JP2020132719A - Nano cellulose-containing resin composition and production method - Google Patents

Abstract

To provide a novel composition capable of forming an optical film or the like.SOLUTION: A resin composition is composed of a nano cellulose and a polymer. When measured using a quartz cell with an optical path length of 10 mm in accordance with JIS Z 8729, YI is 1.7 or less.SELECTED DRAWING: None

Description

The present invention relates to a resin composition containing nanocellulose, a production method, and the like.

Although the transparent resin material has excellent workability, it has a lower elastic modulus and hardness than inorganic glass, and has a drawback that it is easily damaged when used on the outermost surface of a display or the like. It is possible to improve the surface hardness by the hard coating technology, and the transparent resin is required to have a high elastic modulus.

Further, nanocellulose such as cellulose nanofiber (CNF) is known, but it is usually composed of nano-sized fine microfibrils and is a material expected to be used in various applications.

For example, in Patent Document 1, an ethylenically unsaturated monomer is emulsion-polymerized in an aqueous dispersion of cellulose nanofibers to form a composite containing a copolymer composed of cellulose nanofibers and an ethylenically unsaturated monomer. The manufacturing technology is disclosed.

Further, Patent Document 2 discloses an optical film containing a thermoplastic acrylic resin, a cellulose ester resin, and cellulose nanofibers having an average fiber diameter of 4 to 200 nm.

JP-A-2016-155897 Japanese Unexamined Patent Publication No. 2010-197680

An object of the present invention is to provide a novel composition (resin composition) containing nanocellulose and a production method.

Under these circumstances, the present inventor can obtain a resin composition (composite material) having an improved elastic modulus suitable for optical applications by polymerizing a monomer in an organic solvent in the presence of nanocellulose. Was found, and further diligent studies were carried out to complete the present invention.

That is, the method for producing a resin composition of the present invention is characterized in that a monomer is polymerized in an organic solvent in the presence of nanocellulose.

Further, the resin composition of the present invention is a resin composition composed of nanocellulose and a polymer, and has a YI of 1.7 or less measured using a quartz cell having an optical path length of 10 mm in accordance with JIS Z 8729. It is characterized by being a certain resin composition.

INDUSTRIAL APPLICABILITY The present invention can provide a nanocellulose-containing composition (resin composition) having improved elastic modulus and suppressed coloring.

Further, by forming a solution film of such a composition, a highly transparent and low-colored film preferable for use in an optical film can be obtained.

<Composition>
The composition (resin composition) of the present invention is a resin composition containing nanocellulose and a polymer.

As used herein, the term "resin" refers to a broader concept than polymers. The resin may contain one kind or two or more kinds of polymers, and may further contain a material other than the polymer, if necessary.
-Nanocellulose The composition of the present invention contains nanocellulose.

Nanocellulose can be said to be a nano-sized (nano-level) cellulosic material.

Examples of such nanocellulose include cellulose nanofibers (CNF), cellulose nanocrystals (CNC) (or cellulose nanowhiskers (CNW)). As the nanocellulose, cellulose nanofibers are preferable. By using cellulose nanofibers, the elastic modulus of the obtained film is improved, and by forming a solution film, it is possible to obtain a highly transparent and low-colored film preferable for use in an optical film.

Nanocellulose may be used alone or in combination of two or more.

Nanocellulose can be classified according to the raw material, the manufacturing method, and the like.

For example, CNF may be made from plant-derived cellulose microfibrils (or constituent fibers thereof), and may be made of bacterial cellulose (BC) (bacterial nanofiber (bacterial CNF)) or lignocellulose nanofiber (LCNF). ), CNF obtained by electrospinning method and the like are also included.

BC is a CNF produced by microorganisms (CNF derived from bacteria), and is usually different from cellulose derived from plants in purity and structure (diameter and network structure).

LCNF is a CNF (lignin-coated CNF) containing lignin.

The CNF obtained by the electrospinning method (electrospinning method) is a CNF obtained by spinning a solution of a cellulosic material while applying a voltage. Since the solution is used in this method, nanofibers of cellulose derivatives (such as the above-exemplified derivatives such as cellulose acetate) can also be obtained.

Nanocellulose (CNF, etc.) may be modified (modified, modified). The mode of modification can be selected according to the purpose, and examples thereof include hydrophobization and introduction of functional groups. Specific modifications include acid modification [eg, carboxylation (carboxymethylation, etc.), phosphorylation, sulfuric acid or sulfonation, etc.], ester or acylation modification (acetylation, etc.), amine modification, amide modification, epoxy modification, etc. Examples include fluorene modification. The acid group and amine group may form a salt. Of these, nanocellulose that has been hydrophobized is preferable. By using nanocellulose that has been hydrophobized, the elastic modulus of the obtained film is improved, and by forming a solution, it is possible to obtain a highly transparent, low-colored film that is preferable for use in optical films. It becomes.

The modification method can be appropriately selected depending on the mode of modification and the like, and is not particularly limited. For example, the hydroxyl group of cellulose (skeleton) may be used for modification (for example, reaction with a halogenated carboxylic acid).

In the present invention, among the nanocellulose, CNF may be preferably used. Therefore, nanocellulose may contain at least CNF.

The diameter (fiber diameter) of the nanocellulose can be selected according to the type and the like, and is not particularly limited, but the average diameter (average fiber diameter) is, for example, 1 to 800 nm, 2 to 500 nm, 3 to 300 nm, and 4 to 200 nm. It may be 4 to 100 nm, 10 to 50 nm, or the like. The average fiber diameter of nanocellulose is preferably 20 nm or less. By using such nanocellulose, the elastic modulus of the obtained film is improved, and by forming a solution film, it is possible to obtain a highly transparent and low-colored film preferable for use in an optical film.

The length of the nanocellulose can also be selected according to the type and the like, and is not particularly limited. For example, the length (fiber length) of CNF may be an average fiber length of 100 nm or more, 300 nm or more, 500 nm or more, 1000 nm or more, 3000 nm or more, 5000 nm or more, and the like.

The average length of the CNC may be, for example, 5 nm or more, 10 nm or more, 50 nm or more, 100 nm or more (for example, 100 to 500 nm).

The diameter and length can be measured by a conventional method, for example, a microscope (electron microscope or the like).

Nanocellulose may have a crystalline region. In nanocellulose having a crystal region, the ratio of the crystal region may be, for example, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more.

Further, in nanocellulose (nanocellulose having a crystalline region), the proportion of the amorphous region may be, for example, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, and the like. % Or more, 3% or more, 5% or more, and the like.

The crystalline / amorphous region can be observed / measured by a conventional method, for example, X-ray diffraction, structural analysis (structural analysis by an electron microscope or NMR), or the like.

As the nanocellulose, a commercially available product may be used, or one synthesized by a conventional method may be used.
-Polymer The resin composition of the present invention contains nanocellulose and a polymer. The polymer can be appropriately selected according to desired physical properties and the like, and is not particularly limited, and may be a thermoplastic resin, a curable resin, or a combination thereof. Examples of the polymer include (meth) acrylic polymers, olefin-based polymers (for example, polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene), etc.), halogen-based polymers. (For example, vinyl halide-based polymers such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl chloride), styrene-based polymers [for example, polystyrene, styrene-based copolymers (eg, styrene-methyl methacrylate copolymer, for example, Aromas of styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene block copolymers, acrylate-styrene-acrylonitrile copolymers, etc.], polyester polymers (eg, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. Group polyester), polyamide-based polymers (for example, aliphatic polyamide-based polymers such as polyamide 6, polyamide 66, polyamide 610), polyacetal-based polymers, polycarbonate-based polymers, polyphenylene oxide-based polymers, polyphenylene sulfide-based polymers. , Polyether ether ketone polymer, polysulfone polymer, polyethersulfone polymer, rubber polymer [for example, styrene polymer containing rubber (polybutadiene rubber, acrylic rubber, etc.), cellulose weight As the coalescence (cellulose derivative), cellulose ester [for example, cellulose acetate (cellulose diacetate, cellulose triacetate), cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acylate such as cellulose acetate butyrate], Cellulosic ethers [eg, alkyl celluloses (eg, methyl cellulose, ethyl cellulose, etc.), hydroxyalkyl celluloses (eg, hydroxyethyl cellulose, hydroxyalkyl cellulose, etc.), carboxyalkyl celluloses (eg, carboxymethyl cellulose, etc.)], cyanoethyl cellulose, and the like. .. The polymer may be used alone or in combination of two or more.

The polymer preferably contains a (meth) acrylic polymer. With such a composition, the elastic modulus of the film obtained by using it is improved, and by forming a solution film, it becomes possible to obtain a highly transparent and low-colored film preferable for use in an optical film. The polymer preferably contains a (meth) acrylic polymer, but may also contain other resins (resins that do not belong to the category of (meth) acrylic polymers), if necessary.

The content ratio of the (meth) acrylic polymer in the polymer is not particularly limited, and is, for example, more than 90% by mass. For example, it may be 91% by mass or more (for example, 92% by mass or more), preferably 93% by mass or more (for example, 94% by mass or more), and more preferably 95% by mass or more (for example, 96% by mass or more). , 97% by mass or more (for example, 98% by mass or more), 99% by mass or more (for example, 99.5% by mass or more), 99.9% by mass or more (for example, 99.99% by mass or more). .. The more (meth) acrylic polymer, the more the characteristics of acrylic having a ring structure (heat resistance, hardness (strength), solvent resistance, surface hardness, optical characteristics, dimensional stability, shape stability, etc.) are exhibited. It is preferable because it is easy.

When the polymer contains a polymer other than the (meth) acrylic polymer, the content ratio of the other polymer efficiently determines the characteristics of acrylic (optical characteristics such as transparency, hardness, etc.) in the polymer, for example. From the viewpoint of expression, it can be selected from the range of less than 10% by mass (for example, 0.01% by mass or more and less than 10% by mass), and is preferably 8% by mass or less (for example, 0.1% by mass or more and less than 8% by mass). May be 6% by mass or less (for example, 0.1% by mass or more and less than 6% by mass), 5% by mass or less (for example, 0.5 to 5% by mass), and 3% by mass or less (for example, 1 to 1% by mass). 3% by mass), 2% by mass or less, 1% by mass or less, and the like. The lower limit may be 0.01% by mass or more, preferably 0.1% by mass or more. Even when other polymers are contained, the proportion of other polymers (particularly other non-acrylic resins) is preferably small.

On the other hand, from the viewpoint of phase difference expression when used as an optical film, the other polymer is preferably a styrene-based copolymer, and the content ratio of the styrene-based copolymer in the polymer is 1% by mass or more and 50% by mass. Less than, preferably 10% by mass or more and less than 50% by mass, and more preferably 20% by mass or more and less than 40% by mass when used as a retardation film. The content ratio of the (meth) acrylic polymer when used as a retardation film is preferably 50% by mass or more and 90% by mass or less, and more preferably 60% by mass or more and less than 80% by mass in the polymer.

From the viewpoint of imparting strength when used as a molded product or film, the other polymer is preferably a rubber polymer, and the content ratio of the rubber polymer in the polymer is preferably 1% by mass or more, preferably 3% by mass or more. More preferably, it may be 5% by mass or more, 10% by mass or more, and the like. The upper limit of the rubbery polymer in the polymer is preferably less than 30% by mass, and may be less than 25% by mass and less than 20% by mass. The content ratio of the (meth) acrylic polymer in the polymer at that time is preferably 70% by mass or more, preferably 75% by mass or more, 80% by mass or more, 99% by mass or less, 97% by mass or less, 95. It may be 90% by mass or less and 90% by mass or less.

The polymer preferably contains a polymer having a ring structure in the main chain. By containing a polymer having a ring structure in the main chain, it is possible to obtain a composition or film having higher heat resistance and elastic modulus while maintaining transparency.

The content ratio of the ring structure can be selected according to the intended use, desired physical properties, etc., and is not particularly limited, but is, for example, from a range of about 0.1% by mass or more (for example, 0.5% by mass or more) in the polymer. It can be selected, and may be 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, and the like. It is particularly preferable that the polymer is a polymer having a ring structure of 1% by mass or more. Such a polymer can be used as a composition or film having higher heat resistance and elastic modulus while maintaining transparency.

The content ratio of the ring structure (or its upper limit) is not particularly limited, and is, for example, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 55 in the (meth) acrylic polymer. It may be mass% or less, 50 mass% or less, 45 mass% or less, 40 mass% or less, 35 mass% or less, and the like.

When the content ratio of the ring structure is large, it is preferable in terms of heat resistance, solvent resistance, elastic modulus, surface hardness, dimensional stability and the like.

On the other hand, if the content ratio of the ring structure becomes too large, it may become brittle, decrease in transparency, increase the absolute value of the photoelastic coefficient, and the like.

From such a viewpoint, the ring structure may have an appropriate content ratio that is neither too small nor too large.

The weight average molecular weight (Mw) of the polymer is not particularly limited, but is, for example, 10,000 or more (for example, 10000-1000000), preferably 20000 or more (for example, 2500-500000), and more preferably 30,000 or more (for example, 50,000 to 50,000 to). It may be 300000). Particularly preferable ranges are, for example, 70,000 or more and 300,000 or less, the lower limit is 80,000 or more, 90,000 or more, 100,000 or more, 110,000 or more, and the upper limit is 290,000 or less, 280,000 or less, 250,000. The following can be mentioned.

The molecular weight distribution (Mw / Mn) of the polymer is not particularly limited, but is, for example, 1 to 10 (for example, 1.1 to 7.0), preferably 1.2 to 5.0 (for example, 1. It may be about 5 to 4.0), or about 1.5 to 3.0.

The molecular weight (and molecular weight distribution) may be measured by polystyrene conversion using, for example, GPC.

The glass transition temperature (Tg) of the polymer is not particularly limited, but is, for example, 70 ° C. or higher (for example, 80 to 200 ° C.), preferably 90 ° C. or higher (for example, 100 to 180 ° C.), and more preferably 100 ° C. or higher. It may be about (for example, 105 to 160 ° C.), and may be 110 ° C. or higher (for example, 115 to 150 ° C.).
-(Meta) Acrylic Polymer The resin composition of the present invention preferably contains a (meth) acrylic polymer. The acrylic resin constituting the (meth) acrylic polymer may usually have a (meth) acrylic unit [a unit derived from a (meth) acrylic monomer (structural unit)]. The composition (resin composition) of the present invention preferably contains nanocellulose and a (meth) acrylic polymer.

The (meth) acrylic monomer contains (meth) acrylic acid and a derivative thereof, and the α-position or β-position of the (meth) acrylic monomer contains an alkyl group (preferably having 1 to 4 carbon atoms). The alkyl group) may be bonded, and at least a part of the hydrogen atom of the alkyl group may be substituted with a hydroxyl group or a halogen group. The form of the carboxylic acid contained in the unit derived from the (meth) acrylic monomer is not particularly limited, and examples thereof include forms such as free acid, ester, salt, and acid amide.

As the (meth) acrylic unit, it has at least a unit derived from (meth) acrylic acid ester. As the (meth) acrylic acid ester that gives a unit derived from the (meth) acrylic acid ester, a linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon is added to the oxygen atom of the ester bond of the (meth) acrylic acid. Examples thereof include (meth) acrylic acid esters to which hydrogen groups are bonded.

Examples of the (meth) acrylic acid ester having a linear or branched aliphatic hydrocarbon group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate , (Meta) isoamyl acrylate, (meth) n-hexyl acrylate, (meth) 2-ethylhexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Dodecyl acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate and the like are alkyl (meth) acrylates. The alkyl group of the alkyl (meth) acrylate is preferably a C1-18 alkyl group, more preferably a C1-12 alkyl group. In addition, in this specification, the description of "C1-18" and "C1-12" means "carbon number 1-18" and "carbon number 1-12" respectively.

Examples of the (meth) acrylic acid ester having a cyclic aliphatic hydrocarbon group include (meth) cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate. ) Cycloalkyl acrylate; crosslinked cyclic (meth) acrylates such as isobornyl (meth) acrylate. The cycloalkyl group of cycloalkyl (meth) acrylate is preferably a C3-20 cycloalkyl group, and more preferably a C3-12 cycloalkyl group.

Examples of the (meth) acrylic acid ester having an aromatic hydrocarbon group include phenyl (meth) acrylate, trill (meth) acrylate, xsilyl (meth) acrylate, naphthyl (meth) acrylate, and binaphthyl (meth) acrylate. , (Meta) aryl (meth) acrylate such as anthryl (meth) acrylate; aralkyl (meth) acrylate such as benzyl (meth) acrylate; (meth) aryloxyalkyl (meth) acrylate such as phenoxyethyl (meth) acrylate. Can be mentioned. The aryl group of the aryl (meth) acrylate is preferably a C6-20 aryl group, more preferably a C6-14 aryl group. The aralkyl group of aralkyl (meth) acrylate is preferably a C6-10 aryl C1-4 alkyl group. The aryloxyalkyl group of the aryloxyalkyl (meth) acrylate is preferably a C6-10 aryloxy C1-4 alkyl group, more preferably a phenoxy C1-4 alkyl group.

The (meth) acrylic acid ester may have a substituent such as a hydroxyl group, a halogen group, an alkoxy group, or an epoxy group. Examples of such (meth) acrylic acid esters include (meth) hydroxyalkyl acrylates such as 2-hydroxyethyl (meth) acrylate; and (meth) chloromethyl acrylate, 2-chloroethyl (meth) acrylate and the like. Alkyl halides such as meth) acrylate; alkoxyalkyl (meth) acrylate such as 2-methoxyethyl (meth) acrylate; epoxyalkyl (meth) acrylate such as glycidyl (meth) acrylate can be mentioned. The alkyl group of hydroxyalkyl (meth) acrylate and epoxyalkyl (meth) acrylate is preferably a C1-12 alkyl group. The alkoxyalkyl group of the (meth) alkoxyalkyl acrylate is preferably a C1-12 alkoxy C1-12 alkyl group.

The content ratio of the (meth) acrylic unit may be 50% by mass or more (for example, 55% by mass or more), 60% by mass or more, 70% by mass or more, or the like with respect to the polymer. The content ratio of the (meth) acrylic unit in the polymer may be 100% by mass or less, 99% by mass or less, 95% by mass or less, and 90% by mass or less.

The content ratio of the (meth) acrylic acid ester unit in the (meth) acrylic polymer (or the constituent unit of the (meth) acrylic polymer) is, for example, in the range of 10% by mass or more (for example, 20% by mass or more). It can be selected from, preferably 30% by mass or more (for example, 40% by mass or more), more preferably 50% by mass or more (for example, 55% by mass or more), 60% by mass or more, 70% by mass or more, and the like. It may be.

When the (meth) acrylic polymer contains a methacrylic ester unit, the content ratio of the methacrylic ester unit in the (meth) acrylic polymer (or the constituent unit of the (meth) acrylic polymer) is, for example, 10. It can be selected from the range of mass% or more, and may be 20% by mass or more, preferably 30% by mass or more (for example, 40% by mass or more), and more preferably 50% by mass or more (for example, 55% by mass or more). It may be 60% by mass or more, 70% by mass or more, and the like.

When the (meth) acrylic polymer contains a methacrylic acid ester unit, the content ratio of the methacrylic acid ester unit in the (meth) acrylic acid ester unit is, for example, 10% by mass or more (for example, 20% by mass or more), preferably. May be 30% by mass or more (for example, 40% by mass or more), more preferably 50% by mass or more (for example, 60% by mass or more), 70% by mass or more, 80% by mass or more, 90% by mass or more, and the like. It may be.

When the (meth) acrylic polymer contains an alkyl methacrylate ester unit, the content ratio of the alkyl methacrylate ester unit in the (meth) acrylic acid ester unit is, for example, 10% by mass or more (for example, 20% by mass or more). It may be preferably 30% by mass or more (for example, 40% by mass or more), more preferably 50% by mass or more (for example, 60% by mass or more), and 70% by mass or more, 80% by mass or more, 90% by mass or more. It may be the above.

When the (meth) acrylic polymer contains methyl methacrylate units, the content ratio of the methyl methacrylate units in the (meth) acrylic acid ester units is, for example, 10% by mass or more (for example, 20% by mass or more). It may be preferably 30% by mass or more (for example, 40% by mass or more), more preferably 50% by mass or more (for example, 60% by mass or more), and 70% by mass or more, 80% by mass or more, 90% by mass or more. It may be the above.

The (meth) acrylic polymer preferably has a ring structure (cyclic structure), and is preferably a (meth) acrylic polymer having a ring structure in the main chain.

When the content ratio of the ring structure of the (meth) acrylic polymer is large, it is preferable in terms of heat resistance, solvent resistance, elastic modulus, surface hardness, dimensional stability and the like.

On the other hand, if the content ratio of the ring structure of the (meth) acrylic polymer becomes too large, it may become brittle, decrease in transparency, increase the absolute value of the photoelastic coefficient, and the like.

From such a viewpoint, the ring structure may have an appropriate content ratio that is neither too small nor too large.

Since the acrylic resin has a ring structure, various physical properties (for example, heat resistance, solvent resistance, elastic modulus, surface hardness, barrier property of oxygen and water vapor, optical characteristics, dimensional stability, and shape stability) of the acrylic resin are required. (Sex, etc.) can be imparted, improved or improved.

Examples of the ring structure include a cyclic imide structure (for example, a maleimide structure, a glutarimide structure, etc.), a cyclic anhydride structure (for example, a maleic anhydride structure, a glutaric anhydride structure, etc.), a cyclic amide structure (for example, a lactam structure, etc.). ), Cyclic ester structure (for example, lactone ring structure, etc.) and the like.

The (meth) acrylic polymer may have one kind or two or more kinds of ring structures. When having two or more types of ring structures, the two or more types of ring structures may have the same type of ring structure (for example, two or more types of cyclic imide structures), and different types of ring structures (for example, two or more types of ring structures). , A combination of a cyclic imide structure and a lactone structure, etc.).

Examples of the glutarimide structure and the glutaric anhydride structure include structures represented by the following formula (1).

(In the formula, R ¹ and R ² are independently hydrogen atoms or alkyl groups, R ³ is a hydrogen atom or substituent, X ¹ is an oxygen atom or nitrogen atom, and X ¹ is oxygen. When it is an atom, n = 0, and when X ¹ is a nitrogen atom, n = 1.)
In R ¹ and R ² of the formula (1), examples of the alkyl group include a C1-8 alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert. -Butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, 2-ethylhexyl group, etc.) and the like.

R ¹ and R ² are particularly preferably hydrogen atoms or C1-4 alkyl groups.

In R ³ of the formula (1), examples of the substituent include a hydrocarbon group and the like.

Examples of the hydrocarbon group include an aliphatic group, an alicyclic group, and an aromatic group. The hydrocarbon group may further have a substituent such as halogen.

In R ³ of the formula (1), as the aliphatic group, for example, a C1-10 alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group) Groups, n-pentyl groups, isopentyl groups, n-hexyl groups, isohexyl groups, n-heptyl groups, isoheptyl groups, n-octyl groups, 2-ethylhexyl groups, etc.) and the like. Among these alkyl groups, a C1-4 alkyl group, particularly a methyl group, is preferable.

In R ³ of the formula (1), examples of the alicyclic group include a C3-12 cycloalkyl group (for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.). Among these cycloalkyl groups, a C3-7 cycloalkyl group, particularly a cyclohexyl group, is preferable.

In R ³ of the formula (1), the aromatic group includes, for example, a C6-20 aromatic group [for example, a C6-20 aryl group (for example, a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group). Group, 2,3-xylyl group, 2,4-xsilyl group, 2,5-xsilyl group, 2,6-xsilyl group, 3,4-xsilyl group, 3,5-xsilyl group, 1-naphthyl group, 2 -Naphtyl group, binaphthyl group, anthryl group, etc.), C7-20 aralkyl group (for example, benzyl group, etc.), etc.]. Among these aromatic groups, a phenyl group and a tolyl group are preferable.

Typically, in formula (1), R ¹ and R ² are independent hydrogen atoms or methyl groups, and R ³ is a C1-10 alkyl group, C3-12 cycloalkyl group or C6-20 aromatic group. R ¹ and R ² may be independently hydrogen atoms or methyl groups, and R ³ may be a C1-4 alkyl group, a C3-7 cycloalkyl group, a C6-20 aryl group or C7-. It may be a 20 aralkyl group, more preferably R ¹ and R ² are independently hydrogen atoms or methyl groups, and R ³ is a methyl group, cyclohexyl group, phenyl group or trill group, most preferably. , R ¹ and R ² may be independently hydrogen atoms or methyl groups, and R ³ may be cyclohexyl or phenyl groups, respectively.

The ring structure may have one or more types of structures represented by the formula (1).

In particular, when the ring structure has a structure represented by the formula (1), it has a glutarimide structure which is a cyclic non-anhydrous structure (that is, a structure in which X ¹ is a nitrogen atom in the formula (1)). Is preferable.

The glutaric anhydride structure (that is, the structure in which X ¹ is an oxygen atom in the formula (1)) is hydrolyzed, the acid value is increased, the water resistance and heat resistance are lowered, and the optical characteristics are changed. There is a risk of causing it. Therefore, it may be preferable that the ring structure does not substantially have a glutaric anhydride structure, or even if it contains a small amount.

Examples of the maleic anhydride structure and the maleimide structure include structures represented by the following formula (2).

(In the formula, R ⁴ and R ⁵ are independent hydrogen atoms or methyl groups, R ⁶ is a hydrogen atom or a substituent, X ² is an oxygen atom or a nitrogen atom, and X ² is an oxygen atom. When n = 0, and when X ² is a nitrogen atom, n = 1.)
In R ⁶ of the formula (2), examples of the substituent include a hydrocarbon group and the like.

Examples of the hydrocarbon group include an aliphatic group {for example, an alkyl group [for example, a C1-6 linear alkyl group (for example, a methyl group, an ethyl group, etc.), a C1-6 branched alkyl group (for example, an isopropyl group, etc.). ) Etc.], etc.}, alicyclic groups (eg, C3-20 cycloalkyl groups such as cyclopentyl group, cyclohexyl group, etc.), aromatic groups {eg, C6-20 aromatic groups [eg, C6-20 aromatic groups, etc.] , C7-20 aralkyl group (eg, benzyl group, etc.), C6-20 aryl group (eg, phenyl group, etc.)]} and the like. The hydrocarbon group may further have a substituent such as halogen.

When X ² is an oxygen atom, the ring structure represented by the formula (2) is a maleic anhydride structure.

On the other hand, when X ² is a nitrogen atom, the ring structure represented by the formula (2) is a maleimide structure.

In formula (2), when X ² is a nitrogen atom, preferably R ⁴ and R ⁵ are independently hydrogen atoms, and R ⁶ is a C3-20 cycloalkyl group or a C6-20 aromatic group. Often, R ⁴ and R ⁵ may be independently hydrogen atoms and R ⁶ may be a cyclohexyl group, a benzyl group or a phenyl group, respectively.

The ring structure may have one type or two or more types of structures represented by the formula (2).

In particular, when the ring structure has a structure represented by the formula (2), it has a maleimide structure which is a cyclic non-anhydrous structure (that is, a structure in which X ² is a nitrogen atom in the formula (2)). preferable.

The maleic anhydride structure (that is, the structure in which X ² is an oxygen atom in the formula (2)) is hydrolyzed, the acid value is increased, the water resistance and heat resistance are lowered, and the optical characteristics are changed. There is a risk of causing it. Therefore, it may be preferable that the ring structure does not substantially have a maleic anhydride structure, or even if it contains a maleic anhydride structure.

The lactone ring structure is not particularly limited, and may be, for example, a 4- to 8-membered ring, but is preferably a 5-membered ring or a 6-membered ring because of the excellent stability of the ring structure, and is preferably a 6-membered ring. Is more preferable.

The lactone ring structure may be, for example, a structure disclosed in Japanese Patent Application Laid-Open No. 2004-168882, and examples thereof include a structure represented by the following formula (3).

(In the formula, R ⁷ , R ⁸ and R ⁹ are independent hydrogen atoms or substituents.)
In the formula (3), examples of the substituent include organic residues such as a hydrocarbon group.

Examples of the hydrocarbon group include aliphatic groups (for example, C1-20 alkyl groups such as methyl group, ethyl group and propyl group, C2-20 unsaturated aliphatic hydrocarbon groups such as ethenyl group and propenyl group). , Aromatic groups (for example, C6-20 aromatic hydrocarbon groups such as phenyl group and naphthyl group) and the like.

The hydrocarbon group may contain an oxygen atom, and one or more of the hydrogen atoms may be substituted with at least one group selected from a hydroxyl group, a carboxyl group, an ether group and an ester group.

In the formula (3), preferably, R ⁹ may be a hydrogen atom or a methyl group, R ⁷ and R ⁸ may be independently hydrogen atoms or C1-20 alkyl groups, and more preferably R ⁹ is hydrogen. The atom or methyl group, R ⁷ and R ⁸ may be independently hydrogen atoms or methyl groups, respectively.

The ring structure may include one type or two or more types of structures represented by the formula (3).

The lactam ring structure is not particularly limited, and examples thereof include a pyrrolidinone ring structure represented by the following formula (4).

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). Having a pyroridinone ring structure in the main chain means that at least one of the five atoms constituting the basic skeleton of the pyrrolidinone ring structure, which is a 5-membered ring, is typically an amide bond (-N (R) CO-). It means that three carbon atoms that do not constitute the above are located in the main chain of the polymer and form the main chain.

(In the formula, R ^{10 to} R ¹² are independently hydrogen atoms or substituents.)
In R ¹⁰ of the formula (4), examples of the substituent include a hydrocarbon group or -NHCOR ¹³ group (R ¹³ is a hydrogen atom or a hydrocarbon group) and the like.

Examples of the hydrocarbon group in R ¹⁰ or R ¹³ include an aliphatic group, an alicyclic group, an aromatic group and the like.

Examples of the aliphatic group include a C1-18 linear or branched alkyl group such as a C1-18 alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group). Etc.) etc.

Examples of the alicyclic group include a C3-18 cycloalkyl group (for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.).

Examples of the aromatic group include a C6-20 aromatic group [for example, a C6-20 aryl group (for example, a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthryl group, etc.), a C7-20 aralkyl group (for example, for example). Benzyl group, etc.)] and the like.

As R ¹⁰ , a hydrogen atom, a C1-18 linear alkyl group (for example, a methyl group, etc.) and the like are particularly preferable.

Further, as R ¹³ , in particular, a hydrogen atom, a C1-18 linear alkyl group (preferably a C1-12 linear alkyl group, more preferably a C1-4 linear alkyl group, etc.), a C6-20 aryl group, etc. (For example, a phenyl group or the like), a C3-18 cycloalkyl group (preferably a C3-12 cycloalkyl group, more preferably a C3-6 cycloalkyl group or the like) and the like are preferable.

In R ¹¹ of the formula (4), examples of the substituent include -COOR ¹⁴ groups (R ¹⁴ is a hydrogen atom or a hydrocarbon group) and the like.

Examples of the hydrocarbon group in R ¹⁴ include the hydrocarbon groups exemplified in R ¹⁰ or R ¹³ .

Also, a particularly preferred embodiment of R ¹⁴ is the same as a particularly preferred embodiment of R ¹³ .

In R ¹² of the formula (4), examples of the substituent include -COR ¹⁵ groups (R ¹⁵ is a hydrogen atom or a hydrocarbon group) and the like.

Examples of the hydrocarbon group in R ¹⁵ include the hydrocarbon groups exemplified in R ¹⁰ or R ¹³ .

Also, a particularly preferred embodiment of R ¹⁵ is the same as a particularly preferred embodiment of R ¹³ .

The ring structure of the (meth) acrylic polymer has desired physical properties (for example, heat resistance, hardness (strength), solvent resistance, surface hardness, barrier properties of oxygen and water vapor, optical properties, dimensional stability, and shape stability. It may be appropriately selected depending on the sex, etc.). For example, from the viewpoint of heat resistance, the ring structure includes a lactone ring structure, a cyclic imide structure (for example, N-alkyl-substituted maleimide structure, glutarimide structure, etc.), and a cyclic anhydride structure (for example, maleic anhydride structure, glutar anhydride). Acid structure, etc.) may be preferably contained.

Further, from the viewpoint of water resistance, heat resistance and water resistance, the ring structure may preferably contain a cyclic non-anhydrous structure [for example, a lactone ring structure, a cyclic imide structure (particularly, a glutarimide structure, a maleimide structure)]. ..

Further, from the viewpoints of surface hardness, solvent resistance, barrier properties, optical properties, etc., the ring structure may preferably include a lactone ring structure, a glutarimide structure, a glutaric anhydride structure, and the like.

In particular, the ring structure may contain at least a lactone ring structure. By combining a (meth) acrylic polymer having a lactone ring and nanocellulose, it is easy to efficiently obtain a well-balanced composite material. For example, by such a combination, a composition having a good balance of heat resistance, hardness (strength), surface hardness, dimensional stability, etc. while maintaining transparency, low coloration (yellowness, YI), and weather resistance can be obtained. Can be obtained. Further, it is easy to obtain a composition having good solvent resistance (for example, solvent resistance to alcohol-based solvents, hydrocarbon-based solvents such as toluene, aromatic solvents, etc.).

The content ratio of the ring structure of the (meth) acrylic polymer can be selected according to the intended use, desired physical properties, etc., and is not particularly limited. For example, in the (meth) acrylic polymer, 0.1% by mass or more ( For example, it can be selected from a range of about 0.5% by mass or more), and may be 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and 10% by mass or more, 15% by mass or more. , 20% by mass or more. It is particularly preferable that the (meth) acrylic polymer has a ring structure of 1% by mass or more. In such an embodiment, a composition or film having higher heat resistance and elastic modulus can be obtained while maintaining transparency.

The content ratio (or the upper limit value thereof) of the ring structure of the (meth) acrylic polymer is not particularly limited, and is, for example, 90% by mass or less, 80% by mass or less, and 70% by mass in the (meth) acrylic polymer. Hereinafter, it may be 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, and the like.

When the content ratio of the ring structure of the (meth) acrylic polymer is large, it is preferable in terms of heat resistance, hardness (strength), solvent resistance, surface hardness, dimensional stability and the like.

On the other hand, if the content ratio of the ring structure of the (meth) acrylic polymer becomes too large, it may become brittle, decrease in transparency, increase the absolute value of the photoelastic coefficient, and the like.

From such a viewpoint, the ring structure may have an appropriate content ratio that is neither too small nor too large.

Even if an appropriate range (for example, 1 to 70% by mass, 3 to 60% by mass, 5 to 50% by mass, 5 to 40% by mass, etc.) is set by appropriately combining these upper limit values and lower limit values. Good (same below).

In particular, when the (meth) acrylic polymer has a glutarimide structure and / or a glutaric anhydride structure, the content ratio of the glutarimide structure and / or the glutaric anhydride structure is preferably 5% by mass or more, more preferably. It may be 10% by mass or more, more preferably 15% by mass or more, 90% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less. ..

When the (meth) acrylic polymer has a maleic anhydride structure and / or a maleimide structure, the content ratio of the maleic anhydride structure and / or the maleimide structure is, for example, 5 to 90% by mass, preferably 5 to 60% by mass. , More preferably 10 to 50% by mass, still more preferably 10 to 30% by mass.

When the (meth) acrylic polymer has a lactone ring structure, the content ratio of the lactone ring structure is, for example, 1 to 80% by mass, preferably 3 to 70% by mass, and more preferably 5 to 60% by mass (for example). , 10 to 50% by mass).

When the (meth) acrylic polymer has a lactam ring structure, the content ratio of the lactam ring structure is, for example, 1 to 80% by mass, preferably 5 to 70% by mass, and more preferably about 10 to 50% by mass. There may be.

By making the content ratio of the ring structure exceptionally large, it is easy to obtain desired physical properties (for example, heat resistance, hardness (strength), solvent resistance, surface hardness, optical characteristics, dimensional stability, shape stability, etc.). On the other hand, it may reduce other physical properties.

In the present invention, by combining the (meth) acrylic polymer and nanocellulose, such physical properties can be efficiently maintained without significantly increasing the content ratio of the ring structure in the (meth) acrylic polymer (). It is possible to impart, improve or improve desired physical properties while suppressing deterioration of physical properties).

The (meth) acrylic polymer of the present invention may further have units derived from other unsaturated monomers. The other unsaturated monomer is not particularly limited as long as it is a compound having a polymerizable double bond, and is, for example, a vinyl ester such as vinyl acetate or vinyl propionate; styrene, vinyl toluene, methoxystyrene, α-methylstyrene. , 2-Aromatic vinyl compounds such as vinyl pyridine; vinyl silanes such as vinyl trimethoxysilane and γ- (meth) acryloyloxypropyl methoxysilane. The amount of the other unsaturated monomer is not particularly limited, but may be, for example, 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less in the (meth) acrylic polymer.

The weight average molecular weight (Mw) of the (meth) acrylic polymer is not particularly limited, but is, for example, 10000 or more (for example, 10000-1000000), preferably 20000 or more (for example, 2500-500000), and more preferably 30,000 or more. (For example, 50,000 to 350,000) may be used. Particularly preferable ranges are, for example, 70,000 or more and 300,000 or less, the lower limit is 80,000 or more, 90,000 or more, 100,000 or more, 110,000 or more, and the upper limit is 290,000 or less, 280,000 or less, 250,000. The following can be mentioned.

The molecular weight distribution (Mw / Mn) of the (meth) acrylic polymer is not particularly limited, but is, for example, 1 to 10 (for example, 1.1 to 7.0), preferably 1.2 to 5.0. It may be about (for example, 1.5 to 4.0), or about 1.5 to 3.0.

The molecular weight (and molecular weight distribution) may be measured by polystyrene conversion using, for example, GPC.

The glass transition temperature (Tg) of the (meth) acrylic polymer is not particularly limited, but is, for example, 70 ° C. or higher (for example, 80 to 200 ° C.), preferably 90 ° C. or higher (for example, 100 to 180 ° C.), and further. It may be preferably about 100 ° C. or higher (for example, 105-160 ° C.), and may be 110 ° C. or higher (for example, 115-150 ° C.).

When the (meth) acrylic polymer is a copolymer, the form of copolymerization is not particularly limited and may be a random copolymer, and the block copolymer, the alternating copolymer, and the graft can be used together. It may be a polymer or the like.

For example, since the (meth) acrylic polymer has a ring structure, it can usually be said to be a copolymer, but the introduction form of the ring structure is not particularly limited and is selected according to the type of the ring structure and the like. It can be introduced randomly, or it may be introduced as a block, alternate, graft, or the like.

The (meth) acrylic polymer is a polymer chain having a polymer chain (A) having a unit derived from a diene and / or an olefin, a unit derived from a (meth) acrylic monomer, and a unit having a ring structure in the main chain. It may be a copolymer having (B) and. Hereinafter, this copolymer may be referred to as "copolymer (P)".

The copolymer (P) has a structure in which a diene or olefin polymer chain (A) and a (meth) acrylic polymer chain (B) having a ring structure are copolymerized. The type of copolymerization is not limited, but a graft copolymer in which a (meth) acrylic polymer chain (B) having a ring structure is grafted on a diene or olefin polymer chain (A) is preferable. Hereinafter, the diene or olefin polymer chain (A) may be simply referred to as "polymer chain (A)", and the (meth) acrylic polymer chain (B) having a ring structure may be simply referred to as "polymer chain (B)". ..

The (meth) acrylic polymer chain (B) having a ring structure usually gives a hard and brittle resin, but this is copolymerized with a diene or an olefin polymer chain (A) to make the composition of the polymer chain (B) appropriate. By controlling the above, it is possible to obtain a copolymer (P) having both heat resistance and mechanical strength. In addition, it is possible to reduce the generation of gelled products during production. The copolymer (P) thus obtained has high transparency even though it has a diene or olefin component. Further, the copolymer (P) does not impair these properties even when blended with the (meth) acrylic polymer, and does not impair the transparency due to its excellent dispersibility.

When forming a film from the copolymer (P), it is possible to obtain a film having high strength and high heat resistance without performing an orientation treatment such as a stretching treatment. Therefore, a film having desired optical characteristics can be easily obtained. For example, since it has high strength, high heat resistance, and high transparency, it is possible to efficiently form an isotropic film or a low retardation film. On the other hand, since anisotropy can be easily expressed due to the ring structure, a retardation film can be formed by an orientation treatment such as a stretching treatment. Further, when the optical film is used, it is possible to reduce foreign matter and appearance defects.

The polymer chain (A) contained in the copolymer (P) will be described. The polymer chain (A) has at least units derived from diene and / or olefin. Units derived from diene and / or olefins function as soft components in the copolymer (P). By including a unit derived from a diene and / or an olefin, the mechanical strength (for example, impact strength) of the copolymer is increased and the hardness and brittleness are reduced while ensuring the transparency of the copolymer (P). be able to.

Dienes include 1,3-butadiene (also known as butadiene), 2-methyl-1,3-butadiene (also known as isoprene), 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadien, 2, Alkadiene such as 5-dimethyl-1,5-hexadiene (also known as diisoprene) is preferably used, and among them, conjugated diene such as 1,3-butadiene, 2-methyl-1,3-butadiene, and 1,3-pentadiene are used. More preferable. As the olefin, monoolefins such as ethylene, propylene, 1-butene, isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 1-tetradecene and 1-octadecene are preferably used, and among them, carbon- An α-olefin, which is an alkene having a carbon double bond at the α position, is more preferable. The carbon number of these dienes and olefins is preferably 2 or more, more preferably 3 or more, preferably 20 or less, more preferably 10 or less, and even more preferably 6 or less. Units derived from diene and / or olefins are defined as units formed by the polymerization of these diene and / or olefins. The olefin-derived unit is not limited to the one actually formed by (co) polymerization of the olefin, and may be formed by hydrogenating the diene-derived unit.

The polymer chain (A) is an olefin (co) polymer such as polyethylene, polypropylene, polybutene-1, ethylene-propylene copolymer, ethylene-butene copolymer; polyisoprene, polybutadiene, isoprene-butadiene copolymer. Diene (co) polymers such as; ethylene-propylene-diene copolymer, isobutene-isoprene copolymer and other olefin and diene copolymers are included in the structure of the main chain. The olefin (co) polymer is preferably an α-olefin (co) polymer, the diene (co) polymer is preferably a conjugated diene (co) polymer, and the olefin and diene copolymer is α-olefin. Copolymers of conjugated diene are preferred. Among these, a copolymer of α-olefin and conjugated diene such as polyisoprene and isobutene-isoprene copolymer, polyethylene and polypropylene are more preferable.

The polymer chain (A) may have units derived from other unsaturated monomers in addition to units derived from diene and / or olefin. The other unsaturated monomer is not particularly limited as long as it is a compound having a polymerizable double bond, and is, for example, a vinyl ester such as vinyl acetate or vinyl propionate; (meth) acrylic acid, maleic anhydride, (meth). ) Unsaturated carboxylic acids such as methyl acrylate, ethyl (meth) acrylate and esters thereof; aromatic vinyl compounds such as styrene, vinyl toluene, methoxystyrene, α-methylstyrene, 2-vinylpyridine; vinyltrimethoxysilane, Examples thereof include vinyl silanes such as γ- (meth) acryloyloxypropyl methoxysilane. The polymer chain (A) may be a copolymer of these other unsaturated monomers with a diene and / or an olefin. The content of the diene and / or olefin-derived unit in the polymer chain (A) is, for example, preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and 55% by mass. % Or more is even more preferable, 90% by mass or less is preferable, 86% by mass or less is more preferable, and 83% by mass or less is further preferable.

If the polymer chain (A) has units derived from other unsaturated monomers, the polymer chain (A) may be a random copolymer of a diene and / or an olefin with another unsaturated monomer. Often, it may be a block copolymer or a graft copolymer. Among these, a block copolymer is preferable from the viewpoint that the function as a soft component of a unit derived from a diene and / or an olefin is preferably exhibited. In this case, the polymer chain (A) has a polymer block (a1) having a unit derived from a diene and / or an olefin and a polymer block (a2) having a unit derived from another unsaturated monomer. Become.

When the polymer chain (A) has a polymer block (a2) having a unit derived from another unsaturated monomer, the transparency is enhanced while ensuring the mechanical strength of the copolymer (P). The polymer block (a2) is preferably composed of a unit derived from an aromatic vinyl monomer from the viewpoint of easy operation. In this case, in the polymer chain (A), the polymer block (a1) functions as a soft component, and the polymer block (a2) functions as a hard component.

The aromatic vinyl monomer that gives the polymer block (a2) is not particularly limited as long as it is a compound in which a vinyl group is bonded to an aromatic ring. For example, styrene, vinyltoluene, methoxystyrene, α-methylstyrene, α- Styrene-based monomers such as hydroxymethylstyrene and α-hydroxyethylstyrene; Polycyclic aromatic hydrocarbon ring vinyl monomers such as 2-vinylnaphthalene; N-vinylcarbazole, 2-vinylpyridine, vinylimidazole, vinylthiophene Such as aromatic heterocyclic vinyl monomer and the like. Among these, styrene-based monomers are preferable. The styrene-based monomer includes not only styrene but also a styrene derivative in which an arbitrary substituent is bonded to a polymerizable double-bonded carbon of styrene or a benzene ring, and the substituents include an alkyl group, an alkoxy group, and the like. Examples thereof include a hydroxyl group, a halogen group, an amino group, a nitro group and a sulfo group. The alkyl group and alkoxy group bonded to styrene preferably have 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and the alkyl group and alkoxy group bonded to styrene have at least a part of hydrogen atoms hydroxyl groups or halogens. It may be substituted with a group.

Examples of the polymer chain (A) having a polymer block (a1) having a unit derived from diene and / or an olefin and a polymer block (a2) having a unit derived from an aromatic vinyl monomer include styrene-. Hydrohydrates of butadiene block copolymers, styrene-butadiene-styrene block copolymers, styrene-butadiene-styrene block copolymers (eg, styrene-ethylene / butylene-styrene block copolymers, styrene-butadiene / butylene- Polystyrene block copolymer), styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, styrene-isoprene-styrene block copolymer hydrogenated product (for example, styrene-ethylene / propylene-styrene block) Polymer) and the like.

When the polymer chain (A) has a polymer block (a1) having a unit derived from a diene and / or an olefin and a polymer block (a2) having a unit derived from an aromatic vinyl monomer, the polymer chain (a2) In A), it is preferable that the polymer blocks (a2) are bonded to both sides of the polymer block (a1). By constructing the polymer chain (A) in this way, the polymer chain (A) functions as an elastomer, and the mechanical strength of the copolymer can be further increased. In this case, the polymer chain (A) may be a triblock copolymer, a multi-block copolymer, or a radial block copolymer, but of the polymer chain (A). A triblock copolymer is preferable because the characteristics can be easily controlled and the polymer chain (B) can be easily introduced into the polymer (P).

When the polymer chain (A) has a polymer block (a1) having a unit derived from a diene and / or an olefin and a polymer block (a2) having a unit derived from an aromatic vinyl monomer, the polymer block (A1) may have units derived from other unsaturated polymers in addition to units derived from diene and / or olefin. Examples of other unsaturated monomers in this case include vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylic acid, maleic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate and the like. Unsaturated carboxylic acids and esters thereof; aromatic vinyl compounds such as styrene, vinyltoluene, methoxystyrene, α-methylstyrene, 2-vinylpyridine; vinyltrimethoxysilane, γ- (meth) acryloyloxypropylmethoxysilane, etc. Examples include vinyl silane. The polymer block (a1) may be a copolymer of these other unsaturated monomers and a diene and / or an olefin. The polymer block (a1) preferably contains a unit derived from diene and / or olefin as a main component, and the content ratio of the unit derived from diene and / or olefin is 50 in 100% by mass of the polymer block (a1). It is preferably mass% or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The polymer block (a1) may be substantially composed of units derived from diene and / or olefin, and for example, units derived from diene and / or olefin may be 99% by mass or more.

When the polymer chain (A) has a polymer block (a1) having a unit derived from a diene and / or an olefin and a polymer block (a2) having a unit derived from an aromatic vinyl monomer, the polymer block. (A2) may have a unit derived from another unsaturated monomer in addition to the unit derived from the aromatic vinyl monomer. Examples of other unsaturated monomers in this case include vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylic acid, maleic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate and the like. Unsaturated carboxylic acids and esters thereof; aromatic vinyl compounds such as styrene, vinyltoluene, methoxystyrene, α-methylstyrene, 2-vinylpyridine; vinyltrimethoxysilane, γ- (meth) acryloyloxypropylmethoxysilane, etc. Examples include vinyl silane. The polymer block (a2) may be a copolymer of these other unsaturated monomers and an aromatic vinyl monomer. The polymer block (a2) preferably contains a unit derived from an aromatic vinyl monomer as a main component, and the content ratio of the unit derived from an aromatic vinyl monomer in 100% by mass of the polymer block (a2). Is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. The polymer block (a2) may be substantially composed of only units derived from an aromatic vinyl monomer, and for example, units derived from an aromatic vinyl monomer may be 99% by mass or more.

The content ratio of the polymer block (a2) in the polymer chain (A) is preferably 10% by mass or more, more preferably 14% by mass or more, further preferably 17% by mass or more, and preferably 55% by mass or less. , 50% by mass or less is more preferable, and 45% by mass or less is further preferable. As a result, the polymer chain (A) has a soft component and a hard component in a well-balanced manner, and it becomes easy to enhance the transparency while ensuring the mechanical strength of the copolymer (P). From the same viewpoint, the content ratio of the polymer block (a1) in the polymer chain (A) is preferably 45% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and 90% by mass. It is preferably mass% or less, more preferably 86% by mass or less, and even more preferably 83% by mass or less.

The weight average molecular weight of the polymer chain (A) is preferably 10,000 or more, more preferably 5,000 or more, further preferably 10,000 or more, still more preferably 30,000 or more, and preferably 500,000 or less. 300,000 or less is more preferable, 200,000 or less is further preferable, and 100,000 or less is even more preferable. By setting the weight average molecular weight of the polymer chain (A) in such a range, it becomes easy to secure the strength and transparency of the copolymer (P).

The polymer chain (B) contained in the copolymer (P) will be described. The polymer chain (B) has at least a unit derived from a (meth) acrylic monomer and has a ring structure. The polymer chain (B) is preferably grafted onto the polymer chain (A), therefore the copolymer (P) is a graft copolymer and the polymer chain (B) as the graft chain of the graft copolymer. It is preferable to have. The polymer chain (B) can enhance the transparency of the copolymer (P).

The unit derived from the (meth) acrylic monomer of the polymer chain (B) (hereinafter, may be referred to as “(meth) acrylic unit”) is a polymer chain obtained by polymerizing the (meth) acrylic monomer. It can be introduced in (B). The (meth) acrylic monomer contains (meth) acrylic acid and a derivative thereof, and the α-position or β-position of the (meth) acrylic monomer contains an alkyl group (preferably having 1 to 4 carbon atoms). The alkyl group) may be bonded, and at least a part of the hydrogen atom of the alkyl group may be substituted with a hydroxyl group or a halogen group. The form of the carboxylic acid contained in the unit derived from the (meth) acrylic monomer is not particularly limited, and examples thereof include forms such as free acid, ester, salt, and acid amide.

The polymer chain (B) has at least a unit derived from (meth) acrylic acid ester as the (meth) acrylic unit. As the (meth) acrylic acid ester that gives a unit derived from the (meth) acrylic acid ester, a linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon is added to the oxygen atom of the ester bond of the (meth) acrylic acid. Examples thereof include (meth) acrylic acid esters to which hydrogen groups are bonded.

Examples of the (meth) acrylic acid ester having a linear or branched aliphatic hydrocarbon group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate , (Meta) isoamyl acrylate, (meth) n-hexyl acrylate, (meth) 2-ethylhexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Dodecyl acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate and the like are alkyl (meth) acrylates. The alkyl group of the alkyl (meth) acrylate is preferably a C1-18 alkyl group, more preferably a C1-12 alkyl group. In addition, in this specification, the description of "C1-18" and "C1-12" means "carbon number 1-18" and "carbon number 1-12" respectively.

Examples of the (meth) acrylic acid ester having a cyclic aliphatic hydrocarbon group include (meth) cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate. ) Cycloalkyl acrylate; crosslinked cyclic (meth) acrylates such as isobornyl (meth) acrylate. The cycloalkyl group of cycloalkyl (meth) acrylate is preferably a C3-20 cycloalkyl group, and more preferably a C3-12 cycloalkyl group.

Examples of the (meth) acrylic acid ester having an aromatic hydrocarbon group include phenyl (meth) acrylate, trill (meth) acrylate, xsilyl (meth) acrylate, naphthyl (meth) acrylate, and binaphthyl (meth) acrylate. , (Meta) aryl (meth) acrylate such as anthryl acrylate; (meth) aralkyl acrylate such as benzyl (meth) acrylate; (meth) aryloxyalkyl (meth) acrylate such as phenoxyethyl acrylate. Can be mentioned. The aryl group of the aryl (meth) acrylate is preferably a C6-20 aryl group, more preferably a C6-14 aryl group. The aralkyl group of aralkyl (meth) acrylate is preferably a C6-10 aryl C1-4 alkyl group. The aryloxyalkyl group of the aryloxyalkyl (meth) acrylate is preferably a C6-10 aryloxy C1-4 alkyl group, and more preferably a phenoxy C1-4 alkyl group.

The (meth) acrylic acid ester may have a substituent such as a hydroxyl group, a halogen group, an alkoxy group, or an epoxy group. Examples of such (meth) acrylic acid esters include (meth) hydroxyalkyl acrylates such as 2-hydroxyethyl (meth) acrylate; and (meth) chloromethyl acrylate, 2-chloroethyl (meth) acrylate and the like. Alkyl halides such as meth) acrylate; alkoxyalkyl (meth) acrylate such as 2-methoxyethyl (meth) acrylate; epoxyalkyl (meth) acrylate such as glycidyl (meth) acrylate can be mentioned. The alkyl group of hydroxyalkyl (meth) acrylate and epoxyalkyl (meth) acrylate is preferably a C1-12 alkyl group. The alkoxyalkyl group of the (meth) alkoxyalkyl acrylate is preferably a C1-12 alkoxy C1-12 alkyl group.

The polymer chain (B) has, in addition to the (meth) acrylic unit, a unit having a ring structure in the main chain (hereinafter, may be referred to as a “ring structure unit”). Since the polymer chain (B) has a ring structure in the main chain, the heat resistance of the copolymer (P) can be enhanced. Further, improvement of solvent resistance, surface hardness, adhesiveness, barrier property of oxygen and water vapor, and various optical characteristics can be expected. Further, when the copolymer (P) or the resin composition containing the copolymer (P) is made into a film or a sheet, the dimensional stability and the shape stability under high temperature and high humidity conditions can be improved. By stretching the film thus formed, a large retardation can be exhibited due to the ring structure of the polymer chain (B), and the film can be applied as a retardation film. This feature makes it possible to apply the copolymer (P) and the resin composition containing the copolymer (P) to an optical film such as a retardation film or a polarizer protective film having the function of a retardation film.

Examples of the ring structure include a cyclic imide structure represented by the above formulas (1) to (4) (for example, maleimide structure, glutarimide structure, etc.) and a cyclic anhydride structure (for example, maleic anhydride structure, glutar anhydride). Examples thereof include an acid structure (such as an acid structure), a cyclic amide structure (for example, a lactam structure, etc.), and a cyclic ester structure (for example, a lactone ring structure, etc.).

The content ratio of the ring structure unit in the polymer chain (B) is not particularly limited, but the content ratio of the ring structure unit in the polymer chain (B) is preferably 3% by mass or more, more preferably 4% by mass or more, and 5% by mass. % Or more is further preferable, 50% by mass or less is preferable, 45% by mass or less is more preferable, and 40% by mass or less is further preferable. By adjusting the content ratio of the ring structure unit in this way, both heat resistance and mechanical strength can be imparted to the film in a well-balanced manner. When giving high heat resistance and mechanical strength to the film, the content ratio of the structural unit in the polymer chain (B) is 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more. You can also do it.

The weight average molecular weight (Mw) of the copolymer (P) is not particularly limited, but is, for example, 10000 or more (for example, 10000-1000000), preferably 20000 or more (for example, 2500-500000), and more preferably 30,000 or more (for example, 20000-500000). For example, it may be 50,000 to 300,000). Particularly preferable ranges are, for example, 70,000 or more and 300,000 or less, the lower limit is 80,000 or more, 90,000 or more, 100,000 or more, 110,000 or more, and the upper limit is 290,000 or less, 280,000 or less, 250,000. The following can be mentioned.

The molecular weight distribution (Mw / Mn) of the copolymer (P) is not particularly limited, but is, for example, 1 to 10 (for example, 1.1 to 7.0), preferably 1.2 to 5.0 (). For example, it may be about 1.5 to 4.0) or about 1.5 to 3.0.

The molecular weight (and molecular weight distribution) may be measured by polystyrene conversion using, for example, GPC.

The glass transition temperature (Tg) of the copolymer (P) is not particularly limited, but is, for example, 70 ° C. or higher (for example, 80 to 200 ° C.), preferably 90 ° C. or higher (for example, 100 to 180 ° C.), more preferably. May be about 100 ° C. or higher (for example, 105-160 ° C.), and may be 110 ° C. or higher (for example, 115-150 ° C.).
-Composition As described above , the composition of the present invention contains at least a polymer and nanocellulose.

In the composition, the content ratio of nanocellulose to the polymer is preferably 0.1% by mass or more and 10% by mass or less. The upper limit of the content ratio of nanocellulose with respect to the polymer (or (meth) acrylic polymer) is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 7% by mass or less. It may be 6% by mass or less, 5% by mass or less, 4% by mass or less, and the like. The lower limit of the content ratio of nanocellulose with respect to the polymer (or (meth) acrylic polymer) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass. % Or more, 0.4% by mass or more, 0.5% by mass or more, 0.7% by mass or more, and the like. With such a composition, the elastic modulus of the film obtained by using it is improved, and by forming a solution film, it becomes possible to obtain a highly transparent and low-colored film preferable for use in an optical film.

The content ratio of nanocellulose in the composition of the present invention is preferably 0.1% by mass or more and 10% by mass or less. The upper limit of the content ratio of nanocellulose in the composition is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 7% by mass or less, 6% by mass or less, and 5% by mass or less. It may be 4, 4% by mass or less. The lower limit of the content of nanocellulose in the composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and 0.4% by mass. It may be mass% or more, 0.5 mass% or more, 0.7 mass% or more, and the like. With such a composition, the elastic modulus of the film obtained by using it is improved, and by forming a solution film, it becomes possible to obtain a highly transparent and low-colored film preferable for use in an optical film.

In the present invention, sufficient physical properties can be obtained even if the proportion of nanocellulose is relatively small.

In particular, the proportion of nanocellulose is relatively small [for example, in a polymer] in terms of transparency, low melt viscosity, low solution viscosity, low coloration (yellowness, YI), thermal stability, and resistance to brittleness. On the other hand, it may be 10% by mass or less, further 5% by mass or less, 3% by mass or less].

On the other hand, in the present invention, the proportion of nanocellulose can be increased [for example, 50% by mass or more, further 70% by mass or more, 100% by mass or more, etc. with respect to the polymer]. By increasing the size in this way, the properties of nanocellulose (for example, high elastic modulus, high strength, cohesive force, tixonic property, barrier property, etc.) can be efficiently exhibited or exhibited in the composition.

If necessary, the composition may contain other components (components other than the polymer and nanocellulose) as long as desired physical properties can be obtained.

Other components are not particularly limited, but are, for example, conventional additives (for example, ultraviolet absorbers, antioxidants, stabilizers, reinforcing materials, surfactants, antistatic agents, dispersants, flame retardants, antistatic agents). Agents, fillers, plasticizers, lubricants, etc.) may be included.

The composition may contain other components alone or in combination of two or more.

The resin composition of the present invention preferably contains nanocellulose and a (meth) acrylic polymer. The composition [or molded product (described later)] preferably contains a (meth) acrylic polymer having a skeleton of an acrylic resin and a skeleton of a ring structure as a resin component, and this (meth) acrylic polymer. It has a predetermined physical property derived from.

In the present invention, the physical properties (for example, strength, hardness, etc.) can be improved or improved by combining such a (meth) acrylic polymer with nanocellulose.

In addition, in another aspect of the composition of the present invention, new physical properties can be imparted or expressed. For example, by combining nanocellulose with a (meth) acrylic polymer (and adjusting the amount thereof), birefringence or phase difference can be adjusted (variable), and an optically isotropic composition can be obtained. You can also.

Furthermore, in another aspect of the composition of the present invention, another physical property can be imparted, improved or improved without impairing (maintaining) one physical property. For example, a combination of a (meth) acrylic polymer and nanocellulose can also improve or improve other physical properties such as strength and hardness without impairing physical properties such as transparency and high heat resistance.

Specific examples of the physical properties that the composition of the present invention can realize are shown below.

According to JIS Z 8729 of the composition of the present invention, the YI measured using a quartz cell having an optical path length of 10 mm is preferably 1.7 or less. It is more preferably 1.6 or less, 1.5 or less, and particularly preferably 1 or less. By setting the YI of the composition in this range, it is possible to obtain a highly transparent and low-colored film that is preferable for film formation such as solution film formation.

The glass transition temperature of the composition depends on the constituent monomers of the (meth) acrylic polymer, the type of ring structure, and the ratio thereof, but is, for example, 70 ° C. or higher (for example, 80 to 200 ° C.), preferably. It may be about 90 ° C. or higher (for example, 100 to 180 ° C.), more preferably 100 ° C. or higher (for example, 105 to 160 ° C.), and may be 110 ° C. or higher (for example, 115 to 150 ° C.).

The transparency of the composition depends on the ratio of the ring structure in the (meth) acrylic polymer, the type of additive, the presence or absence of its use, and the ratio thereof, but for example, in an unstretched film having a thickness of 100 μm (composition). The internal haze (when an unstretched film having a thickness of 100 μm is used) is 1 or less (for example, 0.8 or less), preferably 0.7 or less (for example, 0.6 or less), and more preferably 0.5 or less (for example, 0.6 or less). For example, it may be about 0.4 or less), and may be 0.3 or less or 0.2 or less.

Further, in an unstretched film having a thickness of 100 μm, the total light transmittance (when the composition is an unstretched film having a thickness of 100 μm) is, for example, 80% or more, preferably 85% or more, more preferably 90% or more, most preferably. It may be preferably 91% or more.

The hardness of the composition is, for example, 3 N / mm ² or more (for example, when the composition is an unstretched film having a thickness of 100 μm) as a universal hardness measured using a 50 μm flat indenter in an unstretched film having a thickness of 100 μm. , 3.5~20N / ^mm 2), preferably 4N / mm ² or more (e.g., 4.5~15N / ^mm 2), more preferably 5N / mm ² or more (e.g., 5.5~10N / mm ² ), And may be 6 N / mm ² or more, 7 N / mm ² or more, and the like.

The higher the hardness, the greater the choice of hard coat material, and depending on the application, the hard coat becomes unnecessary, which is preferable.

Further, in an unstretched film having a thickness of 100 μm (when the composition is an unstretched film having a thickness of 100 μm), the maximum amount of deformation (maximum depth) when the universal hardness is measured using a 50 μm flat indenter is 0.3 μm or less. (For example, 0 or detection limit to 0.28 μm), preferably 0.25 μm or less (for example, 0.01 to 0.22 μm), more preferably 0.2 μm or less (for example, 0.03 to 0.18 μm), and the like. It may be 0.17 μm or less (for example, 0.05 to 0.16 μm), 0.15 μm or less (for example, 0.08 to 0.15 μm), and the like.

The smaller the depth, the more difficult it is to deform, so it is preferable in terms of increasing the choice of hard coat material and eliminating the need for hard coat depending on the application.

In an unstretched film having a thickness of 100 μm (when the composition is an unstretched film having a thickness of 100 μm), the Martens hardness measured using a Vickers indenter having a facing angle of 136 ° is, for example, 150 N / mm ² or more (for example, 170). ~400N / ^mm 2), preferably 180 N / mm ² or more (e.g., 190~350N / ^mm 2), more preferably 200 N / mm ² or more (e.g., 203~300N / mm ²⁾ may be an, It can also be 205 N / mm ² or more (for example, 208 to 250 N / mm ² ), 210 N / mm ² or more, and the like.

The higher the hardness, the greater the choice of hard coat material, and depending on the application, the hard coat becomes unnecessary, which is preferable.

The elastic modulus of the composition is, for example, 1 GPa or more (for example, 1.5 to 30 GPa), preferably 2 GPa or more (for example, 2.5 to 20 GPa), and more preferably 3 GPa or more (for example, 3.3 to 15 GPa). It may be 3.5 GPa or more (for example, 3.8 to 10 GPa).

The coefficient of linear thermal expansion of the composition at 60 to 100 ° C. is in the range of about 500 ppm / K (500 × ^10-6 / K) or less, although it depends on the type and ratio of the ring structure in the (meth) acrylic polymer. It may be selected from 400 ppm / K or less (for example, 0 to 300 ppm / K), preferably 300 ppm / K or less (for example, 1 to 250 ppm / K), and more preferably 200 ppm / K or less (for example, 5 to 180 ppm). It may be about / K), 150 ppm / K or less (for example, 10 to 140 ppm / K), 130 ppm / K or less (for example, 20 to 120 ppm or less), 110 ppm / K or less (for example, 50 to 110 ppm / K). And so on.

The smaller the coefficient of linear expansion, the smaller the change in the usage environment such as the display and the lens, which is preferable in that warpage and optical distortion are less likely to occur.

The stress optical coefficient (Cr) of the composition can be selected according to the type and proportion of the ring structure in the (meth) acrylic polymer. For example, when an optically isotropic composition (expression of optical isotropicity) is assumed, the Cr of the composition has an absolute value of 15 × ^10-11 / Pa or less, preferably 10 × ^10-11 / Pa. Hereinafter, it may be more preferably 5 × ^10-11 / Pa or less, and most preferably 3 × ^10-11 / Pa or less.

Further, when assuming an optically anisotropy composition (expression of optical anisotropy), the Cr of the composition has an absolute value of 20 × ^10-11 / Pa or more, preferably 50 × ^10-11 / Pa. As mentioned above, it may be more preferably 150 × ^10-11 / Pa or more, and most preferably 300 × ^10-11 / Pa or more.

The photoelastic modulus (Cd) of the composition can be selected according to the type and proportion of the ring structure in the (meth) acrylic polymer. For example, when an optically isotropic composition (expression of optical isotropicity) is assumed, the Cd of the composition is an absolute value of 5 × ^10-12 / Pa or less, preferably 3 × ^10-12 /. It may be Pa or less, more preferably 2 × 10 ^-12 / Pa or less, and most preferably 1 × 10 ^-12 / Pa or less.

An unstretched film having a thickness of 100 μm is produced by the method described in Examples described later. Specifically, the dope obtained by stirring and mixing the composition and dichloromethane was spread on a PET film using an applicator, then placed in a dryer together with the PET film and dried at 40 ° C. for 30 minutes and 60 ° C. for 30 minutes. The applied film was peeled off from PET. Wide mountain-shaped clips were attached vertically so that the obtained film would not curl, and the film was hung in a dryer and then dried at 100 ° C. for 12 hours to obtain an unstretched film having a thickness of 100 μm.

The composition of the present invention preferably contains an organic solvent. The organic solvent is preferably one or more solvents selected from a hydrocarbon solvent, a ketone solvent, an ether solvent, an ester solvent, a cellosolve solvent, an alcohol solvent, a nitrile solvent and a halogen solvent. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; tetrahydrofuran, dioxolane, etc. Ether solvents such as dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and anisole; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; methyl cellosolve, ethyl cellosolve , Cellosolve solvents such as butyl cellosolve; alcohol solvents such as methanol, ethanol, isopropanol and n-butanol; nitrile solvents such as acetonitrile, propionitrile, butyronitrile and benzonitrile; halogen solvents such as chloroform and methylene chloride Can be raised. Only one of these solvents may be used, or two or more of these solvents may be used in combination. In the present invention, hydrocarbon solvents, ketone solvents, ether solvents, and halogen solvents are more preferable. Since the composition contains an organic solvent, the resin composition can be suitably used as a dope for film production used in the solution casting method of a film.

When the composition of the present invention contains an organic solvent, the content ratio of the organic solvent in the composition of the present invention is preferably 1% by mass or more and 99% by mass or less. The upper limit of the content ratio of the organic solvent in the composition containing the organic solvent is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less. The lower limit of the content ratio of the organic solvent in the composition containing the organic solvent is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and 30% by mass or more. It may be 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, and the like. With such a composition, the resin composition can be suitably used as a dope for film production used in the solution casting method of a film.

When the composition of the present invention contains an organic solvent, the content ratio of nanocellulose in the composition of the present invention is preferably 0.01% by mass or more and 10% by mass or less. The upper limit of the content ratio of nanocellulose in the composition containing the organic solvent is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 7% by mass or less, and 6% by mass or less. It may be 5% by mass or less, 4% by mass or less, and the like. The lower limit of the content ratio of nanocellulose in the composition containing an organic solvent is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and further preferably 0.05% by mass or more. , 0.08% by mass or more, 0.11% by mass or more, 0.15% by mass or more, and the like. With such a composition, the elastic modulus of the film obtained by using it is improved, and by forming a solution film, it becomes possible to obtain a highly transparent and low-colored film preferable for use in an optical film.

When the composition of the present invention contains an organic solvent, the content ratio of the polymer in the composition of the present invention is preferably 1% by mass or more and 70% by mass or less. The upper limit of the content ratio of the polymer in the composition containing the organic solvent is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and 45% by mass or less. It may be 40% by mass or less, 35% by mass or less, and the like. The lower limit of the content ratio of the polymer in the composition containing the organic solvent is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and 10% by mass or more. It may be 15% by mass or more.

When the composition of the present invention contains an organic solvent, the content ratio of the (meth) acrylic polymer in the composition of the present invention is preferably 1% by mass or more and 70% by mass or less. The upper limit of the content ratio of the (meth) acrylic polymer in the composition containing the organic solvent is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less. It may be 45% by mass or less, 40% by mass or less, 35% by mass or less, and the like. The lower limit of the content ratio of the (meth) acrylic polymer in the composition containing the organic solvent is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. It may be 10% by mass or more, 15% by mass or more, and the like.

When the composition of the present invention contains an organic solvent, the solution viscosity of the resin composition at 25 ° C. is preferably 0.05 Pa · s or more and 50 Pa · s or less. The upper limit of the solution viscosity of the resin composition at 25 ° C. is preferably 40 Pa · s or less, more preferably 30 Pa · s or less, and further preferably 20 Pa · s or less, 10 Pa · s or less, 5 Pa · s. It may be as follows. The lower limit of the solution viscosity of the resin composition at 25 ° C. is preferably 0.05 Pa · s or more, more preferably 0.1 Pa · s or more, still more preferably 0.15 Pa · s or more. With such a solution viscosity, the resin composition can be suitably used as a dope for film production used in the solution casting method of a film. The solution viscosity of the resin composition at 25 ° C. is measured according to JIS Z 8803.

When the composition of the present invention contains an organic solvent, the transmittance measured using a quartz cell having an optical path length of 10 mm in accordance with JIS K7361 is preferably 80% or more.

When the composition of the present invention contains an organic solvent, the haze measured using a quartz cell having an optical path length of 10 mm according to JIS K7136 is 10% or less, 8% or less, 5 or less, 3 or less, 2 or less, 1 The following is preferable.

When the composition of the present invention contains an organic solvent, the resin composition of the present invention is preferably a dope for film production used in the solution casting method of a film. Dope is a light stabilizer, UV absorber, heat stabilizer, matting agent, light diffuser, colorant, dye, pigment, antistatic agent, heat ray reflector, lubricant, plasticizer, UV absorber, stable. It may contain known additives such as agents and fillers.

In the present invention, the optical properties of the composition can be adjusted, for example, an optically isotropic composition can be obtained, or an optically anisotropic composition can be obtained.
<Molded body>
The present invention includes a molded article (molded article) containing the composition (containing the composition).

The shape of such a molded product is not particularly limited, and may be any of a two-dimensional shape [for example, a film (or sheet), etc.], a three-dimensional shape (for example, a block shape, etc.) and the like.

The molded product may be a foam (foam molded product).

The molded product (molded product) may have the same physical properties as the composition. Such physical property values can be selected from the same range as described above. For example, in a molded product (film or the like), the glass transition temperature is, for example, 70 ° C. or higher (for example, 80 to 200 ° C.), preferably 90 ° C. or higher (for example, 100 to 180 ° C.), and more preferably 100 ° C. or higher (for example). For example, it may be about 105 to 160 ° C., and may be 110 ° C. or higher (for example, 115 to 150 ° C.). The elastic modulus may be, for example, 1 GPa or more (for example, 1.5 to 30 GPa), 3 GPa or more (for example, 3.3 to 15 GPa), and the linear thermal expansion coefficient at 60 to 100 ° C. is 300 ppm / K. The following (for example, 1 to 250 ppm / K), 150 ppm / K or less, 100 ppm / K or less may be used.

The present invention is preferably a film containing the above composition, and is preferably an optical film for optical applications.

The internal b * value of the film containing the resin composition of the present invention in terms of 100 μm is preferably 1.0. It may be more preferably 0.9 or less, further preferably 0.8 or less and 0.7 or less, and particularly preferably 0.5 or less. The internal b * value of the film is measured in accordance with JIS Z 8729.

The internal haze of the film containing the resin composition of the present invention in terms of 100 μm is preferably 1.0 or less. It may be more preferably 0.5 or less, further preferably 0.4 or less, and particularly preferably 0.3 or less. The internal haze of the film is measured according to JIS K7136.

The elastic modulus of the film containing the resin composition of the present invention is preferably 1 GPa or more. It is preferably 2 GPa or more, more preferably 3 GPa or more, further preferably 3.5 GPa or more, 4.0 GPa or more, or the like. The elastic modulus of the film can be measured using the method described in Examples described later.

The Martens hardness of the film containing the resin composition of the present invention is preferably 150 N / mm ² or more. 180 N / mm ² or more, more preferably 200 N / mm ² or more, more preferably may also be 205N / mm ² or more, may be a 210N / mm ² or more. The Martens hardness of the film can be measured using the method described in Examples described later.

The film containing the resin composition of the present invention may be an unstretched film or a stretched film. The stretched film may be a uniaxially stretched film, a biaxially stretched film, or particularly a biaxially stretched film. The biaxially stretched film may be either a simultaneous biaxially stretched film or a sequential biaxially stretched film. Further, the direction of the slow axis of the stretched film may be the flow direction of the film, the width direction, or any direction.

The thickness of the film is not particularly limited and can be appropriately adjusted depending on the intended use, but may be, for example, 1 to 500 μm, preferably 3 to 300 μm, and more preferably about 5 to 200 μm. The thickness of the film is measured according to JIS K 7130.
<Manufacturing method of resin composition>
An example of a method for producing the composition (resin composition) of the present invention will be described, but the resin composition of the present invention is not limited thereto.

The polymerization of the monomer component can be carried out by using a known polymerization method such as a massive polymerization method, a solution polymerization method, an emulsion polymerization method, or a suspension polymerization method, but it is preferable to use a solution polymerization method. By using the solution polymerization method, it is possible to suppress the mixing of minute foreign substances into the resin composition, and it becomes easy to be suitably applied to optical material applications and the like. As the polymerization form, for example, either a batch polymerization method or a continuous polymerization method can be used. At the time of polymerization, the monomer components may be charged all at once or may be added in portions.

In the method for producing the resin composition of the present invention, it is preferable to polymerize the monomer in an organic solvent in the presence of nanocellulose. At this time, if the nanocellulose has a functional group or a polymerizable group that can be bonded by reacting with the monomer, the polymer and the nanocellulose can also be bonded.

The nanocellulose in the present invention is as described above.

The content ratio of nanocellulose in the polymerization solution in the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, and preferably 10% by mass or less. 5% by mass or less is more preferable, and 3% by mass or less is further preferable.

The content ratio of nanocellulose to all the monomers in the present invention is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and further preferably 10% by mass or less. It is preferably 7% by mass or less, more preferably 5% by mass or less.

The composition of the present invention preferably contains an organic solvent. The organic solvent is preferably one or more solvents selected from a hydrocarbon solvent, a ketone solvent, an ether solvent, an ester solvent, a cellosolve solvent, an alcohol solvent, a nitrile solvent and a halogen solvent. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; tetrahydrofuran, dioxolane, etc. Ether solvents such as dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and anisole; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; methyl cellosolve, ethyl cellosolve , Cellosolve solvents such as butyl cellosolve; alcohol solvents such as methanol, ethanol, isopropanol and n-butanol; nitrile solvents such as acetonitrile, propionitrile, butyronitrile and benzonitrile; halogen solvents such as chloroform and methylene chloride Can be raised. Only one of these solvents may be used, or two or more of these solvents may be used in combination. In the present invention, hydrocarbon solvents, ketone solvents, ether solvents, and halogen solvents are more preferable. Only one of these solvents may be used, or two or more of these solvents may be used in combination. By carrying out the polymerization reaction in an organic solvent, a resin composition can be produced without leaving emulsifiers, surfactants, etc. in the polymer, so that a resin composition having high transparency and reduced foreign substances can be obtained. Since the composition contains an organic solvent, the resin composition can be suitably used as a dope for film production used in the solution casting method of a film.

The polymerization reaction in the present invention is preferably carried out in the presence of a polymerization catalyst (polymerization initiator). Examples of the polymerization catalyst include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, and dimethyl-2,2'-azobis (2-methylpropio). Nate), azo compounds such as 4,4'-azobis (4-cyanopentanoic acid); persulfates such as potassium persulfate; cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl Peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, t-amylperoxyoctate, t-amylperoxyisononanoate, t-amylperoxy Organic peroxides such as isopropyl carbonate and t-amylperoxy-2-ethylhexyl carbonate can be used. Only one of these may be used, or two or more thereof may be used in combination. Among these, it is preferable to use an organic peroxide having a strong hydrogen abstraction power. The amount of the polymerization catalyst used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the monomer component, for example.

In the polymerization of the acrylic resin, a chain transfer agent may be used at the time of polymerization. The chain transfer agent is not particularly limited, and known compounds can be used.

Examples of the chain transfer agent include thiol compounds such as dodecyl mercaptoethanol, 2-mercaptoethanol and 3-mercaptopropionic acid, halogen compounds such as chloroform and carbon tetrachloride, polycyclic aromatic quinone compounds and α-methylstyrene dimer. Can be mentioned. These chain transfer agents may be used alone or in combination of two or more. The amount of the chain transfer agent used may be appropriately set according to the combination of monomers, reaction conditions, etc., and is not particularly limited.

The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or in an air flow. An azobis-based compound and a peroxide may be used in combination as a polymerization initiator in order to reduce the residual monomer. The reaction temperature is preferably 50 ° C to 200 ° C. The reaction time may be appropriately adjusted while observing the degree of progress of the copolymerization reaction and the degree of formation of the gelled product, and is preferably carried out for, for example, 1 hour to 20 hours.

The total concentration of the monomer components in the reaction solution is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, still preferably 80% by mass or less, and more preferably 70% by mass or less. preferable. The concentration of the polymerization solvent in the reaction solution is preferably 20% by mass or more, more preferably 30% by mass or more, preferably 97% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less. It is also possible to appropriately add a monomer component, a polymerization catalyst, a reaction solvent and the like during the polymerization reaction.

The monomer in the present invention is not particularly limited, but is an addition polymerization-based single amount such as (meth) acrylic-based monomer, olefin-based monomer, halogen-based monomer, and styrene-based monomer. Examples thereof include condensation polymerization-based monomers such as dimers, dicarboxylic acid-based monomers, diamine-based monomers, and diol-based monomers, and ring-opening polymerization-based monomers having an amide bond in the ring. Above all, from the viewpoint of optical properties such as transparency, an addition polymerization type monomer is preferable, and a (meth) acrylic type monomer is preferably contained.

The (meth) acrylic monomer in the present invention is a monomer containing an acrylic group in which a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) is bonded to the α-position and / or β-position. As used in the sense, the alkyl group may have at least a part of the hydrogen atom substituted with a hydroxy group or a halogen group. The (meth) acrylic monomer preferably means a monomer having an acrylic group or a methacrylic group. Further, the (meth) acrylic monomer includes (meth) acrylic acid (that is, a free acid) and a derivative thereof, and the derivative includes an ester, a salt, an acid amide and the like.

As the (meth) acrylic monomer, a (meth) acrylic acid ester is preferable. The (meth) acrylic acid ester is a (meth) acrylic acid ester in which a linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group is bonded to an oxygen atom of an ester bond of (meth) acrylic acid. Can be mentioned.

Examples of the (meth) acrylic acid ester having a linear or branched aliphatic hydrocarbon group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate , (Meta) isoamyl acrylate, (meth) n-hexyl acrylate, (meth) 2-ethylhexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Dodecyl acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate and the like are alkyl (meth) acrylates. The alkyl group of the alkyl (meth) acrylate is preferably a C1-18 alkyl group, more preferably a C1-12 alkyl group, and even more preferably a C1-6 alkyl group. In addition, in this specification, the description of "C1-18" and "C1-12" means "carbon number 1-18" and "carbon number 1-12" respectively.

Examples of the (meth) acrylic acid ester having a cyclic aliphatic hydrocarbon group include (meth) cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate. ) Cycloalkyl acrylate; crosslinked cyclic (meth) acrylates such as isobornyl (meth) acrylate. The cycloalkyl group of cycloalkyl (meth) acrylate is preferably a C3-20 cycloalkyl group, more preferably a C4-12 cycloalkyl group, and even more preferably a C5-10 cycloalkyl group.

Examples of the (meth) acrylic acid ester having an aromatic hydrocarbon group include phenyl (meth) acrylate, trill (meth) acrylate, xsilyl (meth) acrylate, naphthyl (meth) acrylate, and binaphthyl (meth) acrylate. , (Meta) aryl (meth) acrylate such as anthryl (meth) acrylate; aralkyl (meth) acrylate such as benzyl (meth) acrylate; (meth) aryloxyalkyl (meth) acrylate such as phenoxyethyl (meth) acrylate. Can be mentioned. The aryl group of the aryl (meth) acrylate is preferably a C6-20 aryl group, more preferably a C6-14 aryl group. The aralkyl group of aralkyl (meth) acrylate is preferably a C6-10 aryl C1-4 alkyl group. The aryloxyalkyl group of the aryloxyalkyl (meth) acrylate is preferably a C6-10 aryloxy C1-4 alkyl group, more preferably a phenoxy C1-4 alkyl group.

The (meth) acrylic acid ester may have a substituent such as a hydroxy group, an amino group, a halogen group, an alkoxy group, or an epoxy group. In particular, in a (meth) acrylic acid ester having a linear or branched aliphatic hydrocarbon group, it is preferable that the aliphatic hydrocarbon group has a hydroxy group, an amino group, a halogen group, an alkoxy group, an epoxy group and the like. Examples of such (meth) acrylic acid esters include (meth) hydroxyalkyl acrylates such as 2-hydroxyethyl (meth) acrylate; and (meth) chloromethyl acrylate, 2-chloroethyl (meth) acrylate and the like. Alkyl halides such as meth) acrylate; alkoxyalkyl (meth) acrylate such as 2-methoxyethyl (meth) acrylate; epoxyalkyl (meth) acrylate such as glycidyl (meth) acrylate can be mentioned. The alkyl group of hydroxyalkyl (meth) acrylate and epoxyalkyl (meth) acrylate is preferably a C1-12 alkyl group, more preferably a C1-6 alkyl group. The alkoxyalkyl group of the (meth) alkoxyalkyl acrylate is preferably a C1-12 alkoxy C1-12 alkyl group, the alkoxy group is more preferably C1-6, and the alkyl group is more preferably C1-6.

The content ratio of the (meth) acrylic monomer obtained by polymerizing the monomer may be 50% by mass or more (for example, 55% by mass or more) with respect to the polymer, and 60% by mass or more. It may be 70% by mass or more. Further, the content ratio of the (meth) acrylic monomer to the polymer may be 100% by mass or less, 99% by mass or less, 95% by mass or less, or 90% by mass or less.

The content ratio of the (meth) acrylic monomer contained in the monomer in the present invention can be selected from, for example, 10% by mass or more (for example, 20% by mass or more) with respect to all the monomers. It may be preferably 30% by mass or more (for example, 40% by mass or more), more preferably 50% by mass or more (for example, 55% by mass or more), 60% by mass or more, 70% by mass or more, and the like. Good.

The content ratio of the methacrylic acid ester unit contained in the monomer in the present invention is, for example, 10% by mass or more (for example, 20% by mass or more), preferably 30% by mass or more (for example, 40% by mass or more), and further. It may be preferably 50% by mass or more (for example, 60% by mass or more), 70% by mass or more, 80% by mass or more, 90% by mass or more, and the like.

The content ratio of the methacrylic acid alkyl ester unit contained in the monomer in the present invention is, for example, 10% by mass or more (for example, 20% by mass or more), preferably 30% by mass or more (for example) with respect to all the monomers. , 40% by mass or more), more preferably 50% by mass or more (for example, 60% by mass or more), 70% by mass or more, 80% by mass or more, 90% by mass or more, and the like.

When the polymer contains methyl methacrylate units, the content ratio of the methyl methacrylate units to all the monomers is, for example, 10% by mass or more (for example, 20% by mass or more), preferably 30% by mass or more (for example, 20% by mass or more). For example, it may be 40% by mass or more), more preferably 50% by mass or more (for example, 60% by mass or more), 70% by mass or more, 80% by mass or more, 90% by mass or more, and the like.

The monomer in the present invention may further have a vinyl monomer copolymerizable with the (meth) acrylic monomer. The vinyl monomer copolymerizable with the (meth) acrylic monomer is not particularly limited as long as it is a compound having a polymerizable double bond, and is, for example, a styrene-based monomer [for example, styrene, vinyl toluene, etc. Styrene having a substituent (eg, halogen group, alkoxy group, alkyl group, hydroxy group, etc.) (eg, α-methylstyrene, chlorostyrene, etc.), styrenesulfonic acid or a salt thereof, etc.], Vinyl ester (eg, vinyl acetate) Etc.), unsaturated nitriles (eg, acrylonitrile, methacrylonitrile, etc.), olefinic monomers (eg, C _2-10 alkenes such as ethylene, propylene, 1-butene, isobutylene, 1-octene, etc.), containing amide groups Vinyl-based monomers [eg, (meth) acrylamide, N-substituted (meth) acrylamide (eg, N-alkyl (meth) acrylamide such as N-methyl (meth) acrylamide; N such as N-cyclohexyl (meth) acrylamide; -Cycloalkyl (meth) acrylamide; N-aryl (meth) acrylamide such as N-phenyl (meth) acrylamide; N-aralkyl (meth) acrylamide such as N-benzyl (meth) acrylamide, etc.)] and the like.

The vinyl monomer copolymerizable with the (meth) acrylic monomer may be used alone or in combination of two or more.

The monomer of the present invention preferably further contains a monomer having a polymerizable double bond in the ring structure. In addition, two carboxylic acid groups of units derived from adjacent (meth) acrylic monomers can be linked by acid anhydrideization, imidization, etc., or among the units derived from adjacent (meth) acrylic monomers. When one has a protonic hydrogen atom-containing group such as a hydroxy group or an amino group, the protonic hydrogen atom-containing group of the unit derived from one (meth) acrylic monomer and the other (meth) acrylic group It is also preferable that the carboxylic acid group of the unit derived from the monomer is condensed. As a result, a ring structure can be introduced into the main chain of the polymer, and the transparency and heat resistance of the resin composition can be enhanced. Further, improvement of solvent resistance, dimensional stability, surface hardness, adhesiveness, barrier property of oxygen and water vapor, and various optical characteristics can be expected. Further, when a stretched film is obtained from the resin composition, it is possible to develop a phase difference derived from the ring structure depending on the stretching conditions.

The ring structure may be any of a 4-membered ring structure, a 5-membered ring structure, a 6-membered ring structure, a 7-membered ring structure, an 8-membered ring structure and the like, and is preferably a 5-membered ring structure or a 6-membered ring structure.

Examples of the monomer having a polymerizable double bond in the ring structure include maleic anhydride and maleimide-based monomers. Examples of maleimide-based monomers include maleimide; N-alkylmaleimide (eg, NC _1-10 alkylmaleimide such as N-methylmaleimide and N-ethylmaleimide), N-cycloalkylmaleimide (eg, cyclohexylmaleimide, etc.). _{NC 3-20} cycloalkylmaleimide), N-arylmaleimide (eg, _{NC 6-10} arylmaleimide such as N-phenylmaleimide), N-aralkylmaleimide (eg, N-benzylmaleimide such as N-benzylmaleimide) _Examples include N-substituted maleimides such as C7-10 aralkylmaleimide). Maleimide-based monomers are preferable from the viewpoint of moisture resistance, and N-cyclohexylmaleimide and N-phenylmaleimide are more preferable from the viewpoint of heat resistance, transparency, and availability.

In the present invention, it is preferable to carry out a ring structure forming step after the polymerization step. In the ring structure forming step, a ring structure is formed in the main chain of the polymer having the (meth) acrylic unit formed in the polymerization step. Specifically, the substituents of the adjacent (meth) acrylic units of the polymer having the (meth) acrylic unit formed in the polymerization step are condensed with each other to form a ring structure in the main chain. The cyclization condensation reaction includes an esterification reaction, an acid anhydride reaction, an amidation reaction, an imidization reaction and the like. For example, a glutaric anhydride structure can be formed by acid anhydrideizing two carboxylic acid groups of adjacent (meth) acrylic units, and a glutarimide structure can be formed by imidizing. The acrylic resin having a glutarimide structure as a ring structure is a known method such as a method of imidizing an acrylic resin containing a (meth) acrylic acid ester unit (for example, JP-A-2006-309033, JP-A-2006-317560). No., JP-A-2006-328329, JP-A-2006-328334, JP-A-2006-337491, JP-A-2006-337492, JP-A-2006-337493, JP-A-2007-009182. Etc.) can be obtained. Acrylic resin having a glutaric anhydride structure is, for example, a method of causing an intramolecular dealcohol reaction between adjacent (meth) acrylic acid ester units and (meth) acrylic acid units (for example, JP-A-2006-283013, JP-A. It can be obtained by the method described in Japanese Patent Application Laid-Open No. 2006-335902, Japanese Patent Application Laid-Open No. 2006-274118, etc.).

When one of the adjacent (meth) acrylic units has a protic hydrogen atom-containing group such as a hydroxyl group or an amino group, one of the (meth) acrylic units has a protic hydrogen atom-containing group and the other. A lactone ring structure can be formed by condensing with a carboxylic acid group of a (meth) acrylic unit. Examples of (meth) acrylic units having a protonic hydrogen atom-containing group such as a hydroxyl group or an amino group include 2- (hydroxymethyl) acrylate, 2- (hydroxyethyl) acrylate, and 2- (hydroxymethyl) acrylate. Alkyl (eg, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, n-butyl 2- (hydroxymethyl) acrylate, 2- (hydroxy) T-butyl methyl) acrylate, alkyl 2- (hydroxyethyl) acrylate (eg, methyl 2- (hydroxyethyl) acrylate, ethyl 2- (hydroxyethyl) acrylate) and the like are preferred. Examples thereof include 2- (hydroxymethyl) acrylate and alkyl 2- (hydroxymethyl) acrylate, which are monomers having an allyl moiety. Particularly preferred are methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate.

The acrylic resin having a lactam ring structure is, for example, a lactam-based monomer [for example, an N-vinylpyrrolidone-based monomer (for example, N-vinylpyrrolidone, N-vinyl-4-butylpyrrolidone, N-vinyl-4-). Vinylpyrrolidone, N-vinyl-4-ethylpyrrolidone, N-vinyl-4-methylpyrrolidone, N-vinyl-4-methyl-5-ethylpyrrolidone, N-vinyl-4-methyl-5-propylpyrrolidone, N-vinyl -5-Myl-5-ethylpyrrolidone, N-vinyl-5-propylvirolidone, N-vinyl-5-butylpyrrolidone, etc.), N-vinylcaprolactam-based monomers (eg, N-vinylcaprolactam, N- Vinyl-6-methylcaprolactam, N-vinyl-6-propylcaprolactam, N-vinyl-7-butylcaprolacttam, etc.)] and the monomers that make up the acrylic resin ((meth) acrylic acid ester, etc.) are copolymerized. Can be obtained by

In the ring structure forming step, the condensation reaction of adjacent (meth) acrylic units is preferably carried out in the presence of a catalyst (cyclization catalyst). As the cyclization catalyst, at least one selected from the group consisting of acids, bases and salts thereof can be used. Acids, bases and salts thereof may be organic or inorganic, and are not particularly limited. Among them, it is preferable to use an organic phosphorus compound as a catalyst for the cyclization reaction. By using the organic phosphorus compound as a cyclization catalyst, the cyclization condensation reaction can be efficiently carried out, and the coloring of the obtained polymer and resin composition can be reduced.

Organic phosphorus compounds that can be used as cyclization catalysts include, for example, alkyl (aryl) subphosphonic acid and monoesters or diesters thereof; dialkyl (aryl) phosphinic acid and esters thereof; alkyl (aryl) phosphonic acid and these. Monoesters or diesters; alkyl (aryl) subphosphinic acid and their esters; phosphoric acid monoesters, diesters or triesters; methyl phosphate, ethyl phosphate, 2-ethylhexyl phosphate, octyl phosphate, isodecyl phosphate. , Lauryl Phosphate, Stearyl Phosphate, Isostearyl Phosphate, phenyl Phosphate, Dimethyl Phosphate, Diethyl Phosphate, Di-2-ethylhexyl Phosphate, Diisodecyl Phosphate, Dilauryl Phosphate, Distearyl Phosphate, Di Phosphate Phosphate monoesters, diesters or triesters such as isostearyl, diphenyl phosphate, trimethyl phosphate, triethyl phosphate, triisodecyl phosphate, trilauryl phosphate, tristearyl phosphate, triisostearyl phosphate, triphenyl phosphate; Examples thereof include mono-, di- or tri-alkyl (aryl) phosphine; alkyl (aryl) halogen phosphine; mono-, di- or tri-alkyl (aryl) phosphine; tetraalkyl (aryl) phosphonium halide and the like. Only one of these may be used, or two or more thereof may be used in combination. Among these, phosphoric acid monoesters or diesters are particularly preferable because they have high catalytic activity and low colorability. The amount of the cyclization catalyst used is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the polymer obtained in the polymerization step, for example.

The reaction temperature in the ring structure forming step is preferably 50 ° C. to 300 ° C. The reaction time may be appropriately adjusted while observing the progress of the cyclization condensation reaction, and is preferably carried out for, for example, 5 minutes to 6 hours.

In the ring structure forming step, it is preferable to carry out volatilization. Volatilization can be performed by reducing the pressure inside the reactor with a vacuum pump or the like. By volatilization, the polymerization solvent used in the polymerization step and brought into the ring structure forming step, alcohol produced by the cyclization condensation reaction, etc. are removed, and the residual volatile matter in the obtained copolymer (P) is reduced. can do. In addition, since alcohol and the like produced as a by-product in the cyclization condensation reaction are removed, the reaction equilibrium is inclined toward the production side, which is advantageous.

When the cyclization condensation reaction is carried out while devolatile, it is preferable to carry out the cyclization condensation reaction under reduced pressure from the viewpoint of efficient devolatileation. The reduced pressure in the cyclization condensation reaction is, for example, preferably 90 kPa or less, more preferably 80 kPa or less, still more preferably 70 kPa or less as an absolute pressure. On the other hand, the absolute pressure at the time of decompression is preferably 0.1 kPa or more, and more preferably 1 kPa or more, from the viewpoint that the equipment for realizing the depressurized state does not become excessively specified and the equipment cost is kept low. When the cyclization condensation reaction is carried out without volatilization, the cyclization condensation reaction may be carried out under normal pressure or pressure.

When an extruder with a vent is used, it is preferable that the extruder has a cylinder and a screw provided in the cylinder, and is provided with heating means. The cylinder is provided with one or more vents. The vent is preferably provided at least on the downstream side of the raw material charging section with respect to the transfer direction in the extruder, and may also be provided on the upstream side of the raw material charging section.

The cyclization condensation reaction proceeds in the process of transferring the copolymer supplied into the extruder from the upstream side to the downstream side of the extruder while kneading with a screw, and the polymer is discharged from the downstream side of the extruder. It is preferable that a die is provided on the downstream side of the extruder, and the polymer can be formed into a predetermined shape (film shape or rod shape) by discharging the polymer from the die. For example, pellets can be produced by finely cutting a copolymer formed into a rod shape.

When the cyclization condensation reaction is carried out in the presence of a cyclization catalyst in the ring structure forming step, it is preferable to add a deactivating agent after or during the cyclization condensation reaction. For example, when a resin composition containing a polymer is pelletized or filmed, if a cyclization catalyst remains in the resin composition, an alcohol or the like is generated due to a cyclization condensation reaction, which is desired. No foaming can occur. However, such foaming can be prevented by adding a deactivating agent after or during the cyclization condensation reaction.

As the deactivating agent, a substance capable of neutralizing the cyclization catalyst is preferably used. For example, when the cyclization catalyst is an acidic substance, a basic substance can be used as the inactivating agent, and conversely, when the cyclization catalyst is a basic substance, an acidic substance can be used as the inactivating agent. .. As described above, an organic phosphorus compound is preferably used as the cyclization catalyst, and the compound is often an acidic substance. Therefore, it is preferable to use a basic substance as the inactivating agent. The basic substance is not particularly limited as long as it can have a function of stopping the cyclization condensation reaction, and for example, a metal carboxylate, a metal complex, a metal oxide, or the like is used. On the contrary, when a basic substance is used as the cyclization catalyst, an acidic substance that can be used for the cyclization catalyst described above can be used as the deactivating agent.

The timing of adding the deactivating agent is preferably during the cyclization condensation reaction or after the reaction and before pelletizing or filming the resin composition containing the polymer. For example, the deactivating agent may be added to the molten resin composition, or the deactivating agent may be added to the resin composition dissolved in the solvent. When the cyclization condensation reaction is carried out using an extruder as described above, the deactivator may be added at a position after the cyclization condensation reaction is sufficiently carried out in the extruder.

In the polymerization step of the present invention, the copolymer (P1) further having a polymer block (a1) having a unit derived from diene and / or an olefin and a polymer block (a2) having a unit derived from an aromatic vinyl monomer. In the presence of, a polymer chain (B) obtained by polymerizing a monomer component containing a (meth) acrylic monomer and having a unit derived from the (meth) acrylic monomer and a unit having a ring structure in the main chain. A mode for obtaining the copolymer (P) having the above is also preferable. Thereby, high mechanical strength can be efficiently realized.

The copolymer (P1) and (meth) acrylic monomer in the present invention are as described above.

As the copolymer (P1), it is preferable to use a copolymer having an olefinic double bond amount of 0.030 mmol / g or more and 2.3 mmol / g or less. By using the raw material copolymer (P1) having an olefinic double bond amount of 0.030 mmol / g or more, it becomes easy to obtain a highly transparent copolymer (P). On the other hand, by using the raw material copolymer (P1) having an olefin double bond amount of 2.3 mmol / g or less, it becomes easy to obtain the copolymer (P) in which less gelation is generated. The amount of the olefinic double bond of the copolymer (P1) is more preferably 0.040 mmol / g or more, further preferably 0.050 mmol / g or more, and even more preferably 2.0 mmol / g or less. The amount of the olefinic double bond of the copolymer (P1) can be determined by the iodine titration method.

The ring structure of the main chain of the polymer chain (B) may contain a part or all of the (meth) acrylic monomer in the ring structure, and is introduced separately from the (meth) acrylic monomer. It may have a ring structure. When a part or all of the (meth) acrylic monomer is contained in the ring structure, for example, two carboxylic acid groups of units derived from the adjacent (meth) acrylic monomer are acid anhydrideized. , Imidization and the like. When one of the units derived from the adjacent (meth) acrylic monomer has a protic hydrogen atom-containing group such as a hydroxyl group or an amino group, it is derived from this one (meth) acrylic monomer. A ring structure can also be formed by condensing a protic hydrogen atom-containing group of a unit with a carboxylic acid group of a unit derived from the other (meth) acrylic monomer. When the ring structure is introduced separately from the unit derived from the (meth) acrylic monomer, for example, a (meth) acrylic monomer and a monomer having a polymerizable double bond in the ring structure are introduced. It may be copolymerized.

As a method for producing the (meth) acrylic-based (meth) acrylic polymer contained in the present invention, a known method can be used. The meta) acrylic polymer has a polymer chain (A) having a unit derived from a diene and / or an olefin, a unit derived from a (meth) acrylic monomer, and a polymer chain (B) having a unit having a ring structure in the main chain. The copolymer having and is not particularly limited, and the production method described in WO2018 / 131670 can be used.

The resin composition in the present invention may contain various additives. Examples of the additive include ultraviolet absorbers; antioxidants such as hindered phenol-based, phosphorus-based and sulfur-based; stabilizers such as light-resistant stabilizers, weather-resistant stabilizers and heat-stabilizing agents; glass fibers, carbon fibers and the like. Reinforcing material; Near infrared absorber; Flame retardant such as tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide; Phase difference adjusting agent such as phase difference increasing agent, phase difference reducing agent, phase difference stabilizer; Anion system, Antistatic agents containing cationic and nonionic surfactants; colorants such as inorganic pigments, organic pigments and dyes; organic fillers and inorganic fillers; resin modifiers; organic fillers and inorganic fillers; etc. .. The content ratio of each additive in the resin composition is preferably in the range of 0 to 5% by mass, more preferably 0 to 2% by mass.
<Manufacturing method of molded product>
Manufacturing methods such as inflation method, T-die method, calendar method, cutting method, casting method, emulsion method, hot press method, etc. can be used, but coloring suppression, foreign matter defect suppression, optical defect suppression such as die line, etc. can be used. From the viewpoint, the solution casting method by the casting method is preferable.
-Dope production process As a method for producing a dope used in the solution casting method, a step of polymerizing a monomer in the presence of nanocellulose is followed by a step of dissolving the dried resin composition in an organic solvent again. Alternatively, the polymer concentration may be adjusted and used as a dope without drying.
-Cushioning process In the production method of the present invention, it is preferable to provide a casting process.

In the casting step, the dope composition prepared in the dissolving step is cast on a support to form a film, which is dried to form a casting film. As the film forming method, a die coater, a doctor blade coater, a roll coater, a comma coater, a lip coater and the like are preferable, but the film forming method is not limited to these examples, and various commonly used methods are possible. In this casting step, the dope composition is fed to the coating part through a liquid feed pump (for example, a pressurized metering gear pump, a diaphragm pump, etc.) and transferred indefinitely, or an endless metal belt (for example, a stainless steel belt), or It is preferable that the dope composition is cast at a casting position on a metal support such as a rotating metal drum or a support such as a process film. As the coating portion, a pressure die capable of adjusting the slit shape of the base portion and easily making the film thickness uniform is preferable. The pressure die includes a coat hanger die, a T die, and the like, and any of them is preferably used. By making the surface of the metal support a mirror surface, a film having excellent surface smoothness can be obtained, but in order to obtain the required characteristics, the uneven support is coated and the uneven shape is transferred. May be good. In order to increase the film forming speed, two or more pressure dies may be provided on the metal support, and the amount of the dope composition may be divided and layered. Alternatively, it is also preferable to obtain a cast film having a laminated structure by a co-cast method in which a plurality of dope compositions are cast at the same time.

When casting the dope composition, two or more kinds of dope compositions can be co-rolled simultaneously or sequentially. Further, these two co-current spreads may be combined. When performing simultaneous laminated co-casting, a casting die with a feed block attached may be used, or a multi-manifold type casting die may be used. In a film composed of multiple layers by co-flowing, at least one of the thickness of the layer on the air surface side and the thickness of the layer on the support side is preferably 0.5% to 30% of the total film thickness. .. Further, in the case of simultaneous laminating and co-casting, it is preferable that the high-viscosity dope composition is wrapped with the low-viscosity dope composition when the dope composition is cast from the die slit to the support.

In this casting step, co-casting may be performed sequentially.
-Drying step Next, it is preferable to dry the casting film thus obtained. At that time, it is usually heated on the cast film metal support, and the solvent is evaporated until the cast film can be peeled off from the metal support. To evaporate the solvent, there are a method of blowing wind from the casting film side and / or a method of transferring heat from the back surface of the metal support with a liquid, a method of transferring heat from the front and back surfaces with radiant heat, and the like. Is preferable because the drying efficiency is good. A method of combining them is also preferable. In the case of backside liquid heat transfer, it is preferable to heat below the boiling point of the main organic solvent used in the dope composition or the organic solvent having the lowest boiling point. It should be noted that the method of heat transfer of liquid on the back surface is preferably used because the surface is roughened and the flatness is adversely affected when the wind is blown against the saliva film immediately after coating. Further, in that case, it is preferable to carry out in dry air from the viewpoint of preventing dew condensation.
-Peeling step In the production method of the present invention, it is preferable to provide a peeling step.

In the peeling step, the molded body formed in the casting step is peeled from the support. The peeled molded product is sent to the preheating step. The amount of residual solvent at the time of peeling of the molded product on the support is set depending on the drying conditions, the length of the support, and the like, but in the present invention, the molded product is peeled in the range of 5 to 60% by mass. Further, it is preferable to peel off in the range of 10 to 40% by mass. Here, the amount of residual solvent is the content ratio of the solvent to the total solid content of the molded product.
-Drying step after peeling The peeled molded product may be conveyed and dried while grasping the left and right ends in the flow direction. In this case, it is preferable to appropriately adjust the left-right click interval in order to follow the change in the film width due to the heating of the film and the evaporation of the solvent. Further, it may be dried while being alternately passed through a plurality of rolls arranged in the drying device and conveyed. In this case, in order to prevent the film from stretching due to the transport tension, it is preferable to transport the film with a tension of 5 kg / m or less.

Further, the drying furnace may use a plurality of different temperature sections. By setting the drying conditions according to the amount of residual solvent, not only efficient drying can be performed, but also defects such as wrinkles and streaks can be suppressed to obtain a film having excellent flatness.

In the production method of the present invention, a preheating step may be provided. By providing such a preheating step, a molded product having excellent dimensional stability can be obtained. In addition, it is possible to obtain a good planar molded product with less wrinkles.

In the production method of the present invention, a heat treatment step may be provided. By setting the heat treatment temperature within this range, the solvent can be sufficiently dried, and a molded product having excellent dimensional stability can be produced.
-Stretching process When the molded product of the present invention is used as an optical film, it is preferably stretched in the width direction. At this time, the amount of residual solvent in the casting film is preferably less than 1%.

The draw ratio is preferably 105% to 300%, more preferably 110% to 200%. When the draw ratio is 105% or more, a good surface shape is obtained, and when it is 300% or less, the optical film is less likely to break.

The surface temperature of the optical film in the stretching step is lower than the temperature in the heat treatment step, and is preferably Tg + 10 ° C. to Tg + 100 ° C., more preferably Tg + 20 to Tg + 60 ° C. of the optical film. When the Tg of the optical film is + 10 ° C. or higher, the dimensional stability of the optical film does not deteriorate, and it is easy to obtain an optical film having good transparency.

If the Tg of the optical film is + 100 ° C. or less, wrinkles are less likely to occur after the tenter is removed, and the rolled appearance of the roll is less likely to deteriorate.

In the stretching step, after the heat treatment step is performed, the optical film may be wound into a roll once, and then the stretching step may be performed offline on the optical film wound from the roll. After the stretching step, the surface temperature of the film is preferably cooled to Tg or less before the optical film is separated from the tenter.

Further, in order to prevent the film from being fused to the tenter grip portion, the temperature of the grip portion is preferably cooled to Tg or less.
<Use of molded product>
The molded product in the present invention can be applied to various uses, and may be suitably used for, for example, optical applications.

Specific examples of applications include film applications [for example, protective films (optical protective films, etc.), optical films (optical sheets), etc.], lens applications (optical lenses, etc.), and cover applications (lens covers, etc.). ), Foam (foam molded body) applications (for example, cushioning material, heat insulating / heat insulating material, vibration damping material, soundproofing material, sealing material, packing material, etc.).

Examples of the protective film include a protective film for various optical disk (VD, CD, DVD, MD, LD, etc.) substrates, a polarizer protective film used for a polarizing plate for a liquid crystal display device, and the like.

Examples of the optical film (optical sheet) include a retardation film, a zero retardation film (in-plane, thickness direction retardation is extremely small), a viewing angle compensation film, a light diffusion film, a reflection film, an antireflection film, and an antireflection film. Examples thereof include a glare film, a brightness improving film, a conductive film for a touch panel, a diffuser plate, a light guide body, a retardation plate, a zero retardation plate, a prism sheet, and a film for the outermost cover window.
Polarizer protective film In particular, the molded body (film) may be a polarizing element protective film used for a polarizing plate included in an image display device such as a liquid crystal display device (LCD). The film may be used as it is as a polarizer protective film.
· Polarizer invention also contains a polarizing plate provided with the film.

That is, the film can be used as a polarizing plate protective film and used as a polarizing plate.

The method for producing the polarizing plate is not particularly limited, and a conventionally known method may be followed. For example, a polarizing plate can be obtained by laminating the film on at least one surface of the polarizer using a conventional method. In the bonding, the side of the film to be bonded to the polarizer is subjected to alkali saponification treatment, a completely saponified polyvinyl alcohol aqueous solution is applied to at least one side of the polarizer, and then the film of the present invention and the polarizer are bonded. , Can be preferably carried out.

The polarizer is an element that allows only polarized waves in a certain direction to pass through. The polarizer used in the present invention is not particularly limited, and conventionally known ones can be used, and examples thereof include polyvinyl alcohol-based films. As the polyvinyl alcohol-based film, one dyed with iodine and one dyed with a dichroic dye can be used.

The polyvinyl alcohol-based film is, for example, a film obtained by forming an aqueous solution of polyvinyl alcohol and stretching it uniaxially for dyeing, or dyeing and then uniaxially stretching the film, and then preferably performing a durability treatment using a boron compound. Etc. can be preferably used.

The film thickness of the polarizer is preferably 1 to 80 μm, preferably 1 to 40 μm, and more preferably 1 to 20 μm.
-Image display device The present invention also includes an image display device provided with the film. In such an image display device, the use (function) of the film of the present invention is not particularly limited, and for example, in an image display device provided with a polarizing plate, the polarizing plate (polarizer protective film) may be configured. ..

In the present invention, the method for manufacturing the image display device is not particularly limited, and a conventionally known method may be followed. As the image display device, a liquid crystal display device (LCD) or the like is preferable.

The liquid crystal display device provided with the polarizing plate provided with the film of the present invention is preferably composed of, for example, a liquid crystal cell and polarizing plates arranged on both sides thereof, and the film of the present invention is arranged so as to be in contact with the liquid crystal cell. Further, it is preferable that the prism sheet and the diffusion film are further laminated on the liquid crystal display device by using a conventional method.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

Various physical properties were measured and evaluated as follows.
[Polymerization reaction rate, polymer composition analysis]
For the reaction rate during the polymerization reaction and the content of the specific monomer unit in the polymer, the amount of unreacted monomer in the obtained polymerization reaction mixture was gas chromatographed (manufactured by Shimadzu Corporation, device name: GC-). It was determined by measurement using 2014).
[Weight average molecular weight and number average molecular weight]
The weight average molecular weight Mw and the number average molecular weight Mn were determined by polystyrene conversion using gel permeation chromatography (GPC). The equipment and measurement conditions used for the measurement are as follows.

System: Tosoh GPC system HLC-8220
Measurement side column configuration:
・ Guard column (manufactured by Tosoh, TSKguardcolum SuperHZ-L)
-Separation column (manufactured by Tosoh, TSKgel SuperHZM-M) 2 series connection Reference side column configuration:
・ Reference column (manufactured by Tosoh, TSKgel SuperH-RC)
Developing solvent: Chloroform (manufactured by Wako Pure Chemical Industries, Ltd., special grade)
Flow rate of developing solvent: 0.6 mL / min Standard sample: TSK standard polystyrene (Tosoh, PS-oligomer kit)
Column temperature: 40 ° C
[Glass transition temperature (Tg)]
The glass transition temperature was determined in accordance with JIS K 7121. Specifically, using a differential scanning calorimeter (Thermo plus EVO DSC-8230 manufactured by Rigaku Co., Ltd.), a sample of about 10 mg was heated from room temperature to 200 ° C. (heating rate 20 ° C./min) under a nitrogen gas atmosphere. From the DSC curve obtained in the above, the starting point method was used for evaluation. As a reference, α-alumina was used.
[YI (resin composition)]
The degree of yellowness (YI) was determined in accordance with the provisions of JIS Z 8729. Specifically, in the transmission mode of a spectrocolorimeter (manufactured by Nippon Denshoku Industries Co., Ltd .: Coloreter ZE6000), 3 g of a sample was dissolved in 17 g of chloroform, and a 15 mass% solution was measured using a quartz cell having an optical path length of 10 mm.
[YI (dope solution)]
The degree of yellowness (YI) was determined in accordance with the provisions of JIS Z 8729. Specifically, the measurement was performed using a quartz cell having an optical path length of 10 mm in the transmission mode of a spectrocolor difference meter (manufactured by Nippon Denshoku Industries Co., Ltd .: Colormeter ZE6000).
[viscosity]
The viscosity of the dope solution was measured at 25 ° C. using a BHII type viscometer (manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS Z 8803.
[Haze (dope solution)]
The haze of the dope solution was determined in accordance with JIS K7136. Specifically, it was measured using a haze meter (NDH-1001DP, manufactured by Nippon Denshoku Kogyo Co., Ltd.) using a quartz cell having an optical path length of 10 mm.
[Film thickness]
The thickness of the film was determined by a digital micrometer (manufactured by Mitutoyo).
[Internal haze]
Haze was obtained in accordance with the provisions of JIS K7136. Specifically, using a haze meter (NDH-1001DP manufactured by Nippon Denshoku Kogyo Co., Ltd.), a quartz cell having an optical path length of 10 mm is filled with 1,2,3,4-tetrahydronaphthalene (tetralin), and a film is contained therein. Was immersed and measured, and calculated as an internal haze value per 100 μm.
[Total light transmittance]
The total light transmittance was determined in accordance with the provisions of JIS K7361. Specifically, the measurement was performed using a haze meter (NDH-1001DP, manufactured by Nippon Denshoku Kogyo Co., Ltd.).
[Internal b * value]
The degree of yellowness (YI) was determined in accordance with the provisions of JIS Z 8729. Specifically, using a spectrocolorimeter (manufactured by Nippon Denshoku Industries Co., Ltd .: Colormeter ZE6000), a quartz cell having an optical path length of 10 mm is filled with 1,2,3,4-tetrahydronaphthalene (tetralin), and a film is contained therein. Was immersed and measured, and calculated as an internal b * value per 100 μm.
[Martens hardness and elastic modulus (Young's modulus)]
The Martens hardness and elastic modulus (Young's modulus) are determined by an ultrafine hardness tester (Fisher Instruments, Fisherscope) for an unstretched film (thickness 100 μm) obtained by hot-press molding a resin or resin composition. Using HM-2000), evaluation was performed by a method compliant with ISO-145777-1, and Martens hardness and elastic modulus (Young's modulus) were measured at the same time.

The evaluation was carried out with the unstretched film fixed to the glass substrate. The measurement conditions are a square cone-shaped Vickers indenter (face-to-face angle a = 136 °); maximum test load 3 mN; application time 20 seconds when load is applied; creep time 5 seconds; application time 20 seconds when load is reduced; measurement The temperature was room temperature; and the values measured three times were averaged to obtain the value.
<Adjustment of CNF toluene dispersion (T1)>
CNF (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., CNF N-03, methanol dispersion with a solid content of 5% by mass, average fiber diameter of 3 nm) is diluted with toluene, stirred and mixed with ultrasonic waves for 30 minutes, and CNF with a solid content of 1% by mass. The toluene dispersion was prepared.
<Adjustment of CNF toluene dispersion (T2)>
CNF (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., CNF N-03, methanol dispersion having a solid content of 5% by mass, average fiber diameter of 3 nm) was diluted with toluene, stirred and mixed with ultrasonic waves for 30 minutes, and CNF having a solid content of 3% by mass. The toluene dispersion was prepared.
<Example 1>
100 parts of methyl methacrylate (MMA), 0.03 part of n-dodecyl mercaptan (nDM), 100 parts of CNF toluene dispersion (T1) in a reactor equipped with a stirrer, temperature sensor, cooling tube, and nitrogen introduction tube. , 20 parts of toluene was charged, and the temperature was raised to 75 ° C. while passing nitrogen through it. After that, 0.09 part of t-amylperoxy-2-ethylhexanoate (manufactured by Alchema Yoshitomi, Luperox 575) was added as an initiator, and 0.018 part of t-amylperoxy diluted with 1 part of toluene was added. Solution polymerization was carried out at 75-85 ° C. while dropping -2-ethylhexanoate at a constant rate over 2 hours, and further aging was carried out for 4 hours. As a result, a polymerization reaction solution containing a resin composition composed of CNF and an acrylic polymer was obtained. The conversion rate of MMA calculated from the amount of residual monomers in the polymerization reaction solution was 97%.

Next, 200 parts of methyl ethyl ketone (MEK) was added to the obtained polymerization reaction solution to dilute it, and then slowly added to a large amount of methanol with stirring. Then, the precipitated white solid was taken out and dried at 2.6 kPa at 120 ° C. for about 1 hour to remove the solvent to obtain a resin composition (A-1). The weight average molecular weight of the obtained resin composition was 171,000, the glass transition temperature was 105 ° C., and the YI was 0.9.

Next, 1 part of the resin composition A-1 and 4 parts of dichloromethane were mixed, shaken for 1 minute, and then stirred and mixed for 60 minutes to prepare a dope solution B-1 having a solid content of 20%. The viscosity of the dope solution was 0.4 Pa · s, the haze was 0.4%, and the YI was 1.0. When the dope solution was visually confirmed, it was uniformly dispersed, and even if it was allowed to stand overnight, the appearance of the dope solution did not change.

Next, the dope solution B-1 was dripped on the PET film and spread to a film thickness of 500 μm using an applicator. Then, the PET film was placed in a dryer and dried at 40 ° C. for 30 minutes and 60 ° C. for 30 minutes, and then the applied film was peeled off from PET. Wide mountain-shaped clips were attached vertically so that the obtained film would not curl, and the film was hung in a dryer and then dried at 100 ° C. for 12 hours to obtain a film C-1. The internal haze of film C-1 in terms of 100 μm was 0.2, the internal b * value in terms of 100 μm was 0.4, the elastic modulus was 4.5 GPa, and the Martens hardness was 225 N / mm ² .
<Comparative example 1>
A reactor equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introduction tube was charged with 100 parts of methyl methacrylate (MMA), 0.03 part of n-dodecyl mercaptan (nDM), and 100 parts of toluene as a polymerization solvent. The temperature was raised to 75 ° C. while passing nitrogen through. After that, 0.09 part of t-amylperoxy-2-ethylhexanoate (manufactured by Alchema Yoshitomi, Luperox 575) was added as an initiator, and 0.018 part of t-amylperoxy diluted with 1 part of toluene was added. Solution polymerization was carried out at 75-85 ° C. while dropping -2-ethylhexanoate at a constant rate over 2 hours, and further aging was carried out for 4 hours. As a result, a polymerization reaction solution containing an acrylic polymer in which MMA was polymerized was obtained. The conversion rate of MMA calculated from the amount of residual monomers in the polymerization reaction solution was 98%.

Next, 200 parts of methyl ethyl ketone (MEK) was added to the obtained polymerization reaction solution to dilute it, and then slowly added to a large amount of methanol with stirring. Then, the precipitated white solid was taken out and dried at 2.6 kPa at 120 ° C. for about 1 hour to remove the solvent to obtain an acrylic polymer (A-2). The weight average molecular weight of the obtained resin composition was 161,000, the glass transition temperature was 105 ° C., and the YI was 0.3.

Next, 1 part of the resin composition A-2 and 4 parts of dichloromethane were mixed, shaken for 1 minute, and then stirred and mixed for 60 minutes to prepare a dope solution B-2 having a solid content of 20%. The viscosity of the dope solution was 0.3 Pa · s, the haze was 0.2%, and the YI was 0.4. When the dope solution was visually confirmed, it was uniformly dispersed, and even if it was allowed to stand overnight, the appearance of the dope solution did not change.

Next, the dope solution B-2 was dripped on the PET film and spread to a film thickness of 500 μm using an applicator. Then, the PET film was placed in a dryer and dried at 40 ° C. for 30 minutes and 60 ° C. for 30 minutes, and then the applied film was peeled off from PET. Wide mountain-shaped clips were attached up and down so that the obtained film would not curl, and the film was hung in a dryer and then dried at 100 ° C. for 12 hours to obtain a film C-2. The internal haze of film C-2 in terms of 100 μm was 0.1, the internal b * value in terms of 100 μm was 0.1, the elastic modulus was 3.6 GPa, and the Martens hardness was 179 N / mm ² .
<Comparative example 2>
One part of the acrylic polymer (A-2) prepared in Comparative Example 1 was dissolved in 4 parts of toluene, 1 part of CNF toluene dispersion T1 was added, and the mixture was dissolved by stirring and mixing for 2 hours. Then, the resin composition A-3 was obtained by drying at 2.6 kPa and 140 ° C. for about 1 hour to remove the solvent.
The weight average molecular weight of the obtained resin composition was 161,000, the glass transition temperature was 105 ° C., and the YI was 1.8.

Next, 1 part of the resin composition A-3 and 4 parts of dichloromethane were mixed, shaken for 1 minute, and then stirred and mixed for 60 minutes to prepare a dope solution B-3 having a solid content of 20%. The viscosity of the dope solution was 0.4 Pa · s, the haze was 0.9%, and the YI was 1.8. When the dope solution was visually confirmed, it was uniformly dispersed, and even if it was allowed to stand overnight, the appearance of the dope solution did not change.

Next, the dope solution B-3 was dripped on the PET film and spread to a film thickness of 500 μm using an applicator. Then, the PET film was placed in a dryer and dried at 40 ° C. for 30 minutes and 60 ° C. for 30 minutes, and then the applied film was peeled off from PET. Wide mountain-shaped clips were attached vertically so that the obtained film would not curl, and the film was hung in a dryer and then dried at 100 ° C. for 12 hours to obtain a film C-3. The internal haze of film C-3 in terms of 100 μm was 0.4, the internal b * value in terms of 100 μm was 0.8, the elastic modulus was 4.2 GPa, and the Martens hardness was 221 N / mm ² .
<Comparative example 3>
The resin composition A-3 obtained in Comparative Example 2 was press-molded at 220 ° C. to obtain a film C-3. The internal haze of the film C-4 in terms of 100 μm was 0.5, the internal b * value was 2.1, the elastic modulus was 4.2 GPa, and the Martens hardness was 215 N / mm ² .
<Comparative example 4>
One part of the acrylic polymer (A-2) prepared in Comparative Example 1 was dissolved in 4 parts of toluene, 6.7 parts of CNF toluene dispersion T2 was added, and the mixture was dissolved by stirring and mixing for 2 hours. Then, the resin composition A-4 was obtained by drying at 2.6 kPa and 140 ° C. for about 1 hour to remove the solvent.
The weight average molecular weight of the obtained resin composition was 161,000, the glass transition temperature was 105 ° C., and the YI was 4.5.

Next, 1 part of the resin composition A-4 and 4 parts of dichloromethane were mixed, shaken for 1 minute, and then stirred and mixed for 60 minutes to prepare a dope solution B-4 having a solid content of 20%. The viscosity of the dope solution was 1.0 Pa · s, the haze was 8.1%, and the YI was 5.1. When the dope solution was visually confirmed, some agglomerates were confirmed.

Next, the dope solution B-4 was dripped on the PET film and spread to a film thickness of 500 μm using an applicator. Then, the PET film was placed in a dryer and dried at 40 ° C. for 30 minutes and 60 ° C. for 30 minutes, and then the applied film was peeled off from PET. Wide mountain-shaped clips were attached vertically so that the obtained film would not curl, and the film was hung in a dryer and then dried at 100 ° C. for 12 hours to obtain a film C-5. On the appearance of film C-5, a site where CNF was unevenly aggregated was confirmed. The 100 μm-equivalent internal haze was 4.0, and the 100 μm-equivalent internal b * value was 3.2.
<Example 2>
Reactor equipped with agitator, temperature sensor, cooling tube, nitrogen introduction tube, MMA 83.5 parts, 2- (hydroxymethyl) methyl acrylate (MHMA) 12 parts, n-dodecyl mercaptan (nDM) 0.07 parts , 100 parts of CNF toluene dispersion T1 and 20 parts of toluene were charged, and the temperature was raised to 75 ° C. through nitrogen. After that, 0.09 part of t-amylperoxy-2-ethylhexanoate (manufactured by Alchema Yoshitomi, Luperox 575) was added as an initiator, and 4.5 parts of styrene (St) and 1 part of toluene were diluted with 0. Solution polymerization was carried out at 75-85 ° C. while dropping .018 parts of t-amylperoxy-2-ethylhexanoate at a constant rate over 2 hours, and further aging was carried out for 4 hours. 0.07 part of stearyl phosphate was added thereto as a cyclization catalyst, and a cyclization reaction was carried out at a temperature of 70-85 ° C. for 2 hours. As a result, a polymerization reaction solution containing a resin composition composed of an acrylic copolymer having a lactone ring structure in the main chain and CNF, which was polymerized from MMA, MHMA and St, was obtained. The conversion rate of MMA calculated from the amount of residual monomers in the polymerization reaction solution was 97%, the conversion rate of MHMA was 96%, and the conversion rate of St was 99%.

Next, 200 parts of methyl ethyl ketone (MEK) was added to the obtained polymerization reaction solution to dilute it, and then slowly added to a large amount of methanol with stirring. Then, the precipitated white solid was taken out and dried at 2.6 kPa at 120 ° C. for about 1 hour to remove the solvent to obtain a resin composition A-5. The weight average molecular weight of the obtained resin composition was 156,000, the glass transition temperature was 122 ° C., and the YI was 0.8.

Next, 1 part of the resin composition A-5 and 4 parts of dichloromethane were mixed, shaken for 1 minute, and then stirred and mixed for 60 minutes to prepare a dope solution B-5 having a solid content of 20%. The viscosity of the dope solution was 0.4 Pa · s, the haze was 0.9%, and the YI was 1.0. When the dope solution was visually confirmed, it was uniformly dispersed, and even if it was allowed to stand overnight, the appearance of the dope solution did not change.

Next, the dope solution B-5 was dripped on the PET film and spread to a film thickness of 500 μm using an applicator. Then, the PET film was placed in a dryer and dried at 40 ° C. for 30 minutes and 60 ° C. for 30 minutes, and then the applied film was peeled off from PET. Wide mountain-shaped clips were attached vertically so that the obtained film would not curl, and the film was hung in a dryer and then dried at 100 ° C. for 12 hours to obtain a film C-6. The internal haze of the film C-6 in terms of 100 μm was 0.2, the internal b * value in terms of 100 μm was 0.4, the elastic modulus was 4.9 GPa, and the Martens hardness was 242 N / mm ² .
<Example 3>
Polymerization containing a resin composition consisting of an acrylic copolymer having a lactone ring structure in the main chain and CNF in the same manner as in Example 2 except that 1 part of CNF toluene dispersion T2 and 40 parts of toluene were used. A reaction solution was obtained. The conversion rate of MMA calculated from the amount of residual monomers in the polymerization reaction solution was 96%, the conversion rate of MHMA was 95%, and the conversion rate of St was 99%.

Next, 200 parts of methyl ethyl ketone (MEK) was added to the obtained polymerization reaction solution to dilute it, and then slowly added to a large amount of methanol with stirring. Then, the precipitated white solid was taken out and dried at 2.6 kPa at 120 ° C. for about 1 hour to remove the solvent to obtain a resin composition A-6. The weight average molecular weight of the obtained resin composition was 162,000, the glass transition temperature was 122 ° C., and the YI was 1.0.

Next, 1 part of the resin composition A-6 and 4 parts of dichloromethane were mixed, shaken for 1 minute, and then stirred and mixed for 60 minutes to prepare a dope solution B-6 having a solid content of 20%. The viscosity of the dope solution was 0.4 Pa · s, the haze was 0.9%, and the YI was 1.1. When the dope solution was visually confirmed, it was uniformly dispersed, and even if it was allowed to stand overnight, the appearance of the dope solution did not change.

Next, the dope solution B-6 was dripped on the PET film and spread to a film thickness of 500 μm using an applicator. Then, the PET film was placed in a dryer and dried at 40 ° C. for 30 minutes and 60 ° C. for 30 minutes, and then the applied film was peeled off from PET. Wide mountain-shaped clips were attached up and down so that the obtained film would not curl, and the film was hung in a dryer and then dried at 100 ° C. for 12 hours to obtain a film C-7. The internal haze of film C-7 in terms of 100 μm was 0.3, the internal b * value in terms of 100 μm was 0.4, the elastic modulus was 5.5 GPa, and the maltens hardness was 251 N / mm ^2. <Comparative Example 5>
A polymerization reaction solution containing a resin composition composed of an acrylic copolymer having a lactone ring structure in the main chain was prepared in the same manner as in Example 2 except that 100 parts of toluene was used without using the CNF toluene dispersion. Obtained. The conversion rate of MMA calculated from the amount of residual monomers in the polymerization reaction solution was 96%, the conversion rate of MHMA was 96%, and the conversion rate of St was 99%.

Next, 200 parts of methyl ethyl ketone (MEK) was added to the obtained polymerization reaction solution to dilute it, and then slowly added to a large amount of methanol with stirring. Then, the precipitated white solid was taken out and dried at 2.6 kPa at 120 ° C. for about 1 hour to remove the solvent to obtain a resin composition A-7. The weight average molecular weight of the obtained resin composition was 160,000, the glass transition temperature was 122 ° C., and the YI was 0.3.

Next, 1 part of the resin composition A-7 and 4 parts of dichloromethane were mixed, shaken for 1 minute, and then stirred and mixed for 60 minutes to prepare a dope solution B-7 having a solid content of 20%. The viscosity of the dope solution was 0.3 Pa · s, the haze was 0.2%, and the YI was 0.4. When the dope solution was visually confirmed, it was uniformly dispersed, and even if it was allowed to stand overnight, the appearance of the dope solution did not change.

Next, the dope solution B-7 was dripped on the PET film and spread to a film thickness of 500 μm using an applicator. Then, the PET film was placed in a dryer and dried at 40 ° C. for 30 minutes and 60 ° C. for 30 minutes, and then the applied film was peeled off from PET. Wide mountain-shaped clips were attached vertically so that the obtained film would not curl, and the film was hung in a dryer and then dried at 100 ° C. for 12 hours to obtain a film C-8. The internal haze of the film C-8 in terms of 100 μm was 0.1, the internal b * value in terms of 100 μm was 0.1, the elastic modulus was 4.0 GPa, and the Martens hardness was 199 N / mm ² .
<Example 4>
Reactor equipped with stirrer, temperature sensor, cooling tube, nitrogen introduction tube, MMA 77.3 parts, N-phenylmaleimide (PMI) 18.5 parts, n-dodecyl mercaptan (nDM) 0.03 parts, CNF toluene 100 parts of the dispersion liquid T1 and 20 parts of toluene were charged, and the temperature was raised to 75 ° C. while passing nitrogen through the dispersion liquid T1. After that, 0.07 part of t-amylperoxy-2-ethylhexanoate (manufactured by Alchema Yoshitomi Co., Ltd., Luperox 575) was added as an initiator, and 4.2 parts of styrene (St) and 1 part of toluene were diluted with 0. Solution polymerization was carried out at 75-85 ° C. while dropping .014 parts of t-amylperoxy-2-ethylhexanoate at a constant rate over 3 hours, and further aging was carried out for 4 hours. As a result, a polymerization reaction solution containing a resin composition composed of an acrylic copolymer having a maleimide ring structure in the main chain and CNF, which was polymerized from MMA, PMI and St, was obtained. The conversion rate of MMA calculated from the amount of residual monomers in the polymerization reaction solution was 96%, the conversion rate of PMI was 98%, and the conversion rate of St was 99%.

Next, 200 parts of methyl ethyl ketone (MEK) was added to the obtained polymerization reaction solution to dilute it, and then slowly added to a large amount of methanol with stirring. Then, the precipitated white solid was taken out and dried at 2.6 kPa at 120 ° C. for about 1 hour to remove the solvent to obtain a resin composition A-8. The weight average molecular weight of the obtained resin composition was 169,000, the glass transition temperature was 136 ° C., and the YI was 1.2.

Next, 1 part of the resin composition A-8 and 4 parts of dichloromethane were mixed, shaken for 1 minute, and then stirred and mixed for 60 minutes to prepare a dope solution B-8 having a solid content of 20%. The viscosity of the dope solution was 0.5 Pa · s, the haze was 0.9%, and the YI was 1.2. When the dope solution was visually confirmed, it was uniformly dispersed, and even if it was allowed to stand overnight, the appearance of the dope solution did not change.

Next, the dope solution B-8 was dripped on the PET film and spread to a film thickness of 500 μm using an applicator. Then, the PET film was placed in a dryer and dried at 40 ° C. for 30 minutes and 60 ° C. for 30 minutes, and then the applied film was peeled off from PET. Wide mountain-shaped clips were attached vertically so that the obtained film would not curl, and the film was hung in a dryer and then dried at 100 ° C. for 12 hours to obtain a film C-9. The internal haze of the film C-9 in terms of 100 μm was 0.2, the internal b * value in terms of 100 μm was 0.4, the elastic modulus was 4.4 GPa, and the Martens hardness was 230 N / mm ² .
<Comparative Example 6>
A polymerization reaction solution containing a resin composition composed of an acrylic copolymer having a maleimide ring structure in the main chain was prepared in the same manner as in Example 4 except that 100 parts of toluene was used without using the CNF toluene dispersion. Obtained. The conversion rate of MMA calculated from the amount of residual monomers in the polymerization reaction solution was 97%, the conversion rate of PMI was 99%, and the conversion rate of St was 100%.

Next, 200 parts of methyl ethyl ketone (MEK) was added to the obtained polymerization reaction solution to dilute it, and then slowly added to a large amount of methanol with stirring. Then, the precipitated white solid was taken out and dried at 2.6 kPa at 120 ° C. for about 1 hour to remove the solvent to obtain a resin composition A-9. The weight average molecular weight of the obtained resin composition was 157,000, the glass transition temperature was 136 ° C., and the YI was 0.5.

Next, 1 part of the resin composition A-9 and 4 parts of dichloromethane were mixed, shaken for 1 minute, and then stirred and mixed for 60 minutes to prepare a dope solution B-9 having a solid content of 20%. The viscosity of the dope solution was 0.4 Pa · s, the haze was 0.2%, and the YI was 0.6. When the dope solution was visually confirmed, it was uniformly dispersed, and even if it was allowed to stand overnight, the appearance of the dope solution did not change.

Next, the dope solution B-9 was dripped on the PET film and spread to a film thickness of 500 μm using an applicator. Then, the PET film was placed in a dryer and dried at 40 ° C. for 30 minutes and 60 ° C. for 30 minutes, and then the applied film was peeled off from PET. Wide mountain-shaped clips were attached vertically so that the obtained film would not curl, and the film was hung in a dryer and then dried at 100 ° C. for 12 hours to obtain a film C-10. The internal haze of the film C-10 in terms of 100 μm was 0.1, the internal b * value in terms of 100 μm was 0.1, the elastic modulus was 3.9 GPa, and the Martens hardness was 195 N / mm ² .
<Example 5>
One part of the acrylic polymer (A-1) prepared in Example 1 is dissolved in 2.6 parts of toluene, shaken for 1 minute, stirred and mixed for 60 minutes, and the dope solution B- with a solid content of 28% by mass is mixed. 10 was prepared.
The viscosity of the dope solution was 4.5 Pa · s, the haze was 0.5%, and the YI was 1.2. When the dope solution was visually confirmed, it was uniformly dispersed, and even if it was allowed to stand overnight, the appearance of the dope solution did not change.

Next, the dope solution B-10 was dripped on the PET film and spread to a film thickness of 350 μm using an applicator. Then, the PET film was placed in a dryer and dried at 40 ° C. for 30 minutes and 60 ° C. for 30 minutes, and then the applied film was peeled off from PET. Wide mountain-shaped clips were attached vertically so that the obtained film would not curl, and the film was hung in a dryer and then dried at 100 ° C. for 12 hours to obtain a film C-10. The internal haze of the film C-10 in terms of 100 μm was 0.2, the internal b * value in terms of 100 μm was 0.4, the elastic modulus was 4.5 GPa, and the Martens hardness was 229 N / mm ² .

Table 1 shows the physical properties of the resin compositions, dopings, and films in Examples 1-5 and Comparative Examples 1-6.

According to the present invention, it is possible to provide a composition (resin composition) containing nanocellulose with improved elastic modulus and suppressed coloring. Such a composition can form an optical film or the like.

Claims (23)

A method for producing a resin composition, which comprises polymerizing a monomer in an organic solvent in the presence of nanocellulose. The method for producing a resin composition according to claim 1, wherein the monomer contains a (meth) acrylic acid-based monomer. The method for producing a resin composition according to claim 1 or 2, wherein the monomer component further contains a monomer having a polymerizable double bond in the ring structure. The method for producing a resin composition according to claim 1 or 2, further comprising a step of forming a ring structure in the main chain of a polymer chain having a unit derived from the (meth) acrylic monomer formed in the polymerization step. The method for producing a resin composition according to any one of claims 1 to 4, wherein the content ratio of the ring structure in the polymer obtained by polymerizing the monomer is 1% by mass or more and 50% by mass or less. The method for producing a resin composition according to any one of claims 1 to 5, wherein the glass transition temperature of the resin composition is 100 ° C. or higher. The method for producing a resin composition according to any one of claims 1 to 6, wherein the content ratio of nanocellulose to the polymer obtained by polymerizing the monomer is 0.1% by mass or more and 10% by mass or less. The method for producing a resin composition according to any one of claims 1 to 7, wherein the weight average molecular weight of the resin composition is 70,000 or more and 300,000 or less. A method for producing a molded product in which a resin composition obtained by the production method according to any one of claims 1 to 8 is molded by a solution casting method. The method for producing a molded product according to claim 9, wherein the molded product is a film. The method for producing a molded product according to claim 9 or 10, wherein the molded product is an optical film. A resin composition composed of nanocellulose and a polymer having a YI of 1.7 or less as measured using a quartz cell having an optical path length of 10 mm in accordance with JIS Z 8729. The resin composition according to claim 12, wherein the content ratio of nanocellulose to the polymer is 0.1% by mass or more and 10% by mass or less. The resin composition according to claim 12 or 13, wherein the glass transition temperature of the resin composition is 100 ° C. or higher. The resin composition according to any one of claims 12 to 14, wherein the polymer contains an acrylic polymer. The resin composition according to any one of claims 12 to 15, wherein the content ratio of the acrylic polymer to the polymer is 90% by mass or more. The resin composition according to any one of claims 12 to 16, wherein the weight average molecular weight of the resin composition is 70,000 or more and 300,000 or less. The resin composition according to any one of claims 12 to 17, which contains 5% by mass or more of an organic solvent. The resin composition according to any one of claims 12 to 18, wherein the solution viscosity of the resin composition at 25 ° C. is 0.05 Pa · s or more and 50 Pa · s or less. A film containing the resin composition according to any one of claims 12 to 17. The film according to claim 20, wherein the internal b * value in terms of 100 μm is 1.0 or less. The film according to claim 20 or 21, wherein the internal haze in terms of 100 μm is 1.0 or less. The film according to any one of claims 20 to 22, which has an elastic modulus of 1 GPa or more.