WO2015098775A1 - 光学用樹脂組成物、および成形体 - Google Patents
光学用樹脂組成物、および成形体 Download PDFInfo
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- WO2015098775A1 WO2015098775A1 PCT/JP2014/083787 JP2014083787W WO2015098775A1 WO 2015098775 A1 WO2015098775 A1 WO 2015098775A1 JP 2014083787 W JP2014083787 W JP 2014083787W WO 2015098775 A1 WO2015098775 A1 WO 2015098775A1
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- 0 C*(C)C(C)(C(*)(*(C)C)C(N1*)=O)C1=O Chemical compound C*(C)C(C)(C(*)(*(C)C)C(N1*)=O)C1=O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L33/24—Homopolymers or copolymers of amides or imides
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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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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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
Definitions
- the present invention relates to an optical resin composition and a molded body.
- 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, diffusion plates, etc .; in signal reading lens systems of optical disk devices)
- a light transmissive resin is generally used as a material constituting a lens.
- a resin is generally called an “optical resin” or an “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.
- 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.
- the refractive index increases in the direction parallel to the orientation direction of the polymer chain, it is expressed as "Orientation birefringence is positive", and when the refractive index increases in the orthogonal direction, it is expressed as "Orientation birefringence is negative".
- 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.
- 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 the resulting molded article has good transparency, but does not describe improvement in mechanical strength such as photoelastic birefringence and impact resistance. Moreover, heat resistance may fall.
- there is no description of transparency and color tone when used for a thick molded product such as an injection molded product and problems such as poor transparency and color tone are assumed.
- 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 improvement of mechanical strength such as photoelastic birefringence and impact resistance.
- there is no description of transparency and color tone when used for a thick molded product such as an injection molded product and problems such as poor transparency and color tone are assumed.
- 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.
- the glass transition temperature is lower than 100 ° C., and the mechanical strength such as impact resistance is also low.
- the mechanical strength such as impact resistance is also low.
- problems such as becoming.
- problems such as polymer decomposition under severe molding conditions such as high temperature and high shear are also assumed.
- problems such as appearance defects such as foaming due to polymer decomposition and foaming during injection molding, and reduction in mechanical strength such as transparency, color tone, and impact resistance are assumed.
- 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 polymer film, in particular, bending resistance, and optical properties by combining a “shell” type impact resistance improver (hereinafter also referred to as “core-shell polymer”). A method for obtaining a film is presented. However, there is no data on orientation birefringence and photoelastic birefringence in Examples, and the effect of improving birefringence is unknown.
- 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.
- 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.
- the orientation birefringence is larger than that of Comparative Example using only acrylic resin (A), and the photoelasticity is increased.
- the coefficient (photoelastic birefringence) is equivalent to that of the comparative example using only the acrylic resin (A).
- the photoelastic constant of the heat-resistant acrylic resin is negative, and the acrylic rubber (B) is also estimated to have a negative photoelastic constant from the composition.
- the acrylic rubber (B) has orientation birefringence and photoelasticity. Even if the birefringence is deteriorated, it is clear that the technical idea for adjustment is not described in the document. In addition, there is no description of transparency and color tone when used for a thick molded article such as injection molding, and problems such as poor transparency and color tone are assumed.
- An object of the present invention is to provide an optical resin composition excellent in properties and heat resistance, and a molded body thereof, particularly an injection molded body.
- the present invention has found that the above problems can be solved by blending a thermoplastic resin with a crosslinked structure-containing polymer having a specific structure and composition, and has completed the present invention.
- the present invention [1] containing a thermoplastic resin and a crosslinked structure-containing polymer, An optical resin composition, wherein the photoelastic constant of the crosslinked structure-containing polymer is different from the photoelastic constant of the thermoplastic resin, and the haze of the molded product having a thickness of 2 mm is 6% or less; [2] The optical resin composition according to [1], wherein the crosslinked structure-containing polymer has a portion made of a hard polymer. [3] The cross-linked structure-containing copolymer has a cross-linked polymer containing a vinyl monomer having an alicyclic structure, a heterocyclic structure or an aromatic group in the cross-linked structure as a structural unit.
- R 9 represents a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms.
- R 10 represents a substituted or unsubstituted carbon group having 1 to 24 carbon atoms.
- l represents an integer of 1 to 4 carbon atoms and having a monocyclic structure or a heterocyclic structure,
- l represents an integer of 1 to 4
- m is Represents an integer of 0 to 1.
- n an integer of 0 to 10.
- An optical resin composition [7] The optical resin composition according to any one of [1] to [6], wherein the orientation birefringence of the thermoplastic resin and the orientation birefringence of the crosslinked structure-containing polymer are different from each other. [8] A thermoplastic resin and a multistage polymer are contained, and the multistage polymer is copolymerized with the monomer represented by the following general formula (4) in the presence of the crosslinked polymer-containing particles.
- Optical resin composition which is a multistage polymer obtained by polymerizing a monomer mixture containing other possible monofunctional monomers, and the haze of a molded product having a thickness of 2 mm is 6% or less ,
- R 9 represents a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms.
- R 10 represents a substituted or unsubstituted carbon group having 1 to 24 carbon atoms.
- l represents an integer of 1 to 4
- m is Represents an integer of 0 to 1.
- n represents an integer of 0 to 10.
- R 9 represents a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms.
- R 10 represents a substituted or unsubstituted carbon group having 1 to 24 carbon atoms.
- l represents an integer of 1 to 4 carbon atoms and having a monocyclic structure or a heterocyclic structure,
- l represents an integer of 1 to 4
- m is Represents an integer of 0 to 1.
- n an integer of 0 to 10.
- a thermoplastic resin and a multilayer structure polymer are contained, and the multilayer structure polymer is a cross-linked polymer layer, a monomer represented by the following general formula (4), and 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 represents a substituted or unsubstituted carbon group having 1 to 24 carbon atoms.
- l represents an integer of 1 to 4
- m is Represents an integer of 0 to 1.
- n represents an integer of 0 to 10.
- the crosslinked polymer layer is a crosslinked polymer layer formed by polymerizing a monomer mixture containing a monomer represented by the following general formula (4) and a polyfunctional monomer.
- R 9 represents a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms.
- R 10 represents a substituted or unsubstituted carbon group having 1 to 24 carbon atoms.
- l represents an integer of 1 to 4 carbon atoms and having a monocyclic structure or a heterocyclic structure,
- l represents an integer of 1 to 4
- m is Represents an integer of 0 to 1.
- n an integer of 0 to 10.
- the monomer represented by the general formula (4) is selected from the group consisting of benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and phenoxyethyl (meth) acrylate.
- the photoelastic constant of the thermoplastic resin and the photoelastic constant of the multistage polymer or the multilayer structure polymer are different signs, and are described in any one of [8] to [12].
- Optical resin composition is any one of [4] and [8] to [11].
- thermoplastic resin is an acrylic thermoplastic resin
- Styrene obtained by polymerizing a maleimide acrylic resin, a glutarimide acrylic resin, a lactone ring-containing acrylic polymer, a styrene monomer and other monomers copolymerizable with the thermoplastic resin.
- Partially hydrogenated styrene polymer obtained by partial hydrogenation of aromatic ring of polymer, acrylic polymer containing cyclic acid anhydride repeating unit, and acrylic polymer containing hydroxyl group and / or carboxyl group The optical resin composition according to any one of the above [1] to [15], comprising at least one selected from the group consisting of polymers. [17] Any of [1] to [16], wherein the thermoplastic resin contains a maleimide acrylic resin having a maleimide unit and a (meth) acrylic acid ester unit represented by the following general formula (5)
- R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms
- R 13 is a hydrogen atom, an arylalkyl group having 7 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkyl group having 1 to 18 carbon atoms, or the following group
- thermoplastic resin contains a glutarimide acrylic resin having a unit represented by the following formula (1) and a unit represented by the following formula (2).
- 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
- the optical resin composition includes a crosslinked structure contained in the crosslinked structure-containing polymer, a crosslinked polymer-containing particle contained in the multistage polymer, or a crosslinked polymer layer contained in the multilayer structured polymer.
- both orientation birefringence and photoelastic birefringence are very small, excellent in transparency, impact resistance including Izod strength, etc.
- An optical resin composition having excellent mechanical properties and a molded article comprising the composition, particularly an injection molded article, are provided.
- FIG. 1 The photograph which shows the cross Nicol test result of the flat plate sample obtained in Example 1.
- FIG. 2 The photograph which shows the cross Nicol test result of the flat plate sample obtained in Example 2.
- the optical resin composition of the present invention and the molded product thereof contain, as essential components, a thermoplastic resin that serves as a matrix resin and a crosslinked structure-containing polymer that serves as a rubber component.
- the thermoplastic resin can be any resin that 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 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 resin such as resin, and heat-modified acrylic resin modified by imide cyclization, lactone cyclization, methacrylic acid modification, etc., partially modified with polyethylene terephthalate, cyclohexanedimethylene group, iso
- Noncrystalline polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polyarylate, etc., or transparent polyester resins with a refined crystal phase, polyimide resins, polyethersulfone resins, polyamide resins, triacetyl cellulose resins, and other cellulose resins
- thermoplastic resins having transparency such as polyphenylene oxide resin. 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 (meth) acrylic acid ester, but 30 to 100% by weight of methyl methacrylate and 70 to 0% by weight of a monomer copolymerizable therewith. Acrylic resin obtained by polymerizing% 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
- the methyl methacrylate is preferably contained in an amount of 30 to 100% by weight, more preferably 50 to 99.9% by weight, and further preferably 50 to 98% by weight, and is copolymerizable with methyl methacrylate.
- the monomer is preferably contained in an amount of 70 to 0% by weight, more preferably 50 to 0.1% by weight, and still 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 thermoplastic resin 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 a maleimide structure, a glutarimide structure, a glutaric anhydride structure, a (meth) acrylic acid unit, or an acrylic resin containing a lactone ring in the molecule.
- a maleimide structure a glutarimide structure, a glutaric anhydride structure, a (meth) acrylic acid unit, or an acrylic resin containing a lactone ring in the molecule.
- examples thereof include maleimide acrylic resins, glutarimide acrylic resins, glutaric anhydride acrylic resins, lactone ring-containing acrylic resins, acrylic resins containing hydroxyl groups and / or carboxyl groups, and methacrylic resins.
- styrene polymer obtained by polymerizing a styrene monomer and another monomer copolymerizable therewith.
- a partially hydrogenated styrene polymer a polymer containing cyclic acid anhydride repeating units, a polyethylene terephthalate resin, a polybutylene terephthalate resin, and the like.
- the maleimide acrylic resin and / or glutarimide acrylic resin described below is used, the heat resistance of the obtained molded body such as a film, sheet or injection molded body is improved, and stretching or injection is performed. This is particularly preferable because of excellent optical properties in the presence of orientation and residual strain due to molding.
- thermoplastic resin a combination of maleimide acrylic resin and glutarimide acrylic resin is preferable as the thermoplastic resin. Both resins have high compatibility and can be used together to maintain excellent transparency of each resin. Both orientation birefringence and photoelastic birefringence are small, and high thermal stability and solvent resistance can be maintained.
- the maleimide acrylic resin is a copolymer having a maleimide unit and a (meth) acrylic acid ester unit represented by the following general formula (5).
- R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms
- R 13 is a hydrogen atom.
- These are an aryl group having 6 to 14 carbon atoms or an alkyl group having 1 to 12 carbon atoms having a substituent.
- Group A a halogen atom, a hydroxyl group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, and an arylalkyl group having 7 to 14 carbon atoms.
- the alkyl group having 1 to 12 carbon atoms in R 11 and R 12 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
- Examples of the alkyl group having 1 to 12 carbon atoms in R 11 and R 12 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and a 2-ethylhexyl group.
- methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl are used in terms of further improving transparency and weather resistance.
- Group, t-butyl group and 2-ethylhexyl group are preferable, and methyl group is more preferable.
- Examples of the aryl group having 6 to 14 carbon atoms in R 11 and R 12 include a phenyl group, a naphthyl group, and an anthracenyl group, and among these, optical characteristics such as heat resistance and low birefringence are further improved. In this respect, a phenyl group is preferred.
- R 11 and R 12 are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and more preferably a hydrogen atom.
- R 13 examples of the arylalkyl group having 7 to 14 carbon atoms in R 13 include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a 6-phenylhexyl group, and an 8-phenyloctyl group.
- a benzyl group is preferred in that optical properties such as heat resistance and low birefringence are further improved.
- Examples of the aryl group having 6 to 14 carbon atoms in R 13 include a phenyl group, a naphthyl group, and an anthracenyl group, and among these, optical characteristics such as heat resistance and low birefringence are further improved.
- a phenyl group is preferred.
- R 13 may be an aryl group having 6 to 14 carbon atoms having a substituent, wherein the substituent is a halogen atom, hydroxyl group, nitro group, alkoxy group having 1 to 12 carbon atoms, or 1 carbon atom.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- alkoxy group having 1 to 12 carbon atoms as a substituent, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms is more preferable.
- substituent having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, and 2-ethylhexyl. Examples thereof include an oxy group, a 1-decyloxy group, and a 1-dodecyloxy group.
- alkyl group having 1 to 12 carbon atoms as a substituent examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, a nonyl group, Examples thereof include decanyl group, lauryl group, etc.
- methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t- A butyl group and 2-ethylhexyl group are preferable, and a methyl group is more preferable.
- the arylalkyl group having 7 to 14 carbon atoms as a substituent includes a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a 6-phenylhexyl group, and an 8-phenyloctyl group.
- benzyl, 1-phenylethyl, 2-phenylethyl, and 3-phenylpropyl are preferred.
- the aryl group having 6 to 14 carbon atoms having a substituent is preferably a phenyl group having a substituent or a naphthyl group having a substituent.
- the aryl group having 6 to 14 carbon atoms having a substituent include 2,4,6-tribromophenyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 4-bromophenyl group, 2-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 4-ethylphenyl group, 2-methoxyphenyl group, 4-methoxyphenyl group, 2-nitrophenyl group, 4-nitrophenyl group, 2, Examples include 4,6-trimethylphenyl group. Among these, 2,4,6-tribromophenyl group is preferable in terms of imparting flame retardancy.
- Examples of the cycloalkyl group having 3 to 12 carbon atoms for R 13 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, a bicyclooctyl group, a tricyclododecyl group, An isobornyl group, an adamantyl group, a tetracyclododecyl group and the like can be mentioned.
- a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are preferable, and weather resistance, transparency, etc.
- a cyclohexyl group is more preferable from the viewpoint of further improving the optical properties and providing low water absorption.
- the alkyl group having 1 to 18 carbon atoms in R 13 is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.
- Examples of the alkyl group having 1 to 18 carbon atoms in R 13 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n- Examples include hexyl group, n-octyl group, n-dodecyl group, n-octadecyl group, 2-ethylhexyl group, 1-decyl group, 1-dodecyl group, etc. Among these, optical properties such as weather resistance and transparency Therefore, methyl group, ethyl group and isopropyl group are preferable.
- R 13 may be an alkyl group having 1 to 12 carbon atoms having a substituent, wherein the substituent is a group consisting of a halogen atom, a hydroxyl group, a nitro group, and an alkoxy group having 1 to 12 carbon atoms ( Group A).
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- alkoxy group having 1 to 12 carbon atoms as a substituent, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms is more preferable.
- substituent having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, and 2-ethylhexyl. Examples thereof include an oxy group, a 1-decyloxy group, and a 1-dodecyloxy group.
- examples of the alkyl group having 1 to 12 carbon atoms having a substituent include a dichloromethyl group, a trichloromethyl group, a trifluoroethyl group, and a hydroxyethyl group, and among these, a trifluoroethyl group is preferable. It is.
- maleimide unit represented by the general formula (5) examples include an unsubstituted maleimide unit, an N-methylmaleimide unit, an N-phenylmaleimide unit, an N-cyclohexylmaleimide unit, and an N-benzylmaleimide unit.
- maleimide unit Only one type of maleimide unit may be used, or two or more types may be used in combination.
- the content of the maleimide units is not particularly limited, for example, can be appropriately determined in consideration of the structure and the like of R 13.
- the content of maleimide units is preferably 1.0% by weight or more, more preferably 1% by weight to 99% by weight, even more preferably 1% by weight to 80% by weight, based on the total amount of the maleimide acrylic resin.
- the optical isotropy tends to decrease.
- the (meth) acrylic acid ester unit possessed by the maleimide acrylic resin the same units as those represented by the general formula (2) described later for the glutarimide acrylic resin can be used.
- As said (meth) acrylic acid ester unit only 1 type may be used and 2 or more types may be used together.
- the maleimide acrylic resin preferably further has a unit represented by the following general formula (3) in order to adjust optical characteristics.
- 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 maleimide acrylic resin may contain only a single type as a unit represented by the general formula (3), or may contain a plurality of units in which either or both of R 7 and R 8 are different. May be.
- the content of the unit represented by the general formula (3) is not particularly limited, but is preferably 0 to 40% by weight, more preferably 0 to 20% by weight, based on the total amount of the maleimide acrylic resin. ⁇ 15% by weight is particularly preferred.
- the maleimide acrylic resin may further contain other units other than the units described above, if necessary.
- the weight average molecular weight of the maleimide acrylic resin 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, shaping
- the maleimide acrylic resin can be obtained, for example, by the following polymerization step. Moreover, it can refine
- the maleimide acrylic resin can be obtained by polymerizing a monomer group selected from the monomers of the respective structural units.
- a resin composition ratio of the resulting maleimide acrylic resin can be obtained by combining monomers that are close to each other and / or monomers that are highly copolymerizable. Is desirable because it can be easily controlled based on the raw material composition ratio charged into the reaction solution.
- a) a monomer having low reactivity does not react sufficiently and remains as an unreacted monomer
- b) a resulting resin of a maleimide acrylic resin Problems such as difficulty in predicting the composition ratio may occur. In particular, if unreacted monomer remains, there are problems such as deterioration of characteristics of maleimide acrylic resin such as transparency and light resistance.
- maleimide acrylic resin for example, generally used polymerization methods such as cast polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, living radical polymerization, and anionic polymerization can be used.
- polymerization methods such as cast polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, living radical polymerization, and anionic polymerization can be used.
- cast polymerization, solution polymerization, suspension polymerization, and cast polymerization without using suspending agents and emulsifiers It is desirable to use solution polymerization.
- the polymerization mode for example, either a batch polymerization method or a continuous polymerization method can be used.
- the batch polymerization method is desirable from the viewpoint of simple polymerization operation, and the continuous polymerization method is desirably used from the viewpoint of obtaining a polymer having a more uniform composition.
- the temperature and polymerization time at the time of the polymerization reaction can be appropriately adjusted according to the type and ratio of the monomer used.
- the polymerization temperature is 0 to 150 ° C.
- the polymerization time is 0.5 to 24 hours
- the polymerization temperature is 40 to 150 ° C.
- the polymerization time is 1 to 15 hours.
- a polymerization initiator may be added as necessary.
- any initiator generally used in radical polymerization can be used.
- Organic peroxides such as oxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, lauroyl peroxide; 2,2′-azobis (isobutyronitrile), 1,1 ′ -Azo compounds such as azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate; and the like.
- These polymerization initiators may be used alone or in combination of two or more.
- the amount of the polymerization initiator used may be appropriately set according to the combination of monomers and reaction conditions, and is not particularly limited, but is preferably used in the range of 0.005 to 5% by mass.
- molecular weight regulator used as necessary in the polymerization reaction, any one used in general radical polymerization is used.
- mercaptan compounds such as butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-ethylhexyl thioglycolate are particularly preferable. It is mentioned as preferable.
- These molecular weight regulators are added in a concentration range such that the molecular weight is controlled within the aforementioned range.
- examples of the polymerization solvent include aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as tetrahydrofuran; Can be mentioned. These solvents may be used alone or in combination of two or more. If the boiling point of the solvent to be used is too high, the residual volatile content of the finally obtained maleimide acrylic resin will increase, so a solvent having a boiling point of 50 to 200 ° C. is preferred.
- an organic phosphorus compound or an organic acid may be added as necessary.
- side reactions are suppressed and / or the amount of unreacted N-substituted maleimide is reduced, for example, and coloring during molding of the resulting maleimide acrylic resin is reduced. There is a case.
- organic phosphorus compound examples include alkyl (aryl) phosphonous acid and diesters or monoesters thereof; dialkyl (aryl) phosphinic acid and esters thereof; alkyl (aryl) phosphonic acids and diesters or monoesters thereof; alkyl Phosphinic acid and esters thereof; phosphorous acid diester, phosphorous acid monoester, phosphorous acid triester; phosphoric acid diester, phosphoric acid monoester, phosphoric acid triester and the like.
- organophosphorus compounds may be used alone or in combination of two or more.
- the amount of the organophosphorus compound used is preferably 0.001 to 5.0 mass% with respect to the total amount of monomers.
- organic acids examples include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, cyclohexanecarboxylic acid, phthalic acid , Isophthalic acid, terephthalic acid and the like and acid anhydrides thereof. These organic acids may be used alone or in combination of two or more. The amount of the organic acid used is preferably 0.001 to 1.0% by mass with respect to the total amount of monomers.
- the polymer concentration is preferably 10 to 95% by mass, and preferably 75% by mass or less, from the viewpoint of heat removal during polymerization, in order to make the viscosity of the reaction solution appropriate. More preferred is 60% by mass or less. If it is 10 mass% or more, adjustment of molecular weight and molecular weight distribution is easy. If it is 95 mass% or less, a high molecular weight polymer can be obtained.
- a polymerization solvent can be appropriately added.
- heat removal can be controlled and generation of microgel in the reaction solution can be suppressed.
- the form of appropriately adding the polymerization solvent to the polymerization reaction solution is not particularly limited, and for example, the polymerization solvent may be added continuously or the polymerization solvent may be added intermittently.
- the concentration of the maleimide acrylic resin produced in the polymerization reaction solution in this way, the temperature uniformity inside the reactor can be improved and the gelation of the reaction solution can be more sufficiently suppressed.
- the polymerization solvent to be added may be, for example, the same type of solvent used during the initial charging of the polymerization reaction or a different type of solvent, but the solvent used during the initial charging of the polymerization reaction. It is preferable to use the same type of solvent.
- the polymerization solvent to be added may be only one kind of single solvent or two or more kinds of mixed solvents.
- the maleimide acrylic resin is polymerized by the suspension polymerization method, it is carried out in an aqueous medium, and a suspending agent and, if necessary, a suspending aid are added.
- the suspending agent include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, polyoxyethylene-polyoxypropylene block copolymer, polyethylene oxide, and polyacrylamide, and inorganic substances such as calcium phosphate and magnesium pyrophosphate.
- the water-soluble polymer is preferably used in an amount of 0.01 to 2% by mass relative to the total amount of monomers, and the inorganic substance is preferably used in an amount of 0.01 to 2% by mass with respect to the total amount of monomers. preferable.
- Suspension aids include low molecular surfactants such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and the like, boric acid, sodium carbonate, phosphoric acid Water-soluble inorganic salts such as disodium hydrogen, sodium dihydrogen phosphate, and sodium sulfate. As the suspension aid, disodium hydrogen phosphate and sodium dodecylbenzenesulfonate are preferable. Moreover, when using an inorganic substance as a suspending agent, it is preferable to use a suspending aid. The suspension aid is preferably used in an amount of 0.001 to 2% by mass based on 100% by mass of the monomer.
- the devolatilization step means a step of removing a volatile component such as a polymerization solvent, a residual monomer, and moisture under reduced pressure heating conditions as necessary. If this removal treatment is insufficient, the residual volatile content of the obtained maleimide acrylic resin increases, and coloring due to alteration during molding, or molding defects such as bubbles or silver streaks may occur.
- the residual volatile content is 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.4% by mass or less, and still more preferably 0.3% by mass or less, based on 100% by mass of the maleimide acrylic resin. is there.
- the amount of residual volatile matter corresponds to the total amount of residual monomer, polymerization solvent, and side reaction product that did not react during the polymerization reaction described above.
- Examples of the apparatus used in the devolatilization step include a devolatilizer composed of a heat exchanger and a devolatilization tank; an extruder with a vent; an apparatus in which the devolatilizer and the extruder are arranged in series.
- a devolatilizer composed of a heat exchanger and a devolatilization tank
- an extruder with a vent an apparatus in which the devolatilizer and the extruder are arranged in series.
- an extruder with a vent one or a plurality of vents may be used, but it is preferable to have a plurality of vents.
- the temperature in the devolatilization step is preferably 150 to 350 ° C, more preferably 170 to 330 ° C, and still more preferably 200 to 300 ° C. If this temperature is less than 150 ° C., the residual volatile matter may increase. Conversely, when the temperature exceeds 350 ° C., the obtained maleimide acrylic resin may be colored or decomposed.
- the pressure in the devolatilization step is preferably 931 to 1.33 hPa (700 to 1 mmHg), more preferably 800 to 13.3 hPa (600 to 10 mmHg), and still more preferably 667 to 20.0 hPa (500 to 15 mmHg).
- this pressure exceeds 931 hPa (700 mmHg)
- volatile matter may remain easily.
- the pressure is less than 1.33 hPa (1 mmHg), industrial implementation may be difficult.
- the treatment time is appropriately selected depending on the amount of residual volatile matter, but a shorter time is preferable in order to suppress coloring and decomposition of the obtained maleimide acrylic resin.
- the treatment is performed at a high treatment temperature for a long time, but there is a problem that coloring and decomposition are likely to occur.
- the monomer in question is, for example, an aromatic hydrocarbon solvent, a hydrocarbon solvent, or an alcohol solvent in the polymerization solution.
- a homogenizer (emulsification / dispersion) treatment is performed, and the unreacted monomer can be separated from the polymerization reaction solution by a pretreatment such as liquid-liquid extraction or solid-liquid extraction.
- a pretreatment such as liquid-liquid extraction or solid-liquid extraction.
- the glutarimide acrylic resin 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 may contain only a single type as a glutarimide unit, or a plurality of different ones or all of R 1 , R 2 , and R 3 in the general formula (1). The type 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 the glutarimide unit is not particularly limited, and can be appropriately determined in consideration of, for example, the structure of R 3 .
- 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. Further preferred.
- the content of the glutarimide unit is less than the above range, the resulting glutarimide acrylic resin tends to have insufficient heat resistance or its transparency may be impaired.
- the amount is larger than the above range, the heat resistance and melt viscosity are unnecessarily high, and the moldability tends to deteriorate, the mechanical strength of the molded article becomes extremely low, or the transparency tends to be impaired. There is.
- 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 may contain only a single type as a (meth) acrylic acid ester unit, or any or all of R 4 , R 5 and R 6 in the above general formula (2) A plurality of different types may be included.
- the glutarimide acrylic resin 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 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, and more preferably 0 to 15% by weight based on the total amount of the glutarimide acrylic resin. Is particularly preferred. When the content of the aromatic vinyl unit is larger than the above range, sufficient heat resistance of the glutarimide acrylic resin cannot be obtained.
- the glutarimide acrylic resin does not contain an aromatic vinyl unit from the viewpoints of improving bending resistance and transparency, reducing fisheye, and further improving solvent resistance or weather resistance.
- the glutarimide acrylic resin 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 contained in the glutarimide acrylic resin by random copolymerization or by graft copolymerization.
- These other units may be introduced by copolymerizing a monomer constituting the unit with a resin which is a raw material for producing a glutarimide acrylic resin. Further, when the imidization reaction is performed, these other units may be by-produced and included in the glutarimide acrylic resin.
- the weight average molecular weight of the glutarimide acrylic resin 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, shaping
- the glass transition temperature of the glutarimide acrylic resin is preferably 120 ° C. or higher so that the molded product exhibits good heat resistance. More preferably, it is 125 ° C. or higher. When the glass transition temperature is lower than the above range, the molded product cannot exhibit sufficient heat resistance.
- (meth) acrylic acid ester polymer is produced by polymerizing (meth) acrylic acid ester.
- glutarimide acrylic resin 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. By using multiple types of (meth) acrylic acid esters, it is possible to include multiple types of (meth) acrylic acid ester units in the finally obtained glutarimide acrylic resin.
- 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, 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.
- 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 is 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 that generate ammonia or primary amines by heating such as urea, 1,3-dimethylurea, 1,3-diethylurea, 1,3-dipropylurea, 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 can be adjusted by adjusting the ratio of the imidizing agent added.
- 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 can be adjusted in a desired range.
- the acid value of the glutarimide acrylic resin 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 amount of the esterifying agent used is within the above range, the acid value of the glutarimide acrylic resin can be adjusted to an appropriate 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 instead of an extruder, for example, a horizontal biaxial reactor such as Violac manufactured by Sumitomo Heavy Industries, Ltd., a vertical biaxial agitation tank such as Super Blend, etc.
- a high-viscosity reactor can also be suitably used.
- 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 in which the content of glutarimide units is controlled to a specific value can be easily produced.
- maleimide acrylic resin and glutarimide acrylic resin are used in combination
- the content of maleimide acrylic resin can be appropriately determined according to the desired physical properties of the optical resin composition.
- maleimide acrylic resin 1 to 99 parts by weight with respect to a total of 100 parts by weight of the glutarimide acrylic resin.
- the amount is more preferably 1 to 80 parts by weight, still more preferably 5 to 70 parts by weight.
- thermoplastic resin As the matrix resin, both the orientation birefringence and the photoelastic constant can be reduced, and the optical resin composition having high optical isotropy and It is an essential ingredient to do. Furthermore, even a thick molded body such as an injection molded body has excellent transparency and color tone, and improves mechanical strength such as impact resistance.
- the crosslinked structure-containing polymer preferably includes a multistage polymer and a multilayer structure polymer.
- a multi-stage polymer is a polymer obtained by polymerizing a hard monomer mixture in the presence of cross-linked polymer-containing particles, and a multi-layer polymer is a cross-linked polymer layer and a hard polymer layer. It is a polymer having. Both refer to basically the same polymer, but the former specifies the polymer mainly by the production method, and the latter mainly specifies the polymer by the layer structure. The following explanation is mainly given for the latter, but the same applies to the former.
- thermoplastic resin In order to make the optical resin composition optically isotropic, it is important to reduce the orientation birefringence and the photoelastic birefringence. Therefore, here, the concepts of “orientation birefringence” and “photoelastic birefringence” of the thermoplastic resin, the crosslinked structure-containing polymer, the optical resin composition, and the injection molded article of the present invention will be described first.
- orientation of the molded body obtained from the optical resin composition of the present invention Birefringence is affected.
- the polymer is hardly oriented in the injection-molded product and the birefringence is sufficiently small, there is no need to consider so much about the orientation birefringence of the crosslinked structure-containing polymer.
- orientation birefringence of optical resin composition was evaluated by preparing an injection molded article. 1. Oriented birefringence at the center of the injection-molded product Cut out a test piece of 15 mm ⁇ 90 mm (cut out so that 90 mm is in the long side direction) from the center of a flat plate (thickness 2 mm, 15 cm ⁇ 10 cm) obtained by injection molding, Birefringence is measured with a birefringence measuring apparatus. This part is a part where the polymer is relatively difficult to be oriented in one direction. 2.
- the crosslinked structure-containing polymer 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 molded body is cooled to 23 ° C., the sample central portion is sampled, birefringence is measured, and a sign of 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. First, 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. By comparing the photoelastic constants, it is possible to evaluate the birefringence of the polymer when stress is applied.
- the body is an injection-molded body or a press-molded sheet.
- ⁇ Photoelastic constant of optical resin composition> Similar to the above-described measuring method of orientation birefringence, a test piece of 15 mm ⁇ 90 mm (cut out so that 90 mm is in the long side direction) from the center of a flat plate (thickness 2 mm, 15 cm ⁇ 10 cm) obtained by injection molding is obtained. cut. Next, at 23 ° C., one of the long sides of the test piece was fixed, and the other was obtained by measuring the birefringence at each application while applying a load of 0.5 kgf from no load to 4 kgf. From the result, the amount of change in birefringence due to unit stress is calculated, and the photoelastic constant is calculated.
- a press-molded sheet is prepared in the same manner as the above-mentioned “Orientation birefringence”, and the photoelastic constant is obtained by measuring this birefringence.
- a press-molded sheet having a film thickness of 500 ⁇ m is produced, and a 25 mm ⁇ 90 mm test piece is cut out from the center of the obtained press-molded sheet.
- the measurement conditions and the calculation method are the same as in the case of the above-described injection molded body.
- photoelastic birefringence is a characteristic intrinsic to the polymer structure
- the photoelastic constant of the thermoplastic resin when the photoelastic constant of the thermoplastic resin is large, the photoelastic constant of the polymer containing a crosslinked structure is different from the photoelastic constant of the thermoplastic resin. Must be a sign.
- the crosslinked structure-containing polymer has a photoelastic constant different from that of the thermoplastic resin and is large, an optical resin composition comprising the thermoplastic resin and the crosslinked structure-containing polymer, and a molded article thereof
- the amount of the cross-linked structure-containing polymer required to reduce the photoelastic birefringence is small.
- the photoelastic constant of the thermoplastic resin alloy can be reduced by using two types of thermoplastic resins having different signs of photoelastic birefringence, cross-linking for reducing photoelastic birefringence is possible.
- the required amount of structure-containing polymer is even smaller.
- orientation birefringence As described above, in a molded article made of the optical resin composition of the present invention, particularly an injection molded article, 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 large.
- refraction is not a problem in practice, it is not particularly necessary to consider orientation birefringence in the design of the crosslinked structure-containing polymer.
- the orientation birefringence in the obtained molded article is a practical problem, the orientation birefringence of the crosslinked structure-containing polymer must be different from the orientation birefringence of the thermoplastic resin. .
- the crosslinked structure-containing polymer of the present invention may be a polymer having a weight average molecular weight of more than 5000, preferably 10,000 or more, more preferably 20000 or more.
- 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 cross-linked structure-containing polymer is a multi-layered polymer having a cross-linked polymer layer, the mechanical strength, particularly impact resistance, of the optical resin composition can be improved.
- the crosslinked structure-containing polymer preferably has a hard polymer layer from the viewpoint of heat resistance.
- Such a multilayer structure polymer is generally expressed as a graft copolymer or a core-shell polymer, but the crosslinked structure-containing polymer of the present invention also includes these.
- the crosslinked structure-containing polymer has a crosslinked polymer layer and a hard polymer layer, and the size per crosslinked structure-containing polymer is designed to be fine particles of submicron size.
- the matrix-shaped thermoplastic resin has a sea-island structure in which the crosslinked structure-containing polymer is dispersed in a submicron size.
- the cross-linked structure-containing polymer is aggregated to hardly deteriorate transparency and cause foreign matters such as fish eyes.
- the dispersibility in the matrix can be controlled, so that the cross-linked structure-containing polymer can be dispersed in the matrix without having to be completely compatible.
- the crosslinked structure-containing polymer is preferably a multilayer structure polymer (graft copolymer, core-shell polymer) having a soft crosslinked polymer layer and a hard polymer layer.
- a method of adding a soft polymer in order to improve the mechanical strength is also mentioned as a method.
- the matrix resin here, a thermoplastic resin
- the soft polymer are mixed homogeneously, and the resulting molded product is obtained.
- the heat resistance of the resin is lowered.
- the soft cross-linked polymer layer is “island” in the molded product, and a thermoplastic resin. Since the hard polymer layer has a discontinuous sea-island structure that becomes the “sea”, the mechanical strength can be improved and the heat resistance can hardly be lowered. Moreover, since a soft crosslinked polymer usually has a composition different from that of a matrix (thermoplastic resin), it is difficult to uniformly disperse the matrix in a matrix. Cause the defects of the steel, and further decreases the mechanical strength. However, in the case of a multilayer structure polymer having both a soft cross-linked polymer layer and a hard polymer layer, the soft cross-linked 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 optical resin composition containing the crosslinked structure-containing polymer and the heat resistance of the molded product are lowered, or the crosslinked resin is produced when the crosslinked structure-containing polymer is produced. There arises a problem that the structure-containing polymer 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 may be “soft” or “hard”.
- the 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 crosslinked structure-containing polymer is an index representing the weight ratio of the grafted hard polymer layer to the crosslinked polymer layer when 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 crosslinked structure-containing polymer is likely to aggregate in the molded product, which may reduce transparency, cause of foreign matter, and mechanical strength.
- a polymer also referred to as a free polymer
- a free polymer that is not bonded to the crosslinked polymer layer (also referred to as a free polymer) may be present in a part of the hard polymer layer. To include.
- cross-linked polymer layer (Description of cross-linked polymer layer)
- the crosslinked polymer layer in the case where the crosslinked structure-containing polymer is a graft copolymer will be described.
- the role of the “soft” crosslinked polymer layer is to (1) improve the mechanical strength such as impact resistance by being uniformly dispersed in the thermoplastic resin, and (2) have a thermoplastic resin. It has the role of canceling the birefringence, and improving the optical isotropy of the optical resin composition and the molded product of the present invention.
- (1) it can be achieved by appropriately selecting and polymerizing monomers so that the glass transition temperature is less than 20 ° C.
- a rubber made of an acrylic monomer that is, an acrylic rubber is preferable.
- orientation birefringence will be described.
- injection molding the optical resin composition of the present invention depending on the injection conditions, mold shape, gate shape, etc., not only the thermoplastic resin serving as the matrix component, but also the "soft" crosslinked polymer, It was discovered this time that orientation birefringence occurs.
- the degree to which the crosslinked polymer exhibits orientation birefringence depends on the degree of crosslinking, although it depends on the polymer composition constituting the crosslinked polymer. When the degree of cross-linking is high, the cross-linked polymer layer is not easily deformed (or difficult to be oriented) even under molding conditions in which the resin is easily oriented, and orientation birefringence hardly occurs.
- the cross-linked polymer when the degree of cross-linking is low, the cross-linked polymer is also easily oriented depending on the molding conditions, resulting in orientation birefringence.
- thermoplastic resin serving as the matrix is an acrylic resin
- the orientation birefringence of the crosslinked polymer needs to be positive with a different sign because the orientation birefringence of the acrylic resin is negative.
- the crosslinked polymer layer of the present invention is preferably formed by polymerizing a monomer mixture containing a monomer represented by the following general formula (4) and a polyfunctional monomer. .
- 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 monomer represented by formula (4) is preferably a (meth) acrylic monomer in formula (4), wherein R 9 is a substituted or unsubstituted 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 It is more preferable that it is a (meth) acrylic-type monomer which has.
- l is an integer of 1 to 2
- n is an integer of 0 to 2
- a (meth) acrylic monomer
- examples of the monomer having an alicyclic group include dicyclopentanyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate.
- examples of the monomer having an aromatic group include benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like.
- Examples of the monomer having a heterocyclic structure include pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.
- (meth) acrylic monomers represented by the formula (4) from the viewpoint of orientation birefringence and transparency, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) acrylic acid Phenoxyethyl is preferred.
- benzyl (meth) acrylate is the most from the viewpoint of optical isotropy, canceling the orientation birefringence of the thermoplastic resin, and reducing transparency. preferable. Of these, benzyl methacrylate is preferred because it has a higher glass transition temperature in order to increase heat resistance. On the other hand, when strength development is required, benzyl acrylate is preferred because of its low glass transition temperature.
- thermoplastic resin is an acrylic resin
- the orientation birefringence is negative
- benzyl methacrylate having a relatively large positive photoelastic constant
- the amount of benzyl methacrylate used can be reduced.
- the degree of freedom in designing the optical resin composition is increased, for example, the amount of the crosslinked structure-containing polymer used is small.
- acrylic resin is negative in both orientation birefringence / photoelastic birefringence
- benzyl methacrylate is oriented birefringence.
- both photoelastic birefringence is positive, it is possible to reduce the photoelastic birefringence at the same time while reducing the orientation birefringence of the optical resin composition and the molded article.
- the crosslinked polymer layer having the monomer represented by the formula (4) as a structural unit is represented by the formula (4).
- 1 to 100% by weight of the monomer represented, 99 to 0% by weight of another monofunctional monomer copolymerizable therewith and 0.05 to 10 parts by weight of a polyfunctional monomer (formula (4 ) And other monofunctional monomers copolymerizable therewith are preferably polymerized with respect to 100 parts by weight.
- the use amount of the monomer represented by the formula (4) is 100% by weight of the total amount of the monomer represented by the formula (4) and other monofunctional monomers copolymerizable therewith.
- the cross-linked polymer layer may be one obtained by mixing all the monomers and polymerized in one step, or may be obtained 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 monofunctional monomers that can be copolymerized with the monomer represented by the formula (4) include methacrylic acid esters, and methacrylic acid alkyl esters are preferable from the viewpoint of polymerizability and cost.
- an alkyl group having 1 to 12 carbon atoms is 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.
- Acrylic acid esters can also be suitably used. From the viewpoints of polymerization reactivity and cost, acrylic acid alkyl esters are preferable. Specifically, alkyl groups having 1 to 12 carbon atoms are preferable. However, it may be 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.
- maleic anhydride citraconic anhydride, dimethyl maleic anhydride, dichloromaleic anhydride, bromomaleic anhydride, dibromomaleic anhydride, phenylmaleic anhydride, Unsubstituted and / or substituted maleic anhydrides such as diphenylmaleic anhydride, vinyl halides such as vinyl chloride and vinyl bromide, (meth) acrylamides such as acrylamide, methacrylamide and N-methylolacrylamide, acrylonitrile, methacrylonitrile Vinyl cyanides such as vinyl formate, vinyl acetate such as 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 Acrylic acid and its salts such as sodium acrylate
- the crosslinked structure-containing polymer of the present invention may have one or more different crosslinked polymer layers in addition to the above-mentioned crosslinked polymer layer.
- (1) can be achieved by appropriately selecting and polymerizing monomers so that the polymer is easily compatible with the matrix component.
- the photoelasticity of the molded body This can be achieved by making the photoelastic constant of the hard polymer different from that of the matrix (thermoplastic resin) so that the constant becomes extremely small.
- the orientation birefringence in the injection-molded product is relatively large, which is a problem, not only the photoelastic constant of the molded product, but also the light of the hard polymer so that both orientation birefringence becomes extremely small. This can be achieved by making both the elastic constant and the orientation birefringence different from the matrix (thermoplastic resin).
- the effect of canceling the birefringence of the thermoplastic resin as the matrix is larger in the “hard” polymer layer, and the effect of the polymer layer having a crosslinked structure is smaller. Is a point. Any of the cross-linked polymer layer and the hard polymer layer of the cross-linked structure-containing polymer, or both of them may be provided with a function of canceling the birefringence of the thermoplastic resin without limiting the layer.
- the polymer layer is most preferred. The reason is that the polymer of the crosslinked structure-containing polymer is oriented in the direction in which the polymer chain of the matrix is oriented by an external force when the polymer is oriented by molding the matrix (thermoplastic resin) or when stress is applied.
- birefringence can be canceled by aligning the 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 that does not have a crosslinked structure, and even more preferably an outer layer of a crosslinked structure-containing polymer that has a crosslinked structure that is easily in direct contact with the matrix. There is no “hard” polymer layer.
- the photoelastic constants of the thermoplastic resin and the crosslinked structure-containing polymer are different. What is necessary is just to select so that it may become a code
- 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 monomer species used for the hard polymer layer of the crosslinked structure-containing polymer and suitable for canceling the orientation birefringence of the thermoplastic resin the orientation birefringence of each of the thermoplastic resin and the crosslinked structure-containing polymer is different.
- 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 thermoplastic resin is an acrylic resin
- both the orientation birefringence and the photoelastic constant are often negative, so a crosslinked structure-containing polymer (especially a hard polymer layer of the outer layer).
- the monomer represented by the above formula (4) is included in the structural unit.
- the monomer represented by the above formula (4) in the hard polymer layer may be the same as or different from the monomer represented by the formula (4) in the crosslinked polymer layer. May be used.
- the monomer represented by formula (4) is a (meth) acrylic monomer in formula (4), wherein R 9 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 carbon atom.
- R 9 is a hydrogen atom or a substituted or unsubstituted 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 It is more preferable that it is a (meth) acrylic-type monomer which has.
- l is an integer of 1 to 2
- n is an integer of 0 to 2
- a (meth) acrylic 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 thermoplastic resins, and moldability. Furthermore, benzyl methacrylate is preferable in terms of heat resistance because of its high glass transition temperature.
- the thermoplastic resin 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 optical resin composition is increased, for example, the amount of the crosslinked structure-containing polymer used is small.
- the hard polymer layer in the unit is composed of 1 to 99% by weight of the monomer represented by the formula (4), 99 to 1% by weight of other monofunctional monomers copolymerizable therewith, and polyfunctionality. 0 to 2.0 parts by weight of monomer (based on 100 parts by weight of the total amount of the monomer represented by the formula (4) and other monofunctional monomers copolymerizable therewith) Is preferred.
- 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 monofunctional monomers that can be copolymerized with the monomer represented by the formula (4) include methacrylic acid esters, and methacrylic acid alkyl esters are preferable from the viewpoint of polymerizability and cost.
- an alkyl group having 1 to 12 carbon atoms is 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.
- Acrylic acid esters can also be suitably used. From the viewpoints of polymerization reactivity and cost, acrylic acid alkyl esters are preferable. Specifically, alkyl groups having 1 to 12 carbon atoms are preferable. However, it may be 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.
- maleic anhydride citraconic anhydride, dimethyl maleic anhydride, dichloromaleic anhydride, bromomaleic anhydride, dibromomaleic anhydride, phenylmaleic anhydride, Unsubstituted and / or substituted maleic anhydrides such as diphenylmaleic anhydride, vinyl halides such as vinyl chloride and vinyl bromide, (meth) acrylamides such as acrylamide, methacrylamide and N-methylolacrylamide, acrylonitrile, methacrylonitrile Vinyl cyanides such as vinyl formate, vinyl acetate such as 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 Acrylic acid and its salts such as sodium acrylate
- 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 methyl methacrylate in terms of compatibility with acrylic thermoplastic resin, methyl acrylate, ethyl acrylate, or in terms of suppressing zipper depolymerization, or It is preferable to use n-butyl acrylate.
- the use amount of the monomer represented by the formula (4) is 100% by weight of the total amount of the monomer represented by the formula (4) and other monofunctional monomers copolymerizable therewith. It is preferably 1 to 99% by weight, more preferably 5 to 70% by weight, and most preferably 5 to 50% by weight.
- (Meth) acrylic acid and / or a salt thereof is preferably used from the viewpoints of improved thermal stability during molding, improved solvent resistance, and improved dispersibility of the crosslinked structure-containing polymer.
- the salt of (meth) acrylic acid include sodium (meth) acrylate, calcium (meth) acrylate, magnesium (meth) acrylate, and ammonium (meth) acrylate.
- the monomer represented by the formula (4), (meth) acrylic acid and / or a salt thereof and other monofunctional copolymerizable therewith It is preferable that 0.1 to 30% by weight is contained in the total amount of the functional monomers of 100% by weight, more preferably 0.1 to 20% by weight, still more preferably 0.1 to 15% by weight, and 0.1 to 10%. % By weight is more preferred, and 0.1-7% by weight is most preferred.
- (meth) acrylic acid Due to the presence of (meth) acrylic acid and / or its salt-derived structure in the hard polymer layer, (meth) acrylic acid present next to the carboxyl group of (meth) acrylic acid and (meth) acrylic acid
- the alkyl group of the derivative is cyclized by dealkyl alcoholization at the time of molding to take an acid anhydride structure. For example, if (meth) acrylic acid is next to methyl (meth) acrylate, a demethanol reaction occurs, resulting in an acid anhydride structure. Further, if (meth) acrylic acid is next to benzyl (meth) acrylate, a debenzyl alcohol reaction occurs, resulting in an acid anhydride structure.
- the free acid may be in the form of a free acid or a salt such as a magnesium salt, a calcium salt, or an ammonium salt.
- the rate at which (meth) acrylic acid becomes an anhydride structure changes depending on the thermal history such as processing conditions, and not all (meth) acrylic acid need have an acid anhydride structure, and the cyclization rate is a necessary characteristic. Any adjustment may be made accordingly.
- 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 the polyfunctional monomer used in the hard polymer layer (based on 100 parts by weight of the total amount of the monomer represented by the formula (4) and other monofunctional monomers copolymerizable therewith) ) Is preferably from 0 to 2.0 parts by weight, more preferably from 0 to 1.0 parts by weight, still more preferably from 0 to 0.5 parts by weight, from the viewpoint of optical isotropy and dispersibility. 0.04 parts by weight is even more preferred and 0 parts by weight is most preferred.
- the cross-linked structure-containing polymer 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 crosslinked structure-containing polymer may have one or more different hard polymer layers in addition to the hard polymer layer.
- a preferred embodiment of the crosslinked structure-containing polymer has a soft inner layer and a hard outer layer, and the inner layer has a crosslinked polymer layer having the monomer represented by (4) as a constituent unit.
- the form which has the hard polymer layer in which the said outer layer has the monomer represented by the said Formula (4) in a structural unit can be mentioned. This form is preferable from the viewpoint of productivity.
- the crosslinked structure-containing polymer has a hard inner layer, a soft intermediate layer and a hard outer layer, and the inner layer is composed of at least one hard polymer layer, It has a soft polymer layer which consists of a crosslinked polymer layer which has a monomer denoted by the above (4) in a structural unit, and the above-mentioned outer layer has a monomer denoted by the above-mentioned formula (4) in a structural unit
- the form which has a hard polymer layer can be mentioned, This form may have a soft innermost layer further. 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 hardness of the innermost layer hard polymer is 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 comprising 0 to 20% by weight of other monofunctional monomers copolymerizable with methacrylic acid esters, acrylic acid esters, and aromatic vinyl monomers.
- the crosslinked structure-containing polymer includes, for example, a soft inner layer having a crosslinked polymer layer having the monomer represented by the formula (4) as a constituent unit, and the monomer represented by the formula (4).
- a layer structure in which a soft inner layer is completely covered with a hard polymer of an outer layer is a multilayer structure including a hard outer layer having a polymer layer having a structural unit as a structural unit.
- the amount of the hard polymer for forming the layer structure may be insufficient.
- the volume average particle diameter of the crosslinked structure-containing polymer to the crosslinked polymer layer is preferably 20 to 450 nm, more preferably 40 to 350 nm, still more preferably 80 to 300 nm, and most preferably 80 to 250 nm. If it is less than 20 nm, impact resistance may deteriorate. On the other hand, if it exceeds 450 nm, the transparency may decrease.
- 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 crosslinked structure-containing polymer to the crosslinked polymer layer specifically refers to the volume average particle diameter of the particles from the center of the crosslinked structure-containing polymer particle to the crosslinked polymer layer.
- the volume average particle diameter up to the crosslinked polymer layer located on the outermost side with respect to the center is meant.
- the content of the crosslinked polymer in the crosslinked structure-containing polymer is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, and more preferably 30 to 60% by weight when the crosslinked structure-containing polymer is 100% by weight. Is more preferable, and 35 to 55% by weight is most preferable. If it is less than 10% by weight, mechanical strength such as impact resistance of the obtained optical resin composition may be lowered. On the other hand, if it exceeds 90% by weight, the dispersibility of the crosslinked structure-containing polymer is impaired, the smoothness of the surface of the molded article 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 crosslinked structure-containing polymer 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.
- the emulsion polymerization method is particularly preferred for the polymerization of the crosslinked structure-containing polymer.
- the cross-linked structure-containing polymer is preferably obtained by multi-stage polymerization.
- the cross-linked polymer-containing particles having the monomer represented by the formula (4) as a constituent unit are used.
- a multistage polymerization graft obtained by polymerizing a monomer mixture containing the monomer represented by the formula (4) and another monofunctional monomer copolymerizable therewith A copolymer can be preferably used.
- Monomer represented by the formula (4) by polymerization of a monomer mixture containing the monomer represented by the formula (4) and another monofunctional monomer copolymerizable therewith. Is formed as a structural unit.
- Other monofunctional monomers that can be copolymerized 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 monofunctional monomers copolymerizable with the monomer represented by formula (4).
- the polyfunctional monomer and the blending amount thereof are also the same as those described above, and can be preferably used in the same manner.
- the crosslinked polymer-containing particle having a monomer represented by the formula (4) as a constituent unit is a multistage polymer having a crosslinked polymer having at least a monomer represented by the formula (4) as a constituent unit.
- Particles may be used, 50 to 100% by weight of acrylic ester, 50 to 0% by weight of other monofunctional monomer copolymerizable with acrylic ester, and 0.05 to 10% by weight of polyfunctional monomer
- a rubber ((meth) acrylic crosslinked polymer) part obtained by polymerizing a part (based on a total amount of 100 parts by weight of an acrylate ester and another monofunctional monomer copolymerizable therewith) May be.
- 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 crosslinked polymer particle having a monomer represented by the formula (4) as a structural unit is a crosslinked polymer having a monomer represented by the formula (4) as a structural unit as at least one stage polymerization in multistage polymerization.
- the polymer (rubber part) is not particularly limited as long as it is formed, and is hard before and / or after the polymerization stage of the crosslinked polymer having the monomer represented by the formula (4) as a structural unit. Polymerization of the polymer may be performed.
- the crosslinked structure-containing polymer is (b-1) 1 to 100% by weight of the monomer represented by the formula (4) and a monofunctional monomer copolymerizable therewith. 99 to 0% by weight, and 0.05 to 10 parts by weight of a polyfunctional monomer (total amount of the monomer represented by the formula (4) and a monofunctional monomer copolymerizable therewith is 100% by weight (Meth) acrylic rubber-containing polymer particles by polymerizing a monomer mixture consisting of (B-2) 1 to 99% by weight of the monomer represented by the formula (4) in the presence of the crosslinked polymer-containing particles having the monomer represented by the formula (4) as a structural unit.
- the monomer represented by the above formula (4) and this it is preferable to use what is obtained as a graft copolymer by polymerizing a monomer mixture consisting of 100 parts by weight of other monofunctional monomers capable of copolymerization).
- 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.
- the components of the monomer mixture in (b-1) and the preferred amounts thereof to be used are the same as those exemplified in the above-mentioned crosslinked polymer layer.
- 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 of the crosslinked structure-containing polymer up to the crosslinked polymer layer is measured in the same manner as the volume average particle diameter of the crosslinked structure-containing polymer up to the crosslinked polymer layer, and the preferred range is also the same. It is.
- the crosslinked structure-containing polymer When the crosslinked structure-containing polymer 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, poly
- a cationic surfactant such as an alkylamine salt may be used.
- a phosphate ester salt alkali metal or alkaline earth metal
- sodium polyoxyethylene lauryl ether phosphate alkali metal or alkaline earth metal
- the crosslinked structure-containing polymer produced by emulsion polymerization is obtained in a so-called latex state in which primary particles of the crosslinked structure-containing polymer are emulsified and dispersed in the aqueous phase.
- a latex of a crosslinked structure-containing polymer has a larger particle size, often referred to as a scale, which is a by-product of the multi-layer polymerization process of the crosslinked structure-containing polymer particles.
- foreign substances including inorganic substances, dust in the gas phase and water may be mixed from the external environment through the polymerization process.
- Crosslinked structure-containing 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 crosslinked structure-containing polymer can be obtained by treating the resin 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 an acid or salt can be used as the coagulant, but heat stability during molding of the obtained crosslinked structure-containing polymer From the viewpoint of improving properties, it is particularly preferable to use a magnesium salt, particularly magnesium sulfate.
- the crosslinked structure-containing polymer is preferably blended so that 1 to 60 parts by weight of the crosslinked polymer layer or crosslinked polymer-containing particles are contained in 100 parts by weight of the optical resin composition. Preferably, 1 to 25 parts by weight is more preferable. If it is less than 1 part by weight, mechanical strength such as impact resistance is lowered, the photoelastic constant is increased, and optical isotropy may be deteriorated. On the other hand, if it exceeds 60 parts by weight, the heat resistance, surface hardness, transparency, color tone and the like of the molded product tend to deteriorate.
- the blending ratio of the thermoplastic resin and the crosslinked structure-containing polymer is not particularly problematic as long as the above blending conditions are satisfied, and depending on the amount of the crosslinked polymer layer contained in the crosslinked structure-containing polymer,
- the crosslinked structure-containing polymer is preferably 1 to 99% by weight, more preferably 1 to 80% by weight, and even more preferably 1 to 60% by weight. If it is less than 1% by weight, the mechanical strength such as impact resistance of the molded product may be lowered, or optical isotropy such as an increase in photoelastic constant may be inferior. On the other hand, if it exceeds 99% by weight, the heat resistance, surface hardness, transparency, color tone, and surface appearance of the molded product tend to deteriorate.
- the optical resin composition of the present invention is prepared by mixing the respective components in a granular form or pelletized by an extruder, followed by extrusion molding, injection molding, compression molding, blow molding, spinning molding, etc. while heating. It can be set as the molded article of the shape suitable for a use.
- injection molding is a molding method that excels in mass productivity of complicated three-dimensionally shaped members such as lenses, but because molten resin flows into the mold at high speed and is shaped and quenched, For example, there is a problem that both the residual orientation and the residual stress of the molded body are extremely large as compared with cast molding, compression molding, melt extrusion molding and the like.
- the optical resin composition of the present invention depends on the shape and molding conditions. Since the birefringence is extremely small and the difference in refractive index between the crosslinked structure polymer and the thermoplastic resin is designed to be small, the scattering of light in the molded body is small, and the color tone of transmitted light is also less colored.
- An optical member by injection molding having excellent transparency and optical isotropy can be obtained.
- the injection molding is not particularly limited as long as it is a molding method using an apparatus such as a generally known injection molding machine.
- the injection molding machine may be vertical or horizontal. In injection molding, generally known molding techniques can be used.
- the molded product obtained from the optical resin composition of the present invention is characterized by excellent transparency, and when formed into a molded product having a thickness of 2 mm, the haze is 6% or less.
- the haze value of the molded body is more preferably 5.0% or less, further preferably 4.0% or less, still more preferably 3.0% or less, and 2.0% or less. More preferably, it is more preferably 1.5% or less, still more preferably 1.0% or less, and particularly preferably 0.7% or less.
- the haze value of the molded product of the present invention is within the above range, the molded product has sufficiently high transparency and is suitable for optical applications where transparency is required.
- a value obtained by subtracting the refractive index of the crosslinked structure-containing polymer from the refractive index of the thermoplastic resin is preferably in the range of ⁇ 0.02 to +0.001.
- the upper limit is more preferably 0 or less, and still more preferably less than -0.001.
- the lower limit is more preferably ⁇ 0.015 or more, and further preferably ⁇ 0.01 or more.
- Table 3 summarizes the refractive indexes of the thermoplastic resin and the crosslinked structure-containing polymer used in the examples of the present invention.
- the refractive index of the thermoplastic resin A1 of Example 1 is 1.4965
- the refractive index of the containing polymer B3 is 1.5048, and the difference is ⁇ 0.0083.
- the injection molded article of the present invention preferably has a total light transmittance of 80% or more, more preferably 83% or more, further preferably 85% or more, and 88% or more. Is more preferable, and 90% or more is particularly preferable.
- the total light transmittance of the molded article of the present invention is within the above range, the molded article has a sufficiently high transparency and is suitable for optical applications where transparency is required.
- the transmission YI (yellowness) is preferably 18 or less, more preferably 15 or less, and further preferably 10 or less. Preferably, it is 7 or less, more preferably 4 or less, even more preferably 2 or less, and particularly preferably 1 or less.
- the optical resin composition of the present invention is characterized by high mechanical strength, particularly impact resistance. In the Izod impact test which is one of the impact resistance indexes, excellent impact resistance of 2.0 KJ / m 2 or more can be expressed while maintaining high transparency, color tone, and optical isotropy.
- the molded article of the present invention preferably has a glass transition temperature of 100 ° C. or higher, more preferably 115 ° C. or higher, further preferably 120 ° C. or higher, and still more preferably 124 ° C. or higher. If the glass transition temperature is within the above range, a molded article having sufficiently excellent heat resistance can be obtained, which is suitable for applications requiring heat resistance such as optical applications such as lenses, displays, and optical filter members.
- the value of orientation birefringence of the molded product is ⁇ 1.7 ⁇ 10 ⁇ 4. Is preferably 1.7 ⁇ 10 ⁇ 4 , more preferably ⁇ 1.6 ⁇ 10 ⁇ 4 to 1.6 ⁇ 10 ⁇ 4 , and ⁇ 1.5 ⁇ 10 ⁇ 4 to 1.5 ⁇ .
- 10-4 more preferably from 10-4, in that particularly preferably -1.0 ⁇ 10 -4 ⁇ 1.0 ⁇ 10 -4, -0.5 ⁇ 10 -4 ⁇ 0.5 ⁇ 10 -4 It is particularly preferable that it is ⁇ 0.2 ⁇ 10 ⁇ 4 to 0.2 ⁇ 10 ⁇ 4 , more preferably ⁇ 0.1 ⁇ 10 ⁇ 4 to 0.1 ⁇ 10 ⁇ 4. Most preferred.
- the in-plane retardation of the molded body of the present invention is also small. More specifically, the absolute value of 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. It is particularly preferred that The phase difference is an index value calculated based on birefringence, and the in-plane phase difference (Re) can be calculated by the following equation.
- nx and ny represent the refractive index in each axial direction, with the direction of extension (orientation direction of the polymer chain) in the plane being the X axis and the direction perpendicular to the X axis being the Y axis.
- D represents the thickness of the molded body, and nx-ny represents orientation birefringence.
- the optical resin composition of the present invention has a photoelastic constant of ⁇ 3.7 ⁇ 10 ⁇ because the birefringence generated even when stress is applied to the molded body in an environment such as high temperature and high humidity. More preferably from 12 ⁇ 3.7 ⁇ 10 -12, more preferably from -2 ⁇ 10 -12 ⁇ 2 ⁇ 10 -12, -1.5 ⁇ 10 -12 ⁇ 1.5 ⁇ 10 - 12 is more preferable, ⁇ 1 ⁇ 10 ⁇ 12 to 1 ⁇ 10 ⁇ 12 is particularly preferable, and ⁇ 0.5 ⁇ 10 ⁇ 12 to 0.5 ⁇ 10 ⁇ 12 is particularly preferable. The most preferable range is ⁇ 0.3 ⁇ 10 ⁇ 12 to 0.3 ⁇ 10 ⁇ 12 .
- the photoelastic constant is ⁇ 3.7 ⁇ 10 ⁇ 12 to 3.7 ⁇ 10 ⁇ 12 , phase difference unevenness occurs and optical characteristics such as image defocusing occur even when used for an optical member such as a lens. No mechanical defects occur.
- the optical resin composition of the present invention has the meaning of adjusting orientation birefringence, and the inorganic fine particles having birefringence described in Japanese Patent Nos. 3648201 and 4336586, and the birefringence described in Japanese Patent No. 3696649 are used.
- a low molecular weight compound having a molecular weight of 5000 or less, preferably 1000 or less, may be appropriately blended.
- the optical resin composition of the present invention only needs to contain at least one kind of each of a thermoplastic resin and a crosslinked structure-containing polymer.
- Resin can be added without particular limitation.
- the other resin include a thermoplastic resin, a core-shell polymer, a multilayer structure polymer such as a graft copolymer, and a thermoplastic elastomer such as a block polymer.
- the optical resin composition 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, a heat ray reflective material, if necessary.
- Known additives such as lubricants, plasticizers, ultraviolet absorbers, stabilizers and fillers, or other resins may be contained.
- the injection-molded article of the present invention can be used for the following various applications by utilizing properties such as heat resistance, transparency, color tone, mechanical strength such as impact resistance, and optical isotropy.
- interior / exterior of automobiles interior / exterior of personal computers, interior / exterior of solar cells, imaging fields such as cameras, VTRs, projectors, viewfinders, filters, prisms, Fresnel lenses, CD players, DVDs
- imaging fields such as cameras, VTRs, projectors, viewfinders, filters, prisms, Fresnel lenses, CD players, DVDs
- Optical disk pickup lens general camera lens, video camera lens, laser pickup objective lens, diffraction grating, hologram, and collimator lens, f ⁇ lens for laser printer, cylindrical lens, and liquid crystal projector Lenses such as condenser lenses, projection lenses, Fresnel lenses and eyeglass lenses, optical recording fields for optical discs such as CD, DVD and MD
- liquid crystal display members such as light guide plates and diffusion plates for liquid
- volume average particle diameter of the crosslinked structure-containing polymer up to the crosslinked polymer layer was measured in the state of a crosslinked polymer 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 crosslinked structure-containing polymer was dissolved in 50 ml of methyl ethyl ketone, and centrifuged for 1 hour at a rotation speed of 30000 rpm using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E) to dissolve insolubles and solubles. 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.
- 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.
- the refractive index of the thermoplastic resin and the crosslinked structure-containing polymer is determined by processing each composition into a sheet and using an Abbe refractometer 2T manufactured by Atago Co., Ltd. according to JIS K7142, the refractive index at the sodium D-line wavelength. (ND) was measured.
- (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 molded product were measured by the method described in JIS K7105 using Nippon Denshoku Industries NDH-300A.
- the film thickness of the molded body was measured using a Digimatic Indicator (manufactured by Mitutoyo Corporation).
- In-plane retardation Re A test piece of 15 mm ⁇ 90 mm (cut out so that 90 mm is in the long side direction) was cut out from an injection-molded body having a thickness of 2 mm and 15 cm ⁇ 10 cm. 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
- a test piece was cut into a 15 mm ⁇ 90 mm strip from the center of an injection molded body having a thickness of 2 mm and 15 cm ⁇ 10 cm (cut out so that 90 mm comes in the long side direction).
- an automatic birefringence meter (KOBRA-WR manufactured by Oji Scientific Co., Ltd.)
- measurement was performed 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 °.
- the measurement was performed by measuring the birefringence with one of the long sides of the molded body fixed and the other with a load of 0.5 kgf from no load to 4 kgf. From the obtained results, the change in birefringence due to unit stress was measured. The amount was calculated.
- the crosslinked structure-containing polymer alone is pressed at 190 ° C. to produce a pressed plate having a 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.
- the thermoplastic resin was measured in the same manner as described above by producing an injection-molded product in the same manner as in Example 1.
- 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 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, 55.254 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 crosslinked structure-containing polymer 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 crosslinked structure-containing polymer (B1).
- the average particle diameter of the rubber particles (polymer of B-1) of the crosslinked structure-containing polymer (B1) was 133 nm.
- the graft ratio of the crosslinked structure-containing polymer (B1) was 77%.
- the average particle diameter of the rubber particles (polymer of B-1) of the crosslinked structure-containing polymer (B2) was 117 nm.
- the graft ratio of the crosslinked structure-containing polymer (B2) was 69%.
- the average particle size of the rubber particles (polymer of B-1) of the crosslinked structure-containing polymer (B3) was 113 nm.
- the graft ratio of the crosslinked structure-containing polymer (B3) was 84%.
- cylinder temperature T3 250 ° C.
- T2 250 ° C.
- T1 260 using an injection molding machine (160MSP-10 type, manufactured by Mitsubishi Heavy Industries).
- the total light transmittance, haze, and transmission YI were measured as a transparency parameter
- the flat plate samples obtained in Examples 1 and 2 are superior in impact resistance to the flat plate samples obtained in Comparative Examples 3 and 4 and have a small photoelastic constant. Moreover, it turns out that the flat plate sample of Example 1 is excellent in transparency, such as orientation birefringence being small compared with the flat plate sample of Comparative Examples 1 and 2, and also haze being low.
- the flat plate sample (thickness 2 mm, 15 cm ⁇ 10 cm) is placed between two orthogonal polarizing plates, and transmitted light (presence of light leakage)
- a crossed Nicol test was conducted to confirm whether or not 1 to 5 are photographs showing the results of the crossed Nicols test of Examples 1 and 2 and Comparative Examples 1 to 3, respectively.
- the resin tends to be oriented particularly in the vicinity of the gate, and as a result, light leakage due to orientation birefringence is likely to occur (Comparative Example 2, FIG. 4).
- the flat plate sample made of the optical resin composition (Example 1) according to the present invention Although light leakage due to orientation birefringence did not occur in the flat sample of Comparative Example 3, as shown in Table 3, the flat sample of Example 1 has a photoelastic birefringence (compared to the flat sample of Comparative Example 3). (Constant) is quite small, and furthermore, it is understood that the impact resistance is excellent. That is, the optical resin composition according to the present invention is also suitable for injection molded articles for optical applications such as display materials such as lenses, pickup lenses, lens arrays, and head-up displays that require extremely high optical isotropy. Material. It is also suitable for optical applications that require impact resistance.
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Abstract
Description
光学樹脂で光学部材を構成する場合に考慮しなければならない重要な光学的特性の1つに複屈折性がある。即ち、光学樹脂が大きな複屈折性を持つことは、多くの場合好ましくない。特に、上記の例示した用途(液晶表示装置、光ディスク装置、プロジェクションスクリーン等)においては、複屈折性を持つフィルム、シート、レンズ等が光路中に存在すると、像質や信号読み取り性能に悪影響を及ぼすため、複屈折性をできるだけ小さく抑えた光学樹脂で構成された光学部材の使用が望まれる。また、カメラ用のレンズ、眼鏡レンズ等においても、複屈折性は小さい方が望ましいことも言うまでもないことである。
ここで、引張応力がかかっている方向に対して、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] 熱可塑性樹脂、および架橋構造含有重合体を含有し、
前記架橋構造含有重合体の光弾性定数が前記熱可塑性樹脂の光弾性定数と異符号であり、且つ、厚みが2mmの成形体のヘイズが6%以下である、光学用樹脂組成物、
[2] 前記架橋構造含有重合体が、硬質重合体からなる部分を有する、前記[1]に記載の光学用樹脂組成物、
[3] 前記架橋構造含有共重合体が、架橋構造に脂環式構造、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架橋重合体を有する、前記[1]~[2]のいずれか一項に記載の光学用樹脂組成物、
[4] 前記架橋構造含有共重合体が、架橋構造に一般式(4)で表させる単量体を構造単位に含む架橋重合体を有する、前記[1]~[3]のいずれか一項に記載の光学用樹脂組成物、
[5] 前記架橋構造含有共重合体が、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を有する、前記[1]~[4]のいずれか一項に記載の光学用樹脂組成物、
[6] 前記架橋構造含有共重合体が、上記一般式(4)で表させる単量体を構造単位に含む硬質重合体を有する、前記[1]~[5]のいずれか一項に記載の光学用樹脂組成物、
[7] 熱可塑性樹脂の配向複屈折と、架橋構造含有重合体の配向複屈折とが異符号である、前記[1]~[6]のいずれか一項に記載の光学用樹脂組成物。
[8] 熱可塑性樹脂、並びに、多段重合体を含有し、前記多段重合体が、架橋重合体含有粒子の存在下に、下記一般式(4)で表される単量体およびこれと共重合可能な他の単官能性単量体を含む単量体混合物を重合して得られる多段重合体であり、且つ、厚みが2mmの成形体のヘイズが6%以下である、光学用樹脂組成物、
[9] 前記架橋重合体含有粒子が、下記一般式(4)で表される単量体および多官能性単量体を含む単量体混合物を重合して形成される架橋重合体を有する、前記[8]に記載の光学用樹脂組成物、
[10] 熱可塑性樹脂、並びに、多層構造重合体を含有し、前記多層構造重合体が、架橋重合体層、および、下記一般式(4)で表される単量体およびこれと共重合可能な他の単官能性単量体を含む単量体混合物を重合して得られる層を有する多層構造重合体であり、且つ、厚みが2mmの成形体のヘイズが6%以下である、光学用樹脂組成物、
[11] 前記架橋重合体層が、下記一般式(4)で表される単量体および多官能性単量体を含む単量体混合物を重合して形成される架橋重合体層である、前記[10]に記載の光学用樹脂組成物、
[12] 前記一般式(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、前記[4]および[8]~[11]のいずれか一項に記載の光学用樹脂組成物、
[13] 前記熱可塑性樹脂の光弾性定数と、前記多段重合体または前記多層構造重合体の光弾性定数とが異符号である、前記[8]~[12]のいずれか一項に記載の光学用樹脂組成物。
[14] 前記熱可塑性樹脂の配向複屈折と、前記多段重合体または前記多層構造重合体の配向複屈折とが異符号である、前記[8]~[13]のいずれか一項に記載の光学用樹脂組成物、
[15] 前記熱可塑性樹脂が、アクリル系熱可塑性樹脂である、前記[1]~[14]のいずれか一項に記載の光学用樹脂組成物、
[16] 前記熱可塑性樹脂が、マレイミドアクリル系樹脂、グルタルイミドアクリル系樹脂、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種を含む、前記[1]~[15]のいずれか一項に記載の光学用樹脂組成物、
[17] 前記熱可塑性樹脂が、下記一般式(5)で表されるマレイミド単位と(メタ)アクリル酸エステル単位とを有するマレイミドアクリル系樹脂を含有する、[1]~[16]のいずれか一項に記載の光学用樹脂組成物、
R13は、水素原子、炭素数7~14のアリールアルキル基、炭素数6~14のアリール基、炭素数3~12のシクロアルキル基、炭素数1~18のアルキル基、又は、下記A群より選ばれる少なくとも一種の置換基を有する炭素数6~14のアリール基もしくは炭素数1~12のアルキル基である。
[18] 前記マレイミドアクリル系樹脂が、下記一般式(3)で表される単位をさらに有する、前記[17]に記載の光学用樹脂組成物。
[19] 前記熱可塑性樹脂が、下記式(1)で表される単位と、下記式(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を含有する、前記[1]~[18]のいずれか一項に記載の光学用樹脂組成物、
[20] 前記架橋構造含有重合体が含有する架橋構造、前記多段重合体が含有する架橋重合体含有粒子または前記多層構造重合体が含有する架橋重合体層の含有量が、光学用樹脂組成物100重量部において1~60重量部である、前記[1]~[19]のいずれか一項に記載の光学用樹脂組成物、
[21] 前記[1]~[20]のいずれか一項に記載の光学用樹脂組成物からなる成形体、
[22] 前記[1]~[20]のいずれか一項に記載の光学用樹脂組成物からなる射出成形体
に関する。
本発明において、熱可塑性樹脂とは、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性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。
マレイミドアクリル系樹脂とは、具体的には、下記一般式(5)で表されるマレイミド単位と(メタ)アクリル酸エステル単位とを有する共重合体である。
<R11およびR12>
R11及びR12における炭素数1~12のアルキル基としては、炭素数1~6のアルキル基が好ましく、炭素数1~4のアルキル基がより好ましい。また、R11及びR12における炭素数1~12のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基、2-エチルヘキシル基、ノニル基、デカニル基、ラウリル基等が挙げられ、これらのうち、透明性及び耐候性が一層向上する点において、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基、2-エチルヘキシル基が好適であり、メチル基がより好適である。
R13における炭素数7~14のアリールアルキル基としては、ベンジル基、1-フェニルエチル基、2-フェニルエチル基、3-フェニルプロピル基、6-フェニルヘキシル基、8-フェニルオクチル基が挙げられ、これらのうち、耐熱性及び低複屈折性等の光学的特性が一層向上する点において、ベンジル基が好適である。
上記一般式(3)で表される芳香族ビニル単位としては特に限定されないが、スチレン単位、α-メチルスチレン単位が挙げられ、スチレン単位が好ましい。
マレイミドアクリル系樹脂は、上記各構成単位の単量体から選ばれた単量体群を重合することにより得ることができる。
脱揮工程とは、重合溶剤、残存単量体、水分等の揮発分を、必要に応じて減圧加熱条件下で、除去処理する工程を意味する。この除去処理が不充分であると、得られたマレイミドアクリル系樹脂の残存揮発分が多くなり、成形時の変質等により着色することや、泡やシルバーストリーク等の成形不良が起こることがある。残存揮発分量は、マレイミドアクリル系樹脂100質量%に対して1質量%以下、好ましくは0.5質量%以下、より好ましくは0.4質量%以下、更により好ましくは0.3質量%以下である。残存揮発分量とは、前述した重合反応時に反応しなかった残存単量体、重合溶媒、副反応生成物の合計量に相当する。
グルタルイミドアクリル系樹脂は、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。
を用いることもできる。
本発明に用いられる架橋構造含有重合体は、マトリックス樹脂である熱可塑性樹脂に添加することで、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光学用樹脂組成物とするために必須な成分である。さらには、射出成形体のように厚みのある成形体においても、優れた透明性、色調を有し、耐衝撃性などの機械的強度を向上させる。
薄肉成形、複雑形状、低温成形など、射出成形体中でポリマーが配向するような成形以外の、通常の射出成形体を作成した場合、成形体中のポリマーの配向はそれほど大きくない。ただし、このような通常の射出成形体であっても、特にゲート部付近ではポリマー鎖が配向しやすいことが知られている。このようにポリマー鎖が配向しやすい箇所では、PMMAで代表されるアクリル系樹脂においても複屈折が発生する。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、本発明の光学用樹脂組成物をどのように成形するか、成形条件、厚み、形状、ゲート形状、位置、ゲート数等によって、本発明の光学用樹脂組成物から得られる成形体の配向複屈折は左右される。このような成形体中の配向複屈折を小さくするため、架橋構造含有重合体の配向複屈折と熱可塑性樹脂の配向複屈折を設定することが重要となる。ただし先述のとおり、射出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、架橋構造含有重合体の配向複屈折に関してはそれほど考慮する必要が無く、この場合は樹脂設計上、特に制限を受けないことになる。
<光学用樹脂組成物の配向複屈折>
光学用樹脂組成物の配向複屈折は、射出成形体を作成し、評価を実施した。
1.射出成形体の中央部の配向複屈折
射出成形により得られた平板(厚み2mm、15cm×10cm)の中央部から15mm×90mm(長辺方向に90mmがくるように切り出す)の試験片を切り出し、複屈折測定装置にて複屈折を測定する。この部位は比較的ポリマーが一方向に配向しにくい部位である。
2.射出成形体のゲート部の配向複屈折
上述と同じ平板のゲート付近の複屈折を評価する。この部位は非常にポリマー鎖が一方向に配向しやすく、サンプル間の複屈折の差を一番見やすい。評価方法として、上述の平板を、2枚の直交する偏光板の間に置き、透過光(光漏れの有無)が観測されるかを確認するクロスニコル試験を実施する。配向複屈折が大きい樹脂の場合は、配向複屈折に起因した光漏れが生じ易い。
架橋構造重合体は、その組成、構造によっては単独では射出成形することが困難である。よって、プレス成形シートを作成して「配向複屈折」を測定することにする。
(光弾性複屈折(光弾性定数)に関する考え方)
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。
上述の配向複屈折の測定方法と同様に、射出成形により得られた平板(厚み2mm、15cm×10cm)の中央部から15mm×90mm(長辺方向に90mmがくるように切り出す)の試験片を切り出す。次に、23℃において、試験片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。
架橋構造含有重合体については、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 架橋構造含有重合体を190℃でプレスし、膜厚500μmのプレス成形シートを作製し、得られたプレス成形シートの中央部から25mm×90mmの試験片を切り出す。測定条件および算出法は、上述の射出成形体の場合と同じとする。
ここでは、架橋構造含有重合体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。
(1)に関しては、ガラス転移温度を20℃未満にするように、適宜モノマーを選択し、重合することで達成することができる。前述のとおり、アクリルモノマーからなるゴム、すなわちアクリル系ゴムであることが好ましい。
マトリックスとなる熱可塑性樹脂がアクリル系樹脂である場合、アクリル系樹脂の配向複屈折が負であるため、架橋重合体の配向複屈折は異符号の正にする必要がある。
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)架橋構造含有重合体をマトリックス(熱可塑性樹脂)中に均一に分散させること、および、(2)熱可塑性樹脂が有している複屈折を打ち消して、本発明の光学用樹脂組成物、および成形体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、本発明の光学用樹脂組成物、および成形体の光弾性複屈折が小さくなるように、熱可塑性樹脂と架橋構造含有重合体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)上記前記式(4)で表される単量体を構成単位に有する架橋重合体含有粒子の存在下に、前記式(4)で表される単量体1~99重量%、これと共重合可能な他の単官能性単量体99~1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官能性単量体の総量100重量部に対して)からなる単量体混合物を重合して、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、単量体混合物の成分およびこれらの好ましい使用量は、上述の架橋重合体層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。
また、本発明の光学用樹脂組成物は、機械的強度、特に耐衝撃性が高いことが特徴である。耐衝撃性の指標の一つであるIzod衝撃試験において、高い透明性、色調、光学的等方性を維持しながら2.0KJ/m2以上の優れた耐衝撃性を発現することができる。
上記式中において、nx、ny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軸とし、それぞれの軸方向の屈折率を表す。また、dは成形体の厚さを表し、nx-nyは配向複屈折を表す。
架橋構造含有重合体の架橋重合体層までの体積平均粒子径は、架橋重合体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。
重合転化率(%)
=〔(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)
得られた架橋構造含有重合体 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)
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。
(グルタルイミド単位の含有量)
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。
熱可塑性樹脂、および架橋構造含有重合体の屈折率は、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。
(ガラス転移温度)
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。
成形体の全光線透過率、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。
JIS Z8722に準拠した測色色差計(日本電色工業(株)製ZE-2000)を用いた。測定には射出成形で作製した厚み2mmの平板サンプルを用いた。
成形体の膜厚は、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。
射出成形体(厚み2mm、15cm×10cm)の中央部から15mm×90mm(長辺方向に90mmがくるように切り出す)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も測定した。
(面内位相差Reに関しては、その詳細を後述する)
(面内位相差Re)
厚み2mm、15cm×10cmの射出成形体から、15mm×90mm(長辺方向に90mmがくるように切り出す)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。
厚み2mm、15cm×10cmの射出成形体の中央部から15 mm×90mmの短冊状に試験片を切断した(長辺方向に90mm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、成形体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。
熱可塑性樹脂は、実施例1と同様にして射出成形体を製造し、上記記載と同様に測定した。
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。
<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。
<架橋構造含有重合体(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 0.05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。
<架橋構造含有重合体(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45.266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、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99.9%であった。
<架橋構造含有重合体(B3)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、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、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99.6%であった。
比較例3では、A2を100重量部使用した。
A2:PMMA樹脂 スミペックスEX (住友化学株式会社)
実施例1~2、および比較例1~3の組成物を、ベント付単軸押出機(HW-40-28:40m/m、L/D=28、田端機械(株)製)を用い、設定温度C1~C3=210℃、C4=220℃、C5=230℃、D=240℃で押出混練しペレット化した。得られたペレットを90℃で3時間以上乾燥したあと、射出成形機(160MSP-10型、三菱重工(株)製)を使用してシリンダー温度T3=250℃、T2=250℃、T1=260℃、ノズル温度N=260℃、射出速度=19.7%、金型温度=60℃)で射出成形して厚み2mm、15cm×10cmの平板サンプルを得た。得られた平板サンプルについて、透明性の指標として全光線透過率、ヘイズ、透過YIを測定した。
Claims (22)
- 熱可塑性樹脂、および架橋構造含有重合体を含有し、
前記架橋構造含有重合体の光弾性定数が前記熱可塑性樹脂の光弾性定数と異符号であり、且つ、厚みが2mmの成形体のヘイズが6%以下である、光学用樹脂組成物。 - 前記架橋構造含有重合体が、硬質重合体からなる部分を有する、請求項1に記載の光学用樹脂組成物。
- 前記架橋構造含有共重合体が、架橋構造に脂環式構造、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架橋重合体を有する、請求項1~2のいずれか一項に記載の光学用樹脂組成物。
- 前記架橋構造含有共重合体が、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を有する、請求項1~4のいずれか一項に記載の光学用樹脂組成物。
- 熱可塑性樹脂の配向複屈折と、架橋構造含有重合体の配向複屈折とが異符号である、請求項1~6のいずれか一項に記載の光学用樹脂組成物。
- 熱可塑性樹脂、並びに、多段重合体を含有し、
前記多段重合体が、架橋重合体含有粒子の存在下に、下記一般式(4)で表される単量体およびこれと共重合可能な他の単官能性単量体を含む単量体混合物を重合して得られる多段重合体であり、且つ、
厚みが2mmの成形体のヘイズが6%以下である、光学用樹脂組成物。
- 熱可塑性樹脂、並びに、多層構造重合体を含有し、
前記多層構造重合体が、架橋重合体層、および、下記一般式(4)で表される単量体およびこれと共重合可能な他の単官能性単量体を含む単量体混合物を重合して得られる層を有する多層構造重合体であり、且つ、
厚みが2mmの成形体のヘイズが6%以下である、光学用樹脂組成物。
- 前記一般式(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、請求項4および6~11のいずれか一項に記載の光学用樹脂組成物。
- 前記熱可塑性樹脂の光弾性定数と、前記多段重合体または前記多層構造重合体の光弾性定数とが異符号である、請求項8~12のいずれか一項に記載の光学用樹脂組成物。
- 前記熱可塑性樹脂の配向複屈折と、前記多段重合体または前記多層構造重合体の配向複屈折とが異符号である、請求項8~13のいずれか一項に記載の光学用樹脂組成物。
- 前記熱可塑性樹脂が、アクリル系熱可塑性樹脂である、請求項1~14のいずれか一項に記載の光学用樹脂組成物。
- 前記熱可塑性樹脂が、マレイミドアクリル系樹脂、グルタルイミドアクリル系樹脂、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種を含む、請求項1~15のいずれか一項に記載の光学用樹脂組成物。
- 前記熱可塑性樹脂が、下記一般式(5)で表されるマレイミド単位と(メタ)アクリル酸エステル単位とを有するマレイミドアクリル系樹脂を含有する、請求項1~16のいずれか一項に記載の光学用樹脂組成物。
R13は、水素原子、炭素数7~14のアリールアルキル基、炭素数6~14のアリール基、炭素数3~12のシクロアルキル基、炭素数1~18のアルキル基、又は、下記A群より選ばれる少なくとも一種の置換基を有する炭素数6~14のアリール基もしくは炭素数1~12のアルキル基である。
A群:ハロゲン原子、ヒドロキシル基、ニトロ基、炭素数1~12のアルコキシ基、炭素数1~12のアルキル基及び炭素数7~14のアリールアルキル基。) - 前記熱可塑性樹脂が、下記式(1)で表される単位と、下記式(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を含有する、請求項1~18のいずれか一項に記載の光学用樹脂組成物。
- 前記架橋構造含有重合体が含有する架橋構造、前記多段重合体が含有する架橋重合体含有粒子または前記多層構造重合体が含有する架橋重合体層の含有量が、光学用樹脂組成物100重量部において1~60重量部である、請求項1~19のいずれか一項に記載の光学用樹脂組成物。
- 請求項1~20のいずれか一項に記載の光学用樹脂組成物からなる成形体。
- 請求項1~20のいずれか一項に記載の光学用樹脂組成物からなる射出成形体。
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JP7129181B2 (ja) | 2017-03-17 | 2022-09-01 | 旭化成株式会社 | ヘッドマウントディスプレイ用部材 |
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WO2020013203A1 (ja) | 2018-07-13 | 2020-01-16 | 旭化成株式会社 | メタクリル系樹脂、成形体、光学部品又は自動車部品 |
KR20200143426A (ko) | 2018-07-13 | 2020-12-23 | 아사히 가세이 가부시키가이샤 | 메타크릴계 수지, 성형체, 광학 부품 또는 자동차 부품 |
KR20220097535A (ko) | 2018-07-13 | 2022-07-07 | 아사히 가세이 가부시키가이샤 | 메타크릴계 수지, 성형체, 광학 부품 또는 자동차 부품 |
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JP7502507B2 (ja) | 2018-07-13 | 2024-06-18 | 旭化成株式会社 | メタクリル系樹脂、成形体、光学部品又は自動車部品 |
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JP7421404B2 (ja) | 2019-09-06 | 2024-01-24 | 株式会社日本触媒 | アクリル系樹脂組成物 |
Also Published As
Publication number | Publication date |
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US20160319121A1 (en) | 2016-11-03 |
EP3088473A4 (en) | 2017-08-30 |
EP3088473A1 (en) | 2016-11-02 |
CN105874011A (zh) | 2016-08-17 |
CN105874011B (zh) | 2020-05-12 |
JPWO2015098775A1 (ja) | 2017-03-23 |
CN111607181A (zh) | 2020-09-01 |
US11066544B2 (en) | 2021-07-20 |
JP6691778B2 (ja) | 2020-05-13 |
TW201529732A (zh) | 2015-08-01 |
CN111607181B (zh) | 2023-05-05 |
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