JP2015193840A - Novel polymer, resin composition, resin molded body, and method for producing novel polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a novel polymer having a ring structure in a main chain; and a method for producing the same.SOLUTION: A polymer has a pyrrolidinone ring structure in a main chain. The ring structure is, for example, a structure of the following formula (1). Ris hydrogen or -COR, Ris hydrogen or -COOR, Ris hydrogen, methyl, or -NHCOR. R-Rare, independently of one another, hydrogen, methyl, phenyl, straight-chain alkyl having 2-18 carbon atoms, or cycloalkyl having 3-18 carbon atoms.

Description

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

  Resin compositions containing transparent polymers such as acrylic polymers, polycycloolefins, polycarbonates, polystyrenes, and polyesters are widely used for optical members such as lenses, prisms, optical fibers, and optical films. Among them, the acrylic polymer has characteristics such as high optical transparency and a 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 correspond to this. Acrylic polymers also include polymers having a ring structure in the main chain. For example, Patent Document 1 (Japanese Patent No. 4825409) discloses an acrylic polymer having a lactone ring structure in the main chain. Patent Document 2 (Japanese Patent Laid-Open No. 2006-328334) discloses an acrylic polymer having a glutarimide structure in the main chain. Patent Document 3 (Japanese Patent Laid-Open No. 2007-31537) discloses an acrylic polymer having an N-substituted maleimide structure in the main chain.

  In general, even if the glass transition temperature (Tg) of an acrylic polymer is high, it is around 100 ° C., but these documents indicate that an acrylic polymer having a ring structure in the main chain has a higher Tg. Yes. When Tg of a polymer improves, the heat resistance of the resin composition containing the said polymer and the resin molded object comprised from the said composition will improve. When the resin molding is an optical member, a recent strong demand for a product including the optical member, as a specific example, a light source, a power supply unit, and the like from the viewpoint of compactness of the product, high performance, improvement of design flexibility, etc. There is an increased possibility of being able to meet the design requirements for arranging optical members in the vicinity of heating elements such as batteries and circuit boards.

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

  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 monomer group including a vinyl monomer, and has an ester group and / or a carboxyl group and an amide group as side chains. It is a polymer formed by cyclization of a precursor polymer.

  The resin composition of the present invention contains the novel polymer of the present invention.

  The resin molding of this invention is comprised from the said resin composition of this invention.

  In the method for producing a novel polymer according to the present invention, a precursor polymer formed by polymerization of a monomer group including a vinyl monomer, the precursor weight having an ester group and / or a carboxyl group and an amide group as side chains. The polymer is cyclized to obtain 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 spectroscopy analysis (IR) spectrum of the polymers (1-1) produced in Example 1, and (1-2) with the difference. 1 is a diagram showing a ¹ H-nuclear magnetic resonance (NMR) spectrum of a polymer (1-1) produced in Example 1. FIG. 1 is a diagram showing a ¹ H-NMR spectrum of a polymer (1-2) produced in Example 1. FIG. It is a figure which shows the IR spectrum of the polymers (3-1) produced in Example 3, and (3-2) with the difference. 3 is a diagram showing a ¹ H-NMR spectrum of a polymer (3-1) produced in Example 3. FIG. 4 is a diagram showing a ¹ H-NMR spectrum of a polymer (3-2) produced in Example 3. FIG.

[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 lactam structure (γ-lactam structure). The polymer having a pyrrolidinone ring structure in the main chain means that at least one atom, typically an amide bond (—NHCO—), among the five atoms constituting the basic skeleton of the 5-membered pyrrolidinone ring structure. It means that three carbon atoms not constituting are located in the main chain of the polymer and constitute the main chain.

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

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

  The optical characteristic is, for example, a birefringence characteristic. 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 an effect of imparting positive or negative intrinsic birefringence to the polymer (A). More specifically, the pyrrolidinone ring structure basically has a function of imparting positive intrinsic birefringence to the polymer (A), but when the substituent bonded to the basic skeleton of the ring structure is bulky, the polymer (A) may have negative intrinsic birefringence. The positive or negative of the intrinsic birefringence as the polymer (A) is determined by the balance between the birefringence characteristics of the respective structural units of the polymer (A). For example, even when the pyrrolidinone ring structure has an effect of imparting positive intrinsic birefringence to the polymer (A), when the polymer (A) further has a structural unit having an effect of imparting negative intrinsic birefringence, Intrinsic birefringence as a combination (A) may be negative.

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

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

  The application of the polymer (A) is not limited to the optical member. Applications of the polymer (A) include, for example, pressure-sensitive adhesives, conductive adhesives, photosensitive adhesives, building material adhesives, printed circuit board adhesives, transparent sheet or film adhesives, and organic or inorganic fibers. Adhesives such as adhesives; pressure-sensitive adhesive sheets, pressure-sensitive adhesives for films, pressure-sensitive adhesives for electronic devices, heat-resistant pressure-sensitive adhesives, heat-conductive pressure-sensitive adhesives, conductive pressure-sensitive adhesives; secondary battery electrodes, functional fibers , Conductive fine particles, metal fine particles, scaly fillers, dyes, ink jets, color filters, inks, toners, various binder resins; gas barriers, water vapor barriers, display elements, semiconductor encapsulants, solar cells, electronic devices, etc. Sealing material (agent); Medical or daily antibacterial, disinfecting and sterilizing material; hard coat, easy adhesion coat, UV curable resin, EB curable resin, rust inhibitor, anti-fogging agent Various functional coating materials (agents) used for antistatic agents, flame retardant coating agents, shielding coatings, insulation coatings; powder coatings such as thermosetting powder coatings; organic fillers, water retention agents, moisturizing agents, etc. Cosmetic ingredients; printed circuit boards and mounting boards (including flexible boards) used for capacitors, capacitors, electronic devices, etc .; synthetic lubricants such as lubricant additives, viscosity modifiers, viscosity index improvers; nanofillers, nanoparticles, Nanomaterials such as nanostructure molding materials; pulp coagulants, dispersants, paper strength and other agents used in the manufacture and processing of paper; plastic members, films, lenses, packaging materials, tires that require heat resistance, Thermoplastic resins such as optical films and polarizer protective films; fibers such as high-performance fibers, nanofibers, piezoelectric fibers, non-woven fabrics, filter porous membranes; Gelling agent for memory materials such as ink, ink for ink, toner, microcapsule, etc .; thickener used for adjusting the viscosity of various solutions or pastes, as a more specific example, electrode activity of secondary battery Thickeners used in pastes containing particles, toothpaste, liquid detergents, etc .; dispersants or binders used in fibers such as glass fibers or carbon 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 3rd, 4th and 5th positions of the ring structure) that do not constitute an amide bond are the main chain of the polymer (A). Located at (constituting the main chain). The ring structure shown in Formula (1) may be a structural unit (repeating unit) of the polymer (A) or a structure constituting a part of the structural unit. In the latter case, the structural unit includes a pyrrolidinone ring structure represented by the formula (1) as a part of its molecular structure.

In Formula (1), R ¹ is a hydrogen atom or a —COR ⁴ group, 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 3 to 18 carbon atoms. Of the cycloalkyl group. R ² is a hydrogen atom or a —COOR ⁵ group, and R ⁵ 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 ³ is a hydrogen atom, a methyl group or a —NHCOR ⁶ group, and R ⁶ 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 a group. R ^{4 to} R ⁶ may be the same as or different from each other.

  2-12 are preferable and, as for carbon number of a linear alkyl group, 2-4 are more preferable. The straight chain alkyl group is, for example, an ethyl group, a propyl group, or a butyl group. 3-12 are preferable and, as for carbon number of a cycloalkyl group, 3-6 are more preferable. The cycloalkyl group is, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

A specific example of the combination of R ¹ , R ² and R ^{3 is} a combination in which R ¹ is a —COCH ₃ group, R ² is a —COOCH ₃ group, and R ³ is a CH ₃ group. Another example is a combination in which R ¹ is a —COCH ₃ group, R ² is a —COOCH ₃ group, and R ³ is a —NHCOCH ₃ group.

  The pyrrolidinone ring structure represented by the formula (1) may be continuous on the main chain of the polymer (A). In this case, a continuous pyrrolidinone ring structure forms a spiro ring structure with adjacent ring structures. However, when the pyrrolidinone ring structure represented by the formula (1) constitutes a part of the structural unit of the polymer (A), for example, the structural unit possessed by the polymer (A) has the ring structure represented by the formula (1). When the structural unit has a structure in which an alkylene group such as a methylene group is bonded to the carbon atom at the 3-position or the 5-position (a more specific example is a structural unit represented by the formula (2) described later), The continuation of the structural unit in the main chain of the polymer (A) is that the pyrrolidinone ring structure is continuous on the main chain because the alkylene group constituting the main chain of the polymer (A) is located between the ring structures. Not applicable. In this case, it can be said that the pyrrolidinone ring structures are not adjacent to each other on the main chain.

When the pyrrolidinone ring structure represented by the formula (1) is continuous on the main chain of the polymer (A), the two adjacent ring structures are the carbon atom at the 3-position of one ring structure and the 5 of the other ring structure. A spiro ring structure in which the carbon atom at the position is the same carbon atom is formed. R ³ bonded to the ^3rd carbon atom and R ² bonded to the 5th carbon atom do not exist.

  Examples of such a continuous pyrrolidinone ring structure are shown in the following formulas (3) and (4).

The structure shown in Formula (3) is a spiro ring structure in which two pyrrolidinone ring structures are continuous on the main chain of the polymer (A). The carbon atom at the 3rd position of the left ring structure and the carbon atom at the 5th position of the right ring structure adjacent to the ring structure are the same carbon atom. In any ring structure, three carbon atoms from the 3rd position to the 5th position constitute the main chain of the polymer (A). There is no R ³ bonded to the ^3rd carbon atom of the left ring structure and R ² bonded to the 5th carbon atom of the right ring structure. Incidentally, it may be the R ¹ of R ¹ and the right ring structure of the left ring structure optionally substituted by one or more identical to each other, may be identical to one another.

The structure shown in Formula (4) is a spiro ring structure in which three pyrrolidinone ring structures are continuous on the main chain. The carbon atom at the 3rd position of the leftmost ring structure and the carbon atom at the 5th position of the central ring structure adjacent to the ring structure are the same carbon atom. The carbon atom at the 3rd position of the central ring structure and the carbon atom at the 5th position of the rightmost ring structure adjacent to the ring structure are the same carbon atom. In any ring structure, three carbon atoms from the 3rd position to the 5th position constitute the main chain of the polymer (A). R ³ bonded to the ^third carbon atom of the leftmost ring structure, R ² bonded to the fifth carbon atom of the central ring structure and R ³ bonded to the ^third carbon atom, and 5 of the rightmost ring structure There is no R ² bonded to the carbon atom at the position. In addition, R ^{1 of} each ring structure may be the same as or different from each other, and may be the same as each other.

Thus, when the pyrrolidinone ring structure represented by the formula (1) is continuous on the main chain of the polymer (A), R ² and / or R ³ may not be present. At this time, R ² and / R ³ are not present but are adjacent to the ring structure of the carbon atom to which the group is bonded (the bond to the outside of the ring structure to which the group belongs). It can also be expressed as forming.

  When the pyrrolidinone ring structure represented by the formula (1) is continuous on the main chain of the polymer (A), the number of continuous is not limited. In one example, the polymer (A) in which the pyrrolidinone ring structure represented by the formula (1) continues throughout the main chain, in other words, the pyrrolidinone ring structure represented by the formula (1) as a structural unit, only the structural unit. The polymer (A) which is a homopolymer consisting of

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

An example of a structural unit P composed of a pyrrolidinone ring structure and another molecular structure is shown in the following formula (2). R ³ to R ⁵ of formula (2) is the same as R ³ to R ⁵ of formula (1).

The structural unit X shown in Formula (2) is a unit composed of a pyrrolidinone ring structure and a methylene group bonded to the 3-position carbon atom of the ring structure. The carbon atom of the methylene group and the 3rd to 5th carbon atoms of the ring structure constitute the main chain of the polymer (A). The pyrrolidinone ring structure of the structural unit X includes a tertiary amide structure as a molecular structure constituting a part of the ring (a tertiary amide structure is included as a part of the ring structure). The pyrrolidinone ring structure included in the structural unit X is a pyrrolidinone ring structure represented by the formula (1), in which R ¹ is a —COR ⁴ group and R ² is a —COOR ⁵ group.

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

The structural unit X is, for example, a unit in which R ^{3 to} R ⁵ are all methyl groups. The polymer (A) having such a structural unit X includes, for example, a copolymer of methyl methacrylate (MMA) and methyl acetamide acrylate (AcAAM) as a precursor polymer (B), and adjacent MMA units. It can be formed by a cyclization reaction between AcAAM units.

  The polymer (A) is a copolymer composed of the structural unit P and the structural unit Q other than the structural unit P, even if it is a homopolymer composed only of the structural unit P containing a pyrrolidinone ring structure. May be. The copolymer may 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 further properties depending on the type and content of the structural unit Q. The structural unit Q includes, for example, (meth) acrylic acid ester units, (meth) acrylic acid units, N-substituted maleimide units, aromatic vinyl compound units, unsaturated carboxylic acid compound units, vinyl cyanide compound units, heteroaromatics. An α, β-unsaturated monomer unit having a group.

  The polymer (A) may have at least one selected from a (meth) acrylic acid ester unit and a (meth) acrylic acid unit as the structural unit Q. In this case, the optical transparency of the polymer (A) becomes higher, and it is more suitable for use as an optical member, for example. The polymer (A) which is a copolymer preferably has a (meth) acrylic acid ester unit as the structural 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-hydroxyacryl It is a structural unit (derived from each of these monomers) formed by polymerization of each (meth) acrylic acid ester of methyl acid and ethyl α-hydroxyacrylate. The (meth) acrylic acid ester unit is preferably a methyl methacrylate (MMA) unit, an ethyl methacrylate unit, an n-butyl methacrylate unit, a cyclohexyl methacrylate unit, an isobornyl methacrylate unit, or a benzyl methacrylate unit, and an MMA unit. More preferred. At this time, the optical transparency of the polymer (A) is further increased.

  When the content rate of the (meth) acrylic acid ester unit in a polymer (A) exceeds 50 weight%, the said polymer (A) is an acrylic polymer. The polymer (A), which is an acrylic polymer, exhibits properties that acrylic polymers generally have, such as high optical transparency, and a high balance of mechanical strength, molding processability and surface hardness. In the polymer (A) which is an acrylic polymer, the total content of (meth) acrylic acid ester units 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), a copolymer with a (meth) acrylic acid ester such as MMA is used as the precursor polymer (B), and the precursor polymer (B In this case, the polymer (A) can have (meth) acrylic acid ester units as unreacted units.

  In addition, as described above, when the polymer (A) can be formed by advancing the cyclization reaction to the precursor polymer (B) which is a copolymer having a (meth) acrylic acid ester unit as a constituent unit, The union (A) can also be regarded as a derivative of (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 weight or more, 70% by weight or more, 80% by weight or more, and further 90% by weight or more. As will be described later, a precursor polymer (B) that is a copolymer with (meth) acrylic acid ester, that is, a precursor polymer that is a copolymer having (meth) acrylic acid ester units as constituent units ( 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 a partner for copolymerization with the (meth) acrylate is not limited. The monomer is, for example, an amide acrylate ester.

  N-substituted maleimide units include, 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.

  Examples of the aromatic vinyl compound unit include 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, for example, a structural unit formed by polymerization of an acid such as crotonic acid and the alkali metal salt, ammonium salt, or organic amine salt thereof. In the present specification, the unsaturated carboxylic acid compound unit does not include a (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, for example, at least one selected from a vinylcarbazole unit, a vinylpyridine unit, a vinylimidazole unit, and a vinylthiophene unit.

  The structural unit Q is a vinyl compound unit excluding the above-described units, such as vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, butene, isoprene, N-vinyl-2-pyrrolidone, N-vinylformamide, N-vinylacetamide. Divinyl esters such as divinyl adipate and divinyl sebacate; sulfonic acids such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-phenylpropane sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and the like It may be a structural unit formed by polymerization of alkali metal salt, ammonium salt, organic amine salt;

  The polymer (A) may have a structural unit having ultraviolet (UVA) absorption ability. 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 is introduced. In these derivatives, the polymerizable group to be introduced can be appropriately selected, and is, for example, a vinyl group.

  Although the content rate of the structural unit P in a polymer (A) is not limited, in order to acquire the characteristic derived from the structural unit P more reliably, it is 30 mass% or more, for example, 35 mass% or more is preferable, and 40 mass % Or more is more preferable. The upper limit of the content rate of the structural unit P is not specifically limited, 100 mass% or less may be sufficient. When the polymer (A) further includes other structural unit Q, in particular, a (meth) acrylate 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 such as ¹ H nuclear magnetic resonance ( ¹ H-NMR) or infrared spectroscopy (IR).

The pyrrolidinone ring structure that the polymer (A) has in the main chain can be confirmed by a known method such as 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. In the infrared absorption spectrum, the fact that the absorption peak attributed to the stretching vibration of the carbonyl group of the pyrrolidinone ring structure is in the above-mentioned wave number range is published on September 15, 2006 as an infrared absorption region in a 5-membered lactam ring. It is described in “Identification Method of Organic Compounds by Spectrum, 7th Edition, Tokyo Chemical Doujin”.

Specific structure of the pyrrolidinone ring structure, the content of the ring structure in the polymer (A), and the type and content of the structural unit Q when the polymer (A) is a copolymer further having the structural unit Q Depending on the case, it may be difficult to confirm the absorption peak in the infrared absorption spectrum. However, depending on the structure of the polymer (A), reheating the polymer (A) may cause a cyclization reaction between the remaining structural units without the cyclization reaction proceeding during the formation of the polymer (A). In some cases, the same ring structure as that already existing in the polymer (A) can be formed. At this time, the pyrrolidinone ring structure of the main chain can be confirmed by taking the difference between 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 an observed polymer.

  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 the content thereof, the Tg of the polymer (A) is 120 ° C. or higher, 130 ° C. or higher, and more preferably 160 ° C. or higher. Can take the value of

  When the polymer (A) is formed by a dealcoholization cyclocondensation reaction described later, the alcohol generated during the cyclization reaction may remain in the polymer (A). At this time, content of the residual alcohol in a polymer (A) is 10-3000 ppm, for example.

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

  A polymer (A) can be formed with the manufacturing method of the polymer (A) shown below, for example.

[Production Method of Polymer (A)]
In the production method of the present invention, a precursor polymer (B) formed by polymerization of a monomer group containing a vinyl monomer, the precursor polymer having 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 proceeds between an ester group and / or a carboxyl group and an 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. This amine group is a secondary or tertiary amine group as shown in Formula (1).

  An example of such a reaction is shown in the following formula (5).

R ¹ to R ⁴ of formula (5) is the same as R ¹ to R ⁴ of formula (1). R ⁷ 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; 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 ⁷ is preferably a linear alkyl group or a cycloalkyl group, and the carbon number thereof is preferably 1 to 12, and more preferably 1 to 4.

In the reaction represented by the formula (5), 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 ⁷ OH is eliminated. When R ⁷ is a hydrogen atom, water is eliminated, that is, this reaction is a dehydration cyclocondensation reaction. When R ⁷ is an organic residue, the alcohol is eliminated, that is, this reaction is a dealcoholization cyclocondensation reaction. For example, when R ⁷ is a methyl group, methanol is eliminated. This reaction proceeds in the molecular chain of the precursor polymer (B). The structural unit P on the right side of the formula (5) includes a pyrrolidinone ring structure represented by the formula (1) and a methylene group bonded to the 3-position carbon atom of the ring structure.

The precursor polymer (B) has an ester group and / or a carboxyl group in its side chain and an amide group. More specifically, the precursor polymer (B) of the formula (5) has a configuration having an ester group (carboxyl ester group; R ⁷ is an organic residue) and / or a carboxyl group (R ⁷ is a hydrogen atom) in the side chain. A copolymer having a unit and a structural unit having an amide group in the side chain. Any structural unit is a unit derived from a vinyl monomer. Thus, the precursor polymer (B) can be formed by polymerization of a monomer group containing a vinyl monomer. More specifically, the precursor polymer (B) of the formula (5) is formed by polymerization of a monomer group including a vinyl monomer A having an ester group and / or a carboxyl group and a vinyl monomer B having an amide group. Copolymer. In this precursor polymer (B), the side chain ester group and / or carboxyl group and amide group have one methylene group (one carbon atom) located in the main chain of the precursor polymer (B). I) It is in the inserted positional relationship. In the example shown in Formula (5), by the three carbon atoms located in the main chain of the precursor polymer (B), the carbon atom of the carboxyl group and / or the ester group located in the side chain, and the nitrogen atom of the amide group, A pyrrolidinone ring structure is formed.

The —COR ⁴ group is bonded to the nitrogen atom of the side chain of the precursor polymer (B) of the formula (5), but R ¹ (hydrogen atom or hydrogen atom) is attached to the nitrogen atom in the pyrrolidinone ring structure of the structural unit P on the right side. -COR ⁴ group) is bonded. That is, the polymer (A) can take a hydrogen atom as R ¹ . This is because the —COR ⁴ group may be eliminated by heat applied to the polymer during or after the cyclization reaction. The same applies to the examples of the reaction to form the polymer (A) from the precursor polymer (B) shown below. The elimination of the —COR ⁴ group can be promoted, for example, by using a catalyst (cyclization catalyst) in the cyclization reaction described later and allowing the catalyst to remain in the polymer after cyclization.

An example of vinyl monomer A at this time is shown in the following formula (6), and an example of vinyl monomer B is shown in the following formula (7). R ³ of formula (6) is the same as R ³ of formula (1), R ⁷ is the same as R ⁷ of formula (5). R ² and R ⁴ of formula (7) are the same as R ² and R ^4, respectively formula (1). The vinyl monomer A represented by the formula (6) is a (meth) acrylic acid ester unit (R ³ is a hydrogen atom or a methyl group, and R ⁷ is an organic residue) or a (meth) acrylic acid unit (R ³ Is a hydrogen atom or a methyl group, and R ⁷ is a hydrogen atom. Since the optical transparency of the formed polymer (A) becomes higher, the vinyl monomer A is preferably acrylic acid or methyl methacrylate (MMA).

  The precursor polymer (B) may be a polymer formed by polymerization of a monomer group including two or more kinds of vinyl monomers A and / or two or more kinds of vinyl monomers 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. Also good.

  A more specific example of the reaction shown in Formula (5) is shown in Formula (8) below.

R ³ to R ⁵ of the formula (8) is the same as R ³ to R ⁵ of formula (2). R ⁷ is the same as R ⁷ of formula (5). In the reaction represented by the formula (8), a cyclization reaction (reaction that binds the broken line portion in the molecular structure on the left side and desorbs R ⁷ OH) proceeds to the precursor polymer (B) having the molecular structure on the left side. The polymer (A) having the structural unit P on the right side is formed. The structural unit P on the right side is the structural unit X shown in Formula (2).

  The precursor polymer (B) of the formula (8) is a copolymer formed by polymerization of a monomer group including a vinyl monomer A having an ester group and / or a carboxyl group and a vinyl monomer B having an amide group. It is. However, in the precursor polymer (B) of the formula (8), the vinyl monomer B further has an ester group and / or a carboxyl group together with an amide group.

  An example of vinyl monomer A at this time is shown in the following formula (9), and an example of vinyl monomer B is shown in the following formula (10).

R ³ and R ⁷ of formula (9) is the same as R ³ and R ⁷ of formula (5), respectively formula (2). R ⁴ and R ⁵ of formula (10) is the same as R ⁴ and R ^5, respectively formula (2).

  Monomer B shown in formula (10) may be an amido acrylate ester. Amide acrylate is a vinyl monomer having both an ester group and / or a carboxyl group and an amide group.

  The vinyl monomer B represented by the formula (7) and the formula (10) may be an amide acrylate ester. Examples of the amide acrylate ester include methyl acetamidoacrylate (AcAAM), ethyl acetamidoacrylate, and acetamidoacrylic. N-butyl acid, n-d dodecyl acetamidoacrylate, cyclohexyl acetamidoacrylate, and phenyl acetamidoacrylate.

  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 and the structural unit Y2 derived from the monomer B in the polymer (B) Although the ratio of content rate is not specifically limited, In mass ratio, it is Y1: Y2 = 95-50: 5-50, for example, 90-50: 10-50 are preferable, and 85-50: 15-50 are more preferable. . When the structural unit Y1 is a (meth) acrylate unit, the polymer (A) formed from the precursor polymer (B) can have an unreacted (meth) acrylate unit as a structural unit.

  The vinyl monomer A represented by the formulas (6) and (9) and the vinyl monomer B represented by the formulas (7) and (10) may be the same vinyl monomer depending on the type of the substituent. That is, the precursor polymer (B) may be a homopolymer of the same vinyl monomer. As can be understood from the molecular structure shown in each formula, this vinyl monomer is a vinyl monomer C having both an ester group and / or a carboxyl group and an amide group. That is, the precursor polymer (B) may be a polymer formed by polymerization of a monomer group including a vinyl monomer C having an ester group and / or a carboxyl group and an amide group. When the precursor polymer (B) is such a homopolymer, the increase in Tg from the precursor polymer (B) when the polymer (A) is formed is particularly large.

  The vinyl monomer C is, for example, an amide acrylate ester.

  An example of the cyclization reaction for forming the polymer (A) from the precursor polymer (B) which is a homopolymer of the vinyl monomer C is shown in the following formula (11). In the example shown in Formula (11), the cyclization reaction is allowed to proceed to the precursor polymer (B), which is a homopolymer of amide acrylate ester, to form the polymer (A).

R ⁴ and R ⁵ of formula (11) is the same as R ⁴ and R ⁵ of formula (1). In the example shown in the formula (11), the structural unit P including the pyrrolidinone ring structure shown in the formula (1) in which R ² is a —COOR ⁵ group and R ³ is a —NHCOR ⁴ group is formed. In the reaction represented by the formula (11), a cyclization reaction (reaction that binds the broken line portion in the molecular structure on the left side and desorbs R ⁵ OH) proceeds to the precursor polymer (B) having the molecular structure on the left side. The polymer (A) having the structural unit P on the right side is formed.

  Another example of the cyclization reaction for forming the polymer (A) from the precursor polymer (B) which is a homopolymer of the vinyl monomer C is shown in the following formula (12). In the example shown in Formula (12), the cyclization reaction is allowed to proceed to the precursor polymer (B), which is a homopolymer of amide acrylate ester, to form the polymer (A).

R ⁴ and R ⁵ of formula (12) is the same as R ⁴ and R ⁵ of formula (1). In the example shown in Formula (12), the polymer (A) in which the spiro ring structure of two pyrrolidinone ring structures adjacent on the main chain is formed is formed. Each pyrrolidinone ring structure is a structure represented by Formula (1) in which R ² is a —COOR ⁵ group and R ³ is a —NHCOR ⁴ group. In the formula (12), a cyclization reaction (bonding a broken line portion in the molecular structure on the left side and R ⁵ OH between the left and center vinyl monomers C adjacent to each other and between the vinyl monomers C adjacent to the center and right ends. (Desorption reaction) is in progress. As can be understood from this, a polymer which is a homopolymer having only a constitutional unit composed of a pyrrolidinone ring structure represented by formula (1) by advancing a cyclization condensation reaction between all adjacent vinyl monomers C It is also possible to form (A). Further, in the precursor polymer (B) which is a copolymer of vinyl monomers A and B, depending on the type of vinyl monomer B, a pyrrolidinone ring may be formed by a cyclization reaction in a region where the structural units derived from monomer B are continuous. A spiro ring structure of the structure can be formed.

  The polymer (A) in which the spiro ring structure is formed, particularly the polymer (A) that is the homopolymer, is expected to have particularly remarkable characteristics based on the pyrrolidinone ring structure. The characteristic is, for example, a very high Tg. Such a polymer (A) having a very high Tg is expected to be used for applications requiring extremely high heat resistance.

  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 be a copolymer of two or more amide acrylate esters.

  When the precursor polymer (B) is a copolymer formed by polymerization of a monomer group including a vinyl monomer A and a vinyl monomer B, the monomer group may further include a vinyl monomer C. Good. When the precursor polymer (B) is a polymer formed by polymerization of a monomer group including a vinyl monomer C, the monomer group further includes a vinyl monomer A and / or a vinyl monomer B. Also good.

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

(Formation of precursor polymer (B))
The formation method of a precursor polymer (B) is not specifically limited. A 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 a monomer group including the monomer may be polymerized. The monomer group may contain monomers other than the monomer essential for the formation of the polymer (B) as necessary. The monomer is, for example, a monomer that becomes the structural unit Q by polymerization.

  The monomer group includes, for example, a vinyl monomer A having an ester group and / or a carboxyl group and a vinyl monomer B having an amide group. The monomer group includes, for example, a vinyl monomer C having an ester group and / or a carboxyl group and an amide group. Examples of vinyl monomer A are (meth) acrylic acid esters and (meth) acrylic acid, and examples of vinyl monomers B and C are amidoacrylic acid esters.

  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. 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-containing hydrocarbons; alcohols such as methanol and ethanol; water, dimethyl sulfoxide (DMSO), and tetrahydrofuran.

  In the polymerization of the precursor polymer (B), a polymerization initiator, a chain transfer agent, and the like can be used as necessary. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amyl peroxide. 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 is not particularly limited as long as it is appropriately set according to the combination of monomers included in the monomer group or the polymerization conditions.

  The polymerization conditions such as the polymerization temperature can be appropriately set.

  When there is a polymerization rate difference between the monomers contained in the monomer group, the monomer in the precursor polymer (B) formed by polymerization is compared with the content of each monomer contained in the monomer group subjected to polymerization. About the content rate of each structural unit derived from, there exists a tendency for the content rate of the structural unit derived from the monomer with a high polymerization rate to become relatively large. Therefore, a precursor polymer (B) which is a copolymer, and a polymer (B) having a desired value for the content and / or content ratio of each constituent unit constituting the polymer (B). In order to obtain, pay attention to the content of each monomer in the monomer group to be polymerized, or control the polymerization method (for example, supply a part or all of the monomer having a high polymerization rate to the polymerization system dropwise) And the content rate of each structural unit in the formed precursor polymer (B) can be adjusted suitably.

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

  When the cyclization reaction proceeds by heating the precursor polymer (B), the heating temperature is, for example, 70 ° C. or higher, preferably 100 ° C. or higher, and more preferably in the order of 150 ° C. or higher, 200 ° C. or higher. The heating of the precursor polymer (B) can be carried out in any state such as a state where the precursor polymer (B) is in a solid state or a state where the precursor polymer (B) is dissolved in a solvent. In the case of heating in a solid state, it is preferable to use a precursor polymer (B) having a large surface area such as powder and particles for the rapid progress of the cyclization reaction. Further, in order to rapidly advance the cyclization reaction by removing the alcohol or water generated by the cyclization reaction described in the right side of the formulas (5), (8), (11), and (12) Heating under reduced pressure is preferred. The degree of decompression is, for example, 26.6 kPa or less in absolute pressure. That is, you may advance a cyclization reaction by heating a precursor polymer (B) under the pressure of 26.6 kPa or less. The degree of decompression is preferably 13.3 kPa or less, and more preferably 2.7 kPa or less.

  When the cyclization reaction proceeds, a catalyst that promotes the reaction may be used as 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. Kinds 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) containing the polymer (A) or the resin molded product is used for an application in which transparency is regarded as important, the catalyst is used for the transparency. It is preferable to use it in a range that does not decrease and does not cause adverse effects such as coloring.

  The acid is not limited, and examples thereof include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, phosphorous acid, phenylphosphonic acid, organic carboxylic acid, and phosphate ester. The base is not limited, and examples thereof include metal hydroxides, amines, imines, alkali metal derivatives, alkoxides, and ammonium hydroxide salts. The salt of an acid and a base is not limited, For example, they are a metal carboxylate and a metal carbonate. The metal carboxylate or metal carbonate does not impair the properties of the polymer (A), resin composition (C) or resin molded product formed, and does not cause environmental pollution when discarded. Without limitation, for example, alkali metals such as lithium, sodium and potassium; alkaline earth metals such as magnesium, calcium, strontium and barium; zinc; zirconium; copper; The carboxylic acid constituting the metal carboxylate is not limited. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, octylic acid, nonanoic acid, decanoic acid, lauric acid, myristic Acid, palmitic acid, stearic acid, behenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid and adipic acid. A metal complex is not limited, For example, the example of the organic component is acetylacetone. The metal oxide is not limited, and examples thereof include zinc oxide, calcium oxide, and 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 monomer group containing a vinyl monomer, and has an ester group and / or a carboxyl group. 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) includes, for example, a copolymer formed by polymerization of a monomer group including 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. Further, the precursor polymer (B) can be a polymer formed by polymerization of a monomer group including a vinyl monomer C having an ester group and / or a carboxyl group and an amide group. It can also be a homopolymer. Examples of vinyl monomers A, B and C 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, and is an amorphous thermoplastic resin composition. The resin composition (C) can contain two or more polymers (A).

  The resin composition (C) exhibits various characteristics derived from the polymer (A). The characteristic is, for example, a thermal characteristic or an optical characteristic. The thermal characteristic is, for example, Tg, and the Tg of the resin composition (C) is high due to the polymer (A). The Tg of the resin composition (C) is, for example, 110 ° C. or higher, and can take values of 120 ° C. or higher, 140 ° C. or higher, and 160 ° C. or higher depending on the type and content of the polymer (A).

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

  The resin composition (C) may have various other characteristics derived from the polymer (A). Based on these characteristics, the resin composition (C) can be used for applications similar to those for the polymer (A) described above, including optical members.

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

  Examples of the other polymer include olefin polymers such as polyethylene, polypropylene, ethylene-propylene polymer, and poly (4-methyl-1-pentene); halogen-containing polymers such as vinyl chloride and chlorinated vinyl resins. Acrylic polymers such as polymethyl methacrylate; polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamides such as nylon 6, nylon 66 and nylon 610; polyacetals; polycarbonates; polyphenylene oxides; polyphenylene sulfides; Ketone; Polysulfone; Polyethersulfone; Polyoxypentylene; Polyamideimide; Rubbery polymer. The resin composition (C) can 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 a polymer.

  Resin composition (C) can contain materials other than a polymer, for example, an additive. Additives include, for example, antioxidants, light stabilizers, weather stabilizers, heat stabilizers and other stabilizers; phase difference adjusting agents such as phase difference increasing agents, phase difference reducing agents, phase difference stabilizers; glass fibers, Reinforcing materials such as carbon fibers; UV absorbers; near infrared absorbers; flame retardants such as tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide; antistatic agents including anionic, cationic, and nonionic surfactants Agents; colorants such as inorganic pigments, organic pigments, dyes; organic fillers, inorganic fillers, resin modifiers, plasticizers, 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, and further preferably 1% by mass or less.

  The formation method of a resin composition (C) is not specifically limited. If it is a resin composition (C) comprising the polymer (A), the polymer (A) may be used as it is as the resin composition (C), and the resin composition (C) In the case of containing an additive, the polymer (A) can be formed by mixing the other polymer and / or additive with a known mixing method. Mixing can be carried out, for example, by pre-blending with a mixer such as an omni mixer and then kneading the resulting mixture. A kneading machine is not specifically limited, For example, well-known kneading machines, such as extruders, such as a single screw extruder and a twin screw extruder, and a pressure kneader, can be used.

[Resin molding]
The resin molding of this invention is comprised from the thermoplastic resin composition (C) containing a polymer (A). The use of the resin molding is not limited, and can be selected according to the properties obtained from the polymer (A) and other polymers and / or additives contained in the resin composition (C). The resin molding of this invention is an optical member used for an optical use, for example.

  The optical member is, for example, a lens, a prism, an optical fiber, or an optical film. Optical films include, for example, protective films for substrates of various optical disks (VD, CD, DVD, MD, LD, etc.), retardation films and polarizer protective films provided in image display devices such as liquid crystal display devices (LCD), and A viewing angle compensation film, a light diffusion film, a reflection film, an antireflection film, an antiglare film, a brightness enhancement film, and a conductive film for a touch panel.

  The resin molding of the present invention can have heat resistance derived from the high Tg of the polymer (A). For this reason, the freedom degree of the use of the resin molding of this invention is high, and various effects are acquired by use of the resin molding of this invention. For example, the degree of freedom in designing an image display device such as an LCD is improved by using the resin molding of the present invention which is an optical film.

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

  The resin molded product of the present invention may have a low haze on the surface. For example, it is possible to obtain a resin molded body having a haze of 5% or less, 3% or less, and further 2% or less, typically a film, as a haze determined in accordance with the provisions of JIS K7136. .

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

  The resin molding of the present invention can be combined with other members. For example, you may combine the resin molding of this invention which is an optical film with another optical member.

  Various functional coating layers may be formed on the surface of the resin molded body of the present invention as necessary. Functional coating layers include, for example, antistatic layers, adhesive layers, adhesive layers, easy adhesion layers, antiglare (non-glare) layers, antifouling layers such as photocatalyst layers, antireflection layers, hard coat layers, and UV shielding layers. A layer, a heat ray shielding layer, an electromagnetic wave shielding layer, and a gas barrier layer.

  The other use of the resin molding of this invention is a use similar to the use of the polymer (A) mentioned above, for example.

  The formation method of the resin molding of this invention is not specifically limited. The resin composition (C) of the present invention can be formed by molding the resin composition (C) by a known molding method such as a melt extrusion method, a casting method, or a press molding method. As needed, you may combine a shaping | molding method and other well-known methods, for example, the extending | stretching method. In order to obtain a retardation film, it is necessary to stretch a film (original film) obtained by molding a resin composition.

  A product provided with the resin molding of the present invention is not particularly limited, and is, for example, an image display device. An image display apparatus is equipped with the resin molding of this invention which is an optical film, for example. The image display device is not particularly limited. For example, reflective, transmissive, and transflective LCDs; TN, STN, OCB, HAN, VA, IPS, and other driving LCDs; electro A luminescence (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 AcAAM are abbreviations for methyl methacrylate and methyl 2-acetamidoacrylate, respectively.

  Initially, the evaluation method of the polymer produced in the present Example is shown.

[Structural unit structure]
The molecular structure of the structural unit of the produced polymer was evaluated by infrared spectroscopic analysis (IR), ¹ H-nuclear magnetic resonance (NMR), and ¹³ C-NMR. The IR evaluation was carried out 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 . Evaluation of ¹ H-NMR was carried out using a nuclear magnetic resonance spectrometer (manufactured by BRUKER, AV300M). Deuterated chloroform (manufactured by Wako Pure Chemical Industries) was used as a measurement solvent. ¹³ C-NMR was evaluated using a nuclear magnetic resonance spectrometer (manufactured by BRUKER, AVANCE III). Heavy dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a measurement solvent.

[Content of constituent unit in polymer]
The content of AcAAM units in the prepared precursor polymer was calculated from the amount of unreacted monomer 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 JIS K7121 regulations. Specifically, it is obtained by using a differential scanning calorimeter (manufactured by Rigaku, DSC-8230) by heating a sample of about 10 mg from room temperature to 300 ° C. (heating rate 20 ° C./min) in a nitrogen gas atmosphere. The DSC curve was evaluated by the starting point method. Α-alumina was used as a reference.

[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 hot pressing at 210 ° C. to obtain an unstretched film (thickness 190 μm) of the polymer. Next, the produced unstretched film was cut out with a size of 20 mm × 60 mm to obtain a test piece for Cr evaluation. Next, on one short side of the test piece, a weight having a weight that applies a stress of 1 N / mm ² or less is selected and attached to the test piece at the time of stretching, and then the temperature is kept constant at Tg + 20 ° C. It was accommodated in a machine (manufactured by ASONE, DOV-450A) and left for 1 hour. When the test piece is stored in a constant temperature dryer, the other short side of the test piece is fixed with a chuck, and the test piece is uniaxially free in the long side direction (vertical direction) due to the stress applied to the test piece by the weight. It was made to extend | stretch. Moreover, when accommodating, the distance between the chuck and the weight in 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 cool slowly in the dryer. When the temperature in the oven reaches Tg-40 ° C. of the polymer, the test piece (uniaxially stretched film) is taken out, and the thickness of the taken out test piece and the in-plane retardation Re for light with a wavelength of 590 nm are 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 weight load was obtained, and the stress σ (Pa) applied to the film was calculated from the cross-sectional area and the weight load. While changing the weight of the weight, Δn and σ were obtained for each load, the slope of Δn with respect to the obtained σ was obtained by the least square 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 near 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 near 90 ° with respect to the stretching direction, the sign of the stress optical coefficient Cr is 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 (manufactured by Oji Scientific Instruments, KOBRA-WR). The in-plane phase difference Re is the refractive index nx in the slow axis direction (direction showing the maximum refractive index in the film plane) in the test piece (film) plane, and the fast axis direction (slow axis direction in the same plane). 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)
14.90 parts by mass of AcAAM, 84.75 parts by mass of chloroform and 0.068 parts by mass of azobisisobutyronitrile (AIBN) were 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 60 ° C. for 10 hours to proceed the solution polymerization of AcAAM. Next, after the formed polymerization solution is put into excess methyl ethyl ketone and reprecipitated, the obtained precipitate is vacuum-dried at a pressure of 0.13 kPa and a temperature of 60 ° C. for 1 hour or more to remove volatile components. Removal of the solid polymer (1-1) as a precursor polymer was obtained. The Tg of the polymer (1-1) was 198 ° C. The polymer (1-1) is a homopolymer of AcAAM.

  Next, the polymer (1-1) was heated for 1 hour under the conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. to obtain a solid polymer (1-2). The Tg of the polymer (1-2) could not be evaluated at the above measurement temperature up to 300 ° C, and is considered to exceed 300 ° C.

  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 heating at 240 ° C. The vertical axis in FIG. 1 indicates “absorption”, but the baselines of the spectra are offset from each other in order to make the comparison of the three spectra including the difference spectrum easier. No specific numerical value is shown on the vertical axis of. The same applies to the subsequent FIG.

As shown in FIG. 1, an absorption peak (wave number 1704 cm ⁻¹ ) attributed to the stretching vibration of the carbonyl group of the pyrrolidinone ring structure is confirmed in the difference spectrum, and the polymer (1-2) is heated by the above heating at 240 ° C. ) Formed a pyrrolidinone ring structure.

The ¹ H-NMR evaluation results of the polymers (1-1) and (1-2) are shown in FIGS. As shown in FIG. 2, in the NMR spectrum of the polymer (1-1), the peak attributable to the acetamido group of the AcAAM unit is from 1.89 to 1.96 ppm, and the peak attributable to the methyl ester structure is 3. A peak attributed to the secondary amide structure was confirmed at 6.65 ppm at 61-3.69 ppm, respectively. On the other hand, in the NMR spectrum of the polymer (1-2), the peak attributed to the secondary amide structure of the AcAAM unit disappeared, and the large peak attributed to the acetylamide group constituting the ring structure was 2.54 ppm. Newly confirmed. 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, It was confirmed that the pyrrolidinone ring structure represented by the formula (1) was formed by the above heating.

Separately from this, the cyclization rate of the polymer (1-2) was determined from ¹³ C-NMR measurement by a decoupling method with a reverse gate. Assignment of each peak in the ¹³ C-NMR profile was performed by edited-HSQC. The cyclization rate of the polymer (1-2) was determined from the integrated value of the peak attributed to the quaternary carbon in the main chain structure and the integrated value of the peak attributed to the primary carbon of the methoxy group. When the cyclization reaction does not proceed, the integrated value of the peak attributed to the quaternary carbon in the main chain structure is the same as the integrated value of the peak attributed to the primary carbon of the methoxy group from the monomer structure. It is assumed that As the cyclization reaction proceeds, it is assumed that the peak integrated value of the methoxy group decreases due to the demethanol reaction, while the peak integrated value of the quaternary carbon in the main chain structure does not change. That is, after the cyclization reaction, the ratio between the peak integration value of the methoxy group and the peak integration value of the quaternary carbon in the main chain structure indicates the ratio of the residual methoxy group, It means to show an unreacted rate. The unreacted rate (uncyclized rate) of the polymer (1-2) thus determined was 26%, that is, the cyclized rate was 74%. Since the cyclization rate is 50% or more, it is assumed that a spiro ring structure in which two or more pyrrolidinone ring structures are continuous is formed in the polymer (1-2).

(Example 2)
1.07 parts by mass of AcAAM and 14.15 parts by mass of MMA, 84.75 parts by mass of chloroform and 0.032 parts by mass of AIBN were 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 60 ° C. for 10 hours to allow solution polymerization of AcAAM and MMA to proceed. Next, after the formed polymerization solution is poured into excess isopropyl alcohol for reprecipitation, the obtained precipitate is vacuum-dried for 1 hour or more under the conditions of a pressure of 0.13 kPa and a temperature of 60 ° C. The solid polymer (2-1) which is a precursor polymer was obtained. Tg of the polymer (2-1) was 129 ° C., and the content of AcAAM units in the polymer (2-1) was 41.7% by mass. The polymer (2-1) is a copolymer of AcAAM and MMA.

  Next, the polymer (2-1) was heated for 1 hour under conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. to obtain a solid polymer (2-2). Tg of the polymer (2-2) was 148 ° C.

(Example 3)
2.10 parts by mass of AcAAM and 13.10 parts by mass of MMA, 84.75 parts by mass of chloroform and 0.032 parts by mass of AIBN were placed in a reaction vessel, and the inside of the vessel was replaced with nitrogen. Next, the sealed container was heated in an oil bath at 60 ° C. for 10 hours to proceed solution polymerization of AcAAM and MMA. Next, after the formed polymerization solution is poured into excess isopropyl alcohol for reprecipitation, the obtained precipitate is vacuum-dried for 1 hour or more under the conditions of a pressure of 0.13 kPa and a temperature of 60 ° C. Was removed to obtain a solid polymer (3-1) as a precursor. Tg of the polymer (3-1) was 138 ° C., and the content of AcAAM units in the polymer (3-1) was 54.8% by mass. The polymer (3-1) is a copolymer of AcAAM and MMA.

  Next, the polymer (3-1) was heated for 1 hour under the conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. to obtain a solid polymer (3-2). Tg of the polymer (3-2) was 171 ° C.

  The IR evaluation results of the polymers (3-1) and (3-2) are shown in FIG. In FIG. 4, in addition to the IR spectra of the polymers (3-1) and (3-2), the difference obtained by subtracting the IR spectrum of the polymer (3-1) from the IR spectrum of the polymer (3-2) is shown. Also shown. The absorption peak appearing in the difference spectrum corresponds to the molecular structure of the polymer (3-2) formed by the heating at 240 ° C.

As shown in FIG. 4, an absorption peak (wave number 1704 cm ⁻¹ ) attributed to the stretching vibration of the carbonyl group of the pyrrolidinone ring structure was confirmed in the difference spectrum, and the polymer (3-2) was obtained by the above heating at 240 ° C. ) Formed a pyrrolidinone ring structure.

The ¹ H-NMR evaluation results of the polymers (3-1) and (3-2) are shown in FIGS. As shown in FIG. 5, in the NMR spectrum of the polymer (3-1), the peak attributed to the acetamido group of the AcAAM unit is 1.84 to 1.90 ppm, and the peak attributed to the methyl ester structure is 3. A peak attributed to the secondary amide structure was confirmed at 58-3.69 ppm at 6.32 ppm, respectively. On the other hand, in the NMR spectrum of the polymer (3-2), the peak attributed to the secondary amide structure of the AcAAM unit disappeared and the large peak attributed to the acetylamide group constituting the ring structure was 2.49 ppm. Newly confirmed. That is, the polymer (3-1) does not have the pyrrolidinone ring structure represented by the formula (1), but the polymer (3-2) has the pyrrolidinone ring structure represented by the formula (1) in the main chain, It was confirmed that the pyrrolidinone ring structure represented by the formula (1) was formed by the above heating.

Cr of the polymer (3-2) was + 65 × 10 ⁻¹¹ Pa ⁻¹ and the polymer (3-2) had positive intrinsic birefringence. And, when this Cr value is positive, judging from the specific molecular structure of the pyrrolidinone ring structure formed by the cyclization reaction between the MMA unit and the AcAAM unit, the ring structure is a polymer (3-2). ) In the main chain.

Example 4
3.07 parts by mass of AcAAM and 12.16 parts by mass of MMA, 84.75 parts by mass of chloroform and 0.032 parts by mass of AIBN were added to the reaction vessel, and the inside of the vessel was purged with nitrogen. Next, the container was heated with an oil bath at 60 ° C. for 10 hours to proceed the container polymerization of AcAAM and MMA. Next, after the formed polymerization solution is poured into excess isopropyl alcohol for reprecipitation, the obtained precipitate is vacuum-dried for 1 hour or more under the conditions of a pressure of 0.13 kPa and a temperature of 60 ° C. Then, a solid polymer (4-1) as a precursor was obtained. Tg of the polymer (4-1) was 159 ° C., and the content of AcAAM units in the polymer (4-1) was 81.7% by mass. The polymer (4-1) is a copolymer of AcAAM and MMA.

  Next, the polymer (4-1) was heated for 1 hour under the conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. to obtain a solid polymer (4-2). Tg of the polymer (4-2) was 179 ° C.

(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 .

  Table 1 below summarizes the composition of the precursor polymer prepared in each example, and the Tg of the precursor polymer and the polymer.

  The novel polymer of this invention can be used for the use of an optical member, for example. The optical member is, for example, a lens, a prism, an optical fiber, or an optical film.

Claims (19)

  A novel polymer having a pyrrolidinone ring structure in the main chain.   The novel polymer of Claim 1 which has further at least 1 sort (s) chosen from a (meth) acrylic acid ester unit and a (meth) acrylic acid unit as a structural unit.   A novel polymer formed by cyclization of a precursor polymer formed by polymerization of a monomer group containing a vinyl monomer and having an ester group and / or a carboxyl group and an amide group as side chains. The precursor polymer is
A copolymer formed by polymerization of a monomer group including a vinyl monomer A having an ester group and / or a carboxyl group and a vinyl monomer B having an amide group, or an ester group and / or a carboxyl group and an amide group The novel polymer according to claim 3, which is a polymer formed by polymerization of a monomer group containing vinyl monomer C having:   The novel polymer according to claim 4, wherein the vinyl monomer A is at least one selected from (meth) acrylic acid esters and (meth) acrylic acid.   The novel polymer according to claim 4, wherein the precursor polymer is a homopolymer of the vinyl monomer C. The novel polymer in any one of Claims 1-6 which has the pyrrolidinone ring structure shown in the following formula | equation (1) in a principal chain.

In Formula (1), R ¹ is a hydrogen atom or a —COR ⁴ group, 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 3 to 18 carbon atoms. Of the cycloalkyl group. R ² is a hydrogen atom or a —COOR ⁵ group, and R ⁵ 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 ³ is a hydrogen atom, a methyl group or a —NHCOR ⁶ group, and R ⁶ 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 a group.
The pyrrolidinone ring structure represented by the formula (1) may be continuous on the main chain. In this case, the ring structures adjacent to each other are the carbon atom at the 3-position of one of the ring structures and the other ring structure. A spiro ring structure in which the 5-position carbon atom is the same carbon atom, and R ³ bonded to the ^3- position carbon atom and R ² bonded to the 5-position carbon atom do not exist. The novel polymer in any one of Claims 1-7 which has the unit X shown in the following formula | equation (2) as a structural unit.

In the formula (2), R ³ is a hydrogen atom, a methyl group or a —NHCOR ⁶ group, and R ⁶ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a carbon number 3 to 18 cycloalkyl groups. R ⁴ and R ⁵ are each independently 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. In the formula (2), R ³ is a —NHCOR ⁶ group, and R ⁴ , R ⁵ and R ⁶ are independently of each other a methyl group, a linear alkyl group having 2 to 18 carbon atoms, or a carbon number 3 to 3 The novel polymer according to claim 8 which is 18 cycloalkyl groups.   Glass transition temperature is 110 degreeC or more, The novel polymer in any one of Claims 1-9. In the infrared absorption spectrum, the range of wave number 1690 cm ^-1 or 1710 cm ^-1, according to any one of claims 1 to 10 absorption peak attributed to the stretching vibration of the carbonyl group of pyrrolidinone ring structure is observed novel Polymer. When the novel polymer is heated at 200 ° C. or higher,
In the difference of the infrared absorption spectrum before and after heating, novel polymer according to any one of claims 1 to 11 absorption peak in the range of less wave numbers 1690 cm ^-1 or 1710 cm ^-1 is observed.   The content of residual alcohol is 10-3000 ppm, The novel polymer in any one of Claims 1-12.   The resin composition containing the novel polymer in any one of Claims 1-13.   The resin molding comprised from the resin composition of Claim 14.   The resin molded body according to claim 15, which is an optical member.   A precursor polymer formed by polymerization of a monomer group including a vinyl monomer, wherein the precursor polymer having an ester group and / or a carboxyl group and an amide group as side chains is cyclized to form a pyrrolidinone ring in the main chain. A method for producing a novel polymer, which obtains a novel polymer having a structure. The precursor polymer is
A copolymer formed by polymerization of a monomer group including a vinyl monomer A having an ester group and / or a carboxyl group and a vinyl monomer B having an amide group, or
The method for producing a novel polymer according to claim 17, which is a polymer formed by polymerization of a monomer group containing a vinyl monomer C having an ester group and / or a carboxyl group and an amide group.   The method for producing a novel polymer according to claim 17 or 18, wherein the cyclization of the precursor polymer proceeds by heating the precursor polymer.

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