WO2014002491A1 - 非複屈折性樹脂材料、およびフィルム - Google Patents
非複屈折性樹脂材料、およびフィルム Download PDFInfo
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- WO2014002491A1 WO2014002491A1 PCT/JP2013/003992 JP2013003992W WO2014002491A1 WO 2014002491 A1 WO2014002491 A1 WO 2014002491A1 JP 2013003992 W JP2013003992 W JP 2013003992W WO 2014002491 A1 WO2014002491 A1 WO 2014002491A1
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/045—Light guides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
- G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
- G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
- G02B6/0013—Means for improving the coupling-in of light from the light source into the light guide
- G02B6/0023—Means for improving the coupling-in of light from the light source into the light guide provided by one optical element, or plurality thereof, placed between the light guide and the light source, or around the light source
- G02B6/003—Lens or lenticular sheet or layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
Definitions
- the present invention relates to a non-birefringent resin material and a film.
- Optical members such as films, plates, and lenses used in various optical-related devices (for example, films and substrates used in liquid crystal display devices, prism sheets, etc .; lenses and projections in signal reading lens systems of optical disk devices)
- a material constituting a screen Fresnel lens, a lenticular lens, and the like a light-transmitting resin is widely used, and such a resin is generally called “optical resin” or “optical polymer”.
- Birefringence is one of the important optical characteristics that must be taken into account when an optical member is made of an optical resin. That is, it is not preferable in many cases that the optical resin has a large birefringence. In particular, in the above exemplified applications (liquid crystal display device, optical disk device, projection screen, etc.), if a film having a birefringence, a lens, etc. are present in the optical path, the image quality and signal reading performance are adversely affected. It is desired to use an optical member made of an optical resin having a birefringence as low as possible. Needless to say, it is desirable that the birefringence of a camera lens, a spectacle lens, or the like is small.
- the birefringence exhibited by the optical polymer is mainly due to the orientation birefringence in the main chain orientation of the polymer and the photoelastic birefringence due to stress. There is.
- the signs of orientation birefringence and photoelastic birefringence are derived from the chemical structure of the polymer and are unique to each polymer.
- orientation birefringence is birefringence that is generally manifested by the orientation of the main chain (polymer chain) of a chain polymer, and the orientation of the main chain is, for example, a process of extrusion molding or stretching during the production of a polymer film. Alternatively, it occurs in a process involving the flow of material, such as an injection molding process frequently used in the manufacture of optical members of various shapes, and it remains fixed to the optical member.
- Orientation birefringence increases in the direction parallel to the orientation direction of the polymer chain
- Orientation birefringence is positive
- the refractive index increases in the orthogonal direction
- photoelastic birefringence is birefringence caused by elastic deformation (strain) of a polymer.
- elastic deformation strain
- strain remains in the material due to volume shrinkage that occurs when the polymer is cooled to a temperature lower than or equal to the glass transition temperature of the polymer.
- the material is elastically deformed by an external force received in a state where the optical member is fixed to a device used at a normal temperature (below the glass transition temperature), which causes photoelastic birefringence.
- the photoelastic constant is defined as a coefficient ⁇ of ⁇ when the birefringence difference ⁇ n is caused by the stress difference ⁇ as shown in the following equation.
- Patent Document 1 discloses a non-birefringent optical resin material by blending two types of polymer resins having opposite signs of orientation birefringence and completely compatible with each other. .
- due to the difference in the refractive index inherent to the blended polymer resin due to the difference in the refractive index inherent to the blended polymer resin, light scattering occurs due to the non-uniformity of the refractive index, and an optical material excellent in transparency cannot be obtained.
- photoelastic birefringence Although there is no description about photoelastic birefringence, it is expected that the photoelastic birefringence is considerably increased in the polymer compositions of the examples. Furthermore, mechanical strength, particularly impact resistance is not always sufficient, and there are practical problems such as occurrence of problems such as cracks.
- non-birefringence is obtained by adding a low-molecular substance exhibiting orientation birefringence that tends to cancel the orientation birefringence of the polymer resin material to a matrix made of a transparent polymer resin.
- a method for obtaining the optical resin material is disclosed.
- This low molecular weight substance has a molecular weight of 5000 or less and is good in terms of transparency of the obtained molded article, but it does not describe any improvement in photoelastic birefringence or mechanical strength. Moreover, heat resistance may fall.
- Patent Document 3 discloses a fine inorganic substance that is oriented in the same direction as the orientation direction of the binding chain as the polymer resin is oriented by an external force and has a birefringence in a transparent polymer resin.
- a method of obtaining an optical resin material having low orientation birefringence by blending is disclosed. Although this method can suppress orientation birefringence, it does not describe photoelastic birefringence or improvement of mechanical strength.
- Patent Document 4 for an optical material having a composite component system of three or more components including a copolymer system of two or more components, the optical material indicates the combination and component ratio (composition ratio) of the components of the composite component system.
- a method of obtaining a non-birefringent optical resin material with small orientation birefringence and photoelastic birefringence by selecting both the orientation birefringence and the photoelastic birefringence simultaneously is disclosed. With this method, both orientation birefringence and photoelastic birefringence, which could not be realized in the past, can be made extremely small simultaneously.
- Patent Document 5 discloses a graft copolymer (“core / core”) obtained by graft-polymerizing an acrylic resin having a glass transition temperature of 120 ° C. or more and an acrylic rubber-like polymer with a vinyl group polymerizable monomer. Resin composition excellent in mechanical strength as a film, in particular, bending resistance, and optical film by having a combination of a “shell” type impact resistance improver, also referred to as a core-shell polymer) A way to get it is presented.
- a “shell” type impact resistance improver also referred to as a core-shell polymer
- the description of the graft copolymer does not describe any influence on birefringence. Since there is no description regarding orientation birefringence and photoelastic birefringence, it is clear that there is no technical idea that the graft copolymer has a function of adjusting birefringence.
- Patent Document 6 discloses an optical film formed by molding a resin composition containing an acrylic resin (A) and an acrylic rubber (B), wherein the acrylic resin (A) is derived from a methacrylate monomer.
- a heat-resistant acrylic resin (A-1) containing a repeating unit derived from a vinyl aromatic monomer, a repeating unit derived from a methacrylate monomer having an aromatic group, and a cyclic acid anhydride repeating unit.
- the optical film characterized by this is disclosed. This document describes that the optical film has high heat resistance, excellent trimming properties, and excellent optical characteristics even during stretching. However, although there is a description about the improvement of the trimming property, there is no description about the mechanical strength other than the trimming property such as the cracking resistance when the film is bent.
- the birefringence (orientation birefringence) at 100% stretching (at twice stretching) remains high in the examples, and both the orientation birefringence and the photoelastic coefficient (photoelastic birefringence) are both small. There is no improvement in birefringence.
- the acrylic rubber (B) of the document is a so-called graft copolymer (core-shell polymer) from Examples, and is added for the purpose of improving mechanical strength while maintaining transparency such as haze. However, no consideration is given to the influence on birefringence.
- the present invention provides a non-birefringent resin material and a film made of the same material that can provide a molded product that is very small in both orientation birefringence and photoelastic birefringence, has high transparency, and has few foreign matter defects.
- the purpose is to do.
- the present invention provides an acrylic resin composition and a film comprising the composition that can provide a molded article that is very small in both orientation birefringence and photoelastic birefringence, has high transparency, and has few foreign matter defects. For the purpose.
- the present invention provides a non-birefringent resin material having both very small orientation birefringence and photoelastic birefringence, high transparency, few foreign matter defects, and excellent mechanical strength, and It aims at providing the film which consists of the same material.
- the present invention has two types of polymer components, resin (A) as a matrix component and polymer (B) as essential components, so that both the compound birefringence and the photoelastic constant are low.
- resin (A) as a matrix component
- polymer (B) as essential components
- the present invention is as follows. [1] Contains resin (A) and polymer (B), has an orientation birefringence of ⁇ 1.7 ⁇ 10 ⁇ 4 to 1.7 ⁇ 10 ⁇ 4 , and a photoelastic constant of ⁇ 4 ⁇ 10 ⁇ 12 to 4 A non-birefringent resin material that is ⁇ 10 ⁇ 12 Pa ⁇ 1 . [2] The resin (A) and the polymer (B) are contained, the photoelastic constant of the resin (A) and the photoelastic constant of the polymer (B) have different signs, and the light of the resin (A) A non-birefringent resin material whose elastic constant is offset by the photoelastic constant of the polymer (B).
- the polymer (B) includes a (meth) acrylic crosslinked polymer layer and a hard heavy containing a vinyl monomer having an alicyclic structure, a heterocyclic structure, or an aromatic group in a structural unit.
- Non-birefringence according to [13], wherein the vinyl monomer having an alicyclic structure, a heterocyclic structure or an aromatic group is a monomer represented by the following formula (4): Resin material.
- R 9 represents a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms.
- R 10 is a substituted or unsubstituted aromatic group having 1 to 24 carbon atoms, or a substituted or unsubstituted alicyclic group having 1 to 24 carbon atoms, and has a monocyclic structure or a heterocyclic structure.
- Have. l represents an integer of 1 to 4.
- m represents an integer of 0 to 1.
- n represents an integer of 0 to 10.
- the hard polymer layer having the monomer represented by the formula (4) as a constituent unit is 1 to 100% by weight of the monomer represented by the formula (4), and can be copolymerized therewith.
- the (meth) acrylic crosslinked polymer layer comprises 50 to 100% by weight of an acrylic acid alkyl ester, 50 to 0% by weight of another monomer copolymerizable therewith, and a polyfunctional monomer 0 Any one of [11] to [15], obtained by polymerizing .05 to 10 parts by weight (with respect to 100 parts by weight of the total amount of the alkyl acrylate ester and the other monomers copolymerizable therewith)
- the non-birefringent resin material according to Item 1.
- the hard polymer layer constitutes an outermost layer, and the outermost layer is a hard polymer layer having a monomer represented by the formula (4) as a constituent unit.
- the polymer (B) has a hard inner layer, a soft intermediate layer, and a hard outer layer, the inner layer is composed of at least one hard polymer layer, and the intermediate layer is the (meth) acrylic type.
- the inner layer is composed of at least one hard polymer layer
- the intermediate layer is the (meth) acrylic type.
- the monomer represented by the formula (4) is at least selected from the group consisting of benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and phenoxyethyl (meth) acrylate.
- the non-birefringent resin material according to any one of [14] to [21], which is one kind.
- the content of the (meth) acrylic crosslinked polymer layer contained in the polymer (B) is 1 to 60 parts by weight in 100 parts by weight of the non-birefringent resin material. 23].
- the non-birefringent resin material according to any one of [1] to [25] further comprising a low-molecular compound having birefringence.
- the non-birefringent resin material according to any one of the above.
- R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 3 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 3 to 12 carbon atoms
- R 3 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 3 to 12 carbon atoms
- R 4 and R 5 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms; R 6 is an alkyl group having 1 to 18 carbon atoms or cycloalkyl having 3 to 12 carbon atoms) Or a substituent having 5 to 15 carbon atoms including an aromatic ring.
- R 4 and R 5 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms; R 6 is an alkyl group having 1 to 18 carbon atoms or cycloalkyl having 3 to 12 carbon atoms
- a substituent having 5 to 15 carbon atoms including an aromatic ring [28]
- R 9 represents a hydrogen atom, or a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms.
- R 10 is a substituted or unsubstituted aromatic group having 1 to 24 carbon atoms, or a substituted or unsubstituted alicyclic group having 1 to 24 carbon atoms, and has a monocyclic structure or a heterocyclic structure.
- Have. l represents an integer of 1 to 4.
- m represents an integer of 0 to 1.
- n represents an integer of 0 to 10.
- the hard polymer layer having the monomer represented by the formula (4) as a constituent unit is 1 to 100% by weight of the monomer represented by the formula (4), and can be copolymerized therewith.
- the acrylic resin composition according to [36] which is obtained by polymerizing a monomer mixture consisting of 100 parts by weight of the total body.
- the (meth) acrylic crosslinked polymer layer comprises 50 to 100% by weight of an acrylic acid alkyl ester, 50 to 0% by weight of another monomer copolymerizable therewith, and a polyfunctional monomer 0 Obtained by polymerizing a monomer mixture consisting of 0.05 to 10 parts by weight (based on 100 parts by weight of the total amount of the alkyl acrylate ester and other monomers copolymerizable therewith) [36] Or the acrylic resin composition as described in [37].
- (B) A (meth) acrylic rubber-containing graft copolymer obtained by multistage polymerization, wherein in at least one stage of the multistage polymerization, in the presence of (meth) acrylic rubber-containing polymer particles, the formula (4 ) And a polymer formed by polymerizing a mixture containing another monomer copolymerizable therewith.
- R 9 represents a hydrogen atom, or a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms.
- R 10 is a substituted or unsubstituted aromatic group having 1 to 24 carbon atoms, or a substituted or unsubstituted alicyclic group having 1 to 24 carbon atoms, and has a monocyclic structure or a heterocyclic structure.
- Have. l represents an integer of 1 to 4.
- m represents an integer of 0 to 1.
- n represents an integer of 0 to 10.
- the (meth) acrylic rubber-containing polymer particles are: 50 to 100% by weight of an acrylic acid alkyl ester, 50 to 0% by weight of another monomer copolymerizable therewith, and 0.05 to 10 parts by weight of a polyfunctional monomer (the acrylic acid alkyl ester and the same)
- the polymer (B) is (B-1) 50 to 100% by weight of alkyl acrylate ester, 50 to 0% by weight of other monomers copolymerizable therewith, and 0.05 to 10 parts by weight of polyfunctional monomer (the acrylic acid (Meth) acrylic rubber-containing polymer particles by polymerizing a monomer mixture comprising an alkyl ester and a total amount of 100 parts by weight of other monomers copolymerizable therewith, (B-2) In the presence of the (meth) acrylic rubber-containing polymer particles, 1 to 100% by weight of the monomer represented by the formula (4), 99 to 0% by weight of another monomer copolymerizable therewith, and 0 to 2.0 parts by weight of a polyfunctional monomer ( Obtained by polymerizing a monomer mixture comprising the monomer represented by the formula (4) and the other monomer copolymerizable with the monomer (100 parts by weight).
- polyfunctional monomer the acrylic acid (Meth) acrylic rubber-containing polymer particles by polymerizing a
- the monomer represented by the formula (4) is at least selected from the group consisting of benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and phenoxyethyl (meth) acrylate.
- the acrylic resin composition as described in any one of.
- R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 3 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 3 to 12 carbon atoms
- R 3 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 3 to 12 carbon atoms
- a film comprising the acrylic resin composition according to any one of [36] to [51].
- the film according to [52] which is obtained by a melt extrusion method.
- the orientation birefringence is ⁇ 1.7 ⁇ 10 ⁇ 4 to 1.7 ⁇ 10 ⁇ 4
- the photoelastic constant is ⁇ 4 ⁇ 10 ⁇ 12 to 4 ⁇ 10 ⁇ 12 Pa ⁇ 1 [52] or [53].
- the orientation birefringence is ⁇ 1.7 ⁇ 10 ⁇ 4 to 1.7 ⁇ 10 ⁇ 4
- the photoelastic constant is ⁇ 4 ⁇ 10 ⁇ 12 to 4 ⁇ 10 ⁇ 12 Pa ⁇ 1
- the tensile elongation at break is A resin film having a degree of 10% or more and a thickness of 10 ⁇ m or more and 500 ⁇ m or less.
- the resin film according to [56] wherein the glass transition temperature is 100 ° C. or higher.
- An optical film comprising the resin film according to any one of [56] to [59].
- the non-birefringent resin material of the present invention it is possible to provide a molded product, particularly an optical film, in which both orientation birefringence and photoelastic birefringence are very small, transparency is high, and foreign matter defects are small.
- the acrylic resin composition of the present invention it is possible to obtain a molded product in which both orientation birefringence and photoelastic birefringence are very small, transparency is high, and there are few foreign matter defects, and it is particularly suitable for film formation.
- the present invention is a non-birefringent molded article having both very small orientation birefringence and photoelastic birefringence, high transparency, few foreign matter defects, and excellent mechanical strength, In particular, an optical film can be provided.
- a molded product obtained by molding the non-birefringent resin material of the present invention, particularly an optical film is excellent in optical isotropy even when stretched. It can be suitably used as an optical member.
- the optical film of the present invention has excellent mechanical strength, it can reduce film transportability, crack resistance during actual use, and generation of fine cracks in the film trimming process during production. Is possible.
- it since it has high mechanical strength, it does not require the stretching process necessary to improve the film strength, so that it is difficult to produce with a stretched film, for example, to produce a thick film with a thickness of 80 ⁇ m or more. Is also possible.
- the optical film of the present invention can achieve high heat resistance, the curing temperature and drying speed in the film coating process can be increased, and productivity can be improved.
- the non-birefringent resin material of the present invention and the film thereof have, as essential components, a resin (A) serving as a matrix component, and a photoelastic constant and an orientation birefringence different from those of the resin (A). It preferably contains the polymer (B).
- the resin (A) can be used as long as it is generally transparent.
- polycarbonate resin represented by bisphenol A polycarbonate, polystyrene, styrene-acrylonitrile copolymer, styrene-maleic anhydride resin, styrene-maleimide resin, styrene- (meth) acrylic acid resin, styrene-based thermoplastic elastomer
- Aromatic vinyl resins and their hydrogenated products amorphous polyolefins, transparent polyolefins with a refined crystal phase
- polyolefin resins such as ethylene-methyl methacrylate resin, polymethyl methacrylate, styrene-methyl methacrylate
- Acrylic resins such as resins, heat-resistant acrylic resins modified by imide cyclization, lactone cyclization, methacrylic acid modification, etc., polyethylene terephthalate, polycyclohexane dimethylene group,
- Amorphous polyester resins such as tylene terephthalate, polyethylene naphthalate, and polyarylate, or transparent polyester resins with a refined crystal phase, polyimide resins, polyethersulfone resins, polyamide resins, cellulose resins such as triacetyl cellulose resins, polyphenylene
- thermoplastic resins having transparency such as oxide resins are exemplified. In consideration of actual use, it is preferable to select a resin so that the total light transmittance of the obtained molded body is 85% or more, preferably 90%, more preferably 92% or more.
- acrylic resins are particularly preferable in terms of excellent optical properties, heat resistance, moldability, and the like.
- the acrylic resin may be a resin obtained by polymerizing a vinyl monomer containing a (meth) acrylic acid alkyl ester, but 30 to 100% by weight of methyl methacrylate and a monomer 70 to 0 copolymerizable therewith.
- An acrylic resin obtained by polymerizing wt% is more preferable.
- (meth) acrylic acid ester having 1 to 10 carbon atoms in the alkyl residue (excluding methyl methacrylate) is preferable.
- Specific examples of other vinyl monomers copolymerizable with methyl methacrylate include ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, epoxy cyclohexyl methyl methacrylate, methacrylic acid.
- Methacrylic acid esters such as 2-hydroxyethyl acid, 2-hydroxypropyl methacrylate, dicyclopentanyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, isobornyl methacrylate Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, epoxycyclohexylmethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy acrylate
- Acrylic esters such as roxypropyl; carboxylic acids such as methacrylic acid and acrylic acid and esters thereof; vinylcyans such as acrylonitrile and methacrylonitrile; vinyl arenes such as styrene, ⁇ -methylstyrene, monochlorostyrene, dichlorostyrene Maleic acid, fumaric acid and esters thereof; vinyl
- methyl methacrylate is contained in an amount of 30 to 100% by weight, preferably 50 to 99.9% by weight, more preferably 50 to 98% by weight.
- the monomer copolymerizable with methyl methacrylate is It is contained in an amount of 70 to 0% by weight, preferably 50 to 0.1% by weight, more preferably 50 to 2% by weight. If the content of methyl methacrylate is less than 30% by weight, the optical characteristics, appearance, weather resistance, and heat resistance unique to acrylic resins tend to be lowered. Moreover, it is desirable not to use a polyfunctional monomer from the viewpoint of processability and appearance.
- the glass transition temperature of the resin (A) used in the present invention can be set according to the conditions and applications to be used.
- the glass transition temperature is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, further preferably 115 ° C. or higher, and most preferably 120 ° C. or higher.
- the acrylic resin having a glass transition temperature of 120 ° C. or higher include an acrylic resin containing a glutarimide structure, a glutaric anhydride structure, a (meth) acrylic acid unit, and a lactone ring in the molecule.
- examples thereof include polyglutarimide acrylic resins, glutaric anhydride acrylic resins, lactone cyclized acrylic resins, acrylic resins containing hydroxyl groups and / or carboxyl groups, and methacrylic resins.
- Other resins having a glass transition temperature of 120 ° C. or higher can be obtained by partially hydrogenating the aromatic ring of a styrene polymer obtained by polymerizing a styrene monomer and another monomer copolymerizable therewith.
- styrene polymer a polymer containing cyclic acid anhydride repeating units, a polyethylene terephthalate resin, a polybutylene terephthalate resin, and the like.
- glutarimide acrylic resin (D) is particularly preferable because the heat resistance of the resulting film is improved and the optical properties during stretching are also excellent.
- the glutarimide acrylic resin (D) has a glass transition temperature of 120 ° C. or higher, and includes a unit represented by the following general formula (1) and a unit represented by the following general formula (2).
- R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 3 is hydrogen, an alkyl group having 1 to 18 carbon atoms, A cycloalkyl group having 3 to 12 carbon atoms, or a substituent having 5 to 15 carbon atoms including an aromatic ring.
- the unit represented by the general formula (1) is also referred to as “glutarimide unit”.
- R 1 and R 2 are each independently hydrogen or a methyl group, and R 3 is hydrogen, a methyl group, a butyl group, or a cyclohexyl group, and more preferably, R 1 is a methyl group, R 2 is hydrogen, and R 3 is a methyl group.
- the glutarimide acrylic resin (D) may contain only a single type as a glutarimide unit, and any or all of R 1 , R 2 , and R 3 in the general formula (1) A plurality of different types may be included.
- the glutarimide unit can be formed by imidizing a (meth) acrylic acid ester unit represented by the following general formula (2). Further, an acid anhydride such as maleic anhydride, a half ester of the acid anhydride and a linear or branched alcohol having 1 to 20 carbon atoms, or an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid (for example, acrylic acid)
- an acid anhydride such as maleic anhydride, a half ester of the acid anhydride and a linear or branched alcohol having 1 to 20 carbon atoms, or an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid (for example, acrylic acid)
- the glutarimide unit can also be formed by imidizing methacrylic acid, maleic acid, itaconic acid, crotonic acid, fumaric acid, citraconic acid).
- the content of glutarimide units is not particularly limited, for example, can be appropriately determined in consideration of the structure of R 3 or the like.
- the content of the glutarimide unit is preferably 1.0% by weight or more, more preferably 3.0% by weight to 90% by weight, and more preferably 5.0% by weight to 60% by weight of the total amount of the glutarimide acrylic resin (D). More preferred is weight percent.
- the content of the glutarimide unit is less than the above range, the resulting glutarimide acrylic resin (D) tends to have insufficient heat resistance or its transparency may be impaired.
- it exceeds the above range the heat resistance and melt viscosity will be unnecessarily high, the molding processability will be poor, the mechanical strength during film processing will be extremely low, and the transparency will be impaired. Tend.
- the content of glutarimide unit is calculated by the following method.
- 1 H-NMR BRUKER Avance III 400 MHz
- 1 H-NMR measurement of the resin was performed to determine the content (mol%) of each monomer unit such as glutarimide unit or ester unit in the resin.
- the amount (mol%) is converted to the content (% by weight) using the molecular weight of each monomer unit.
- a resin comprising a glutarimide unit in which R 3 is a methyl group in the above general formula (1) and a methyl methacrylate unit
- R 3 is a methyl group in the above general formula (1)
- a methyl methacrylate unit it is derived from the O—CH 3 proton of methyl methacrylate appearing in the vicinity of 3.5 to 3.8 ppm.
- the content (% by weight) of the glutarimide unit should be obtained by the following formula. Can do.
- content (weight%) of a glutarimide unit can be calculated
- the content of glutarimide units is preferably 20% by weight or less, more preferably 15% by weight or less, because birefringence is easily suppressed. 10 wt% or less is more preferable.
- R 4 and R 5 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 6 is an alkyl group having 1 to 18 carbon atoms or 3 to 3 carbon atoms. 12 cycloalkyl groups or substituents having 5 to 15 carbon atoms including an aromatic ring.
- the unit represented by the general formula (2) is also referred to as “(meth) acrylic acid ester unit”.
- (meth) acryl refers to “methacryl or acrylic”.
- R 4 and R 5 are each independently hydrogen or a methyl group
- R 6 is hydrogen or a methyl group
- 5 is a methyl group
- R 6 is a methyl group
- the glutarimide acrylic resin (D) may contain only a single type as a (meth) acrylic acid ester unit, or any one of R 4 , R 5 and R 6 in the general formula (2). Alternatively, a plurality of different types may be included.
- the glutarimide acrylic resin (D) may further contain a unit represented by the following general formula (3) (hereinafter also referred to as “aromatic vinyl unit”) as necessary.
- R 7 is hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 8 is an aryl group having 6 to 10 carbon atoms.
- the aromatic vinyl unit represented by the general formula (3) is not particularly limited, and examples thereof include a styrene unit and an ⁇ -methylstyrene unit, and a styrene unit is preferable.
- the glutarimide acrylic resin (D) may contain only a single type as an aromatic vinyl unit, or may contain a plurality of units in which either or both of R 7 and R 8 are different. .
- the content of the aromatic vinyl unit is not particularly limited, but is preferably 0 to 50% by weight, more preferably 0 to 20% by weight based on the total amount of the glutarimide acrylic resin (D). 0 to 15% by weight is particularly preferable. When the content of the aromatic vinyl unit is larger than the above range, sufficient heat resistance of the glutarimide acrylic resin (D) cannot be obtained.
- the glutarimide acrylic resin (D) may not contain an aromatic vinyl unit from the viewpoints of improving bending resistance and transparency, reducing fish eye, and further improving solvent resistance or weather resistance. preferable.
- the glutarimide acrylic resin (D) may further contain other units other than the glutarimide unit, the (meth) acrylic acid ester unit, and the aromatic vinyl unit, if necessary.
- Examples of other units include amide units such as acrylamide and methacrylamide, glutar anhydride units, nitrile units such as acrylonitrile and methacrylonitrile, maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. And maleimide-based units.
- These other units may be included in the glutarimide acrylic resin (D) by random copolymerization or may be included by graft copolymerization.
- These other units are obtained by copolymerizing the monomers constituting the units with the glutarimide acrylic resin (D) and / or the resin used as a raw material for producing the resin (D). It may be introduced. Moreover, when performing the said imidation reaction, what was byproduced by these other units and contained in resin (D) may be used.
- the weight average molecular weight of the glutarimide acrylic resin (D) is not particularly limited, but is preferably in the range of 1 ⁇ 10 4 to 5 ⁇ 10 5 . If it is in the said range, moldability will not fall or the mechanical strength at the time of film processing will not be insufficient. On the other hand, when the weight average molecular weight is smaller than the above range, the mechanical strength when formed into a film tends to be insufficient. Moreover, when larger than the said range, the viscosity at the time of melt-extrusion is high, there exists a tendency for the moldability to fall and for the productivity of a molded article to fall.
- the glass transition temperature of the glutarimide acrylic resin (D) is preferably 120 ° C. or higher so that the film exhibits good heat resistance. More preferably, it is 125 ° C. or higher. If the glass transition temperature is lower than the above range, the film cannot exhibit sufficient heat resistance.
- (meth) acrylic acid ester polymer is produced by polymerizing (meth) acrylic acid ester.
- glutarimide acrylic resin (D) contains an aromatic vinyl unit
- a (meth) acrylic acid ester and an aromatic vinyl are copolymerized to produce a (meth) acrylic acid ester-aromatic vinyl copolymer.
- examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid t.
- -Butyl, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate are preferably used, and methyl methacrylate is more preferably used.
- (Meth) acrylic acid ester may be used alone or in combination of two or more.
- the finally obtained glutarimide acrylic resin (D) can contain a plurality of types of (meth) acrylic acid ester units.
- the structure of the above (meth) acrylic acid ester polymer or the above (meth) acrylic acid ester-aromatic vinyl copolymer is not particularly limited as long as the subsequent imidization reaction is possible. Specific examples include linear polymers, block polymers, core-shell polymers, branched polymers, ladder polymers, and crosslinked polymers.
- a block polymer it may be any of AB type, ABC type, ABA type, and other types of block polymers.
- the core-shell polymer it may be composed of only one core and one shell, or one or both of the core and shell may be composed of multiple layers.
- an imidization reaction is performed by reacting the (meth) acrylic acid ester polymer or the (meth) acrylic acid ester-aromatic vinyl copolymer with an imidizing agent.
- an imidizing agent for reacting the (meth) acrylic acid ester polymer or the (meth) acrylic acid ester-aromatic vinyl copolymer with an imidizing agent.
- the imidizing agent is not particularly limited as long as it can generate the glutarimide unit represented by the general formula (1).
- ammonia or a primary amine can be used.
- the primary amine include aliphatic hydrocarbon group-containing primary amines such as methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, tert-butylamine, and n-hexylamine;
- Examples include aromatic hydrocarbon group-containing primary amines such as aniline, benzylamine, toluidine, and trichloroaniline, and alicyclic hydrocarbon group-containing primary amines such as cyclohexylamine.
- urea compounds such as urea, 1,3-dimethylurea, 1,3-diethylurea, 1,3-dipropylurea and the like that generate ammonia or primary amine by heating can also be used.
- imidizing agents ammonia, methylamine, and cyclohexylamine are preferably used, and methylamine is particularly preferably used from the viewpoint of cost and physical properties.
- a ring closure accelerator may be added as necessary.
- the content of glutarimide units in the resulting glutarimide acrylic resin (D) can be adjusted by adjusting the addition ratio of the imidizing agent.
- the method for carrying out the imidation reaction is not particularly limited, and a conventionally known method can be used.
- the imidization reaction can be advanced by using an extruder or a batch type reaction vessel (pressure vessel).
- the extruder is not particularly limited, and various types of extruders can be used. For example, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, or the like can be used.
- twin screw extruder mixing of the raw material polymer and the imidizing agent (in the case of using a ring closure accelerator, an imidizing agent and a ring closure accelerator) can be promoted.
- twin-screw extruder examples include a non-meshing type same-direction rotating type, a meshing type same-direction rotating type, a non-meshing type different direction rotating type, and a meshing type different direction rotating type.
- the meshing type co-rotating type is preferable. Since the meshing type co-rotating twin-screw extruder can rotate at a high speed, the mixing of the raw material polymer with the imidizing agent (in the case of using a ring closure accelerator, an imidizing agent and a ring closure accelerator) It can be further promoted.
- the above-explained extruders may be used singly or a plurality may be connected in series.
- an esterification step of treating with an esterifying agent can be included.
- the carboxyl group contained in the resin, which is by-produced in the imidization step can be converted into an ester group.
- the acid value of glutarimide acrylic resin (D) can be adjusted in a desired range.
- the acid value of the glutarimide acrylic resin (D) is not particularly limited, but is preferably 0.50 mmol / g or less, and more preferably 0.45 mmol / g or less. Although a minimum in particular is not restrict
- the acid value can be calculated by, for example, a titration method described in JP-A-2005-23272.
- the esterifying agent is not particularly limited.
- the amount of the esterifying agent used is not particularly limited, but is 0 to 12 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer or the (meth) acrylic acid ester-aromatic vinyl copolymer. It is preferably 0 to 8 parts by weight. If the usage-amount of an esterifying agent is in the said range, the acid value of glutarimide acrylic resin (D) can be adjusted to a suitable range. On the other hand, outside the above range, unreacted esterifying agent may remain in the resin, which may cause foaming or odor generation when molding is performed using the resin.
- a catalyst can be used in combination.
- the type of the catalyst is not particularly limited, and examples thereof include aliphatic tertiary amines such as trimethylamine, triethylamine, and tributylamine. Among these, triethylamine is preferable from the viewpoint of cost and reactivity.
- the esterification step can be advanced by using, for example, an extruder or a batch type reaction vessel, as in the imidization step.
- This esterification step can be carried out only by heat treatment without using an esterifying agent.
- the heat treatment can be achieved by kneading and dispersing the molten resin in the extruder.
- dehydration reaction between the carboxyl groups in the resin by-produced in the imidization step and / or dealcoholization reaction between the carboxyl group in the resin and the alkyl ester group in the resin For example, part or all of the carboxyl group can be converted to an acid anhydride group.
- a ring closure accelerator catalyst
- a vent port that can be depressurized to an atmospheric pressure or lower in the extruder to be used. According to such a machine, unreacted imidizing agent, esterifying agent, by-products such as methanol, or monomers can be removed.
- glutarimide acrylic resin (D) instead of an extruder, for example, a horizontal biaxial reactor such as Violac manufactured by Sumitomo Heavy Industries, Ltd. or a vertical biaxial agitation tank such as Super Blend
- a reaction apparatus corresponding to high viscosity can also be used suitably.
- the structure of the batch type reaction vessel is not particularly limited. Specifically, it has a structure in which the raw material polymer can be melted by heating and stirred, and an imidizing agent (in the case of using a ring closure accelerator, an imidizing agent and a ring closure accelerator) can be added. However, it is preferable to have a structure with good stirring efficiency. According to such a batch-type reaction vessel, it is possible to prevent the polymer viscosity from increasing due to the progress of the reaction and insufficient stirring.
- a batch type reaction tank having such a structure for example, a stirred tank max blend manufactured by Sumitomo Heavy Industries, Ltd. and the like can be mentioned.
- a glutarimide acrylic resin (D) in which the content of glutarimide units is controlled to a specific value can be easily produced.
- Polymer (B) By adding the polymer (B) used in the present invention to the resin (A), both the orientation birefringence and the photoelastic constant can be reduced, and a non-birefringent resin material having high optical isotropy is obtained. It is an essential ingredient. In order to make it optically isotropic, it is important how to reduce the orientation birefringence and the photoelastic birefringence. Therefore, here, the concept of “orientation birefringence” and “photoelastic birefringence” of the resin (A), polymer (B), non-birefringent resin material and film of the present invention will be described first.
- the polymer when the molding conditions in which the polymer is oriented or when the raw film is subjected to a stretching process, the polymer is oriented in the film, resulting in birefringence.
- the birefringence in this case is generally called birefringence because it is birefringence generated by the orientation of the polymer.
- how to mold the non-birefringent resin material of the present invention, and in the case of a film, whether to stretch, a molded body obtained from the non-birefringent resin material of the present invention particularly In order to reduce the orientation birefringence of the optical film, it is necessary to set the orientation birefringence of the polymer (B) and the orientation birefringence of the resin (A).
- orientation birefringence is a birefringence expressed by the orientation of the polymer chain, but the birefringence (orientation birefringence) in the polymer film varies depending on the degree of orientation of the polymer chain. Therefore, in the present invention, the “alignment birefringence” is defined as measurement under the following conditions.
- the resin (A), the polymer (B), and the non-birefringent resin material need to be formed into some form, and their orientation birefringence needs to be measured.
- the form is a film or a sheet.
- a melt-extruded film and a press-formed sheet will be described.
- the polymer (B) is pressed at 190 ° C. to produce a press-formed sheet having a thickness of 500 ⁇ m.
- a test piece of 25 mm ⁇ 90 mm was cut out from the center part of the obtained press-molded sheet, and both short sides were held and kept at glass transition temperature + 30 ° C. for 2 minutes, which was twice as long (also referred to as 100% stretch).
- the film is stretched uniaxially at a speed of 200 mm / min in this direction (in this case, both long sides are not fixed). Thereafter, the obtained film is cooled to 23 ° C., the sample central portion is sampled, the birefringence is measured, and the sign of the orientation birefringence is obtained.
- the stretching temperature is preferably ⁇ 30 ° C. to + 30 ° C., more preferably + 0 ° C. to + 30 ° C. with respect to the glass transition temperature, and may be set as appropriate, for example, within the temperature range of + 5 ° C. to + 30 ° C.
- photoelastic birefringence is birefringence caused by elastic deformation (strain) of a polymer in a molded body when stress is applied to the molded body.
- strain elastic deformation
- the degree of photoelastic birefringence of the material can be evaluated by obtaining a “photoelastic constant” specific to the polymer.
- stress is applied to the polymer material, and birefringence is measured when elastic distortion occurs.
- the proportional constant between the obtained birefringence and stress is the photoelastic constant.
- the resin (A), the polymer (B) and the non-birefringent resin material need to be formed into some molded body, and the photoelastic birefringence needs to be measured.
- the molded body is a film or a sheet. Here, a melt-extruded film and a press-formed sheet will be described.
- the polymer (B) is pressed at 190 ° C. to produce a 500 ⁇ m-thick press-molded sheet, and a 25 mm ⁇ 90 mm test piece is cut out from the center of the obtained press-molded sheet.
- the measurement conditions and calculation method are the same as those for the melt-extruded film described above.
- photoelastic birefringence is a characteristic characteristic of the polymer structure
- the photoelastic constant of the polymer (B) is relative to the photoelastic constant of the resin (A).
- the blending amount of the polymer (B) it is necessary to add an amount of the polymer (B) that can cancel the photoelastic birefringence of the resin (A). It is known that additivity is established between the photoelastic constant of the polymer (copolymer) obtained and the photoelastic constant of each homopolymer corresponding to the monomer species used for the copolymerization.
- the polymer (B) has a photoelastic constant different from that of the resin (A) and is large, the non-birefringent resin material comprising the resin (A) and the polymer (B), and The required amount of the polymer (B) for reducing the photoelastic birefringence of the film is small.
- the degree of orientation of the polymer in the molded article is not so large, and the orientation birefringence of the molded article is not so large.
- orientation birefringence in the design of the polymer (B).
- the orientation birefringence in the obtained molded article becomes a practical problem, it is necessary to make the orientation birefringence of the polymer (B) different from the orientation birefringence of the resin (A). is there.
- the polymer (B) of the present invention may be a polymer having a weight average molecular weight exceeding 5000, preferably 10,000 or more, more preferably 20000 or more.
- the weight average molecular weight is 5000 or less, physical properties such as mechanical properties, heat resistance, and hardness of the molded body may be deteriorated, or the surface of the molded body may be bleed out during high-temperature molding and the appearance of the molded body may be impaired.
- the polymer (B) preferably has a crosslinked structure portion in part from the viewpoint of improving mechanical strength, and examples thereof include a multilayer structure polymer having a crosslinked polymer layer.
- the polymer (B) preferably has a hard polymer portion from the viewpoint of heat resistance, and preferably has a non-crosslinked structure from the viewpoint of reducing birefringence. It preferably has a polymer part.
- a multilayer structure polymer having a hard polymer layer is exemplified.
- the polymer (B) is more preferably a multilayer structure polymer including a crosslinked polymer layer and a hard polymer layer.
- the multilayer structure polymer is also expressed as a graft copolymer or a core-shell polymer, but the polymer (B) of the present invention includes these.
- the polymer (B) has a crosslinked polymer (layer) and a hard polymer (layer), and the size of each polymer (B) is submicron-sized fine particles.
- the polymer (B) is dispersed in a submicron size in the matrix resin (A).
- the polymer (B) agglomerates indefinitely, such as several centimeters, and hardly deteriorates transparency and causes foreign matters such as fish eyes. Since the dispersibility in the matrix can be controlled by designing the polymer (B) to a submicron size in advance in this way, the polymer (B) can be dispersed in the matrix even if the compatibility is not completely exhibited.
- the polymer can be designed with a high emphasis on birefringence control, and the degree of freedom in designing the polymer can be increased for both the resin (A) and the polymer (B) as the matrix. This is the second important technical idea.
- the polymer (B) is added to the resin (A) as a matrix component, so that the mechanical strength is increased.
- the polymer (B) is preferably a graft copolymer (core-shell polymer) having a soft crosslinked polymer layer and a hard polymer layer.
- a method of adding a soft polymer to improve the mechanical strength is also mentioned as a method, but in this case, the matrix resin (here, the resin (A)) and the soft polymer are homogeneously mixed, and the resulting molding is obtained.
- the soft cross-linked polymer layer is “island” in the molded body, and the resin (A) and the hard polymer. Since it has a discontinuous sea-island structure in which the layer becomes the “sea”, it is possible to improve the mechanical strength and bring about an excellent effect of hardly reducing the heat resistance.
- the soft crosslinked polymer usually has a composition different from that of the matrix (resin (A)), it is difficult to uniformly disperse the matrix in the matrix. It becomes a defect such as.
- the graft copolymer has both a soft crosslinked polymer layer and a hard polymer layer, the soft crosslinked polymer can be uniformly dispersed in the matrix as described above.
- the glass transition temperature of the polymer is less than 20 ° C. From the viewpoint of enhancing the impact absorbing ability of the soft layer and enhancing the impact resistance improving effect such as crack resistance, the glass transition temperature of the polymer is preferably less than 0 ° C, more preferably less than -20 ° C. .
- “hard” as used herein means that the glass transition temperature of the polymer is 20 ° C. or higher.
- the heat resistance of the non-birefringent resin material blended with the polymer (B) and the film is reduced, and the polymer (B) is heavy when produced. There arises a problem that the coalescence (B) is likely to be coarsened or agglomerated.
- the glass transition temperatures of the “soft” and “hard” polymers are calculated using the Fox equation using the values described in the Polymer Handbook (Polymer Hand Book (J. Brandrup, Interscience 1989)). The calculated value is used (for example, polymethyl methacrylate is 105 ° C. and polybutyl acrylate is ⁇ 54 ° C.).
- the crosslinked polymer layer is “soft” or “hard”.
- this definition is as described above.
- graft ratio is used to express how much the hard polymer layer is covalently bonded to the crosslinked polymer layer.
- the graft ratio of the polymer (B) is an index representing the weight ratio of the grafted hard polymer layer to the crosslinked polymer layer, where the weight of the crosslinked polymer layer is 100.
- the graft ratio is preferably 10 to 250%, more preferably 40 to 230%, and most preferably 60 to 220%. If the graft ratio is less than 10%, the polymer (B) tends to aggregate in the molded product, which may reduce transparency or cause foreign matter. Moreover, there exists a tendency for the elongation at the time of a tensile fracture to fall and to become easy to generate
- This free polymer is also a polymer (B). To include.
- “Soft” Crosslinked Polymer layer will be described.
- “soft” means that the glass transition temperature of the polymer is less than 20 ° C., and a rubbery polymer is preferably used.
- Specific examples include butadiene-based crosslinked polymers, (meth) acrylic crosslinked polymers, and organosiloxane-based crosslinked polymers. Of these, (meth) acrylic crosslinked polymers are particularly preferred in terms of the non-birefringent resin material and the weather resistance (light resistance) and transparency of the film.
- the (meth) acrylic crosslinked polymer in the (meth) acrylic crosslinked polymer layer is not particularly limited as long as it is a (meth) acrylic crosslinked polymer. From the viewpoint of impact resistance such as crack resistance, acrylic 50 to 100% by weight of acid alkyl ester, 50 to 0% by weight of vinyl monomer copolymerizable with alkyl acrylate, and 0.05 to 10 parts by weight of polyfunctional monomer (alkyl acrylate and this) And a polymer obtained by polymerizing a vinyl monomer copolymerizable with 100 parts by weight in total). A layer formed by mixing all the monomer components and polymerizing in one step may be used, or a layer formed by polymerizing in two or more steps by changing the monomer composition.
- the alkyl acrylate used here is preferably an alkyl group having 1 to 12 carbon atoms from the viewpoint of polymerization reactivity and cost, and may be linear or branched. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, and n-octyl acrylate. , ⁇ -hydroxyethyl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate and the like, and these monomers may be used alone or in combination of two or more.
- the acrylic acid alkyl ester is preferably 50 to 100% by weight, more preferably 60 to 100% by weight based on the entire monofunctional monomer (total amount of the acrylic acid alkyl ester and the vinyl monomer copolymerizable therewith). 70 to 100% by weight is preferred. If it is less than 50% by weight, the crack resistance of the film may deteriorate.
- Examples of the monomer copolymerizable with an acrylic acid alkyl ester include, for example, methacrylic acid alkyl ester, which are polymerizable and cost-effective. More preferably, the alkyl group has 1 to 12 carbon atoms, and may be linear or branched.
- examples thereof include glycidyl acid.
- Other copolymerizable monomers include vinyl halides such as vinyl chloride and vinyl bromide, (meth) acrylamides such as acrylamide, methacrylamide and N-methylolacrylamide, acrylonitrile, methacrylonitrile and the like.
- Vinyl esters such as vinyl cyanide, vinyl formate, vinyl acetate and vinyl propionate, aromatic vinyl such as styrene, vinyltoluene and ⁇ -methylstyrene and derivatives thereof, vinylidene halides such as vinylidene chloride and vinylidene fluoride, acrylic acid And acrylic acid such as sodium acrylate and calcium acrylate and salts thereof, methacrylic acid such as methacrylic acid, sodium methacrylate and calcium methacrylate and salts thereof, and the like. Two or more of these monomers may be used in combination.
- the polyfunctional monomers used here include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl maleate, divinyl adipate, divinyl Benzene ethylene glycol dimethacrylate, divinylbenzene ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, trimethylolpropane tri Methacrylate, trimethylolpropane triacrylate, tetramethylol methane tetramethacrylate, tetramethylol methane tetraacrylate, dipropylene glycol dim
- the addition amount of the polyfunctional monomer with respect to the monofunctional monomer is preferably 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the monofunctional monomer. Is more preferable. If the addition amount of the polyfunctional monomer is less than 0.05 parts by weight, there is a tendency that a crosslinked product cannot be formed, and even if it exceeds 10 parts by weight, the crack resistance of the film tends to be lowered.
- Hard crosslinked Polymer Layer
- hard means that the glass transition temperature of the polymer is 20 ° C. or higher.
- the glass transition temperature is 20 ° C. or higher.
- the monomers described in the description of the “soft” crosslinked polymer layer can be used as appropriate.
- (1) can be achieved by appropriately selecting and polymerizing monomers so that the polymer is easily compatible with the matrix component.
- the orientation birefringence in the molded body such as a film is not so large and does not become a problem, for example, it does not go through a stretching process, it is hard so that the photoelastic constant of the molded body becomes extremely small.
- This can be achieved by making the photoelastic constant of the polymer different from that of the matrix (resin (A)).
- the orientation birefringence in a molded article such as a film is relatively large due to a stretching process or the like, not only the photoelastic constant of the molded article but also the orientation birefringence both become extremely small.
- both the photoelastic constant and orientation birefringence of the hard polymer can be achieved by making the matrix (resin (A)) have different signs.
- the effect of canceling the birefringence of the resin (A) that is the matrix is larger in the “hard” polymer layer, and the effect of the polymer layer having a crosslinked structure is smaller. That is the point.
- birefringence can be canceled by orienting polymer chains.
- the polymer layer having a crosslinked structure is not easily deformed by an external force, the polymer chain is difficult to be oriented, and the effect of canceling the birefringence of the matrix becomes small.
- the crosslink density is low, it can be easily deformed by an external force, so even a polymer layer having a crosslink structure can be expected to have some effect of canceling the birefringence of the matrix.
- the polymer layer may have a function of canceling the birefringence of the matrix.
- a polymer layer other than the cross-linked polymer layer is used, and a polymer layer that can be oriented by external force is preferable, and specifically, a “hard” polymer layer is used. More preferably, it is a “hard” polymer layer having no cross-linked structure, and still more preferably an outer layer of the polymer (B) having a cross-linked structure at a site that is easily in direct contact with the matrix. There is no “hard” polymer layer.
- the photoelastic constants of the resin (A) and the polymer (B) are used. May be selected so as to have different signs.
- the orientation birefringence of the copolymer polymer is additive with the intrinsic birefringence of each homopolymer corresponding to the monomer species used for the copolymerization.
- the orientation birefringence of each of the resin (A) and the polymer (B) is What is necessary is just to select so that it may become a different sign.
- orientation birefringence of the polymer examples of specific monomers to be used as reference (inherent birefringence of homopolymers composed of the monomers) are described below, but are not limited thereto.
- the intrinsic birefringence is birefringence (orientation birefringence) when the polymer is completely oriented in one direction.
- Polymer exhibiting positive intrinsic birefringence Polybenzyl methacrylate [+0.002] Polyphenylene oxide [+0.210] Bisphenol A polycarbonate [+0.106] Polyvinyl chloride [+0.027] Polyethylene terephthalate [+0.105] Polyethylene [+0.044] Polymer exhibiting negative intrinsic birefringence: Polymethyl methacrylate [-0.0043] Polystyrene [-0.100]
- the photoelastic constant and orientation birefringence data of some polymers have been described. Depending on the polymer, the birefringence of both has the same sign, such as “positive” for orientation birefringence and “negative” for photoelastic constant. Not necessarily.
- Table 1 below shows examples of signs of orientation birefringence and photoelastic birefringence (constant) of some homopolymers.
- the resin (A) is an acrylic resin, both the orientation birefringence and the photoelastic constant are often negative, so the polymer (B) (especially the outer hard polymer layer).
- the polymer (B) The composition of the hard polymer is not particularly limited as long as the viewpoint of improving the dispersibility in the resin (A) (that is, increasing the compatibility) is satisfied.
- a monomer (monomer) that can be particularly preferably used is a vinyl monomer having a ring structure such as an alicyclic structure, a heterocyclic structure, or an aromatic group in the molecular structure.
- a vinyl monomer having an alicyclic structure, a heterocyclic structure or an aromatic group is more preferable.
- the ring structure is preferably a polycyclic structure, and more preferably a condensed cyclic structure.
- the structural unit contains a monomer represented by the following formula (4).
- the monomer having an alicyclic structure include (meth) acrylic acid dicyclopentanyl, dicyclopentenyloxyethyl (meth) acrylate, and the like.
- the monomer having an aromatic group include vinyl arenes such as styrene, ⁇ -methylstyrene, monochlorostyrene, dichlorostyrene, benzyl (meth) acrylate, phenyl (meth) acrylate, and (meth) acrylic.
- Phenoxyethyl acid etc. can be mentioned.
- Examples of the monomer having a heterocyclic structure include pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. Of these, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and phenoxyethyl (meth) acrylate are preferred.
- R 9 represents a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms.
- R 10 is a substituted or unsubstituted aromatic group having 1 to 24 carbon atoms, or a substituted or unsubstituted alicyclic group having 1 to 24 carbon atoms, and has a monocyclic structure or a heterocyclic structure.
- substituents that R 9 and R 10 may have include, for example, halogen, hydroxyl group, carboxyl group, alkoxy group, carbonyl group (ketone structure), amino group, amide group, epoxy group, and carbon-carbon group.
- Examples thereof include at least one selected from the group consisting of a double bond, an ester group (carboxyl group derivative), a mercapto group, a sulfonyl group, a sulfone group, and a nitro group.
- at least one selected from the group consisting of halogen, hydroxyl group, carboxyl group, alkoxy group, and nitro group is preferable.
- l represents an integer of 1 to 4, preferably 1 or 2.
- m is an integer of 0 to 1.
- n represents an integer of 0 to 10, preferably an integer of 0 to 2, and more preferably 0 or 1.
- the vinyl monomer having an alicyclic structure, a heterocyclic structure or an aromatic group is preferably a (meth) acrylic monomer having an alicyclic structure, a heterocyclic structure or an aromatic group.
- R 9 is preferably a (meth) acrylate monomer which is a substituted or unsubstituted, linear or branched alkyl group having 1 carbon atom.
- R 10 is a substituted or unsubstituted aromatic group having 1 to 24 carbon atoms, or a substituted or unsubstituted alicyclic group having 1 to 24 carbon atoms, and a monocyclic structure More preferably, it is a (meth) acrylate monomer.
- l is an integer from 1 to 2
- n is an integer from 0 to 2, more preferably a (meth) acrylate monomer.
- (meth) acrylic monomers represented by the formula (4) benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and phenoxyethyl (meth) acrylate are preferable.
- benzyl (meth) acrylate is most preferable in terms of optical isotropy, compatibility with the resin (A), and moldability. Furthermore, benzyl methacrylate is preferable in terms of heat resistance because of its high glass transition temperature.
- the resin (A) is an acrylic resin
- the photoelastic constant is negative
- the amount of benzyl methacrylate used can be reduced by using benzyl methacrylate having a relatively large positive photoelastic constant.
- the degree of freedom in designing the non-birefringent resin material is increased, for example, the amount of the polymer (B) used is small.
- the hard polymer contained in the unit is 1 to 100% by weight of the monomer represented by the formula (4), 99 to 0% by weight of another monomer copolymerizable therewith, and 0% of the multifunctional monomer. It is preferable to polymerize .about.2.0 parts by weight (with respect to 100 parts by weight of the total amount of the monomer represented by the formula (4) and other monomers copolymerizable therewith).
- the hard polymer layer may be formed by mixing all the monomers and polymerizing in one step, or may be formed by polymerizing in two or more steps by changing the monomer composition. .
- any of benzyl methacrylate, benzyl acrylate, dicyclopentanyl (meth) acrylate, and phenoxyethyl (meth) acrylate is preferably used. Any one or a combination of them can be used. For applications requiring higher heat resistance, it is preferable to use benzyl methacrylate from the viewpoint of glass transition temperature.
- Examples of other monomers copolymerizable with the monomer represented by the formula (4) include methacrylic acid alkyl esters, which have 1 to 12 carbon atoms in the alkyl group from the viewpoint of polymerizability and cost. Those are preferable, and may be linear or branched. Specific examples thereof include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, octyl acrylate, ⁇ -hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate. Etc.
- alkyl acrylates can also be suitably used, and those having an alkyl group with 1 to 12 carbon atoms are preferred from the viewpoint of polymerization reactivity and cost, and may be linear or branched. Specific examples include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and ⁇ -acrylate. -Hydroxyethyl, dimethylaminoethyl acrylate, glycidyl acrylate and the like.
- copolymerizable monomers include maleic anhydride, citraconic anhydride, dimethyl maleic anhydride, dichloromaleic anhydride, bromomaleic anhydride, dibromomaleic anhydride, phenylmaleic anhydride, diphenylmaleic anhydride.
- Unsubstituted and / or substituted maleic anhydrides such as acids, vinyl halides such as vinyl chloride and vinyl bromide, (meth) acrylamides such as acrylamide, methacrylamide and N-methylolacrylamide, and cyanides such as acrylonitrile and methacrylonitrile Vinyl esters such as vinyl fluoride, vinyl formate, vinyl acetate, vinyl propionate, aromatic vinyl such as styrene, vinyl toluene, ⁇ -methyl styrene, and derivatives thereof, vinylidene halides such as vinylidene chloride and vinylidene fluoride, acrylic acid, Acrylic acid Acrylic acid and its salts such as thorium and calcium acrylate, methacrylic acid and its salts such as methacrylic acid, sodium methacrylate and calcium methacrylate, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate And (hydroxyalkyl) acrylic acid esters such as 2- (
- These monomers may be used alone or in combination of two or more.
- methacrylic acid alkyl ester and acrylic acid alkyl ester are preferable, and further, methyl methacrylate in terms of compatibility with acrylic resin (A), methyl acrylate, ethyl acrylate in terms of suppressing zipper depolymerization, Alternatively, n-butyl acrylate is preferably used.
- the amount of the monomer represented by the formula (4) is 1 to 100 in a total amount of 100% by weight of the monomer represented by the formula (4) and other monomers copolymerizable therewith. % By weight is preferred, 5 to 70% by weight is more preferred, and 5 to 50% by weight is most preferred.
- the hard polymer layer having the (meth) acrylate monomer represented by the formula (4) as a structural unit has a polyfunctionality having two or more non-conjugated reactive double bonds per molecule.
- Monomers may be used.
- the polyfunctional monomer which can be used for a crosslinked polymer layer can be used similarly.
- the amount of polyfunctional monomer used in the hard polymer layer (based on the total amount of the monomer represented by the formula (4) and the vinyl monomer copolymerizable therewith is 100 parts by weight) is: From the viewpoint of optical isotropy and dispersibility, 0 to 2.0 parts by weight is preferable, 0 to 1.0 parts by weight is more preferable, 0 to 0.5 parts by weight is further preferable, and 0 to 0.04 parts by weight. Part by weight is even more preferred and 0 part by weight is most preferred.
- the polymer (B) preferably has a hard polymer layer having the monomer represented by the formula (4) as a constituent unit in a multilayer structure.
- this outermost layer It is more preferable to have a hard polymer layer having a monomer represented by the formula (4) as a structural unit.
- a soft layer having a (meth) acrylic crosslinked polymer layer ((meth) acrylic rubber) may be adjacent to the inside of the hard outermost layer.
- the polymer (B) is a multilayer polymer having at least one (meth) acrylic crosslinked polymer layer and at least one hard polymer layer having the monomer represented by the formula (4) as a constituent unit. It is preferable.
- a preferred embodiment of the polymer (B) has a soft inner layer and a hard outer layer, the inner layer has a (meth) acrylic crosslinked polymer layer, and the outer layer is represented by the formula (4).
- the form which has the hard polymer layer which has the monomer represented by a structural unit can be mentioned. This form is preferable from the viewpoint of productivity.
- the polymer (B) has a hard inner layer, a soft intermediate layer and a hard outer layer, the inner layer is composed of at least one hard polymer layer, and the intermediate layer is Examples include a soft polymer layer composed of a (meth) acrylic crosslinked polymer layer, and the outer layer having a hard polymer layer having a monomer represented by the formula (4) as a constituent unit. This form may also have a softer innermost layer. In the present invention, these may be used singly or in combination of two or more.
- a soft inner layer, a soft intermediate layer, and a soft layer refer to an inner layer, an intermediate layer, and a layer made of at least one soft polymer.
- the hard (outermost) outer layer and the hard inner layer in the present application refer to the (outermost) outer layer and inner layer made of at least one hard polymer.
- “soft” and “hard” are the same as “soft” and “hard” described above.
- the innermost layer hard polymer has a hardness of From the standpoint of crack resistance balance, methacrylic acid ester 40 to 100% by weight, acrylic acid ester 0 to 60% by weight, aromatic vinyl monomer 0 to 60% by weight, polyfunctional monomer 0 to 10% by weight %, And a hard polymer composed of 0 to 20% by weight of a vinyl monomer copolymerizable with a methacrylic acid ester, an acrylic acid ester, and an aromatic vinyl monomer.
- the polymer (B) is, for example, a hard inner layer having a soft inner layer having a (meth) acrylic crosslinked polymer layer and a polymer layer having a monomer represented by the formula (4) as a constituent unit.
- a layer structure in which a soft inner layer is completely covered with a hard polymer of the outer layer is common, but depending on the weight ratio of the soft inner layer and the hard outer layer, the layer structure may be There may be cases where the amount of hard polymer to form is insufficient.
- the volume average particle diameter of the polymer (B) to the (meth) acrylic crosslinked polymer layer is preferably 20 to 450 nm, more preferably 20 to 300 nm, still more preferably 20 to 150 nm, and most preferably 30 to 80 nm. If it is less than 20 nm, crack resistance may deteriorate. On the other hand, if it exceeds 450 nm, the transparency may decrease. Furthermore, it is preferable to make it less than 80 nm from a viewpoint of bending whitening resistance. From the viewpoint of trimming properties, 20 to 450 nm is preferable, 50 to 450 nm is more preferable, 60 to 450 nm is more preferable, and 100 to 450 nm is still more preferable.
- the volume average particle diameter can be measured by a dynamic scattering method, for example, by using MICROTRAC UPA150 (manufactured by Nikkiso Co., Ltd.).
- the volume average particle diameter of the polymer (B) to the (meth) acrylic crosslinked polymer layer is specifically the (meth) acrylic crosslinked polymer layer from the center of the polymer (B) particles. Refers to the volume average particle diameter of the particles up to.
- the content of the acrylic crosslinked polymer in the polymer (B) is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, and more preferably 30 to 60% when the polymer (B) is 100% by weight. % By weight is more preferred, and 35 to 55% by weight is most preferred. If it is less than 10% by weight, the mechanical strength such as crack resistance of the obtained non-birefringent resin material may be lowered. On the other hand, if it exceeds 90% by weight, the dispersibility of the polymer (B) is impaired, the smoothness of the surface of the molded product cannot be obtained, and there is a tendency that appearance defects such as fish eyes occur. Further, the content of the hard polymer is not sufficient, and there is a tendency that optical isotropy cannot be maintained, for example, the birefringence during alignment and the photoelastic constant are increased.
- the production method of the polymer (B) is not particularly limited, and a known emulsion polymerization method, emulsion-suspension polymerization method, suspension polymerization method, bulk polymerization method or solution polymerization method can be applied.
- An emulsion polymerization method is particularly preferred for the polymerization of the polymer (B).
- the polymer (B) is preferably obtained by multistage polymerization, and is represented by the above formula (4) in the presence of (meth) acrylic rubber-containing polymer particles as at least one stage of this multistage polymerization.
- a multi-stage polymerization (meth) acrylic rubber-containing graft copolymer obtained by polymerizing a monomer-containing monomer and a mixture containing another monomer copolymerizable therewith can be preferably used.
- the mixture containing the monomer represented by the formula (4) and another monomer copolymerizable therewith is composed of the monomer represented by the formula (4) and the other copolymerizable therewith.
- the content of the monomer represented by the formula (4) is preferably 1 to 100% by weight, more preferably 5 to 70% by weight, and 5 to 50% by weight. Most preferred.
- This mixture may contain a polyfunctional monomer, and the total amount of the monomer represented by the formula (4) and other monomers copolymerizable therewith is 100 parts by weight.
- the monofunctional monomer is preferably used in an amount of 0 to 2.0 parts by weight, more preferably 0 to 1.0 part by weight, further preferably 0 to 0.5 part by weight, and 0 to 0.04 part by weight. Even more preferred is 0 part by weight.
- a hard polymer having the monomer represented by the formula (4) as a constituent unit is formed.
- Other monomers copolymerizable with the monomer represented by the formula (4) are the same as those exemplified above, and can be preferably used in the same manner. The same applies to the preferred content of other monomers copolymerizable with the monomer represented by the formula (4).
- the polyfunctional monomer is the same as the above-described example, and can be preferably used similarly.
- the (meth) acrylic rubber-containing polymer particles need only be multistage polymer particles containing at least (meth) acrylic rubber, and can be copolymerized with 50 to 100% by weight of acrylic acid alkyl ester and acrylic acid alkyl ester. 50 to 0% by weight of other monomers and 0.05 to 10 parts by weight of a polyfunctional monomer (based on a total amount of 100 parts by weight of alkyl acrylate ester and other monomers copolymerizable therewith) It is preferable to have a rubber ((meth) acrylic cross-linked polymer) part obtained by polymerizing.
- the rubber part may be polymerized in one stage by mixing all the monomer components, or may be polymerized in two or more stages by changing the monomer composition.
- the (meth) acrylic rubber-containing polymer particles are not particularly limited as long as a (meth) acrylic crosslinked polymer (rubber part) is formed as at least one stage of polymerization in multistage polymerization.
- the hard polymer may be polymerized before and / or after the polymerization step of the system cross-linked polymer.
- the polymer (B) is composed of (b-1) 50 to 100% by weight of an acrylic acid alkyl ester, 50 to 0% by weight of a monomer copolymerizable therewith, and a polyfunctional monomer.
- the monomer mixture in the polymerization stage (b-1) and / or the monomer mixture in the polymerization stage (b-2) may be polymerized in one stage by mixing all the monomer components.
- the polymerization may be carried out in two or more stages by changing the monomer composition.
- an alkyl acrylate ester, a monomer copolymerizable therewith and a polyfunctional monomer, and preferred amounts thereof are used in the above-mentioned (meth) acrylic acid crosslinked polymer. This is the same as illustrated.
- the components of the monomer mixture and the preferred amounts thereof to be used are the same as those in the above-mentioned hard polymer layer.
- the volume average particle diameter to the (meth) acrylic rubber layer of the (meth) acrylic rubber-containing graft copolymer is the volume average of the polymer (B) to the (meth) acrylic crosslinked polymer layer. It is measured in the same manner as the particle diameter, and the preferred range is also the same.
- the polymer (B) When the polymer (B) is produced by emulsion polymerization, it can be produced by ordinary emulsion polymerization using a known emulsifier. Specifically, for example, anionic interfaces such as sodium alkyl sulfonate, sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, sodium lauryl sulfate, fatty acid sodium, polyoxyethylene lauryl ether sodium phosphate, etc. Activators, alkylphenols, nonionic surfactants such as reaction products of aliphatic alcohols with propylene oxide and ethylene oxide are shown. These surfactants may be used alone or in combination of two or more.
- anionic interfaces such as sodium alkyl sulfonate, sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, sodium lauryl sulfate, fatty acid sodium, polyoxyethylene lau
- a cationic surfactant such as an alkylamine salt may be used.
- phosphate ester salts alkali metal or alkaline earth metal
- sodium polyoxyethylene lauryl ether phosphate it is preferable to polymerize using.
- the multilayer structure polymer latex obtained by emulsion polymerization is, for example, spray-dried, freeze-dried, or coagulated by adding a salt such as calcium chloride or magnesium chloride, or an acid such as hydrochloric acid or sulfuric acid as a coagulant.
- a powdery multilayer structure polymer is obtained by treating the resin component solidified by heat treatment or the like by a known method such as separation from the aqueous phase, washing and drying.
- a known coagulant such as acid or salt can be used as a coagulant, but the thermal stability during molding of the obtained copolymer is improved. It is particularly preferable to use a magnesium salt, particularly magnesium sulfate, from the viewpoint of making it possible.
- the polymer (B) is preferably blended so that 1 to 60 parts by weight of the (meth) acrylic crosslinked polymer ((meth) acrylic rubber) is contained in 100 parts by weight of the non-birefringent resin material. 1 to 30 parts by weight is more preferable, and 1 to 25 parts by weight is further preferable. If it is less than 1 part by weight, the crack resistance and vacuum formability of the film may deteriorate, the photoelastic constant may increase, and optical isotropy may deteriorate. On the other hand, when it exceeds 60 parts by weight, the heat resistance, surface hardness, transparency, and bending whitening resistance of the film tend to deteriorate.
- the blending ratio of the resin (A) and the polymer (B) is not particularly problematic as long as the blending conditions are satisfied, and also depends on the amount of the acrylic crosslinked polymer contained in the polymer (B).
- the polymer (B) is preferably 1 to 99% by weight, more preferably 1 to 80% by weight, and more preferably 1 to 60% by weight. Further preferred. If it is less than 1% by weight, the crack resistance and vacuum formability of the film may be deteriorated, the photoelastic constant may be increased, and the optical isotropy may be deteriorated. On the other hand, if it exceeds 99% by weight, the heat resistance, surface hardness, transparency and folding whitening resistance of the film tend to deteriorate.
- the non-birefringent resin material of the present invention is suitable for use by being in a granular form or pelletized by an extruder, followed by extrusion molding, injection molding, compression molding, blow molding, spinning molding, etc. while heating.
- the molded product can be shaped. It is particularly useful as a film, and can be satisfactorily processed by, for example, an ordinary melt extrusion method such as an inflation method, a T-die extrusion method, a calendar method, or a solvent casting method. Among them, it is preferable to use a melt extrusion method that does not use a solvent. According to the melt extrusion method, it is possible to reduce the burden on the global environment and the working environment due to manufacturing costs and solvents.
- the non-birefringent resin material of the present invention has a birefringence value of ⁇ 15 ⁇ 10 ⁇ 4 to 15 ⁇ 10 from the viewpoint that birefringence during molding processing does not occur and a molded product having no practical problem can be obtained. It is preferably ⁇ 4 , more preferably ⁇ 10 ⁇ 10 ⁇ 4 to 10 ⁇ 10 ⁇ 4 , and still more preferably ⁇ 5 ⁇ 10 ⁇ 4 to 5 ⁇ 10 ⁇ 4 . Further, from the viewpoint of obtaining stable optical characteristics, it is preferably ⁇ 1.7 ⁇ 10 ⁇ 4 to 1.7 ⁇ 10 ⁇ 4 , and ⁇ 1.6 ⁇ 10 ⁇ 4 to 1.6 ⁇ 10 ⁇ 4.
- the non-birefringent resin material of the present invention has a photoelastic constant of ⁇ 10 ⁇ 10 ⁇ 12 to 10 ⁇ because the birefringence generated even when stress is applied to the molded body in an environment such as high temperature and high humidity.
- 10 ⁇ 12 is preferable, ⁇ 4 ⁇ 10 ⁇ 12 to 4 ⁇ 10 ⁇ 12 is more preferable, ⁇ 2 ⁇ 10 ⁇ 12 to 2 ⁇ 10 ⁇ 12 is further preferable, and ⁇ 1.
- the photoelastic constant is ⁇ 4 ⁇ 10 ⁇ 12 to 4 ⁇ 10 ⁇ 12 , even if it is made into a film and used in a liquid crystal display device, phase difference unevenness occurs, contrast at the periphery of the display screen decreases, There will be no light leakage.
- the non-birefringent resin material of the present invention is characterized by high mechanical strength.
- the mechanical strength can be evaluated by, for example, tensile elongation at break in a tensile test, and the tensile elongation at break is preferably 10% or more, more preferably 20% or more, and 30% or more. More preferably, it is still more preferably 40% or more, further preferably 50% or more, particularly preferably 60% or more, and most preferably 90% or more.
- the non-birefringent resin material of the present invention exhibiting a tensile elongation at break within the above range is extremely excellent in productivity, for example, no problems such as cracking occur during molding. In addition, troubles such as cracks do not occur when actually used as a product.
- the tensile strength at break at break is correlated with the crackability, and the higher the tensile elongation at break, the better the crack resistance.
- the surface of the film can be formed by simultaneously contacting (sandwiching) both sides of the film with a roll or a metal belt, particularly by contacting the roll or metal belt heated to a temperature close to the glass transition temperature. It is also possible to obtain a film having better properties.
- film lamination and biaxial stretching can be used to modify the film.
- the non-birefringent resin material of the present invention can produce a film without causing contamination of the molding machine or film defects due to scattering of the UV absorber even under high temperature molding conditions using T-die film formation. Can do.
- melt extrusion film a film formed by the melt extrusion method is distinguished from a film formed by another method such as a solution casting method and is referred to as a “melt extrusion film”.
- the non-birefringent resin material according to the present invention is formed into a film by a melt extrusion method, first, the non-birefringent resin material according to the present invention is supplied to an extruder, and the non-birefringent resin material is heated and melted.
- the non-birefringent resin material is preferably pre-dried before being supplied to the extruder. By performing such preliminary drying, foaming of the resin extruded from the extruder can be prevented.
- the method of preliminary drying is not particularly limited.
- the raw material that is, the non-birefringent resin material according to the present invention
- the raw material can be formed into pellets or the like, and can be performed using a hot air dryer or the like.
- the extruder for molding the non-birefringent resin material according to the present invention preferably has one or more devolatilizers for removing volatile components generated during heating and melting.
- a deaeration device By having a deaeration device, it is possible to reduce deterioration of the film appearance due to resin foaming and decomposition degradation reaction.
- melt extrusion for molding the non-birefringent resin material according to the present invention it is preferable to supply an inert gas such as nitrogen or helium to the cylinder of the extruder along with the supply of the resin material.
- an inert gas such as nitrogen or helium
- the non-birefringent resin material heated and melted in the extruder is supplied to the T die through a gear pump and a filter.
- a gear pump is used, the uniformity of the extrusion amount of the resin can be improved and thickness unevenness can be reduced.
- a filter is used, the foreign material in a non-birefringent resin material can be removed and the film excellent in the external appearance without a defect can be obtained.
- the type of filter it is preferable to use a stainless steel leaf disc filter capable of removing foreign substances from the molten polymer, and it is preferable to use a fiber type, a powder type, or a composite type thereof as the filter element.
- the filter can be suitably used for an extruder or the like used for pelletization or film formation.
- the non-birefringent resin material supplied to the T die is extruded from the T die as a sheet-like molten resin.
- the sheet-like molten resin is preferably sandwiched between two cooling rolls and cooled to form a film.
- One of the two cooling rolls sandwiching the sheet-like molten resin is a rigid metal roll having a smooth surface, and the other has a metal elastic outer cylinder having a smooth surface and capable of elastic deformation.
- a flexible roll is preferred.
- cooling roll is used to mean “touch roll” and “cooling roll”.
- each cooling roll is metal
- the surfaces of the cooling roll come into contact with each other.
- the outer surface may be scratched, or the cooling roll itself may be damaged.
- the film is obtained by sandwiching and cooling the sheet-like molten resin with the two cooling rolls. It is done.
- the film of the present invention is very tough and rich in flexibility, there is no need to stretch for improving the strength, and there are advantages in terms of productivity and cost by omitting the stretching step.
- the film of the present invention is highly transparent and can have a thickness of 10 ⁇ m or more with high strength. Furthermore, orientation birefringence due to stretching hardly occurs and is optically isotropic. In addition, shrinkage due to heat during secondary molding such as vacuum molding or during use at high temperatures is small.
- the film of the present invention exhibits the above-described effects even as an unstretched film, but it can be further stretched, thereby improving strength and improving film thickness accuracy.
- a film with small thickness unevenness can be easily produced without substantially causing birefringence and without substantially increasing haze.
- the non-birefringent resin material according to the present invention is once formed into an unstretched film, and then uniaxially stretched or biaxially stretched.
- Uniaxially stretched film or biaxially stretched film can be produced.
- the sheet-like molten resin is sandwiched and cooled by the two cooling rolls, and an unstretched film having a thickness of 150 ⁇ m is once acquired. Thereafter, the film may be stretched by biaxial stretching in the vertical and horizontal directions to produce a film having a thickness of 40 ⁇ m.
- a film before being stretched after the non-birefringent resin material according to the present invention is formed into a film shape, that is, an unstretched film is referred to as a “raw film”.
- the raw material film When stretching the raw material film, the raw material film may be stretched immediately after the raw material film is formed, or after the raw material film is molded, the raw material film is temporarily stored or moved to stretch the raw material film. You may go.
- the state of the raw material film may be stretched in a very short time (in some cases, instantaneously) in the film manufacturing process. May be stretched after a certain period of time.
- the raw material film When the film of the present invention is used as a stretched film, the raw material film only needs to maintain a film shape sufficient to be stretched, and does not have to be a complete film.
- the method for stretching the raw material film is not particularly limited, and any conventionally known stretching method may be used. Specifically, for example, transverse stretching using a tenter, longitudinal stretching using a roll, sequential biaxial stretching in which these are sequentially combined, and the like can be used.
- the raw material film is stretched, it is preferable that the raw material film is once preheated to a temperature 0.5 to 5 ° C., preferably 1 to 3 ° C. higher than the stretching temperature, and then cooled to the stretching temperature and stretched.
- the thickness of the raw material film can be maintained with high accuracy, and the thickness accuracy of the stretched film does not decrease and thickness unevenness does not occur. Further, the raw material film does not stick to the roll and does not loosen due to its own weight.
- the preheating temperature of the raw material film is too high, there is a tendency that the raw material film sticks to the roll or is loosened by its own weight.
- the difference between the preheating temperature and the stretching temperature of the raw material film is small, it tends to be difficult to maintain the thickness accuracy of the raw material film before stretching, the thickness unevenness increases, or the thickness accuracy tends to decrease.
- the non-birefringent resin material according to the present invention is stretched after being formed into a raw material film, it is difficult to improve the thickness accuracy by utilizing a necking phenomenon. Therefore, in the present invention, it is important to manage the preheating temperature in order to maintain or improve the thickness accuracy of the obtained film.
- the stretching temperature when stretching the raw material film is not particularly limited, and may be changed according to the mechanical strength, surface property, thickness accuracy, and the like required for the stretched film to be produced.
- the temperature range is preferably (Tg ⁇ 30 ° C.) to (Tg + 30 ° C.), and (Tg ⁇ 20 ° C.) to (T Tg + 20 ° C. is more preferable, and a temperature range of (Tg) to (Tg + 20 ° C.) is more preferable.
- the stretching temperature is within the above temperature range, thickness unevenness of the obtained stretched film can be reduced, and further, mechanical properties such as elongation, tear propagation strength, and fatigue resistance can be improved. Moreover, generation
- the stretching temperature is higher than the above temperature range, the thickness unevenness of the stretched film obtained tends to be large, and the mechanical properties such as elongation, tear propagation strength, and fatigue resistance cannot be improved sufficiently. There is. Furthermore, there is a tendency that troubles such as the film sticking to the roll tend to occur.
- the stretching temperature is lower than the above temperature range, the resulting stretched film has a large haze, or in extreme cases, the process tends to cause problems such as tearing or cracking of the film. is there.
- the stretch ratio is not particularly limited, and may be determined according to the mechanical strength, surface property, thickness accuracy, and the like of the stretched film to be produced. Although it depends on the stretching temperature, the stretching ratio is generally preferably selected in the range of 1.1 to 3 times, more preferably in the range of 1.3 to 2.5 times. Preferably, it is more preferably selected in the range of 1.5 times to 2.3 times.
- the draw ratio is within the above range, the mechanical properties such as the elongation rate of the film, tear propagation strength, and fatigue resistance can be greatly improved. Therefore, it is possible to produce a stretched film having a thickness unevenness of 5 ⁇ m or less, a birefringence of substantially zero, and a haze of 2.0% or less.
- the film according to the present invention can be used by laminating another film with an adhesive or the like, or by forming a coating layer such as a hard coat layer on the surface, if necessary.
- the non-birefringent resin material of the present invention includes, if necessary, a polyglutarimide acrylic resin, a glutaric anhydride acrylic resin, a lactone cyclized acrylic resin, a methacrylic resin, a polyethylene terephthalate resin, and a polybutylene terephthalate resin. Etc. can also be blended.
- the blending method is not particularly limited, and a known method can be used.
- the non-birefringent resin material of the present invention has the meaning of adjusting orientation birefringence, and the inorganic fine particles having birefringence described in Patent Nos. 3648201 and 4336586, and the birefringence described in Patent No. 3696649
- a low molecular weight compound having a molecular weight of 5000 or less, preferably 1000 or less may be appropriately blended.
- the non-birefringent resin material of the present invention only needs to contain at least one kind each of the resin (A) and the polymer (B).
- Other resins can be added without particular limitation.
- the other resin include thermoplastic resins mentioned in the resin (A), multilayer structure polymers such as core-shell polymers and graft copolymers, and thermoplastic elastomers such as block polymers.
- the non-birefringent resin material of the present invention includes a light stabilizer, an ultraviolet absorber, a heat stabilizer, a matting agent, a light diffusing agent, a colorant, a dye, a pigment, an antistatic agent, and a heat ray reflective material as necessary. Further, known additives such as lubricants, plasticizers, ultraviolet absorbers, stabilizers, fillers, or other resins may be contained.
- the film of the present invention can reduce the gloss of the film surface by a known method, if necessary. For example, it can be carried out by a method of kneading an inorganic filler or crosslinkable polymer particles with a non-birefringent resin material. Further, the gloss of the film surface can be reduced by embossing the obtained film.
- the film of the present invention can be used by being laminated on metal, plastic, or the like.
- Film lamination methods include laminate molding, wet laminating after applying an adhesive to a metal plate such as a steel plate, and then drying and laminating the film on a metal plate, dry laminating, extrusion laminating, hot melt laminating, etc. Can be given.
- the film is placed in a mold and then placed in a mold after insert molding or laminate injection press molding in which resin is filled by injection molding, or after the film is preformed.
- In-mold molding in which resin is filled by injection molding can be used.
- the laminated product of the film of the present invention can be used as a substitute for painting such as automobile interior materials and automobile exterior materials, window frames, bathroom equipment, wallpaper, flooring materials and other building materials, household goods, furniture and electrical equipment housings, It can be used for housings of office automation equipment such as facsimiles, notebook computers, copiers, etc., front plates of liquid crystal screens of terminals such as mobile phones, smartphones and tablets, and parts of electrical or electronic devices.
- office automation equipment such as facsimiles, notebook computers, copiers, etc.
- front plates of liquid crystal screens of terminals such as mobile phones, smartphones and tablets, and parts of electrical or electronic devices.
- the film of the present invention can be used for the following various applications by utilizing properties such as heat resistance, transparency and flexibility.
- Examples of uses of molded articles other than non-birefringent resin material films in the present invention include, for example, general camera lenses, video camera lenses, laser pickup objective lenses, diffraction gratings, holograms, collimator lenses, and lasers.
- the film according to the present invention has an orientation birefringence of ⁇ 1.7 ⁇ 10 ⁇ 4 to 1.7 ⁇ 10 ⁇ 4 , a photoelastic constant of ⁇ 4 ⁇ 10 ⁇ 12 to 4 ⁇ 10 ⁇ 12 , and a tensile elongation at break.
- a thickness of 10 ⁇ m or more and 500 ⁇ m or less can be provided while the degree satisfies 10% or more.
- optical properties such as optical homogeneity and transparency are excellent. Therefore, it can use especially suitably for well-known optical uses, such as a liquid crystal display periphery, such as an optically isotropic film, a polarizer protective film, and a transparent conductive film, using these optical characteristics.
- the film of the present invention can be attached to a polarizer and used as a polarizing plate. That is, the film according to the present invention can be used as a polarizer protective film for a polarizing plate.
- the polarizer is not particularly limited, and any conventionally known polarizer can be used. Specific examples include a polarizer obtained by containing iodine in stretched polyvinyl alcohol.
- the film of the present invention may be subjected to surface treatment as necessary.
- a surface treatment such as a coating process or another film is laminated on the surface of the film of the present invention
- the film of the present invention is preferably subjected to a surface treatment. .
- adhesion between the film of the present invention and the coating material or another film to be laminated can be improved.
- the purpose of the surface treatment for the film of the present invention is not limited to the above.
- the film of the present invention may be subjected to surface treatment regardless of its use.
- Such surface treatment is not particularly limited, and examples thereof include corona treatment, plasma treatment, ultraviolet irradiation, and alkali treatment. Of these, corona treatment is preferred.
- the thickness of the film of the present invention is not particularly limited, but is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, and particularly preferably 200 ⁇ m or less. Further, it is preferably 10 ⁇ m or more, more preferably 30 ⁇ m or more, further preferably 50 ⁇ m or more, and particularly preferably 100 ⁇ m or more. If the thickness of the film is within the above range, there is an advantage that it is difficult to be deformed when vacuum forming is performed using the film, and it is difficult to cause breakage at the deep drawing portion, and the optical characteristics are uniform, A film with good transparency can be produced.
- the film of the present invention preferably has a haze value of 2.0% or less, more preferably 1.0% or less, further preferably 0.8% or less, and 0.5% or less. It is particularly preferred. If the haze value of the film of the present invention is within the above range, the transparency of the film is sufficiently high, and it is suitable for optical use, decoration use, interior use, or vacuum forming use that requires transparency. .
- the film of the present invention preferably has a total light transmittance of 85% or more, more preferably 88% or more. If the total light transmittance is within the above range, the transparency of the film is sufficiently high, and it can be suitably used in optical applications, decoration applications, interior applications, or vacuum forming applications that require transparency. .
- the film of the present invention preferably has a glass transition temperature of 100 ° C. or higher, more preferably 115 ° C. or higher, still more preferably 120 ° C. or higher, and still more preferably 124 ° C. or higher.
- a glass transition temperature is within the above range, a film having sufficiently excellent heat resistance can be obtained.
- the film of the present invention preferably has a tensile elongation at break of 10% or more, more preferably 20% or more, further preferably 30% or more, and still more preferably 40% or more. 50% or more is particularly preferable, 60% or more is particularly preferable, and 90% or more is most preferable.
- the film of the present invention showing the tensile elongation at break within the above range is less likely to crack when trimming the film with a Thomson blade or a cutter blade (trimming property), and when the film is wound on a roll, Or it is hard to fracture
- the crack resistance when the film is bent is high, and troubles such as cracking do not occur not only in the post-processing process but also in actual use as a product.
- the tensile strength at break at break is correlated with the crackability, and the higher the tensile elongation at break, the better the crack resistance.
- the film of the present invention can be used as an optical film as described above.
- the optical anisotropy is small.
- both the in-plane retardation and the absolute value of the thickness direction retardation are small.
- the in-plane retardation is preferably 10 nm or less, more preferably 6 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less.
- the absolute value of the thickness direction retardation is preferably 50 nm or less, more preferably 20 nm or less, further preferably 10 nm or less, and most preferably 5 nm or less.
- a film having such a retardation can be suitably used as a polarizer protective film provided in a polarizing plate of a liquid crystal display device.
- the in-plane retardation of the film exceeds 10 nm or the absolute value of the thickness direction retardation exceeds 50 nm
- the contrast is increased in the liquid crystal display device. Problems such as degradation may occur.
- the retardation is an index value calculated based on birefringence, and the in-plane retardation (Re) and the thickness direction retardation (Rth) can be calculated by the following equations, respectively.
- both the in-plane retardation Re and the thickness direction retardation Rth are zero.
- nx, ny, and nz are respectively the in-plane stretching direction (polymer chain orientation direction) as the X axis, the direction perpendicular to the X axis as the Y axis, and the thickness direction of the film as the Z axis.
- And represents the refractive index in the respective axial directions.
- D represents the thickness of the film
- nx-ny represents orientation birefringence.
- the MD direction is the X axis
- stretch direction is the X axis.
- the molded body made of the non-birefringent resin material of the present invention preferably has an orientation birefringence value of ⁇ 15 ⁇ 10 ⁇ 4 to 15 ⁇ 10 ⁇ 4 , and ⁇ 10 ⁇ 10 ⁇ 4 to 10 ⁇ 10.
- ⁇ 4 is more preferable, ⁇ 5 ⁇ 10 ⁇ 4 to 5 ⁇ 10 ⁇ 4 is further preferable, ⁇ 1.6 ⁇ 10 ⁇ 4 to 1. 6 ⁇ 10 ⁇ 4 is still more preferable.
- the orientation birefringence is within the above range, a birefringence at the time of molding processing does not occur, and a molded product having no practical problem can be obtained.
- the film made of the non-birefringent resin material of the present invention preferably has an orientation birefringence value of ⁇ 1.7 ⁇ 10 ⁇ 4 to 1.7 ⁇ 10 ⁇ 4 , and ⁇ 1.6 ⁇ 10 ⁇ 4 to 1.6 ⁇ 10 ⁇ 4 is more preferable, ⁇ 1.5 ⁇ 10 ⁇ 4 to 1.5 ⁇ 10 ⁇ 4 is further preferable, and ⁇ 1.0 ⁇ 10 ⁇ 4 to More preferably, it is 1.0 ⁇ 10 ⁇ 4 , particularly preferably ⁇ 0.5 ⁇ 10 ⁇ 4 to 0.5 ⁇ 10 ⁇ 4 , and ⁇ 0.2 ⁇ 10 ⁇ 4 to 0.2 ⁇ . Most preferably, it is 10 ⁇ 4 .
- the orientation birefringence is within the above range, stable optical characteristics can be obtained without causing birefringence during molding. It is also very suitable as an optical film used for liquid crystal displays and the like.
- the molded body made of the non-birefringent resin material of the present invention preferably has a photoelastic constant of ⁇ 10 ⁇ 10 ⁇ 12 to 10 ⁇ 10 ⁇ 12 , and ⁇ 4 ⁇ 10 ⁇ 12 to 4 ⁇ 10 ⁇ 12. More preferably, it is ⁇ 2 ⁇ 10 ⁇ 12 to 2 ⁇ 10 ⁇ 12 , further preferably ⁇ 1 ⁇ 10 ⁇ 12 to 1 ⁇ 10 ⁇ 12 , and ⁇ 0.5 It is more preferably from ⁇ 10 ⁇ 12 to 0.5 ⁇ 10 ⁇ 12 , and most preferably from ⁇ 0.3 ⁇ 10 ⁇ 12 to 0.3 ⁇ 10 ⁇ 12 .
- the photoelastic constant is in the above range, a birefringence generated even when stress is applied to the molded body in an environment such as high temperature and high humidity, and a molded body having no practical problem can be obtained.
- the film made of the non-birefringent resin material of the present invention preferably has a photoelastic constant of ⁇ 4 ⁇ 10 ⁇ 12 Pa ⁇ 1 to 4 ⁇ 10 ⁇ 12 Pa ⁇ 1 , and ⁇ 1.5 ⁇ 10 ⁇ 12. Pa ⁇ 1 to 1.5 ⁇ 10 ⁇ 12 Pa ⁇ 1 is more preferable, ⁇ 1.0 ⁇ 10 ⁇ 12 Pa ⁇ 1 to 1.0 ⁇ 10 ⁇ 12 Pa ⁇ 1 is further preferable, More preferably, it is ⁇ 0.5 ⁇ 10 ⁇ 12 Pa ⁇ 1 to 0.5 ⁇ 10 ⁇ 12 Pa ⁇ 1 , and ⁇ 0.3 ⁇ 10 ⁇ 12 Pa ⁇ 1 to 0.3 ⁇ 10 ⁇ 12 Pa ⁇ Most preferably, it is 1 or less.
- the photoelastic constant is within the above range, even if the film according to the present invention is used in a liquid crystal display device, the birefringence generated even when stress is applied to the molded body in an environment such as high temperature and high humidity is small. There is no occurrence of phase difference unevenness, lowering of the contrast around the display screen, or light leakage.
- volume average particle diameter to (meth) acrylic crosslinked polymer layer of graft copolymer The volume average particle diameter (volume average particle diameter of acrylic rubber particles) up to the (meth) acrylic crosslinked polymer layer of the graft copolymer was measured in the state of acrylic rubber particle latex. The volume average particle diameter ( ⁇ m) was measured using MICROTRAC UPA150 manufactured by Nikkiso Co., Ltd. as a measuring device.
- Polymerization conversion rate (%) [(Total weight of charged raw material x solid component ratio-total weight of raw materials other than water and monomer) / weight of charged monomer] x 100 (Graft rate) 2 g of the obtained polymer (B) was dissolved in 50 ml of methyl ethyl ketone, and centrifuged for 1 hour at 30000 rpm using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E). Minutes were separated (total of 3 sets of centrifugation work). The graft ratio was calculated by the following formula using the obtained insoluble matter.
- Graft rate (%) ⁇ (weight of methyl ethyl ketone insoluble matter ⁇ weight of crosslinked polymer layer) / weight of crosslinked polymer layer ⁇ ⁇ 100
- the weight of the crosslinked polymer layer is the charged weight of the monofunctional monomer constituting the crosslinked polymer layer.
- the imidation ratio was calculated as follows using IR.
- the product pellets were dissolved in methylene chloride, and the IR spectrum of the solution was measured at room temperature using a TravelIR manufactured by SensIR Technologies. From the obtained IR spectrum, and the absorption intensity attributable to the ester carbonyl group of 1720cm -1 (Absester), the imidization ratio from the ratio of the absorption intensity attributable to the imide carbonyl group of 1660cm -1 (Absimide) (Im% ( IR)).
- the “imidation rate” refers to the ratio of the imide carbonyl group in the total carbonyl group.
- each composition was processed into a sheet shape, and the refractive index (nD) at the sodium D-line wavelength was measured using an Abbe refractometer 2T manufactured by Atago Co., Ltd. according to JIS K7142.
- Glass-transition temperature Using a differential scanning calorimeter (DSC) SSC-5200 manufactured by Seiko Instruments Inc., the sample was once heated to 200 ° C. at a rate of 25 ° C./minute, held for 10 minutes, and then at a rate of 25 ° C./minute to 50 ° C. Measurement is performed while the temperature is raised to 200 ° C. at a rate of temperature increase of 10 ° C./min through preliminary adjustment to lower the temperature, and an integral value is obtained from the obtained DSC curve (DDSC), and the glass transition temperature is determined from the maximum point. Asked.
- DSC differential scanning calorimeter
- Total light transmittance / haze value The total light transmittance and haze value of the film were measured by the method described in JIS K7105 using Nippon Denshoku Industries NDH-300A.
- the film thickness was measured using a Digimatic Indicator (manufactured by Mitutoyo Corporation).
- the obtained film was cooled to 23 ° C., the center portion of the sample was sampled, and an automatic birefringence meter (KOBRA-WR manufactured by Oji Scientific Co., Ltd.) was used at a temperature of 23 ⁇ 2 ° C. and a humidity of 50 ⁇ 5%.
- the birefringence (orientation birefringence) was measured at a wavelength of 590 nm and an incident angle of 0 °.
- the in-plane retardation Re and the thickness direction retardation Rth (incident angle 40 °) were also measured. (Details of the in-plane retardation Re and the thickness direction retardation Rth will be described later).
- the polymer (B) alone was pressed at 190 ° C. to prepare a pressed plate having a thickness of 500 ⁇ m.
- a test piece of 25 mm ⁇ 90 mm was cut out from the center of the obtained press plate and measured in the same manner as described above.
- Resin (A) was prepared in the same manner as in Example 1, and an unstretched film having a thickness of 125 ⁇ m was produced and measured in the same manner as described above.
- In-plane retardation Re and thickness direction retardation Rth A test piece of 40 mm ⁇ 40 mm was cut out from a film having a thickness of 125 ⁇ m.
- the in-plane retardation Re of this test piece was measured using an automatic birefringence meter (KOBRA-WR manufactured by Oji Scientific Co., Ltd.) at a temperature of 23 ⁇ 2 ° C. and a humidity of 50 ⁇ 5% at a wavelength of 590 nm and an incident angle of 0 °. It was measured.
- KOBRA-WR automatic birefringence meter
- the measured value was multiplied by 100 ( ⁇ m) / film thickness ( ⁇ m) to obtain a converted value of 100 ⁇ m, and is shown in Table 3.
- a test piece was cut into a strip of 15 mm ⁇ 90 mm in the TD direction from a film having a thickness of 125 ⁇ m (cut out so that the long side comes in the TD direction).
- the measurement was performed by measuring the birefringence with one of the long sides of the film fixed and the other with a load of 0.5 kgf from no load to 4 kgf. From the obtained results, the amount of change in birefringence due to unit stress was measured. Was calculated.
- the polymer (B) alone is pressed at 190 ° C. to prepare a press plate having a film thickness of 500 ⁇ m.
- a test piece of 15 mm ⁇ 90 mm was cut out from the center of the obtained press plate and measured in the same manner as described above.
- Resin (A) was prepared in the same manner as in Example 1, and an unstretched film having a thickness of 125 ⁇ m was produced and measured in the same manner as described above.
- Trimming property evaluation A film having a film thickness of 125 ⁇ m was cut with a cutter knife and evaluated as follows. ⁇ : No cracks are observed on the cut surface. ⁇ : Cracks are observed on the cut surface. X: Cracks are remarkably generated on the cut surface.
- Tensile elongation at break A film having a thickness of 125 ⁇ m was used.
- the tensile test was based on ISO527-3 (JIS K 7127), the test piece was measured at test piece type 5, the test speed was 200 mm / min in the MD direction, the temperature was 23 ⁇ 2 ° C., and the humidity was 50 ⁇ 5%.
- the obtained resin composition was measured for melt viscosity under conditions according to JIS K7199 (die temperature 260 ° C., shear rate 24 sec ⁇ 1 , capillary die diameter 1 mm, residence time 1 hour), and residence time 10 minutes.
- the melt viscosity reduction rate represented by the following formula for the melt viscosity at a residence time of 1 hour with respect to the melt viscosity was calculated as a thermal stability index.
- the presence or absence of foaming derived from the thermal decomposition of the resin was also observed in the strand after the test.
- Melt viscosity reduction rate (Melt viscosity at a residence time of 10 minutes ⁇ melt viscosity at a residence time of 1 hour) / (melt viscosity at a residence time of 10 minutes) ⁇ 100 (%) Thermal stability and melt viscosity were evaluated according to the following criteria.
- ⁇ The melt viscosity is low and extrusion is possible without problems.
- X The melt viscosity is high, the filter is broken, and the filtration accuracy is not good.
- the meshing type co-directional twin-screw extruder having a diameter of 75 mm for both the first and second extruders and L / D (ratio of the length L to the diameter D of the extruder) of 74.
- the raw material resin was supplied to the raw material supply port of the first extruder using a constant weight feeder (manufactured by Kubota Corporation).
- the decompression degree of each vent in the first extruder and the second extruder was ⁇ 0.095 MPa. Furthermore, the pressure control mechanism in the part connects the first extruder and the second extruder with a pipe having a diameter of 38 mm and a length of 2 m, and connects the resin discharge port of the first extruder and the raw material supply port of the second extruder. Used a constant flow pressure valve.
- the resin (strand) discharged from the second extruder was cooled with a cooling conveyor and then cut with a pelletizer to form pellets.
- the discharge port of the first extruder, the first extruder and the first extruder Resin pressure gauges were provided at the center of the connecting parts between the two extruders and at the discharge port of the second extruder.
- a polymethyl methacrylate resin (Mw: 105,000) was used as a raw material resin, and monomethylamine was used as an imidizing agent to produce an imide resin intermediate 1.
- the temperature of the highest temperature part of the extruder was 280 ° C.
- the screw rotation speed was 55 rpm
- the raw material resin supply amount was 150 kg / hour
- the addition amount of monomethylamine was 2.0 parts with respect to 100 parts of the raw material resin.
- the constant flow pressure valve was installed immediately before the raw material supply port of the second extruder, and the monomethylamine press-fitting portion pressure of the first extruder was adjusted to 8 MPa.
- the imidizing agent and by-products remaining in the rear vent and vacuum vent were devolatilized, and then dimethyl carbonate was added as an esterifying agent to produce an imide resin intermediate 2.
- each barrel temperature of the extruder was 260 ° C.
- the screw rotation speed was 55 rpm
- the addition amount of dimethyl carbonate was 3.2 parts with respect to 100 parts of the raw resin.
- it was extruded from a strand die, cooled in a water tank, and then pelletized with a pelletizer to obtain a glutarimide acrylic resin (A1).
- the obtained glutarimide acrylic resin (A1) is an acrylic resin obtained by copolymerizing a glutamylimide unit represented by the general formula (1) and a (meth) acrylic acid ester unit represented by the general formula (2). (A).
- the imidization rate, the content of glutarimide units, the acid value, the glass transition temperature, and the refractive index were measured according to the above-described methods.
- the imidation ratio was 13%
- the content of glutarimide units was 7% by weight
- the acid value was 0.4 mmol / g
- the glass transition temperature was 130 ° C.
- the refractive index was 1.50.
- the sign of the photoelastic constant of the glutarimide acrylic resin (A1) was ⁇ (minus).
- the internal temperature was set to 60 ° C., and 0.2 part of sodium formaldehyde sulfoxide was charged. Then, 55.554 parts of the raw polymer mixture (B-2) shown in Table 2 was added for 210 minutes. Then, the polymerization was continued for 1 hour to obtain a graft copolymer latex. The polymerization conversion rate was 100.0%. The obtained latex was salted out and coagulated with magnesium sulfate, washed with water and dried to obtain a white powdery graft copolymer (B1).
- the average particle diameter of the rubber particles (polymer of B-1) of the graft copolymer (B1) was 73 nm.
- the graft ratio of the graft copolymer (B1) was 85%.
- the internal temperature was set to 60 ° C., and 0.2 part of sodium formaldehyde sulfoxide was charged. Then, 55.554 parts of the raw polymer mixture (B-2) shown in Table 2 was added for 210 minutes. Then, the polymerization was continued for 1 hour to obtain a graft copolymer latex. The polymerization conversion rate was 100.0%. The obtained latex was salted out and coagulated with magnesium sulfate, washed with water and dried to obtain a white powdered graft copolymer (B2).
- the average particle diameter of the rubber particles (polymer of B-1) of the graft copolymer (B2) was 121 nm.
- the graft ratio of the graft copolymer (B2) was 56%.
- the average particle diameter of the rubber particles (polymer of B-1) of the graft copolymer (B3) was 72 nm.
- the graft ratio of the graft copolymer (B3) was 87%.
- the internal temperature was adjusted to 60 ° C., 0.2 part of sodium formaldehyde sulfoxylate and 0.2 part of sodium dioctylsulfosuccinate were charged, and then the hard polymer layer (B-2 shown in Table 2) was prepared. ) was continuously added over 210 minutes, and the polymerization was further continued for 1 hour to obtain a graft copolymer latex.
- the polymerization conversion rate was 100.0%.
- the obtained latex was salted out and coagulated with calcium chloride, washed with water and dried to obtain a white powdered graft copolymer (B4).
- the average particle diameter of the rubber particles (polymer of B-1) of the graft copolymer (B4) was 72 nm.
- the graft ratio of the graft copolymer (B4) was 87%.
- the internal temperature was set to 60 ° C., and 0.2 part of sodium formaldehyde sulfoxide was charged. Then, 55.254 parts of the raw material mixture of the hard polymer layer (B-2) shown in Table 2 was added for 165 minutes. Then, the polymerization was continued for 1 hour to obtain a graft copolymer latex. The polymerization conversion rate was 100.0%. The obtained latex was salted out and coagulated with magnesium sulfate, washed with water and dried to obtain a white powdered graft copolymer (B5).
- the average particle diameter of the rubber particles (polymer of B-1) of the graft copolymer (B5) was 133 nm.
- the graft ratio of the graft copolymer (B5) was 77%.
- the internal temperature was adjusted to 60 ° C., 0.11 part of sodium polyoxyethylene lauryl ether phosphate and 0.2 part of sodium formaldehyde sulfoxylate were charged, and then the hard polymer layer (B -2) 55.254 parts of the raw material mixture was continuously added over 165 minutes, and the polymerization was further continued for 1 hour to obtain a graft copolymer latex.
- the polymerization conversion rate was 97.2%.
- the obtained latex was salted out and coagulated with magnesium sulfate, washed with water and dried to obtain a white powdered graft copolymer (B6).
- the average particle diameter of the rubber particles (polymer of B-1) of the graft copolymer (B6) was 117 nm.
- the graft ratio of the graft copolymer (B6) was 69%.
- the internal temperature was adjusted to 60 ° C., 0.11 part of sodium polyoxyethylene lauryl ether phosphate and 0.2 part of sodium formaldehyde sulfoxylate were charged, and then the hard polymer layer (B -2) 55.254 parts of the raw material mixture was continuously added over 165 minutes, and the polymerization was further continued for 1 hour to obtain a graft copolymer latex.
- the polymerization conversion rate was 99.4%.
- the obtained latex was salted out and coagulated with magnesium sulfate, washed with water and dried to obtain a white powdered graft copolymer (B7).
- the average particle diameter of the rubber particles (polymer of B-1) of the graft copolymer (B7) was 118 nm.
- the graft ratio of the graft copolymer (B7) was 85%.
- the obtained pellet was used with a single-screw extruder equipped with a leaf disk filter with an opening of 5 ⁇ m and a T-die connected to the outlet, the set temperature of the temperature adjustment zone of the extruder was 260 ° C., and the screw rotation speed was 20 rpm.
- the pellets were supplied at a rate of 10 kg / hr and melt extruded to obtain films having the film thicknesses shown in Table 3. Various physical properties of these films were evaluated.
- Examples 1 and 7 have high heat resistance, high transparency, and excellent mechanical strength such as trimming properties. Further, the orientation birefringence of the film is low, and even when stretched, the orientation birefringence hardly occurs.
- the photoelastic constant is also a very small value, and it can be seen that the optical anisotropy is extremely small, such that almost no birefringence occurs even when stress is applied to the film.
- it since it has high thermal stability and low melt viscosity, it can be filtered with a filter having a small opening such as 5 ⁇ m at the time of molding, and a film free from foreign matters such as fish eyes can be obtained. It can be seen that Examples 2 to 6 and 8 have excellent mechanical strength in addition to the excellent effects obtained in Examples 1 and 7.
- Comparative Example 4 (Preparation of molded body and evaluation of physical properties) In Comparative Example 4, 100 parts by weight of A7 was used. A7: PMMA resin Sumipex EX (Sumitomo Chemical Co., Ltd.) In Comparative Example 5, as in Comparative Example 3, 100 parts by weight of A1 was used.
- C1 to C3 200 ° C.
- C4 210 ° C.
- C5 220 ° C.
- D 230 ° C.
- the total light transmittance and haze were measured as a transparency parameter
- Example 3 has a small photoelastic constant and excellent impact resistance.
- the flat plate sample is placed between two orthogonal polarizing plates, and it is confirmed whether transmitted light (light leakage) is observed. A crossed Nicol test was performed.
- Example 3 has a considerably smaller photoelastic birefringence (constant) than Comparative Example 5, and further has a resistance to resistance. It can be seen that the impact properties are significantly superior. That is, the acrylic resin composition according to the present invention is a material suitable for injection molded articles such as lenses, pickup lenses, and lens arrays that require extremely high optical isotropy.
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Abstract
Description
ここで、引張応力がかかっている方向(ポリマー鎖の配向方向)に対して、平行方向に屈折率が大きくなる場合は「光弾性複屈折は正」、直行する方向に屈折率が大きくなる場合は「光弾性複屈折は負」と表現する。
[1] 樹脂(A)および重合体(B)を含有し、配向複屈折が-1.7×10-4から1.7×10-4、光弾性定数が-4×10-12から4×10-12Pa-1、である、非複屈折性樹脂材料。
[2] 樹脂(A)および重合体(B)を含有し、前記樹脂(A)の光弾性定数と前記重合体(B)の光弾性定数が異符号であり、前記樹脂(A)の光弾性定数が前記重合体(B)の光弾性定数により相殺されている、非複屈折性樹脂材料。
[3] 引張破断点伸度が10%以上であることを特徴とする、[1]又は[2]に記載の非複屈折性樹脂材料。
[4] 前記樹脂(A)がアクリル系樹脂であることを特徴とする、[1]~[3]のいずれか1項に記載の非複屈折性樹脂材料。
[5] 前記樹脂(A)の光弾性定数と前記重合体(B)の光弾性定数が異符号であることを特徴とする、[1]、[3]および[4]のいずれか1項に記載の非複屈折性樹脂材料。
[6] 前記重合体(B)が、架橋構造を有することを特徴とする、[1]~[5]のいずれか1項に記載の非複屈折性樹脂材料。
[7] 前記重合体(B)が、硬質重合体部を有することを特徴とする、[1]~[6]のいずれか1項に記載の非複屈折性樹脂材料。
[8] 前記重合体(B)が、非架橋構造を有することを特徴とする、[1]~[7]のいずれか1項に記載の非複屈折性樹脂材料。
[9] 前記重合体(B)が、多層構造重合体であることを特徴とする、[1]~[8]のいずれか1項に記載の非複屈折性樹脂材料。
[10] 前記重合体(B)が、架橋重合体層および硬質重合体層を含む多層構造重合体であることを特徴とする、[9]に記載の非複屈折性樹脂材料。
[11] 前記重合体(B)が、(メタ)アクリル系架橋重合体層、および硬質重合体層を有する多層構造重合体であることを特徴とする、[10]に記載の非複屈折性樹脂材料。
[12] 前記硬質重合体層が、非架橋の硬質重合体層を含む、[10]~[11]のいずれか一項に記載の非複屈折性樹脂材料。
[13] 前記重合体(B)が、(メタ)アクリル系架橋重合体層、および、脂環式構造、複素環式構造または芳香族基を有するビニル系単量体を構造単位に含む硬質重合体層を有することを特徴とする、[10]~[12]のいずれか一項に記載の非複屈折性樹脂材料。
[14] 前記脂環式構造、複素環式構造または芳香族基を有するビニル系単量体が、下記式(4)で表される単量体である、[13]に記載の非複屈折性樹脂材料。
[15] 前記式(4)で表される単量体を構成単位に有する硬質重合体層は、前記式(4)で表される単量体1~100重量%、これと共重合可能な他の単量体99~0重量%、および多官能性単量体0~2.0重量部(前記式(4)で表される単量体および前記これと共重合可能な他の単量体の総量100重量部に対して)を重合してなる、[14]に記載の非複屈折性樹脂材料。
[16] 前記(メタ)アクリル系架橋重合体層は、アクリル酸アルキルエステル50~100重量%、これと共重合可能な他の単量体50~0重量%、および多官能性単量体0.05~10重量部(前記アクリル酸アルキルエステルおよび前記これと共重合可能な他の単量体の総量100重量部に対して)を重合してなる、[11]~[15]のいずれか1項に記載の非複屈折性樹脂材料。
[17] 前記重合体(B)において、前記硬質重合体層が最外層を構成し、前記最外層が前記式(4)で表される単量体を構成単位に有する硬質重合体層である、[14]~[16]のいずれか一項に記載の非複屈折性樹脂材料。
[18] 前記重合体(B)において、前記最外層の内側に、前記(メタ)アクリル系架橋重合体層を有する軟質層が隣接している、[17]に記載の非複屈折性樹脂材料。
[19] 前記重合体(B)は、軟質の内層および硬質の外層を有し、前記内層が前記(メタ)アクリル系架橋重合体層を有し、前記外層が前記式(4)で表される単量体を構成単位に有する硬質重合体層を有する、[14]~[16]のいずれか一項に記載の非複屈折性樹脂材料。
[20] 前記重合体(B)は、硬質の内層、軟質の中間層および硬質の外層を有し、前記内層が少なくとも一種の硬質重合体層からなり、前記中間層が前記(メタ)アクリル系架橋重合体層からなる軟質重合体層を有し、前記外層が前記式(4)で表される単量体を構成単位に有する硬質重合体層を有する、[14]~[16]のいずれか一項に記載の非複屈折性樹脂材料。
[21] 前記重合体(B)が、軟質の最内層をさらに有する、[20]に記載の非複屈折性樹脂材料。
[22] 前記式(4)で表される単量体が、(メタ)アクリル酸ベンジル、(メタ)アクリル酸ジシクロペンタニル、及び(メタ)アクリル酸フェノキシエチルからなる群より選択される少なくとも1種であることを特徴とする、[14]~[21]のいずれか一項に記載の非複屈折性樹脂材料。
[23] 前記重合体(B)の前記(メタ)アクリル系架橋重合体層までの体積平均粒子径が20~450nmである、[11]~[22]のいずれか一項に記載の非複屈折性樹脂材料。
[24] 前記重合体(B)が含有する前記(メタ)アクリル系架橋重合体層の含有量が、非複屈折性樹脂材料100重量部において1~60重量部である、[11]~[23]のいずれか一項に記載の非複屈折性樹脂材料。
[25] 複屈折性を有する無機微粒子をさらに含有することを特徴とする、[1]~[24]のいずれか1項に記載の非複屈折性樹脂材料。
[26] 複屈折性を有する低分子化合物をさらに含有することを特徴とする、[1]~[25]のいずれか1項に記載の非複屈折性樹脂材料。
[27] 前記樹脂(A)が、下記一般式(1)で表される単位と、下記一般式(2)で表される単位とを有するグルタルイミドアクリル系樹脂(D)、ラクトン環含有アクリル系重合体、スチレン単量体およびそれと共重合可能な他の単量体を重合して得られるスチレン系重合体の芳香族環を部分水素添加して得られる部分水添スチレン系重合体、環状酸無水物繰り返し単位を含有するアクリル系重合体、並びに、水酸基および/またはカルボキシル基を含有するアクリル系重合体、からなる群より選択される少なくとも1種である、[1]~[26]のいずれか一項に記載の非複屈折性樹脂材料。
[28] 前記グルタルイミドアクリル系樹脂(D)が下記一般式(3)で表される単位を含まない、[27]に記載の非複屈折性樹脂材料。
[29] 光弾性定数が-4×10-12から4×10-12Pa-1である、[2]~[28]のいずれか1項に記載の非複屈折性樹脂材料。
[30] 配向複屈折が-1.7×10-4から1.7×10-4である、[2]~[29]のいずれか1項に記載の非複屈折性樹脂材料。
[31] [1]~[30]のいずれか一項に記載の非複屈折性樹脂材料からなるフィルム。
[32] 溶融押出法により得られることを特徴とする、[31]に記載のフィルム。
[33] 配向複屈折が-1.7×10-4から1.7×10-4、光弾性定数が-4×10-12から4×10-12Pa-1であることを特徴とする、[31]又は[32]に記載のフィルム。
[34] 引張破断点伸度が10%以上である、[31]~[33]のいずれか一項に記載のフィルム。
[35] フィルムの厚みが10~500μmである、[31]~[34]のいずれか一項に記載のフィルム。
[36] 次の樹脂(A)および重合体(B)を含有するアクリル系樹脂組成物。
(A)アクリル系樹脂。
(B)(メタ)アクリル系架橋重合体層、および、下記式(4)で表される単量体を構成単位に有する硬質重合体層を有する、重合体。
[37] 前記式(4)で表される単量体を構成単位に有する硬質重合体層が、前記式(4)で表される単量体1~100重量%、これと共重合可能な他の単量体99~0重量%、および多官能性単量体0~2.0重量部(前記式(4)で表される単量体および前記これと共重合可能な他の単量体の総量100重量部に対して)からなる単量体混合物を重合して得られる、[36]に記載のアクリル系樹脂組成物。
[38] 前記(メタ)アクリル系架橋重合体層は、アクリル酸アルキルエステル50~100重量%、これと共重合可能な他の単量体50~0重量%、および多官能性単量体0.05~10重量部(前記アクリル酸アルキルエステルおよび前記これと共重合可能な他の単量体の総量100重量部に対して)からなる単量体混合物を重合して得られる、[36]又は[37]に記載のアクリル系樹脂組成物。
[39] 前記重合体(B)が、
(B-1)アクリル酸アルキルエステル50~100重量%、これと共重合可能な他の単量体50~0重量%、および多官能性単量体0.05~10重量部(前記アクリル酸アルキルエステルおよび前記これと共重合可能な他の単量体の総量100重量部に対して)からなる単量体混合物を重合して(メタ)アクリル系架橋重合体層を得、
(B-2)前記(メタ)アクリル系架橋重合体層の存在下に、前記式(4)で表される単量体1~100重量%、これと共重合可能な他の単量体99~0重量%、および多官能性単量体0~2.0重量部(前記式(4)で表される単量体および前記これと共重合可能な他の単量体の総量100重量部に対して)からなる単量体混合物を重合して前記式(4)で表される単量体を構成単位に有する硬質重合体層を形成し、得られる、
[36]に記載のアクリル系樹脂組成物。
[40] 前記重合体(B)の前記(メタ)アクリル系架橋重合体層までの体積平均粒子径が20~450nmである、[36]~[39]のいずれか一項に記載のアクリル系樹脂組成物。
[41] 前記重合体(B)が含有する前記(メタ)アクリル系架橋重合体層の含有量が、アクリル系樹脂組成物100重量部において1~60重量部である、[36]~[40]のいずれか一項に記載のアクリル系樹脂組成物。
[42] 次の樹脂(A)および重合体(B)を含有するアクリル系樹脂組成物。
(A)アクリル系樹脂。
(B)多段重合で得られる(メタ)アクリル系ゴム含有グラフト共重合体であって、前記多段重合の少なくとも1段において、(メタ)アクリル系ゴム含有重合体粒子の存在下に、式(4)で表される単量体およびこれと共重合可能な他の単量体を含有する混合物を重合することで形成される、重合体。
[43] 前記式(4)で表される単量体およびこれと共重合可能な他の単量体の混合物が、前記式(4)で表される単量体1~100重量%、これと共重合可能な他の単量体99~0重量%、および多官能性単量体0~2.0重量部(前記式(4)で表される単量体および前記これと共重合可能な他の単量体の総量100重量部に対して)から構成される、[42]に記載のアクリル系樹脂組成物。
[44] 前記(メタ)アクリル系ゴム含有重合体粒子は、
アクリル酸アルキルエステル50~100重量%、これと共重合可能な他の単量体50~0重量%、および多官能性単量体0.05~10重量部(前記アクリル酸アルキルエステルおよび前記これと共重合可能な他の単量体の総量100重量部に対して)を重合してなるゴム部を有する、[42]又は[43]に記載のアクリル系樹脂組成物。
[45] 前記重合体(B)が、
(B-1)アクリル酸アルキルエステル50~100重量%、これと共重合可能な他の単量体50~0重量%、および多官能性単量体0.05~10重量部(前記アクリル酸アルキルエステルおよび前記これと共重合可能な他の単量体の総量100重量部に対して)からなる単量体混合物を重合して(メタ)アクリル系ゴム含有重合体粒子を得、
(B-2)前記(メタ)アクリル系ゴム含有重合体粒子の存在下に、
前記式(4)で表される単量体1~100重量%、これと共重合可能な他の単量体99~0重量%、および多官能性単量体0~2.0重量部(前記式(4)で表される単量体および前記これと共重合可能な他の単量体の総量100重量部に対して)からなる単量体混合物を重合して得られる、
[42]に記載のアクリル系樹脂組成物。
[46] 前記重合体(B)の前記(メタ)アクリル系ゴム含有重合体粒子までの体積平均粒子径が20~450nmである、[42]~[45]のいずれか一項に記載のアクリル系樹脂組成物。
[47] 前記重合体(B)が含有する前記(メタ)アクリル系ゴム含有重合体粒子の含有量が、アクリル系樹脂組成物100重量部において1~60重量部である、[42]~[46]のいずれか一項に記載のアクリル系樹脂組成物。
[48] 前記式(4)で表される単量体が、(メタ)アクリル酸ベンジル、(メタ)アクリル酸ジシクロペンタニル、及び(メタ)アクリル酸フェノキシエチルからなる群より選択される少なくとも1種であることを特徴とする、[36]~[47]のいずれか1項に記載のアクリル系樹脂組成物。
[49] 前記アクリル系樹脂(A)のガラス転移温度が100℃以上であることを特徴とする、[36]~[48]のいずれか1項に記載のアクリル系樹脂組成物。
[50] 前記アクリル系樹脂(A)が、下記一般式(1)で表される単位と、下記一般式(2)で表される単位とを有するグルタルイミドアクリル系樹脂(D)、ラクトン環含有アクリル系重合体、スチレン単量体およびそれと共重合可能な他の単量体を重合して得られるスチレン系重合体の芳香族環を部分水素添加して得られる部分水添スチレン系重合体、環状酸無水物繰り返し単位を含有するアクリル系重合体、並びに、水酸基および/またはカルボキシル基を含有するアクリル系重合体、からなる群より選択される少なくとも1種である、[36]~[49]のいずれか一項に記載のアクリル系樹脂組成物。
[51] 前記グルタルイミドアクリル系樹脂(D)が下記一般式(3)で表される単位を含まない、[50]に記載のアクリル系樹脂組成物。
[52] [36]~[51]のいずれか一項に記載のアクリル系樹脂組成物からなるフィルム。
[53] 溶融押出法により得られることを特徴とする、[52]に記載のフィルム。
[54] 配向複屈折が-1.7×10-4から1.7×10-4、光弾性定数が-4×10-12から4×10-12Pa-1であることを特徴とする、[52]又は[53]に記載のフィルム。
[55] フィルムの厚みが10~500μmである、[52]~[54]のいずれか一項に記載のフィルム。
[56] 配向複屈折が-1.7×10-4から1.7×10-4、光弾性定数が-4×10-12から4×10-12Pa-1であり、引張破断点伸度が10%以上であり、厚みが10μm以上、500μm以下である、樹脂フィルム。
[57] ガラス転移温度が100℃以上であることを特徴とする、[56]に記載の樹脂フィルム。
[58] 前記樹脂フィルムがアクリル系樹脂フィルムであることを特徴とする、[56]又は[57]に記載の樹脂フィルム。
[59] 前記樹脂フィルムが未延伸フィルムである、[56]~[58]のいずれか一項に記載の樹脂フィルム。
[60] [56]~[59]のいずれか一項に記載の樹脂フィルムからなる、光学フィルム。
[61] [56]~[59]のいずれか一項に記載の樹脂フィルムを基材に積層してなる積層品。
本発明において、樹脂(A)とは、一般に透明性を有している樹脂であれば使用可能である。具体的には、ビスフェノールAポリカーボネートに代表されるポリカーボネート樹脂、ポリスチレン、スチレン-アクリロニトリル共重合体、スチレン-無水マレイン酸樹脂、スチレン-マレイミド樹脂、スチレン-(メタ)アクリル酸樹脂、スチレン系熱可塑エラストマー等の芳香族ビニル系樹脂及びその水素添加物、非晶性ポリオレフィン、結晶相を微細化した透明なポリオレフィン、エチレン-メタクリル酸メチル樹脂等のポリオレフィン系樹脂、ポリメタクリル酸メチル、スチレン-メタクリル酸メチル樹脂等のアクリル系樹脂、およびそのイミド環化、ラクトン環化、メタクリル酸変性等により改質された耐熱性のアクリル系樹脂、ポリエチレンテレフタレートあるいはシクロヘキサンジメチレン基やイソフタル酸等で部分変性されたポリエチレンテレフタレート、ポリエチレンナフタレート、ポリアリレート等の非晶ポリエステル樹脂あるいは結晶相を微細化した透明なポリエステル樹脂、ポリイミド樹脂、ポリエーテルサルホン樹脂、ポリアミド樹脂、トリアセチルセルロース樹脂等のセルロース系樹脂、ポリフェニレンオキサイド樹脂等の透明性を有する熱可塑性樹脂が幅広く例示される。実使用を考えた場合、得られた成形体の全光線透過率が85%以上、好ましくは90%、より好ましくは92%以上になるように樹脂を選定することが好ましい。
グルタルイミドアクリル系樹脂(D)は、ガラス転移温度が120℃以上であり、下記一般式(1)で表される単位と、下記一般式(2)で表される単位とを含むものである。
[メチルメタクリレート単位の含有量A(mol%)]=100×a/(a+b)
[グルタルイミド単位の含有量B(mol%)]=100×b/(a+b)
[グルタルイミド単位の含有量(重量%)]=100×(b×(グルタルイミド単位の分子量))/(a×(メチルメタクリレート単位の分子量)+b×(グルタルイミド単位の分子量))
なお、モノマー単位として上記以外の単位を含む場合においても、樹脂中の各モノマー単位の含有量(mol%)と分子量から、同様にグルタルイミド単位の含有量(重量%)を求めることができる。
本発明に用いられる重合体(B)は、樹脂(A)に添加することで、配向複屈折および光弾性定数をともに小さくでき、光学的等方性の高い非複屈折性樹脂材料とするために必須な成分である。光学的に等方にするためには、配向複屈折と光弾性複屈折をいかに小さくするかというのが重要である。そのため、ここではまず本発明の樹脂(A)、重合体(B)、非複屈折性樹脂材料、フィルムの「配向複屈折」「光弾性複屈折」の考え方について説明する。
高吐出条件、フィルム引取条件、低温成形など、フィルム中でポリマーが配向するような成形以外の、通常の溶融押出成形にてフィルムを作成した場合、フィルム中のポリマーの配向はそれほど大きくない。実際にPMMAで代表されるアクリル系樹脂であれば、意図的な延伸工程がない溶融押出フィルム(以下、原反フィルム、原料フィルムとも呼ぶ)の複屈折はそれほど大きくなく、用途にもよるが実用上問題が無い場合もある。もちろん、ポリマーが配向するような成形条件や、原反フィルムを延伸工程させた場合には、フィルム中でポリマーが配向し、その結果複屈折が発生する。この場合の複屈折は、ポリマーが配向することによって発生する複屈折であるため、一般に配向複屈折と呼ばれる。以上、本発明の非複屈折性樹脂材料をどのように成形するか、またフィルムの場合には延伸させるのか、ということによって、本発明の非複屈折性樹脂材料から得られる成形体、特には光学フィルムの配向複屈折を小さくするため、重合体(B)の配向複屈折と樹脂(A)の配向複屈折を設定する必要がある。逆に、フィルム等の成形体中でポリマーがほとんど配向せず、複屈折が十分に小さい場合には、重合体(B)の配向複屈折に関してはそれほど考慮する必要が無く、樹脂設計上、特に制限を受けないことになる。
まず、膜厚125μmのフィルム(原反フィルム)から、25mm×90mmの試験片を切り出し(MD方向に長辺が来るように切り出す)、両短辺を保持してガラス転移温度+30℃にて2分保ち、2倍(100%に延伸とも言う)に長さ方向へ200mm/分の速度で一軸に延伸する(この際、両長辺は固定なし)。その後、得られたフィルムを23℃に冷却し、サンプル中央部分をサンプリングし、複屈折を測定する。
重合体(B)が少なくとも架橋構造を有する場合、その構造によっては単独でフィルム化することは困難となる。よって、重合体(B)は、プレス成形シートを作製して「配向複屈折」を測定する。また、樹脂(A)などが、重合体(B)と同様に、フィルム化が困難である場合にも、プレス成形シートを作製して配向複屈折を測定する。
先に説明したとおり、光弾性複屈折は成形体に応力が加わった場合に成形体中のポリマーの弾性的な変形(歪)に伴って引き起こされる複屈折である。実際には、そのポリマーに固有の「光弾性定数」を求めることで、その材料の光弾性複屈折の度合いを評価することができる。まずポリマー材料に応力を印加し、弾性的な歪みが生じた際の複屈折を測定する。得られた複屈折と応力との比例定数が光弾性定数である。この光弾性定数を比較することにより、ポリマーの応力印加時の複屈折性を評価することができる。
上記「配向複屈折」の項の記載同様、膜厚125μmのフィルム(原反フィルム)から、TD方向に15mm×90mmの短冊状に試験片を切断する(TD方向に長辺がくるように切り出す)。次に、23℃において、試験片フィルムの長辺の一方を固定し、他方は無荷重から4kgfまで0.5kgfずつ荷重をかけた状態で、各々の印加時の複屈折を測定し、得られた結果から、単位応力による複屈折の変化量を算出し、光弾性定数を算出する。
重合体(B)については、上記の「配向複屈折」の項と同様にプレス成形シートを作製し、この複屈折を測定することにより、光弾性定数を求める。また、樹脂(A)などが、重合体(B)と同様に、フィルム化が困難である場合にも、プレス成形シートにより光弾性複屈折を測定する。
ここでは、重合体(B)がグラフト共重合体である場合の架橋重合体層について説明する。
まず、「軟質」の架橋重合体層について説明する。先述のとおり、「軟質」とは重合体のガラス転移温度が20℃未満であれば良く、ゴム状重合体が好適に使用される。具体的には、ブタジエン系架橋重合体、(メタ)アクリル系架橋重合体、オルガノシロキサン系架橋重合体などが挙げられる。なかでも、非複屈折性樹脂材料、およびフィルムの耐候性(耐光性)、透明性の面で、(メタ)アクリル系架橋重合体が特に好ましい。
ここでは「硬質」の架橋重合体層について説明する。先述のとおり、「硬質」とは、重合体のガラス転移温度が20℃以上であるものを示す。
先述のとおり、硬質重合体層を形成する「硬質」の重合体に必要な特性として、(1)重合体(B)をマトリックス(樹脂(A))中に均一に分散させること、および、(2)樹脂(A)が有している複屈折を打ち消して、本発明の非複屈折性樹脂材料、およびフィルムの光学的等方性を高める役割がある。
正の光弾性複屈折を示すモノマー:
ベンジルメタクリレート [48.4×10-12Pa-1]
ジシクロペンタニルメタクリレート [6.7×10-12Pa-1]
スチレン [10.1×10-12Pa-1]
パラクロロスチレン [29.0×10-12Pa-1]
負の光弾性複屈折を示すモノマー:
メチルメタクリレート [-4.3×10-12Pa-1]
2,2,2-トリフルオロエチルメタクリレート [-1.7×10-12Pa-1]
2,2,2-トリクロロエチルメタクリレート [-10.2×10-12Pa-1]
イソボルニルメタクリレート [-5.8×10-12Pa-1]
共重合体ポリマーの光弾性定数は、共重合に用いたモノマー種に対応するそれぞれのホモポリマーの光弾性定数との間に加成性が成り立つことが知られている。例えば、メチルメタクリレート(MMA)とベンジルメタクリレート(BzMA)の2元共重合系については、poly-MMA/BzMA=92/8(wt%)にて光弾性複屈折がほぼゼロになることが報告されている。また、2種以上のポリマー混合(アロイ)についても同様であり、各ポリマーが有する光弾性定数との間に加成性が成り立つ。以上のことから、本発明の非複屈折性樹脂材料、およびフィルムの光弾性複屈折が小さくなるように、樹脂(A)と重合体(B)の光弾性定数を異符号にし、且つその配合量(wt%)を調整することが必要である。
ポリベンジルメタクリレート [+0.002]
ポリフェニレンオキサイド [+0.210]
ビスフェノールAポリカーボネート [+0.106]
ポリビニルクロライド [+0.027]
ポリエチレンテレフタレート [+0.105]
ポリエチレン [+0.044]
負の固有複屈折を示すポリマー:
ポリメチルメタクリレート [-0.0043]
ポリスチレン [-0.100]
以上、一部のポリマーの光弾性定数、配向複屈折のデータを記載したが、ポリマーによっては配向複屈折は「正」、光弾性定数は「負」など、両方の複屈折が同じ符号であるとは限らない。次の表1に一部のホモポリマーの配向複屈折と光弾性複屈折(定数)の符号の例を示す。
(b-2)上記(メタ)アクリル系ゴム含有重合体粒子の存在下に、前記式(4)で表される単量体1~100重量%、これと共重合可能な他の単量体99~0重量%および多官能性単量体0~2.0重量部(前記式(4)で表される単量体およびこれと共重合可能な他の単量体の総量100重量部に対して)からなる単量体混合物を重合して、(メタ)アクリル系ゴム含有グラフト共重合体として得られるものを使用するのが好ましい。ここで、(b-1)重合段階の単量体混合物、および/または(b-2)重合段階の単量体混合物は、単量体成分を全部混合して1段で重合してもよいし、単量体組成を変化させて2段以上で重合してもよい。また、(b-1)における、アクリル酸アルキルエステル、これと共重合可能な単量体および多官能性単量体、並びにこれらの好ましい使用量は、上述の(メタ)アクリル酸架橋重合体における例示と同様である。(b-2)における、単量体混合物の成分およびこれらの好ましい使用量は、上述の硬質重合体層における例示と同様である。
Rth=((nx+ny)/2-nz)×d
上記式中において、nx、ny、およびnzは、それぞれ、面内において伸張方向(ポリマー鎖の配向方向)をX軸、X軸に垂直な方向をY軸、フィルムの厚さ方向をZ軸とし、それぞれの軸方向の屈折率を表す。また、dはフィルムの厚さを表し、nx-nyは配向複屈折を表す。なお、溶融押出フィルムの場合は、MD方向がX軸、さらに延伸フィルムの場合は延伸方向がX軸となる。
グラフト共重合体の(メタ)アクリル系架橋重合体層までの体積平均粒子径(アクリル系ゴム粒子の体積平均粒子径)は、アクリル系ゴム粒子ラテックスの状態で測定した。測定装置として、日機装株式会社製のMICROTRAC UPA150を用いて体積平均粒子径(μm)を測定した。
まず、得られたスラリーの一部を採取・精秤し、それを熱風乾燥器中で120℃、1時間乾燥し、その乾燥後の重量を固形分量として精秤した。次に、乾燥前後の精秤結果の比率をスラリー中の固形成分比率として求めた。最後に、この固形成分比率を用いて、以下の計算式により重合転化率を算出した。なお、この計算式において、連鎖移動剤は仕込み単量体として取り扱った。
=〔(仕込み原料総重量×固形成分比率-水・単量体以外の原料総重量)/仕込み単量体重量〕×100
(グラフト率)
得られた重合体(B)2gをメチルエチルケトン50mlに溶解させ、遠心分離機(日立工機(株)製、CP60E)を用い、回転数30000rpmにて1時間遠心分離を行い、不溶分と可溶分とを分離した(遠心分離作業を合計3セット)。得られた不溶分を用いて、次式によりグラフト率を算出した。
なお、架橋重合体層の重量は、架橋重合体層を構成する単官能性単量体の仕込み重量である。
イミド化率の算出は、IRを用いて下記の通り行った。生成物のペレットを塩化メチレンに溶解し、その溶液について、SensIR Tecnologies社製TravelIRを用いて、室温にてIRスペクトルを測定した。得られたIRスペクトルより、1720cm-1のエステルカルボニル基に帰属する吸収強度(Absester)と、1660cm-1のイミドカルボニル基に帰属する吸収強度(Absimide)との比からイミド化率(Im%(IR))を求めた。ここで、「イミド化率」とは、全カルボニル基中のイミドカルボニル基の占める割合をいう。
1H-NMR BRUKER AvanceIII(400MHz)を用いて、樹脂の1H-NMR測定を行い、樹脂中のグルタルイミド単位またはエステル単位などの各モノマー単位それぞれの含有量(mol%)を求め、当該含有量(mol%)を、各モノマー単位の分子量を使用して含有量(重量%)に換算した。
得られたグルタルイミドアクリル系樹脂0.3gを37.5mlの塩化メチレンおよび37.5mlのメタノールの混合溶媒の中で溶解した。フェノールフタレインエタノール溶液を2滴加えた後に、0.1Nの水酸化ナトリウム水溶液を5ml加えた。過剰の塩基を0.1N塩酸で滴定し、酸価を、添加した塩基と中和に達するまでに使用した塩酸との間のミリ当量で示す差で算出した。
各組成物の屈折率は、それぞれの組成物をシート状に加工し、JIS K7142に準じて、アタゴ社製アッベ屈折計2Tを用いて、ナトリウムD線波長における屈折率(nD)を測定した。
セイコーインスツルメンツ製の示差走査熱量分析装置(DSC)SSC-5200を用い、試料を一旦200℃まで25℃/分の速度で昇温した後10分間ホールドし、25℃/分の速度で50℃まで温度を下げる予備調整を経て、10℃/分の昇温速度で200℃まで昇温する間の測定を行い、得られたDSC曲線から積分値を求め(DDSC)、その極大点からガラス転移温度を求めた。
フィルムの全光線透過率、ヘイズ値は、(株)日本電色工業 NDH-300Aを用い、JIS K7105に記載の方法にて測定した。
フィルムの膜厚は、デジマティックインジケーター(株式会社ミツトヨ製)を用いて測定した。
未延伸の膜厚125μmの原反フィルムから、25mm×90mmの試験片を切り出し(MD方向に長辺が来るように切り出す)、両短辺を保持してガラス転移温度+30℃にて2分保ち、2倍(100%に延伸とも言う)に長さ方向へ200mm/分の速度で一軸に延伸した(この際、両長辺は固定なし)。その後、得られたフィルムを23℃に冷却し、サンプル中央部分をサンプリングし、自動複屈折計(王子計測株式会社製 KOBRA-WR)を用いて、温度23±2℃、湿度50±5%において、波長590nm、入射角0°にて複屈折(配向複屈折)を測定した。同時に、面内位相差Re、厚み方向位相差Rth(入射角40°)も測定した。(面内位相差Re、厚み方向位相差Rthに関しては、その詳細を後述する)
なお、重合体(B)単体の一軸延伸フィルム、および配向複屈折の測定に関しては、重合体(B)単品を、190℃でプレスし、膜厚500μmのプレス板を作成した。得られたプレス板中央部から、25mm×90mmの試験片を切り出し、上記記載と同様に測定した。
未延伸の原反フィルム(膜厚125μm)から40mm×40mmの試験片を切り出し、自動複屈折計(王子計測株式会社製 KOBRA-WR)を用いて、温度23±2℃、湿度50±5%において、波長590nm、入射角0°にて測定した。同時に、面内位相差Re、厚み方向位相差Rth(入射角40°)も測定した。(面内位相差Re、厚み方向位相差Rthに関しては、その詳細を後述する)
(面内位相差Reおよび厚み方向位相差Rth)
膜厚125μmのフィルムから、40mm×40mmの試験片を切り出した。この試験片の面内位相差Reを、自動複屈折計(王子計測株式会社製 KOBRA-WR)を用いて、温度23±2℃、湿度50±5%において、波長590nm、入射角0゜で測定した。
膜厚125μmのフィルムからTD方向に15mm×90mmの短冊状に試験片を切断した(TD方向に長辺がくるように切り出す)。自動複屈折計(王子計測株式会社製 KOBRA-WR)を用いて、温度23±2℃、湿度50±5%において、波長590nm、入射角0°にて測定した。測定は、フィルムの長辺の一方を固定し、他方は無荷重から4kgfまで0.5kgfずつ荷重をかけた状態で複屈折を測定し、得られた結果から、単位応力による複屈折の変化量を算出した。
得られたフィルムから1m2分を切り出し、20μm以上の異物数をマイクロスコープ観察などでカウントし、合計して異物数とした。
○:100個/m2未満
×:100個/m2以上
(機械的強度の評価)
機械的強度は、トリミング性評価と、耐割れ性の指標である引張破断点伸度(引張伸び:%)で評価した。
○:切断面にクラック発生が認められない。
△:切断面にクラック発生が認められる。
×:切断面にクラック発生が著しく認められる。
得られた樹脂組成物を、JIS K7199に準拠した条件下(ダイス温度260℃、剪断速度24sec-1、キャピラリーダイ径1mm、滞留時間1時間)にて溶融粘度を測定し、滞留時間10分時における溶融粘度に対する滞留時間1時間時における溶融粘度の下記計算式に表される溶融粘度低下率を算出し、熱安定性の指標とした。また、試験後のストランド中に、樹脂の熱分解に由来する発泡の有無も観察した。
溶融粘度低下率=
(滞留時間10分時における溶融粘度-滞留時間1時間時における溶融粘度)/(滞留時間10分時における溶融粘度) × 100 (%)
熱安定性および溶融粘度を以下の基準で評価した。
熱安定性:
○:溶融粘度低下率が20%未満で、ストランド中に発泡なし
×:溶融粘度低下率が20%以上で、ストランド中に発泡あり
溶融粘度:
○:溶融粘度が低く、問題なく押出可能である。
×:溶融粘度が高く、フィルターが破損し、ろ過精度がでない。
<グルタルイミドアクリル系樹脂(A1)の製造>
原料樹脂としてポリメタクリル酸メチル、イミド化剤としてモノメチルアミンを用いて、グルタルイミドアクリル系樹脂(A1)を製造した。
<グラフト共重合体(B1)の製造>
撹拌機付き8L重合装置に、以下の物質を仕込んだ。
脱イオン水 200部
ポリオキシエチレンラウリルエーテルリン酸ナトリウム 0.45部
ソディウムホルムアルデヒドスルフォキシレ-ト 0.11部
エチレンジアミン四酢酸-2-ナトリウム 0.004部
硫酸第一鉄 0.001部
重合機内を窒素ガスで充分に置換し実質的に酸素のない状態とした後、内温を40℃にし、表2に示したアクリル系ゴム粒子(B-1)の原料混合物46.391部を225分かけて連続的に添加した。(B-1)追加開始から50分後にポリオキシエチレンラウリルエーテルリン酸ナトリウム(ポリオキシエチレンラウリルエーテルリン酸(東邦化学工業株式会社製、商品名:フォスファノールRD-510Yのナトリウム塩)0.2部を重合機に添加した。添加終了後、さらに0.5時間重合を継続し、アクリル系ゴム粒子((B-1)の重合物)を得た。重合転化率は99.7%であった。
<グラフト共重合体(B2)の製造>
撹拌機付き8L重合装置に、以下の物質を仕込んだ。
脱イオン水 200部
ポリオキシエチレンラウリルエーテルリン酸ナトリウム 0.05部
ソディウムホルムアルデヒドスルフォキシレ-ト 0.11部
エチレンジアミン四酢酸-2-ナトリウム 0.004部
硫酸第一鉄 0.001部
重合機内を窒素ガスで充分に置換し実質的に酸素のない状態とした後、内温を40℃にし、表2に示したアクリル系ゴム粒子(B-1)の原料混合物45.491部を225分かけて連続的に添加した。(B-1)追加開始から20分後、40分後、60分後にポリオキシエチレンラウリルエーテルリン酸ナトリウム(ポリオキシエチレンラウリルエーテルリン酸(東邦化学工業株式会社製、商品名:フォスファノールRD-510Yのナトリウム塩)0.2部ずつ重合機に添加した。添加終了後、さらに0.5時間重合を継続し、アクリル系ゴム粒子((B-1)の重合物)を得た。重合転化率は98.6%であった。
<グラフト共重合体(B3)の製造>
表2に示したアクリル系ゴム粒子(B-1)、硬質重合体層(B-2)の組成により製造例2と同様に重合を行い、凝固、水洗、乾燥をして白色粉末状のグラフト共重合体(B3)を得た。
<グラフト共重合体(B4)の製造>
撹拌機付き8L重合装置に、以下の物質を仕込んだ。
脱イオン水 200部
ジオクチルスルフォコハク酸ナトリウム 0.58部
ソディウムホルムアルデヒドスルフォキシレ-ト 0.11部
エチレンジアミン四酢酸-2-ナトリウム 0.004部
硫酸第一鉄 0.001部
重合機内を窒素ガスで充分に置換し実質的に酸素のない状態とした後、内温を40℃にし、表2に示したアクリル系ゴム粒子(B-1)の原料混合物46.391部を225分かけて連続的に添加した。添加終了後、さらに0.5時間重合を継続し、アクリル系ゴム粒子((B-1)の重合物)を得た。重合転化率は99.7%であった。
<グラフト共重合体(B5)の製造>
撹拌機付き8L重合装置に、以下の物質を仕込んだ。
脱イオン水 200部
ポリオキシエチレンラウリルエーテルリン酸ナトリウム 0.05部
ソディウムホルムアルデヒドスルフォキシレ-ト 0.11部
エチレンジアミン四酢酸-2-ナトリウム 0.004部
硫酸第一鉄 0.001部
重合機内を窒素ガスで充分に置換し実質的に酸素のない状態とした後、内温を40℃にし、表2に示したアクリル系ゴム粒子(B-1)の原料混合物45.266部を135分かけて連続的に添加した。(B-1)追加開始から12分後、24分後、36分後にポリオキシエチレンラウリルエーテルリン酸ナトリウム(ポリオキシエチレンラウリルエーテルリン酸(東邦化学工業株式会社製、商品名:フォスファノールRD-510Yのナトリウム塩)0.2部ずつ重合機に添加した。添加終了後、さらに0.5時間重合を継続し、アクリル系ゴム粒子((B-1)の重合物)を得た。重合転化率は99.4%であった。
<グラフト共重合体(B6)の製造>
攪拌機付き8L重合装置に、以下の物質を仕込んだ。
脱イオン水 200部
ポリオキシエチレンラウリルエーテルリン酸ナトリウム 0.05部
ソディウムホルムアルデヒドスルフォキシレ-ト 0.11部
エチレンジアミン四酢酸-2-ナトリウム 0.004部
硫酸第一鉄 0.001部
重合機内を窒素ガスで充分に置換し実質的に酸素のない状態とした後、内温を40℃にし、表2に示したアクリル系ゴム粒子(B-1)の原料混合物45.266部を135分かけて連続的に添加した。(B-1)追加開始から12分後、37分後、62分後、87分後にポリオキシエチレンラウリルエーテルリン酸ナトリウム(ポリオキシエチレンラウリルエーテルリン酸(東邦化学工業株式会社製、商品名:フォスファノールRD-510Yのナトリウム塩)を、各0.21部、0.21部、0.21部、0.11部ずつ重合機に添加した。添加終了後、さらに1時間重合を継続し、アクリル系ゴム粒子((B-1)の重合物)を得た。重合転化率は97.8%であった。
<グラフト共重合体(B7)の製造>
攪拌機付き8L重合装置に、以下の物質を仕込んだ。
脱イオン水 200部
ポリオキシエチレンラウリルエーテルリン酸ナトリウム 0.05部
ソディウムホルムアルデヒドスルフォキシレ-ト 0.11部
エチレンジアミン四酢酸-2-ナトリウム 0.004部
硫酸第一鉄 0.001部
重合機内を窒素ガスで充分に置換し実質的に酸素のない状態とした後、内温を40℃にし、表2に示したアクリル系ゴム粒子(B-1)の原料混合物45.266部を135分かけて連続的に添加した。(B-1)追加開始から12分後、37分後、62分後、87分後にポリオキシエチレンラウリルエーテルリン酸ナトリウム(ポリオキシエチレンラウリルエーテルリン酸(東邦化学工業株式会社製、商品名:フォスファノールRD-510Yのナトリウム塩)を、各0.21部、0.21部、0.21部、0.11部ずつ重合機に添加した。添加終了後、さらに1時間重合を継続し、アクリル系ゴム粒子((B-1)の重合物)を得た。重合転化率は99.0%であった。
A2: メタクリル酸メチル-メタクリル酸共重合体 Altuglas HT-121 (Arkema Inc.)、光弾性定数の符号は-(マイナス)
A3: 無水マレイン酸-スチレン-メタクリル酸メチル共重合体 PLEXIGLAS hw55 (EVONIK INDUSTRIES)、光弾性定数の符号は-(マイナス)
(実施例1~8、比較例1~3)
直径40mmのフルフライトスクリューを用いた単軸押出機を用い、押出機の温度調整ゾーンの設定温度を255℃、スクリュー回転数を52rpmとし、表3に示すアクリル系樹脂(A)、および重合体(B)の混合物を、10kg/hrの割合で供給した。押出機出口に設けられたダイスからストランドとして出てきた樹脂を水槽で冷却し、ペレタイザでペレット化した。
比較例4では、A7を100重量部使用した。
A7:PMMA樹脂 スミペックスEX (住友化学株式会社)
比較例5では、比較例3と同様、A1を100重量部使用した。
ASTM D-256に準じて、アイゾット試験(温度23℃、湿度50%)により評価した。
Claims (38)
- 樹脂(A)および重合体(B)を含有し、配向複屈折が-1.7×10-4から1.7×10-4、光弾性定数が-4×10-12から4×10-12Pa-1、である、非複屈折性樹脂材料。
- 樹脂(A)および重合体(B)を含有し、前記樹脂(A)の光弾性定数と前記重合体(B)の光弾性定数が異符号であり、前記樹脂(A)の光弾性定数が前記重合体(B)の光弾性定数により相殺されている、非複屈折性樹脂材料。
- 引張破断点伸度が10%以上であることを特徴とする、請求項1又は2に記載の非複屈折性樹脂材料。
- 前記樹脂(A)がアクリル系樹脂であることを特徴とする、請求項1~3のいずれか1項に記載の非複屈折性樹脂材料。
- 前記樹脂(A)の光弾性定数と前記重合体(B)の光弾性定数が異符号であることを特徴とする、請求項1、3および4のいずれか1項に記載の非複屈折性樹脂材料。
- 前記重合体(B)が、架橋構造を有することを特徴とする、請求項1~5のいずれか1項に記載の非複屈折性樹脂材料。
- 前記重合体(B)が、硬質重合体部を有することを特徴とする、請求項1~6のいずれか1項に記載の非複屈折性樹脂材料。
- 前記重合体(B)が、非架橋構造を有することを特徴とする、請求項1~7のいずれか1項に記載の非複屈折性樹脂材料。
- 前記重合体(B)が、多層構造重合体であることを特徴とする、請求項1~8のいずれか1項に記載の非複屈折性樹脂材料。
- 前記重合体(B)が、架橋重合体層および硬質重合体層を含む多層構造重合体であることを特徴とする、請求項9に記載の非複屈折性樹脂材料。
- 前記重合体(B)が、(メタ)アクリル系架橋重合体層、および硬質重合体層を有する多層構造重合体であることを特徴とする、請求項10に記載の非複屈折性樹脂材料。
- 前記硬質重合体層が、非架橋の硬質重合体層を含む、請求項10~11のいずれか一項に記載の非複屈折性樹脂材料。
- 前記重合体(B)が、(メタ)アクリル系架橋重合体層、および、脂環式構造、複素環式構造または芳香族基を有するビニル系単量体を構造単位に含む硬質重合体層を有することを特徴とする、請求項10~12のいずれか一項に記載の非複屈折性樹脂材料。
- 前記式(4)で表される単量体を構成単位に有する硬質重合体層は、前記式(4)で表される単量体1~100重量%、これと共重合可能な他の単量体99~0重量%、および多官能性単量体0~2.0重量部(前記式(4)で表される単量体および前記これと共重合可能な他の単量体の総量100重量部に対して)を重合してなる、請求項14に記載の非複屈折性樹脂材料。
- 前記(メタ)アクリル系架橋重合体層は、アクリル酸アルキルエステル50~100重量%、これと共重合可能な他の単量体50~0重量%、および多官能性単量体0.05~10重量部(前記アクリル酸アルキルエステルおよび前記これと共重合可能な他の単量体の総量100重量部に対して)を重合してなる、請求項11~15のいずれか1項に記載の非複屈折性樹脂材料。
- 前記重合体(B)において、前記硬質重合体層が最外層を構成し、前記最外層が前記式(4)で表される単量体を構成単位に有する硬質重合体層である、請求項14~16のいずれか一項に記載の非複屈折性樹脂材料。
- 前記重合体(B)において、前記最外層の内側に、前記(メタ)アクリル系架橋重合体層を有する軟質層が隣接している、請求項17に記載の非複屈折性樹脂材料。
- 前記重合体(B)は、軟質の内層および硬質の外層を有し、前記内層が前記(メタ)アクリル系架橋重合体層を有し、前記外層が前記式(4)で表される単量体を構成単位に有する硬質重合体層を有する、請求項14~16のいずれか一項に記載の非複屈折性樹脂材料。
- 前記重合体(B)は、硬質の内層、軟質の中間層および硬質の外層を有し、前記内層が少なくとも一種の硬質重合体層からなり、前記中間層が前記(メタ)アクリル系架橋重合体層からなる軟質重合体層を有し、前記外層が前記式(4)で表される単量体を構成単位に有する硬質重合体層を有する、請求項14~16のいずれか一項に記載の非複屈折性樹脂材料。
- 前記重合体(B)が、軟質の最内層をさらに有する、請求項20に記載の非複屈折性樹脂材料。
- 前記式(4)で表される単量体が、(メタ)アクリル酸ベンジル、(メタ)アクリル酸ジシクロペンタニル、及び(メタ)アクリル酸フェノキシエチルからなる群より選択される少なくとも1種であることを特徴とする、請求項14~21のいずれか一項に記載の非複屈折性樹脂材料。
- 前記重合体(B)の前記(メタ)アクリル系架橋重合体層までの体積平均粒子径が20~450nmである、請求項11~22のいずれか一項に記載の非複屈折性樹脂材料。
- 前記重合体(B)が含有する前記(メタ)アクリル系架橋重合体層の含有量が、非複屈折性樹脂材料100重量部において1~60重量部である、請求項11~23のいずれか一項に記載の非複屈折性樹脂材料。
- 複屈折性を有する無機微粒子をさらに含有することを特徴とする、請求項1~24のいずれか1項に記載の非複屈折性樹脂材料。
- 複屈折性を有する低分子化合物をさらに含有することを特徴とする、請求項1~25のいずれか1項に記載の非複屈折性樹脂材料。
- 前記樹脂(A)が、下記一般式(1)で表される単位と、下記一般式(2)で表される単位とを有するグルタルイミドアクリル系樹脂(D)、ラクトン環含有アクリル系重合体、スチレン単量体およびそれと共重合可能な他の単量体を重合して得られるスチレン系重合体の芳香族環を部分水素添加して得られる部分水添スチレン系重合体、環状酸無水物繰り返し単位を含有するアクリル系重合体、並びに、水酸基および/またはカルボキシル基を含有するアクリル系重合体、からなる群より選択される少なくとも1種である、請求項1~26のいずれか一項に記載の非複屈折性樹脂材料。
(式中、R1およびR2は、それぞれ独立して、水素または炭素数1~8のアルキル基であり、R3は、水素、炭素数1~18のアルキル基、炭素数3~12のシクロアルキル基、または、芳香環を含む炭素数5~15の置換基である。)
(式中、R4およびR5は、それぞれ独立して、水素または炭素数1~8のアルキル基であり、R6は、炭素数1~18のアルキル基、炭素数3~12のシクロアルキル基、または、芳香環を含む炭素数5~15の置換基である。) - 光弾性定数が-4×10-12から4×10-12Pa-1である、請求項2~28のいずれか1項に記載の非複屈折性樹脂材料。
- 配向複屈折が-1.7×10-4から1.7×10-4である、請求項2~29のいずれか1項に記載の非複屈折性樹脂材料。
- 請求項1~30のいずれか一項に記載の非複屈折性樹脂材料からなるフィルム。
- 溶融押出法により得られることを特徴とする、請求項31に記載のフィルム。
- 配向複屈折が-1.7×10-4から1.7×10-4、光弾性定数が-4×10-12から4×10-12Pa-1であることを特徴とする、請求項31又は32に記載のフィルム。
- 引張破断点伸度が10%以上である、請求項31~33のいずれか一項に記載のフィルム。
- フィルムの厚みが10~500μmである、請求項31~34のいずれか一項に記載のフィルム。
- 次の樹脂(A)および重合体(B)を含有するアクリル系樹脂組成物。
(A)アクリル系樹脂。
(B)多段重合で得られる(メタ)アクリル系ゴム含有グラフト共重合体であって、前記多段重合の少なくとも1段において、(メタ)アクリル系ゴム含有重合体粒子の存在下に、式(4)で表される単量体およびこれと共重合可能な他の単量体を含有する混合物を重合することで形成される、重合体。
R9は、水素原子、または、置換もしくは無置換で直鎖状もくしは分岐状の炭素数1~12のアルキル基を表す。R10は、置換もしくは無置換の炭素数1~24の芳香族基、または、置換もしくは無置換の炭素数1~24の脂環式基であり、単素環式構造または複素環式構造を有する。lは1~4の整数を示す。mは0~1の整数を示す。nは0~10の整数を示す。 - 配向複屈折が-1.7×10-4から1.7×10-4、光弾性定数が-4×10-12から4×10-12Pa-1であり、引張破断点伸度が10%以上であり、厚みが10μm以上、500μm以下である、樹脂フィルム。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014522432A JP6236002B2 (ja) | 2012-06-26 | 2013-06-26 | 非複屈折性樹脂材料、およびフィルム |
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US14/406,086 US10035888B2 (en) | 2012-06-26 | 2013-06-26 | Non-birefringent resin material and film |
CN201380027881.XA CN104334635B (zh) | 2012-06-26 | 2013-06-26 | 非双折射性树脂材料及膜 |
EP13809071.7A EP2865716A4 (en) | 2012-06-26 | 2013-06-26 | NON-DOUBLE-BREAKING RESIN MATERIAL AND FOIL |
BR112014030481A BR112014030481A2 (pt) | 2012-06-26 | 2013-06-26 | material de resina não birrefringente e filme |
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Also Published As
Publication number | Publication date |
---|---|
JPWO2014002491A1 (ja) | 2016-05-30 |
US20150147550A1 (en) | 2015-05-28 |
BR112014030481A2 (pt) | 2017-06-27 |
US10035888B2 (en) | 2018-07-31 |
CN104334635B (zh) | 2017-11-10 |
KR102089115B1 (ko) | 2020-03-13 |
TWI515251B (zh) | 2016-01-01 |
TW201404817A (zh) | 2014-02-01 |
KR20150023238A (ko) | 2015-03-05 |
EP2865716A4 (en) | 2015-12-23 |
EP2865716A1 (en) | 2015-04-29 |
JP6236002B2 (ja) | 2017-11-22 |
CN104334635A (zh) | 2015-02-04 |
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