JP7567174B2 - Resin composition, resin molded body, and optical element - Google Patents

Description

The present invention relates to a resin composition, a resin molded body, and an optical element.

In recent years, alicyclic structure-containing polymers such as cyclic olefin polymers have been attracting attention as materials for optical elements and medical containers.

For example, Patent Document 1 discloses a resin composition containing an alicyclic structure-containing polymer resin and an antiblocking agent having a predetermined particle size distribution and apparent specific gravity. Patent Document 2 discloses a thermoplastic saturated norbornene-based resin composition comprising a thermoplastic saturated norbornene-based resin and a compounding agent incompatible with the thermoplastic saturated norbornene-based resin, the amount of the compounding agent being within a predetermined range. Patent Document 3 discloses a thermoplastic saturated norbornene-based resin composition comprising a thermoplastic saturated norbornene-based resin and a compounding agent incompatible with the thermoplastic saturated norbornene-based resin, the compounding agent forming microdomains having a diameter of a predetermined length or less and being dispersed in the matrix of the thermoplastic saturated norbornene-based resin.

JP 2005-008779 A Patent No. 3417480 Patent No. 3189364

When a molded product containing an alicyclic structure is mixed with such an incompatible compounding agent, microcracks occur inside the molded product and the product becomes cloudy when the molded product is returned to room temperature after a high-temperature, high-humidity test. This causes a problem in that the haze changes significantly when the molded product is returned to room temperature after being placed in a high-temperature, high-humidity environment.

Therefore, the present invention aims to provide a resin composition that can suppress haze changes even when it is placed in a high-temperature and high-humidity environment and then returned to room temperature, and a resin molded body and an optical element that use the resin composition.

The present inventors have conducted extensive research to solve the above problems, and have newly discovered that a resin composition containing an alicyclic structure-containing polymer and acrylic styrene particles having a volume average particle diameter d within a predetermined range can suppress a change in haze before and after a high-temperature, high-humidity test.
Based on the above-mentioned new findings, the present inventors have completed the present invention.

That is, the present invention aims to advantageously solve the above problems, and the resin composition of the present invention contains an alicyclic structure-containing polymer and acrylic styrene particles having a volume average particle diameter d in the range of 0.15 μm < d < 1 μm.

In addition, in the resin composition of the present invention, it is preferable that the absolute value of the difference between the refractive index of the acrylic styrene particles and the refractive index of the alicyclic structure-containing polymer is 0.01 or less.

In addition, in the resin composition of the present invention, the acrylic styrene particles may be optionally crosslinked particles.

The resin molded article of the present invention is a molded article of the above-mentioned resin composition. The optical element of the present invention also contains the above-mentioned resin composition.

The present invention also aims to advantageously solve the above problems, and the optical element of the present invention is characterized by containing the above-mentioned resin composition. If it contains the above-mentioned alicyclic structure-containing copolymer, it can be advantageously used as a material for optical elements, etc.

The present invention provides a resin composition that can suppress haze changes even when the resin composition is placed in a high-temperature, high-humidity environment and then returned to room temperature, as well as a resin molded body and an optical element that use the resin composition.

The following describes an embodiment of the present invention in detail.

(Resin composition)
The resin composition of the present invention contains an alicyclic structure-containing polymer and acrylic styrene particles having a volume average particle diameter d in the range of 0.15 μm<d<1 μm.

<Alicyclic structure-containing polymer>
In this specification, the term "alicyclic structure-containing polymer" refers to a polymer obtained by polymerizing an alicyclic structure-containing monomer and/or a hydrogenated product thereof. When the alicyclic structure-containing monomer is polymerized to obtain the alicyclic structure-containing polymer, only the alicyclic structure-containing monomer may be polymerized, or the alicyclic structure-containing monomer and the alicyclic structure-containing monomer may be polymerized together. The monomer may be copolymerized with a monomer other than the monomer contained therein.

As the alicyclic structure-containing polymer, for example, a polymer obtained by addition polymerization of an alicyclic structure-containing monomer (alicyclic structure-containing addition polymer) may be used, but because of its excellent mechanical strength, it is more preferable to use a polymer obtained by ring-opening polymerization of an alicyclic structure (alicyclic structure-containing ring-opening polymer) or a hydrogenated product thereof, and it is even more preferable to use a hydrogenated alicyclic structure-containing ring-opening polymer.

Specific examples of monomers containing an alicyclic structure include, but are not limited to, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclopentadiene, 1,3-cyclohexadiene, and other alicyclic structures containing one ring (single ring) and derivatives thereof having a substituent on the ring;

Bicyclo[2.2.1]hept-2-ene (common name: norbornene, hereafter sometimes abbreviated as "NB"), 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-hexyl -Bicyclo[2.2.1]hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5-propenyl-bicyclo[2.2.1]hept-2-ene, and other derivatives containing a two-ring alicyclic structure and having a substituent on the ring;

Tricyclo[5.2.1.0 ^2,6 ]deca-3,8-diene (common name: dicyclopentadiene, hereinafter sometimes abbreviated as "DCP"), tricyclo[5.2.1.0 ^2,6 ]deca-3-ene, tricyclo[6.2.1.0 ^2,7 ]undeca-3,9-diene, tricyclo[6.2.1.0 ^2,7 ]undeca-4,9-diene, tricyclo[6.2.1.0 ^2,7 ]undec-9-ene, 5-cyclopentyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexenyl-bicyclo[2.2.1]hept-2-ene, 5-phenyl-bicyclo[2.2.1]hept-2-ene, and other derivatives containing a three-ring alicyclic structure and having a substituent on the ring;

Tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodec-4-ene (also simply referred to as "tetracyclododecene"; hereinafter sometimes abbreviated as "TCD"). 9-methyltetracyclo[6.2.1.1 ^3,6 . ^{0 2,7} ]dodec-4-ene, 9-ethyltetracyclo[6.2.1.1 ^{3,6 . 0 2,7 ]dodec-4-ene (hereinafter sometimes abbreviated as "ETD"). 9-methylidenetetracyclo[6.2.1.1 3,6 . 0 2,7} ]dodec-4-ene, 9-ethylidenetetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodec-4-ene, 9-vinyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyl-tetracyclo[6.2.1.1 ^3,6 . ^{0 2,7} ] dodec-4-ene, tetracyclo[9.2.1.0 ^2,10 . 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a,9a-tetrahydrofluorene, hereinafter sometimes abbreviated as "MTF"), tetracyclo[10.2.1.0 ^{2,11 .} 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a,9,9a,10-hexahydroanthracene), and their derivatives having a 4-ring alicyclic structure and a substituent on the ring;

9-Cyclopentyl-tetracyclo[6.2.1.1 ^3,6 . ^{0 2,7} ] dodec-4-ene, 9-cyclohexyl-tetracyclo[6.2.1.1 ^3,6 . ^{0 2,7} ] dodec-4-ene, 9-cyclohexenyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, pentacyclo[6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ]-4-hexadecene, pentacyclo[6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ]-4-pentadecene, pentacyclo[7.4.0.0 ^2,7 . 1 ^3,6 . 1 ^10,13 ]-4-pentadecene, 9-phenyl-cyclopentyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodec-4-ene, heptacyclo[8.7.0.1 ^2,9 . ^{1 4,7} . 1 ^11,17 . 0 ^3,8 . 0 ^12,16 ]-5-eicosene, heptacyclo[8.7.0. ^12,9 . ^{0 3,8} . ^{1 4,7} . 0 ^12,17 . 1 ^13,16 ]-14-eicosene, and the like, and derivatives thereof having an alicyclic structure with five or more rings and a substituent on the ring; and the like.

The substituent that the above derivatives have on the ring is not particularly limited, and examples thereof include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group.

In addition, the other monomers other than the alicyclic structure-containing monomer are not particularly limited as long as they are copolymerizable with the above alicyclic structure-containing monomer. For example, other monomers that can be addition-copolymerized with the alicyclic structure-containing monomer include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene, and derivatives thereof; non-conjugated dienes, such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene; and the like.

Here, when an alicyclic structure-containing monomer and a monomer other than the alicyclic structure-containing monomer are polymerized to obtain an alicyclic structure-containing polymer, the mass ratio of the amount of the other monomer to the amount of the alicyclic structure-containing monomer (other monomer/alicyclic structure-containing monomer) is not particularly limited, but is preferably 30/70 or less, more preferably 20/80 or less, even more preferably 10/90 or less, and particularly preferably 0/100.

The above-mentioned alicyclic structure-containing ring-opening polymer can be produced, for example, by a method using a metathesis reaction catalyst (ring-opening polymerization catalyst) such as the ruthenium carbene complex catalyst described in WO 2010/110323, or a method using a ring-opening polymerization catalyst such as the tungsten (phenylimide) tetrachloride-tetrahydrofuran complex described in JP 2015-54885 A.

Furthermore, examples of a method for producing a hydrogenated ring-opening polymer containing an alicyclic structure by hydrogenating an alicyclic structure-containing ring-opening polymer include a method using a hydrogenation catalyst described in International Publication No. 2010/110323. In addition, for example, after producing an alicyclic structure-containing polymer using the above-mentioned ruthenium carbene complex catalyst as a ring-opening polymerization catalyst, the ruthenium carbene catalyst can be used as a hydrogenation catalyst as it is to hydrogenate the alicyclic structure-containing ring-opening polymer to produce a hydrogenated ring-opening polymer containing an alicyclic structure.

The hydrogenation rate of the hydrogenated alicyclic structure-containing ring-opening polymer is preferably 90% or more, more preferably 95% or more, and even more preferably 99% or more. When the hydrogenation rate of the hydrogenated alicyclic structure-containing ring-opening polymer is the above-mentioned predetermined value or more, the weather resistance and heat resistance can be improved.
The hydrogenation rate of the hydrogenated alicyclic structure-containing ring-opening polymer can be measured by the method described in the Examples of this specification.

The glass transition temperature of the alicyclic structure-containing polymer is not particularly limited and varies depending on the type of polymer, but is preferably -10°C or higher, more preferably 30°C or higher, and even more preferably 50°C or higher, and is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower.

The melting point of the alicyclic structure-containing polymer is not particularly limited, but is preferably 50° C. or higher, more preferably 100° C. or higher, even more preferably 130° C. or higher, and is preferably 400° C. or lower, more preferably 350° C. or lower, and even more preferably 300° C. or lower. If the melting point of the polymer is above the lower limit, the produced polymer has excellent heat distortion resistance when actually used. On the other hand, if the melting point of the polymer is below the upper limit, the produced polymer has sufficient fluidity when melted and is excellent in moldability.
The melting point of the polymer can be measured by the method described in the Examples of this specification.

The alicyclic structure-containing polymer may be either an amorphous resin or a crystalline resin. When the alicyclic structure-containing polymer is an amorphous resin, the alicyclic structure-containing polymer may be either a ring-opening polymer or an addition polymer.
In addition, when the alicyclic structure-containing polymer is a crystalline alicyclic structure-containing ring-opening polymer hydrogenation product, the alicyclic structure-containing ring-opening polymer hydrogenation product preferably has a syndiotactic stereoregularity. If the alicyclic structure-containing ring-opening polymer hydrogenation product is syndiotactic, the produced polymer can have improved physical properties such as heat resistance, mechanical strength, and solvent resistance. Here, the syndiotactic ratio is not particularly limited, but from the viewpoint of increasing the crystallinity of the alicyclic structure-containing ring-opening polymer hydrogenation product and making the heat resistance particularly good, it is preferable that the syndiotactic ratio is higher. More specifically, the ratio of racemo-dyads in the repeating unit obtained by ring-opening polymerization of the alicyclic structure-containing monomer and then hydrogenation is preferably 51% or more, more preferably 60% or more, and particularly preferably 70% or more. The higher the racemo-dyad ratio, that is, the higher the syndiotactic ratio, the higher the melting point of the dicyclopentadiene ring-opening polymer hydrogenation product. The ratio of the racemo dyad can be measured and quantified by 13C-NMR spectrum analysis. A specific method of quantification is to carry out 13C-NMR measurement using orthodichlorobenzene-d4 as a solvent at 150°C by applying the inverse-gated decoupling method, and determine the ratio of the racemo dyad from the meso/racemo ratio calculated from the intensity ratio of the signal at 43.35 ppm derived from the meso dyad and the signal at 43.43 ppm derived from the racemo dyad, with the peak at 127.5 ppm of orthodichlorobenzene-d4 as the reference shift.
Here, "crystallinity" refers to a property that enables the melting point to be observed by differential scanning calorimetry (DSC) by optimizing the measurement conditions, etc., and is a property determined by the stereoregularity of the polymer chain.

The weight average molecular weight of the alicyclic structure-containing polymer is appropriately selected depending on the intended use, but is in the range of 5,000 to 500,000, preferably 8,000 to 250,000, and more preferably 10,000 to 200,000. A molecular weight in this range is preferred because it provides a high level of balance between the mechanical strength and moldability of the resin. In the present invention, the weight average molecular weight is a value calculated in terms of polyisoprene or polystyrene, measured by gel permeation chromatography of a cyclohexane solution (a toluene solution if the polymer resin does not dissolve).

The alicyclic structure-containing polymer resin preferably has a glass transition temperature (Tg) of 50°C or higher, and more preferably in the range of 60°C to 170°C. A Tg in this range is preferable in terms of heat resistance and durability. In the present invention, Tg is a value measured by differential scanning calorimetry (DSC) based on JIS-K7121.

<Acrylic styrene particles>
＜＜Material＞＞
"Acrylic styrene particles" are particles made of acrylic styrene. "Acrylic styrene" refers to a copolymer containing an acrylic compound unit and a styrene unit. "Acrylic compound" refers to a compound containing an acrylic acid structure, such as acrylic acid, methacrylic acid, and derivatives thereof (e.g., acrylic acid esters such as methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; methacrylic acid esters such as methyl methacrylate and butyl methacrylate). "Acrylic compound unit" refers to a polymerization unit formed by an acrylic compound. The acrylic compound unit may be a single type or a mixture of multiple types. "Styrene unit" refers to a polymerization unit formed by styrene. The acrylic styrene is preferably a copolymer of an acrylic acid ester or a methacrylic acid ester and styrene, more preferably a copolymer of a methacrylic acid ester and styrene, and most preferably a methyl methacrylate-styrene copolymer.
The monomer ratio of the acrylic compound unit and the styrene unit (acrylic compound unit/styrene unit) in the acrylic styrene is not particularly limited, and may be adjusted appropriately to obtain a desired refractive index. That is, if the refractive indexes of the acrylic compound monomer unit and the styrene monomer unit are known, the monomer ratio can be set so as to obtain a desired refractive index based on the refractive index of each monomer unit. For example, when a methyl methacrylate-styrene copolymer is used as the acrylic styrene, the refractive index can be adjusted to a low value by increasing the ratio of methyl methacrylate within a range in which the refractive index is about 1.49 to about 1.58, and the refractive index can be adjusted to a high value by increasing the ratio of styrene.
The acrylic styrene particles may be non-crosslinked particles or crosslinked particles. The acrylic styrene particles are preferably crosslinked particles. By using crosslinked particles as the acrylic styrene particles, it is possible to suppress the decomposition of acrylic styrene, the blocking of acrylic styrene particles, and the shape change of acrylic styrene particles during melt kneading. Crosslinking may be performed by, for example, UV crosslinking, thermal crosslinking, or electron beam crosslinking.
The acrylic styrene particles are preferably made of a material that maintains a particulate state at a temperature of 300°C, more preferably a material that maintains a particulate state at a temperature of 290°C, and even more preferably a material that maintains a particulate state at a temperature of 280°C.
The acrylic styrene particles are preferably incompatible with the alicyclic structure-containing polymer.
It is expected that the acrylic styrene particles have a relatively high moisture adsorption property compared to the alicyclic structure-containing polymer. Therefore, by blending the acrylic styrene particles with the alicyclic structure-containing polymer, it is considered that the residual moisture that causes internal microcracks after the high-temperature, high-humidity test is absorbed from the alicyclic structure-containing polymer, which contributes to suppression of haze changes (e.g., haze increase) before and after the high-temperature, high-humidity test, and optical properties can be maintained at a good level.
Furthermore, the acrylic styrene particles impart unevenness to the surface of the resin composition, thereby reducing the coefficient of friction and making it possible to suppress blocking between resin compositions (for example, blocking between resin compositions in the form of a film).
Moreover, since acrylic styrene has transparency due to the inclusion of both acrylic compound monomer units and styrene monomer units, it is suitable as a component of optical elements.
In addition, the refractive index of acrylic styrene is close to that of the alicyclic structure-containing polymer, and can be appropriately adjusted depending on the monomer ratio of the acrylic compound to styrene (acrylic compound/styrene). Therefore, even if acrylic styrene is blended with the alicyclic structure-containing polymer, the optical properties are maintained.
<<Refractive Index>>
The refractive index of the acrylic styrene particles may be appropriately set so as to be close to the refractive index of the alicyclic structure-containing polymer depending on the type of the alicyclic structure-containing polymer. The absolute value of the difference between the refractive index of the acrylic styrene particles and the refractive index of the alicyclic structure-containing polymer is preferably 0.00 or more and 0.01 or less, more preferably 0.000 or more and 0.009 or less, and even more preferably 0.000 or more and 0.008 or less. For example, when the refractive index of the alicyclic structure-containing polymer is in the range of 1.4 to 1.6, the refractive index of the acrylic styrene particles may be set so that the difference with the refractive index of the alicyclic structure-containing polymer is within the above-mentioned range. The refractive index of the acrylic styrene particles can be appropriately set based on the type of monomer unit in the acrylic styrene and the monomer ratio of the acrylic compound and styrene (acrylic compound/styrene). For example, when a methyl methacrylate-styrene copolymer is used as the acrylic styrene, the refractive index can be adjusted to be low by increasing the ratio of methyl methacrylate within the range of about 1.49 to about 1.58, and the refractive index can be adjusted to be high by increasing the ratio of styrene.
It is considered that by making the difference between the refractive index of the acrylic styrene particles and the refractive index of the alicyclic structure-containing polymer fall within the above-mentioned low value range, the change in haze before and after the high temperature and high humidity test can be suppressed, and the optical properties can be maintained even better.
The refractive index of the acrylic styrene particles can be measured using a method known in the art, and may be measured, for example, using the method described in the Examples of this specification.
<<Particle size>>
The volume average particle diameter (d) of the acrylic styrene particles is preferably 0.15 μm<d, more preferably 0.17 μm<d, and even more preferably 0.19 μm<d from the viewpoint of preventing secondary aggregation of the particles. Also, the volume average particle diameter of the acrylic styrene particles is preferably d<1 μm, more preferably d<0.8 μm, and even more preferably d<0.6 μm from the viewpoint of making the particles less likely to be captured by a polymer filter.
From the viewpoint of making the optical properties of the resin composition uniform, the particle size distribution of the acrylic styrene particles preferably has a single peak, and more preferably has a sharp single peak.
The volume average particle size and particle size distribution of the acrylic styrene particles can be measured using a method known in the art, and may be measured, for example, using the method described in the Examples of this specification.
<<Particle Addition Amount>>
The amount of the acrylic styrene particles added to the alicyclic structure-containing polymer in the resin composition of the present invention may be, for example, 0.01 wt% or more, preferably 0.05 wt% or more, more preferably 0.1 wt% or more, and may be, for example, 1 wt% or less, preferably 0.5 wt% or less, more preferably 0.2 wt% or less. When the resin composition of the present invention has a stretched film shape, the addition of a small amount of acrylic styrene particles can impart unevenness to the surface of the film, reducing the friction coefficient and suppressing blocking between films. Therefore, if the resin composition in the shape of a stretched film contains the above-mentioned amount of acrylic styrene particles, blocking between films can be suppressed.

<Other compounding agents>
The resin composition of the present invention may contain other known additives as necessary within the range that does not impair the effects of the invention. Examples of other known additives include lubricants, dispersing aids, lubricants, antioxidants, heat stabilizers, light stabilizers, UV absorbers, antistatic agents, dispersants, chlorine scavengers, flame retardants, crystallization nucleating agents, antifogging agents, pigments, organic fillers, neutralizing agents, decomposers, metal deactivators, antifouling agents, antibacterial agents, other resins, and thermoplastic elastomers.

Examples of lubricants include fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid, fatty acid metal salts composed of fatty acids and metals such as lithium, sodium, magnesium, calcium, and zinc, and fatty acid amides such as oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, stearyl erucamide, and oleyl palmitamide. Of these, fatty acid metal salts are preferred, and calcium stearate is particularly preferred.
Examples of the dispersion aid include silane-based or titanium-based coupling agents.
The amount of such a lubricant or dispersing aid is not particularly limited, but is preferably 0.4 to 0.001 parts by weight, more preferably 0.1 to 0.01 parts by weight, based on 100 parts by weight of the alicyclic structure-containing polymer resin. If the ratio is within this range, it is favorable in terms of dispersibility of the antiblocking agent (B) in the resin composition and prevention of resin scorching.

Examples of lubricants include polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and low molecular weight polybutylene; natural plant waxes such as candelilla, carnauba, rice, wood wax, and jojoba; petroleum waxes and modified waxes such as paraffin, microcrystalline, and petroleum wax; synthetic waxes such as Fischer-Tropsch wax; and polyfunctional ester compounds such as pentaerythritol tetrapalmitate, pentaerythritol tetramyristate, dipentaerythritol hexamyristate, and dipentaerythritol hexapalmitate.

Examples of antioxidants include phenol-based antioxidants, organic phosphite-based antioxidants, and sulfur-based antioxidants. Examples of light stabilizers include hindered amine-based stabilizers. Examples of UV absorbers include benzophenone-based UV absorbers and benzotriazole-based UV absorbers.

Antistatic agents include nonionic antistatic agents, cationic antistatic agents, and anionic antistatic agents. Dispersants include bisamide-based dispersants, wax-based dispersants, and organometallic salt-based dispersants. Flame retardants include phosphate-based flame retardants, antimony trioxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, red phosphorus, etc.

Examples of other resins include amorphous resins and crystalline resins, etc. Among them, it is particularly preferable to use crystalline resins from the viewpoint of the mechanical strength and moisture resistance of the film.
Examples of the amorphous resin include aromatic petroleum resins, terpene resins, coumarone-indene resins, and hydrogenated products thereof, amorphous polyvinyl chloride, polymethyl methacrylate, polystyrene, polyacrylonitrile, polyacrylonitrile-styrene copolymers, high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymers (ABS resins), polycarbonates, polyarylates, polysulfones, polyethersulfones, polyphenylene ethers, and the like. From the viewpoints of the moisture resistance and mechanical strength of the film, polyvinyl chloride, polystyrene, high impact polystyrene, and polyphenylene ethers are preferred.

Crystalline resins include some of the resins exemplified in the section on amorphous resins above, but are distinguished by the fact that their crystalline melting points can be observed in thermal measurements. Specific examples include polyethylene-based crystalline resins such as linear or branched high-density polyethylene, low-density polyethylene, and ultra-high molecular weight polyethylene, polypropylene-based crystalline resins such as linear or branched high-density polypropylene and low-density polypropylene, and polyolefin-based crystalline resins such as polymethylpentene, polybutene, polymethylbutene, polymethylhexene, polyvinylnaphthalene, and polyxylene, and polyester-based resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate, and aromatic polyester. Examples of the crystalline resin include polyamide-based crystalline resins represented by the group consisting of crystalline resins, nylon-6, nylon-66, nylon-12, polyamideimide, etc., fluorine-based crystalline resins represented by the group consisting of polyvinylidene fluoride, polytetrafluoroethylene, etc., and other crystalline resins such as rosin-based resins, polyvinylidene chloride, polyacrylonitrile, syndiotactic polystyrene, polyoxymethylene, polyphenylene sulfide (PPS), polyether ether ketone (PEEK), cellulose, acetal resins, chlorinated polyethers, ethylene-vinyl acetate copolymers, and liquid crystal polymers (aromatic polycyclic condensation polymers). Among these, polyolefin-based crystalline resins, polyester-based crystalline resins, and polyamide-based crystalline resins are preferred from the viewpoint of moisture resistance and mechanical strength, polyolefin-based crystalline resins are more preferred, and polyethylene-based crystalline resins and polypropylene-based crystalline resins are particularly preferred. In the present invention, the crystalline resin includes not only resins in which the entire resin is crystallized, but also resins in which the resin is partially crystallized.

Thermoplastic elastomers include styrene-butadiene-styrene block copolymer, SEBS, styrene-isoprene-styrene block copolymer, SEPS, etc.

<Production and Form of Resin Composition>
The resin composition of the present invention is not particularly limited by its manufacturing method. For example, the resin composition of the present invention can be manufactured by kneading an alicyclic structure-containing polymer and acrylic styrene particles. The resin composition may be obtained, for example, in the form of resin pellets. The kneading temperature is not particularly limited, but may be, for example, 180°C or higher, preferably 190°C or higher, more preferably 200°C or higher, and may be, for example, 300°C or lower, preferably 290°C or lower, more preferably 280°C or lower.

In addition, a preferred method from the viewpoint of productivity is, for example, a method in which acrylic styrene particles and additives used as necessary are mixed at a high concentration with an alicyclic structure-containing polymer, kneaded to form a master batch, and then the master batch and the alicyclic structure-containing polymer are mixed in a desired ratio and then melt-kneaded. The concentrations of the acrylic styrene particles and various additives in the master batch are not particularly limited, but are preferably 10 to 30 times, and more preferably 15 to 25 times, the concentrations in the final product.

The mixing method is not particularly limited, but for example, the alicyclic structure-containing polymer, the acrylic styrene particles, and the additives used as necessary can be mixed using a mixer such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender, or further after this mixing, the mixture can be melt-kneaded using a single-screw extruder, a twin-screw extruder, a kneader, or the like to obtain a resin composition.
The shape of the resin composition is not particularly limited, but it is preferable to granulate, crush, or pelletize the resin composition so that it can be easily molded into molded products such as optical elements and films.

<Molded body>
The resin composition of the present invention can be used as a molded product (resin molded product). The molded product of the resin composition of the present invention is obtained by molding the resin composition of the present invention. The molded product obtained from the resin composition of the present invention can be advantageously used as an optical element (an optical element containing the resin composition of the present invention) or the like.

The molding method for the molded body may be, for example, injection molding, extrusion blow molding, injection blow molding, two-stage blow molding, multi-layer blow molding, connection blow molding, stretch blow molding, rotational molding, vacuum molding, extrusion molding, calendar molding, solution casting, heat press molding, inflation molding, etc.

<Film>
The resin composition of the present invention can also be formed into a film.
The film may be formed by any known method, such as a T-die method, an inflation method, a press molding method, etc. The thickness of the film is not particularly limited, but is preferably in the range of 1 to 500 μm, and more preferably in the range of 4 to 100 μm.
The resin composition of the present invention and the film made of the resin composition have high transparency and a small coefficient of friction. Furthermore, since there are no irregularities (lumps) on the surface due to the antiblocking agent, the printability is good.

When the resin composition of the present invention is made into a film, the film is preferably a stretched film. By making the resin composition of the present invention into a stretched film, the addition of a small amount of acrylic styrene particles can impart unevenness to the film surface, reducing the coefficient of friction and suppressing blocking between films.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

<Measurement and evaluation methods of physical properties>
Measurement and evaluation of various physical properties were carried out according to the following methods.

(Method of measuring weight average molecular weight Mw)
The weight average molecular weight Mw was measured by gel permeation chromatography (GPC) using cyclohexane as an eluent, and was calculated as a value converted into standard polyisoprene. Standard polyisoprene manufactured by Tosoh Corporation was used as the standard polyisoprene. When the sample was not soluble in cyclohexane, it was measured by GPC using tetrahydrofuran (THF) as an eluent, and was calculated as a value converted into standard polystyrene. Standard polystyrene manufactured by Tosoh Corporation was used as the standard polystyrene.

(Method of measuring glass transition temperature)
The glass transition temperature (Tg) was measured using a differential scanning calorimeter (manufactured by Nano Technology Corporation, product name: DSC6220SII) in accordance with JIS K 6911 at a temperature rise rate of 10° C./min.

(Measurement of refractive index of alicyclic structure-containing polymer resin)
The alicyclic structure-containing polymer was molded into a sheet having a thickness of 5 mm, and allowed to stand in an atmosphere of [glass transition temperature (Tg)-15]° C. for 20 hours to obtain a resin which was used as a measurement sample.
The refractive index (n d , n C , and n F ) of the obtained measurement samples at 25° C. was measured using a precision refractometer (manufactured _by Shimadzu Corporation, product name: KPR-200, light source = He lamp (wavelength: _587.6 nm) and _H2 lamp (wavelengths: 656.3 _nm and 486.1 nm). The table shows the refractive index for light with a wavelength of 587.6 nm.

(Refractive index measurement of acrylic styrene particles)
The refractive index of the polymer particles was measured by the Becke method. In the refractive index measurement by the Becke method, the resin particles were placed on a slide glass, and a plurality of refractive liquids were prepared with a refractive index difference of 0.002 increments, and then dropped. Then, after thoroughly mixing the polymer particles and the refractive liquid, the outline of the polymer particles was observed from above using an optical microscope while irradiating light from a high-pressure sodium lamp (model number "NX35", central wavelength 589 nm) manufactured by Iwasaki Electric Co., Ltd. from below. Then, when the outline was not visible, it was determined that the refractive index of the refractive liquid and the polymer particles were equal.

(Volume average particle size measurement of acrylic styrene particles)
The volume average particle diameter of the polymer particles was calculated by filling pores with an electrolyte solution having a pore diameter of 20 to 400 μm and determining the volume from the change in the conductivity of the electrolyte solution when the particles pass through the electrolyte solution. Specifically, the volume average particle diameter of the polymer particles was measured using a Coulter-type precision particle size distribution measuring device "Multisizer III" (manufactured by Beckman Coulter, Inc.) (arithmetic mean diameter in volume-based particle size distribution). In addition, when measuring, the Multisizer III was calibrated using an aperture suitable for the particle diameter of the polymer particles to be measured according to "Reference MANUAL FOR THE COULTER MULTISIZER" (1987) issued by Coulter Electronics Limited, and the measurement was performed.

(Measurement of haze value of molded body)
The molded article described in the examples was sandwiched between mirror-finished SUS plates at 200°C and 40 MPa and pressed to a 3 mm plate. The haze value before the high-temperature, high-humidity test (initial haze value after pressing) was measured using a turbidimeter NDH-300A manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7361-1997. The sample was then left to stand in a high-temperature, high-humidity chamber (oven) at a temperature of 85°C and a humidity of 85% for 500 hours, and the haze value 24 hours after removal from the oven (haze value after high-temperature, high-humidity test) was measured. The difference between the haze value after the high-temperature, high-humidity test and the initial haze value after pressing was taken as the haze change.
The evaluation is
A change in total haze between before and after is 1% or less: 〇 A change in total haze between before and after is more than 1% but less than 2%: △
If the total haze change before and after is 2% or more, it is considered as ×
I went as.

<Preparation of Molded Body>
The molded body was produced according to the following method.

(Injection Molding)
An injection molding method was carried out using the resin composition described in the examples as the injection molding material to produce an optical lens as a molded body. The injection molding machine used was a "ROBOSHOT S2000i100A" manufactured by FANUC CORPORATION. A 16-cavity mold was used as the injection molding mold. Using these, 160 optical lenses were produced by carrying out 10 manufacturing steps at an injection speed of 30 mm/sec and a holding pressure of 80 MPa.

Example 1
(1-1) Production of norbornene-based ring-opening polymer In a glass reaction vessel with the inside replaced with nitrogen, 200 parts of dehydrated cyclohexane, 0.7 mol% 1-hexene, 0.15 mol% diisopropyl ether, 0.05 mol% triisobutylaluminum, and 0.054 mol% isobutanol were placed in the reactor at room temperature relative to a total of 100 parts by weight of the monomers described below, and mixed. Thereafter, while maintaining the temperature at 50° C., 100 wt% ethylidenetetracyclododecene (ETD) as a monomer and 0.02 mol% tungsten hexachloride (0.65 wt% toluene solution) were continuously added in parallel to the reactor over a period of 2 hours, and polymerization was performed. Next, 0.6 mol% isopropyl alcohol was added to the polymerization solution to inactivate the polymerization catalyst, and the polymerization reaction was stopped. In the above explanation, the amount indicated by the unit "mol%" is a value in which the total amount of the monomers is 100 mol%. The weight average molecular weight Mw of the resulting norbornene ring-opening polymer was 3.5 × 10 ^4. The conversion rate of the monomer to the polymer was 100%.

(1-2) Production of norbornene-based hydride by hydrogenation Next, 670 g of cyclohexane was added to 1830 g of the reaction solution containing the norbornene-based ring-opening polymer obtained in the above step (1-1), and 1.8 wt % of a diatomaceous earth-supported nickel catalyst ("T8400RL" manufactured by JGC Chemical Industries, Ltd., nickel loading rate 57%) was further added as a hydrogenation catalyst. The amount of hydrogenation catalyst represents a value relative to 100 wt % of the norbornene-based ring-opening polymer contained in the reaction solution. Thereafter, the reaction solution was pressurized to 4.5 MPa with hydrogen and heated to a temperature of 190° C. while stirring, and the hydrogenation reaction was carried out for 8 hours. As a result, a reaction solution containing a norbornene-based hydride as a hydrogenated product of the norbornene-based ring-opening polymer was obtained.

The reaction solution was filtered under pressure at a pressure of 0.25 MPa (Fundaback Filter, manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.) using Radiolite #500 as a filter bed to remove the hydrogenation catalyst, and a colorless, transparent solution was obtained. The resulting solution was poured into a large amount of isopropanol to precipitate a norbornene-based hydrogenated product. After filtering out the precipitated norbornene-based hydrogenated product, 2.0 parts of a xylene solution containing 0.1 parts of an antioxidant [pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by Ciba Specialty Chemicals, product name: Irganox (registered trademark) 1010)] was added per 100 parts of norbornene-based hydrogenated product. The mixture was then dried in a vacuum dryer (200°C, 1 Torr) for 6 hours to obtain a norbornene-based hydrogenated product as a thermoplastic norbornene-based resin. The weight average molecular weight of the norbornene-based hydride was 4.0 × 10 ^4. The glass transition temperature Tg of the thermoplastic norbornene-based resin was 138 ° C. The refractive index was 1.525. The norbornene-based hydride obtained as the thermoplastic norbornene-based resin (hereinafter referred to as "COP1") was used as an alicyclic structure-containing polymer for use in preparing a resin composition.

(1-3) Preparation of Resin Composition 100 parts of the above norbornene hydride (COP1) as the alicyclic structure-containing polymer and 0.2 parts of crosslinked acrylic styrene particles having a volume average particle size of 0.3 μm ("Techpolymer" manufactured by Sekisui Chemical Co., Ltd., material: crosslinked methyl methacrylate-styrene copolymer, refractive index 1.525, hereinafter referred to as "particle A") as the acrylic styrene particles were kneaded at a temperature of 280° C. to obtain a resin composition as resin pellets.

(1-4) Production of Molded Product, Measurement of Haze Value, and Evaluation of Haze Change The resin pellets were molded into an optical lens having a thickness of 3 mm and a diameter of 50 mm by injection molding using an injection molding machine ("ROBOSHOT S2000i100A" manufactured by Fanuc Corporation). The haze value of the lens was measured by the method described above, and was 0.20% before the high temperature and high humidity test and 0.69% after the high temperature and high humidity test, with a small change of 0.49%. The results are summarized in Table 1.

Example 2
In the production of the resin composition, except that 0.1 parts of particles A were added as acrylic styrene particles, the resin composition and the molded body were produced, and the haze value of the molded body was measured and the haze change was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3
The combination of monomers used in step (1-1) of Example 1 was changed to 50% by weight of tetracyclododecene (TCD), 47% by weight of methanotetrahydrofluorene (MTF), and 3% by weight of ethylidenetetracyclododecene (ETD). Also, 1-hexene was changed to 0.73 mol%. The weight average molecular weight Mw of the obtained norbornene ring-opening polymer was 3.7 × 10 ^4. The weight average molecular weight of the obtained norbornene hydrogenated product was 4.2 × 10 ^4. The glass transition temperature Tg of the obtained thermoplastic norbornene resin was 160 ° C. The refractive index was 1.535. The norbornene hydrogenated product obtained as the thermoplastic norbornene resin (hereinafter referred to as "COP2") was used as an alicyclic structure-containing polymer for use in preparing a resin composition.

100 parts of the above norbornene hydride (COP2) as the alicyclic structure-containing polymer and 0.15 parts of cross-linked acrylic styrene particles with a volume average particle size of 0.5 μm ("Techpolymer" manufactured by Sekisui Chemical Co., Ltd., material: cross-linked methyl methacrylate-styrene copolymer, refractive index 1.530, hereinafter referred to as "particle B") as the acrylic styrene particles were kneaded at a temperature of 280°C to obtain a resin composition in the form of resin pellets.

These resin pellets were molded into optical lenses with a thickness of 3 mm and a diameter of 50 mm by injection molding using an injection molding machine (ROBOSHOT S2000i100A manufactured by Fanuc Corporation). The haze value of the lens was measured using the method described above, and was 0.40% before the high-temperature, high-humidity test and 0.75% after the high-temperature, high-humidity test, with a small haze change of 0.35%. The results are summarized in Table 1.

Example 4
In the production of the resin composition, except that 0.05 parts of particles A were added as acrylic styrene particles, the resin composition and the molded article were produced, and the haze value of the molded article was measured and the change in haze was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 5
[Production Example: Production of hydrogenated product of ring-opening polymer of dicyclopentadiene]
A metallic pressure-resistant reactor was thoroughly dried and then purged with nitrogen. 154.5 parts of cyclohexane, 42.8 parts of a 70% cyclohexane solution of dicyclopentadiene (endo isomer content of 99% or more) (30 parts as the amount of dicyclopentadiene), and 1.9 parts of 1-hexene were added to the metallic pressure-resistant reactor, and the reactor was heated to 53°C.

A catalyst solution was prepared by adding 0.061 parts of a 19% diethylaluminum ethoxide/n-hexane solution to a solution prepared by dissolving 0.014 parts of tetrachlorotungsten phenylimide (tetrahydrofuran) complex in 0.70 parts of toluene and stirring for 10 minutes.
The catalyst solution was added to the pressure-resistant reactor to initiate the ring-opening polymerization reaction. The reaction was then continued for 4 hours while maintaining the temperature at 53° C., to obtain a solution of a ring-opening polymer of dicyclopentadiene.
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resulting ring-opened polymer of dicyclopentadiene were 8,750 and 28,100, respectively, and the molecular weight distribution (Mw/Mn) calculated from these was 3.21.

0.037 parts of 1,2-ethanediol was added as a terminator to 200 parts of the resulting solution of ring-opened dicyclopentadiene polymer, and the mixture was heated to 60°C and stirred for 1 hour to terminate the polymerization reaction. 1 part of a hydrotalcite-like compound (Kyowa Chemical Industry Co., Ltd.'s "Kyoward (registered trademark) 2000") was added to the mixture, which was heated to 60°C and stirred for 1 hour. 0.4 parts of a filter aid (Showa Chemical Industry Co., Ltd.'s "Radiolite (registered trademark) #1500") was then added, and the adsorbent and solution were filtered using a PP pleated cartridge filter (Advantec Toyo Co., Ltd.'s "TCP-HX").

100 parts of cyclohexane were added to 200 parts of the filtered ring-opening polymer solution (polymer amount 30 parts), and 0.0043 parts of chlorohydridocarbonyltris(triphenylphosphine)ruthenium was added, and a hydrogenation reaction was carried out at 6 MPa hydrogen pressure and 180°C for 4 hours. This produced a reaction liquid containing a hydrogenated product of the ring-opening polymer of dicyclopentadiene. The hydrogenated product precipitated from this reaction liquid, forming a slurry solution.

The hydrogenated product and the solution contained in the reaction liquid were separated using a centrifuge and dried under reduced pressure at 60°C for 24 hours to obtain 28.5 parts of a hydrogenated product of a crystalline ring-opening polymer of dicyclopentadiene. The hydrogenation rate of this hydrogenated product was 99% or more, the glass transition temperature (Tg) was 95°C, and the melting point (Tm) was 262°C.

[Preparation of resin composition]
As the alicyclic structure-containing polymer, 100 parts of the norbornene-based hydride (crystalline COP) and 0.15 parts of crosslinked acrylic styrene particles having a volume average particle diameter of 0.5 μm ("Techpolymer" manufactured by Sekisui Chemical Co., Ltd., material: crosslinked methyl methacrylate-styrene copolymer, refractive index 1.525, hereinafter referred to as "particles C") as acrylic styrene particles were kneaded at a temperature of 300° C. to obtain a resin composition as resin pellets.

[Production of Molded Product, Measurement of Haze Value, and Evaluation of Haze Change]
The resin pellets were molded into an optical lens having a thickness of 3 mm and a diameter of 50 mm by injection molding using an injection molding machine ("ROBOSHOT S2000i100A" manufactured by Fanuc Corporation). The haze value of the lens was measured by the method described above, and was 0.92% before the high temperature and high humidity test and 1.68% after the high temperature and high humidity test, with a small change of 1.72%. The results are summarized in Table 1.

Example 6
100 parts of the norbornene hydride (COP1) used in Example 1 as the alicyclic structure-containing polymer and 0.15 parts of non-crosslinked acrylic styrene particles having a volume average particle size of 0.3 μm ("Techpolymer" manufactured by Sekisui Chemical Co., Ltd., material: non-crosslinked methyl methacrylate-styrene copolymer, refractive index 1.525, hereinafter referred to as "particle D") as the acrylic styrene particles were kneaded at a temperature of 240° C. to obtain a resin composition as resin pellets.

Optical lenses were molded from these resin pellets using the injection molding method in the same manner as in Example 1. The haze value of the lenses was measured using the method described above. The results are summarized in Table 1.

(Example 7)
100 parts of APEL5014CL (manufactured by Mitsui Chemicals) as the alicyclic structure-containing polymer and 0.15 parts of crosslinked acrylic styrene particles having a volume average particle diameter of 0.3 μm ("Techpolymer" manufactured by Sekisui Chemical Co., Ltd., material: crosslinked methyl methacrylate-styrene copolymer, refractive index 1.540, hereinafter referred to as "particles E") as the acrylic styrene particles were kneaded at a temperature of 260° C. to obtain a resin composition as resin pellets.

These resin pellets were molded into optical lenses with a thickness of 3 mm and a diameter of 50 mm by injection molding using an injection molding machine (ROBOSHOT S2000i100A manufactured by Fanuc Corporation). The haze value of the lens was measured using the method described above, and was 0.23% before the high-temperature, high-humidity test and 1.14% after the high-temperature, high-humidity test, with a small haze change of 0.91%. The results are summarized in Table 1.

(Comparative Example 1)
In producing the resin composition, 0.1 parts of crosslinked acrylic styrene particles having a volume average particle size of 3 μm ("Techpolymer" manufactured by Sekisui Chemical Co., Ltd., material: crosslinked methyl methacrylate-styrene copolymer, refractive index 1.525, hereinafter referred to as "Particle F") were added as the acrylic styrene particles. The resin composition and molded body were produced, and the haze value of the molded body was measured and the change in haze was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
In producing the resin composition, 0.2 parts of crosslinked acrylic styrene particles having a volume average particle size of 0.13 μm ("Techpolymer" manufactured by Sekisui Chemical Co., Ltd., material: crosslinked methyl methacrylate-styrene copolymer, refractive index 1.525, hereinafter referred to as "Particle G") were added as the acrylic styrene particles, and the resin composition and molded body were produced, and the haze value of the molded body was measured and the change in haze was evaluated in the same manner as in Example 1. The results are shown in Table 1.

The present invention provides a resin composition that can suppress haze changes even when the resin composition is placed in a high-temperature, high-humidity environment and then returned to room temperature, as well as a resin molded body and an optical element that use the resin composition.

Claims (4)

A resin composition comprising a cyclic olefin polymer and acrylic styrene particles having a volume average particle diameter d in the range of 0.15 μm<d<1 μm,
the absolute value of the difference between the refractive index of the acrylic styrene particles and the refractive index of the cyclic olefin polymer is 0.00 or more and 0.01 or less;
Resin composition (provided that
A resin composition for use in forming a base film for a gas barrier film, comprising a norbornene-based resin having a polar group and polymer fine particles containing a structural unit derived from a (meth)acrylic monomer and a structural unit derived from a styrene-based monomer;
A resin composition containing a norbornene-based resin having a polar group and polymer fine particles containing a structural unit derived from a (meth)acrylic monomer and a structural unit derived from a styrene-based monomer , the resin composition being formed into a substrate film for a gas barrier film; and
(Excluding resin compositions containing resins, organic fine particles, and 1 ppm or more of halogenated hydrocarbons as organic solvents ). The resin composition according to claim 1, wherein the acrylic styrene particles are crosslinked particles. A resin molded product molded from the resin composition according to claim 1 or 2. An optical element obtained by molding the resin composition according to claim 1 or 2.