, more preferably from 8,000 to 500,000, more preferably from 15,000 to 450,000, and more It is preferably 15,000 to 300,000, and more preferably 20,000 to 200,000. When the Mn of the polymer (A) is within the aforementioned range, the flexibility and mechanical strength of the cured product are improved, and the resin composition has a low viscosity.

In addition, the number average molecular weight (Mn) in this specification means the number average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

Melt viscosity of the polymer (A) used in the present invention at 38 ° C It is more preferably 0.1 to 3,000 Pa‧s, more preferably 0.2 to 3,000 Pa‧s, more preferably 0.2 to 2,800 Pa‧s, and even more preferably 0.3 to 2,600 Pa‧s. When the melt viscosity of the polymer (A) is within the aforementioned range, the polymer can be applied uniformly without spot on the surface to be coated, so that the applicability becomes good.

In addition, in this specification, the melt viscosity of a polymer is a value calculated | required by the method described in the Example mentioned later.

The number of polymerizable functional groups per one molecular chain of the polymer (A) used in the present invention is preferably 1 to 150, more preferably 1.5 to 75, and even more preferably 1.5 to 30. When the number of polymerizable functional groups per one molecular chain is within the aforementioned range, the viscosity of the polymer (A) can be reduced, the curing speed can be increased, and the shrinkage during curing can be reduced.

The number of polymerizable functional groups per one 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) by the following formula.

(Number of polymerizable functional groups per 1 molecular chain) = (Mn) / (functional group equivalent)

The functional group equivalent refers to the amount of "the molecular weight of the polymer per one functional group". For example, when the polymerizable functional group is a methacrylfluorenyl group, the functional group equivalent is called "methacrylfluorenyl equivalent", which means "the molecular weight of the polymer per one methacrylfluorenyl group". The functional group equivalent can be calculated based on the reaction rate of the modifier, and can be obtained by using various analysis equipment such as infrared spectroscopy and nuclear magnetic resonance spectroscopy.

The polymer (A) used in the present invention may be used alone or in combination of two or more kinds of the polymer (A) having different monomer units or molecular weights and different types of functional groups.

The content of the polymer (A) in the total resin composition is preferably 1 to 99% by mass, more preferably 2 to 98% by mass, more preferably 5 to 95% by mass, and even 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, and transparency can be imparted.

<Polymer (B)>

The polymer (B) is a polymer containing a monomer unit (b1) derived from bacteriolide and having no polymerizable functional group. As the bacteriolide, the same ones as described in the aforementioned polymer (A) can be used. The monomer unit constituting the polymer (B) may include only the monomer unit (b1) derived from bacteriolide, or may include the monomer unit (b1) derived from bacteriolide and monomers derived from monomers other than bacteriolide Monomer unit (b2).

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

The conjugated diene compound is preferably a conjugated diene compound having a carbon number of 12 or less, and the conjugated diene compound having a carbon number of 12 or less includes, for example, butadiene, isoprene, 2 , 3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3 -Octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, chloroprene, and the like. Among them, isoprene and butadiene are preferred. These conjugated diene compounds may be used individually by 1 type, and may use 2 or more types together.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene. 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, diethylene Aromatic vinyl compounds such as phenylbenzene and the like. Among them, styrene, α-methylstyrene, and 4-methylstyrene are preferred.

In the case of using a monomer unit (b2) derived from a monomer other than bacteriolide, the monomer unit (b2) derived from a monomer other than bacteriolide in the copolymer The total ratio of (b1) and monomer units (b2) derived from monomers other than bacteriolide is from the viewpoint of reducing the viscosity of the resin composition, from the viewpoint of increasing the curing speed, and from the good stretching of the cured film From the viewpoint of characteristics and softness, it is more preferably 1 to 99% by mass, more preferably 1 to 80% by mass, more preferably 1 to 70% by mass, and even more preferably 1 to 50% by mass.

The number average molecular weight (Mn) of the polymer (B) used in the present invention is preferably 10 to 1 million, preferably 1,000 to 500,000, more preferably 1,000 to 200,000, more preferably 5,000 to 200,000, more It is preferably 5,000 to 150,000. When the Mn of the polymer (B) is within the aforementioned range, the flexibility and mechanical strength of the cured product are improved, and the resin composition has a low viscosity.

The melt viscosity of the polymer (B) used in the present invention at 38 ° C is more preferably 0.1 to 3,000 Pa · s, more preferably 0.2 to 3,000 Pa · s, more preferably 0.2 to 2,800 Pa · s, and even more preferably 0.3. ~ 2,600Pa‧s. When the melt viscosity of the polymer (B) is within the aforementioned range, it can be spotless on the surface to be coated. Since the resin composition is applied uniformly, the applicability becomes good.

The molecular weight distribution (Mw / Mn) of the polymer (B) used in 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 deviation of the obtained polymer (B) becomes small.

The glass transition temperature of the polymer (B) used in the present invention varies depending on the bonding pattern (microstructure) or the amount of monomers derived from bacteriolide and further monomers other than bacteriolide, if used, which is more preferably A range of -90 to 0 ° C, preferably a range of -90 to -10 ° C. When it is in the said range, a soft hardened | cured material can be obtained, and in the adhesive for optics which is one of the uses of this invention, a step followability or impact absorption becomes favorable.

The polymer (B) used in the present invention may be used singly or in combination of two or more kinds of the polymer (B) having different monomer units or different molecular weights. The polymer (B) used in the present invention can be produced by an emulsion polymerization method, a method described in International Publication No. 2010/027463, International Publication No. 2010/027464, and the like. Among these, an emulsion polymerization method or a solution polymerization method is preferable, and a solution polymerization method is more preferable.

(Emulsion polymerization method)

As for the emulsion polymerization method for obtaining the polymer (B), a known method can be applied. For example, a predetermined amount of bacteriolide is emulsified and dispersed in the presence of an emulsifier, and emulsification polymerization is performed using a radical polymerization initiator.

As the emulsifier, for example, a chain-length fatty acid salt or rosinate having a carbon number of 10 or more is used. Specific examples include potassium or sodium salts of fatty acids such as capric acid, glyceryl trilaurate lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid.

As a dispersant, water is usually used, and in the range which does not inhibit the stability at the time of superposition | polymerization, it can contain water-soluble organic solvents, such as methanol and ethanol.

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

In order to adjust the molecular weight of the polymer, a chain shifting agent may be used. Examples of the chain shifting agent include thiols such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpene, terpineol, and γ- Terpinene, α-methylstyrene dimer, etc.

The emulsification polymerization temperature can be appropriately selected according to the type of the radical polymerization initiator used, and it is generally preferably 0 to 100 ° C, and more preferably 0 to 60 ° C. The polymerization form may be any of continuous polymerization and batch polymerization. The polymerization reaction can be stopped by the addition of a polymerization stopper.

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

After the polymerization reaction is stopped, an anti-aging agent may be added as required. After the polymerization reaction is stopped, unreacted monomers are removed from the obtained latex as required, and then, using sodium chloride, calcium chloride, potassium chloride and other salts as coagulants, acids such as nitric acid and sulfuric acid are added as needed, and the coagulation system is After adjusting the pH to a predetermined value, the polymer was recovered by separating the dispersion solvent after the polymer was solidified. Subsequently, after washing with water and dehydration, the polymer was obtained by drying. In addition, at the time of coagulation, the latex may be mixed with the stretching oil used as an emulsified dispersion in advance as needed, and the polymer as an oil spread may be recovered.

(Solution polymerization method)

As a solution polymerization method for obtaining a polymer, a well-known method can be applied. For example, a Ziegler-based catalyst, a metallocene-based catalyst, and an anionically polymerizable active metal are used in a solvent, and a bacteriolide monomer is polymerized in the presence of a polar compound as desired.

Examples of the anion-polymerizable active metal include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; and lanthanide-based rare earth metals such as lanthanum and scandium. Among them, alkali metals and alkaline earth metals are preferred, and alkali metals are particularly preferred. More preferably, an organic alkali metal compound is used.

Examples of the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; and lipids such as cyclopentane, cyclohexane, and methylcyclopentane. Cyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, etc.

Examples of the organic alkali metal compound include organic monolithic compounds such as methyl lithium, ethyl lithium, n-butyl lithium, second butyl lithium, third butyl lithium, hexyl lithium, phenyl lithium, and stilbene lithium. Lithium compounds; polyfunctional lithium such as dilithium methane, dilithium naphthalene, 1,4-dilithium butane, 1,4-dilithium-2-ethylcyclohexane, 1,3,5-trilithiumbenzene Compounds; sodium naphthalene, potassium naphthalene, etc. Among these, an organic lithium compound is more preferable, and an organic monolithium compound is more preferable. The usage amount of the organic alkali metal compound can be appropriately determined according to the molecular weight of the required polymer, and it is preferably 0.01 to 100 parts by mass with respect to the total amount of bacteriolide and monomers other than bacteriolide used as needed. 7 parts by mass.

The organic alkali metal compound can also be reacted with secondary amines such as dibutylamine, dihexylamine, and benzylamine, and used as an organic alkali metal amine.

The polar compound is used to prevent the reaction from being inactivated during anionic polymerization and to adjust the microstructure of the bacteriolide site, and examples thereof include ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol diethyl ether; Tertiary amines such as methylethylenediamine and trimethylamine; alkali metal alkoxides, phosphine compounds, etc. The polar compound is preferably used in the range of 0.01 to 1,000 mol equivalents relative to the organic alkali metal compound.

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

The polymerization reaction can be stopped by adding alcohols such as methanol and isopropanol as polymerization stopping agents. The polymer may be precipitated by injecting the obtained polymerization reaction solution into a weak solvent such as methanol to separate the polymer, or by washing with water to separate the polymerization reaction solution, followed by drying.

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

In the present invention, the melt viscosity of at least one of the polymer (A) and the polymer (B) at 38 ° C is preferably 0.1 to 3,000 Pa · s, and the polymer (A) and the polymer (B) are more preferable. ) The melt viscosity of both sides is in the range of 0.1 ~ 3,000Pa · s.

<Polymerization initiator (C)>

Examples of the polymerization initiator (C) used in the present invention include photopolymerization initiated by polymerization reaction by irradiation of active energy rays such as ultraviolet rays and the like. An initiator or a thermal polymerization initiator that initiates a polymerization reaction by heat. Among them, a photopolymerization initiator is preferred from the viewpoint of curing the resin by short-term irradiation without deteriorating the substrate and obtaining a cured product, and more preferably light that initiates the polymerization reaction by irradiation of ultraviolet rays. Polymerization initiator. Examples of the photopolymerization initiator include a cationic photopolymerization initiator and a radical polymerization initiator.

Examples of the cationic photopolymerization initiator include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, and metallocene compounds.

As a cationic photopolymerization initiator of an aromatic diazonium salt, "P-33 (trade name)" (made by ADEKA Corporation) and the like are known.

As for the cationic photopolymerization initiator of an aromatic iodonium salt, "Rhodorsil Photo Initiator 2074 (trade name)" (manufactured by Rhodia Co., Ltd.), "IRGACURE 250 (trade name)" (BASF Corporation Limited) Company system) and so on.

As the cationic photopolymerization initiator of an aromatic sulfonium salt, "FC-509 (trade name)" (manufactured by Sumitomo 3M Co., Ltd.) and "IRGACURE 270 (trade name)" (BASF Co., Ltd.) are known.制) and so on.

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

Examples of the radical-based photopolymerization initiator include acetophenone-based, benzophenone-based, alkylphenol-based, fluorenylphosphine oxide-based, benzoin-based, ketal-based, anthraquinone-based, Disulfide-based, thioxanthone-based, chalcogenide-based, fluoroamine-based and the like. Among them, an alkylphenol-based or fluorenylphosphine oxide-based radical photopolymerization initiator is preferred.

Examples of the alkylphenol-based radical photopolymerization initiator include hydroxyalkylphenol-based, aminoalkylphenol-based, and the like. Examples of the hydroxyalkylphenol-based radical photopolymerization initiator include "DAROCUR 1173 (trade name)" (2-hydroxy-2-methyl-1-phenylpropan-1-one), and " IRGACURE 184 (trade name) '' (1-hydroxycyclohexylphenyl ketone), `` IRGACURE 2959 (trade name) '' (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2 -Methyl-1-propan-1-one) and the like.

Examples of the amino radical phenol-based radical photopolymerization initiator include "IRGACURE 907 (trade name)" (2-methyl-1- (4-methylthiophenyl) -2- Porphyrin-1-one), `` IRGACURE 369 (trade name) '' (2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -1-butanone) and the like.

Examples of the fluorenylphosphine oxide-based radical photopolymerization initiator include "LUCIRIN TPO (trade name)" (2,4,6-trimethylbenzyldiphenylphosphine oxide), " IRGACURE 819 (trade name) "(bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide) (both manufactured by BASF Corporation) and the like.

Among these, a hydroxyalkylphenol-based radical photopolymerization initiator is more preferable, and 2-hydroxy-2-methyl-1-phenylpropan-1-one is more preferable. These may be used alone or in combination of two or more.

The content of the polymerization initiator (C) in the total amount of the resin composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass, more preferably 1.0 to 20% by mass, and even more preferably 1.0 to 15% by mass, preferably 1.0 to 10% by mass. When the content of the polymerization initiator (C) is within the aforementioned range, it is preferable in terms of the hardening speed and the mechanical properties.

<Monomer (D)>

The resin composition of the present invention may contain a monomer (D) as necessary in order to further increase the viscosity, handleability, and strength after curing of the resin composition. The monomer (D) preferably contains a functional group obtained by reacting with the polymer (A). Examples thereof include a (meth) acrylfluorenyl group, an epoxy group, an oxetanyl group, Vinyl ether and alkoxysilyl compounds.

Specific compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and butyl ethyl (meth) acrylate Oxyester, butylethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentenyl (meth) acrylate, dimethacrylate Cyclopentenyloxyethyl, dicyclopentyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isoamyl (meth) acrylate, ( 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, (meth) acrylic acid Phosphonoester, phenoxyethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, (formaldehyde) Base) glycidyl acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, etc. Functional (meth) acrylates; 1,4-butanebutanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate Base) acrylate, dimethylol tricyclodecane di (meth) acrylate, ethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, ethylene oxide modified bis Bifunctional (meth) acrylates such as phenol A di (meth) acrylate, triethylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, ethylene oxide modification Trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, bis-trimethylolpropane tetra Multifunctional (meth) acrylates such as (meth) acrylates; 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate, 1,2-epoxy Epoxy compounds such as 4-vinylcyclohexane, 1,2: 8,9-diepoxy limonene, 2,6,6-trimethyl-2,3-epoxybicyclo [3.1.1] heptane ; 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 3-ethyl-3- (Phenoxymethyl) oxetane, bis [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) ) Oxetane compounds such as oxetane; vinyl ether compounds such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether; mercaptomethyltrimethyl Silane compounds such as oxysilane, glycidoxymethyltrimethoxysilane, and vinylmethyltrimethoxysilane.

Among them, the monomer (D) preferably contains a monomer selected from the group consisting of monofunctional (meth) acrylate and difunctional (meth) acrylate from the viewpoint of good compatibility with the polymer (A). And at least one kind of polyfunctional (meth) acrylate, preferably at least one kind selected from monofunctional (meth) acrylate and difunctional (meth) acrylate. Among them, particularly preferred are dicyclopentenyloxyethyl (meth) acrylate, 1,9-nonanediol di (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid 2- Ethylhexyl, bicyclic (meth) acrylate Pentenyl esters, phenoxyethyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

The monomer (D) is capable of reacting with a polymerizable functional group of the polymer (A) through a polymerization initiator such as a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator. The content of the aforementioned monomer (D) is preferably 0.01 to 1,000 parts by mass, more preferably 0.1 to 800 parts by mass, and more preferably 1.0 relative to 100 parts by mass of the total of the polymer (A) and the polymer (B). ~ 600 parts by mass, more preferably 1.0 ~ 400 parts by mass. When the content of the monomer (D) is within the aforementioned range, the viscosity is reduced and the handleability is improved. In addition, when the resin composition of the present invention is cured, since the fracture strength and tensile elongation of the cured film are increased, a cured product having excellent flexibility is obtained.

<Hindered amine compound (E)>

The resin composition of the present invention may contain a hindered amine-based compound (E) in the molecule as necessary in order to further improve the heat resistance and weather resistance of the resin composition and the cured product obtained therefrom. In addition, as the hindered amine compound (E), a hindered amine compound having no secondary amine group in the molecule is preferably used. By using the hindered amine compound (E) which does not have a secondary amine group in the molecule, it is possible to remarkably improve the reduction of the mechanical properties of the resin composition and the hardened material obtained therefrom, or the color tone. Variety.

As such, for the hindered amine-based compound (E) having no secondary amine group in the molecule, for example, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) decane Acid ester, 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, sebacate 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-butanetetracarboxylic acid (1,2,2,6,6-pentamethyl-4-piperidinyl), 1,2,2,6,6-pentamethyl-4-piperidinylmethyl Acrylate, etc.

Among them, 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 (1,2,2,6,6-pentamethyl-4-piperidinyl) and the like. These may be used alone or in combination of two or more.

The content of the hindered amine-based compound (E) in the total amount of the resin composition 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-based compound (E) is within the aforementioned range, it is preferable to improve heat resistance and improve mechanical properties of the cured product.

The resin composition of the present invention may contain, in addition to the polymer (A) and the polymer (B), as long as the effect of the present invention is not impaired, a polymer obtained by polymerizing a conjugated diene compound other than bacteriolide. Polymerizable functional group conjugated diene polymer. Examples of conjugated diene compounds other than bacteriolides include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, and 1,3-pentene. Diene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3- Octadiene, 1,3,7-octatriene, myrcene, chloroprene, etc.

The resin composition of the present invention may contain, in addition to the polymer (A) and the polymer (B), as long as the effect of the present invention is not impaired, a conjugated diene compound other than bacteriolide and Conjugated diene compound of polymerizable functional group obtained by copolymerization of aromatic vinyl compound Polymer-aromatic vinyl compound copolymer. As an example of the conjugated diene compound, the same ones as described above can be used.

Examples of the aromatic vinyl compound 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 -Diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene, and the like.

The content of the conjugated diene-based polymer and the conjugated diene compound-aromatic vinyl compound-based 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 even more preferably 10% by mass or less.

<Manufacturing method of resin composition>

The manufacturing method of the resin composition of this invention is not specifically limited, For example, the said polymer (A), the said polymer (B ), A polymerization initiator (C), and other components used as required, and produced by mixing.

<Melting viscosity of resin composition>

The melt viscosity of the resin composition of the present invention at 38 ° C. is preferably 15 Pa · s or lower, preferably 12 Pa · s or lower, and more preferably 10 Pa · s or lower. When the melt viscosity of the resin composition is within the aforementioned range, the resin composition can be evenly applied to the surface to be coated, and air bubbles can be easily prevented. Since it is mixed, the applicability becomes good. In addition, in this specification, the melt viscosity of a resin composition is a value calculated | required by the method described in the Example mentioned later.

The resin composition of the present invention has low melt viscosity and excellent hardenability, and can further obtain a hardened material having excellent strength, softness, and transparency. Therefore, it is suitable for use as an adhesive, an adhesive (especially, an optical adhesive), Coating agent, sealing material and printing ink.

[Hardened matter]

The cured product of the present invention is obtained by curing the resin composition of the present invention. For example, by irradiating the resin composition of the present invention with energy rays or applying heat, the polymer (A) and polymerization are initiated. Agent (C) reacts to harden.

As for the energy rays used for hardening, ultraviolet rays are preferred. Examples of the ultraviolet source include a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a microwave-type excimer lamp. The environment in which ultraviolet rays are irradiated is preferably an environment in which an inert gas environment such as nitrogen or carbon dioxide or an oxygen concentration is reduced.

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

[Optical Adhesive]

The optical adhesive of the present invention contains the resin composition of the present invention, and is suitable for use in electronic devices such as smartphones, liquid crystal displays, and organic EL displays.

The above-mentioned optical adhesive is within a range not deviating from the object of the present invention, and various additives can be appropriately added as necessary. As before Examples of the additives include adhesion-imparting agents, plasticizers, pigments, colorants, anti-aging agents, and ultraviolet absorbers.

[Example]

Hereinafter, the present invention is described in detail by examples, but the present invention is not limited to these examples.

Each component used in this example and a comparative example is as follows.

<Polymer (A)>

‧Polymers (A-1) and (A-2) obtained in Production Examples 1 and 2 described later

<Polymer (B)>

‧Polymers (B-1) and (B-2) obtained in Production Examples 3 and 4 described later

<Polymerization initiator (C)>

‧Polymerization initiator (C-1)

2-hydroxy-2-methyl-1-phenylpropan-1-one

Product name "DAROCUR 1173" made by BASF Corporation

<Monomer (D)>

‧Dicyclopentenyloxyethyl methacrylate

"Fancryl FA-512M" manufactured by Hitachi Chemical Industries, Ltd.

<Hindered amine compound (E)>

‧Hindered amine compound (E-1)

Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidinylsebacate Acid mixture

Made by BASF Co., Ltd. under the brand name "TINUVIN 765"

<Other polymers (X)>

‧Polymer (X-1) ~ (X-3)

The polymers (X-1), (X-2), and (X-3) obtained in Production Examples 5 to 7 described later.

<Manufacturing Examples 1 to 7>

Production Example 1: Production of polyisoprene (A-1) having a methacrylfluorene group in the molecule

Polyisoprene having a number average molecular weight of 36,000 was obtained by anionic polymerization of isoprene in n-hexane using n-butyllithium as a starter. By adding 1.5 parts by mass of maleic anhydride to 100 parts by mass of this polyisoprene, and reacting it at 180 ° C for 15 hours, a polyisoprene having an average of 3 acid anhydride groups per molecule was obtained. . Next, by adding 2.0 parts by mass of 2-hydroxyethyl methacrylate to 100 parts by mass of the polyisoprene having an average of three acid anhydride groups per molecule, and reacting at 120 ° C. for 10 hours after blocking the light In order to obtain a modified polyisoprene (hereinafter, also referred to as "polymer (A-1)") having an average of 3 methacrylfluorene groups per molecule. The physical properties of the polymer (A-1) are shown in Table 1.

Production Example 2: Production of polybacterene (A-2) having a methacrylfluorene group in the molecule

In a 5 liter autoclave with nitrogen substitution capacity, 1520 g of cyclohexane and 7.8 g of a 10.5% by mass cyclohexane solution of second butyl lithium were fed, and then the temperature was raised to 50 ° C, and 1510 g of β-bacteria were added. Greenene was polymerized for 2 hours. The obtained polymerization solution was poured into methanol to reprecipitate and filter the unmodified polymer, and vacuum dried at 80 ° C. for 10 hours to obtain 1200 g of polybacterene (unmodified polymer).

100 parts by mass of polybacterene obtained by feeding in a 1-liter autoclave with nitrogen substitution, and 1.5 parts by mass of maleic acid was added Anhydride and 1 part by mass of BHT (2,6-di-third-butyl-4-cresol, manufactured by Honshu Chemical Industry Co., Ltd.) were reacted at 160 ° C for 20 hours to obtain an average of 11 molecules per molecule. Anhydride-based polybacterene. Next, by adding 2.0 parts by mass of 2-hydroxyethyl methacrylate to 100 parts by mass of the polybacterene, the mixture was reacted at 80 ° C for 6 hours after being shielded from light to obtain an average of 11 formazan per molecule. Modified liquid polybacterene based on acrylonitrile (hereinafter, also referred to as "polymer (A-2)"). The physical properties of the polymer (A-2) are shown in Table 1.

Production Example 3: Production of Polybacterene (B-1)

In a pressure-resistant container substituted with nitrogen and dried, 241 g of cyclohexane as a solvent and 28.3 g of second butyl lithium (10.5 mass% cyclohexane solution) as a starter were fed, and the temperature was raised to 50 ° C. After that, 342 g of β-bacteriolide were added for polymerization for 1 hour. The obtained polymerization reaction solution was treated with methanol, and the polymerization reaction solution was washed with water. The washed polymerization reaction solution was separated from water and dried at 70 ° C. for 12 hours to obtain a liquid polybacterene (hereinafter, also referred to as “polymer (B-1)”). The physical properties of the polymer (B-1) are shown in Table 1.

Production Example 4: Production of Polybacterene (B-2)

In a pressure-resistant container substituted with nitrogen and dried, 304 g of cyclohexane as a solvent and 1.5 g of second butyl lithium (10.5 mass% cyclohexane solution) as a starter were fed, and the temperature was raised to 50 ° C. After that, 302 g of β-bacteriolide were added for polymerization for 1 hour. The obtained polymerization reaction solution was treated with methanol, and the polymerization reaction solution was washed with water. The washed polymerization reaction solution was separated from water and dried at 70 ° C. for 12 hours to obtain a liquid polybacterene (hereinafter, also referred to as “polymer (B-2)”). The physical properties of the polymer (B-2) are shown in Table 1.

Production Example 5: Production of polyisoprene (X-1)

Anisoprene was anionically polymerized in n-hexane using n-butyllithium as a starter to obtain a liquid polyisoprene having a number average molecular weight of 20,000. The physical properties of polyisoprene (X-1) are shown in Table 1.

Production Example 6: Production of polybutadiene (X-2)

By anionic polymerization of butadiene in n-hexane using n-butyllithium as a starter, a liquid polybutadiene having a number average molecular weight of 9,000 was obtained. The physical properties of polybutadiene (X-2) are shown in Table 1.

Production Example 7: Production of polybutadiene (X-3)

By anionic polymerization of butadiene in n-hexane using n-butyllithium as a starter, a liquid polybutadiene having a number average molecular weight of 44,000 was obtained. The physical properties of polybutadiene (X-3) are shown in Table 1.

<Examples 1 to 9>

The polymers (A-1), (A-2), (B-1), (B-2), (X-2) and (X-2) obtained in each production example were polymerized at the ratios shown in Table 2. The initiator (C-1), the monomer (D), and the hindered amine compound (E) were put into a 300 mL container made of stainless steel and mixed at room temperature for 20 minutes using a stirring blade to produce 200 g of a resin composition. The obtained resin composition was evaluated by the following method. The results are shown in Table 2.

<Comparative Examples 1 to 6>

Except for the polymers (A-1), (A-2), (X-1) to (X-3) and the polymerization initiator (C-1) obtained by blending each of the production examples in the ratio shown in Table 3. Except for the monomer (D), a resin composition was produced in the same manner as in Example 1 and evaluated. The results are shown in Table 3.

<Evaluation method>

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

GPC-8020 manufactured by TOSOH Co., Ltd. was used to adjust and measure at a concentration of sample / tetrahydrofuran = 5 mg / 10 mL.

The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) are obtained by GPC (gel permeation chromatography) in terms of molecular weight in terms of standard polystyrene. The measurement devices and conditions are shown below.

‧Device: GPC device "GPC8020" manufactured by TOSOH Corporation

‧Separation column: "TSKgelG4000HXL" manufactured by TOSOH Co., Ltd.

‧Detector: "RI-8020" manufactured by TOSOH Corporation

‧Eluent: Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.)

‧Dissolution flow: 1.0ml / min

‧Concentration of sample: 5mg / 10ml

‧Column temperature: 40 ℃

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

The polymers (A-1), (A-2), (B-1), (B-2), and (X) obtained by the aforementioned manufacturing examples were measured using a Brook non-viscosity meter (manufactured by BROOKFIELD ENGINEERING LABS. INC.). -1) to (X-3) and the melt viscosity of the resin composition obtained in each of Examples and Comparative Examples at 38 ° C.

10 mg of the polymer obtained in Manufacturing Examples 1 to 7 was taken in an aluminum pan, and the thermal analysis chart was measured by differential scanning calorimetry (DSC) under the condition of a heating rate of 10 ° C / min, and the value of the peak of DDSC was taken Glass transition temperature.

¹ H-NMR measurement using the apparatus manufactured by JEOL, Ltd. (500 MHz), at a sample / deuterated chloroform = concentration of 100mg / 1mL cumulative number of 512 times, measurement temperature 50 ℃, mass spectrometry ¹ H-NMR measurement.

The mass spectrum obtained by measuring the polymer (A) is calculated from the area ratio of the peak portion of the double bond derived from the methacryl group and the peak portion of the double bond derived from the main chain of the polymer chain to the methacryl group The mass of the polymer with 1 equivalent of the group, that is, the functional group equivalent.

The number of polymerizable functional groups per one molecular chain is calculated from the number average molecular weight of the polymer (A) and the functional group equivalents obtained by the method described above.

(3) Appearance

The resin compositions obtained in the examples and comparative examples were poured into a template having a length of 70 mm, a width of 70 mm, and a thickness of 0.5 mm. The surface of the composition was covered with a PET film having a thickness of 50 μm, and then a UV irradiation device (manufactured by GS Yuasa Corporation, HAK125L-F was used as a mercury lamp), the illuminance was set to 45 mW / cm ² , the transport speed was set to 0.25 m / min, and 1,000 mJ / cm ² of UV was irradiated in one operation. This was repeated three times to obtain a cured product. After the PET film was peeled from the cured product, it was visually observed and the transparency was evaluated according to the following criteria.

<Evaluation Criteria>

5: colorless and transparent

4: Very slight coloring is observed, but it is transparent

3: Staining is slightly observed, but is transparent

2: Obvious coloring is observed, but it is transparent

1: opaque

(4) Breaking strength and elongation at break

The hardened product obtained in the above (3) was a specimen having a width of 6 mm and a length of 70 mm, and a tensile tester manufactured by Instron Corporation was used to measure the breaking strength and tensile strength when the tensile test was performed at a tensile speed of 50 mm / min. Elongation at break.

From Tables 2 and 3, the resin compositions of Examples 1 to 3 and Examples 6 and 7 contain polyisoprene (A-1) and polybacteria green that contain a methacrylfluorenyl group having a polymerizable functional group. The olefin (B-1 or B-2) has a lower viscosity than Comparative Example 4 containing only polyisoprene (A-1) having a methacrylfluorene group, and does not damage the appearance and elongation at break. Degree increase. Moreover, in Examples 2, 3, and 6, the breaking strength was also improved as compared with Comparative Example 4. Furthermore, even when another conjugated diene polymer as shown in Example 8 was used in combination, the effect of reducing the viscosity and the effect of improving the elongation at break of the cured film were similarly observed. Furthermore, it is clear from the comparison between Example 9 and Comparative Example 6 that the viscosity reduction effect, the elongation at break and the fracture of the cured film were similarly observed even in the resin composition having a large amount of monomer (D). Strength improvement effect.

The resin compositions of Examples 4 and 5 are polymerizable because they contain Functional methacryl group-containing polybacterene (A-2) and polybacterene (B-1), and polybacterene (A-2) containing only methacryl group Compared with Comparative Example 5, the viscosity, elongation at break, and breaking strength were improved.

On the other hand, the resin compositions of Comparative Examples 1 to 3 are polyisoprene (A-1) or polybutadiene (X-1) blended with polyisoprene (A-1) having a methacrylfluorene group in the molecule. The composition of the diene (X-2 or X-3), but the elongation at break was lower than those of Examples 1 to 3 in which the polybacterene was blended.

In addition, according to the comparison between Example 1 and Comparative Example 2, among polybacterene (B-1) and polybutadiene (X-2) having the same molecular weight, the viscosity of those who used polybacterene was significantly reduced. The effect is better.

Claims (17)

A resin composition comprising a polymer (A) having a polymerizable functional group containing a monomer unit (a1) derived from a conjugated diene compound, and a monomer unit (b1) containing a bacteriolide The polymer (B) and the polymerization initiator (C) without polymerizable functional groups, the mass ratio [(A) / (B)] of the polymer (A) to the polymer (B) is 0.01 to 100 . For example, the resin composition of claim 1 further contains 0.01 to 1,000 parts by mass of the monomer (D) based on 100 parts by mass of the total of the polymer (A) and the polymer (B). For example, the resin composition of claim 1 or 2, wherein the content of the polymerization initiator (C) in the total amount of the resin composition is 0.1 to 20% by mass. The resin composition according to claim 1 or 2, further comprising 0.01 to 10% by mass of a hindered amine compound (E) in the total amount of the resin composition. For example, the resin composition of claim 1 or 2, wherein the melt viscosity of at least one of the polymer (A) and the polymer (B) at 38 ° C is 0.1 to 3,000 Pa · s. For example, the resin composition of claim 1 or 2, wherein the number average molecular weight of the polymer (B) is 10 to 1 million. The resin composition according to claim 1 or 2, wherein the monomer unit constituting the polymer (B) includes only the monomer unit (b1) derived from bacteriolide. For example, the resin composition of claim 1 or 2, wherein the monomer unit constituting the polymer (B) contains a monomer unit (b1) derived from a bacteriolide and a monomer unit (a b2). The resin composition according to claim 8, wherein the monomer unit (b2) is a monomer unit derived from a conjugated diene compound other than bacteriolide. The resin composition of claim 8, wherein the monomer unit (b2) is derived from A monomer unit of an aromatic vinyl compound. The resin composition according to claim 1 or 2, wherein the monomer unit constituting the polymer (A) includes only the monomer unit (a1) derived from the conjugated diene compound. The resin composition according to claim 1 or 2, wherein the monomer unit constituting the polymer (A) contains a monomer unit (a1) derived from a conjugated diene compound and a monomer other than the conjugated diene compound. Of the monomer unit (a2). The resin composition according to claim 11, wherein the conjugated diene compound as the monomer unit (a1) is at least one selected from the group consisting of bacteriolide, isoprene, and butadiene. For example, the resin composition of claim 1 or 2, wherein the polymerizable functional group of the polymer (A) may have a substituent and is selected from (meth) acrylfluorenyl, epoxy, and propylene oxide At least one of a vinyl group, a vinyl ether group, and an alkoxysilyl group. For example, the resin composition of claim 1 or 2, wherein the number of polymerizable functional groups per one molecular chain of the polymer (A) is 1 to 150. A hardened material obtained by hardening the resin composition according to any one of claims 1 to 15. An optical adhesive comprising the resin composition according to any one of claims 1 to 15.