JP2012233041A - (meth)acrylic resin composition and optical component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a (meth)acrylic resin composition excellent in heat resistance, transparency, and mechanical characteristic, and to provide an optical component using it.SOLUTION: This (meth)acrylic resin composition is a block copolymer containing a segment A polymerized using (meth)acrylic acid ester monomer as a principal ingredient and a segment B polymerized using, as a principal ingredient, (meth)acrylic acid ester monomer containing an adamantane structure represented by general formula (1). In the formula, R-Rindependently show a group selected from a hydrogen atom, hydroxyl group, halogen atom, 1-20C alkyl group, and 3-20C cycloalkyl group. Rshows a hydrogen atom or methyl group. Y shows a group selected from a phenyl group, 1-20C alkylene group, and 3-20C cycloalkylene group, and n is 0 or 1.

Description

  The present invention relates to a (meth) acrylic resin composition excellent in heat resistance, transparency and mechanical properties, and an optical component using the same.

  Conventionally, a (meth) acrylic resin or the like has been used as a resin for plastic optical components. In particular, polymethyl methacrylate resin (PMMA) is transparent to light in the visible region, but its heat resistance is insufficient (Tg: 105 ° C), so it has a shape in applications and places where heat resistance is required. Can be used only in an environment up to about 70 ° C. Therefore, epoxy resin is often used for parts that require heat resistance and mechanical properties, but epoxy resin has high transparency in the visible region, but sufficient transparency cannot be obtained in the ultraviolet to near ultraviolet region. .

  On the other hand, it is known that when an adamantane structure is introduced into the side chain of a (meth) acrylic resin, a Tg increases, and at the same time, a low hygroscopic and low birefringence resin is obtained. However, when an adamantane structure is introduced into the side chain, there is a problem that mechanical properties are lowered and the material becomes brittle. Therefore, various studies have been made on resins in which an adamantane structure is introduced into the side chain of a (meth) acrylic resin having excellent heat resistance and mechanical properties.

  For example, Patent Document 1 proposes a resin obtained by polymerizing methyl methacrylate and methyl methacrylate having a side chain introduced with an adamantane structure. However, Tg is lowered because methyl methacrylate is copolymerized. There's a problem.

  Patent Document 2 proposes a resin having a weight average molecular weight of 1 million or more obtained by polymerizing methyl methacrylate having an adamantane structure introduced in the side chain, but the mechanical strength is not sufficiently improved, and the weight average molecular weight is not sufficient. Since it is 1 million or more, there exists a problem that a moldability falls. In order to improve the mechanical strength, it is also proposed to use a crosslinkable monomer together. However, by crosslinking a resin having a weight average molecular weight of 1 million or more, the moldability is further lowered, and general extrusion molding, injection molding, etc. There is a problem that difficult molding is difficult.

  Therefore, a (meth) acrylic resin composition excellent in heat resistance, transparency and mechanical properties has been conventionally demanded.

  Moreover, since adamantane has a unique characteristic and is expensive, it is required to reduce the amount of adamantane used.

  As will be described later, the (meth) acrylic resin composition of the present invention is a (meth) acrylic resin composition that can be obtained by a polymerization method such as a living radical polymerization method. Patent Documents 3 and 4 disclose organic tellurium compounds that can be used as polymerization initiators in living radical polymerization methods. Patent Document 5 discloses an aqueous polymerization method using an organic tellurium compound as a polymerization initiator.

JP 2005-281363 A JP 2006-213851 A International Publication No. 2004/14848 Pamphlet International Publication No. 2004/14962 Pamphlet JP 2006-225524 A

  The objective of this invention is providing the (meth) acrylic-type resin composition and optical component excellent in heat resistance, transparency, and a mechanical characteristic.

  The (meth) acrylic resin composition of the present invention is represented by the segment A having a glass transition temperature of 30 ° C. or lower polymerized mainly with a (meth) acrylic acid ester monomer, and the following general formula (1). A block copolymer containing a segment B having a glass transition temperature of 105 ° C. or higher polymerized mainly with a (meth) acrylic acid ester monomer having an adamantane structure, and the weight ratio of segment A to segment B (A : B) is 1-50: 99-50.

(In the formula, R ^{1 to} R ³ each independently represents a group selected from a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms. R ⁴ represents Y represents a hydrogen atom or a methyl group, Y represents a group selected from a phenyl group, an alkylene group having 1 to 20 carbon atoms, and a cycloalkylene group having 3 to 20 carbon atoms, and n is 0 or 1.)

The (meth) acrylic resin composition of the present invention is preferably obtained by polymerization by a living radical polymerization method using an organic tellurium compound polymerization initiator, and the organic tellurium compound polymerization initiator is
(A) an organic tellurium compound represented by the general formula (2),
(B) a mixture of an organic tellurium compound represented by the general formula (2) and an azo polymerization initiator,
(C) a mixture of an organic tellurium compound represented by the general formula (2) and an organic ditellurium compound represented by the general formula (3), or (d) an organic tellurium compound represented by the general formula (2), an azo type It is preferably any of a mixture of a polymerization initiator and an organic ditellurium compound represented by the general formula (3).

(In the formula, R ⁵ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ⁶ and R ⁷ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁸ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group or a cyano group.

(Wherein, R ⁵ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group or an aromatic heterocyclic group.)

  Moreover, it is preferable that the weight average molecular weight (Mw) of a block copolymer is the range of 50,000-2,000,000.

  Further, the content of the low molecular weight component having a molecular weight of less than 10,000 in the block copolymer is preferably 1% by weight or less.

  Moreover, it is preferable that ratio (Mw / Mn) of the weight average molecular weight (Mw) with respect to the number average molecular weight (Mn) of a block copolymer is the range of 1.05-2.00.

  The (meth) acrylic resin composition of the present invention can be used, for example, for optical parts, and more preferably for optical lenses.

  The optical component of the present invention is characterized by being formed using the (meth) acrylic resin composition of the present invention.

  In the present invention, the term “(meth) acryl” means methacryl and acryl.

  According to the present invention, a (meth) acrylic resin excellent in heat resistance, transparency, and mechanical properties can be obtained. Therefore, it can be suitably used as a material for optical parts such as light guide plates, prisms, liquid crystal panels, MD / CD / DVD optical parts, optical lenses, projector lenses, and headlamp lenses.

  As described above, the (meth) acrylic resin composition of the present invention is characterized by comprising a block copolymer containing segment A and segment B.

  In the present invention, the (meth) acrylic acid ester monomer that is the main component of the segment A can be used without particular limitation.

  For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth ) S-butyl acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, (meth) acrylic Acid n-stearyl, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acryl Bornyl, and (meth) isobornyl acrylic acid. The “(meth) acrylic acid” is a general term for “acrylic acid” and “methacrylic acid”.

  Preferred (meth) acrylate monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, and t-butyl acrylate. N-hexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, n-lauryl acrylate, n-acrylate -Stearyl. When the main chain structure is an acrylate structure, thermal decomposition does not occur even in an environment of 250 ° C. or higher, which is preferable from the viewpoint of heat resistance.

  In this invention, the said monomer may be used individually by 1 type so that the glass transition temperature of the segment A may be 30 degrees C or less, and may use 2 or more types together.

  The glass transition temperature of segment A is preferably 30 ° C. or lower, more preferably 20 ° C. or lower. Segment A is not preferable because the block copolymer is self-assembled by heat treatment and acts as an impact absorbing component (soft segment). If the glass transition temperature is higher than 30 ° C., flexibility at room temperature decreases. .

  In the present invention, as the main component of the segment B, a (meth) acrylic acid ester monomer containing an adamantane structure represented by the general formula (1) is used.

  The (meth) acrylic acid ester monomer containing an adamantane structure represented by the general formula (1) can be used without particular limitation.

  For example, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 1-adamantylmethyl (meth) acrylate, 1-adamantylethyl (meth) acrylate, 1-adamantylpropyl (meth) acrylate, 1-adamantylbutyl ( (Meth) acrylate, 1-adamantylpentyl (meth) acrylate, 1-adamantylhexyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate 3,5-dihydroxy-1-adamantyl (meth) acrylate, 5,7 -Dimethyl-3-hydroxy-1-adamantyl (meth) acrylate, adamantyl di (meth) acrylate, adamantyl tri (meth) acrylate, adamantyl tetra (meth) acrylate and the like. More preferably 1-adamantyl acrylate, 2-adamantyl acrylate, 1-adamantyl methyl acrylate, 1-adamantyl ethyl acrylate, 1-adamantyl propyl acrylate, 1-adamantyl butyl acrylate, 1-adamantyl pentyl acrylate, 1-adamantyl hexyl acrylate, 3 -Hydroxy-1-adamantyl acrylate 3,5-dihydroxy-1-adamantyl acrylate, 5,7-dimethyl-3-hydroxy-1-adamantyl acrylate, and the like are preferably used. When the main chain structure is an acrylate structure, thermal decomposition does not occur even in an environment of 250 ° C. or higher, which is preferable from the viewpoint of heat resistance.

  In the present invention, as the monomer, the resin may be used alone so that the glass transition temperature of the segment B is 105 ° C. or higher, or two or more types may be used in combination.

  Moreover, you may use together the (meth) acrylic acid ester monomer illustrated as a structural component of the segment A as needed.

  In the present invention, the “main component” in segment A and segment B means a component contained in each segment by 70 mol% or more.

  The glass transition temperature of segment B is preferably set to 105 ° C. or higher, more preferably 120 ° C. or higher. In the segment B, the block copolymer is self-assembled by heat treatment to act as a heat-resistant component (hard segment). Therefore, when the glass transition temperature is less than 105 ° C., the heat distortion temperature is lowered, which is not preferable.

  The glass transition temperatures of the segments A and B can be calculated by using the following calculation formula (1) (Fox formula) derived from an empirical rule.

  1 / Tg = Wa / Tga + Wb / Tgb + Wc / Tgc + (1)

(In the formula, Tg represents a set glass transition temperature (K), Tgx represents a glass transition temperature (K) of a homopolymer composed of each constituent monomer, Wx represents a weight ratio of each constituent monomer, and the total is 1.)

  In the present invention, for the purpose of improving the physical properties of the block copolymer, the vinyl monomers exemplified below may be used in combination as necessary.

Carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride;
2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, Hydroxyalkyl ester of (meth) acrylic acid having 1 to 12 carbon atoms such as (meth) acrylic acid 12-hydroxylauryl; polyethylene glycol derivative of (meth) acrylic acid; caprolactone adduct of (meth) acrylic acid; hydroxy Hydroxyl group-containing ether monomers such as methyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether;
Hydroxyl group-containing ketone monomers such as hydroxymethyl vinyl ketone, hydroxyethyl vinyl ketone, and hydroxypropyl vinyl ketone; Epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; Isocyanate group-containing vinyl monomers such as 2-methacryloyloxyethyl isocyanate; Reactive functional groups such as vinyl monomer containing vinyl group such as ethylene glycol dimethacrylate, vinyl monomer containing sulfonic acid group such as 2-acrylamido-2-methylpropane sulfonic acid, and vinyl monomer containing phosphoric acid group such as 2-hydroxyethylacryloyl phosphate Containing vinyl monomers;
Styrene, α-methylstyrene, 4-methylstyrene (p-methylstyrene), 2-methylstyrene (o-methylstyrene), 3-methylstyrene (m-methylstyrene), 4-methoxystyrene (p-methoxystyrene) , Pt-butylstyrene, pn-butylstyrene, p-tert-butoxystyrene, 2-hydroxymethylstyrene, 2-chlorostyrene (o-chlorostyrene), 4-chlorostyrene (p-chlorostyrene), Styrenic monomers such as 2,4-dichlorostyrene;
Aromatic unsaturated monomers such as 1-vinylnaphthalene, divinylbenzene, p-styrenesulfonic acid or alkali metal salts thereof (sodium salt, potassium salt, etc.), 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1- Heterocycle-containing unsaturated monomers such as vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine;
Vinyl amides such as N-vinylformamide and N-vinylacetamide; (meth) acrylamides such as (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide monomer;
Α-olefins such as 1-hexene, 1-octene and 1-decene; dienes such as butadiene, isoprene, 4-methyl-1,4-hexadiene and 7-methyl-1,6-octadiene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl benzoate; hydroxyethyl (meth) acrylate; (meth) acrylonitrile; methyl vinyl ketone; vinyl chloride; vinylidene chloride

  The block copolymer used in the present invention is obtained, for example, by a living radical polymerization method. Living radical polymerization is a polymerization method that allows precise control of the molecular structure while maintaining the simplicity and versatility of radical polymerization, and is very effective in the synthesis of new polymer materials. This polymerization method includes a method using a transition metal catalyst (ATRP), a method using a sulfur-based reversible chain transfer agent (RAFT), and a method using an organic tellurium compound depending on the method for stabilizing the polymerization growth terminal ( TERP) and other types. Among them, it is preferable to use the method (TERP) using an organic tellurium compound described in Patent Document 3 and Patent Document 4 from the viewpoint of diversity of usable monomers and molecular weight control in the polymer region.

In particular,
(A) an organic tellurium compound represented by the general formula (2),
(B) a mixture of an organic tellurium compound represented by the general formula (2) and an azo polymerization initiator,
(C) a mixture of an organic tellurium compound represented by the general formula (2) and an organic ditellurium compound represented by the general formula (3), or (d) an organic tellurium compound represented by the general formula (2), azo Polymerization is performed using an organic tellurium compound-based polymerization initiator which is one of a mixture of a system polymerization initiator and an organic ditellurium compound represented by the general formula (3).

  The organic tellurium compound used in the present invention is represented, for example, by the general formula (2).

Specific examples of the group represented by R ⁵ in the general formula (2) are as follows.

  Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclobutyl group, and n-pentyl. Examples thereof include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms such as a group, n-hexyl group, n-heptyl group and n-octyl group. A preferable alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms. More preferably, a methyl group, an ethyl group, or an n-butyl group is good.

  Examples of the aryl group include a phenyl group and a naphthyl group. A preferred aryl group is a phenyl group. Examples of the substituted aryl group include a phenyl group having a substituent and a naphthyl group having a substituent.

Examples of the substituent of the aryl group having the above substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by —COR ^a (R ^a = carbon number 1 -8 alkyl groups, aryl groups, C1-8 alkoxy groups, aryloxy groups), sulfonyl groups, trifluoromethyl groups, and the like.

  A preferred substituted aryl group is a trifluoromethyl-substituted phenyl group.

  These substituents may be substituted one or two, and the para position or ortho position is preferable.

  Examples of the aromatic heterocyclic group include a pyridyl group, a pyrrole group, a furyl group, and a thienyl group.

The groups represented by R ⁶ and R ⁷ in the general formula (2) are specifically as follows.

Examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as those described above for R ⁵ .

Specific examples of each group represented by R ⁸ in the general formula (2) are as follows.

Examples of the aryl group, substituted aryl group, and aromatic heterocyclic group include the same groups as those described above for R ⁵ .

  Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.

  Examples of the amide group include carboxylic acid amides such as acetamide, malonamide, succinamide, maleamide, benzamide, and 2-fluamide, thioamides such as thioacetamide, hexanedithioamide, thiobenzamide, and methanethiosulfonamide, selenoacetamide, hexanediselenoamide, Examples include selenoamides such as selenobenzamide and methaneselenosulfonamide, N-substituted amides such as N-methylacetamide, benzanilide, cyclohexanecarboxanilide, and 2,4′-dichloroacetanilide.

Examples of the oxycarbonyl group include a group represented by -COOR ^b (R ^b = H, an alkyl group having 1 to 8 carbon atoms, an aryl group).

  Specifically, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group, etc. Can be mentioned.

  Preferred oxycarbonyl groups are a methoxycarbonyl group and an ethoxycarbonyl group.

Each group represented by R ⁸ is preferably an aryl group, a substituted aryl group, an oxycarbonyl group or a cyano group.

  A preferred aryl group is a phenyl group.

  Preferred examples of the substituted aryl group include a halogen atom substituted phenyl group and a trifluoromethyl substituted phenyl group.

  In addition, in the case of a halogen atom, these substituents are preferably substituted by 1 to 5 pieces.

  In the case of an alkoxy group or a trifluoromethyl group, one or two substituents may be substituted. In the case of one substitution, the para position or the ortho position is preferable, and in the case of two substitutions, the meta position is preferable. .

  Preferred oxycarbonyl groups are a methoxycarbonyl group and an ethoxycarbonyl group.

As an organic tellurium compound represented by the general formula (2), R ⁵ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁶ and R ⁷ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. And a compound in which R ⁸ is an aryl group, a substituted aryl group or an oxycarbonyl group is preferable.

Particularly preferably, R ⁵ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ⁶ and R ⁷ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁸ represents a phenyl group, A substituted phenyl group, a methoxycarbonyl group, and an ethoxycarbonyl group are preferable.

  The organic tellurium compound represented by the general formula (2) is specifically as follows.

  (Methylteranylmethyl) benzene, (methylterranylmethyl) naphthalene, ethyl-2-methyl-2-methylterranyl-propionate, ethyl-2-methyl-2-n-butylterranyl-propionate, etc. All of the organic tellurium compounds described in 1) can be exemplified.

  The method for producing the organic tellurium compound represented by the general formula (2) is not particularly limited, and can be produced by a known method described in Patent Documents 3 and 4 above. For example, the compound of the general formula (2) can be produced by reacting the compound of the general formula (4), the compound of the general formula (5) and metal tellurium.

(In the formula, R ⁶ , R ⁷ and R ⁸ are the same as described above. X represents a halogen atom.)

  Examples of the group represented by X include halogen atoms such as fluorine, chlorine, bromine and iodine. Preferably, chlorine and bromine are good.

(R ⁵ is the same as above. M represents an alkali metal, alkaline earth metal or copper atom. When M is an alkali metal, m is 1, when M is an alkaline earth metal, m is 2, M. When is a copper atom, m represents 1 or 2.)

  Examples of M include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, and copper. Lithium is preferable.

When M is magnesium, the compound of the general formula (5) may be Mg (R ⁵ ) ₂ or a compound (Grignard reagent) represented by R ⁵ MgX (X is a halogen atom). X is preferably chlorine or bromine.

  Another example of the organic ditellurium compound used in the present invention is represented by the general formula (3).

The group represented by R ⁵ in the general formula (3) is as shown in the general formula (2).

As a preferable compound represented by the general formula (3), R ⁵ is preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group.

  Specific examples of the compound represented by the general formula (3) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, di-n. -Butyl ditelluride, di-sec-butyl ditelluride, di-tert-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis- ( p-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthylditelluride, dipyridylditelluride and the like. Preferred are dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride, and diphenyl ditelluride.

  In the present invention, an azo polymerization initiator may be used for the purpose of accelerating the polymerization rate. The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization.

  For example, 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis (2-methylbutyronitrile) (AMBN), 2,2'-azobis (2,4-dimethylvaleronitrile) ) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid ) (ACVA), 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methylbutyramide), 2,2′-azobis (4-methoxy-2,4) -Dimethylvaleronitrile), 2,2'-azobis (2-methylamidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], , 2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), and the like.

  These azo initiators are preferably selected as appropriate according to the reaction conditions. For example, in the case of low temperature polymerization (40 ° C. or lower), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) In the case of intermediate temperature polymerization (40 to 80 ° C.), 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), dimethyl-2 2,2′-azobisisobutyrate (MAIB), 1,1′-azobis (1-acetoxy-1-phenylethane), 4,4′-azobis (4-cyanovaleric acid) (ACVA), 2,2 '-Azobis (2-methylbutyramide), 2,2'-azobis (2-methylamidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], high temperature In the case of combination (80 ° C. or higher), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2- Methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis [2-methyl -N- (2-hydroxyethyl) propionamide] may be used.

  The amount of the compound of the general formula (2) may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the block copolymer to be obtained. Usually, the amount of the compound of the general formula (2) is 1000 g with respect to the obtained block copolymer. The compound may be 0.5 to 20 mmol, preferably 1 to 10 mmol.

  When the compound of the general formula (2) and the compound of the general formula (3) are used in combination, the amount used is usually 0.01% of the compound of the general formula (3) with respect to 1 mol of the compound of the general formula (2). ˜100 mol, preferably 0.05 to 10 mol, particularly preferably 0.1 to 5 mol.

  The ratio of the compound of the general formula (2) and the azo polymerization initiator is usually 0.01 to 100 mol, preferably 0.1 to 10 mol mol of the azo polymerization initiator with respect to 1 mol of the compound of the general formula (2). Particularly preferably, the content is 0.1 to 5 mol.

  When the compound of the general formula (2), the compound of the formula (3) and the azo polymerization initiator are used in combination, the amount used is usually 1 mol of the compound of the formula (1) and the compound of the formula (2). On the other hand, the azo polymerization initiator may be 0.01 to 100 mol, preferably 0.1 to 10 mol, particularly preferably 0.1 to 5 mol.

  The reaction can be carried out without a solvent, but can be carried out using an organic solvent or an aqueous solvent generally used in radical polymerization. Examples of organic solvents that can be used include benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, hexafluoroisopropol, chloroform, tetrachloride. Examples thereof include carbon, tetrahydrofuran (THF), ethyl acetate, trifluoromethylbenzene and the like. Examples of the aqueous solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, diacetone alcohol and the like. The amount of the solvent used may be adjusted as appropriate. For example, the amount of the solvent is 0.01 to 50 L, preferably 0.05 to 10 L, particularly preferably 0.1 to 100 g of the obtained block copolymer. 1-5L is good.

  Next, the mixture is stirred. The reaction temperature and reaction time may be adjusted as appropriate depending on the molecular weight or molecular weight distribution of the block copolymer to be obtained, but are usually stirred at 0 to 150 ° C. for 1 minute to 100 hours. Preferably, stirring is performed at 20 to 100 ° C. for 0.1 to 30 hours. Particularly preferably, stirring is performed at 20 to 80 ° C. for 0.1 to 15 hours. Thus, even with a low polymerization temperature and a short polymerization time, a high yield and a precise molecular weight distribution can be obtained. At this time, the pressure is usually a normal pressure, but may be increased or decreased.

When the organic tellurium compounds represented by the general formula (2) and the general formula (3) are used as an initiator, a tellurium atom may remain at the polymer terminal in the form of -TeR ⁵ (R ⁵ is the same as above. ).

  The polymer in which the tellurium atom remains at the terminal is colored and is a metallic element. Therefore, from the viewpoint of improving the transparency of the optical component blended with the obtained block copolymer and preventing contamination with foreign matter, The metal content including atoms is 1000 ppm or less, and particularly preferably 500 ppm or less, based on the entire resin.

  The tellurium atom remaining at the molecular end is adsorbed after completion of the polymerization reaction using a radical reduction method such as tributylstannane or a thiol compound, and further activated carbon, silica gel, activated alumina, activated clay, molecular sieves and polymer adsorbent. , A method of adsorbing metal with ion exchange resin, etc., or adding a peroxide such as hydrogen peroxide or benzoyl peroxide, or blowing air or oxygen into the system to oxidize the tellurium atom at the end of the polymer In liquid state such as liquid-liquid extraction method or solid-liquid extraction method that removes residual tellurium compounds by combining with water washing and appropriate solvent, and ultrafiltration that extracts and removes only those with specific molecular weight or less A purification method and these methods can also be combined.

  After completion of the reaction, the solvent or residual monomer used is removed under reduced pressure by a conventional method to take out the target block copolymer, or the target product is isolated by reprecipitation using a target block copolymer insoluble solvent. Can do. The reaction treatment can be performed by any treatment method as long as there is no problem with the object.

  In addition, since the organic tellurium compound used as an initiator in the present invention is stable to water, the block copolymer of the present invention can be synthesized by an aqueous polymerization method described in Patent Document 5 and the like.

  That is, the emulsion polymerization method uses a surfactant and polymerizes mainly in micelles. You may use dispersing agents, such as water-soluble polymers, such as polyvinyl alcohol, as needed. These surfactants can be used alone or in combination of two or more. It is preferable that the usage-amount of this surfactant is 0.3-50 weight part with respect to 100 weight part of all the monomers, More preferably, it is 0.5-50 weight part. Moreover, it is preferable that the usage-amount of water is 50-2000 weight part with respect to 100 weight part of all the monomers, More preferably, it is 70-1500 weight part. Although superposition | polymerization temperature is not specifically limited, It is preferable to carry out in the range of 0-100 degreeC, More preferably, it is 40-90 degreeC. What is necessary is just to set reaction time suitably so that a polymerization reaction may be completed according to reaction temperature or the composition of the monomer composition to be used, the kind of surfactant or a polymerization initiator, etc. Preferably within 24 hours.

  In the suspension polymerization method, a dispersant is used, and polymerization is mainly performed without using micelles. If necessary, a dispersing aid such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, or manganese sulfate may be used in combination with these dispersing agents. The amount of the water dispersion stabilizer used is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, particularly preferably 0.1 to 0.1 parts by weight based on 100 parts by weight of the total monomers. 5 parts by weight. Moreover, it is preferable that the usage-amount of water is 50-2000 weight part with respect to 100 weight part of all the monomers, More preferably, it is 70-1500 weight part. Although superposition | polymerization temperature is not specifically limited, It is preferable to carry out in the range of 0-100 degreeC, More preferably, it is 40-90 degreeC. What is necessary is just to set reaction time suitably so that a polymerization reaction may be completed according to reaction temperature or the composition of the monomer composition to be used, the kind of water dispersion stabilizer, a polymerization initiator, etc. Preferably within 24 hours.

  In the miniemulsion polymerization method, a surfactant and a co-surfactant are used, and after the monomers are forcibly dispersed using a homogenizer or an ultrasonic device, the polymerization is performed mainly without passing through micelles. The amount of the surfactant or cosurfactant used is 0.3 to 50 parts by weight, particularly preferably 0.5 to 50 parts by weight, based on the total monomers. The ultrasonic irradiation time is 0.1 to 10 minutes, particularly preferably 0.2 to 5 minutes.

  The block copolymer of the present invention can be obtained by sequentially polymerizing each segment. The block copolymer can obtain a polymer according to the order of segments to be polymerized regardless of the type of monomer. When a block copolymer is obtained by polymerizing segment A and segment B, either AB or BA can be obtained depending on the order of polymerization reaction, and as a result, AB or B or B can be obtained. It is also possible to obtain a triblock copolymer such as -A-B, A-B-A-B-A, or B-A-B-A-B, a pentablock copolymer, and the like.

  In the above, after the polymerization reaction of each segment, the polymerization reaction of the next segment may be started as it is, or the polymerization reaction of the next segment may be started after purification after finishing the polymerization reaction once. Isolation of the block copolymer can be performed by a usual method.

  In the block copolymer of the present invention, the weight ratio (A) :( B) of segment A to segment B is 1-50: 99-50, more preferably 5-45: 95-55, particularly preferably. It is good to set it as 10-40: 90-60.

  If the segment A is less than 1 part by weight, the block copolymer is less likely to self-assemble and does not act as a shock absorbing component (soft segment), and if it exceeds 50 parts by weight, the heat resistance of the block copolymer decreases. Therefore, it is not preferable.

  Further, for the purpose of improving the physical properties of the block copolymer, a segment different from the segment A and the segment B may be introduced to form a triblock copolymer such as ABC.

  In addition, since a random copolymer, for example, a resin composition obtained by random copolymerization of segment A and segment B does not cause the above self-organization, the heat resistance is reduced and the shock absorption (flexibility) is reduced. Is not preferable.

  The molecular weight of the block copolymer obtained in the present invention can be adjusted by the reaction time, the amount of the compound of the general formula (2) and the amount of the compound of the general formula (3), but the weight average molecular weight is 50,000-2. 1,000,000, more preferably a weight average molecular weight of 100,000 to 1,000,000. If the weight average molecular weight is less than 50,000, the strength of the resulting block copolymer is not sufficient, and if the weight average molecular weight exceeds 2,000,000, the handling properties during polymerization and the moldability will deteriorate, such being undesirable. .

  The content of the low molecular weight component having a molecular weight of less than 10,000 in the block copolymer is preferably 1% by weight or less. When the content of the low molecular weight component is more than 1% by weight, it is not preferable because mechanical properties are deteriorated and bubbles are easily generated during molding.

  The molecular weight distribution (PD = Mw / Mn) of the block copolymer is controlled between 1.05 and 2.00. Furthermore, a block copolymer having a narrower molecular weight distribution with a molecular weight distribution of 1.05 to 1.80, more preferably 1.05 to 1.50 can be obtained. When the molecular weight distribution is larger than 2.00, the ratio of the low molecular weight component that lowers the mechanical properties in the resin composition and the high molecular weight component that lowers the flow properties at the time of molding increases.

  Moreover, another component can also be added to the resin composition of this invention as needed. Examples of additives include dyes, pigments, pigments, optical brighteners, wetting agents, surface tension adjusters, thickeners, antifungal agents, preservatives, oxygen absorbers, ultraviolet absorbers, near infrared absorbers, water-soluble agents. -Based quenchers, antioxidants, fragrances, metal deactivators, nucleating agents, antistatic agents, flame retardants, lubricants, processing aids, silane coupling agents, etc., and these are obtained from resin compositions. Depending on the use and purpose of use of the optical component material, it is appropriately selected and blended.

<Synthesis of polymer composition>
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these at all. In Examples and Comparative Examples, various physical properties were measured using the following equipment.

¹ H-NMR: Bruker BioSpin AVANCE 500 (500 MHz)
Bruker BioSpin AVANCE 300 (300 MHz)
Gel permeation chromatograph (GPC):
Tosoh CCPCRE-8020 (column: Tosoh TSK-GEL GMH _XL + TSK-GEL Multipore H _XL- M, polystyrene standard: Tosoh TSK Standard)

Synthesis Example 1 (Ethyl-2-methyl-2-n-butylteranyl-propionate)
6.38 g (50 mmol) of metal tellurium (manufactured by Aldrich, trade name: Tellurium (-40 mesh)) is suspended in 50 ml of THF, and 34.4 ml of n-butyllithium (manufactured by Aldrich, 1.6 M hexane solution) is added thereto. 55 mmol) was slowly added dropwise at room temperature (10 minutes). The reaction solution was stirred until the metal tellurium disappeared completely (20 minutes). To this reaction solution, 10.7 g (55 mmol) of ethyl-2-bromo-isobutyrate was added at room temperature and stirred for 2 hours. After completion of the reaction, the solvent was concentrated under reduced pressure, followed by distillation under reduced pressure to obtain 8.98 g (yield 59.5%) of a yellow oil.

^{From 1} H-NMR, it was confirmed to be ethyl-2-methyl-2-n-butylterranyl-propinate.

¹ H-NMR (500 MHz, CDCl ₃ ) 0.93 (t, J = 7.5 Hz, 3H), 1.25 (t, J = 7.2 Hz, 3H), 1.37 (m, 2H), 1 .74 (s, 6H), 1.76 (m, 2H), 2.90 (t, J = 7.5 Hz, 2H, CH ₂ Te), 4.14 (q, J = 7.2 Hz, 2H)

Synthesis Example 2 (Acrylic acid 1-adamantyl)
To a solution obtained by diluting 50 g (328 mmol) of 1-adamantanol (manufactured by Aldrich) with 300 mL of dichloromethane, 45.5 mL (328 mmol) of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred. Under an argon atmosphere, 26.5 mL (328 mmol) of acryloyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was slowly added dropwise while keeping the temperature at 5 ° C. or lower in an ice bath, and stirred overnight at room temperature. The generated triethylamine hydrochloride was removed by filtration, and the dichloromethane layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, water, and saturated brine, and then dried over anhydrous sodium sulfate. After distilling off dichloromethane with an evaporator, the crude product was isolated by silica gel chromatography (developing solvent: hexane / ethyl acetate = 9/1), the fraction containing the desired product was cooled to −20 ° C., and the precipitated crystals By suction filtration and drying, 29.8 g (yield 44%) of white crystals were obtained.

¹ H-NMR confirmed that it was 1-adamantyl acrylate.

¹ H-NMR (300 MHz, CDCl ₃ ) 1.67 (br, 6H), 2.15 (br, 9H), 5.61 (dd, J = 1.6, 10.3 Hz, 1H), 5.91 (Dd, J = 10.3, 17.3 Hz, 1H), 6.17 (J = 1.6, 10.3 Hz, 1H)

Example 1 (Synthesis of n-butyl polyacrylate-polyacrylic acid 1-adamantyl diblock copolymer)
Synthesis of segment A: 4.46 μL (19.5 μmol) of ethyl-2-methyl-2-n-butylterranyl-propionate prepared in Synthesis Example 1 in a glove box substituted with argon, n-butyl acrylate [Tokyo Kasei Co., Ltd. 0.5 g (3.9 mmol), anisole [same as above] 1.0 g and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) [same as above] 1.2 mg (3.9 μmol) was reacted at 50 ° C. for 3 hours. ^{From 1} H-NMR (300 MHz) analysis, the polymerization rate was 79%. Moreover, it was Mn = 22,000 and PD = 1.18 from the GPC analysis.

Synthesis of segment B: Next, 3.23 g (15.7 mmol) of 1-adamantyl acrylate and 3.7 g of anisole [same as above] obtained in Synthesis Example 2 were added to the reaction solution of segment A obtained above. The reaction was carried out at 50 ° C. for 4 hours. ^{From 1} H-NMR (300 MHz) analysis, the polymerization rate of 1-adamantyl acrylate was 92%, and the polymerization rate of n-butyl acrylate was 93%.

  After completion of the reaction, the block polymer solution is poured into 500 mL of stirring methanol, and the precipitated polymer is suction filtered and dried to obtain a white powdered poly (n-butyl acrylate-polyacrylate 1-adamantyl diblock copolymer). 3.4 g (yield 81%) was obtained.

  From GPC analysis, it was Mn = 190,000 and PD = 1.24. The content of low molecular weight components having a molecular weight of less than 10,000 was 0% by weight.

Example 2 (Synthesis of n-butyl polyacrylate-polyacrylic acid 1-adamantyl diblock copolymer)
Synthesis of segment A: In a glove box substituted with argon, 5.0 μL (21.8 μmol) of ethyl-2-methyl-2-n-butylterranyl-propionate prepared in Synthesis Example 1 and n-butyl acrylate [same as above] 0 0.7 g (5.5 mmol), anisole [same as above] 1.4 g and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) [same as] 1.35 mg (4.4 μmol) at 50 ° C. The reaction was performed for 3 hours. ^{According to 1} H-NMR (300 MHz) analysis, the polymerization rate was 89%. Moreover, it was Mn = 33,000 and PD = 1.14 from the GPC analysis.

Synthesis of segment B: Next, 3.39 g (16.4 mmol) of 1-adamantyl acrylate and 4.1 g of anisole [same as above] obtained in Synthesis Example 2 were added to the reaction solution of segment A obtained above. The reaction was carried out at 50 ° C. for 4 hours. ^{From 1} H-NMR (300 MHz) analysis, the polymerization rate of 1-adamantyl acrylate was 90%, and the polymerization rate of n-butyl acrylate was 96%.

  After completion of the reaction, the block polymer solution is poured into 500 mL of stirring methanol, and the precipitated polymer is suction filtered and dried to obtain a white powdered poly (n-butyl acrylate-polyacrylate 1-adamantyl diblock copolymer). 3.3 g (yield 83%) was obtained.

  From the GPC analysis, it was Mn = 130,000 and PD = 1.21. The content of low molecular weight components having a molecular weight of less than 10,000 was 0% by weight.

Example 3 (Synthesis of n-butyl polyacrylate-polyacrylic acid 1-adamantyl diblock copolymer)
Synthesis of segment A: 3.75 μL (16.4 μmol) of ethyl-2-methyl-2-n-butylteranyl-propionate prepared in Synthesis Example 1 in a glove box substituted with argon, n-butyl acrylate [same as above] 0 0.7 g (5.5 mmol), anisole [same as above] 1.4 g and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) [same as] 1.01 mg (3.3 μmol) at 50 ° C. The reaction was performed for 3 hours. ^{From 1} H-NMR (300 MHz) analysis, the polymerization rate was 86%. Moreover, it was Mn = 38,000 and PD = 1.19 from the GPC analysis.

Synthesis of segment B: Next, 2.26 g (11.0 mmol) of 1-adamantyl acrylate obtained in Synthesis Example 2 and 3.0 g of anisole [same as above] were added to the reaction solution of segment A obtained above. The reaction was carried out at 50 ° C. for 4 hours. ^{From 1} H-NMR (300 MHz) analysis, the polymerization rate of 1-adamantyl acrylate was 85%, and the polymerization rate of n-butyl acrylate was 95%.

  After completion of the reaction, the block polymer solution is poured into 100 mL of stirring methanol, and the precipitated polymer is suction filtered and dried to obtain a white powdered poly (n-butyl acrylate-polyacrylate 1-adamantyl diblock copolymer). 3.3 g (yield 79%) was obtained.

  From GPC analysis, it was Mn = 119,000 and PD = 1.23. The content of low molecular weight components having a molecular weight of less than 10,000 was 0% by weight.

Example 4 (Synthesis of n-butyl polyacrylate-polyacrylic acid 1-adamantyl diblock copolymer)
Synthesis of Segment B: 4.7 μL (20.6 μmol) of ethyl-2-methyl-2-n-butylterranyl-propionate prepared in Synthesis Example 1 in an argon-substituted glove box, acrylic acid 1 obtained in Synthesis Example 2 -2.13 g (10.3 mmol) of adamantyl, 3.45 g of anisole [same as above] and 1.27 mg (4.1 μmol) of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) [same as above] The reaction was carried out at 50 ° C. for 3 hours. ^{From 1} H-NMR (300 MHz) analysis, the polymerization rate was 95%. Moreover, it was Mn = 12,000 and PD = 1.29 from the GPC analysis.

Synthesis of segment A: Next, 1.32 g (10.3 mmol) of n-butyl acrylate [same as above] and 1.32 g of anisole [same as above] were added to the reaction solution of segment B obtained above at 50 ° C. 3. Reacted for 3 hours. ^{From 1} H-NMR (300 MHz) analysis, the polymerization rate of 1-adamantyl acrylate was 99%, and the polymerization rate of n-butyl acrylate was 89%.

  After completion of the reaction, the block polymer solution is poured into 100 mL of stirring methanol, and the precipitated polymer is suction filtered and dried to obtain a white powdered poly (n-butyl acrylate-polyacrylate 1-adamantyl diblock copolymer). 2.57 g (74% yield) was obtained.

  From the GPC analysis, it was Mn = 129,000 and PD = 1.44. The content of low molecular weight components having a molecular weight of less than 10,000 was 0% by weight.

Comparative Example 1 (Synthesis of 1-adamantyl polyacrylate)
In a 15 mL volumetric flask, 3.1 g (15 mmol) of 1-adamantyl acrylate obtained in Synthesis Example 2 and 2,2′-azobis (isobutyronitrile) [reagent purified by Wako Pure Chemical Industries, Ltd. by recrystallization in methanol 2.46 mg (0.015 mmol) was added, and toluene (a reagent manufactured by Wako Pure Chemical Industries, Ltd. was used after being purified by distillation under reduced pressure) to make a 15 mL solution. The solution was transferred to a Pyrex (registered trademark) tube, and the freezing-degassing-thawing cycle was repeated 5 times to remove dissolved oxygen. After reacting at 60 ° C. for 16 hours, the mixture was cooled with dry ice / methanol (−78 ° C.) to terminate the polymerization, poured into 500 mL of stirring methanol, and the precipitated polymer was suction filtered and dried to obtain a white powder. In this way, 2.4 g (yield 78%) of 1-adamantyl polyacrylate was obtained.

  From the GPC analysis, it was Mn = 132,000 and PD = 2.9. The content of low molecular weight components having a molecular weight of less than 10,000 was 2.1% by weight.

Comparative Example 2 (Synthesis of n-butyl polyacrylate-polyacrylic acid 1-adamantyl random copolymer)
In a 15 mL volumetric flask, 0.38 g (3 mmol) of n-butyl acrylate [same as above], 2.48 g (12 mmol) of 1-adamantyl acrylate obtained in Synthesis Example 2, and 2,2′-azobis (isobutyronitrile) [Same as above] 2.46 mg (15 μmol) was added, and toluene was added to make a 15 mL solution. The solution was transferred to a Pyrex (registered trademark) tube, and the freezing-degassing-thawing cycle was repeated 5 times to remove dissolved oxygen. After reacting at 60 ° C. for 16 hours, the mixture was cooled with dry ice / methanol (−78 ° C.) to terminate the polymerization, poured into 500 mL of stirring methanol, and the precipitated polymer was suction filtered and dried to obtain a white powder. 2.32 g (yield 81%) of poly (n-butyl acrylate-polyacrylate 1-adamantyl random copolymer) was obtained.

  From the GPC analysis, it was Mn = 95,000 and PD = 2.9. The content of low molecular weight components having a molecular weight of less than 10,000 was 2.0% by weight.

Comparative Example 3 (Synthesis of poly (n-butyl acrylate) -poly (acrylate) 1-adamantyl random copolymer)
In a 15 mL volumetric flask, 0.64 g (5 mmol) of n-butyl acrylate [same as above], 2.07 g (10 mmol) of 1-adamantyl acrylate obtained in Synthesis Example 2 and 2,2′-azobis (isobutyronitrile) [Same as above] 2.46 mg (15 μmol) was added, and toluene was added to make a 15 mL solution. The solution was transferred to a Pyrex (registered trademark) tube, and the freezing-degassing-thawing cycle was repeated 5 times to remove dissolved oxygen. After reacting at 60 ° C. for 16 hours, the reaction was stopped by cooling with dry ice / methanol (−78 ° C.), poured into 500 mL of stirring methanol, and the precipitated polymer was suction filtered and dried to obtain a white rubber. 1.95 g (yield 72%) of poly (n-butyl acrylate-polyacrylate 1-adamantyl random copolymer) was obtained.

  From GPC analysis, it was Mn = 98,000 and PD = 2.9. The content of low molecular weight components having a molecular weight of less than 10,000 was 0% by weight. The results are shown in Table 1.

Comparative Example 4 (Synthesis of poly (n-butyl acrylate) -poly (acrylate) 1-adamantyl diblock copolymer)
Synthesis of segment B: 6.0 gL (26.2 μmol) of ethyl-2-methyl-2-n-butylteranyl-propionate prepared in Synthesis Example 1 in the glove box substituted with argon, acrylic acid 1 obtained in Synthesis Example 2 -1.35 g (6.5 mmol) of adamantyl, 3.85 g of anisole [same as above] and 1.61 mg (5.3 μmol) of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) [same as above] The reaction was carried out at 50 ° C. for 2 hours. ^{From 1} H-NMR (300 MHz) analysis, the polymerization rate was 94%. Moreover, it was Mn = 37,000 and PD = 1.27 from the GPC analysis.

Synthesis of segment A: Next, 2.51 g (19.5 mmol) of n-butyl acrylate [same as above] and 2.51 g of anisole [same as above] were added to the reaction solution of segment B obtained above at 50 ° C. The reaction was performed for 3 hours. ^{From 1} H-NMR (300 MHz) analysis, the polymerization rate of 1-adamantyl acrylate was 96%, and the polymerization rate of n-butyl acrylate was 66%.

  After completion of the reaction, the block polymer solution is poured into 100 mL of stirring methanol, and the precipitated polymer is suction filtered and dried to obtain a white powdered poly (n-butyl acrylate-polyacrylate 1-adamantyl diblock copolymer). 2.47 g (yield 64%) was obtained.

  From GPC analysis, it was Mn = 12,000 and PD = 1.29. The content of low molecular weight components having a molecular weight of less than 10,000 was 0% by weight.

<Physical property evaluation>
(Transparency evaluation)
100-micrometer-thick cast film of Examples 1-4, Comparative Examples 1-4, and polymethyl methacrylate [made by Wako Pure Chemical Industries] (Comparative Example 5) was produced. The total light transmittance of the obtained cast film was measured at a measurement wavelength of 380 nm using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, JACSO V-500). The results are shown in Table 1.

[Heat resistance evaluation]
The glass transition temperature and thermal decomposition temperature of Examples 1 to 4, Comparative Examples 1 to 4 and Comparative Example 5 were measured. The glass transition temperature and the thermal decomposition temperature were measured as follows, and the results are shown in Table 1.

・ Glass transition temperature (Tg)
The glass transition temperature of the polymer composition was measured using a differential scanning calorimeter (Seiko Instruments, DSC6200). The glass transition temperature obtained by raising the temperature from 25 ° C. to 10 ° C./min under a nitrogen stream was measured.

-Thermal decomposition temperature The thermal decomposition temperature of the polymer composition was measured using the thermogravimetry meter (the Seiko Instruments company make, TG / DTA6200). The temperature at which the mass decreased by 5% in the mass change curve obtained by raising the temperature from 25 ° C. to 10 ° C./min under a nitrogen stream was defined as the thermal decomposition temperature.

(Mechanical property evaluation)
Example 1, Example 3, Example 4, Comparative Example 1, Comparative Example 3 and Comparative Example 4 were compression molded at 150 ° C. for 1 hour to prepare 1BA type dumbbell test pieces. The elastic modulus of the obtained dumbbell test piece was measured according to JIS K7161. The results are shown in Table 1. Since the comparative example 1 was cracked at the time of shaping | molding, it was not able to shape | mold the dumbbell test piece which measures an elasticity modulus. Since Comparative Example 4 was soft, a dumbbell test piece for measuring the elastic modulus could not be molded.

  The following can be understood from the above physical property evaluation.

  Examples 1 to 4 which are block copolymers have higher transmittance than Comparative Examples 2 and 3 which are random copolymers and Comparative Example 4 which is a block copolymer having a high soft segment ratio. Yes. Furthermore, the transmittance is superior to Comparative Example 1 which is a homopolymer.

  In Examples 1 to 4, which are block copolymers, Tg derived from a hard segment is observed at a temperature higher than that of Comparative Example 5 (PMMA) by self-assembly, and is excellent in heat resistance. In Example 4 in which the synthesis was performed in order from the hard segment (segment B), since the hard segment did not contain a monomer derived from the soft segment, a high Tg equivalent to that of the homopolymer was observed. On the other hand, Tg of Comparative Example 2 and Comparative Example 3 which are random copolymers is low because self-organization does not occur, and is lower than Comparative Example 5 (PMMA), and does not have sufficient heat resistance. In Comparative Example 5 (PMMA), since the main chain has a methacrylate structure, thermal decomposition due to depolymerization occurs at a low temperature, and the thermal decomposition temperature is about 100 ° C. compared with Examples 1-4 and Comparative Examples 1-4. Low.

  Comparative Example 1 which is a homopolymer of a hard segment was brittle and could not produce a dumbbell specimen, but Examples 1, 3 and 4 which were block copolymers were brittle due to the soft segment. Improved and successfully created dumbbell specimens.

  As described above, in the present invention, a (meth) acrylate resin composition excellent in heat resistance, transparency and mechanical properties can be obtained.

Claims (9)

A segment A having a glass transition temperature of 30 ° C. or less polymerized mainly with a (meth) acrylic acid ester monomer;
A segment B having a glass transition temperature of 105 ° C. or higher polymerized mainly with a (meth) acrylic acid ester monomer having an adamantane structure represented by the following general formula (1):
(Meth) acrylic resin composition, wherein the weight ratio (A: B) of segment A to segment B is 1 to 50:99 to 50.

(In the formula, R ^{1 to} R ³ each independently represents a group selected from a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms. R ⁴ represents Y represents a hydrogen atom or a methyl group, Y represents a group selected from a phenyl group, an alkylene group having 1 to 20 carbon atoms, and a cycloalkylene group having 3 to 20 carbon atoms, and n is 0 or 1.) Obtained by polymerizing by a living radical polymerization method using an organic tellurium compound polymerization initiator, the organic tellurium compound polymerization initiator is
(A) an organic tellurium compound represented by the general formula (2),
(B) a mixture of an organic tellurium compound represented by the general formula (2) and an azo polymerization initiator,
(C) a mixture of an organic tellurium compound represented by the general formula (2) and an organic ditellurium compound represented by the general formula (3), or (d) an organic tellurium compound represented by the general formula (2), an azo type The (meth) acrylic resin composition according to claim 1, wherein the composition is any one of a mixture of a polymerization initiator and an organic ditellurium compound represented by the general formula (3).

(In the formula, R ⁵ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ⁶ and R ⁷ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁸ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group or a cyano group.

(Wherein, R ⁵ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group or an aromatic heterocyclic group.)   The (meth) acrylic resin composition according to claim 1 or 2, wherein the block copolymer has a weight average molecular weight (Mw) in the range of 50,000 to 2,000,000.   The (meth) acrylic resin composition according to any one of claims 1 to 3, wherein the content of the low molecular weight component having a molecular weight of less than 10,000 in the block copolymer is 1% by weight or less. .   The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the block copolymer is in the range of 1.05 to 2.00. The (meth) acrylic resin composition according to item 1.   The (meth) acrylic resin composition according to any one of claims 1 to 5, which is used for optical parts.   The (meth) acrylic resin composition according to claim 6, which is for optical lenses.   It forms using the (meth) acrylic-type resin composition of any one of Claims 1-5, The optical component characterized by the above-mentioned. A method for producing the (meth) acrylic resin composition according to any one of claims 1 to 5,
In the living radical polymerization method using an organic tellurium compound polymerization initiator,
Polymerizing a monomer constituting one segment of segment A and segment B and polymerizing one segment;
(Meth) acrylic resin composition comprising: polymerizing one segment, then polymerizing a monomer constituting the other segment of segment A and segment B, and polymerizing the other segment Manufacturing method.