JP6809777B2 - A method for producing a thermoplastic polymer, a resin composition, a resin molded product, an optical member, and a thermoplastic polymer. - Google Patents

Description

The present invention relates to a novel polymer having a ring structure in a main chain, a method for producing the same, and a resin composition and a resin molded product containing the polymer.

Resin compositions containing transparent polymers such as acrylic polymers, polycycloolefins, polycarbonates, polystyrenes and polyesters are widely used in applications of optical components such as lenses, prisms, optical fibers and optical films. Among them, the acrylic polymer has features such as high optical transparency, high balance of weather resistance, mechanical strength, molding processability and surface hardness.

Among the transparent polymers, there is a polymer having a ring structure in the main chain. Among the above-mentioned polymers, polycycloolefin, polycarbonate, polyethylene terephthalate (PET), which is a kind of polyester, and the like fall under this category. Acrylic polymers also include polymers having a ring structure in the main chain. For example, Patent Document 1 (Patent No. 4825409) discloses an acrylic polymer having a lactone ring structure in the main chain. Patent Document 2 (Japanese Unexamined Patent Publication No. 2006-328334) discloses an acrylic polymer having a glutarimide structure in the main chain. Patent Document 3 (Japanese Unexamined Patent Publication No. 2007-31537) discloses an acrylic polymer having an N-substituted maleimide structure in the main chain.

Generally, the glass transition temperature (Tg) of an acrylic polymer is around 100 ° C. even if it is high, but these documents show that an acrylic polymer having a ring structure in the main chain has a higher Tg. There is. When the Tg of the polymer is improved, the heat resistance of the resin composition containing the polymer and the resin molded product composed of the composition is improved. When the resin molded body is an optical member, there has been a strong demand in recent years for products equipped with an optical member. As a specific example, from the viewpoint of making the product compact, improving its performance, and improving the degree of freedom in design, the light source, power supply unit, This will increase the possibility of meeting design requirements for arranging optical members in the vicinity of heating elements such as batteries and circuit boards.

Patent No. 4825409 Japanese Unexamined Patent Publication No. 2006-328334 JP-A-2007-31537

One of the objects of the present invention is to provide a novel polymer having a ring structure in the main chain and a method for producing the same.

The novel polymer of the present invention has a pyrrolidinone ring structure in the main chain.

The novel polymer of the present invention viewed from another aspect is a precursor polymer formed by polymerization of a group of monomers containing a vinyl monomer, and has an ester group and / or a carboxyl group and an amide group as side chains. It is a polymer obtained by cyclizing the precursor polymer having.

The resin composition of the present invention contains the above-mentioned novel polymer of the present invention.

The resin molded product of the present invention is composed of the above-mentioned resin composition of the present invention.

In the method for producing a novel polymer of the present invention, a precursor polymer formed by polymerization of a group of monomers containing a vinyl monomer and having an ester group and / or a carboxyl group and an amide group as side chains. The coalescence is cyclized to give a novel polymer having a pyrrolidinone ring structure in the main chain.

According to the present invention, a novel polymer having a ring structure in the main chain and a method for producing the same are provided.

It is a figure which shows the infrared spectroscopic analysis (IR) spectrum of the polymer (1-1) and (1-2) produced in Example 1 together with the difference. Is a diagram showing the ¹ H- nuclear magnetic resonance (NMR) spectrum of the polymer prepared in Example 1 (1-1). It is a figure which shows the ¹ H-NMR spectrum of the polymer (1-2) produced in Example 1.

[Polymer (A)]
The polymer (A) of the present invention is a novel polymer having a pyrrolidinone ring structure in the main chain. The polymer (A) is typically an amorphous thermoplastic polymer.

The pyrrolidinone ring structure has a 5-membered amide ring structure (cyclic amide structure) as a basic skeleton. This cyclic amide structure is also a 5-membered ring lactam structure (γ-lactam structure). When a polymer has a pyrrolidinone ring structure in the main chain, it means that at least one atom out of five atoms constituting the basic skeleton of the pyrrolidinone ring structure, which is a 5-membered ring, typically an amide bond (-NHCO-) is formed. It means that three carbon atoms that do not form the polymer are located in the main chain of the polymer and form the main chain.

The polymer (A) has a property derived from the pyrrolidinone ring structure located in the main chain. The characteristics are, for example, thermal characteristics and optical characteristics.

The thermal property is, for example, the glass transition temperature (Tg), and the Tg of the polymer (A) is higher than that in the case where the main chain does not have a pyrrolidinone ring structure.

The optical property is, for example, a birefringence property. The birefringence expression (phase difference expression) of the polymer (A) is improved by the pyrrolidinone ring structure located in the main chain. The pyrrolidinone ring structure has the effect of imparting positive or negative intrinsic birefringence to the polymer (A). More specifically, the pyrrolidinone ring structure basically has an action of giving positive birefringence to the polymer (A), but when the substituent bonded to the basic skeleton of the ring structure is bulky, the polymer (A) may be given a negative intrinsic birefringence. The positive or negative of the intrinsic birefringence as the polymer (A) is determined by the balance of the birefringence characteristics exhibited by each structural unit of the polymer (A). For example, even when the pyrrolidinone ring structure has an action of giving a positive intrinsic birefringence to the polymer (A), when the polymer (A) further has a structural unit having an action of giving a negative intrinsic birefringence, it is heavy. The intrinsic birefringence as coalescence (A) may be negative.

The polymer (A) may have other properties, such as hydrophilicity, adhesion, hydrolysis resistance, and thermostable decomposition resistance based on the (cyclic) amide structure contained in the pyrrolidinone ring structure.

The polymer (A) can be used for various purposes based on each of these properties. Applications are, for example, optical members. The thermal and optical properties of the polymer (A) described above can be advantageous features of the optical member. A high Tg leads to, for example, an improvement in the heat resistance of the optical member containing the polymer (A), and such an optical member improves the degree of freedom in designing a product including the optical member. As a specific example, with respect to an optical film which is a kind of optical member, the film can be arranged close to a heating element such as a light source, a power supply unit, or a circuit board, so that a liquid crystal display device (LCD) or the like can be arranged. The degree of freedom in designing the image display device is improved. The high birefringence expression leads to an improvement in the retardation value per unit thickness of the optical film, for example, and an optical film that achieves the designed retardation value while being thinner is realized. The birefringence manifestation can be evaluated by, for example, the stress optical coefficient Cr. The larger the absolute value of Cr, the higher the birefringence expression. The action of imparting positive intrinsic birefringence to the polymer (A) leads to, for example, the realization of a positive retardation film in which the retardation Rth in the thickness direction is positive. High adhesion, hydrolysis resistance, and heat decomposition resistance are also advantageous points as an optical member.

The use of the polymer (A) is not limited to the optical member. The polymer (A) is used, for example, for pressure-sensitive adhesives, conductive adhesives, photosensitive adhesives, building material adhesives, printed substrate adhesives, transparent sheet or film adhesives, organic or inorganic fibers. Adhesives such as adhesives; adhesives such as adhesive sheets, adhesives for films, adhesives for electronic devices, heat-resistant adhesives, thermally conductive adhesives, conductive adhesives; secondary battery electrodes, functional fibers , Conductive fine particles, metal fine particles, scaly fillers, dyes, inkjets, color filters, inks, various binder resins used for toner, etc .; various types used for gas barriers, water vapor barriers, display elements, semiconductor encapsulation, solar cells, electronic devices, etc. Encapsulant (agent); medical or daily antibacterial, sterilizing and sterilizing material; hard coat, easy adhesive coat, UV curable resin, EB curable resin, rust preventive, antifogging agent, antistatic agent, flame retardant Various functional coating materials (agents) used for coating agents, shielding coatings, insulating coatings, etc .; powder coatings such as heat-curable powder coatings; cosmetic ingredients such as organic fillers, water-retaining agents, and moisturizing agents; capacitors, capacitors , Printed substrates and mounting substrates (including flexible substrates) used for electronic devices, etc .; Synthetic lubricants such as lubricating oil additives, viscosity modifiers, viscosity index improvers; Nanofillers, nanoparticles, materials for nanostructure molding, etc. Nanomaterials; Chemicals used in the manufacture and processing of paper, such as pulp flocculants, dispersants, and paper strength enhancers; Plastic components, films, lenses, packaging materials, tires, optical films, protector protective films that require heat resistance Thermoplastic resins such as: high-performance fibers, nanofibers, piezoelectric fibers, non-woven fabrics, porous membranes for filters, etc .; inks, inkjet inks, toners, gelling agents for storage materials such as microcapsules; various solutions or Thickeners used to adjust the viscosity of pastes, more specifically thickeners used in pastes containing electrode active particles of secondary batteries, toothpaste, liquid detergents, etc .; glass fiber or carbon Dispersants or binders used for fibers such as fibers;

The polymer (A) has, for example, a pyrrolidinone ring structure represented by the following formula (1) in the main chain. In this ring structure, as shown in the formula (1), three carbon atoms (carbon atoms at the 3-position, 4-position and 5-position of the ring structure) that do not form an amide bond are the main chains of the polymer (A). Located in (constituting the main chain). The ring structure represented by the formula (1) may be a structural unit (repeating unit) of the polymer (A) or a structure that constitutes a part of the structural unit. In the latter case, the structural unit will include the pyrrolidinone ring structure represented by the formula (1) as a part of its molecular structure.

In the formula (1), R ¹ is a hydrogen atom or −COR ⁴ groups, and R ⁴ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or 3 to 18 carbon atoms. It is a cycloalkyl group of. R ² and R ³ are independent hydrogen atoms or methyl groups.

The linear alkyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 4 carbon atoms. The linear alkyl group is, for example, an ethyl group, a propyl group, or a butyl group. The cycloalkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The cycloalkyl group is, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

An example of a combination of R ¹ , R ² and R ^{3 is} a combination in which R ¹ is a -COR ⁴ group and R ² and R ³ are independent of each other, a hydrogen atom or a methyl group. At this time, R ⁴ can be a hydrogen atom, a methyl group, a linear alkyl group or a cycloalkyl group, a methyl group or a linear alkyl group, or a methyl group. A further specific example of the combination of R ¹ , R ² and R ^{3 is} a combination in which R ¹ is -COCH ₃ groups, R ² is a hydrogen atom and R ³ is CH ₃ groups.

The polymer (A) will have a structural unit P containing a pyrrolidinone ring structure (for example, a pyrrolidinone ring structure represented by the formula (1)). The structural unit P may be composed of only the pyrrolidinone ring structure, or may be composed of the pyrrolidinone ring structure and another molecular structure. The other molecular structure is, for example, a molecular structure that is bonded to a carbon atom at the 3-position and / or 5-position of the pyrrolidinone ring structure to form a main chain of the polymer (A) together with the ring structure, and is more specific. An example is an alkylene group such as the methylene group described above.

An example of the structural unit P composed of the pyrrolidinone ring structure and another molecular structure is shown in the following formula (2). R ² to R ⁴ of formula (2) is the same as R ² to R ⁴ of formula (1).

The structural unit X represented by the formula (2) is a unit composed of a pyrrolidinone ring structure and a methylene group bonded to a carbon atom at the 3-position of the ring structure. The carbon atom of the methylene group and the carbon atom at the 3- to 5-position of the ring structure form the main chain of the polymer (A). The pyrrolidinone ring structure of the structural unit X contains a tertiary amide structure as a molecular structure forming a part of the ring (the tertiary amide structure is included as a part of the ring structure). The pyrrolidinone ring structure included in the structural unit X is the pyrrolidinone ring structure represented by the formula (1), and is a ring structure in which R ¹ is −COR ⁴ groups. At this time, R ² is, for example, a hydrogen atom. At this time, R ³ is, for example, a methyl group. R ⁴ can be a hydrogen atom, a methyl group, a linear alkyl group or a cycloalkyl group, a methyl group or a linear alkyl group, or a methyl group.

The structural unit X has an action of imparting positive intrinsic birefringence to the polymer (A). The structural unit having an action of giving a positive (or negative) intrinsic birefringence to the polymer indicates a positive (or negative) intrinsic birefringence when the homopolymer of the unit is formed. A unit. The positive or negative of the intrinsic birefringence as the polymer (A) is determined not only by the structural unit X but also by the balance with the birefringence characteristics of the other structural units of the polymer (A).

The structural unit X is, for example, a unit in which R ² is a hydrogen atom and R ³ and R ⁴ are both methyl groups. The polymer (A) having such a structural unit X is, for example, a copolymer of methyl methacrylate (MMA) and N-vinylacetamide (NVA) as a precursor polymer (B), and is used as an adjacent MMA unit. It can be formed by advancing the cyclization reaction with the NVA unit.

The polymer (A) is a copolymer composed of a structural unit P and a structural unit Q other than the structural unit P, even if it is a homopolymer composed of only the structural unit P containing a pyrrolidinone ring structure. You may. The copolymer can be a random copolymer, a block copolymer, or a graft copolymer.

The polymer (A) may have two or more kinds of structural units P, and may have two or more kinds of structural units Q.

When the polymer (A) is a copolymer composed of the structural unit P and the structural unit Q, the polymer (A) exhibits various additional properties depending on the type and content of the structural unit Q. The structural unit Q is, for example, a (meth) acrylic acid ester unit, a (meth) acrylic acid unit, an N-substituted maleimide unit, an aromatic vinyl compound unit, an unsaturated carboxylic acid compound unit, a vinyl cyanide compound unit, or a complex aromatic. It is an α, β-unsaturated monomer unit having a group.

The polymer (A) may have at least one selected from the (meth) acrylic acid ester unit and the (meth) acrylic acid unit as the constituent unit Q. In this case, the optical transparency of the polymer (A) becomes higher, which makes it more suitable for use as an optical member, for example. The polymer (A) preferably has a (meth) acrylic acid ester unit as a constituent unit Q.

The (meth) acrylic acid ester unit is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, α-hydroxyacrylic It is a structural unit (derived from each of these monomers) formed by polymerization of each (meth) acrylic acid ester of methyl acrylate and ethyl α-hydroxyacrylate. The (meth) acrylic acid ester unit is preferably methyl methacrylate (MMA) unit, ethyl methacrylate unit, n-butyl methacrylate unit, cyclohexyl methacrylate unit, isobornyl methacrylate unit, or benzyl methacrylate unit, and the MMA unit is preferable. More preferred. At this time, the optical transparency of the polymer (A) is further increased.

When the content of the (meth) acrylic acid ester unit in the polymer (A) exceeds 50% by weight, the polymer (A) is an acrylic polymer. The polymer (A), which is an acrylic polymer, exhibits properties generally possessed by the acrylic polymer, such as high optical transparency, and a high balance of mechanical strength, moldability and surface hardness. In the polymer (A) which is an acrylic polymer, the total content of the (meth) acrylic acid ester unit may be 60% by mass or more, 70% by mass or more, 80% by mass or more, and further 90% by mass or more.

Depending on the type of the structural unit P, including the structural unit X represented by the formula (2), the copolymer (B) with a (meth) acrylic acid ester such as MMA is used as the precursor polymer (B). ) Can be allowed to proceed with the cyclization reaction to form the polymer (A). In this case, the polymer (A) may have a (meth) acrylic acid ester unit as an unreacted unit.

Further, as described above, when the cyclization reaction is allowed to proceed with the precursor polymer (B), which is a copolymer having a (meth) acrylic acid ester unit as a constituent unit, to form the polymer (A), the weight thereof. The coalescence (A) can also be regarded as a derivative of the (meth) acrylic acid ester. In this case, when the total content of the structural unit P and the (meth) acrylic acid ester unit in the polymer (A) exceeds 50% by mass, the polymer (A) is an acrylic polymer. The total content may be 60% by mass or more, 70% by mass or more, 80% by mass or more, and even 90% by mass or more. As will be described later, the precursor polymer (B), which is a copolymer with the (meth) acrylic acid ester, that is, the precursor polymer (B), which is a copolymer having a (meth) acrylic acid ester unit as a constituent unit ( In B), as long as an ester group and / or a carboxyl group and an amide group are present in the side chain of the polymer (B), the monomer that is the partner of the copolymerization with the (meth) acrylic acid ester is not limited. The monomer is, for example, an amide group-containing vinyl monomer such as N-vinylcarboxylic acid amide such as N-vinylformamide and N-vinylacetamide.

The N-substituted maleimide units are, for example, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-tribromophenylmaleimide, N-. It is a structural unit derived from each monomer of laurylmaleimide and N-benzylmaleimide. The N-substituted maleimide unit is preferably an N-cyclohexylmaleimide unit or an N-phenylmaleimide unit.

The aromatic vinyl compound unit is, for example, styrene, α-methylstyrene, α-chlorostyrene, pt-butylstyrene, p-methylstyrene, p-chlorostyrene, o-chlorostyrene, 2,5-dichlorostyrene, It is a structural unit derived from each aromatic vinyl compound of 3,4-dichlorostyrene and divinylbenzene. The aromatic vinyl compound unit is preferably a styrene unit.

The unsaturated carboxylic acid compound unit is a structural unit formed by polymerization of an acid such as crotonic acid and an alkali metal salt, an ammonium salt, or an organic amine salt thereof. In the present specification, the unsaturated carboxylic acid compound unit does not include the (meth) acrylic acid unit.

The vinyl cyanide compound unit is, for example, a (meth) acrylonitrile unit.

The α, β-unsaturated monomer unit having a heteroaromatic group is at least one selected from, for example, vinyl carbazole unit, vinyl pyridine unit, vinyl imidazole unit and vinyl thiophene unit.

The structural unit Q is a vinyl compound unit other than the above-mentioned units, for example, vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, butene, isoprene, N-vinyl-2-pyrrolidone; divinyl adipate, divinyl sebacate, etc. Divinyl esters; sulfonic acids such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-phenylpropane sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid and alkali metal salts, ammonium salts and organic amine salts thereof. Can be a structural unit formed by the polymerization of;

The polymer (A) may have a structural unit capable of absorbing ultraviolet (UVA). The structural unit is, for example, a structural unit formed by polymerization of a benzotriazole derivative, a triazine derivative or a benzophenone derivative into which a polymerizable group has been introduced. In these derivatives, the polymerizable group to be introduced can be appropriately selected, for example, a vinyl group.

The content of the structural unit P in the polymer (A) is not limited, but in order to more reliably obtain the characteristics derived from the structural unit P, for example, it is 30% by mass or more, preferably 35% by mass or more, preferably 40% by mass. % Or more is more preferable. The upper limit of the content of the structural unit P is not particularly limited, and may be 100% by mass or less. When the polymer (A) further has another structural unit Q, particularly (meth) acrylic acid ester unit, the upper limit of the structural unit P is, for example, 90% by mass or less, 85% by mass or less, and 82% by mass or less. sell.

The content of each structural unit in the polymer (A) can be determined by a known method, for example, ¹ H nuclear magnetic resonance ( ¹ H-NMR) or infrared spectroscopic analysis (IR).

The pyrrolidinone ring structure of the polymer (A) in the main chain can be confirmed by a known method, for example, ¹ H-NMR or IR. Examples of specific confirmation, in the infrared absorption spectrum, the range of wave number 1690 cm ^-1 or 1710 cm ^-1, whether absorption peak attributed to the stretching vibration of the carbonyl group of pyrrolidinone ring structure is observed Confirmation. The fact that the absorption peak attributed to the expansion and contraction vibration of the carbonyl group of the pyrrolidinone ring structure in the infrared absorption spectrum is in the above wavenumber range was published on September 15, 2006 as an infrared absorption region in the 5-membered lactam ring. It is described in "" Identification method by spectrum of organic compound 7th edition "Tokyo Kagaku Dojin."

The specific structure of the pyrrolidinone ring structure, the content of the ring structure in the polymer (A), and the type and content of the constituent unit Q when the polymer (A) is a copolymer further having the constituent unit Q. Depending on the case, it may be difficult to confirm the absorption peak in the infrared absorption spectrum. However, depending on the composition of the polymer (A), by reheating the polymer (A), the cyclization reaction does not proceed during the formation of the polymer (A), and the cyclization reaction is performed again between the remaining structural units. May be able to form the same ring structure as the ring structure already present in the polymer (A). At this time, the pyrrolidinone ring structure of the main chain can be confirmed by taking the difference in the infrared absorption spectra before and after the reheating of the polymer (A). In other words, this time the polymer (A), upon heating the polymer at 200 ° C. or higher, the difference between the infrared absorption spectra before and after heating, the absorption peak in the range of less wave numbers 1690 cm ^-1 or 1710 cm ^-1 It can be the polymer observed.

The polymer (A) exhibits a high Tg based on the pyrrolidinone ring structure of the main chain. The Tg of the polymer (A) is, for example, 110 ° C. or higher. Depending on the type and content of the pyrrolidinone ring structure, or the structure of the structural unit P containing the pyrrolidinone ring structure and its content, the Tg of the polymer (A) is 120 ° C. or higher, 130 ° C. or higher, and further 160 ° C. or higher. Can take the value of.

When the polymer (A) is formed by the dealcohol cycloaddition reaction described later, the alcohol produced during the cyclization reaction may remain in the polymer (A). At this time, the content of the residual alcohol in the polymer (A) is, for example, 10 to 3000 ppm.

The polymer (A) may be crosslinked with a crosslinking agent or the like.

The polymer (A) can be formed, for example, by the following method for producing the polymer (A).

[Method for producing polymer (A)]
In the production method of the present invention, a precursor polymer (B) formed by polymerization of a group of monomers containing a vinyl monomer, which has an ester group and / or a carboxyl group and an amide group as side chains. (B) is cyclized to obtain a polymer (A) having a pyrrolidinone ring structure in the main chain. In this cyclization, a cyclization condensation reaction is allowed between the ester group and / or the carboxyl group and the amide group to form a 5-membered amide ring structure. At this time, the ester group and / or the carboxyl group is changed to a carbonyl group containing a carbon atom at the 2-position of the pyrrolidinone ring structure, and the amide group is changed to an amine group containing a nitrogen atom at the 1-position of the pyrrolidinone ring structure. As shown in the formula (1), this amine group is a secondary or tertiary amine group.

An example of such a reaction is shown in the following formula (3).

R ¹ to R ⁴ of formula (3) is the same as R ¹ to R ⁴ of formula (1). R ⁵ is a hydrogen atom or an organic residue having 1 to 18 carbon atoms. The organic residue is, for example, an alkyl group such as a methyl group, an ethyl group or a propyl group; an unsaturated aliphatic hydrocarbon group such as an ethenyl group or a propenyl group; an aromatic hydrocarbon group such as a phenyl group or a naphthyl group; the above alkyl. In the group, the unsaturated aliphatic hydrocarbon group and the aromatic hydrocarbon group, one or more hydrogen atoms are substituted with at least one group selected from a hydroxyl group, a carboxyl group, an ether group and an ester group. ;. R ⁵ is preferably a linear alkyl group or a cycloalkyl group, and the carbon number thereof is preferably 1 to 12, more preferably 1 to 4. R ⁵ can be a linear alkyl group or a cycloalkyl group.

In the reaction represented by the formula (3), the cyclization reaction is allowed to proceed to the precursor polymer (B) having the molecular structure on the left side to form the polymer (A) having the structural unit P on the right side. This cyclization reaction is a condensation reaction in which the broken line portion shown on the left side is bonded and R ⁵ OH is eliminated. Water is desorbed when R ⁵ is a hydrogen atom, that is, this reaction is a dehydration cyclization condensation reaction. Alcohol is eliminated when R ⁵ is an organic residue, i.e. this reaction is a dealcohol cyclization condensation reaction. For example, when R ⁵ is a methyl group, methanol is eliminated. This reaction proceeds within the molecular chain of the precursor polymer (B). The structural unit P on the right side of the formula (3) includes a pyrrolidinone ring structure represented by the formula (1) and a methylene group bonded to a carbon atom at the 3-position of the ring structure.

The precursor polymer (B) has an ester group and / or a carboxyl group in its side chain and also has an amide group. More specifically, the precursor polymer (B) of the formula (3) has an ester group (carboxyl ester group; R ⁵ is an organic residue) and / or a carboxyl group (R ⁵ is a hydrogen atom) in the side chain. It is a copolymer having a unit and a constituent unit having an amide group in the side chain. Each structural unit is a unit derived from a vinyl monomer. As described above, the precursor polymer (B) can be formed by polymerizing a group of monomers containing a vinyl monomer. More specifically, the precursor polymer (B) of the formula (3) is formed by polymerization of a monomer group containing a vinyl monomer A having an ester group and / or a carboxyl group and a vinyl monomer B having an amide group. It is a copolymer. In this precursor polymer (B), the ester group and / or carboxyl group of the side chain and the amide group have one methylene group (one carbon atom) located in the main chain of the precursor polymer (B) between them. One) It is in the inserted positional relationship. In the example shown in the formula (3), the three carbon atoms located in the main chain of the precursor polymer (B), the carbon atoms of the carboxyl group and / or the ester group located in the side chain, and the nitrogen atom of the amide group are used. A pyrrolidinone ring structure is formed.

^Four -COR groups are bonded to the nitrogen atom in the side chain of the precursor polymer (B) of the formula (3), but R ¹ (hydrogen atom or hydrogen atom or) is attached to the nitrogen atom in the pyrrolidinone ring structure of the structural unit P on the right side. -COR ⁴ groups) are bonded. That is, the polymer (A) can take a hydrogen atom as R ¹ . This is because the heat applied to the polymer during or after the cyclization reaction can cause elimination of ⁴ -COR groups. Desorption of -COR ⁴ groups can be promoted, for example, by using a catalyst (cyclization catalyst) in the cyclization reaction described later and leaving the catalyst in the polymer after cyclization.

An example of the vinyl monomer A at this time is shown in the following formula (4), and an example of the vinyl monomer B is shown in the following formula (5). R ³ of formula (4) is the same as R ³ of formula (1), R ⁵ is the same as R ⁵ in formula (3). R ² and R ⁴ of formula (5) are the same as R ² and R ^4, respectively formula (1). The vinyl monomer A represented by the formula (4) is a (meth) acrylic acid ester unit (R ³ is a hydrogen atom or a methyl group and R ⁵ is an organic residue), or a (meth) acrylic acid unit (R ^3). Is a hydrogen atom or a methyl group, and R ⁵ is a hydrogen atom). The vinyl monomer A is preferably acrylic acid or methyl methacrylate (MMA) because the polymer (A) formed has higher optical transparency. The vinyl monomer B represented by the formula (5) is N-vinylformamide (R ² and R ⁴ are hydrogen atoms), N-vinylcarboxylic acid amide (R ² is a hydrogen atom, R ⁴ is a methyl group, a linear alkyl group or It can be an amide group-containing vinyl monomer (cycloalkyl group). R ⁴ can be a hydrogen atom, a methyl group or a linear alkyl group, a methyl group or a linear alkyl group, or a methyl group. When R ² is a hydrogen atom and R ⁴ is a methyl group, the vinyl monomer B represented by the formula (5) is N-vinylacetamide (see formula (6)).

The precursor polymer (B) may be a polymer formed by polymerizing a group of monomers containing two or more kinds of vinyl monomer A and / or two or more kinds of vinyl monomer B. That is, the precursor polymer (B) has two or more structural units derived from two or more vinyl monomers A and / or two or more structural units derived from two or more vinyl monomers B. May be good.

When the precursor polymer (B) is a copolymer of vinyl monomer A and vinyl monomer B, the structural unit Y1 derived from the monomer A in the polymer (B) and the structural unit Y2 derived from the monomer B The content ratio is not particularly limited, but the mass ratio is, for example, Y1: Y2 = 95 to 50: 5 to 50, preferably 90 to 50: 10 to 50, and more preferably 85 to 50: 15 to 50. .. When the structural unit Y1 is a (meth) acrylic acid ester unit, the polymer (A) formed from the precursor polymer (B) may have an unreacted (meth) acrylic acid ester unit as a structural unit.

When the precursor polymer (B) is a copolymer, the polymer (B) can be a random copolymer or an alternating copolymer.

The precursor polymer (B) may further have a structural unit derived from a monomer other than vinyl monomer A and vinyl monomer B. In this case, the polymer (A) further having the structural unit can be formed. The structural unit is, for example, a structural unit Q other than the structural unit P described above in the description of the polymer (A).

(Formation of precursor polymer (B))
The method for forming the precursor polymer (B) is not particularly limited. The monomer may be selected so that the formed precursor polymer (B) has an ester group and / or a carboxyl group and an amide group as side chains, and the monomer group containing the monomer may be polymerized. The monomer group may contain a monomer other than the monomer essential for the formation of the polymer (B), if necessary. The monomer is, for example, a monomer that becomes a constituent unit Q by polymerization.

The monomer group includes, for example, vinyl monomer A having an ester group and / or a carboxyl group, and vinyl monomer B having an amide group. Examples of vinyl monomer A are at least one selected from (meth) acrylic acid ester and (meth) acrylic acid, and examples of vinyl monomer B are amide groups such as N-vinylformamide and N-vinylcarboxylic acid amide. It is a vinyl monomer contained. The vinyl monomer B can be at least one selected from N-vinylformamide and N-vinylacetamide.

The polymerization method of the monomer group is not particularly limited, and a known polymerization method such as solution polymerization can be applied. When solution polymerization is selected, the polymerization solvent is not particularly limited, and for example, aromatic hydrocarbons such as toluene, xylene and ethylbenzene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; chloroform, methylene chloride, 1,2-dichloroethane and the like. Halogen-based hydrocarbons; alcohols such as methanol and ethanol; water, dimethylsulfoxide (DMSO), tetrahydrofuran.

In the polymerization of the precursor polymer (B), a polymerization initiator, a chain transfer agent, or the like can be used, if necessary. The polymerization initiator is not particularly limited, but for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amylper. Organic peroxides such as oxy-2-ethylhexanoate; azo compounds such as azobisisobutyronitrile (AIBN); These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used may be appropriately set according to the combination of the monomers contained in the monomer group, the polymerization conditions, and the like, and is not particularly limited.

Polymerization conditions such as polymerization temperature can be set as appropriate.

When there is a difference in polymerization rate between the monomers contained in the monomer group, the monomer in the precursor polymer (B) formed by the polymerization has a higher content ratio than the content of each monomer contained in the monomer group to be polymerized. Regarding the content of each of the derived structural units, the content of the structural units derived from the monomer having a high polymerization rate tends to be relatively large. Therefore, a precursor polymer (B) which is a copolymer and a polymer (B) having a desired value for the content rate and / or the content rate ratio of each structural unit constituting the polymer (B). In order to obtain the polymer, pay attention to the content of each monomer in the monomer group to be polymerized, control the polymerization method (for example, supply a part or all of the monomers having a high polymerization rate to the polymerization system by dropping). Therefore, the content of each structural unit in the formed precursor polymer (B) can be appropriately adjusted.

(Cyclic reaction)
The method for cyclizing the precursor polymer (B) is not limited. For example, by heating the precursor polymer (B), the cyclization condensation reaction, which is an amide cyclization reaction, can proceed in the molecular chain of the polymer (B) to form the polymer (A).

If allowed to proceed cyclization reaction by heating of the precursor polymer (B), the heating temperature is 1 50 ° C. or more For example, preferably at least 200 ° C.. The heating of the precursor polymer (B) can be carried out in any state such as a state in which the precursor polymer (B) is in a solid state or a state in which the precursor polymer (B) is dissolved in a solvent. When heating in a solid state, it is preferable to use a precursor polymer (B) having a large surface area such as powder or particles for the rapid progress of the cyclization reaction. Further, heating under reduced pressure is preferable in order to allow the cyclization reaction to proceed rapidly by removing the alcohol or water generated by the cyclization reaction described on the right side of the formula (3). The degree of decompression is, for example, 26.6 kPa or less in terms of absolute pressure. That is, the cyclization reaction may proceed by heating the precursor polymer (B) under a pressure of 26.6 kPa or less. The degree of depressurization is preferably 13.3 kPa or less, more preferably 2.7 kPa or less.

When proceeding with the cyclization reaction, a catalyst that promotes the reaction may be used, if necessary. When a catalyst is used, heating in a state where the precursor polymer (B) is dissolved in a solvent is preferable for a uniform reaction.

As the catalyst, for example, at least one selected from acids, bases and salts thereof, metal complexes, and metal oxides can be used. The types of acids, bases and salts thereof, metal complexes, and metal oxides are not particularly limited. When the polymer (A) to be formed, or the resin composition (C) or resin molded product containing the polymer (A) is used in applications where transparency is important, the catalyst has these transparency. It is preferable to use the product within a range in which the amount does not decrease and adverse effects such as coloring do not occur.

The acid is not limited, for example, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, phosphite, phenylphosphonic acid, organic carboxylic acid, phosphoric acid ester. The base is not limited, and includes, for example, metal hydroxides, amines, imines, alkali metal derivatives, alkoxides, and ammonium hydroxide salts. Salts of acids and bases are not limited, for example, metal carboxylates, metal carbonates. The metal of the metal carboxylate and the metal carbonate does not impair the characteristics of the polymer (A), the resin composition (C) or the resin molded product to be formed, and does not cause environmental pollution at the time of disposal thereof. Not limited, for example, alkali metals such as lithium, sodium, potassium; alkaline earth metals such as magnesium, calcium, strontium, barium; zinc; zirconium; copper; iron. The carboxylic acids that make up the metal carboxylate are not limited, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanic acid, octanoic acid, octyl acid, nonanoic acid, decanoic acid, lauric acid, myristine. Acids, palmitic acid, stearic acid, bechenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid. The metal complex is not limited, and an example of its organic component is acetylacetone. The metal oxide is not limited, for example, zinc oxide, calcium oxide, magnesium oxide.

The polymer (A) of the present invention viewed from the aspect of such a production method is a precursor polymer (B) formed by polymerization of a group of monomers containing a vinyl monomer, and is an ester group and / or a carboxyl. It is a polymer formed by cyclizing a precursor polymer (B) having a group and an amide group as side chains.

As described above, the precursor polymer (B) has a copolymer weight formed by, for example, polymerization of a monomer group containing a vinyl monomer A having an ester group and / or a carboxyl group and a vinyl monomer B having an amide group. Can be coalesced. Examples of vinyl monomers A and B are as described above. Specifically, the vinyl monomer A is at least one selected from, for example, (meth) acrylic acid ester and (meth) acrylic acid.

[Resin composition (C)]
The resin composition (C) of the present invention contains a polymer (A). The resin composition is typically a thermoplastic resin composition, which is an amorphous thermoplastic resin composition. The resin composition (C) may contain two or more polymers (A).

The resin composition (C) exhibits various properties derived from the polymer (A). The characteristics are, for example, thermal characteristics and optical characteristics. The thermal property is, for example, Tg, and the Tg of the resin composition (C) is increased due to the polymer (A). The Tg of the resin composition (C) is, for example, 110 ° C. or higher, and may be 120 ° C. or higher, 140 ° C. or higher, or 160 ° C. or higher depending on the type and content of the polymer (A).

The optical property is, for example, birefringence property, and the resin composition (C) exhibits high birefringence expression (phase difference expression) derived from the polymer (A). The high retardation property can be evaluated by, for example, the absolute value of the high stress optical coefficient Cr. Depending on the type and content of the polymer (A), the resin composition (C) exhibits positive birefringence, and at this time, the resin composition (C) can form, for example, a positive retardation film. The intrinsic birefringence as the resin composition (C) is determined by the balance with the intrinsic birefringence exhibited not only by the polymer (A) but also by other polymers contained in the resin composition (C).

The resin composition (C) may have various other properties derived from the polymer (A). Based on these characteristics, the resin composition (C) can be used for the same purposes as the above-mentioned polymer (A), including the optical member.

The resin composition (C) may contain a polymer other than the polymer (A). When the resin composition (C) is used for the optical member, it is preferable that the other polymer is compatible with the polymer (A) in order to ensure the optical transparency.

The other polymer is, for example, an olefin polymer such as polyethylene, polypropylene, ethylene-propylene polymer, poly (4-methyl-1-pentene); a halogen-containing polymer such as vinyl chloride or chlorinated vinyl resin. Acrylic polymers such as polymethylmethacrylate; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polyamides such as nylon 6, nylon 66, nylon 610; polyacetal; polycarbonate; polyphenylene oxide; polyphenylene sulfide; polyether ether Ketone; polysulfone; polyether sulfone; polyoxypendylene; polyamideimide; rubbery polymer. The resin composition (C) may contain two or more of these polymers.

The content of the polymer (A) in the resin composition (C) is usually 50% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more. The resin composition (C) may contain only the polymer (A) as the polymer.

The resin composition (C) can contain a material other than the polymer, for example, an additive. Additives include, for example, stabilizers such as antioxidants, light-resistant stabilizers, weather-resistant stabilizers, and heat-stabilizing agents; retardation modifiers such as retardation enhancers, retardation reducing agents, and retardation stabilizers; glass fiber, Reinforcing materials such as carbon fiber; UV absorbers; Near infrared absorbers; Flame retardants such as tris (dibromopropyl) phosphates, triallyl phosphates, antimony oxides; Antistatic agents containing anionic, cationic and nonionic surfactants Agents; colorants such as inorganic pigments, organic pigments, and dyes; organic fillers, inorganic fillers, resin modifiers, plasticizers, and lubricants. The content of the additive in the resin composition (C) is preferably less than 7% by mass, more preferably 2% by mass or less, still more preferably 1% by mass or less.

The method for forming the resin composition (C) is not particularly limited. If the resin composition (C) is made of the polymer (A), the polymer (A) may be used as it is as the resin composition (C), and the resin composition (C) may be used with the above-mentioned other polymers. When / or an additive is contained, the polymer (A) can be formed by mixing the other polymer and / or the additive by a known mixing method. Mixing can be carried out by pre-blending with a mixer such as an omni mixer and then kneading the obtained mixture. The kneader is not particularly limited, and for example, a known kneader such as an extruder such as a single-screw extruder or a twin-screw extruder or a pressure kneader can be used.

[Resin molded product]
The resin molded product of the present invention is composed of the thermoplastic resin composition (C) containing the polymer (A). The use of the resin molded product is not limited, and it can be selected depending on the properties obtained from the polymer (A) and other polymers and / or additives contained in the resin composition (C). The resin molded product of the present invention is, for example, an optical member used for optical applications.

The optical member is, for example, a lens, a prism, an optical fiber, or an optical film. The optical film includes, for example, a protective film for the substrate of various optical disks (VD, CD, DVD, MD, LD, etc.), a retardation film and a polarizer protective film included in an image display device such as a liquid crystal display (LCD), and It is a viewing angle compensation film, a light diffusing film, a reflective film, an antireflection film, an antiglare film, a brightness improving film, and a conductive film for a touch panel.

The resin molded product of the present invention may have heat resistance derived from the high Tg of the polymer (A). Therefore, the degree of freedom of use of the resin molded product of the present invention is high, and various effects can be obtained by using the resin molded product of the present invention. For example, the use of the resin molded product of the present invention, which is an optical film, improves the degree of freedom in designing an image display device such as an LCD.

The resin molded product of the present invention may have high optical transparency. For example, the total light transmittance determined in accordance with the provisions of JIS K7361 can be a resin molded product of 85% or more, 90% or more, and further 91% or more, typically a film. ..

The resin molded article of the present invention may have a low surface haze. For example, the haze obtained in accordance with the provisions of JIS K7136 can be a resin molded product having a haze of 5% or less, 3% or less, and further 2% or less, typically a film. ..

The resin molded product of the present invention can be a retardation film. The retardation film is, for example, a positive retardation film in which the retardation Rth in the thickness direction is positive. The retardation film can be, for example, a λ / 4 plate or an elliptical polarizing plate.

The resin molded product of the present invention can be combined with other members. For example, the resin molded product of the present invention, which is an optical film, may be combined with other optical members.

Various functional coating layers may be formed on the surface of the resin molded product of the present invention, if necessary. Functional coating layers include, for example, antistatic layers, adhesive layers, adhesive layers, easy-adhesive layers, antiglare layers, antifouling layers such as photocatalytic layers, antireflection layers, hard coat layers, and ultraviolet shielding. It is a layer, a heat ray shielding layer, an electromagnetic wave shielding layer, and a gas barrier layer.

Other uses of the resin molded product of the present invention are, for example, the same uses as those of the polymer (A) described above.

The method for forming the resin molded product of the present invention is not particularly limited. The resin composition (C) can be molded by a known molding method such as a melt extrusion method, a casting method, or a press molding method to form the resin molded product of the present invention. If necessary, the molding method may be combined with another known method, for example, a stretching method. In order to obtain a retardation film, it is necessary to stretch the film (raw film) obtained by molding the resin composition.

The product including the resin molded product of the present invention is not particularly limited, and is, for example, an image display device. The image display device includes, for example, the resin molded product of the present invention, which is an optical film. The image display device is not particularly limited, and for example, a reflective, transmissive, semi-transmissive LCD; an LCD of various drive systems such as TN, STN, OCB, HAN, VA, and IPS; A liquid crystal display (EL) display; a plasma display (PD); a field emission display (FED).

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to the examples shown below.

In this example, MMA and NVA are abbreviations for methyl methacrylate and N-vinylacetamide, respectively.

First, the evaluation method of the polymer produced in this example will be shown.

[Structure of structural unit]
About what structural units was produced polymer has what molecular structures were evaluated by infrared spectroscopy (IR) and ¹ H- nuclear magnetic resonance (NMR). The IR was evaluated by the total reflection measurement method (ATR method) using an infrared spectroscopic analyzer (Varian, Excalibur Series). The measurement conditions were a scan speed of 5 kHz and a resolution of 4 cm ^-1 . ^{1 1} H-NMR evaluation was carried out using a nuclear magnetic resonance spectrometer (BRUKER, AV300M). Deuterated dimethyl sulfoxide (DMSO-d6; manufactured by Wako Pure Chemical Industries, Ltd.) was used as the measurement solvent.

[Content rate of structural units in polymer]
The content of NVA units in the produced precursor polymer was calculated from the amount of unreacted monomers remaining in the polymerization solution obtained during the polymerization reaction. The amount of unreacted monomer was determined by gas chromatography (manufactured by Shimadzu Corporation, GC2010).

[Glass transition temperature (Tg)]
The Tg of the produced polymer (including the precursor polymer) was determined in accordance with the regulations of JIS K7121. Specifically, it is obtained by raising the temperature of a sample of about 10 mg from room temperature to 200 ° C. (heating rate 20 ° C./min) under a nitrogen gas atmosphere using a differential scanning calorimeter (manufactured by Rigaku, DSC-8230). The DSC curve was evaluated by the starting point method. As a reference, α-alumina was used.

[Stress optical coefficient Cr]
The stress optical coefficient Cr (measurement wavelength 590 nm) when the produced polymer was used as a film was determined as follows.

First, the produced polymer was formed into a film by a hot press at 250 ° C. to obtain an unstretched film (thickness 190 μm) of the polymer. Next, the produced unstretched film was cut out to a size of 20 mm × 60 mm to obtain a test piece for Cr evaluation. Next, a weight having a weight of 1 N / mm ² or less applied to the test piece during stretching was selected and attached to one short side of the test piece, and then dried at a constant temperature held at Tg + 20 ° C. of the polymer. It was housed in a machine (manufactured by AS ONE, DOV-450A) and left for 1 hour. When the test piece is housed in a constant temperature dryer, the other short side of the test piece is fixed by a chuck, and the stress applied to the test piece by a weight causes the test piece to move in the long side direction (vertical direction). It was made to be stretched. Further, when accommodating, the distance between the chuck and the weight of the test piece was set to 40 mm.

After heating and stretching for 1 hour, the heater of the dryer was turned off, and the test piece was allowed to slowly cool in the dryer as it was. When the temperature in the oven reached Tg-40 ° C of the polymer, the test piece (uniaxially stretched film) was taken out, and the thickness of the taken out test piece and the in-plane retardation Re with respect to light having a wavelength of 590 nm were measured. The in-plane birefringence Δn of the test piece was calculated. Separately from this, the cross-sectional area of the test piece after being stretched by the load of the weight was obtained, and the stress σ (Pa) applied to the film was calculated from the cross-sectional area and the load of the weight. While changing the weight of the weight, Δn and σ were obtained for each load, and the slope of Δn with respect to the obtained σ was obtained by the least squares method, and this was defined as the stress optical coefficient Cr (Pa ^-1 ). When the orientation angle when measuring the in-plane retardation Re is close to 0 ° with respect to the stretching direction (load application direction), the sign of the stress optical coefficient Cr is positive. In this case, the intrinsic birefringence of the polymer is positive. On the other hand, when the orientation angle is close to 90 ° with respect to the stretching direction, the sign of the stress optical coefficient Cr becomes negative. In this case, the intrinsic birefringence of the polymer is negative. The larger the absolute value of Cr, the higher the expression of birefringence due to stretching.

The in-plane phase difference Re (nm) of the test piece was determined using a phase difference measuring device (KOBRA-WR, manufactured by Oji Measuring Instruments). The in-plane phase difference Re is the refractive index nx in the slow-phase axial direction (the direction showing the maximum refractive index in the film plane) in the test piece (film) plane, and the phase-advancing axial direction (slow-phase axial direction) in the same plane. It is a value represented by the formula (nx−ny) × d using the refractive index ny in the direction orthogonal to) and the thickness d (nm) of the film. The value of nx−ny corresponds to the in-plane birefringence Δn.

(Example 1)
14.0 parts by mass NVA, 26.0 parts by mass MMA, 59.9 parts by mass methyl ethyl ketone and 0.08 parts by mass t-amylperoxy-2-ethylhexanoate (Alchema Yoshitomi, Luperox (registered) The trademark) 575) was placed in a reaction vessel, and the inside of the vessel was replaced with nitrogen. Next, the container was heated in an oil bath at 70 ° C. for 4 hours to allow the copolymerization of NVA and MMA to proceed. Next, the formed polymerization solution was poured into excess 2-propanol for reprecipitation, and then the obtained precipitate was vacuum dried for 1 hour or more under the conditions of a pressure of 0.13 kPa and a temperature of 60 ° C. to volatilize. The component was removed to obtain a solid polymer (1-1) which was a precursor polymer. The Tg of the polymer (1-1) was 113 ° C., and the content of NVA units in the polymer (1-1) was 29.0% by mass.

Next, the polymer (1-1) was heated at a pressure of 0.13 kPa and a temperature of 240 ° C. for 1 hour to obtain a solid polymer (1-2). The Tg of the polymer (1-2) was 133 ° C. That is, an increase in Tg was confirmed before and after this heating. The residual amount of methanol in the polymer (1-2) was evaluated by gas chromatography (manufactured by Shimadzu Corporation, GC2010) and found to be 40 ppm.

The IR evaluation results of the polymers (1-1) and (1-2) are shown in FIG. In FIG. 1, in addition to the IR spectra of the polymers (1-1) and (1-2), the difference obtained by subtracting the IR spectrum of the polymer (1-1) from the IR spectrum of the polymer (1-2) is shown. Also shown. The absorption peak appearing in the difference spectrum corresponds to the molecular structure of the polymer (1-2) formed by the above heating at 240 ° C. Although the vertical axis of FIG. 1 indicates “absorption”, since the baselines of the respective spectra are offset from each other in order to facilitate the comparison of the three spectra including the difference spectrum, FIG. No specific numerical value is shown on the vertical axis of.

As shown in FIG. 1, an absorption peak (wave number 1698 cm ^-1 ) attributed to the expansion and contraction vibration of the carbonyl group of the pyrrolidinone ring structure was confirmed in the difference spectrum, and the polymer (1-2) was heated by the above heating at 240 ° C. ) Was confirmed to have a pyrrolidinone ring structure.

The ¹ H-NMR evaluation results of the polymers (1-1) and (1-2) are shown in FIGS. 2 and 3, respectively. As shown in FIG. 2, in the NMR spectrum of the polymer (1-1), the peak assigned to the proton of the methine group located in the main chain of the NVA unit is 3.10-3.20 ppm, and acetamide of the NVA unit. The peak attributed to the proton of the methyl group contained in the structure is 0.90-1.10 ppm, the peak attributed to the methyl ester structure is 3.50-3.60 ppm, and the proton of the secondary amide structure (nitrogen) The peaks attributed to the protons bonded to the atoms) were confirmed at 6.90-7.50 ppm, respectively. On the other hand, in the NMR spectrum of the polymer (1-2), the peak attributed to the proton of the methine group located in the main chain of the NVA unit decreases, and the peak attributed to the pyrrolidinone ring is 2.30-2. It was newly confirmed at 40 ppm. The peak of 2.50 ppm in the NMR spectrum of the polymer (1-2) is due to the residual protons in the measurement solvent. That is, the polymer (1-1) does not have the pyrrolidinone ring structure represented by the formula (1), but the polymer (1-2) has the pyrrolidinone ring structure represented by the formula (1) in the main chain, that is, It was confirmed that the pyroridinone ring structure represented by the formula (1) was formed by the above heating.

The Cr of the polymer (1-2) was + 90.8 × 10 ^-11 Pa ^-1 . Further, since the value of Cr was positive, it was confirmed that the polymer (1-2) had positive intrinsic birefringence. The fact that the Cr value is positive is judged from the specific molecular structure of the pyrrolidinone ring structure formed by the cyclization reaction between the MMA unit and the NVA unit, and the ring structure is a polymer (1-2). ) Is further supported by its presence in the main chain.

(Example 2)
7.2 parts by mass NVA, 32.8 parts by mass of MMA, 59.9 parts by mass of methyl ethyl ketone and 0.08 parts by mass of t-amylperoxy-2-ethylhexanoate (Alchema Yoshitomi, Luperox (registered) A solid precursor polymer (2-1), which is a copolymer of NVA and MMA, was obtained in the same manner as in Example 1 except that the trademark) 575) was housed in the reaction vessel. The Tg of the polymer (2-1) was 108 ° C., and the content of NVA units in the polymer (2-1) was 15.0% by mass.

Next, the polymer (2-1) was heated at a pressure of 0.13 kPa and a temperature of 240 ° C. for 1 hour to obtain a solid polymer (2-2). The Tg of the polymer (2-2) was 126 ° C. That is, an increase in Tg was confirmed before and after this heating. When the residual amount of methanol in the polymer (2-2) was evaluated in the same manner as in Example 1, it was 30 ppm.

The Cr of the polymer (2-2) was +4.7 × 10 ^-11 Pa ^-1 . Further, since the value of Cr was positive, it was confirmed that the polymer (2-2) had positive intrinsic birefringence. The positive value of Cr is determined from the specific molecular structure of the pyrrolidinone ring structure formed by the cyclization reaction between the MMA unit and the NVA unit, and the ring structure is a polymer (2-2). ) Is further supported by its presence in the main chain.

(Reference example)
When Tg and Cr of commercially available polymethyl methacrylate (PMMA, Sumipex EX manufactured by Sumitomo Chemical Co., Ltd.) were evaluated, Tg was 105 ° C. and Cr was -15 × 10 ^-11 Pa ^-1 .

The composition of the precursor polymer prepared in each example, the Tg of the precursor polymer and the polymer, and the Cr of the polymer are summarized in Table 1 below.

The novel polymer of the present invention can be used, for example, in applications of optical members. The optical member is, for example, a lens, a prism, an optical fiber, or an optical film.

Claims (26)

A thermoplastic polymer having a pyrrolidinone ring structure represented by the following formula (1) in the main chain.

In the formula (1), R ¹ is − COR ⁴ groups, and R ⁴ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl having 3 to 18 carbon atoms. It is the basis. R ² and R ³ are independent hydrogen atoms or methyl groups. The thermoplastic polymer according to claim 1, further comprising at least one selected from a (meth) acrylic acid ester unit and a (meth) acrylic acid unit as a constituent unit. It has a pyrrolidinone ring structure represented by the following formula (1) in the main chain.
It also has a (meth) acrylic ester unit as a constituent unit.
A thermoplastic polymer having a content of the (meth) acrylic ester unit of 60% by mass or more.

In equation (1), R ¹ Is a hydrogen atom or -COR ^Four Is the basis and R ^Four Is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms. R ² And R ³ Are independent of each other, a hydrogen atom or a methyl group. The thermoplastic polymer according to claim 3, wherein the (meth) acrylic acid ester unit is a methyl methacrylate unit. The thermoplastic polymer according to any one of claims 1 to 4 , wherein the glass transition temperature is 110 ° C. or higher. In the infrared absorption spectrum, the range of wave number 1690 cm ^-1 or 1710 cm ^-1, heat according to any one of claims 1 to 5, the absorption peak attributed to the stretching vibration of the carbonyl group of pyrrolidinone ring structure is observed Plastic polymer. When the thermoplastic polymer is heated at 200 ° C. or higher,
In the difference of the infrared absorption spectrum before and after heating, the thermoplastic polymer according to any one of claims 1 to 6, the absorption peak in the range of wave number 1690 cm ^-1 or 1710 cm ^-1 is observed. The thermoplastic polymer according to any one of claims 1 to 7 , wherein the content of the residual alcohol is 10 to 3000 ppm. As the structural unit P containing the pyrrolidinone ring structure, it has only the unit composed of the pyrrolidinone ring structure and / or the unit represented by the following formula (2).
The thermoplastic polymer according to any one of claims 1 to 8 , wherein the content of the structural unit P is 30% by mass or more.

In the formula (2), R ⁴ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms. R ² and R ³ are independent hydrogen atoms or methyl groups. As the structural unit P containing the pyrrolidinone ring structure, it has only the unit composed of the pyrrolidinone ring structure and / or the unit represented by the following formula (2).
It also has a (meth) acrylic ester unit as a constituent unit.
The thermoplastic polymer according to claim 1, wherein the total content of the structural unit P and the (meth) acrylic acid ester unit is 50% by mass or more.

In the formula (2), R ⁴ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms. R ² and R ³ are independent hydrogen atoms or methyl groups. The thermoplastic polymer according to any one of claims 1 to 10, which is used for an optical member. A resin composition containing the thermoplastic polymer according to any one of claims 1 to 11 . A resin molded product composed of the resin composition according to claim 12 . Resin molded article according to claim 1 3 is an optical member. An optical member containing a thermoplastic polymer having a pyrrolidinone ring structure represented by the following formula (1) in the main chain.

In equation (1), R ¹ Is a hydrogen atom or -COR ^Four Is the basis and R ^Four Is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms. R ² And R ³ Are independent of each other, a hydrogen atom or a methyl group. The optical member according to claim 15, wherein the thermoplastic polymer further has at least one selected from a (meth) acrylic acid ester unit and a (meth) acrylic acid unit as a constituent unit. A method for producing a thermoplastic polymer.
The thermoplastic polymer has a pyrrolidinone ring structure represented by the following formula (1) in the main chain.
In the above-mentioned production method, a precursor polymer formed by polymerization of a group of monomers containing a vinyl monomer and having an ester group and / or a carboxyl group and an amide group as side chains is cyclized. A method for producing a thermoplastic polymer, which obtains the thermoplastic polymer.

In the formula (1), R ¹ is a hydrogen atom or −COR ⁴ groups, and R ⁴ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or 3 to 18 carbon atoms. It is a cycloalkyl group of. R ² and R ³ are independent hydrogen atoms or methyl groups. The 17th claim, wherein the precursor polymer is a copolymer formed by polymerization of a monomer group containing a vinyl monomer A having an ester group and / or a carboxyl group and a vinyl monomer B having an amide group. Method for producing a thermoplastic polymer. The method for producing a thermoplastic polymer according to claim 18, wherein the vinyl monomer A is at least one selected from (meth) acrylic acid ester and (meth) acrylic acid. The method for producing a thermoplastic polymer according to claim 18 or 19, wherein the vinyl monomer B is at least one selected from N-vinylformamide and N-vinylacetamide. The method for producing a thermoplastic polymer according to any one of claims 18 to 20, wherein the content of the structural unit Y2 derived from the vinyl monomer B in the precursor polymer is 10 to 50% by mass. The ratio of the content of the structural unit Y1 derived from the vinyl monomer A to the content of the structural unit Y2 derived from the vinyl monomer B in the precursor polymer is a mass ratio of Y1: Y2 = 95: 50. The method for producing a thermoplastic polymer according to any one of claims 18 to 20, which is ~ 5:50. The method for producing a thermoplastic polymer according to any one of claims 17 to 22 , wherein the cyclization of the precursor polymer is promoted by heating the precursor polymer. The method for producing a thermoplastic polymer according to claim 23 , wherein the heating temperature is 150 ° C. or higher. Method for producing a thermoplastic polymer according to the heating to claim 23 or 2 4 By proceeding under reduced pressure. The heating method for producing a thermoplastic polymer according to claim 23 or 2 4 in the absolute pressure to proceed in the following reduced pressure 26.6 kPa.

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